Comprehensive Nuclear Materials. Vol.5

Comprehensive nuclear materials
EDITOR IN CHIEF
Rudy J. M. Konings
European Commission, Joint Research Centre,
Institute for Transuranium Elements, Karlsruhe, Germany
SECTION EDITORS
Todd R. Allen
Department of Engineering Physics, University of Wisconsin, Madison, WI, USA
Roger E. Stoller
Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, TN, USA
Shinsuke Yamanaka
Division of Sustainable Energy and Environmental Engineering, Graduate School of Engineering, Osaka University,
Osaka, Japan
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Radiation Effects in UO2
TRISO-Coated Particle Fuel Performance
Composite Fuel (cermet, cercer)
Metal Fuel-Cladding Interaction
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EDITORS BIOGRAPHIES
Rudy Konings is currently head of the Materials Research Unit in the
Institute for Transuranium Elements (ITU) of the Joint Research Centre
of the European Commission. His research interests are nuclear reactor
fuels and actinide materials, with particular emphasis on high temperature
chemistry and thermodynamics. Before joining ITU, he worked on nuclear
fuel-related issues at ECN (the Energy Research Centre of the Netherlands)
and NRG (Nuclear Research and Consultancy Group) in the Netherlands.
Rudy is editor of Journal of Nuclear Materials and is professor at the Delft
University of Technology (Netherlands), where he holds the chair of
Chemistry of the nuclear fuel cycle.
Roger Stoller is currently a Distinguished Research Staff Member in the

Materials Science and Technology Division of the Oak Ridge National
Laboratory and serves as the ORNL Program Manager for Fusion Reactor
Materials for ORNL. He joined ORNL in 1984 and is actively involved in
research on the effects of radiation on structural materials and fuels for
nuclear energy systems. His primary expertise is in the area of computational modeling and simulation. He has authored or coauthored more than
100 publications and reports on the effects of radiation on materials, as well
as edited the proceedings of several international conferences.
Todd Allen is an Associate Professor in the Department of Engineering

Physics at the University of Wisconsin Madison since 2003. Todds research
expertise is in the area of materials-related issues in nuclear reactors, specifically radiation damage and corrosion. He is also the Scientific Director for
the Advanced Test Reactor National Scientific User Facility as well as the
Director for the Center for Material Science of Nuclear Fuel at the Idaho
National Laboratory, positions he holds in conjunction with his faculty
position at the University of Wisconsin.
vi
Editors Biographies
Shinsuke Yamanaka is a professor in Division of Sustainable Energy and

Environmental Engineering, Graduate School of Engineering, Osaka
University since 1998. He has studied the thermophysics and thermochemistry of nuclear fuel and materials. His research for the hydrogen behavior in
LWR fuel cladding is notable among his achievements and he received
the Young Scientist Awards (1980) and the Best Paper Awards (2004) from
Japan Atomic Energy Society. Shinsuke is the program officer of Japan
Science and Technology Agency since 2005 and the visiting professor of
Fukui University since 2009, and he is also the associate dean of Graduate
School of Engineering, Osaka University since 2011.
PREFACE
There are essentially three primary energy sources for the billions of people living on the earths surface: the
sun, radioactivity, and gravitation. The sun, an enormous nuclear fusion reactor, has transmitted energy to the
earth for billions of years, sustaining photosynthesis, which in turn produces wood and other combustible
resources (biomass), and the fossil fuels like coal, oil, and natural gas. The sun also provides the energy that
steers the climate, the atmospheric circulations, and thus fuelling wind mills, and it is at the origin of
photovoltaic processes used to produce electricity. Radioactive decay of primarily uranium and thorium
heats the earth underneath us and is the origin of geothermal energy. Hot springs have been used as a source
of energy from the early days of humanity, although it took until the twentieth century for the potential of
radioactivity by fission to be discovered. Gravitation, a non-nuclear source, has been long used to generate
energy, primarily in hydropower and tidal power applications.
Although nuclear processes are thus omnipresent, nuclear technology is relatively young. But from the
moment scientists unraveled the secrets of the atom and its nucleus during the twentieth century, aided by
developments in quantum mechanics, and obtained a fundamental understanding of nuclear fission and fusion,
humanity has considered these nuclear processes as sources of almost unlimited (peaceful) energy. The first fission
reactor was designed and constructed by Enrico Fermi in 1942 in Chicago, the CP1, based on the fission of
uranium by neutron capture. After World War II, a rapid exploration of fission technology took place in the United
States and the Union of Soviet Socialist Republics, and after the Atoms for Peace speech by Eisenhower at the
United Nations Congress in 1954, also in Europe and Japan. A variety of nuclear fission reactors were explored for
electricity generation and with them the fuel cycle. Moreover, the possibility of controlled fusion reactions has
gained interest as a technology for producing energy from one of the most abundant elements on earth, hydrogen.
The environment to which materials in nuclear reactors are exposed is one of extremes with respect to
temperature and radiation. Fuel pins for nuclear reactors operate at temperatures above 1000 C in the center of
the pellets, in fast reactor oxide fuels even above 2000 C, whereas the effects of the radiation (neutrons, alpha
particles, recoil atoms, fission fragments) continuously damage the material. The cladding of the fuel and the
structural and functional materials in the fission reactor core also operate in a strong radiation field, often in a
dynamic corrosive environment of the coolant at elevated temperatures. Materials in fusion reactors are
exposed to the fusion plasma and the highly energetic particles escaping from it. Furthermore, in this
technology, the reactor core structures operate at high temperatures. Materials science for nuclear systems
has, therefore, been strongly focussed on the development of radiation tolerant materials that can operate in a
wide range of temperatures and in different chemical environments such as aqueous solutions, liquid metals,
molten salts, or gases.
The lifetime of the plant components is critical in many respects and thus strongly affects the safety as well as
the economics of the technologies. With the need for efficiency and competitiveness in modern society, there is
a strong incentive to improve reactor components or to deploy advanced materials that are continuously
developed for improved performance. There are many examples of excellent achievements in this respect. For
example, with the increase of the burnup of the fuel for fission reactors, motivated by improved economics and a
more efficient use of resources, the Zircaloy cladding (a ZrSn alloy) of the fuel pins showed increased
susceptibility to coolant corrosion, but within a relatively short period, a different zirconium-based alloy was
developed, tested, qualified, and employed, which allowed reliable operation in the high burnup range.
xxi
xxii
Preface
Nuclear technologies also produce waste. It is the moral obligation of the generations consuming the energy
to implement an acceptable waste treatment and disposal strategy. The inherent complication of radioactivity,
the decay that can span hundreds of thousands of years, amplifies the importance of extreme time periods in the
issue of corrosion and radiation stability. The search for storage concepts that can guarantee the safe storage
and isolation of radioactive waste is, therefore, another challenging task for materials science, requiring a close
examination of natural (geological) materials and processes.
The more than 50 years of research and development of fission and fusion reactors have undoubtedly
demonstrated that the statement technologies are enabled by materials is particularly true for nuclear
technology. Although the nuclear field is typically known for its incremental progress, the challenges posed
by the next generation of fission reactors (Generation IV) as well as the demonstration of fusion reactors will
need breakthroughs to achieve their ambitious goals. This is being accompanied by an important change in
materials science, with a shift of discovery through experiments to discovery through simulation. The progress
in numerical simulation of the material evolution on a scientific and engineering scale is growing rapidly.
Simulation techniques at the atomistic or meso scale (e.g., electronic structure calculations, molecular dynamics, kinetic Monte Carlo) are increasingly helping to unravel the complex processes occurring in materials
under extreme conditions and to provide an insight into the causes and thus helping to design remedies.
In this context, Comprehensive Nuclear Materials aims to provide fundamental information on the vast variety of
materials employed in the broad field of nuclear technology. But to do justice to the comprehensiveness of the
work, fundamental issues are also addressed in detail, as well as the basics of the emerging numerical simulation
techniques.
R.J.M. Konings
European Commission, Joint Research Centre,
Institute for Transuranium Elements, Karlsruhe, Germany
T.R. Allen
Department of Engineering Physics,
Wisconsin University, Madison, WI, USA
R. Stoller
Materials Science and Technology Division,
Oak Ridge National Laboratory, Oak Ridge, TN, USA
S. Yamanaka
Division of Sustainable Energy and Environmental Engineering,
Graduate School of Engineering, Osaka University, Osaka, Japan
FOREWORD
Nuclear materials denotes a field of great breadth and depth, whose topics address applications and facilities
that depend upon nuclear reactions. The major topics within the field are devoted to the materials science and
engineering surrounding fission and fusion reactions in energy conversion reactors. Most of the rest of the field
is formed of the closely related materials science needed for the effects of energetic particles on the targets and
other radiation areas of charged particle accelerators and plasma devices. A more complete but also more
cumbersome descriptor thus would be the science and engineering of materials for fission reactors, fusion
reactors, and closely related topics. In these areas, the very existence of such technologies turns upon our
capabilities to understand the physical behavior of materials. Performance of facilities and components to the
demanding limits required is dictated by the capabilities of materials to withstand unique and aggressive
environments. The unifying concept that runs through all aspects is the effect of radiation on materials. In this
way, the main feature is somewhat analogous to the unifying concept of elevated temperature in that part of
materials science and engineering termed high-temperature materials.
Nuclear materials came into existence in the 1950s and began to grow as an internationally recognized field
of endeavor late in that decade. The beginning in this field has been attributed to presentations and discussions
that occurred at the First and Second International Conferences on the Peaceful Uses of Atomic Energy, held in
Geneva in 1955 and 1958. Journal of Nuclear Materials, which is the home journal for this area of materials
science, was founded in 1959. The development of nuclear materials science and engineering took place in the
same rapid growth time period as the parent field of materials science and engineering. And similarly to the
parent field, nuclear materials draws together the formerly separate disciplines of metallurgy, solid-state
physics, ceramics, and materials chemistry that were early devoted to nuclear applications. The small priesthood of first researchers in half a dozen countries has now grown to a cohort of thousands, whose home
institutions are anchored in more than 40 nations.
The prodigious work, Comprehensive Nuclear Materials, captures the essence and the extensive scope of the
field. It provides authoritative chapters that review the full range of endeavor. In the present day of glance and
click reading of short snippets from the internet, this is an old-fashioned book in the best sense of the
word, which will be available in both electronic and printed form. All of the main segments of the field are
covered, as well as most of the specialized areas and subtopics. With well over 100 chapters, the reader finds
thorough coverage on topics ranging from fundamentals of atom movements after displacement by energetic
particles to testing and engineering analysis methods of large components. All the materials classes that have
main application in nuclear technologies are visited, and the most important of them are covered in
exhaustive fashion. Authors of the chapters are practitioners who are at the highest level of achievement
and knowledge in their respective areas. Many of these authors not only have lived through a substantial
part of the history sketched above, but they themselves are the architects. Without those represented here
in the author list, the field would certainly be a weaker reflection of itself. It is no small feat that so many
of my distinguished colleagues could have been persuaded to join this collective endeavor and to make the
real sacrifices entailed in such time-consuming work. I congratulate the Editor, Rudy Konings, and
xxiii
xxiv
Foreword
the Associate Editors, Roger Stoller, Todd Allen, and Shinsuke Yamanaka. This book will be an important
asset to young researchers entering the field as well as a valuable resource to workers engaged in the
enterprise at present.
Dr. Louis K. Mansur
Oak Ridge, Tennessee, USA
Permission Acknowledgments
The following material is reproduced with kind permission of Cambridge University Press
Figure 15 of Oxide Dispersion Strengthened Steels
Figure 15 of Minerals and Natural Analogues
Table 10 of Spent Fuel as Waste Material
Figure 21b of Radiation-Induced Effects on Microstructure
www.cambridge.org
The following material is reproduced with kind permission of American Chemical Society
Figure 2 of Molten Salt Reactor Fuel and Coolant
Figure 22 of Molten Salt Reactor Fuel and Coolant
Table 9 of Molten Salt Reactor Fuel and Coolant
Figure 6 of Thermodynamic and Thermophysical Properties of the Actinide Nitrides
www.acs.org
The following material is reproduced with kind permission of Wiley
Table 3 of Properties and Characteristics of SiC and SiC/SiC Composites
Figure 5 of Advanced Concepts in TRISO Fuel
Figure 6 of Advanced Concepts in TRISO Fuel
Figure 30 of Material Performance in Supercritical Water
Figure 32 of Material Performance in Supercritical Water
Figure 19 of Tritium Barriers and Tritium Diffusion in Fusion Reactors
Figure 9 of Waste Containers
Figure 11 of Carbide Fuel
Figure 2 of The UF system
Figure 18 of Fundamental Point Defect Properties in Ceramics
Table 1 of Fundamental Point Defect Properties in Ceramics
Figure 17 of Radiation Effects in SiC and SiC-SiC
Figure 21 of Radiation Effects in SiC and SiC-SiC
Figure 6 of Radiation Damage in Austenitic Steels
Figure 7 of Radiation Damage in Austenitic Steels
Figure 17 of Ceramic Breeder Materials
Figure 33a of Carbon as a Fusion Plasma-Facing Material
Figure 34 of Carbon as a Fusion Plasma-Facing Material
i
ii

Table 5 of Carbon as a Fusion Plasma-Facing Material
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The following material is reproduced with kind permission of Springer
Figure 4 of Neutron Reflector Materials (Be, Hydrides)
Figure 6 of Neutron Reflector Materials (Be, Hydrides)
Figure 1 of Properties and Characteristics of SiC and SiC/SiC Composites
Figure 22d of Fission Product Chemistry in Oxide Fuels
Figure 3 of Behavior of LWR Fuel During Loss-of-Coolant Accidents
Figure 14a of Irradiation Assisted Stress Corrosion Cracking
Figure 14b of Irradiation Assisted Stress Corrosion Cracking
Figure 14c of Irradiation Assisted Stress Corrosion Cracking
Figure 25a of Irradiation Assisted Stress Corrosion Cracking
Figure 25b of Irradiation Assisted Stress Corrosion Cracking
Figure 1 of Properties of Liquid Metal Coolants
Figure 5b of Fast Spectrum Control Rod Materials
Figure 3 of Oxide Fuel Performance Modeling and Simulations
Figure 51 of Phase Diagrams of Actinide Alloys
Figure 6 of Thermodynamic and Thermophysical Properties of the Actinide Oxides
Figure 7b of Thermodynamic and Thermophysical Properties of the Actinide Oxides
Figure 9b of Thermodynamic and Thermophysical Properties of the Actinide Oxides
Figure 35 of Thermodynamic and Thermophysical Properties of the Actinide Oxides
Table 11 of Thermodynamic and Thermophysical Properties of the Actinide Oxides
Figure 18 of Radiation Damage of Reactor Pressure Vessel Steels
Figure 7 of Radiation Damage Using Ion Beams
Figure 9b of Radiation Damage Using Ion Beams
Figure 36d of Radiation Damage Using Ion Beams
Table 3 of Radiation Damage Using Ion Beams
Figure 5 of Radiation Effects in UO2

Figure 9a of Ab Initio Electronic Structure Calculations for Nuclear Materials
Figure 9b of Ab Initio Electronic Structure Calculations for Nuclear Materials
Figure 9c of Ab Initio Electronic Structure Calculations for Nuclear Materials
Figure 10a of Ab Initio Electronic Structure Calculations for Nuclear Materials
Figure 23 of Thermodynamic and Thermophysical Properties of the Actinide Carbides
Figure 28a of Thermodynamic and Thermophysical Properties of the Actinide Carbides
Figure 28b of Thermodynamic and Thermophysical Properties of the Actinide Carbides
Figure 2 of Physical and Mechanical Properties of Copper and Copper Alloys
Figure 5 of Physical and Mechanical Properties of Copper and Copper Alloys
Figure 6 of The Actinides Elements: Properties and Characteristics
Table 1 of The Actinides Elements: Properties and Characteristics
Table 6 of The Actinides Elements: Properties and Characteristics
Figure 25 of Fundamental Properties of Defects in Metals
Table 1 of Fundamental Properties of Defects in Metals
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The following material is reproduced with kind permission of Taylor & Francis
Figure 9 of Radiation-Induced Segregation
Figure 6 of Radiation Effects in Zirconium Alloys
Figure 1 of Dislocation Dynamics
Figure 4 of Radiation-Induced Effects on Material Properties of Ceramics (Mechanical and Dimensional)
Figure 18a of Primary Radiation Damage Formation
Figure 18b of Primary Radiation Damage Formation
Figure 18c of Primary Radiation Damage Formation
Figure 18d of Primary Radiation Damage Formation
Figure 18e of Primary Radiation Damage Formation
Figure 18f of Primary Radiation Damage Formation
Figure 1 of Radiation-Induced Effects on Microstructure
Figure 27 of Radiation-Induced Effects on Microstructure
Figure 5 of Performance of Aluminum in Research Reactors
Figure 2 of Atomic-Level Dislocation Dynamics in Irradiated Metals
Figure 10a of Atomic-Level Dislocation Dynamics in Irradiated Metals
Figure 10b of Atomic-Level Dislocation Dynamics in Irradiated Metals
Figure 10c of Atomic-Level Dislocation Dynamics in Irradiated Metals
iii
iv
Figure 10d of Atomic-Level Dislocation Dynamics in Irradiated Metals

Figure 16e of Atomic-Level Dislocation Dynamics in Irradiated Metals
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5.01
Corrosion and Compatibility
S. Lillard
Los Alamos National Laboratory, Los Alamos, NM, USA
2012 Elsevier Ltd. All rights reserved.
5.01.1
Theory
5.01.1.1
5.01.1.2
5.01.1.3
5.01.1.4
5.01.1.5
5.01.1.6
5.01.2
5.01.2.1
5.01.2.2
5.01.2.3
5.01.2.4
References
Introduction
Half Cell Reactions
Cell Potentials and the Nernst Equation
Reference Electrodes and Their Application to Nuclear Systems
The Thermodynamics of Corrosion from Room Temperature to the PWR
Kinetics of Dissolution and Passive Film Formation
Analytical Methods
Introduction
Potentiodynamic Polarization
Electrochemical Impedance Spectroscopy
MottSchottky Analysis
Abbreviations
BWR
CNLS
Boiling water reactor

Complex nonlinear least squares fitting of
the data
EC
Electrical equivalent circuit
EIS
Electrochemical impedance
spectroscopy
EPBRE External pressure-balanced reference
electrode
FFTF
Fast Flux Test Facility
HIC
Hydrogen-induced cracking
HIFER Hi-Flux Isotope Reactor
IG
Intergranular
LBE
Leadbismuth eutectic
PWR
Pressurized water reactor
SCC
Stress corrosion cracking
SS
Stainless steel
Symbols
A
ai
C
ci
CR
E
EW
Ecorr
f
Surface area
Activity of species i
Capacitance
Concentration of species i
Corrosion rate
Potential
Equivalent weight
Corrosion potential
Mass fraction
F
i
icorr
ji
k
L
M
MM
n
ND
Q
r
R
Rp
RV
S
t
ti
T
Vo
z
Z
Z0
Z00
jZj
b
ba
bc
d
2
2
3
4
6
8
10
10
11
12
14
16
Fugacity
Faradays constant
Current density
Corrosion current density
Square root of 1
Rate constant
Oxide thickness
Molecular weight
Metal cation
Number of electrons
Donor concentration
Reaction quotient
Rate of reaction
Gas constant
Polarization resistance
Solution resistance
Entropy of transport
Time
Transport number of species i
Temperature
Oxygen vacancy
Charge
Impedance
Real part of the impedance
Imaginary part of the impedance
Magnitude of the impedance
Symmetry factor
Anodic Tafel slope
Cathodic Tafel slope
Double layer thickness

0
DCp Change in standard partial molar heat

capacity
DE0 Standard reduction potential
DG Change in Gibbs energy
DG0 Standard Gibbs energy
DS0 Standard entropy change
Electronic charge
Permittivity of space
0
f
Applied potential
h
Overpotential
u
Phase angle
r
Material density
v
Frequency
5.01.1 Theory
5.01.1.1
Introduction
Mars Fontana identified eight forms of corrosion in

his book Corrosion Engineering1 and it is quite easy
to find examples of almost all of these in nuclear
reactors in both the primary and secondary cooling
water systems. For example, galvanic corrosion in
zirconiumstainless steel couples,2,3 crevice corrosion in tube sheets4 and former baffle bolts,5 and
pitting corrosion in alloy 600 steam generator
tubes.6,7 Perhaps the most infamous form of corrosion
observed in nuclear reactors is stress corrosion cracking (SCC), or environmental fracture, as we shall
refer to it here, which has numerous examples in
the literature. Environmental fracture includes both
intergranular SCC (IG), such as that which occurs in
austenitic stainless steel, and hydrogen-induced cracking (HIC), frequently observed in nickel base alloys.
Failure by one of these mechanisms results from an
interplay between stress, microstructure, and the environment (e.g., the electrochemical interface). The goal
of this chapter is not to address each of the corrosion
mechanisms outlined by Fontana individually, that will
be accomplished in the following chapters. Rather,
this chapter is meant to provide the reader with the
fundamental electrochemical theory necessary to
critically evaluate the data and discussions in the
corrosion chapters that follow.
In this section, we will review the fundamental
theory of the electrochemical interface. In the first
three subsections, we review Half Cell Reaction, Cell
Potentials and the Nernst Equation, and Reference
Electrodes in Nuclear Systems. In these sections, we
develop the theory necessary to understand the role of
electrochemical potential in environmental fracture
and corrosion mechanisms. For example, intergranular

stress corrosion cracking (IGSCC) is only observed at
potentials more positive than a critical value while HIC
is only observed at potentials more negative than a
critical value. In the remaining two sections, we review
the Thermodynamics from Room Temperature to the
pressurized water reactor (PWR) and Kinetics of Dissolution and Passive Film Formation. These sections
should help the reader to understand the role of the
passive film in the corrosion mechanism and the competition that occurs between film formation and metal
dissolution rate. As the fundamental role of irradiation
in corrosion and environmental fracture mechanism is
far from well established, in each section, we incorporate empirical irradiation data as examples and discuss
concepts that are more broadly important to nuclear
systems.
5.01.1.2
Half Cell Reactions
The electrochemical interface is characterized by an

electrode (in this case a metal such as a cooling pipe)
and an electrolyte (e.g., the cooling water in a reactor). While the bulk electrolyte contributes to variables such as solution chemistry and ohmic drop
(solution resistance is discussed later in this chapter),
it is the first nanometer of electrolyte that plays the
most important role in electrochemistry. In this short
distance, referred to as the electrochemical double
layer, a separation of charge occurs. It is this separation of charge that provides the driving force
(potential drop) for corrosion reactions. For example,
a 100 mV-applied potential across a typical double
layer will result in an electric field on the order of
106 V cm2. In the model proposed by Helmholtz,8
the double layer may be thought of as capacitor, with
positive charge on the metal electrode and the
adsorption of negatively charged cations on the solution side (Figure 1). The capacitance of the double
layer is equal to that in its electrical analog e0D/d,
where e0 is the permittivity of space, D is the dielectric, and d is the thickness of the layer. For most
electrochemical double layers, C is on the order of
106 F cm2.
Electrochemical reactions that take place in the
double layer are reactions in which a transfer of
charge (electrons) occurs. There are two different
types of cells in which electrochemical reactions
may occur9:
Electrolytic cells in which work, in the form of electrical
energy, is required to bring about a nonspontaneous reaction.
Metal
Because the system cannot store charge, the electrons

produced during the anodic reaction must be used.
This occurs at the cathode where typical reactions
may include oxygen reduction:
Excess negative
charge
Excess positive
charge
Bulk solution
Acid: O2 4H 4e ) 2H2 O
Base: O2 2H2 O 4e ) 4OH

+
II
III
or hydrogen reduction:
2H 2e ) H2
fmetal
IV
From eqns [I] and [III], the general corrosion of an

Fe surface in basic solution may then be written as:
2Fe O2 2H2 O ) 2FeOH2
fsolution
Double
layer
Figure 1 A diagram depicting the separation of charge at
the electrochemical double layer and the associated
potential drop (f).
H2O
2H+
ClH2
H2O
H+
H2O
ClH2O
Cl-
H+
Oxide
Fe
For any chemical reaction the driving force, the

Gibbs energy, may be written as10:
Figure 2 Diagram of what the anodic and cathodic

reactions may look like on an iron surface depicting the
separation of reactions and ionic conduction.
DG DG 0 RT lnQ
Voltaic cells in which a spontaneous reaction occurs

resulting in work in the form of electrical energy.
Electrolytic cells cover a fairly large number of
electrochemical reactions but may generally be
thought of as plating or electrolysis type reactions
and will not be treated here. Corrosion reactions are
voltaic cells and will be the focus of this chapter. As in
an electrolytic cell, voltaic cells are characterized by
two separate electrodes, an anode and a cathode. In
corrosion, reactions at the anode take the form of
metal dissolution, the formation of a soluble metal
cation:
Fe ) Fe2 2e
where Fe(OH)2 is the corrosion product.

An example of what the anodic and cathodic reactions on Fe electrode might look like is presented in
Figure 2. Though the anodic and cathodic reactions
occur at physically separate locations, as shown in
this figure, the reactions must be connected via an
electrolyte (aqueous solution). Figure 2 also suggests
that corrosion reactions are controlled by variables
such as mass transport (diffusion, convection, migration), concentration, and ohmic drop (resistivity of
the electrolyte). These variables will be considered in
our discussion of corrosion kinetics.
5.01.1.3 Cell Potentials and the Nernst
Equation
Fe2+
e-
V
I
1
where DG0 is the standard Gibbs energy, Q is the

reaction quotient equal to the product of the activities (assumed to obey Raoults Law for dilute solutions and, thus, equal to the concentration) of the
products divided by the reactants, R is the gas constant, and T is temperature. The electrical potential,
E, is related to the Gibbs energy of a cell by the
relationship:
nFE DG
2
where n is the number of electrons participating

in the reaction and F is Faradays constant. For the
reduction of hydrogen on platinum:
1
e Pt , H2g
Haq
2
VI
The reaction quotient, Q (starting conditions) becomes:

Q
fH2 1=2
H
3
where fH2 is the fugacity of hydrogen gas. Substituting

eqns [2] and [3] into eqn [1], we find for the reduction
of hydrogen on platinum that:
"
#
RT fH2 1=2
0
4
ln
E DE
H
F
where F is Faradays constant and DE0 is the standard
reduction potential for the reaction in eqn [VI]. Equation [10] is commonly referred to as the Nernst equation and defines the equilibrium reduction potential of
the half cell and is pH dependent. The Nernst equation
is commonly expressed in its generalized form as:
E DE 0
RT
lnQ
F
5
5.01.1.4 Reference Electrodes and Their

Application to Nuclear Systems
In Equation [4], all of the parameters are easily
calculated with one exception, DE0. Therefore, we
define DE0 0 in eqn [4] for a set of specific parameters and refer to this cell as the standard hydrogen
electrode (SHE): H2 pressure of 1 atm, a pH 0, and
a temperature of 25 C. This provides a reference
from which we can calculate the standard potentials
for all other reduction reactions using eqn [5]. These
are referred to as standard reduction potentials and a
few examples are provided in Table 1.
While the SHE is the accepted standard, from
a practical standpoint, this reference electrode is
difficult to construct and maintain. As such, experimentalists have taken advantage of a number of other
reduction reactions to construct reference electrodes
for laboratory use. The reaction selected typically
depends on the application. One common reference
electrode is the silversilver chloride electrode
(Ag/AgCl) which is based on the reduction of Ag
in a solution of potassium chloride:
Ag e , Ags
VII
Ag Cl , AgCls
VIII
and the overall reaction being:

Ags Cl , AgCls e
XI
Table 1
Standard reduction potentials for several reactions important to the nuclear power industry
Reduction reaction
Standard reduction
potential (V)
Au3 3e Au
Cl2 2e 2Cl
O2 4H 4e 2H2O
Ag e Ag
Fe3 e Fe2
O2 2H2O 4e 4OH
AgCl e Ag Cl
2H 2e H2 (NHE)
Ni2 2e Ni
Fe2 2e Fe
Cr3 3e Cr
Zr4 4e Zr
Al3 3e Al
Li e Li
1.52
1.36
1.23
0.80
0.77
0.4
0.22
0.0
0.25
0.44
0.74
1.53
1.66
3.04
The Nernst equation for eqn [XI] is equal to:

aAgCl
RT
0
E DEAg=AgCl
ln
aAg aCl
F
0
DEAg=AgCl
lnaCl
6
where aCl is the activity of chloride and for which

the concentration (mCl ) in molal (mol kg1) is frequently substituted. In the corrosion lab, the reference electrode is constructed by electrochemically
depositing an AgCl layer onto a silver wire. This
wire is then placed in a glass capillary filled with a
solution of potassium chloride the concentration of
which then defines the cell potential (aCl in eqn [6]).
One end of the capillary is sealed using a porous frit
(typically a porous polymer) that acts as a junction
between the solution of the reference electrode and
the environment of the corrosion experiment.
While the Ag/AgCl reference electrode construction described above is straightforward for the lab,
there are several obstacles that must be overcome
before it can be used in a nuclear power plant setting,
namely, radiation flux, pressure, and temperature. As it
turns out, the primary impact of ionizing radiation
on laboratory reference electrodes relates to damage
of the cotton wadding and polymer frits used in their
construction and no change in cell potential occurs.11
As such, two approaches based on the Ag/AgCl
reference electrode have been used to measure electrode potential in nuclear power reactors. In the first
approach, an internal reference electrode operates in
the same high-temperature environment as the reactor. In this case, one must consider the solubility of
Sapphire lid
AgCl pellet
Rulon adapter
Compression fitting
Sapphire
container
Pt cap
Ni wire
Alumina
insulators
Ceramic to
metal braze
Restrainer
Ag/AgCl
Kovar
TIG weld
304SS
Seal
Coaxial
cable
Figure 3 Diagram of an internal Ag/AgCl reference
electrode used in BWRs. Top end is inserted into the cooling
loop, while the coaxial cable provides electrical connection.
Reprinted from Indig, M. E. In 12th International Corrosion
Congress, Corrosion Control for Low-Cost Reliability; NACE
International: Houston, TX, 1993; p 4224, with permission
from NACE International.
Ag/Cl complexes that form as a function of temperature eqn [6].12,13 That is, reactions in addition to eqns
[VIII] and [XI] must be considered. From a construction viewpoint, the internal reference electrode
consists of a silver chloride pellet on a platinum foil
(Figure 3).14 External potential measurement is made
via contact with a nickel wire which is connected to an
electrometer via a coaxial cable. The electrode is
housed in a sapphire tube that is sealed via a porous
sapphire cap. In this configuration, there is no internal
electrolyte per se. Upon placing the electrode in a
boiling water reactor (BWR), the porous cap allows
the cooling water to penetrate the electrode and the
potential is determined from eqn [6] and the solubility
of AgCl in high purity water as a function of
temperature.15
In the second approach, an external pressurebalanced reference electrode is used (EPBRE).
In the EPBRE, the reference electrode is maintained
at room temperature and pressure and the corresponding constants are used in eqn [6]. The
reference is connected to the high-temperature environment via a nonisothermal salt bridge sealed with a
porous zirconia plug (Figure 4).16 As a result of this
configuration, the EPBRE is not susceptible to
Compression fitting
1/4 NPT
Pure water or
0.01 M KCl
Glass wick
1/4 OD SS
tube
Heat-shrinkable
PTFE tube
SS nut
Rulon sleeve
Zirconia plug
Figure 4 A diagram of a pressure-balanced reference

electrode is used in BWRs. Bottom of figure is sealed into
pressure vessel via compression fitting while Ag/AgCl
electrode (top) remains at room temperature and pressure.
Reprinted from Oh, S. H.; Bahn, C. B.; Hwang, I. S.
J. Electrochem. Soc. 2003, 150, E321, with permission from
The Electrochemical Society.
potential deviations owing to the solubility of AgCl

and its complexes as a function of temperature. However, the temperature gradient between the reactor
and the reference electrode results in a junction
potential that must be subtracted from eqn [6]. The
corresponding thermal liquid junction potential
(ETLJ)17 is given by:

1 T2 tM SM tCl SCl
dT
7
ETLJ
zM
zCl
F T1
where t, S, and z represent the transport number, the
entropy of transport, and the charge on the cation,
respectively. The symbol M in eqn [7] represents the
metal in the chloride salt, MCl, and is commonly Li, Na,
or K. In addition to ETLJ, there is also the isothermal
liquid junction potential, EILJ, which arises due to the
differences in cation and anion mobilities through
the porous frits and the fact that the electrolyte in the
external reference (typically KCl) is vastly different
from the reactor cooling water in which it is immersed17:
RT T2 ti
EILJ
dlnai
8
F T1 zi
where the subscript i denotes a species that may be

transported through the zirconia plug and for a nuclear
power reactor may include species ions as Ag, Cl,
H, OH, K, and B(OH4).
It has been shown that both ETLJ and EILJ each
increase by as much as 0.15 V over the temperature
range of 25350 C. The result is a decrease in the
measured potential of 0.30 V at 350 C. While these
junction potentials can be calculated and used to
correct eqn [7], it has been shown that there is
some deviation at higher temperatures (>200 C)
and an experimental fitting procedure is the preferred method for calibration of the reference
electrode.
reactions with two soluble species
3
Fe
11
Fe2 Fe3 e E 0 0:771 0:059log
Fe2
solubility of iron and its oxides

Fe Fe2 2e E 0 0:440 0:0295logFe2
2Fe2 3H2 O Fe2 O3 6H 2e

E 0 0:728 0:177pH 0:059logFe2
An atlas of electrochemical equilibria has been created by M. Pourbaix for metals in aqueous solution at
room temperature.18 This atlas contains potential
pH diagrams, so-called Pourbaix diagrams, which
define three equilibrium thermodynamic domains
for metals in aqueous solutions: immunity, passivity,
and corrosion. Immunity is defined as the state where
the base metal is stable while corrosion is defined
as the formation of soluble metal cations and passivity the formation of a stable oxide film. Pourbaixs
derivation requires that the values of the standard
chemical potential, m0, for all of the reacting substances are known for the standard state at the
temperature and pressure of interest. For chemical
reactions at room temperature, the equilibrium conditions are defined by the relationship18:
P 0
nm
9
logK
5708
and for electrochemical reactions at room temperature (Table 1) equilibrium is defined by:
P 0
nm
0
10
E
96485n
where K is the equilibrium constant for the reaction,
m0 is in Joules per mole, v is the stoichiometric coefficient for the species, n is the number of electrons, 5708
is a conversion constant equal to RT/(log10e) where
T is temperature (298.15 K) and R the ideal gas constant (8.314472 J (K mol)1), and 96 485 is Faradays
constant in J (mol V)1.
As an example of these diagrams, consider the
ironwater system and the solid substances Fe,
Fe3O4, and Fe2O3. Pourbaix18 defined the relevant
equations for this system as:
13

Fe 2H2 O HFeO
2 3H 2e
E 0 0:493 0:089pH 0:0295logHFeO

2
5.01.1.5 The Thermodynamics of Corrosion

from Room Temperature to the PWR
12
14

3HFeO
2 H Fe3 O4 2H2 O 2e
E 0 1:819 0:029pH 0:088logHFeO

2
15
reaction of two solid substances

3Fe 4H2 O Fe3 O4 8H 8e
E 0 0:085 0:059pH
16
2Fe3 O4 H2 O 3Fe2 O3 H 2e

E 0 0:221 0:059pH
17
An example of a simplified Pourbaix diagram for Fe

at room temperature based on the reactions in eqns
[11][17] is presented in Figure 5, where Eq. [12]
corresponds to figure line 23, [13] to line 28, [14] to
line 24, [15] to line 27, [16] to line 13 and [17] to line
17. Note that Eq. [11] is the boundary between Fe2
and Fe3 and was not drawn in the original figure.
In addition to the lines separating the domains for Fe,
Pourbaix diagrams will typically include the domains
associated with water stability (oxidation and reduction) represented by the dashed lines marked a and b
in Figure 5. Upon inspection of this diagram one
would conclude what is know from experience with
Fe: that iron is passive in alkaline solutions and at
higher applied potentials owing to oxide film formation while at more acidic solutions Fe is susceptible to
corrosion owing to Fe2. It is worth noting again that
these potentialpH domains are defined solely by the
thermodynamic stability of the species within them
and these diagrams do not consider kinetics which
will be addressed later in this chapter. This is important as while a species/reaction may be thermodynamically stable it may be kinetically hindered.
While the use of Pourbaix diagrams to characterize room temperature corrosion reactions is
1.5
Fe3+
1.5
Fe3+
20
20
1.0
1.0
b
Fe2O3
Fe2+
EH2 (200 C) (V)
28
EH (25 C) (V)
0.5
a
26
-0.5
17
Fe3O4
23
0.5
Fe2+
26
13
-1.0
HFeO-2
17
Fe3O4
23
27
24
Fe
Fe2O3
a
-0.5
13
-1.0
28
Fe
HFeO22-
-1.5
-1.5
0
10
15
pH
widespread, these diagrams and the method for generating them as presented thus far cannot be used at
the higher temperatures associated with nuclear power
reactors. This is due to the lack of standard potentials
at elevated temperature as required by eqns [9] and
[10] (e.g., the application of Table 1 to higher temperature). In the absence of these high-temperature thermodynamic data, Townsend19 used an extrapolation
method introduced by Criss and Coble (the correspondence principle). The method allows for empirical
entropy data of ionic species at 25 C to be extrapolated to higher temperatures. In this method, the standard Gibbs free energy is calculated from the
relationship:
T
T
250
250
DC p T dlnT
DC p T dT
18
0
where DS is the standard entropy change and DC p is

the change in standard partial molar heat capacity. The
potentialpH diagram for the FeH2O system and the
solid substances Fe, Fe3O4, and Fe2O3 at 200 C calculated by Townsend is presented in Figure 6. In comparison with the diagram at 25 C (Figure 5), the
Fe2O3 and Fe3O4 regions are extended to lower pH
and potentials. As a result the area associated with
corrosion at lower solution pH is decreased. However,
0
24
10
15
pH
Figure 5 A simplified potentialpH diagram for the

FeH2O system and the solid substances Fe, Fe3O4, and
Fe2O3 at 25 C based on the reactions in eqns [11][17].
Reprinted from Townsend, H. E. Corrosion Sci. 1970,
10, 343, with permission from Elsevier.
DDG 0 DT DS 0 250
29
27
Figure 6 The potentialpH diagram for the FeH2O

system and the solid substances Fe, Fe3O4, and Fe2O3 at
200 C. Most dramatic influence of increased temperature is
the presence of a large region of soluble species (corrosion)
at high pH. Reprinted from Townsend, H. E. Corrosion Sci.
1970, 10, 343, with permission from Elsevier.
the most notable change in the diagram is at high pH

where the area associated with corrosion owing to the
soluble HFeO
2 has increased dramatically. The Criss
and Coble method is limited, however, to the
150200 C range and, to extend the Pourbaix to the
temperatures of power reactors, Beverskog used a
HelgesonKirkhamFlowers model to extend the
heat capacity data to 300 C.20
Thus far, we have described a method for generating electrochemical equilibria diagrams and regions
of passivity, corrosion, and immunity for pure metals
from 25 to 300 C. From an engineering standpoint,
we would like to know this information for structural
alloys such as austenitic stainless steels and super
nickel alloys. At temperatures near 25 C, the predominant oxide responsible for passivity is Cr2O3 and it is
sufficient to rely only on the Cr potentialpH diagram
for alloys with a high Cr content. However, at higher
temperatures other oxides form such as Fe(Fe,Cr)2O4,
(Cr,Fe)2O3, (Cr,Fe,Ni)3O4, and (Cr,Fe,Ni)2O3, and it is
desirable to know the thermodynamic stability of the
alloy. Beverskog has developed the ternary potential
pH diagrams for the FeCrNiH2OH2 system for
temperatures up to 300 C using heat capacitance data
and the revised HelgesonKirkhamFlowers model
described above.21 However, FeCrNi phases lack
thermodynamic data and the ternary oxides were,
npH
2
H2CrO4(aq)
HCrO4-
Potential (VSHE)
CrO42Cr(OH)2+
0
NiCr2O4(cr)
Cr2+
FeCr2O4(cr)
-1
Cr2O3(cr)
Cr(cr)
-2
6
pH300 C
10
Figure 7 PotentialpH diagram for chromium species in

FeCrNi at 300 C. Concentration of aqueous species is
106 molal. Reprinted from Beverskog, B.; Puigdomenech, I.
Corrosion 1999, 55, 1077, with permission from NACE
International.
thus, not considered. The diagrams assumed that the

metallic elements in the alloy had unit activity, that is,
equal amounts of iron, chromium, and nickel. An
example of the potentialpH diagram for chromium
species in FeCrNi at 300 C and aqueous species
with a concentration of 106 molal is presented in
Figure 7. Unlike the Fe diagram, where the presence
of soluble HFeO2
2 species increased with temperature
(Figure 6), the diagram for Cr in FeCrNi is dominated by passive region where the stable oxides of
Cr2O3, FeCr2O4, and NiCr2O4 are formed.
5.01.1.6 Kinetics of Dissolution and
Passive Film Formation
The study of dissolution kinetics, corrosion rate,
attempts to answer the question: What are the relationships that govern the flow of current across a
corroding interface and how is this current flow
related to applied potential? Consider the anodic
dissolution of a metal with an activation barrier
equal to G1a nFE (eqn [2]). If we increase the driving
force (potential) from its equilibrium condition, E0, to
a new value, f, the new barrier is given by the
relationship22:
decreasing the barrier, that is, not all of the applied

potential is dropped across the electrochemical double layer. The rate (ra) of this reaction is expressed in
the same, Arrhenius, form as for chemical reactions:

DGa
20
ra ia =nF ka co exp
RT
where ia is the anodic current density, ka is the rate
constant, co is the concentration of oxidized species,
and DGa is the change in free energy for the anodic
reaction. Substituting G2a G1a in eqn [20] for DGa in
eqn [19], we express the anodic reaction rate as22:

1 bnF

21
ia nFka cR exp
RT
where (the overpotential) represents a departure
from equilibrium and is equal to f E0. We can derive
a similar expression for the cathodic reaction22:

bnF

22
ic nFkc co exp
RT
where ic is the cathodic current density, kc is the rate
constant, and co is concentration of oxidized species.
Combining eqns [21] and [22] and rearranging them,
we can write an expression for the total current, i:

1 bnF
bnF
exp

23
i io exp
RT
RT
where io is the exchange current density and is equal to
b b
nFkcc1b
o ka cR . This expression is commonly referred
to as the ButlerVolmer equation.
To apply eqn [23] to corrosion reactions, we need
to be able to relate to the corrosion potential, Ecorr ,
that is, as it stands the ButlerVolmer equation is
derived for equilibrium conditions. Returning to our
definition of the overpotential f E0, by both
subtracting and adding Ecorr from the right side of
this definition, inserting the resulting expression back
into eqn [23] and rearranging we find22:

1 bF
Ecorr Ea
icorr ia exp
RT

bF
ic exp Ecorr Ec
25
RT
19
For small applied potentials around Ecorr , the Stern

Geary approximation of eqn [24] is used23:

ba bc
f Ecorr
26
i 2:303icorr
ba bc
where b is the symmetry factor and reflects the fact

that not all of the increase in potential goes to
where ba and bc are defined as the anodic and

cathodic Tafel slopes (discussed in Section
Ga2 Ga1 1 bnF f E0
0.4
0.1
0.35
0
Current density (A m-2)
Potential (V vs. SCE)
0.3
0.25
0.2
Beam on at 100 nA
~540 s
0.15
0.1
500
1000
Time (s)
1500
2000
5.01.2.2) having units of volts and are empirical factors related to the symmetry factor by the relationships22:
RT
1 bnF
bc 2:303
RT
bnF
-0.1
-0.2
Increasing radiation flux
Increasing cathodic reaction rate
-0.3
-0.4
-0.5
Figure 8 Influence of proton irradiation on the Ecorr of a

SS 304L electrode in dilute sulfuric acid, pH 1.6. The
increase is caused by the production of water radiolysis
products.
ba 2:303
Beam = 35 na
Beam = 62 na
Beam = 100 na
27
28
As it relates to the nuclear power industry, eqn [24] not

only relates the corrosion rate (icorr) to the applied
potential, f, but it can also help us to rationalize
other processes such as the influence of water radiolysis
products on corrosion rate. For example, it is generally
observed that ionizing radiation (g, neutron, proton,
etc.) increases Ecorr potential (Figure 8) and corrosion
rate at Ecorr .24 The flux of ionizing radiation on the
cooling water results in radiolysis, the breaking of
chemical bonds. During the course of water radiolysis,
a wide variety of intermediate products are formed,
such as O2, eaq, and the OH radical.25 The vast majority of these species have very fast reaction rates so that
the end result is a handful of stable species. These
stable products are typically oxidants, such as O2, H2,
and H2O2. That is, these products readily consume
electrons (eqns [II][IV]) and increase cathodic reaction rate (Figure 9). From eqn [25] we see that an
increase in the cathodic reaction rate, ic, necessarily
results in an increase in corrosion rate, icorr , consistent
with the observation described.
While the development of dissolution kinetics is
straightforward, the kinetics associated with passive
-0.6
-0.2
-0.1
0
0.1
0.2
0.3
0.4
0.5
Figure 9 Influence of proton irradiation on the cathodic

reactions on a Au electrode in dilute sulfuric acid, pH 1.6.
The increase is caused by the production of water radiolysis
products.
film formation and breakdown are less well understood yet equally as important to our understanding
of corrosion mechanisms. One such example is the
case of localized corrosion where the probability for
a pit to transition from a metastable to a stable state is
governed by the ability of the active surface to repassivate. Another example is the initiation of SCC where
passive film rupture results in very high dissolution
rates and, correspondingly, crack advance rate which is
controlled by the activation kinetics described above as
the bare metal dissolves.2628 During the propagation
stage of SCC, the crack tip must propagate faster than
(1) the oxide film can repassivate the surface and (2)
the corrosion rate on the unstrained crack sides so that
dissolution of the walls does not result in blunt notch.
To evaluate the role of repassivation kinetics
in SCC and corrosion mechanisms in general, investigators set about measuring three critical experimental parameters, namely film: ductility,29,30 bare
surface dissolution rates,3133 and passive film formation rates34,35 for various alloys. Each of these techniques involves the depassivation of a metal electrode
using a tensile frame or a nano-indenter (in the case
of ductility studies) or scratching/breaking an electrode (bares surface current density and repassivation
studies) and measuring the resulting current transient
as a function of time. An example of a current transient for SS 304L in chloride solution is presented
in Figure 10. The surface was under potentiostatic
control and was bared using a diamond scribe. The
data were collected using a high-speed oscilloscope.
10
7.0 104
6.0 104
Current (A)
5.0 104
td
tr
0.002 0.004 0.006 0.008

Time (s)
4.0 104
3.0 104
2.0 104
1.0 104
0.0
0.01
0.012
Figure 10 Scratch test current transient from a SS 304L

electrode in 0.1 M NaCl. The transient is characterized by a
growth period, td, and a repassivation period, tr.
The transient is characterized by two separate processes, anodic dissolution and repassivation represented by td and tr in Figure 10. To analyze the
repassivation rates, the period tr is typically fit to an
expression and evaluated as a function of solution pH
or electrode potential. The most prolific work in this
field is probably on the alloy SS 304L. For this alloy, it
has been proposed that the kinetics of film growth are
controlled by ion migration under high electric
field.3638 The kinetics of high-field film growth
were first proposed by Cabrera and Mott39 to obey
the kinetic relationship:

BV
29
i Aexp
L
where i is the current density, V is the voltage, L is the
oxide thickness, and A and B are constants.
5.01.2 Analytical Methods

5.01.2.1
Introduction
In this section, we will review the principle analytical

methods used to probe the electrochemical interface.
In the Section 5.01.2.2 Potentiodynamic Polarization, we discuss linear polarization resistance and
the practical application of corrosion kinetics, eqns
[25] and [26]. In that section, we also describe the
salient points of the anodic polarization curve. In the
Section 5.01.2.3 Electrochemical Impedance Spectroscopy, we introduce an ac method for interrogating
the electrochemical interface. This technique is
probably the most versatile experimental method

available to scientists and researchers. As it relates
to nuclear reactors, this technique has the ability to
subtract out the contribution of the solution resistance to polarization resistance measurements which,
if not accounted for in highly resistive cooling water
measurements will result in nonconservative corrosion rates. In the final section, we introduce a more
seldom used technique, MottSchottky analysis.
While this is by no means a common experimental
method, it provides a conduit for the reader to
become familiar with defects in the oxide film, their
transport and ways to quantify it. This has particular
interest here as ionizing radiation may promote corrosion rates by increasing transport of these defects
through the passive oxide film.
Regretfully, the scope of this chapter is limited,
and we are not able to discuss the step-by-step details
of the experimental methods that are used to make
corrosion measurements. A comprehensive guide
to experimental methods in corrosion has been
published by Kelly et al.40 as well as Marcus and
Mansfeld41 while a more broad description of electrochemical methods has been published by Bard and
Faulkner.42 The reader is also encouraged to become
familiar with the equipment that is used to make
electrochemical measurements and a good introductory chapter on this topic has been presented by
Schiller.43 The most important instrument is, no
doubt, the potentiostat. While this instrument is the
cornerstone of corrosion science, it does have its pitfalls including bandwidth limitations and the potential for ground loop circuits when used in conjunction
with other equipment such as load frames, autoclaves
and cooling loops. The latter can be overcome using
proper instrumentation such as potentiostat with a
floating ground, or isolation amplifiers.
To investigate the influence of the neutron flux
on corrosion rates and mechanisms, real-time in-situ
corrosion measurements are often made in-reactor
or at neutron facilities such as Oak Ridge National
Labs Hi-Flux Isotope Reactor (HIFER) and Argonne
National Labs Fast Flux Test Facility (FFTF). Alternately, neutron damage can be simulated using ion
beams. As it relates to ion irradiation, this method
provides opportunities for studying the interaction
of the components of reactor environments (radiation, stress, temperature, aggressive media) that are
not possible with in-reactor or neutron irradiation
facilities. For a full discussion of this topic, see
Chapter 1.07, Radiation Damage Using Ion
Beams. To summarize these experiments, controlled
11
environmental cells are coupled to accelerator beamlines to study the interaction of the environment and
irradiation on structural materials. Corrosion at the
substrateenvironment interface is studied in real
time by numerous electrochemical techniques
including those described below. With respect to
dose, light ions can be used to reach doses up
to 10 dpa in several days. However, the depth of
penetration is low (tens or micrometers), which puts
unrealistic limitations on electrochemical cell construction. Heavy ion irradiation can reach several
hundred displacements per atom in a matter of days
but the penetration depth is much less.
5.01.2.2
Potentiodynamic Polarization
During our development of ButlerVolmer reaction

kinetics, we introduced the SternGeary approximation and defined Tafel slopes within the context of the
symmetry factor without much further explanation.
To understand the empirical source of the Tafel
slopes, we rearrange eqn [26] to define the polarization resistance Rp in units of O cm2:
Rp
ba bc
DE
2:303icorr ba bc Di
30
The Tafel slopes can be obtained from a plot of

potential as a function of the logarithm of current
density as shown for the cathodic curve in Figure 11
where bc has units of volts. A similar anodic plot can
be generated to obtain ba. It is important to realize
that these slopes are frequently not equal as they are
related to separate mechanisms on the electrode surface. From a plot of both the anodic and cathodic
Tafel slopes, we can also obtain icorr (Figure 11).
With knowledge of icorr , ba, and bc, the polarization
iOH2
EH
20
10
Slope =
Applied current
curve
Ecorr
+
20
20
iapp(cathodic)
icorr
E
iOM
h(mv)
40
H+
/H2
resistance can then be determined from eqn [30]. For

small voltage perturbations, the slope of a plot of
applied potential (DE ) versus the change in current
density (Di ) is equal to Rp (Figure 12), often referred
to as the linear polarization resistance as the slope is
only linear for small voltage perturbations around Ecorr .
Errors not accounted for in eqn [30] include
uncompensated solution resistance (RO) and choosing
a scan rate that is too fast. From a reactor standpoint,
the value of RO in the cooling water or a simulant
where the resistivity is high may be a significant
contribution to the measured Rp and, therefore, result
in a nonconservative corrosion rate, that is, the calculated corrosion rate will be too low. For a complete
standardized method of conducting potentiodynamic
polarization resistance measurements and data analysis, the reader is referred to the appropriate ASTM
standards G3, G59, and G102.4446
Potentiodynamic polarization curves can also be
used to assess corrosion rate as well as determine if a
material is passive, active, or susceptible to pitting
corrosion in a given environment. Consider the curve
in Figure 13. It plots the applied potential as a
function of the log of the absolute value of the current
density. The corrosion potential and corrosion current density are shown at the intersection of the
cathodic and anodic curves. Mass loss (m, in grams)
for a given period of exposure can then be
DE
Diapp
40
iapp(anodic)
-10
Tafel region
- EM/M+
log iapplied
Figure 11 Diagram depicting the cathodic polarization of

an electrode near Ecorr. Tafel extrapolation showing the
determination of icorr is also presented. Reprinted from
Fontana, M. G. Corrosion Engineering; McGraw Hill:
New York, 1986, with permission from McGraw Hill.
-20
h(mv)
Figure 12 Diagram depicting the linear polarization for an
electrode about Ecorr. Slope, DE/Di, is equal to the
polarization resistance. Reprinted from Fontana, M. G.
Corrosion Engineering; McGraw Hill: New York, 1986, with
permission from McGraw Hill.
12
positive hysteresis in the reverse portion of the curve

that is not observed in the case of solution oxidation
or transpassivity.
Epit
Potential
Erepass
5.01.2.3 Electrochemical Impedance

Spectroscopy
Eflade
ba
ipass
icorr
bc
Ecorr
Log current density

Figure 13 Diagram depicting the potentiodynamic
polarization of an electrode far from Ecorr. Relevant
potentials and currents are defined in the text.
determined from the corresponding icorr using

Faradays Law, for a pure metal40:
icorr t EW
31
FA
where t is time in seconds, icorr has units of A (cm2),
A is surface area, and EW is equivalent weight and is
equal to molecular weight (M) divided by the number of electrons in the reaction. Similarly, for an alloy:
m
EW P
1
n
i
i fi =Mi
32
where the subscript i denotes the alloying element of

interest and f is the mass fraction of that element
in the alloy. From Faradays law, it is also possible to
calculate corrosion rate, the penetration depth owing
to corrosion over a period of time in units of mm
year1 (CR):
CRmm year1
3:27 103 icorr EW

r
33
where r is the material density in g cm3.

Other critical parameters in Figure 13 include
the Flade potential (EFlade) which marks the critical
potential necessary for passive film formation, the
passive current density (ipass), the pitting potential
(Epit), and the repassivation potential (Erepass). With
respect to EFlade, this active to passive transition is not
observed for materials that are spontaneously passive
in a given environment such as SS in a BWR. In
such a case, the current would be limited by the
film dissolution current (ipass). As it relates to Epit,
the onset of localized corrosion is characterized by a
sharp increase in current at a given potential. As such,
materials that are more susceptible to pitting have
lower Epit values. Pitting is also characterized by a
While potentiodynamic polarization is typically considered a destructive technique, that is, it alters the
surface of the corrosion sample, electrochemical
impedance spectroscopy (EIS) is a powerful nondestructive technique for obtaining a wealth of data
including Rp.47 Further, this technique has the ability
to subtract out the uncompensated solution resistance (RO) from the measurement which, for highly
resistive reactor cooling water environments, is a
significant advantage.
In EIS, a small sinusoidal voltage perturbation
(10 mV) is applied across the electrode interface
over a broad frequency range (mHz to MHz). By
measuring the transfer function of the applied voltage
to the system current, the system impedance may be
obtained. For corrosion systems, the impedance (Z)
is a complex number and may be represented in
Cartesian coordinates by the relationship:
Zo Z0 Z00
34
where o is the applied frequency in radians, Z0 is the

real part of the impedance, and Z00 is the imaginary
part of the impedance, and the magnitude of the
impedance jZj is given by:
q
35
jZj Z0 2 Z00 2
In its simplest form, the electrochemical interface can
be thought of as an electrical equivalent circuit (EC):
a resistor (R) with an impedance Z(o) R and a
capacitor (C) with Z(o) 1/joC where j is the square
root of 1.48 Thus, the impedance of a resistor is
purely real and independent of frequency while the
impedance of a capacitor is purely imaginary and
inversely proportional to frequency. With respect to
the electrochemical interface, the polarization resistance is in parallel with the double layer capacitance
(Cdl, owing to adsorption of charged anions/cations
in the electrolyte). These two components act in
series with the solution resistance, RO as seen in the
EC in Figure 14. This circuit is referred to as a
simple Randles circuit and represents an ideal interface. Commonly, however, Cdl does not behave as an
ideal capacitor and its impedance is better represented by the expression
13
-6 104
Rp
RW
-5 104
-4 104
Figure 14 Simplified Randles equivalent circuit of an

electrochemical interface where Rp is the polarization
resistance, Cdl is the double layer capacitance, and RO is the
geometric resistance associated with the solution
resistance.
Z (W)
Cd1
-3 104
-2 104
-1 104
105
1 104 2 104 3 104 4 104 5 104 6 104

Z (W)
Rp + RW
Figure 16 Nyquist format for data in Figure 15 where

Rp 5 104 O, Cdl 4 106, and RO 200 O.
104
|Z| (W)
Zo 1=C j oa
103
RW
102
10-3 10-2 10-1 100 101 102
(a)
Frequency (Hz)
103
104
105
0
-10
Q ()
-30
-40
-50
-70
wmax
-80
-90
10-3 10-2 10-1 100 101 102
(b)
Frequency (Hz)
where a is typically found to be between 0.5 and 1.

The element that represents this behavior is known
as a constant phase element (Ccpe).49
The response of a simple Randles circuit as a
function of frequency is shown in Figure 15(a) and
15(b). These plots are referred to as the Bode magnitude plot (eqn [35]) and the Bode phase plot50 where
the phase angle, y, is equal to:
00
Z
37
y tan1
Z0
This phase angle is a result of the double layer
capacitance where the current leads the applied ac
voltage perturbation as is the case for pure capacitors.
The parameters Rp and RO may be determined graphically from the Bode magnitude plot as shown in
Figure 15(a) while Cdl is determined from the graphical parameter omax (converted to radians, 2pf) in
Figure 15(b) and the relationship40:
1 q
1 Rp =RO
38
Cdl
omax Rp
-20
-60
36
103
104
105
Figure 15 (a) Bode magnitude and (b) Bode phase plots.

Data were generated from an electrical equivalent of a
simplified Randles circuit (Figure 13) where Rp 5 104 O,
Cdl 4 106, and RO 200 O.
Alternately, the data may be presented using the

Nyquist format which plots the imaginary impedance
as a function of the real impedance as seen in
Figure 16 (sometimes referred to as a ColeCole
plot). As graphical analysis is somewhat imprecise,
commercially available complex nonlinear least
squares fitting of the data (CNLS) is commonly
used to obtain these parameters (Figure 17).
14
|Z| exper.
|Z| fit
102
ROX
RW
-10
|Z| (W m2)
-30
Q exper.
Q fit
-40
-50
100
Q (degrees)
-20
101
-60
COX
Figure 19 Equivalent circuit of an oxide-covered metal in
liquid PbBi eutectic (LBE) where Rox is the resistance of the
passive film, Cox is the double layer capacitance of the
oxide, and RO is the geometric resistance associated with
the LBE.
-70
10-1
10-3
10-2
10-1
100
101
102
-80
103
Frequency (Hz)
Figure 17 Bode magnitude and Bode phase plots for SS
304L during proton irradiation in a pressurized deionized
cooling water loop at 125 C showing experimental data and
complex nonlinear least squares fit of equivalent circuit in
Figure 14.
Corrosion rate (mm year 1)
6.0
5.0
4.0
3.0
Photons
Neutrons
2.0
1.0
Protons
20
100 120
40
60
80
Flux (particles m2 per proton)
140
Figure 18 Corrosion rate as a function of particle flux

for a SS 304L electrode during proton irradiation in a
pressurized deionized cooling water loop at 125 C.
EIS has been used successfully to investigate the

passive films on Zr alloys,5153 SS 304L,54 and nickel
base alloys55 in environments that simulate reactor
cooling water systems. In addition, it has also been
used to measure the real-time corrosion rates of
materials during irradiation. Lillard et al.56,57 measured the corrosion rate of materials as a function of
immersion time in a deionized water cooling loop
during proton irradiation. In that work, radiationhardened probes made from Alloy 718, SS 304L,
and Al 60 601 were exposed to a proton beam at
various current densities. The impingement of the

beam on the probes resulted in a mixed neutron,
photon, and proton flux. It was shown that corrosion
rate was almost linear with photon and neutron flux
as compared to proton flux where anomalies existed
at intermediate fluxes (Figure 18). The data were
ultimately used to extrapolate lifetimes for accelerator materials.
In other studies, EIS has also been applied to
investigate passive films on metals in sodium (Na)cooled and leadbismuth (LBE) systems that simulate reactor environments. The equivalent circuit
(EC) used to model the data is similar to the simplified Randles circuit; however, in this case, there is no
electrochemical double layer, only the impedance
and capacitance associated with the oxide
(Figure 19). In this EC, Rox is the dc resistance of
the oxide, Cox is the oxide capacitance, and RO is the
geometric resistance associated with the liquid metal
(Na or LBE). In one such study, Isaacs investigated
the capacitance of anodized films on Zr in liquid Na.
In that study, it was shown that both Rox and Cox were
a function of Na temperature between 50 and 400 C.
Lillard et al.58 reported similar trends for HT-9 in
LBE. At constant temperature, Rox and Cox for HT-9 in
LBE were a function of immersion time (Figure 20).
The data were used to calculate oxide thickness as a
function of time. In addition, Rox was related to ionic
transport through the film and corrosion rates were
calculated using Wagners oxidation theory. Upon irradiation in a proton beam, this rate fell even further.59
Additional information about leadeutectic coolants
may be found in Chapter 5.09, Material Performance in Lead and Lead-bismuth Alloy.
5.01.2.4
MottSchottky Analysis
The formation and growth of passive oxide films is

driven, fundamentally, by interfacial reactions and
defect, electron and ion transport processes. Yet the
105
ROX
15
5.5 1010
101
5.0 1010
104
Prior to irradiation
Fit
Beam on
Fit
101
101
1 C-2 (cm4 F-2)
ROX (W cm2)
Rp = 0.9 t1.7
102
COX (nF cm2)
100
103
4.5 1010
4.0 1010
3.5 1010
102
COX
100
101
50
50
100
Immersion time (h)
150
3.0 1010
103
200
2.5 1010
-0.2
0.2
0.4
0.6
0.8
Figure 20 Impedance capacitance for the oxide on

an HT-9 steel as a function of immersion in liquid PbBi
eutectic. Reprinted from Lillard, R. S.; Valot, C.;
Hanrahan, R. J. Corrosion 2004, 60, 1134, with
permission from the author.
Figure 21 MottSchottky plots for a SS 304L electrode in

dilute sulfuric acid, pH 1.6. Before and after proton
irradiation. Reprinted from Lillard, R. S.; Vasquez,
G. J. Electrochem. Soc. 2008, 155, C162, with permission
from the author.
nature and relative importance of these processes

are still far from being understood. Key to oxide
growth, and, therefore, passivation, is the mobility of
these defects, specifically vacancies. Under irradiation, however, the defect properties of the oxide
are undoubtedly changed, and the extent of corrosion is related both to the microstructure and transport properties of defects. One way to probe the
transport properties of the oxide film is by using
MottSchottky theory.
Returning to our discussion of EIS above, the
oxide capacitance may be obtained at high frequency
from the relationship
depends on what type of semiconductor the oxide is

(p vs. n) and this effects the sign of the slope.
Lillard used MottSchottky analysis to examine
the influence of proton irradiation on defect generation and transport in the oxide film on SS 304L.61
The passive film on SS 304L is an n-type semiconducting oxide and the major defect is the oxygen
vacancy which acts as an electron donor. According
to the Point Defect Model62 for oxide growth, oxygen
vacancies are produced at the metalfilm interface by
the injection of a metal atom into the oxide lattice:
Z00 o 1=oC or C 1=oZ00 olim
39
By measuring Z00 as a function of applied dc voltage

at the high frequency limit (olim) and calculating the
film capacitance from eqn [39], it is possible to evaluate donor concentration (ND) in the oxide film from
the well-known MottSchottky relationship:

1
kT
40
2=ee
N
U

U
0
D
fb
C2
q
where e0 is the permittivity of space and is equal to
8.854 1014 F cm1, e is the electronic charge and
is equal to 1.602 1019 C, U is the applied potential
in V, Ufb is the flatband potential in V, kT/q is equal to
25 mV at 25 C, and ND is the donor concentration
(oxygen vacancies) in cm3.60 ND is the slope of a plot
of 1/C2 versus applied potential. The type of defect
m ! MM x=2Vo xe
41
where m is a metal atom, MM is a metal cation, Vo is a

oxygen vacancy, e is an electron, and x is the stoichiometric coefficient. In pH 1.6 H2SO4, it was found
that the cation vacancy concentration in the oxide
increased from 2.94 1021 in the absence of irradiation to 3.41 1021 during irradiation (Figure 21).
It was proposed that the film on SS 304L is composed
of an inner Cr-rich p-type semiconductor and an
outer Fe-rich n-type semiconductor. This bilayer
film results in a pn junction where the two layers
meet. On the p side of the junction, there is a surplus
of holes, while on the n side of the junction, a surplus
of electrons exists. The energy bands are such that
it is uphill (an increase in energy) for electrons
moving across the junction (from the n side to the
p side). On a related topic, a discussion of defects in
bulk oxides can be found in Chapter 1.02, Fundamental Point Defect Properties in Ceramics.
16
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5.02
Water Chemistry Control in LWRs
C. J. Wood
Electric Power Research Institute, Palo Alto, CA, USA
5.02.1
Introduction
18
5.02.2
5.02.2.1
5.02.2.2
5.02.2.3
5.02.2.4
5.02.2.5
5.02.3
5.02.3.1
5.02.3.2
5.02.3.3
5.02.3.4
5.02.4
5.02.4.1
5.02.4.2
5.02.4.3
5.02.4.4
5.02.5
5.02.6
References
BWR Chemistry Control

Evolution of BWR Chemistry Strategies
Mitigating Effects of Water Chemistry on Degradation of Reactor Materials
Radiation Field Control
Fuel Performance Issues
Online Addition of Noble Metals
PWR Primary Water Chemistry Control
Evolution of PWR Primary Chemistry Strategies
Materials Degradation
PWR Radiation Field Control
Fuel Performance
PWR Secondary System Water Chemistry Experience
Evolution of PWR Secondary Chemistry Strategies
Chemistry Effects on Materials Degradation of SGs
Control of Sludge Fouling of SGs
Lead Chemistry
Chemistry Control for FAC in BWRs and PWRs
Water Chemistry Control Strategies
19
19
20
23
26
27
27
27
29
33
35
37
37
40
43
44
45
45
46
Abbreviations
AO
AVT
BOP
BRAC
BWR
CGR
CRUD
DMA
DZO
EBA
ECP
Axial offset, referring to localized

flux depression in reactor core
caused by buildup of boroncontaining deposits. Originally
called AOA for axial offset anomaly.
All-volatile treatment, suing
ammonia for pH control in steam
generators
Balance of plant
BWR radiation and control,
referring to designated standard
points in BWR reactors for
radiation field measurements
Crack growth rate
Corrosion product deposits on
fuel element surfaces
Dimethylamine
Depleted zinc oxide (BWRs)
Enriched boric acid (PWRs)
Electrochemical corrosion
potential
ETA
FAC
GE
HWC
HWC-L
HWC-M
IGA
IGSCC
LWR
MOX
MPA
MRC
NDE
NMCA
NWC
OD IGA/SCC
Ethanolamine
Flow-assisted corrosion
General electric, the vendor for
BWRs in the United States and
some other countries
Hydrogen water chemistry
HWC (low) with 0.20.5 ppm
hydrogen
HWC (moderate) with 1.62.0 ppm
hydrogen
Intergranular attack
Intergranular stress corrosion
cracking
Light water reactor
Mixed oxide fuel
3-methoxypropylamine
Molar ratio control (PWR
secondary side)
Nondestructive examination
Noble metal chemical addition
Normal water chemistry (BWRs)
Outside diameter IGA/SCC in
steam generator tubes
17
18
OLNC
OTSG
PAA
PbSCC
PWR
PWSCC
SCC
SG
SHE
On-line noble chemistry

Once through steam generator
Poly acrylic acid
Lead assisted stress corrosion
cracking
Primary water stress corrosion
cracking
Steam generator
Standard hydrogen electrode (for
ECP measurements)
5.02.1 Introduction
Other chapters of this comprehensive describe the various degradation processes affecting the structural materials used in the construction of nuclear power plants
(see Chapter 5.04, Corrosion and Stress Corrosion
Cracking of Ni-Base Alloys; Chapter 5.05, Corrosion and Stress Corrosion Cracking of Austenitic
Stainless Steels; and Chapter 5.06, Corrosion and
Environmentally-Assisted Cracking of Carbon and
Low-Alloy Steels). This chapter describes the influence
of water chemistry on corrosion of the most important
materials in light water reactors (LWRs). In particular,
alloys susceptible to intergranular attack (IGA) and stress
corrosion cracking (SCC) are significantly impacted
by water chemistry, most notably, sensitized 304 stainless steel in boiling water reactors (BWRs) and nickelbased alloys in pressurized water reactors (PWRs).
Excellent water quality is essential if material
degradation is to be controlled. In the early days of
nuclear power plant operation, impurities in the
coolant water were a major factor in causing excessive
corrosion. Chlorides and sulfates are particularly
aggressive in increasing intergranular stress corrosion
cracking (IGSCC) and other corrosion processes.
Transient increases of impurities in the coolant that
occur during fault conditions (e.g., condenser leaks
and ingress of oil or ion exchange resins) proved to be
particularly damaging. Thus, water chemistry was
traditionally regarded as a key cause of material degradation. Initial efforts to improve water quality
brought about a slow but steady reduction in impurities through improved design and operation of purification systems. Not only were the average
concentrations of impurities reduced over time, but
the frequency and magnitude of impurity spikes
from transient fault conditions were also diminished.
However, excellent water chemistry alone was not

sufficient to control corrosion. Hence, programs to
modify water chemistry were introduced, including
minimizing oxygen to reduce the electrochemical
corrosion potential (ECP) in BWRs, and oxygen and
pH control in PWRs. More recently, additives to
further inhibit the corrosion process have been developed and are now in widespread use. As a result,
water chemistry advances are now an important part
of the overall operating strategy to control material
degradation.
Primary system water chemistry also affects fuel
performance through the deposition of corrosion
products on fuel pin surfaces, and influences radiation fields outside the core. Core uprating through
increased fuel duty has reduced margins for tolerating corrosion products (CRUD) on BWR fuel pin
surfaces. In PWRs, increasing fuel cycle duration
has increased the challenge of controlling pH within
the optimum range. At the same time, regulatory
limits on worker radiation exposure are tending to
be tightened worldwide, putting pressure on the
operators to reduce radiation dose rates. Successful
operation of PWR steam generators (SGs) and the
remainder of the secondary system demand strict
water chemistry control in secondary side systems if
corrosion problems are to be avoided.
Other operating parameters also influence the
optimization process, for example, life extension (to
60 years) has emphasized the importance of controlling
degradation of circuit materials. Therefore, although
control of structural material degradation remains the
highest priority, water chemistry must be optimized
between the sometimes-conflicting requirements affecting other parts of the reactor.
Advances in water chemistry have enabled plant
operators to respond successfully to these technical
challenges, and the overall performance has steadily
improved in recent years.1 Plant-specific considerations sometimes influence or indeed limit the options
for controlling water chemistry, so we see different
chemistry specifications at different plants. This is especially true internationally and significant differences
between countries are noted. The US industry started
developing water chemistry guidelines 2530 years
ago, and these now provide the technical basis for
guidelines in many other countries. The early editions
of these guidelines presented impurity specifications
and required action if limits were exceeded. When
advanced water chemistries were developed and qualified, the guidelines evolved into a menu of options
within an envelope of specifications that should not be
exceeded. Guidance is now provided on how to select

a plant-specific water chemistry strategy.2
The basis for water chemistry control was discussed in detail by Cohen.3 The remainder of this
chapter describes more recent water chemistry developments for BWRs, PWR primary systems, and
PWR secondary systems including SGs, with a
short section on flow-assisted corrosion (FAC) in
both BWRs and PWRs.
5.02.2 BWR Chemistry Control

5.02.2.1 Evolution of BWR Chemistry
Strategies
BWR water chemistry has to be optimized between
the requirements to minimize material degradation,
avoid fuel performance issues, and control radiation
fields. These factors are depicted in Figure 1,4 which
also includes the main chemistry changes involved in
the optimization process.
Plant-specific considerations sometimes influence
or indeed limit the options for controlling water chemistry, so we see different chemistry specifications at
different plants. This is especially true internationally
and significant differences in chemistry strategies
between countries are noted. Design features are an
important reason for these different chemistry regimes,
to which must be added the effects of different operational strategies in recent years. For example, a key
issue facing BWRs in the United States concerns
IGSCC of reactor internals, as discussed in other
chapters. The occurrence of IGSCC resulted in the
Clad corrosion
crud deposition:
Limits on
feedwater zinc
Impurity control:
Monitoring/analysis
required
implementation of hydrogen water chemistry, with or

without noble metal chemical addition (NMCA), to
ensure that extended plant lifetimes are achieved.
German plants use 347 stainless steel, which is less
susceptible to IGSCC than sensitized 304 stainless
steel used originally in US-designed plants. Some
Swedish and Japanese plants have replaced 304 stainless steel reactor internals with 316 nuclear grade
material to minimize potential problems, as this material is less susceptible to IGSCC. As a result, many of
these plants continue to use oxygenated normal water
chemistry, whereas all US plants control IGSCC
through the use of hydrogen water chemistry (HWC)
with or without normal metal chemical addition to
improve the efficiency of the hydrogen in reducing
ECP. Second, BWRs in United States undoubtedly
have greater cobalt sources than plants in most other
countries, despite strong efforts to replace cobalt
sources. This resulted in higher out-of-core radiation
fields, leading all US plants to implement zinc injection
to control fields, whereas only a small number of plants
of other designs use zinc. Third, the move to longer fuel
cycles and increased fuel duty at US plants, while
having major economic benefits, has led to new constraints on chemistry specifications in order to avoid
fuel performance issues.
Figure 2 depicts the changing chemistry strategies over the past 30 years, showing the focus on
improving water quality in the early 1980s and the
move to educing chemistry to control IGSCC, which
in turn resulted in increased radiation fields, subsequently controlled by zinc injection.
Materials
degradation
and mitigation
Water
chemistry
guidelines
Fuel
performance
Chemistry
control issues
Figure 1 Boiling water reactor chemistry interactions.
19
BWR internals
IGSCC, IASCC:
HWC or NMC
required
Radiation
exposure
Radiation fields
crud bursts:
Zinc required
20
Increasing concerns about core internals cracking led to the need to increase hydrogen injection
rates, which in turn resulted in the introduction
of NMCA to reduce operating radiation fields from
N-16. Figure 3 shows the rate of implementation of
HWC, zinc and NMCA, and online noble metal
addition (OLNC). The rationale and implications of
these developments are discussed in greater detail in
subsequent sections.
The goal for BWRs is therefore to specify chemistry
regimes that, together with the improved materials
used in replacement components (e.g., 316 nuclear
grade stainless steel), will ensure that the full extended
life of the plants will be achieved without the need for
further major replacements. At the same time, radiation dose rates, and hence worker radiation exposure,
must be closely controlled, and fuel performance must
not be adversely affected by chemistry changes.
The first requirement of plant chemistry is to maintain high-purity water in all coolant systems, including
the need to avoid impurity transients, which are
beyond the scope of this paper. The performance of
all plants has improved steadily over the years, as
shown by the trend for reactor water conductivity for
GE-designed plants, given in Figure 4. This figure
shows that conductivity now approaches the theoretical minimum for pure water. In fact, deliberately added
chemicals, such as zinc (discussed in the following
section), account for much of the difference between
measured values and the theoretical minimum.
The conductivity data are consistent with the
reactor water concentrations for sulfate and chloride.
In fact, sulfate is the most aggressive impurity from
the viewpoint of IGSCC, and much effort has gone
into reducing it.
5.02.2.2 Mitigating Effects of Water
Chemistry on Degradation of Reactor
Materials
1977: Neutral,
oxygenated water
Corrosion, radiation buildup issues
1980s: Purer is better
IGSCC was first observed in small bore piping using

sensitized 304 stainless steel fairly soon after BWRs
started operation. Laboratory studies showed that
impurities increased IGSCC rates, and in fact water
quality in BWRs gradually improved in the early
1980s. However, the same studies found IGSCC in
high-purity oxygenated water typical of good BWR
operations. The key parameter affecting IGSCC was
found to be ECP, as shown in Figure 5. In this laboratory test, the change from oxidizing conditions
typical of normal water chemistry (NWC) operation
Chemistry guidelines
Late 1980s1990s:
HWC, zinc
Controlling IGSCC,
radiation buildup
2000s: Noble metal

chemical addition
Core internals cracking

control with lower fields
Promising new option
20062008:
Online Noblechem
Figure 2 Evolution of Boiling water reactor chemistry

options from 1977 to 2008.
40
Number of BWRs
35
Zn injection
NMCA
HWC (no NMCA)
OLNC
30
25
20
15
10
5
0
1983
1988
1993
1998
2003
2008
Figure 3 Implementation of zinc injection, hydrogen water chemistry, noble metals chemical addition, and online noble
metal at US boiling water reactors.
21
0.40
0.35
EPRI action level 1
Conductivity ( S cm1)
0.30
0.25
0.20
0.15
0.10
0.05
Theoretical conductivity limit, 25 C
0.00
1980
1982
1984
1986
1988
1990
1992
1994
1996
1998
2000
2002
2004
2006
2008
Figure 4 Boiling water reactor mean reactor water conductivity at US boiling water reactor.
250
0.4950
0.4945
200
2.7 108 mm s1
1 106
mm s1
150
0.4935
0.4930
0.4925
100
CT2 #7-304SS 4 dpa
Constant load, 19 ksiin.
Dissolved O2
Outlet cond: 0.30 S cm1
50
Inlet cond: 0.27 S cm1 Na2SO4
0.4920
0.4915
1488
Dissolved oxygen (ppb)
Crack length (in.)
0.4940
1508
1528
1548
1568
1588
0
1608
Test time (h)

Figure 5 Laboratory results showing the effect of reducing oxygen concentration on crack growth of 304 stainless steel.
to reducing conditions greatly reduced the rate of

crack growth.
Furthermore, hydrogen injection was effective at
reducing the ECP in BWRs, as shown in Figure 6.
In this figure, it can be seen that crack growth rates
(CGR) for Alloy 182 were low in hydrogen water
chemistry (HWC), but increased greatly when the

plant reverted to normal water chemistry (NWC).
These results indicated that continuous hydrogen
injection was required to fully mitigate cracking.
Examination of extensive inspection data from several
plants indicated that no IGSCC was observed with an
22
901.00
900.00
HWC
ECP = 510 mV (SHE)
NWC
ECP = +110 mV (SHE)
Crack length
174 miles year-1
HWC
< 5 miles year-1
899.00
898.00
897.00
< 5 miles year -1
Alloy 182
896.00
895.00
800
900
1000
1100
1200
1300
Time (h)
1400
1500
1600
1700
Figure 6 Effect of hydrogen water chemistry on crack growth of Alloy 182.
ECP of 230 mV or lower, using a standard hydrogen

electrode (SHE). This is the basis for the 230 mV
requirement used by US plants for IGSCC control.
In BWRs, the radiation field in the core decomposes
water to hydrogen and oxygen species, most of which
immediately recombine back to water. But some
remain as oxygen or hydrogen peroxide, because some
hydrogen is stripped into the steam phase before it can
recombine. These same radiolysis reactions cause
hydrogen to react with oxygen or peroxide to reduce
ECP. These reactions occur mainly in the downcomer,
and relatively low hydrogen concentrations are effective at lowering ECP in out-of-core regions of the
system. More than half the BWRs in the United States
adopted low hydrogen injection rates of 0.20.5 ppm
(called HWC-L), which, coupled with the replacement
of recirculation piping using 316 stainless steel, mitigated IGSCC of recirculation piping.
In the 1990s, concerns about the cracking of core
internals increased, but the low concentrations of
hydrogen used to protect out-of-core regions were
not sufficient to reduce ECP enough to mitigate
IGSCC of in-core materials, because of the radiolysis
of water occurring in the core. As a result, it was
necessary to increase hydrogen concentrations to
1.62.0 ppm to lower the in-core ECP sufficiently to
provide protection in the reactor vessel (termed
HWC-M for moderate concentrations of hydrogen).
Although this approach was effective in protecting
core internals, it also increased radiation fields in the
steam side of the circuit, including the turbines, as a
result of carryover of nitrogen-16 under reducing
chemistry. (Under the oxidizing conditions of NWC,
most of the N-16 remains in the water as soluble
species such as nitrate, and only a small percent is

transported with the steam.) In some plants, local
shielding of turbine components has reduced the
impact of the gamma radiation to acceptable levels,
but the projected 46-fold increase did in fact curtail
plans for increased hydrogen injection rates at many
plants. Note that these N-16 radiation fields are a
problem only when the plant is at power, as rapid
decay occurs at shutdown because of the short halflife of N-16. (By contrast, out-of-core radiation fields
from Cobalt-60 persist after shutdown and impact on
maintenance work during outages.)
NMCA was developed to increase the efficiency
of hydrogen in BWR cores, to avoid high N-16 fields.
In this process, a nanolayer of platinum rhodium is
deposited on the wetted surfaces of the reactor. These
treated surfaces catalyze the hydrogen redox reaction, converting oxygen back to water. When the
addition of hydrogen to the feedwater raises the
molar ratio of H2 to O2 to 2 or higher, the ECP of
the treated surfaces drops to the hydrogen/oxygen
redox potential, which is about 450 mV (SHE). This
can be achieved with hydrogen concentrations of
only about 0.2 ppm, and under these conditions, the
main steam radiation level is not increased to an
unacceptable level. The first plant used NMCA successfully in 1997, and over 25 plants have already
followed, with excellent results. Field measurements
show that NMCA has been effective in providing
mitigation against IGSCC by lowering the ECP
below the 230 mV (SHE) threshold with relatively
low hydrogen injection rates.
The NMCA process is typically applied at refueling outage, before new fuel is inserted into the core,
additional benefit with NMCA on the upper, outer

shroud regions, as indicated by the additional shading
in the left-hand side of the figure5. It is estimated that
noble metals protect slightly more of the outer core
region than does moderate HWC (HWC-M), but the
difference is not significant.
Figure 8 shows the dramatic benefit of noble
metals in reducing the rate of stub tube cracking at
Nine Mile Point 1 since the application in 2000.
Before 2000, several stub tubes had to be repaired
or replaced at each outage, but since the application,
only one tube leaked, and this was believed to have
already cracked before NMCA.
Recently, attention has been focused on the online
application of noble metals, with the first application
at the KKM plant in Switzerland. By April 2008,
there were four applications in the United States.
This is discussed in a later section.
HWC protected regions
NMCA protected regions
and is effective for about three fuel cycles, before

reapplication is necessary. The regions of the reactor
vessel internals that are protected by HWC-M or
NMCA are shown in Figure 7. While both techniques offer significant areas of mitigation, there is an
5.02.2.3
Radiation Field Control
Corrosion products deposited on the fuel become

activated, are released back into the coolant, and
may be deposited on out-of-core surfaces. Both soluble and insoluble species may be involved, the latter
tending to deposit in stagnate areas (crud traps). The
chemistry changes to control IGSCC resulted in
increased out-of-core radiation fields, and the implementation by most plants of depleted zinc injection to
Figure 7 Mitigated regions of the boiling water reactor

core.
Number of stub tubes identified with IGSCC

throughwall cracking based on leakage
12
10
Noble metal applied

mid cycle
may 2000
0
19841985 19861987 19881990
23
1991
1993
1995
1997
1999
2001
2003
2005
2007
RFO-11
RFO-12
RFO-13
RFO-14
RFO-15
RFO-16
RFO-17
RFO-18
RFO-19
Year
Figure 8 Mitigation of stub tube cracking at Nine Mile Point Unit 1.
24
control dose rates, as discussed later in this section.

During shutdowns, the major radiation source for
personnel exposure is activated corrosion products,
deposited on primary system surfaces. Exposures are
generally accumulated at high-radiation field locations
where maintenance work is frequently needed.
Although improvement of maintenance equipment
and procedures, reduction of maintenance requirements, increased hot-spot shielding, and control of
contamination dispersion have significantly reduced
total exposure, further reduction of radiation fields is
a major goal in programs for minimizing occupational
radiation exposure.
The primary source of radiation field buildup on
out-of-core surfaces in BWRs is 60Co, which in
mature plants usually accounts for 8090% of the
total dose. 60Co has a relatively long half-life of
5.27 years. The higher the soluble 60Co concentration
in the coolant, the more 60Co is incorporated and
deposited on out-of-core systems and components,
resulting in higher dose rates on recirculation piping,
the reactor water cleanup system, dead legs, and
other crud traps in the system. Other activated transition metals such as 54Mn, 58Co, 59Fe, and 65Zn
contribute the remainder of the dose. 51Cr also contributes significantly to the piping dose in some
NMCA plants. The radiation fields commonly
measured in a BWR at the straight vertical section
of recirculation pipes are considered to be more
representative for the purposes of radiation buildup
trending and comparison with other plants. These
measurements are done in a prescribed manner
developed under the EPRI BWR Radiation and Control program and are called BRAC point measurements. These measurements represent primarily the
incorporation of soluble 60Co into the corrosion film
on the piping surfaces and tend to be a fairly good
predictor of drywell dose rates. The deposition of
particulate oxides that contain 60Co and other activated species can also contribute significantly to outof-core radiation levels in BWRs, especially in hot
spots. The particulate oxides, which vary in size,
originate primarily from corrosion of the steam/condensate system and are introduced via the feedwater.
The sole precursor of the gamma-emitting 60Co
isotope is 59Co. 59Co is present as an impurity in the
nickel in structural alloys used in BWRs (e.g., Type
304 stainless steel) and is the main constituent of
wear-resistant alloys (e.g., Stellite), used as hard facing in valves and other applications requiring outstanding wear resistance. Corrosion and wear lead to
release of 59Co into the coolant from these sources,
which is transported to the core and incorporated

into the crud that deposits on the fuel rods. The
59
Co is activated to 60Co by neutron activation,
released back into the coolant, and incorporated as
a minor constituent into the passive films that form
on components that are inspected, repaired, and
replaced by maintenance personnel. Components in
the neutron flux (e.g., the control blades) directly
release 60Co. Cobalt source removal is clearly important if radiation fields are to be minimized. Another
gamma-emitting isotope, 58Co, is formed by the activation of nickel from stainless steel and nickel-based
alloys. 58Co has a shorter half-life and is not as major
a contributor to radiation fields as 60Co in BWRs, but
is much more significant in PWRs.
Shutdown drywell dose rates increase when coolant chemistry is changed for the first time from
oxidizing (NWC) to reducing (HWC) conditions.
This results from a partial restructuring of the oxides
formed under the oxidizing conditions of NWC
(Fe2O3 type) to a more reducing spinel type oxide
compound (Fe3O4 type). The oxides affected are the
fuel deposits, the corrosion films on stainless steel
piping, and out-of core deposits. This results in an
increase in the chemical cobalt (and 60Co) concentration in the oxide because of the higher solid-state
solubility of transition metals in the spinel structure.
The presence of a higher soluble reactor 60Co concentration released from fuel crud while this conversion is occurring only aggravates the situation. The
processes are depicted in Figure 9. The net result at
most plants is a temporary increase in reactor water
60
Co, both soluble and insoluble forms, which leads to
significantly increased shutdown dose rates because
of both the increased reactor water concentrations
and the increased capacity for transition metal uptake
by the spinel phases.6
Oxide stable
under normal
water chemistry
Fe2O3
(containing 60Co,
58Co, 54Mn, etc.)
Corrosion films
Vessel crud
Fuel crud
Restructuring under
HWC conditions
Fe3O4
form of oxide
Small insoluble
particles containing
60Co, 54Mn, etc.
Soluble 60Co, etc.
released during
restructure
Figure 9 Boiling water reactor oxide behavior under

reducing conditions.
25
0.8
Before Zn addition
After Zn addition
RxW 60Co (Ci kg 1)
0.6
0.4
0.2
0
Brunswick-1
Brunswick-2
Dresden-2
Figure 10 Hydrogen water chemistry plant RxW
60
Duane Arnold
Fitz patrick
Monticello
Pilgrim
Co response to zinc addition.
As mentioned earlier, zinc addition reduces radiation field buildup. The mechanism of the zinc ion effect
is complex, as release of 60Co from fuel crud is reduced,
and deposition out-core is also reduced. Overall, reactor water 60Co is decreased significantly after zinc
addition, as shown by plant data in Figure 10.
Aqueous zinc ion promotes the formation of a
more protective spinel-structured corrosion film on
stainless steel, especially when reducing conditions
are present. Second, both cobalt and zinc favor tetrahedral sites in the spinel structure, but the site preference energy favors zinc incorporation. Thus, the
available sites have a higher probability of being filled
with a zinc ion than a cobalt ion (or 60Co ion), and
hence the uptake of 60Co into the film will be significantly less if zinc ion is present in the water. The
60
Co remains longer in the water and is eventually
removed by the cleanup system.
The zinc was originally added to the feedwater as
ZnO, but it was quickly found that the 65Zn that was
created by activation of the naturally occurring 64Zn
isotope in natural zinc created problems. With the
use of zinc oxide depleted in the 64Zn isotope, called
depleted zinc oxide (DZO), this drawback was eliminated. Because of the high cost of DZO, feedwater
zinc injection was not implemented widely until
HWC shutdown dose issues emerged.
For the case of plants treated with NMCA and
injecting hydrogen, the oxidant concentration on the
surface of the stainless steel is zero (due to the Pt
and Rh catalyzing the reaction of any oxidant with

the surplus hydrogen). The net result is that the ECP
is at or very near the hydrogen redox potential,
typically about 490 mV (SHE) for neutral BWR
water. This low potential causes a much more thorough restructuring of the oxides to the spinel state
than observed under moderate hydrogen water
chemistry (HWC-M).
Feedwater iron ingress has a significant influence
on the effectiveness of zinc injection. As discussed in
the next section, deposits on fuel cladding surfaces
(called CRUD) are mainly composed of iron oxides,
with other constituents. Therefore, reducing iron
ingress from the feedwater has the benefit of minimizing crud buildup, which is important for fuel
reliability (next section). For these reasons, extensive
efforts have been made to reduce iron ingress, with
significant success. Furthermore, fuel crud has a large
capacity for incorporating zinc and is in fact where
most of the zinc ends up. The lower the amount of
crud on the fuel, the greater the proportion of zinc
that remains in solution and can subsequently be
incorporated in out-of-core surfaces. Therefore, at
plants with low feedwater iron, less zinc is captured
by the crud on the fuel, so a relatively greater amount
remains in solution and is available to control out-of
core radiation fields. This is very important, as zinc
injection rates are limited by fuel performance concerns, and hence lowering feedwater iron is essential
for maintaining lower radiation fields.
26
5.02.2.4
Fuel Performance Issues
Fuel durability has improved over the years, and

failures have declined, helped by improvements in
water purity. In operation, zircaloy fuel cladding
develops a thin oxide layer (ZrO2), which typically
does not adversely affect performance. However, an
increase of deposition of corrosion product deposits
(crud) on this oxide film is undesirable because it
can reduce heat transfer and increase fuel pin temperatures, with resultant increased corrosion of the
fuel cladding, ultimately increasing the risk of fuel
failure. Moreover, the addition of additives to control
corrosion may increase the risk of crud buildup on
the fuel. For example, zinc and noble metals in BWRs
tend to increase the adherence of crud deposits on
the fuel, which can result in undesirable oxide spalling in higher-rated cores. In fact, corrosion-related
fuel failures occurred at four plants in the United
States between 1999 and 2003. Although the precise
root cause of fuel failures is often difficult to determine, it is clear that excessive crud buildup played a
role in these failures. With progressive uprating of
fuel duty in both PWRs (and BWRs), the margin to
tolerate crud has been reduced and additional care
has to be taken in specifying the water chemistry to
avoid undesirable fuel performance issues. Despite
these more demanding conditions, fuel failures have
decreased in recent years.
Concern about the possibility of adverse effects of
NMCA on fuel has prompted imposition of a strict
limit on the amount of noble metal that can end up on
the fuel and guidance on the injection of zinc. Plant
data indicate that spalling of the corrosion layer from
fuel cladding, which is often regarded as a precursor

to cladding failure, is prevented if the cycle average
feedwater zinc is maintained below 0.4 ppb in NMCA
plants (0.6 ppb for non-NMCA plants). More recent
data indicate that quarterly averages may be as high
as 0.5 ppb for NMCA plants, without occurrence of
spalling.5
These feedwater zinc data are the basis for limits
in the water chemistry guidelines. The 2008 chemistry guidelines7 retain the cycle average feedwater
zinc limit of 0.4 ppb (0.6 ppb for non-NMCA plants)
but enable a slight increase in the quarterly average
to 0.5 ppb, which may allow flexibility in controlling
radiation buildup in parts of the cycle.
The tighter control of water chemistry in recent
years has been successful in controlling crud formation on fuel cladding, and Figure 118 shows failures
from pelletclad interaction causing SCC, fabrication
defects, debris, and crud/corrosion. Note that there
have been zero crud/cladding related fuel failures in
US BWRs since 2004 (although assessment of 2007
failures is not yet complete, crud/corrosion is not
believed to be a factor here).
Analysis of recent plant data confirms that control
of feedwater iron ingress has the positive benefit of
reducing the amount of crud on the fuel. Control of
copper, which generally originates from admiralty
brass alloys, is also beneficial; not only can copper
have detrimental effects on the fuel, but it also limits
the ability of hydrogen to reduce the ECP, and it also
leads to higher radiation fields. As a result, most US
plants have replaced condensers containing brass
tubing.
Number of failed assemblies
30
25
20
PCI-SCC
Unknown
Fabrication
Debris
Crud/corrosion
15
10
5
0
2000
2001
2002
2003
2004
EOC year
2005
2006
Figure 11 US boiling water reactor fuel failures by mechanism for each end-of-cycle (EOC) year.
2007
5.02.2.5
Online Addition of Noble Metals
As discussed earlier, the classic NMCA process is

generally applied during refueling outages before
the new fuel is loaded into the core. Reapplication
after about three cycles of operation takes approximately 2 days, while the plant maintains 107154 C
as it enters the refueling outage. To reduce this outage
time, GE-Hitachi developed OLNC, first demonstrated at KKM (a GE design of plant in Switzerland)
in 2005, with several more additions subsequently.
Preliminary results indicate that there have been no
unexpected chemistry effects during the first OLNC
applications, and shutdown radiation fields actually
decreased at KKM after OLNC.5 Subsequently, CGR
of susceptible welds decreased significantly, as shown
by the decrease in slopes in Figure 12 after OLNC
initiation for two welds that have been monitored for
several years.
The effects of OLNC on fuel have been extensively studied in fuel removed from KKM, and no
adverse effects have been observed. The jury is still
out on this concern, but the general assessment is that
OLNC will have no more impact than the classic
application, and may well prove to be of less concern.
More IGSCC and fuel measurements are planned,
but with no issues emerging to date, it appears that
OLNC applications about every 12 months would be
effective and economical, avoiding the critical path
time necessitated for the classic NMCA application
during refueling outages. Initial OLNC applications
have been carried out at plants that had previously
applied noble metals in the classic off-power manner.
However, the first OLNC application at a plant that

has not used noble meals previously occurred in late
2008, but no results are available.
5.02.3 PWR Primary Water

Chemistry Control
5.02.3.1 Evolution of PWR Primary
Chemistry Strategies
In the very early days of PWR operation, heavy crud
buildup on fuel cladding surfaces was caused by the
transport of corrosion products from the SGs into the
reactor core. As a result, activated corrosion products
caused high-radiation fields on out-of-core surfaces
(Figure 13), fuel performance was compromised, and
even coolant flow issues were observed in some
plants.
These problems were initially mitigated by imposing
a hydrogen overpressure on the primary system, to
reduce the ECP, and raising the primary chemistry
pH. Materials degradation in primary systems was
then not a major concern, with most of the emphasis
focused on secondary side corrosion issues in the
SGs. Commercial PWR power plants use a steadily
decreasing concentration of boric acid as a chemical
shim (for reactor control) throughout the fuel cycle,
which results in the use of lithium hydroxide to
control pH. Some 30 years ago, the concept of
coordinated boron and lithium was developed,
whereby the concentration of LiOH was gradually
reduced in line with the boric acid reduction to
maintain a constant pH.
300
NC
appl.
HWC
Indication length (mm)
250
Ind 9
Ind10
Not inspected in 00, 01,04
200
150
100
50
27
OLNC
37 g
OLNC
98 g
OLNC
198 g
OLNC
199 g
Indications 9,10
may be seeing
mitigation by OLNC
0
1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009
Year
Figure 12 Ultrasonic inspection results after online noble metal chemical addition.
28
Corrosion products
deposit out of core
Pressurizer
Steam generator
Corrosion
products
activated in
reactor core
Corrosion products
released from SG tubing
Coolant pump
Reactor
Primary loop
Figure 13 Transport and activation of corrosion products in pressurized water reactor primary systems.
Corrosion products released from the steam generator tubes are transported, dissolved, or deposited
by the coolant on the basis of solubility differences.
The solubility of nickel and iron depend on pH,
temperature, and redox potential, all of which vary
with location around the nonisothermal system.
Originally, a constant at-temperature pH of 6.9 was
recommended, based on the minimum temperature
coefficient of solubility of magnetite. In fact, it was
determined that heavy fuel crud buildup was avoided
if a constant pH of at least 6.9 was maintained. This
was possible with 12-month fuel cycles, but fuel cladding corrosion concerns limited the maximum LiOH
concentration to 2.2 ppm. Consequently, plants often
started the fuel cycle with pH below 6.9, which
resulted in deposition of corrosion products on the
fuel, activation of cobalt and nickel, and subsequent
transport to out-of-core surfaces, resulting in radiation fields remaining relatively high.
Even though detailed studies of fuel crud showed
that the prime constituent of the crud was nickel
ferrite (for which the optimum pH is 7.4), this coordinated chemistry had remained the standard for
many years, until higher pHs became the norm in
the 1990s. Although research and plant demonstrations showed that the 2.2 ppm limit was excessively
conservative, the move to higher Li concentrations
has been slow. However, detailed fuel examinations
from a recent plant demonstration (that will be discussed later) have indicated that Li can be raised to as
high as 6 ppm.
About 25 years ago, primary water stress corrosion cracking (PWSCC) of Alloy 600 SG tubes was
observed in a few plants, leading to studies on mitigating this effect. Following successful demonstration of zinc injection in BWRs, initial field tests at
PWRs showed that radiation fields were reduced,
and laboratory studies indicating that PWSCC was
reduced were eventually confirmed. As a result, zinc
injection is being implemented at an increasing rate,
although concerns about fuel performance at highduty plants have not been completely resolved. Most
recently, buildup of boron-containing crud in areas
of subcooled nucleate boiling leading to localized
flux depression has encouraged the use of higher Li
concentrations to minimize corrosion product transport. Concerns about the potential adverse effects of
zinc deposited in high-crud regions have resulted in
several highly rated plants applying in situ ultrasonic
fuel cleaning before implementing zinc injection.
Although zinc injection was developed for radiation field control, laboratory studies showed that it
also inhibited SCC under PWR conditions. The
identification of PWSCC in reactor vessel penetrations in the last 1520 years has encouraged the use
of zinc injection, but has also focused attention on
the effects of dissolved hydrogen, for which the
recommended range has remained 2550 ml kg1
for 30 years. It now appears that raising hydrogen
will reduce PWSCC rates, while lowering it may
delay initiation of PWSCC. The interactions of
materials, radiation fields, and fuels in PWR primary
PWSCC:
pH (Li, B) minimal effect
Zn beneficial
dissolved H2 effect
Plant
operations
29
Dissolved H2
control range
Materials
degradation
PWR
chemistry
control
Fuel
performance
Plant
dose
rates
Radiation fields:
pH (Li, B), Zn
beneficial
Crud deposition:
Zn concern for
highly rated cores
Figure 14 Pressurized water reactor primary chemistry optimization. Reproduced from Fruzzetti, K.; Perkins, D. PWR
chemistry: EPRI perspective on technical issues and industry research. In VGB NPC08 Water Chemistry Conference, Berlin,
Sept 1418, 2008.
Dissolved (H2) range changes
Elevated constant pH (7.3/7.4)

Ultrasonic fuel cleaning
Elevated constant pH (7.1/7.2)
Zinc injection
Modified elevated lithium program
EPRI water chemistry guidelines
Elevated lithium program
Constant pH 6.9
1975
1980
1985
1990
1995
2000
2006 2008
Figure 15 Pressurized water reactor primary chemistry

changes at US plants.
chemistry and optimization issues covered in the

water chemistry guidelines, which are discussed
later, are depicted in Figure 14.
The evolution of water chemistry control in PWR
primary systems in the United States over the last
30 years is shown in Figure 15.
The following sections address the three main
factors pH control, zinc injection, and dissolved
hydrogen control that have dominated PWR primary chemistry strategies in the past and continue to
do so today.9 Each of these factors is considered from
the viewpoint of materials degradation, radiation
field control, and fuel performance concerns.
5.02.3.2
Materials Degradation
Materials degradation has been covered in detail in

Chapter 5.04, Corrosion and Stress Corrosion
Cracking of Ni-Base Alloys and Chapter 5.05, Corrosion and Stress Corrosion Cracking of Austenitic
Stainless Steels, and here only the specific effects of
water chemistry variables on materials in PWR primary systems will be reviewed, particularly those that
may affect the chemistry of optimization process.
Recent papers by Andresen et al.10,11 provide
detailed results of a comprehensive study of the effects
of PWR primary water chemistry on PWSCC of
nickel-based alloys. Extensive studies have been carried out to determine the effect of lithium, boron, and
pH on PWSCC, and the generally held conclusion is
that any effects are minimal, especially compared to
material susceptibility, stress state and temperature,
and other operational issues. Crack initiation tests
using the most reliable types of reverse U-bend specimens indicate that pH has a relatively small effect on
crack initiation (generally less than a factor of 2).
Although the most rapid crack initiation occurred at
pH310 C 7.25, with slower rates at higher or lower pHs,
CGR tests generally confirm that pH has minimal
effect.
The effect of lithium is even smaller than the pH
effect, and the influence of boron is minor or nonexistent. Andresen et al. concluded that the effects of relevant variations in PWR primary water chemistry (B, Li,
30
and pH) have little effect on the SCC growth rate in

Alloy 600, and thus provide little opportunity for mitigation of PWSCC. Plant data have found no adverse
effects from increasing lithium and pH in primary
systems. As a result, it is considered that adjusting
pH, lithium, or boron to minimize crack initiation
may be of minimal value. The 2007 edition of the
PWR Primary Water Chemistry Guidelines12 reviewed
the most recent data and concluded that pH strategy
changes based on PWSCC considerations are not warranted. This means that plants have the flexibility to
pursue B/Li/pHt chemistry adjustments to minimize
crud transport and radiation buildup without concern
for negative effects on PWSCC susceptibility of nickelbased alloys, although of course chloride and sulfate
impurities should continue to be minimized.
Following good experience in BWRs, zinc injection has been implemented in the primary systems of
PWRs, both to reduce primary side cracking of nickelbased alloys and to control dose rates. The qualification
work for BWRs showed that zinc inhibited SCC, but
the benefit was not sufficient to avoid the need for
hydrogen water chemistry to mitigate IGSCC. Thus,
the motivation for BWR zinc injection was exclusively
radiation field control.
The situation in PWRs is different, as laboratory
work13 showed that initiation of PWSCC was significantly delayed by zinc injection, and hence the motivation for the initial applications of zinc in most US
PWRs at the 1030 ppb level was to control PWSCC
of SG tubing. Additionally, German-designed PWRs
and a few US plants used 5 ppb depleted zinc for
radiation control.
Figure 16 shows the rate of introduction of zinc

injection at PWRs worldwide.
Zinc injection produces thinner, more protective
oxides on stainless steel and Alloy 600, with zinc
displacing Co2, Ni2, and Fe2 from normal spinels
to give ZnCr2O4, which is very stable. The benefits
of PWR zinc injection have been clearly demonstrated in reducing PWSCC degradation (especially
growth rate) of Alloy 600 SG tubes, and in controlling
radiation fields. Evaluation of currently available
laboratory data2 indicates that PWSCC initiation
will be reduced, and PWSCC CGR may be reduced
in thicker cross-section components, depending upon
other factors such as the stress intensity factor of the
specimen. Andresen et al.11 concluded that crack
growth mitigation by adding Zn requires further
study, although two of four tests show a decrease
in growth rate of >3. Molander et al.14 also found
that the effect of zinc on CGR was minor. Hence,
more work is needed before making definitive conclusions from laboratory studies regarding the benefit
of zinc in mitigating CGR.
SG tube nondestructive examination (NDE) data
from eight plants injecting zinc indicated reduction
in the incidence of PWSCC by a factor of 210.9 An
example from a 2-unit PWR showing the effect of
zinc on SG tubing over successive cycles is given in
Figure 17.
The largest effect of zinc appears to be on initiation of cracking, with a smaller effect on CGR, with
the data indicating a factor of 210 reduction for
initiation and about a factor of 1.5 reduction in CGR,
consistent with the extensive laboratory work,11
Application of zinc in world PWRs
Number of plants and percentage

of PWR injecting zinc
50
45
Percent of PWRs injecting
Number of units injecting
40
35
30
25
20
15
10
5
0
1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007
Year
Figure 16 Application of zinc injection in pressurized water reactors worldwide.
31
140
X indicates last refueling outage
before
start of zinc injection
Number of new tubes affected
120
100
80
Unit 1
Unit 2
60
40
20
0
X3
X2
X1
X+1
X
Refueling outage
X+2
X+3
X+4
Figure 17 Effect of zinc on steam generator tube degradation at a US pressurized water reactor.
70
60
Number of plants
indicating that zinc inhibits mainly by delaying the

initiation of PWSCC. However, the SG NDE data
also showed that zinc reduced the rate of crack propagation (depth) by 1760%.
These results are consistent with initial laboratory
test data indicating that zinc reduced crack propagation by a factor of approximately 3 at low stress
intensities, but had no effect at higher stress intensities. In addition, the lack of cracking in the Farley
PWR pressure vessel head penetrations (exposed to
zinc for over 12 years), compared to PWSCC indications in similar pressure vessel heads in other plants,
suggests that zinc addition is beneficial for Alloy 600
(and possibly Alloy 82/182) thick-section components under PWR primary service conditions.
Recent work has studied the influence of dissolved
hydrogen on PWSCC. In the early days of PWR
operation, the lower limit on hydrogen was set at
25 ml kg1, to provide adequate margin against radiolysis and heavy crud formation. Plant tests in France
showed that this limit was excessively conservative
and that less than 10 ml kg1 would be satisfactory,
provided good control of oxygen was maintained in
makeup water. Several workers have found that the
maximum in PWSCC CGR occurs close to the ECP
corresponding to the Ni/NiO thermodynamic equilibrium condition.15 Although this potential is unaffected by lithium/boron/pH (consistent with the fact
that these do not greatly influence PWSCC over the
range of practical relevance), the equilibrium potential is significantly affected by the dissolved hydrogen
50
40
30
20
10
0
2530
3035
3540
4045
4550
Cycle average hydrogen concentration (cm3 kg1)
Figure 18 US plant data for dissolved hydrogen.
concentration. Andresen et al. found that the peak in

SCC growth rate versus H2 fugacity was temperature
dependent, but generally fell within the hydrogen
concentration range used in PWRs. This provides
an opportunity for mitigation, by perhaps a factor of
2 in Alloy 600 and a factor of 5 in Alloys 182, 82,
and X750, as the median value of the dissolved
hydrogen concentration for US plants is approximately 35 ml kg1.
US PWRs currently operate within dissolved
hydrogen within the recommended 2550 ml kg1
range, with the majority in the 3040 ml kg1 range,
but none with more than 44 ml kg1 (Figure 18).
The lower limit is set conservatively to provide an
operating margin over the level of hydrogen required
32
to suppress water radiolysis in the reactor core. Somewhat lower concentrations are used in other countries.
The dissolved hydrogen concentrations corresponding to the peak CGR for a typical range of
PWR primary operating temperatures are 4.3 ml kg1
at 290 C, 10.4 ml kg1 at 325 C, and 16.5 ml kg1
at 343 C.15 Andresen et al.11 published Figure 19,
which indicates the proposed factors of improvement
on changing from an initial hydrogen concentration
of 25 ml kg1. It can be seen that raising the hydrogen provides benefit, but lowering it is detrimental
below 330 C.
In response to the data showing the benefit of

increasing hydrogen in reducing CGR, the US industry program in progress focuses on the extent to
which dissolved hydrogen can be increased without
adverse consequences to other parts of the system.
Other countries, including Japan, are also investigating lowering hydrogen, because laboratory data
suggest that the initiation of cracking is delayed at
lower hydrogen concentrations. This is depicted in
Figure 20, as discussed by Molander.14
The lower line in this figure shows the time to
initiate cracking, based on laboratory tests using
Factor of improvement from H2
4.0
Based on Alloy 182,
a current H2 level of 25 cm3 kg1
3.5
70 cm3 kg-1 H2
25
3.0
45 cm3 kg-1 H2
25
2.5
2.0
1.5
Good
1.0
25
0.5
0.0
270
280
290
1 cm3 kg-1 H2
300
310
320
Temperature (C)
4 cm3 kg-1 H2
25
330
340
Bad
350
Figure 19 Effect of dissolved H2 on primary water stress corrosion cracking crack growth rate at different temperatures.
ml H2/kg H2O (330 C)

10
15
20
25
30
Crack initiation time (h)
Jenssen data on Alloy 600
35
1E07
Growth
8E08
20 000
6E08
15 000
4E08
10 000
Initiation
2E08
5000
0
0
10
Hydrogen activity (kPa)
15
Crack growth rate (mm s1)
5
25 000
0E+00
20
Figure 20 Dependencies between the dissolved hydrogen content in pressurized water reactor primary coolant on the
crack initiation time observed on initially smooth surfaces and on the crack propagation rate.
reverse U-bend specimens, whereas the upper line

shows crack growth data over a similar concentration
range. Thus, the lowering of hydrogen appears feasible. However, the relative importance of crack initiation
and crack propagation is very dependent on material
and plant conditions. In the United States, concern
about increased crack propagation at low hydrogen
and low temperatures, as shown in Figure 19, has
resulted in moving to higher hydrogen being preferred
to the alternative of reducing hydrogen. Several factors
combine to make higher H2 the preferred way to mitigate SCC, including the importance of bottom-head
penetrations (which are exposed to 290 C water)
and the recent observation that the CGR in coldworked Alloy 600 is not mitigated at low H2.11
The preferred strategy in the United States is
to gradually increase hydrogen to the upper end of
the existing range, with the potential to move higher
(say to 60 ml kg1) when the ongoing qualification
work is completed. This will include evaluation of
the effects of dissolved hydrogen on radiation fields
and fuel performance, although any such effects are
expected to be minimal.16
5.02.3.3
PWR Radiation Field Control
Corrosion products released from out-of-core materials (primarily SG tubing) deposit on the fuel and
become activated, are released back into the coolant,
and may be deposited on out-of-core surfaces. Both
soluble and insoluble species may be involved, with the
latter tending to deposit in stagnate areas (crud traps).
In addition to the chemistry items discussed later in
this section, it must be stressed that other factors are
important to the goal of reducing radiation fields. In
particular, the success of the later German-designed
plants in eliminating cobalt sources in hardfacing alloys,
thereby achieving very low radiation fields, demonstrates the benefits of cobalt source reduction. With
many plants replacing SGs, a correlation between
recontamination rates and surface finish of the new
SG tubing has been noted by Hussey et al.17
Typical PWR fuel cycles start with a relatively high boric acid concentration, which gradually
reduces to zero at the end of the cycle. Lithium
hydroxide is added to maintain an approximately
constant pH. As the duration of fuel cycles increased,
more boric acid was required at the start of cycle,
which in turn necessitated increased LiOH to maintain the desired pH (Figure 21).
As mentioned earlier, radiation field buildup can
be controlled by minimizing corrosion product
33
transport and activation. Initially, coordination of

lithium hydroxide with boron to maintain a constant
at-temperature pH of 6.9 was recommended, based
on the minimum solubility of magnetite. In fact, the
prime constituent of the crud turned out to be nickel
ferrite, requiring a pH of 7.4 for minimum solubility. Fruzzetti et al.15 have recently reviewed the data
on elevated pH, which provides a number of benefits
including decreased general corrosion (and thus
reduced corrosion product transport to the core).
Field-tests of pHs greater than 6.9 confirmed that
radiation fields were lower. Although no adverse
effects were observed on the fuel, many plants were
slow to abandon a 2.2 ppm limit, established to avoid
excessive zircaloy corrosion. However, there were
indications of heavier crud formation after long periods operating below pH 6.9, and as fuel concerns
relaxed, a gradual move toward a maximum of 3 ppm
lithium resulted. Moreover, pHs in the range 7.17.2
became more popular in the late 1990s, with 7.37.4
eventually gaining favor.
Figure 22 shows the maximum lithium concentrations reported by US PWRs in recent years. It can
be seen that 95% are now using greater than 3 ppm
at full power: a significant change from earlier in
the decade.
A demonstration of elevated Lithium/pH is in
progress at Comanche Peak PWR.18 The goal was to
reduce radiation fields and reduce susceptibility to the
Axial Offset Anomaly (AOA) by reducing crud
buildup. This test involved increasing the primary
system pH from 7.1/7.2 to 7.3 and then two cycles at
7.4. No significant adverse trends have been noted,
either in the area of chemistry or core performance.
Radiation fields measured have shown a modest but
continued improvement. On the basis of the positive
trends and absence of any negative effects, Comanche
Peak has established elevated constant pHTave 7.4 as
the primary chemistry regime for both units.
Without the increases in pH/lithium that have
taken place, radiation fields would have been
expected to increase significantly for longer fuel
cycles. The increase in boiling in localized regions
of the core (called subcooled nucleate boiling)
in PWRs resulting from power uprating has resulted
in higher crud buildup on the upper fuel surfaces, and
there is growing evidence from US PWRs that radiation fields are indeed higher for the highest rated cores.
Enriched boric acid (EBA), that is boric acid
enriched with B-10, enables a given pH to be
achieved with less lithium hydroxide, as the required
concentration of B-10 can be obtained with less total
34
Constant pH 7.2
6
Lithium
Li high limit
Li low limit
5
Li target = 6.0 E7 B2 + 0.0023B + 0.4413
Lithium (ppm)
4
3.5 ppm limit
3
2.2 ppm limit
2
Start of 18-month
cycle
Start of 12-month cycle
20
80
140
200
260
320
380
440
500
560
620
680
740
800
860
920
980
1040
1100
1160
1220
1280
1340
1400
1460
1520
1580
1640
1700
Boron (ppm)
Figure 21 Lithium concentrations required to maintain pH 7.2 for different fuel cycle lengths.
boric acid. EBA is used at several plants in Europe,

typically to increase shutdown margin when using
mixed oxide fuel (MOX), but has not been applied
to date in the United States. However, consideration
is being given to using EBA at some plants that will
use MOX fuel in the future. Despite the transition to
the use of EBA in operating plants, designing for it in
new plants is recommended.19
As discussed earlier, the motivation for the initial
applications of zinc in most US PWRs was to control
PWSCC of SG tubing. However, German-designed
PWRs and a few US plants used 5 ppb depleted
zinc for radiation control, mostly with depleted zinc
to avoid zinc-65 formation. A recent paper Understanding the zinc behavior in PWR primary coolant: a
comparison between French and German experience
by Tigeras et al.20 provides a European perspective on
this topic.
This paper concludes that zinc injection seems to
present the most positive and clearest results: in all
the units injecting zinc, a dose rate reduction has
been detected after a certain period of exposure
without leading to any negative impact on plant
systems, components, and operation. Thus zinc

injection should be considered as a strategy with
benefits in short, medium, and long term. Its application as soon as possible in the life of nuclear power
plants and especially before SG replacement and fuel
cycles modifications seems to be an excellent decision to contribute to ensuring the passivation process
of new components, the fuel performance, the full
power operation of the units, and the long life of
materials and components.
Figure 23 shows the effect of zinc in reducing
radiation dose rates at several plants. It can be seen
that the reduction factor approximately correlates
with the cumulative zinc exposure in ppb months
(the product of the average zinc concentration and
the duration of zinc addition). As little as 5 ppb
zinc has been shown to reduce radiation fields by
3550% at operating plants, based on zinc exposures
of 700 ppb months. There is relatively little difference between plants with Alloy 600/690 SG tubing
and those with Alloy 800 tubing, but plants using
depleted zinc show greater benefit than those using
natural zinc, as shown in the figure.
35
Percentage of units within range
70
<3 ppm
3.03.5 ppm
>3.5 ppm
60
50
40
30
20
10
0
2000
2001
2002
2003
2004
2005
2006
2007
EOC year
Figure 22 Maximum reported coolant lithium (full power) at US pressurized water reactors.
Cumulative dose rate reduction fraction
1.2
Alloy 800 w/depleted zinc
Alloy 600 and 690 w/depleted zinc
Alloy 600 and 690 w/natural zinc
Log Alloy 800 plants
Log Alloy 600 and 690 w/depleted zinc
Log Alloy 600 and 690 w/natural zinc
0.8
0.6
0.4
0.2
0
0
200
400
600
800 1000 1200 1400 1600
Cumulative zinc exposure (ppb months)
1800
2000
Figure 23 Effect of zinc injection on radiation dose rates.
5.02.3.4
Fuel Performance
With progressive uprating of fuel duty, the margin to

tolerate crud has been reduced and additional care
has to be taken in specifying the water chemistry to
avoid undesirable fuel performance issues. Figure 24
shows the root causes of PWR fuel failures since
2000, including failures from pelletclad interaction
causing SCC, fabrication defects, debris, grid fretting, and crud/corrosion. In contrast to the BWR
situation, shown in Figure 11, very few failures in

recent years have been attributed to crud/corrosion
(the exceptions to this comment are discussed in a
following section).
A phenomenon called axial offset (AO) has caused
concern over the past 10 years.21 AO is a measure of
the relative power produced in the upper and lower
parts of the core and is normally expressed as a
percent, with a positive percent indicating that
36
Number of failed assemblies
120
Unknown
Debris
Crud/corrosion
100
Fabrication
PCI-SCC
Grid fretting
80
60
40
20
0
2000
2001
2002
2003
2004
2005
2006
2007
EOC year
Figure 24 US pressurized water reactor fuel failures by mechanism.
more power is produced in the upper part of the core.

AOA occurs when boron concentrates in corrosion
product deposits (crud) on the upper spans of fuel
assemblies undergoing subcooled nucleate boiling,
causing a reduction in neutron flux. AOA has affected
at least 20 PWRs in the United States, as well as
several in other countries.
Clearly, fuel crud is involved in the AO phenomenon, and water chemistry effects must be considered
in controlling AO. Besides their axial asymmetry, the
composition of fuel deposits in boiling cores is different from nonboiling fuel. The nickel-rich deposits on
boiling cores tend to be removed much less effectively
by conventional chemistry shutdown evolutions than
the nickel-ferrite deposits on nonboiling cores. Alternative methods are therefore required for removing
corrosion product deposits from reload fuel from highduty cores, including ultrasonic fuel cleaning.
An important difference exists between plants
with Alloy 600 or 690 SG tubing and those (such as
German-designed plants) with Alloy 800 tubing.
The latter have a much lower proportion of nickel
in fuel crud and have not experienced the AO
phenomenon.22
Early work showed that lithium increased zircaloy oxidation rates, although the adverse effects
were reduced in the presence of boric acid. As a
result, a limit of 2.2 ppm lithium was generally
imposed to reduce zircaloy corrosion, although
excessive crud formation at low pHs was likely to
be more detrimental to the cladding than higher
lithium concentrations, especially as the resistance
to corrosion of zircaloy improved. This was confirmed by one of the few failures in recent years
that was uniquely attributed to crud buildup. In this
example, a move to a longer fuel cycle necessitated
increasing the boron concentration at start of cycle;
however, the 2.2 ppm lithium limit was retained,
resulting in the pH being well below 6.9 for the
initial period of the cycle. This in turn caused
heavy crud formation, to which subsequent fuel failures were attributed.
The move in the past ten years to greater fuel duty,
with operation of fuel at higher temperatures (with
localized subcooled nucleate boiling), has caused
crud-related problems to reappear, particularly the
localized flux depression as a result of buildup of
boron-containing crud, which were discussed earlier.
This in turn has renewed interest in elevated pH/
lithium to minimize corrosion product transport, the
use of EBA and the more immediate mitigation that
can be obtained from fuel cleaning.
Fuel performance is always a concern with changes
in water chemistry, such as zinc injection. On the basis
of current experience, the impact appears to be minimal for the majority of plants, but insufficient data
exist for plants with the highest fuel duties to allow
application without postexposure fuel inspections.
Data from US plants suggest little or no fuel concerns
for coolant zinc levels up to 40 ppb for plants with
less-highly rated cores. Extended experience at these
plants, over at least 10 years of operation, indicates no
adverse effects on fuel at zinc concentrations from
15 to 25 ppb. However, there have been no data
available until recently for higher zinc concentrations

in higher duty cores where significant subcooled
nucleate boiling occurs on the fuel clad surface.23
Perkins et al.24 comment that fuel performance must
be considered prior to injecting zinc and additional
monitoring and fuel surveillances to understand and
evaluate the impact and the role of zinc may be
required in some circumstances.
5.02.4 PWR Secondary System Water

Chemistry Experience
5.02.4.1 Evolution of PWR Secondary
Chemistry Strategies
The objectives of PWR secondary water chemistry
control are to maximize secondary system integrity
and reliability by minimizing impurity ingress and
transport, minimizing SG fouling, and minimizing corrosion damage of SG tubes. Since secondary side
corrosion damage of SG tubes is primarily caused by
impurities in boiling regions, where high concentrations of impurities occur in occluded regions of
the SG formed by corrosion product deposits, new
approaches are continually sought to control corrosion
product transport to and fouling within the SGs.25
PWRs have experienced IGA on both the primary
and secondary sides of the Alloy 600 SG tubing, which
has been a major contributing cause of the replacement of most of the SGs with mill-annealed tubing,
not only in the United States but internationally.
Figure 25 illustrates the various corrosion processes
found in different locations in a recirculating SG.26
PWR secondary system water chemistry has
evolved through many changes over the years, largely
in response to emerging technical issues associated
with this degradation of structural materials in SGs.
In the early days of PWR operation, wastage became
a problem in the secondary side of PWR SGs, resulting in a switch from the use of sodium phosphate
inhibitor to all-volatile treatment (AVT) using
ammonia, which in turn brought about the denting
phenomenon. Tighter control of impurities, oxidizing potential, and pH were necessary to mitigate
the denting problem. Despite continued chemistry
improvements, many plants have had to replace
SGs of earlier designs (e.g., those tubed with Alloy
600MA), as shown in Figure 26.
Newer generation SGs are performing well,
although there remain concerns about the adverse
effects of lead impurity, causing Pb-assisted stress
corrosion cracking (PbSCC), which is discussed later.
37
Lead has been observed in various flow streams (final

feedwater, heater drains, etc.) in the secondary systems
of PWRs. Lead is detected at some concentration in
nearly all deposit analyses (SG and other locations).
Lead is present in trace concentrations in secondary
system materials of construction, as well as in chemical
additives such as hydrazine.15
Figure 27 shows the worldwide causes of SG
repairs through 2004. It can be seen that IGA is
currently the most prevalent form of degradation.
Figure 28 compares the behavior of three types of
SG tubing, Alloy 600MA (mill-annealed material used
in early plants, Alloy 600TT (thermally treated material used in later plants), and Alloy 690TT (an
improved alloy used in most replacement SGs). This
diagram is taken from the 2008 PWR Secondary Water
Chemistry Guidelines,27 which contains a much more
detailed account of corrosion processes. 600TT has
reduced susceptibility under mildly oxidizing highalkaline conditions, that is, SCC is not observed until
higher pH than for 600MA, and 600TT has approximately the same susceptibility as 600MA under acidic
conditions. 690TT is indicated as having a still smaller
region of susceptibility in the high-alkaline region and
as having no susceptibility in the acid region except
under highly oxidizing conditions that are unlikely to
occur in plants. However, other work indicates that
SCC can occur in 690TT at an acidic pH, especially
if lead is present. Also, SCC occurs in both 600MA and
600TT in the mid pH region if lead is present.
In the 1990s, improved pH control using amines
became a regular practice, and fine-tuning, including
using mixtures of different amines to control pH
throughout the circuit and coordination with resin
utilization, continues today. Hydrazine is used to
remove oxygen from the system. Hydrazine levels
have continually been reviewed and optimized, with
due regard to any impact on FAC in secondary systems, as FAC rates increase at very low oxygen concentrations. Molar ratio control (MRC) describes a
control strategy that adjusts the bulk water chemistry,
generally sodium and chloride, such that the solution
that is developed in the flow-occluded region is targeted to be near neutral. MRC can involve the addition of chloride ions to balance the cations that
cannot be reduced via source term reduction programs. MRC was widely practiced to minimize SCC
concerns, but has not been actively employed at plants
replacing to SGs tubed with Alloy 690TT. With
more plants replacing their SGs, less plants are adopting the MRC program. Only ten plants were doing
MRC in 2007,28 and they are all with original SGs with
38
U-bend cracks
(PWSCC)
Fatigue
Free span
ODSCC
IGA
ODSCC
PWSCC
Expansion
transition
PWSCC
PWSCC or
ODSCC
ODSCC
Denting
Fretting, wear, corrosion,

thinning
Tubesheet
Pitting
IGA
Expansion
transition
Tubesheet
ODSCC
Sludge
Tubesheet
PWSCC tube-end
cracking
Tubesheet
Figure 25 Corrosion processes in recirculating steam generators, showing primary water stress corrosion cracking and
outside diameter stress corrosion cracking on the secondary side.
39
140
Operating plants
Plants w/replacement SGs
120
134
84
88
81
134
134
134
72
64
67
59
52
45
51
37
22
29
17
10
3
5
7
78
134
134
132
131
132
134
131
131
132
132
133
134
12
132
134
12
133
133
130
121
63
68
55
46
1973
1974
1975
1976
1977
1978
1979
1980
1981
1982
1983
1984
1985
1986
1987
1988
1989
1990
1991
1992
1993
1994
1995
1996
1997
1998
1999
2000
2001
2002
2003
2004
2005
2006
2007
22
20
31
41
40
11
93
99
60
108
115
127
80
79
Number of plants
100
Year
Figure 26 Steam generator replacement status worldwide.
100
90
80
Percent
70
60
50
40
30
20
10
1973
1974
1975
1976
1977
1978
1979
1980
1981
1982
1983
1984
1985
1986
1987
1988
1989
1990
1991
1992
1993
1994
1995
1996
1997
1998
1999
2000
2001
2002
2003
2004
0
Year
IGA
Impingement Pitting
Other
Wear
Thinning
Fatigue
Unknown
SCC
Preventive
Figure 27 Worldwide causes of steam generator tube repair.
600MA and 600TT tubing. Currently, no plants with

replaced SGs are believed to be using MRC.
Titanium-based inhibitors to minimize corrosion are also employed at some plants. Boric acid
treatment (BAT) involves the addition of boric acid

to feedwater. Such approaches are worthy of consideration, on the basis of plant-specific degradation mechanisms, operational considerations, and
40
1.0
TT690
Potential (V vs. Ec )
0.8
Some tests indicate that 690 TT may be
susceptible in the low pH region, especially if lead is
690 TT U-bend cracked
present
in near neutral AVT
with lead and oxidizing sludge
TT690
TT600
TT600
MA600
0.6
0.4
MA600
0.2
600 MA and 600 TT can be susceptible
in mid pH range if lead or reduced
sulfur is present.
6
7
8
pH 300 C (572 F)
10
11
12
Figure 28 Corrosion mode diagram for Alloys 600MA, 600TT and 690TT (based on Constant Extension Rate Tensile
Tests at 300 C), showing regions where materials are susceptible to attack.
interactions. The most recent developments are

aimed at reducing deposit buildup in crevices,
including the use of dispersants, such as polyacrylic
acid (PAA), that is discussed in more detail later.
The historical trends in PWR secondary chemistry are shown in Figure 29.
5.02.4.2 Chemistry Effects on Materials
Degradation of SGs
Corrosion of SG tubes has been the major issue
affecting selection of secondary water chemistry
parameters. However, corrosion and FAC of SG
internals and other secondary system components
are also important concerns.
Corrosion of SG tube materials is mainly affected
by the following water chemistry related factors, in
addition to nonwater chemistry factors such as material susceptibility, temperature, and stress:
pH Corrosion of several different types, including IGA/SCC and pitting, are strongly affected
by the local pH. High pH (caustic conditions)
and low pH (acidic conditions) accelerate the
rates of IGA/SCC.
ECP The ECP is a measure of the strength of the
oxidizing or reducing conditions present at the
metal surface. The rate of corrosion processes are

strongly affected by the ECP. Secondary side SCC in
tube alloys tends to be accelerated by increases in
ECP, that is, by the presence of oxidizing conditions.
Specific species Some impurity species accelerate
corrosion of tubing alloys as a result of their effects
on pH and ECP. In addition, lead and reduced
sulfur species (e.g., sulfides) appear to interfere
with formation of protective oxide films on the
tube metal surfaces, and thereby increase risks of
IGA/SCC, independent of influences on pH or
potential. Similarly, chlorides tend to increase the
probability of pitting.
These factors have been most thoroughly explored
for mill-annealed Alloy 600 (600MA). As discussed
in Chapter 5.04, Corrosion and Stress Corrosion
Cracking of Ni-Base Alloys, tests indicate that the
other tubing alloys, that is, stress-relieved Alloy
600 (600SR), thermally treated Alloy 600 (600TT),
nuclear grade Alloy 800 (800NG), and thermally
treated Alloy 690 (690TT), exhibit similar tendencies, but have increased resistance to corrosive attack,
in the order listed, with 690TT having the highest
resistance. Laboratory tests and plant experience indicate that 690TT has very high resistance to IGA/SCC
on the outside diameter on tubing (OD IGA/SCC) in
41
Pb remediation
Dispersants
Titanium
Molar ratio control
MPA, DMA
ETA chemistry
Morpholine chemistry
Boric acid addition
EPRI water chemistry guidelines
Ammonia chemistry
Phosphate
1975
1980
1985
1990
1995
2000
2005
Figure 29 Evolution of water chemistry for pressurized water reactor secondary systems.
normally expected crevice conditions, but OD IGA/

SCC could possibly occur as a result of upsets or as a
result of long-term fouling and accumulation of aggressive species in deposit-formed crevices. Alloy 800NG
also has high resistance to OD IGA/SCC, but laboratory tests indicate that it is about twice as susceptible as
Alloy 690TT, and it has experienced limited amounts
of IGA/SCC in plants, while no operation-related
corrosion of 690TT has been reported. Laboratory
tests and some plant experience indicate that 600TT
is significantly more resistant than 600MA but less
resistant than 800NG and 690TT.
Water chemistry selected to protect SG tubes
appears to be satisfactory for most balance-of-plant
(BOP) components such as turbines. The main corrosion concerns in the BOP that affect secondary
system water chemistry are FAC of carbon steel piping, tubing, and heat exchanger internals and shells,
and ammonia attack of copper and copper alloy
tubes. In addition, FAC has also affected some recirculating SG internal components (e.g., feedrings,
swirl vanes). FAC is mainly influenced by the
at-temperature pH and oxygen content around the
secondary system. Ammonia attack of copper alloys
is mainly influenced by the concentrations of ammonia and oxygen at the copper alloy locations, but is
also accelerated by increases in concentrations and
pH associated with other amines, although not as
strongly as by increases in ammonia.
Once-through steam generators (OTSGs) have
different thermal hydraulics and (in original SGs)
tube materials than recirculating steam generators

(RSGs). These differences have led to OTSGs
having somewhat different tube corrosion experience than RSGs of the same vintage. For the most
part, OTSGs have experienced somewhat lower
rates of tube degradation. However, significant
IGA/IGSCC has been detected in the upper bundle
free spans of several units, especially at scratches,
and SG replacement has been performed or is
planned at all units.
The locations in SGs that are most affected by
IGA/IGSCC are those where free circulation of secondary water is impeded by the local geometry, for
example, in crevices formed by tube support plates or
by sludge piles that can accumulate on the tube sheet.
Impurities in the secondary water can concentrate in
these locations by boiling and evaporation in a process called hideout.
The key issue influencing water chemistry regimes
in PWR secondary system is to minimize SG degradation by controlling sludge buildup, reducing (and
balancing, e.g., MRC) the concentration of impurities
(i.e., sodium, chloride and sulfate) in deposits at the
tube-tubesheet and tube-tube support plate interfaces. The use of advanced amines to control pH has
increased significantly in the past few years, as discussed in a following section. Figure 30 shows the
main approaches used in typical chemistry control
strategies.
Impurities are removed from SGs by blowdown of
the coolant. Over the past 20 years or so, average
42
Key issue: Mitigating IGA/IGSCC

in concentrating regions
Approach: Control local chemistry
Molar ratio control
Reduce Na
increase Cl
Reduce iron
Redox potential
Amines
dispersants
Reduce Cu
increase N2H4
Inhibitors
Boric acid
TiO2
Figure 30 Pressurized water reactor secondary chemistry control strategies.
blowdown impurity concentrations in US SGs have

been reduced from several ppb to the sub-ppb range.
Many PWRs today have SG blowdown concentrations near or below the analytical detection limit.
Minimization of impurities is recommended but has
been insufficient to prevent or completely mitigate
IGA/IGSCC at most plants with susceptible tube
material and design, as it can result in sodium-rich
feedwater. Cations such as sodium can be more effectively retained by boiling in a crevice than chloride.
Hence, excess cations over anions or anions over
cations result in specific corrosion issues because of
concentration processes in local environments.
The original all-volatile treatment used ammonia
to control pH, but a less-volatile chemical than ammonia would improve pH control throughout the circuit.
Early work employed morpholine, but now several
other amines are used. Since the initial application of
advanced amine chemistry about 15 years ago, there
has been tremendous success in reducing the transport
of corrosion products to the SGs by improving the attemperature pH around the BOP, especially in the
two-phase regions. This has resulted in mitigation of
FAC and thus reduced generation of corrosion products that ultimately get transported to the SGs. Ethanolamine (ETA) remains the most used amine at US
plants, with 75% of the US plants using ETA or
ETA with other amines, such as dimethylamine
(DMA) or 3-methoxypropylamine (MPA), to control
secondary cycle pH, as shown in Figure 31.17 Several
plants now use a mixture of amines to achieve the
optimum pH throughout the secondary system, with
25% of the US plants using MPA or MPA with other
amines while 12% of the plants use morpholine or
morpholine with other amines.
0%
4%
5%
4%
16%
56%
2%
7%
6%
ETA
MPA
ETA/DMA
ETA/MPA
MPA/DMA MPA/Morph
Morph/DMA
ETA/Morph
Morph
Figure 31 Amines used in the secondary systems of

US pressurized water reactors.
The proper control of oxygen in pressurized water

reactor (PWR) secondary feedwater, using an oxygen
scavenger such as hydrazine and/or carbohydrazide,
has been an enduring issue. The requirements for
oxygen concentration necessitate that some optimization take place. Maintaining reducing conditions
that is, low electrochemical potential in the SG is
essential to minimize SCC. On the other hand, some
oxygen in the feedwater counteracts corrosion of
1985
< 1992
1993
1994
1995
1996
1998
43
2005
% of US PWRs using advanced water chemistries

120
99
100
80
60
76
62
73
40
58
40
68
44
44
20
23
Using advanced
amines
57
30
23
30 30
50
41
31 33
28
On molar ratio
control
Using >100 ppb

FW N2H4
35
19
37 41
17
Using boric acid

treatment
Figure 32 Pressurized water reactor secondary chemistry trends.
carbon steel surfaces and the transport of corrosion

products to the SG. Recent work has investigated the
effect of hydrazine and oxygen on the ECP of SG
tubing materials (Alloys 600 and 690) as well as
stainless steel (304 and 316) and carbon steel during
PWR startup conditions.
These laboratory studies have shown that changes
in the concentration of hydrazine, used to ensure a
reducing potential in the SG, within the typical range
allowed and employed (e.g., 20150 ppb) have no
discernable effect on FAC at feedwater temperatures
(e.g., 180235 C).
Figure 32 shows the trends in using advanced
water chemistry regimes in the secondary systems
at US plants.
5.02.4.3
Control of Sludge Fouling of SGs
Corrosion products in the secondary side of PWR

SGs primarily deposit on the SG tubes. These deposits can inhibit heat transfer, lead to thermalhydraulic
instabilities through blockage of tube supports, and
create occluded regions where corrosive species can
concentrate along tubes and within tube-to-tube support plate crevices. The performance of the SGs can
be compromised not only through formation of an
insulating scale, but also through the removal of tubes
from service due to corrosion.
Although the application of various amines to
control the at-temperature pH (pHT) in specific
locations of PWR secondary systems has been
successful in reducing the corrosion of BOP metals

and thus reducing corrosion product transport to
SGs, a complementary strategy now exists for significantly reducing SG fouling through online application of dispersant, which inhibits deposition. By
inhibiting deposition of the corrosion products, the
dispersant facilitates more effective removal from the
SGs via blowdown. This strategy has been employed
at fossil boilers for many decades. However, due to the
use of inorganic polymerization initiators (containing
sulfur and other impurities), polymeric dispersants had
not been utilized in the nuclear industry. Only recently
has a PAA dispersant been available that meets the
criteria for nuclear application, and progress has been
made in reducing SG fouling by application of an
online dispersant to substantially improve the efficiency of blowdown iron removal. Dispersant application is proving to be a highly promising technology for
markedly decreasing SG fouling, delaying (or possibly
eliminating) the need for expensive chemical cleaning
and effectively reducing the frequency of sludge lancing for SG maintenance.
Online application of PAA to the feedwater system has been successfully demonstrated to greatly
increase the efficiency of the blowdown system
in eliminating feedwater corrosion products from
fouling the SGs. The first application occurred at
Arkansas Nuclear One Unit 2 for a three-month
trial in early 2000, which demonstrated a significant
improvement in the blowdown iron removal efficiency from 2% to 60% with 46 ppb PAA in
44
With dispersant
Iron removal efficiency
100
10
Without dispersant
1
0
0.5
1
1.5
2
Dispersant concentration (ppb)
Figure 33 Iron removal efficiency during dispersant test

at McGuire pressurized water reactor.
the feedwater. The second application, in 20052006,

at McGuire Unit 2 for a 69 month trial in their
replacement SGs tubed with Alloy 690TT showed
a similar significant improvement., as shown in
Figure 33.15
The following conclusions are evident from the
McGuire 2 demonstration described in the above
reference:
PAA is an effective dispersant. A feedwater PAA
concentration approximately equal to the feedwater iron concentration (2 ppb in this case)
appears to effectively remove approximately 50%
of the influent feedwater iron under steady-state
operating conditions.
Although blowdown copper spikes with initial
PAA application (albeit to a much lesser extent
than iron), it quickly returns to normal levels and
remains there.
Filter element consumption is manageable.
Blowdown cation conductivity and ammonia behavior changed during the trial, but these changes are
believed to be mainly due to changes in plant configuration and not PAA.
The SG thermal performance level has improved
slightly with dispersant application, most likely
due to slight beneficial changes in the tube deposit
thermal properties.
The long-term trial at McGuire 2 demonstrated
the significant improvement in blowdown iron
removal efficiency with application of PAA dispersant (a follow up to the successful short-term trial
at ANO-2 in 2000). Based on the success of the
McGuire 2 long-term trial, evaluations are in progress with SG vendors looking toward technical
concurrence for long-term use in their fleet of recirculating SGs.
5.02.4.4
Lead Chemistry
PbSCC is a serious concern that can affect all SG

tubing materials currently employed. A better understanding of lead behavior is needed at SG and
feedwater temperatures before possible mitigation
techniques can be successfully developed. It is well
known that soluble lead at very low concentrations
can contribute to SCC of nickel alloys. Likewise, it
is well known that some locations on the secondary
side of PWR SGs will accumulate lead in the solid
state (i.e., deposit) with local concentrations considerably in excess of those observed to accelerate
cracking in laboratory testing. Recent investigations
using analytical transmission electron microscopy15
have identified lead in the cracks of many tubes
pulled from PWRs. However, the absence of extensive operating SG tube failures at rates comparable to
what might be predicted based on laboratory studies
of PbSCC indicates that some mitigating phenomenon could be present.15
EPRI has published a sourcebook on lead29 that
summarizes the state-of-knowledge regarding PbSCC
and its effects on PWRs. It incorporates PbSCC laboratory testing, the current understanding of lead
transport and other physical chemistry aspects of
lead, and the accumulated industry experience
regarding PbSCC and its mitigation.
Three clearly understood and accepted facts regarding lead in PWR secondary water systems became clear
as this sourcebook was being put together:
In laboratory testing, the presence of lead accelerates SCC of mill-annealed 600MA, stress-relieved
600SR, and thermally treated 600TT stainless
steels as well as thermally treated Alloy 690
(690TT).
In operating PWRs, lead is present in the secondary system.
In two cases, a large ingress of lead to the secondary system has occurred as a result of lead blankets
having been left behind in SGs; the tubes in the
affected SGs cracked sooner and faster than in
the other SGs at the same units.
Set against these known facts are the following four
points:
The mechanisms by which lead is transported from
its ultimate source to the SG tube and into a crack
are not well understood, and a comprehensive
evaluation of possible mechanisms has not been
performed.
The threshold concentration at which lead will

accelerate SCC in SGs is not well defined.
No definitive indicator of PbSCC is available.
There is no well-characterized mechanism by
which lead accelerates SCC.
Recent work has shown that adsorption/desorption
of Pb on corrosion products and SG tubing surfaces
could potentially be a major sink/source, respectively,
for Pb microscopy.15 There is no direct evidence of
adsorption in SGs; however, there is sufficient potential
for this mechanism that direct high-temperature measurements under SG conditions have been performed.
As a result of ongoing laboratory studies, microscopy15 speculates that formation of a lead layer slows
repassivation, after a passive film at the crack tip is
disrupted, potentially to an extent to which a crack
can initiate and propagate.
5.02.5 Chemistry Control for FAC in

BWRs and PWRs
FAC causes wall thinning of carbon steel piping,
vessels, and components, as discussed in Chapter
5.06, Corrosion and Environmentally-Assisted
Cracking of Carbon and Low-Alloy Steels. The
wall thinning is caused by an increased rate of dissolution of the normally protective oxide layer, for
example, magnetite, that forms on the surface of
carbon and low-alloy steels when exposed to highvelocity water or wet steam. The oxide layer reforms
and the process continues. If the thinning is not
detected in time, the reduced wall cannot withstand
the internal pressure and other applied loads. The
result can be either a leak or a complete rupture.
The rate of wall loss (wear rate) of a given component is affected by temperature, fluid bulk velocity,
the effect of component geometry on local hydrodynamics, the at-temperature pH, the liquid phase
dissolved oxygen concentration, and the alloy composition. The addition of chromium to steels decreases
the rate of FAC. Materials used to replace piping
damaged by FAC include low-alloy steels containing
chromium and molybdenum (P11, 1.25% Cr0.5%
Mo and P22, 2.25% Cr1% Mo) and carbon or lowalloy steels clad with stainless steel. Corrosion models
are used to estimate wall thinning and determine where
monitoring is required. An example of the approach
commonly used in the United States is described by
Chexal and Horowitz.30
45
The main chemistry factors that affect the rate

of FAC are pH and dissolved oxygen concentration. FAC is not an issue for PWR primary systems.
As indicated earlier, laboratory studies have shown
that changes in the concentration of hydrazine in the
PWR secondary system feedwater, used to ensure a
reducing potential in the SG, have no discernable
effect on FAC at feedwater temperatures, within the
typical range allowed and employed.
The chemistry parameter that a BWR plant has
some degree of control over is dissolved oxygen.
Oxygen affects the form and solubility of the oxide
layer, the dissolution of which is inherent in FAC.
Several plants inject oxygen into the system, as the
rate of FAC increases dramatically if the oxygen
concentration is less than about 25 ppb. Plant data
are shown in Figure 34.
Use of HWC in a BWR can significantly reduce
the amount of oxygen in the main steam, extraction
steam, and heater drain systems, thus potentially
increasing the FAC rates in these areas of the plant.
The effect of NMCA on the corrosion behavior
of carbon steel in 550 F (288 C) water containing
various amounts of oxygen and hydrogen has been
studied and the data confirm that there is no adverse
effect of NMCA on FAC.7
The carbon steel segments of the BWR vessel
bottom-head drain line have been identified as
being FAC susceptible because of the flow conditions
and the potential for low dissolved oxygen concentrations. However, a significant number of inspections
have been performed recently at US plants and little
thinning has been observed.
The 2008 edition of the BWR Water Chemistry
Guidelines7 recommends that feedwater oxygen
should be maintained above 30 ppb to minimize FAC
of carbon and low-alloy steels.
5.02.6 Water Chemistry Control

Strategies
Sometimes, step changes in chemistry strategy are
unavoidable, as with the move to reducing chemistry
in BWRs. In these cases, the operators must be
prepared to deal with adverse effects. Some BWRs
adopting reducing conditions experienced a large
jump in out-of-core radiation fields, which may be
avoided with prior zinc injection. Addition of new
chemicals requires extensive qualification. For example,
the successful demonstrations of BWR online noble
Relative FAC wear rate

(expressed as percentage of the average wear
rate of components at 10 pbb oxygen)
46
160
140
Plant A
120
Plant A
100
Plant B
Plant C
80
Plant D
60
Average
40
20
0
0
10
20
30
40
50
60
70
80

Figure 34 Plant data showing the relationship between flow-assisted corrosion and dissolved oxygen. (Oxygen values
are localized, calculated by the CHECWORKS codes from measured values at condensate or feedwater locations.)
chemistry and PAA dispersants in PWR SGs resulted

from detailed monitoring and evaluation during the
first injections. If possible, changes in chemistry
should be made in baby steps, with monitoring at
each step, before further changes are implemented.
Examples of this strategy are the gradual increases in
lithium/pH and dissolved hydrogen in PWR primary
systems. These incremental changes minimize adverse
side-effects and allow a planned approach to the optimum plant-specific chemistry control program.
The US nuclear power industry produces guidance documents to assist plant personnel in determining a plant-specific chemistry control strategy. The
early versions of these documents, developed in the
1980s, listed water chemistry specifications and
actions to be taken if the limits were exceeded. As
more chemistry options became available, the guidelines evolved into providing guidance on selecting the
most appropriate chemistry for a specific plant. Thus,
the 2008 BWR Water Chemistry Guidelines7 offers
recommendations on controlling ECP, zinc injection,
and feedwater iron control. Likewise, the 2007 PWR
Primary Water Chemistry Guidelines12 provides
guidance on pH control and zinc injection, and the
2008 PWR Secondary Water Chemistry Guidelines27
discusses impurity control, amines, and dispersants.
Theses documents are used by all US nuclear power
plants and provide the technical basis for similar
guidelines used in many other countries. Development of a strategic water chemistry plan, as discussed
in these documents, is seen as crucial to controlling
material degradation in the future.
References
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
Swan, T.; Wood, C. J. In Developments in Nuclear Power

Plant Water Chemistry, VIIIth International Conference on
Water Chemistry of Nuclear Reactor Systems, Oct 2326,
2000; BNES: Bournemouth, UK, 2000.
Fruzzetti, K.; Wood, C. J. In Developments in Nuclear
Power Plant Water Chemistry. International Conference on
Water Chemistry of Nuclear Reactor System, Jeju Island,
Korea, Oct 2326, 2006.
Cohen, P. Water Coolant Technology of Power Reactors;
Gordon and Breach: New York, 1969.
Jones, R. L. In International Water Chemistry Conference,
San Francisco, Oct 1115, 2004; EPRI: Palo Alto, CA,
2004.
Garcia, S.; Wood, C. Recent advances in BWR water
chemistry. In VGB NPC08 Water Chemistry Conference,
Berlin, Sept 1418, 2008.
Cowan, R.; Hussey, D. Radiation field trends as related to
chemistry in United States BWRs. In 2006 International
Conference on Water Chemistry of Nuclear Reactor
Systems, Jeju Island, Korea, Oct 2326, 2006.
EPRI. Boiling Water Reactor Water Chemistry Guidelines
2008 Revision; EPRI: Palo Alto, CA, 2008.
Edsinger, K. In Nuclear News; Tompkins, B., Ed.; 2008;
pp 3436.
Fruzzetti, K.; Perkins, D. PWR chemistry: EPRI
perspective on technical issues and industry research.
In VGB NPC08 Water Chemistry Conference, Berlin,
Sept 1418, 2008.
Andresen, P.; Ahluwalia, A.; Hickling, J.; Wilson, J.
Effects of PWR primary water chemistry on PWSCC of
Ni alloys. In 13th International Conference on
Environmental Degradation of Materials in Nuclear Power
Systems, Whistler, Canada, Aug 1923, 2007.
Andresen, P.; Ahluwalia, A.; Wilson, J.; Hickling, J.
Effects of dissolved H2 and Zn on PWSCC of Ni alloys.
Sept 1418, 2008.
EPRI. Pressurized Water Reactor Primary Water Chemistry
Guidelines: Revision 6; EPRI: Palo Alto, CA, 2007.

13. Pathania, R.; Yagnik, S.; Gold, R. E.; Dove, M.;
Kolstad, E. Evaluation of zinc addition to PWR
primary coolant. In 7th International Symposium on
Environmental Degradation of Materials in Nuclear
Power Systems, Breckenridge, CO, NACE: Houston,
TX, 1995; pp 163176.
14. Molander, A.; Jenssen, A.; Norring, K.; Konig, M.;
Andersson, P.-O. Comparison of PWSCC initiation
and crack growth data for Alloy 600. In VGB
NPC08 Water Chemistry Conference, Berlin,
Sept 1418, 2008.
15. Fruzzetti, K.; Rochester, D.; Wilson, L.; Kreider, M.;
Miller, A. Dispersant application for mitigation of steam
generator fouling: Final results from the McGuire
2 long-term trial and an industry update and EPRI
perspective for long-term use. In VGB NPC08 Water
Chemistry Conference, Berlin, Sept 1418, 2008.
16. Haas, C.; Ahluwalia, A.; Kucuk, A.; Perkins, D. PWR
operation with elevated hydrogen. In VGB NPC08 Water
Chemistry Conference, Berlin, Sept 1418, 2008.
17. Hussey, D.; Perkins, D.; Choi, S. Benchmarking
radioactivity transport and deposition in PWRs. In VGB
NPC08 Water Chemistry Conference, Berlin, Sept 1418,
2008.
18. Stevens, J.; Bosma, J. Elevated RCS pH program at
Comanche peak. In VGB NPC08 Water Chemistry
Conference, Berlin, Sept 1418, 2008.
19. Nordmann, F. Worldwide chemistry objectives and
solutions for NPP. In VGB NPC08 Water Chemistry
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
47
Tigeras, A.; Stellwag, B.; Engler, N.; Bretelle, J.; Rocher, A.

Understanding the zinc behavior in PWR primary coolant:
A comparison between French and German experience.
Sept 1418, 2008.
Frattini, P. L.; Blok, J.; Chauffriat, S.; Sawicki, J.; Riddle, J.
In VIIIth International Conference on Water Chemistry of
Nuclear Reactor Systems, Oct 2326, 2000; BNES:
Bournemouth, UK, 2000.
Riess, R. Personal communication, 2008.
Byers, W.; Wang, G.; Deshon, J. Limits of zinc addition in
high duty PWRs. In VGB NPC08 Water Chemistry
Perkins, D.; Ahluwalia, A.; Deshon, J.; Haas, C. An EPRI
perspective and overview of PWR zinc injection. In VGB
NPC08 Water Chemistry Conference, Berlin, Sept 1418,
2008.
Millett, P. J; Hundley, F. Nucl. Energ. 1997;
36, pp 251258.
EPRI. Personal communication from K. Fruzzetti, 2009.
EPRI. Pressurized Water Reactor Secondary Water
Chemistry Guidelines Revision 6; EPRI: Palo Alto, CA, 2008.
Choi, S. Personal communication, 2009.
EPRI. Pressurized Water Reactor Lead Sourcebook; EPRI:
Palo Alto, CA, 2006.
Chexal, V.; Horowitz, J. ChexalHorowitz flowaccelerated corrosion model Parameters and influences.
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5.03
Corrosion of Zirconium Alloys
T. R. Allen
University of Wisconsin, Madison, WI, USA
R. J. M. Konings
European Commission, Joint Research Centre, Institute for Transuranium Elements, Karlsruhe, Germany
A. T. Motta
The Pennsylvania State University, University Park, PA, USA
5.03.1
5.03.2
5.03.2.1
5.03.2.2
5.03.2.3
5.03.3
5.03.3.1
5.03.3.2
5.03.3.3
5.03.3.4
5.03.3.4.1
5.03.3.4.2
5.03.3.4.3
5.03.4
5.03.5
5.03.5.1
5.03.5.2
5.03.5.3
5.03.5.4
5.03.5.5
5.03.6
5.03.7
References
Introduction
General Considerations
Oxidation
Hydrogen Uptake
Controlling Factors for Corrosion
Uniform Oxidation
Mechanism
Temperature and Heat Flux
Coolant Chemistry
Irradiation Effects
Radiolysis
Irradiation effects in the oxide layer
Changes in the metallurgical state of the metal
Nodular Oxidation
Hydrogen Embrittlement
Hydrogen Production During Aqueous Corrosion of Zirconium-Base Materials
Hydrogen Absorption
Hydride Formation
Hydride Formation Rates
Formation of Hydride Rim
Delayed Hydride Cracking
Summary and Outlook
Abbreviations
BWR
CANDU
CRUD
DHC
IAEA
M5TM
PWR
tHM
VVER
ZIRLOTM
Zry

Canadian Deuterium Uranium
Chalk River unidentified deposits
Delayed hydride cracking
International Atomic Energy Agency
Zirconium alloy material with niobium
(AREVA)
Ton heavy metal
Voda Voda Energy Reactor
Zirconium alloy material with niobium,
tin, and iron (Westinghouse)
Zircaloy
49
50
50
51
52
53
53
57
57
59
59
60
60
61
61
62
62
62
63
64
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5.03.1 Introduction
Zirconium alloys are widely used for fuel cladding
and in pressure tubes, fuel channels (boxes), and fuel
spacer grids in almost all water-cooled reactors: light
water reactors such as the pressurized water reactor
(PWR) and the boiling water reactor (BWR) as well
as the Canadian designed Canadian Deuterium
Uranium (CANDU) heavy water reactor. Since
its employment in the first commercial nuclear
power plant (Shippingport) in the 1960s, Zircaloy, a
zirconiumtin alloy, has shown satisfactory behavior
during many decades. However, degradation due to
waterside corrosion can limit the in-reactor design life
of the nuclear fuel. The critical phenomenon is the
49
50
hydrogen ingress into the cladding during corrosion,

which can cause cladding embrittlement. As utilities
are striving to achieve higher fuel burnups, the
nuclear industry has made several efforts to understand the mechanisms of corrosion and to mitigate
its effects.
In striving for increased burnup of the nuclear fuel
from 33 000 to 50 000 MWd/tHM and beyond in
PWRs, associated studies have shown that the corrosion of the Zircaloy-4 cladding accelerates under
these higher burnup conditions. Although alloys
that are more modern have not yet shown evidence
of this high-burnup acceleration, this is a potential
concern. Also, the efforts to increase the thermalcycle efficiency in PWRs by operating at higher
temperatures (power uprates), combined with the
more aggressive chemistry (introduction of B and Li
for example) related to the use of high-burnup fuel,
have resulted in increased fuel duty,1 and in increased
corrosion rates. This has led to the introduction
of cladding tubes of new zirconium alloys such as
zirconiumniobium, which are much more corrosion
resistant.2,3 With the introduction of these materials,
the nuclear industry aims at zero tolerance for fuel
failure in the future.4
Many reviews on the corrosion of zirconium alloys
both out- and in-reactor, have been published.511
The extensive reviews made by an international
expert group of the International Atomic Energy
Agency (IAEA) and published as IAEA-TECDOCs
684 and 99612,13 are major references in this respect.
As mentioned by Cox,6,7 the number of publications
on this topic is so enormous that it is impossible for a
short review to be comprehensive. This also applies
to the current chapter, which therefore focuses on the
main issues, naturally relying on the above-mentioned
existing reviews and updating the information where
possible with new results and insights.
protective, thus limiting the access of oxidizing species

to the bare metal. Much evidence exists to indicate
that Zr oxidation occurs by inward migration of oxygen ions through the oxide layer, either through
grain boundaries or through the bulk.5,12,13
Zr O2 ZrO2
As shown in Figure 1, the growth of the oxide
layer on the metal surface depends on the kinetics of
the oxygen diffusion through this layer. Because the
corrosion kinetics slow down as the oxide thickness
increases, it has been argued that the rate controlling
step in the oxidation process is the transport of atomic
species in the protective oxide, by either oxygen diffusion through the oxide film14,15 or diffusion of electrons through the oxide film. These processes are
necessarily coupled to maintain electroneutrality.
Electron transport is, however, difficult in zirconium
dioxide, as it is an electrical insulator when undoped.
Although this is not positively confirmed, it is likely
that the role of doping elements in the determination
of corrosion kinetics is done through their influence
on the electron or oxygen transport in the oxide layer.
Several types of corrosion morphologies have
been observed in nuclear reactors and in autoclave
experiments, of which the most important are
1. Uniform: The formation of a thin uniform layer of
zirconium dioxide on the surface of a zirconium
alloy component (see Figure 2).
2. Nodular : The formation of local, small, circular
zirconium oxide blisters (see Figure 3).
3. Shadow: The formation of local corrosion regions
that mirror the shape (suggestive of a shadow)
of other nearby noble reactor core components
(Figure 4).
H2O O2 + 2H+
Coolant
5.03.2 General Considerations

5.03.2.1
Oxidation
Corrosion of zirconium alloys in an aqueous environment is principally related to the oxidation of the
zirconium by the oxygen in the coolant, dissolved
or produced by radiolysis of water. A small amount
of oxygen can be dissolved in the metal, but once the
thermodynamic solubility limit is exceeded, ZrO2 is
formed on the metal. (All zirconium components normally have a thin oxide film (25 nm) on their surface
in their as-fabricated state.) The oxide formed is
H+
O2
H+
Oxide
H+ + e
Zr + 2O2 ZrO2 + 4e
H0
Metal
Figure 1 Schematic presentation of the corrosion of the

zirconium alloys. Corrosion of zirconium alloys in nuclear
power plants; TECDOC-684; International Atomic Energy
Agency, Vienna, Austria, Jan 1993.
51
Zr + H2O = ZrO2 + H2
ZrH2x
ZrO2
Figure 2 Uniform oxide layer formation and hydride precipitation in Zircaloy cladding. European Atomic Energy
Commission.
The occurrence of these morphologies is strongly

dependent on the reactor operating conditions and
chemical environment (particularly the concentration of oxygen in the coolant), which are distinctly
different in PWRs, BWRs, and CANDU (Table 1).
In both BWRs and PWRs, a uniform oxide layer is
observed, although its thickness is normally greater in
PWR than in BWR, primarily because of the higher
operating temperature. Nodular corrosion occurs
occasionally in BWRs because a much higher oxygen
concentration occurs in the coolant because of water
radiolysis and boiling. Shadow corrosion is also occasionally observed in BWRs and is a form of galvanic
corrosion.
1 mm
5.03.2.2
100 m
Figure 3 General appearance of nodules formed on

zirconium alloy following a 500 C steam test at 10.3 MPa. In
the bottom, a cross-section view of a nodule is shown,
exhibiting circumferential and vertical cracks. Photo courtesy
of R. Ploc and NFIR (Nuclear Fuel Industry Research Group).
Reproduced from Lemaignan, C.; Motta, A. T. Zirconium
Alloys in Nuclear Applications, Materials Science and
Technology, Nuclear Materials Pt. 2; VCH
Verlagsgesellschaft mbH, Weinheim, Germany, 1994.
Hydrogen Uptake
The formation of an oxide layer would not bring

severe consequences to cladding behavior were it
not for the fact that in parallel with the corrosion
process, a fraction of the hydrogen, primarily produced by the oxidation reaction as well as by radiolysis of water, diffuses through the oxide layer into the
metal. Zirconium has a very low solubility for hydrogen (about 80 wt ppm at 300 C and 200 wt ppm at
400 C) and once the solubility limit is exceeded, the
hydrogen precipitates as a zirconium hydride phase
(Figure 2):
ZrH; sln H2 ZrH1:6 or ZrH2
As a result, the following effects have been reported
(although not all confirmed) to occur in the cladding:
hydrogen embrittlement due to excess hydrogen
or its localization into a blister or rim,16,17 loss of
52
fracture toughness, delayed hydride cracking (DHC),

and acceleration of corrosion and of irradiation
growth. Hydrogen embrittlement impacts the
mechanical resistance of the Zircaloy cladding to
failure and it is thus of key importance to understand

its underlying mechanisms. The ductility reduction
due to hydrogen embrittlement is dependent on the
volume fraction of hydride present, the orientation of
the hydride precipitates in the cladding, and their
degree of agglomeration.18,19
Oxide
5.03.2.3
Oxide
(b)
(a)
Figure 4 Zirconium oxides near (b) and away from
(a) a stainless steel control blade bundle, showing the effect
of shadow corrosion. Reproduced from Adamson, R. B.;
Lutz, D. R.; Davies, J. H. Hot cell observations of shadow
corrosion phenomena. In Proceedings Fachtagung der
KTG-Fachgruppe, Brennelemente und Kernbautelle,
Forschungszentrum Karlsruhe, Feb 29Mar 1, 2000.
Table 1
Controlling Factors for Corrosion
The oxidation and hydrogen uptake of Zircaloy is of

course determined by many factors. First of all, the
chemical and physical state of the material: composition, metallurgical condition, and surface condition.
These conditions are often specific to the material
and sometimes batch-specific and also related to the
fabrication process, as discussed in detail in Chapter
2.07, Zirconium Alloys: Properties and Characteristics. This is evident from the different behavior
of Zircaloy and ZrNb alloys, as shown in Figure 5
for two different zirconium alloys employed in the
French PWRs, Zircaloy and Zr1% Nb (M5). The
peak oxide layer thickness of Zircaloy-4 (oxide thickness at the hottest fuel grid span) increases significantly with burnup (i.e., residence time in the
reactor), whereas that of Zr1%Nb shows a moderate
increase.
In addition, a number of environmental factors
affecting the corrosion of zirconium alloys must be
considered:
1. Coolant Chemistry: It is obvious that the dissolved
oxygen and hydrogen play a major role in the
corrosion process, but other dissolved species
must also be taken into account. To control the
pH of the coolant at slightly alkaline conditions,
Typical reactor environments to which the zirconium alloys are exposed
Coolant
Inlet temperature ( C)
Outlet temperature ( C)
Pressure (MPa)
Neutron fluxa (n cm2 s1)
Coolant chemistry
[O2] (ppb)
[H2] (ppm)
pH
B (as H3BO3) (ppm)
Li (as LiOH) (ppm)
Na (as NaOH) (ppm)
K (as KOH) (ppm)
NH3 (ppm)
BWR
PWR
VVER
CANDU
H2O
272278
280300
7
47 1013
H2O
280295
310330
15
69 1013
H2O
290
320
15
57 1013
D2O
255
300
10
2 1012
200
0.03
7
<0.05
25
6.97.4
02200
0.55
< 0.1
<5
0.51
10.210.8
0140016
0.050.6
0.030.35
520
630
a
E > 1 MeV.
Corrosion of zirconium alloys in nuclear power plants; TECDOC-684; International Atomic Energy Agency, Vienna, Austria, Jan 1993.
53
60
50
Oxide thickness (mm)
M5
Zirc-4
40
30
20
10
0
0
20
40
60
80
Burnup (MWd kgU1)

Figure 5 Peak oxide layer thickness as a function of burnup for Zircaloy-4 and Zr1%Nb (M5). Reproduced from Bossis, P.;
Pecheur, D.; Hanifi, K.; Thomazet, J.; Blat, M. J. ASTM Int. 2006, 3(1), Paper ID JAI12404.
LiOH is added and H3BO3 (boric acid) is added

for reactivity control in PWRs. Furthermore,
impurities (Cl, F) and coolant-borne species (Cu,
Ni, etc.) must be considered.
2. Radiation: In reactor, the Zircaloy and the coolant
are subjected to the effects of energetic particles.
The principal effect is the production of oxidizing
species such as O2 in the coolant.
3. Temperature : In the range of water reactor operation
(240330 C), the combined effect of temperature
and radiation on zirconium alloy oxidation and
hydriding have been characterized extensively,
varying from almost no effect to acceleration of
oxidation by factors of up to two orders of magnitude, depending on environment and radiation level.
4. In addition, the presence of boiling and CRUD
(the term CRUD stands for Chalk River unidentified deposits, the nuclear power plant in which the
effect was observed for the first time) deposition in
PWR can enhance corrosion.
5.03.3 Uniform Oxidation

5.03.3.1
Mechanism
Uniform corrosion is defined as a process that occurs

approximately with the same speed on the entire
surface of an object (ISO 8044). It can be considered
as an electrochemical cell process, in which the metal
is anodically oxidized:
Zr 2O2 ZrO2 2Vo 4e
O
o
where VO
indicates a lattice vacancy in the ZrO2
layer. The corresponding cathodic reaction at the
oxide/coolant interface can be the reduction of
water:
2H2 O 4e 2Vo 2O2 4H

O
or, when the water contains dissolved oxygen:

2H2 O O2 2VOo 4e 4OH
The oxygen ions diffuse preferentially via the oxide
crystallite boundaries to the oxide/metal interface,
whereas the vacancies diffuse in the opposite direction. The hydrogen can combine with electrons to
form atomic/molecular hydrogen that dissolves in
the coolant water or diffuses to the metal.
Uniform corrosion is a passivating event since a
protective layer of zirconium oxide is formed as a
result of the reaction with the O2 ions or the OH
radicals. Electron microscopy shows that the oxide
layer is microcrystalline, initially equiaxed, later
growing into columnar grains that are formed in a
dense packing, of which the mean crystallite size
increases as the oxide thickens.15 Figure 6 shows
typical microstructures of the oxide layer for several
zirconium-based cladding materials. Figure 6(c), in
particular, shows the columnar grains extending right
near the oxide/metal interface.
The corrosion kinetics have been studied extensively. As mentioned above, because the corrosion
rate slows down with oxide thickness, the rate
controlling step is thought to be the transport of
oxidizing species in the layer.15,20 During corrosion,
54
Zircaloy-4
ZIRLO
(a)
Zr2.5Nb
(b)
(c)
150 nm
150 nm
150 nm
Figure 6 Grain size, shape, and orientation comparison near the oxide/metal interface of (a) Zircaloy-4, (b) ZIRLO, and
(c) Zr2.5Nb alloy oxides formed in 360 C pure water environments. The hand-drawn sketch below each bright-field image
shows oxide crystallite grain boundaries. Black arrows indicate oxide growth direction. Reproduced from Yilmazbayhan, A.;
Breval, E.; Motta, A. T.; Comstock, R. J. J. Nucl. Mater. 2006, 349, 265281.
a potential develops across the oxide layer. The negative potential at the oxide/metal interface accelerates the electron migration process and retards the
O2 diffusion until both operate at the same rate.
Bossis et al.22 argue that the surface reactions are
rate-determining in some Nb-containing alloys.
The measurements of the weight gain kinetics for
zirconium and its alloys (the weight gain is due to
oxygen ingress and follows the overall corrosion
kinetics) were found to fall into two stages, referred
to as pre- and posttransition. For constant temperature and pressure, the pretransition corrosion kinetics
are independent of pH between about 1 and 13 (if no
specifically aggressive species such as LiOH are present) and of the source of the oxygen. The kinetics of
the pretransition oxide layer formation, as measured
from weight gain (DW ), have been found to approximately follow a cubic rate law21:
3
DW k1 t
1
where k1 is the preexponential factor and t is time.

More recent results have shown that the rate law
depends on the alloys according to (DW)n kt, with

n between 2 and 5.22 The temperature dependence of
k1 follows an Arrhenius-type equation:

Q1
2
k1 B1 exp
RT
where B1 is an empirical constant, R is the universal gas constant, T is the absolute temperature,
and Q1 is the activation energy for pretransition
oxidation. The values for B1 are Q1 are obtained empirically from fitting of experimental data, for example,
B1 6.36 1011 (mg dm2)3 per day and Q1/R
13640 K, as found by Kass21 for Zry-2 and Zry-4.
The posttransition kinetics, on the contrary, are
approximately linear (n 1) in time23:
DW k2 t C
with
k2 B2 exp

Q2
RT
3
4
and C the weight gain at transition. B2 is the empirical

constant and Q2 the activation energy for posttransition
oxidation. Hillner et al.23 discussed the results of

numerous analyses of experimental corrosion studies
on Zircaloy with varying time and temperature to
derive B2 and Q2. As discussed by these authors,
most studies suffer from paucity of data for extended
exposures. Their own results for Zry-2 and Zry-4
cover a wide range of time and weight gain and the
posttransition kinetics were interpreted to consist of
two linear stages (with a change at about 400 mg dm2
or about 30 mm) with B2 2.47 108 mg dm2 day1
and Q2/R 12880 K for stage 1, and B2 3.47 107
mg dm2day1 and Q2/R 11452 K for stage 2.
Whether or not Hillners interpretation of a change
in mechanism is correct, certainly the data is best
described by a two-stage empirical fit.
A schematic representation of these pre- and posttransition kinetics is shown in Figure 7 as the dashed
lines. Also shown in this graph is the more recent
view that three stages can be discriminated for zirconium alloy corrosion processes23:
1. The early pretransition regime, characterized by
the formation of a thin, black, tightly adherent
corrosion film that grows thicker in accordance
with a nearly cubic rate law.
2. The intermediate stage that lies between the preand posttransition stages. As initially shown by
Bryner,24 this region appears to comprise a series
of successive cubic curves, similar to the initial
cubic kinetic curve. This linear rate results from
the superposition of various regions of the oxide
layer following pretransition growth rate but
slightly out of phase with each other.
Oxide thickness
Posttransition
(linear)
Transitory
(cyclic)
Pretransition
(cubic)
Time
Figure 7 Schematic representation of the zirconium alloy

corrosion showing the pretransition, transitory, and
posttransition regions. The dashed lines indicate early
models that recognized only the pre- and posttransition
regimes. Reproduced from Hillner, E.; Franklin, D. G.;
Smee, J. D. J. Nucl. Mater. 2000, 278, 334.
55
3. The linear posttransition kinetic regime.

In the very early stages of the oxide formation, the
layer is dense and composed of grains that have a
predominantly tetragonal or cubic structure. As the
grains grow, columnar grain growth is established and
the tetragonal grains tend to transform to monoclinic
oxide, which constitutes the majority of the oxide
formed.20 Although the tetragonal phase has often
been associated with protective behavior, this correlation is noncausal and in fact, oxides with lower tetragonal fraction have been found to be more protective.26,27
The diffusion of oxygen takes place along the grain
boundaries in the oxide layer,4 the kinetics of which
are given by eqn [1]. The size of the columnar grains
and their grain-to-grain misorientation (Figure 6)
have been related to the transition thickness.
Studies of Zircaloy corrosion in autoclaves clearly
reveal the cyclic corrosion kinetics,20,24 the oxide
layer appearing to be composed of successive layers
of 23 mm thickness (Figures 810), for which the
oxidation kinetics progressively decrease as a result
of the growth of the oxide layer, in accordance with
eqn [1]. The cycles are separated by transitions during which the kinetics appears to accelerate. The
transitions are caused by the destabilization of the
oxide layer, as a result of which the passivating layer
becomes porous and fractured at the end of the cycle,
losing its protective role, and reopening for rapid
oxidation. A new oxidation cycle then starts. Several
processes have been suggested for the destabilization
of the oxide layer, such as7,2527:
(a) Cracking of the oxide as a result of the accumulation of compressive stresses in the oxide from
imperfect accommodation of the volume expansion attendant upon oxide formation.
(b) Cracking of the oxide as a result of the transformation of initially tetragonal ZrO2 to the monoclinic modification,10 or as a result of the
oxidation of intermetallic precipitates initially
incorporated in metallic form, both of which
result in a volume increase.
(c) The porosity formed in the oxide reaches a percolation condition, leading to easy access of the
coolant to the underlying metal.
The first factor is normally considered to be the main
driver, although the other factors have also been
proposed to contribute. The levels of stress accumulation depend on the phase transformation tensor
(various levels of accommodation of the PillingBedworth strains in the in-plane directions), which
56
Oxide thickness (m)
15
12
Zircaloy-4
9
M5
6
3
0
200
400
600
800
Time (days)
Figure 8 Results of oxidation tests of Zircaloy-4 and of M5 in autoclaves, at 360 C, with 10 ppm Li and 650 ppm B,
showing the cyclic nature of the oxidation. Redrawn from Bataillon, C.; Feron, D.; Marchetti, L.; et al. E-DEN Monograph
Corrosion Commissariat a` lEnergie Atomique; 2008.
Zr4
Zr4
20 mm
20 mm
ZIRLO
ZIRLO
Figure 9 Optical micrographs of oxide layers formed in Zircaloy-4 and in ZIRLO, in reflected (left) and transmitted
light (right). The regular periods formed during the cyclic corrosion process correspond to the oxide transitions in the two
alloys. Photo courtesy of G. Sabol, Westinghouse Electric Co.
has been shown to vary from alloy to alloy, thus likely

causing the consistent differences seen among the
oxide thicknesses at transition for various alloys.
Thus, each alloy has a reproducible transition thickness
in a given environment. This cyclic process has been
shown to reproduce itself with remarkable regularity
upward of 17 transitions,26,27 as shown in Figure 9. This
can also be seen in the SEM micrograph in Figure 10
which suggests that cracking occurs at transition.
As discussed by Battaillon et al.,25 the kinetics of the

cyclic process can be described by a succession of
equations similar to [1] and [2], each representing a
specific cycle. The length of the cycle seems to
be material dependent as shown in Figure 8. Also,
Zircaloy contains second phase precipitates of Zr(Cr,
Fe)2 and tin as a dissolved element (see Chapter 2.07,
Zirconium Alloys: Properties and Characteristics).
The intermetallic precipitates are known to have a
57
1000
Weight gain (mg dm2)
800
10 m
Figure 10 The oxide layer formed on M5 in autoclaves
at 360 C, with 10 ppm Li and 650 ppm B dissolved in
the water showing the layered nature of the oxide, with
periodic cracking. Bataillon, C.; Feron, D.; Marchetti, L.;
et al. E-DEN Monograph Corrosion Commissariat a`
lenergie atomique, 2008. From DEN Monographs
Corrosion and Alteration of Nuclear Materials, ISBN
978-2-281-11369-3 (2010), editions du Moniteur, CEA.
600
400
200
280
300
320
Temperature (C)
340
360
Figure 12 The effect of temperature on the oxidation

kinetics of Zircaloy-4, as derived from autoclave test in
water for 2500 days. Reproduced from Hillner, E.; Franklin,
D. G.; Smee, J. D. J. Nucl. Mater. 2000, 278, 334.
experimentally. As shown in Figure 12, the corrosion

kinetics accelerate above about 310 C. An increase
of 5 C for a typical cladding temperature of 335 C
results in a 26% increase in weight gain.
The temperature of the metaloxide interface (Ti)
is, however, not only dependent on the temperature of
the coolant, but also on the heat flux (f in W cm2):
higher oxidation resistance than the zirconium

matrix.28,29 When the oxidation of the zirconium progresses, the Zr(Cr,Fe)2 precipitates are incorporated
in metallic form into the oxide layer (Figure 11).
However, the iron is progressively dissolved in the
zirconium oxide. Tin is present in the oxide layer as
nanoparticles of b-Sn, SnO, or Sn(OH)2. The slower
oxidation kinetics of ZrNb alloys have been attributed to the absence of the second phase precipitates.7
fe
l
where Ts is the temperature at the wateroxide
layer boundary, e the oxide layer thickness (in cm),
and l the thermal conductivity of the oxide layer
(W cm1 K1). Considering that zirconium oxide is
a poor thermal conductor, the oxide layer will act
as an insulator increasing the temperature of the
metaloxide interface. For typical values for a
PWR (f 55 W cm2) and a thermal conductivity
of 0.022 W cm1 K1, the interface temperature
increases 1 K for an oxide layer of 4 mm.25
As a related effect, nucleate boiling can occur at the
oxidewater boundary, once this boundary reaches
the saturation temperature (344.5 C at 15.5 MPa in
a PWR). As a result, an enrichment of Li in the liquid
phase near the oxidewater boundary can occur
(Figure 13), which can reach a factor of 3.25 This is
not expected to increase the corrosion significantly
for conditions typical for PWRs.
5.03.3.2
5.03.3.3
100 nm
Figure 11 Zr(Cr,Fe)2 precipitates incorporated in metallic
form into the oxide layer on Zircaloy-4. Adapted from
Pecheur, D.; Lefebvre, F.; Motta, A. T.; Lemaignan, C.;
Charquet, D. Oxidation of Intermetallic Precipitates in
Zircaloy-4: Impact of Irradiation. In 10th International
Symposium on Zirconium in the Nuclear Industry, ASTM
STP 1245; Baltimore, MD, 1994; 68770; Pecheur, D.;
Lefebvre, F.; Motta, A. T.; Lemaignan, C.; Wadier,
J. F. J. Nucl. Mater. 1992, 189, 2318332.
Temperature and Heat Flux
An increase of temperature increases the oxidation

kinetics, as is evident from eqn [1], and confirmed
Ti Ts
Coolant Chemistry
The corrosion of Zircaloy is influenced by the chemical composition of the coolant. The PWR coolant
58
activation.) In addition, the coolant may contain

small concentrations of anionic impurities that play a
role in the corrosion mechanism (Figure 14).
Extensive research has been performed to understand the role of lithium hydroxide and boric acid on
the kinetics of the corrosion of zirconium alloys.
Experiments in autoclaves have shown that the rate
of oxidation of Zircaloy-4 increases significantly
when boric acid is absent.25 After an initial stage
where the corrosion kinetics are as expected, corrosion is accelerated in conjunction with a decrease of
the thickness of the protective oxide layer,30,31 as
derived from microscopic observations, especially
by the ingress of Li into the oxide (Figure 15).
Enhanced dissolution of the crystallite grain boundaries has been suggested as the mechanism.32 This
effect was absent in the presence of boric acid, and no
significant difference was observed for the oxidation
kinetics for LiOH concentrations between 70 and
1.5 ppm (Figure 14). The protective effect of boric
acid has been suggested to be related to the plugging
of the porosity in the oxide by a borate compound.33
The coolant chemistry also influences the solubility of coolant-borne metallic impurities (e.g., iron,
nickel, copper, etc. arising from corrosion release
from circuit surfaces), which may deposit on fuel
rod surfaces as CRUD, which is composed of metal
oxides such as Fe2O3 (hematite), Fe3O4 (magnetite),
FeOOH (goethite), or (Ni,Co)xFe3-xO4 (spinel).3436
Such CRUD deposits are occurring specifically at
positions with sub-cooled boiling and may have, in
some cases, appeared to contribute to accelerated
contains boron and lithium. Boron, present as boric

acid (10002000 ppm at the beginning of the cycle,
depending on the cycle length, and about zero at the
end of the cycle), is added to control the core reactivity through neutron absorption of 10B. The boric acid
is weakly dissociated, particularly at high temperature,
which could lead to a slightly acidic environment. To
counteract this, small quantities of lithium hydroxide
(510 ppm) are added in the water, to obtain a slightly
alkaline pH, to avoid deposition of corrosion products
on the cladding and limit the corrosion of core structures made of stainless steel or Inconel alloys. (Lithium
enriched over 99% of 7Li is used, as the use of
6
Li produces the undesirable tritium through
Oxide
Water
Steam
bubble
Enrichment of species
of low volatility
Figure 13 Schematic representation of the enrichment of

species at the oxidewater boundary during nucleate
boiling. Adapted from DEN Monographs Corrosion and
Alteration of Nuclear Materials, ISBN 978-2-281-11369-3
(2010), editions du Moniteur, CEA.
20
70 ppm Li
(B=0)
18
Oxide thickness (m)
16
10 ppm Li
650 ppm B
14
12
3.5 ppm Li
1000 ppm B
10
70 ppm Li
650 ppm B
1.5 ppm Li
650 ppm B
6
4
2
0
0
100
200
300
400
500
Time (days)
Figure 14 The effect of Li and B on the oxidation kinetics of Zircaloy-4. Bataillon, C.; Feron, D.; Marchetti, L.; et al. E-DEN
Monograph Corrosion Commissariat a` lEnergie Atomique, 2008. From DEN Monographs Corrosion and
Alteration of Nuclear materials, ISBN 978-2-281-11369-3 (2010), editions du Moniteur, CEA.
increased significantly above the coolants nominal

level, the increased corrosion caused by CRUD
deposits is thought to be due to the role of Li, in
combination with the increased metal/oxide interface temperature.37
Fluorine is produced in the coolant water by neutron capture in 18O to give 19F. Laboratory experiments have shown that the corrosion of Zircaloy-4
begins to accelerate between 19 and 190 ppm fluorine
at 360 C, which is well above the coolant specification in most reactors (0.15 ppm).
16
14
12
59
10
8
6
4
5.03.3.4
A wealth of information exists on the in-reactor

behavior of Zircaloy from worldwide fuel monitoring
programs as well as from experimental research programs, from which information about the radiation
effects on zirconium alloy corrosion can be deduced.
These effects can be of multiple origin and include
radiolysis of the coolant, changes in the metallurgical
condition, displacement damage, or phase transformations. As discussed by Cox,7 no in-reactor effects
are evident for an oxide layer thickness below
56 mm. Above that thickness, a departure from data
with radiation field and for in-reactor conditions
suggests an irradiation-induced acceleration of the
oxide breakdown. Bataillon et al.25 suggest a factor
of 2 for the oxidation rate of Zircaloy-4 between
in-reactor and autoclave experiments during the
first two reactor cycles. This increases to about 4
during cycles 5 and 6. This effect is shown in
Figure 17, in which the thickness of the oxide layer
on Zircaloy-4 as a function of exposure time is compared for three cases: (a) autoclaves without thermal
gradient, (b) corrosion loop with thermal gradient
generated by an electrical heating inserted in the
cladding tube, and (c) in-reactor, with the effects of
thermal gradient and irradiation.38
0
0
50
100
150
200
Time (days)
Figure 15 The evolution of the microstructure of the oxide
layer on Zircaloy-4 after oxidation in an autoclave with
70 ppm Li, without boron (360 C). The blue line shows the
total oxide thickness, whereas the red line shows the
thickness of the protective inner layer. Reproduced from
Bataillon, C.; Feron, D.; Marchetti, L.; et al. M. E-DEN
Monograph Corrosion Commissariat a` lEnergie
Atomique; 2008.
Loose deposit
Adherent deposit
Oxidized cladding
Figure 16 Schematic representation of the CRUD
morphology.
oxidation of both BWR and PWR cladding. CRUD

can have a wide variety of morphologies, from dense
to porous, thus having very different thermal conductivity. The CRUD structure can generally be
described an inner deposit that is tightly adherent
to the oxide layer and an outer deposit that has a
loose structure (Figure 16). However, the thermal
conductivity of CRUD is generally better than that
of zirconium oxide and therefore its added effect on
deterioration of the heat flux through the corrosion
layer rarely results in excessive cladding temperatures. Because the lithium concentration in the
CRUD, where it is deposited as lithium borate, is
Irradiation Effects
5.03.3.4.1 Radiolysis
The ionizing radiation will interact with water molecules producing a variety of reaction products:
hv
H2 O ! e ; H; OH; H2 O2 ; H2
Figure 18(a) shows the results of a typical computer

simulation of the speciation as a function of time.15
As one can see, numerous oxidizing species such as
O2, O., HO2, and H2O2 that could accelerate the
corrosion are formed. For this reason, the coolant
water in PWRs is hydrogenated. This effect is
60
shown in Figure 18(b), which indicates that the

presence of hydrogen significantly reduces the
steady-state concentration of the oxidizing species.
5.03.3.4.2 Irradiation effects in the oxide layer
Because the growth of the oxide layer on zirconium

alloys is strongly related to the diffusion of oxygen ions
through the layer, as discussed above, the displacement
5.03.3.4.3 Changes in the metallurgical

state of the metal
PWR, 346 C
40
Corrosion loop, 346 C

Autoclave, 354 C
0
0
300
600
Time (days)
Figure 17 The thickness of the oxide layer on Zircaloy-4

as a function of exposure time for three cases: (a)
autoclaves without thermal gradient, (b) corrosion loop with
thermal gradient generated by an electrical heating inserted
in the cladding tube, and (c) in-reactor, with the effects of
thermal gradient and irradiation. Reproduced from Gilbon,
D.; Bonin, B. E_DEN Monograph Les Combustibles
Nucleaires, Commissariat a` lEnergie Atomique; 2008.
Fast neutron irradiation can change the relative concentration of alloying elements between precipitate
and matrix by a variety of mechanisms including
ballistic mixing by a primarily knock-on effect.41 Fe
and Cr can be dissolved from the intermetallic Zr(Cr,
Fe)2 particles into the surrounding a-Zr matrix.42,43
The dissolution is linked to precipitate amorphization and the modified equilibrium between the
amorphous precipitate and the matrix.44 As a result
of the precipitate dissolution, the smallest particles
dissolve completely, and the largest are significantly
reduced in size. The ultimate location of the Fe
is determined by thermal diffusion effects in the
vicinity of the intermetallic particles where c-type
dislocations may have formed. Postirradiation45
corrosion of such specimens shows progressive
-5
-3
-6
-4
H2
Dissolved H2 0 ppb
Dissolved O2 0 ppb
-8
O2
O-2
-9
OH
-10
HO2
-11
-12
-13
HO-2
H2O2
(a)
-6
-7
O2
Dissolved O2 200 ppb
Dissolved H2 500 ppb
H2O2
-8
O-2
-9
HO2
-10
OH
-11
HO-2
-12
-14
-15
-4
H2
-5
H2O2
Conc. (mol l1) in log scale
-7
Conc. (mol l1) in log scale
of ions from their lattice sites by fast neutron damage

could lead to enhanced point defect concentrations,
enhanced diffusion, and hence enhanced corrosion
in-reactors.39,40 However, experimental studies have
shown no clear evidence for this.
Formation of electronhole pairs and Compton electrons by b and g radiation could also theoretically lead to a significant increase in the
electron conduction (electrical conductivity). The
experimental evidence for this is, however, not
conclusive.
-3
-2
-1
Time (s) in log scale
-13
-4
(b)
-3
-2
-1
Time (s) in log scale
Figure 18 Typical result of a computer simulation or radiolysis of water at 250 C for a dose rate of 4.5 102 Gy h1; (a) pure
water; (b) with dissolved O2 and H2. Reproduced from Waterside Corrosion of Zirconium Alloys in Nuclear Power Plants;
IAEA-TECDOC-996; International Atomic Energy Agency, Vienna, Austria, 1998.
degradation of the posttransition corrosion rates

with increasing dose, although other studies have
shown nodular corrosion improvement of irradiated
material.46 Cox7 concluded that this effect is now
seen as a primary contributor to enhanced corrosion
in PWRs, since alloys that do not contain Fe or in
which the Fe is incorporated in radiation-resistant
particles, show lower in-reactor corrosion kinetics.
5.03.4 Nodular Oxidation

In BWR conditions (Table 1), nonuniform, so-called
nodular oxidation can also take place (Figure 19).
The mechanism for nodular oxidation is yet to be
fully understood, as it has proved to be challenging to
study in laboratory experiments. Oxidation studies in
500 C steam demonstrated the dependence of nodular corrosion on second phase precipitate size and
distribution,47 typical for various cladding batches
and their metallurgical structure. However, other
factors also affect nodule formation, as batches of
the same cladding can behave quite differently.
Such differences can be related to in-reactor phenomena such as galvanic effects, impurities, radiolytic species, and local power and flux.7,15 The
question of whether nodular corrosion nucleates at
intermetallic particles, between intermetallic particles,
or as a collective property of a group of grains, is yet to
be resolved.6 As discussed by the IAEA Expert group,6
the experimental evidence points toward the fact that
nodules form away from intermetallic precipitates in
61
the alloys. In his review, Cox7 concluded that the

redistribution of Fe from secondary phase particles
diminishes nodular corrosion, but enhances uniform
corrosion.
5.03.5 Hydrogen Embrittlement

Absorption of hydrogen is a major contributor
to degradation of zirconium alloys during service
in nuclear systems.22 This degradation is primarily
attributed to the formation of zirconium hydrides, a
brittle phase that can embrittle cladding, and reduce
its fracture toughness, thus enhancing the susceptibility to cracking.48 Recent studies have also shown
that the addition of hydrogen can increase the creep
rates in Zr2.5Nb49 and possibly irradiation growth.
The hydrogen can come from a variety of sources,
some of them detailed in a 1998 report from an IAEA
Expert group14:
(i)
Hydrogen left over in the Zircaloy tubing after

fabrication or from residual moisture due to
surface preparation (the initial concentrations
of hydrogen in the cladding, postfabrication
but prereactor service, are on the order of
10 wt ppm).
(ii) Desorption of water from incompletely dried
up fuel.
(iii) Hydrogen produced by (n,p) reactions in the
cladding.
(iv) Hydrogen ingress from the coolant water into
the cladding during reactor exposure.
Uniform oxide
Nodular oxide
Zircaloy
20 m
Figure 19 Typical appearance of nodular corrosion in visual inspection and metallographic examination.
Figures courtesy of Ron Adamson.
62
(v)
Absorption during the normal corrosion processes that occur in high-temperature aqueous
solutions.
(vi) Direct reaction of a clean (no species other
than zirconium) surface with gaseous hydrogen. This hydrogen nominally could come
from three sources: protons released by oxidation that form hydrogen gas, hydrogen produced by radiolysis of the water exposed to
a high-energy neutron flux, and hydrogen specifically added to the cooling water to control
stress corrosion cracking (see Chapter 5.02,
Water Chemistry Control in LWRs and
Chapter 5.08, Irradiation Assisted Stress
Corrosion Cracking).
(vii) Diffusion of hydrogen through a metallic bond
with a dissimilar metal in which hydrogen has a
higher activity.
(viii) Cathodic polarization of zirconium in an electrolyte (typical for low-temperature reactors).
By far, the largest source comes from the normal
corrosion processes (v).
5.03.5.1 Hydrogen Production During
Aqueous Corrosion of Zirconium-Base
Materials
The reaction of Zr with water to form zirconium
oxide produces atomic hydrogen (a proton)
Zr 2H2 O ! ZrO2 2H2
Ia
Zr 2H2 O ! ZrO2 4H
Ib
The proton released in the oxidation of Zr either

combines with another proton to form gaseous hydrogen (eqn I(a)) or diffuses into the zirconium (eqn I(b)),
where it can form zirconium hydrides. The majority of
the protons formed during oxidation combine to form
hydrogen gas but a fraction enters the metal. The term
hydrogen pickup fraction fH is used to relate the
hydrogen absorbed to the hydrogen liberated during
the corrosion reaction.
fH
H absorbed in cladding
H generated in corrosion
Although the total amount of hydrogen absorbed is

proportional to oxide thickness, the proportionality
constant, the hydrogen pickup fraction, changes from
alloy to alloy such that alloy design can significantly
improve cladding performance. The pickup fraction
also changes with corrosion temperature and with

corrosion time, but the mechanisms by which this
occurs are not yet resolved.
5.03.5.2
Hydrogen Absorption
A detailed overview of the process of the absorption of

hydrogen into zirconium-base materials is provided
in the IAEA Technical Document Waterside Corrosion of Zirconium Alloys in Nuclear Power Plants.15
The oxide itself generally presents an effective barrier
to the absorption of hydrogen such that the structure
of the oxide and the electron transport mechanism
can be linked to hydrogen uptake. There is some
evidence that the nickel content in Zircaloy-2
increases the absorption of hydrogen (Figure 20),
either by supporting direct dissociation of water or
by mitigating recombination of hydrogen and oxygen.5052 This was one reason why the nickel was
removed in the formulation of Zircaloy-4. The Zr
(Fe,Ni)2 intermetallic particles that exist in Zircaloy
may provide a significant pathway for hydrogen
uptake. Specifically, the electron current flows primarily at sites where intermetallic particles partially,
or completely, short-circuit the oxide.53 Additionally,
flaws have been found to exist in the oxide that are not
associated with existing intermetallic particles but are
at pits that may have resulted from intermetallic dissolution during pickling. These flaws allow the
cathodic process to proceed. These locations are evidenced by cracks or small holes visible in the oxide.54
For some alloys, the amount of absorbed hydrogen varies as a function of oxide thickness. For
example, Cox55 has shown that for Zircaloy-2, an
initially high hydrogen absorption rate decreases as
the oxide thickness increases, but then picks up
again after the oxide reaches the transition region.
Other researchers have shown an increase in
H uptake just before the oxide transition.56 The additional porosity in the oxide, after transition, makes
hydrogen pickup more likely. For Zircaloy-4, the
pickup appears to be constant with the growth of
the oxide. Oxygen additions to the water normally
reduce the hydrogen uptake and hydrogen additions
increase it.57
5.03.5.3
Hydride Formation
Hydrogen absorbed into the zirconium alloy cladding

at levels more than the terminal solid solubility
can embrittle the cladding through the formation
of hydrides. The stress concentration at the ends of
. Zircaloy-2, as rolled
. Zircaloy-2, -treated
. Zircaloy-4, as rolled
. Zircaloy-4, -treated
Hydrogen pickup (PPM)
60
63
~100-mil Thick specimens

Zircaloy-2, -treated
50
40
Zircaloy-2 as-rolled
30
Zircaloy-4,
as-rolled or -treated
20
10
0
0
500
1000
1500
2000
2500
3000
Hydrogen overpressure (PSI)

Figure 20 Hydrogen pickup in Zircaloy-2 and Zircaloy-4 as a function of hydrogen overpressure after 14 days in 343 C
water. Reproduced from Hillner, E. Hydrogen absorption in Zircaloy during aqueous corrosion, Effect of Environment,
U.S Rep. WAPD-TM-411, Bettis Atomic Power Lab., W Mifflin, PA, 1964.
larger plate-type hydrides, as well as the localized

deformation in the ligaments between the hydrides,
leads to material weakness. As confirmed by Kerr
et al.,58 performing recent in situ fracture work at the
Advanced Photon Source at Argonne National Laboratory, in materials with large pregrown hydrides
(100 mm), the residual stress field of the zirconium
matrix governs the residual stress state of the hydride
and load is shed to the notch tip hydride phase on
increasing applied load.
The hydrides, if formed, can be circumferential
or radial (see Figure 21). The embrittlement is
influenced by the orientation of hydrides relative to
the stress. Hydrides that are oriented normal to the
tensile load enhance embrittlement by providing
an easy path for the growth of cracks through the
hydrides.59 Radial hydrides are of greater concern,
as they are oriented perpendicular to the hoop stress
that arises during operation of the cladding tube.
As one example, the stress ratio (hoop stress/axial
stress sy/sz) from gas pressurization anticipated
during a loss of coolant accident has an approximate
value of two and most of the deformation is in the
hoop direction.60
The hydrides observed in fuel cladding exposed to
reactor environment are most often fcc delta hydrides
ZrHx (where x 1.6). For a fixed amount of hydrogen
uptake, the density and size of the formed hydrides is
a strong function of the material microstructure. Initial hydride orientation has been shown to be a function of the texture of the Zircaloy-4 that develops
during fabrication.61,62 As an example, as reported by
Singh and coworkers,63 Zr2.5Nb that has been

quenched and aged forms a higher density of smaller
hydrides than Zr2.5Nb that was cold-rolled and
stress relieved, and the difference was attributed to
the underlying grain structure, which acted as the
nucleation host for the formation of hydrides. If sufficient stress is applied during the formation of the
hydrides, the hydride platelets will form perpendicular to the applied stress.
A specific example of deleterious hydride orientation is from DHC, in which circumferentially oriented hydrides dissolve and reprecipitate at the crack
tip, parallel to the crack orientation. Understanding
DHC is of specific concern for CANDU pressure
tubes and ensuring the long-term stability of spent
fuel during storage and is discussed later in this
section.6469
5.03.5.4
Hydride Formation Rates
At reactor operating temperatures, the stable phases

in the ZrH phase diagram are (i) hcp-Zr with dissolved hydrogen and the delta hydride ZrHx, where x
varies between 1.45 and 1.2 at high temperature.
The terminal solid solubility of H in hcp-Zr is
H
CaZr
A expEH =T
5
where A is a constant equal to 1.2 105 wt ppm (or

0.8 mole H per cm3), and the activation energy for
solid solution is 4300 K (the temperature validity for
this equation is up to 865 C, the limit of the alpha
phase region).
64
250 mm
(a)
100 m
Figure 22 Hydride-rim formation in cladding on

high-burnup (67 GWd/t) PWR fuel. (cladding from the
H. B. Robinson plant, courtesy R. Daum ANL).
hydride precipitation), the hydrogen concentration in

the cladding is essentially homogeneous.
5.03.5.5
(b)
100 m
Figure 21 (a) Circumferential and (b) radial hydrides.

Figures courtesy of Ron Adamson.
Hydrogen is very mobile in a-Zr and once it is

absorbed in the cladding, it migrates easily in
response to concentration, temperature, and stress
gradients. The diffusion coefficient of H in Zr is
H
D0H expEmH =kB T
DZr
EmH
3
6
0:47eV and the preexponential factor

where
is 7 10 cm2 s1. This results in a high diffusion
coefficient at the reactor operating temperatures (at
355 C (average cladding temperature), the diffusion
coefficient is 1.1 106 cm2 s1), so that hydrogen
responds quickly to changed conditions to establish
a new steady state. The characteristic time to attain
significant hydrogen ingress by diffusion through the
thickness of the cladding at this temperature is about
12 min, which is much smaller than normal reactor
exposure times. This means that at any given time,
the hydrogen distribution in the cladding can be
considered to be in quasi-steady state, that is, temporal variations need not be considered. Because of
this, when the hydrogen is in solid solution (before
Formation of Hydride Rim
As, from eqn [5], the hydrogen solubility in Zircaloy

decreases with decreasing temperature, the outer
cladding arrives at the solubility limit before the
inner cladding does. For an outer cladding temperature of 325 C and an inner cladding temperature of
385 C, the hydrogen solubilities are respectively 90
and 170 wt ppm. This causes hydrides to form preferentially at the outer cladding diameter.
Metallographic examinations performed on cladding hydrided below the solubility limit show a more
or less homogeneous hydride distribution through
the thickness of the cladding. These hydrides presumably have precipitated out during the cooling
from operation temperature, so that at reactor temperature, the hydrogen is in solution.
As the overall hydrogen content increases as a
result of increased corrosion, eventually the outer
layer of the cladding reaches saturation and a hydride
rim starts to form, whose thickness will increase
with increasing reactor exposure. Figure 22 shows a
metallograph of high-burnup cladding showing enhanced hydride formation near the outer diameter of
the cladding.
The hydride distribution response to stress and
temperature gradients is at the root of several degradation mechanisms, such as DHC, secondary hydriding, and the degradation of cladding ductility from
oxide spalling.
5.03.6 Delayed Hydride Cracking

A detailed summary of the DHC phenomena is available in the report of an IAEA (International Atomic
Energy Agency) Coordinated Research Project.70 An
overview is presented here.
The classic theory of DHC comes from the work
of Dutton and Puls.71 The basis of the Dutton and
Puls theory is sketched in Figure 23. The basis of the
theory is that the crack tip hydride grows as hydrogen
migrates from hydrides in the bulk of the material to
the crack tip. The driving force for the diffusion of
the hydrogen is the difference in the chemical potential of hydrogen between the bulk material and the
crack tip hydride in response to hydrostatic stress.70,72
Dutton and Puls theory follows the following
logic. The partial molar volume of hydrogen in the
hydrides is positive. An increasing hydrostatic tensile
stress reduces the chemical potential of hydrogen in
the hydride relative to the bulk. This chemical potential difference causes hydrogen in solution to diffuse
to the crack tip where it precipitates. In this model,
the hydrides in the bulk dissolve to maintain the
hydrogen concentration at the hydride interface at
the solubility limit for the temperature at which the
cracking is occurring. As the precipitate grows at the
crack tip, it will eventually reach a critical size that is
dependent on the stress intensity factor at the crack

tip and the crack will then progress an additional
distance that is related to the hydride size. The relationship between crack velocity and stress intensity
factor for this type of cracking is shown in Figure 24.
The stable crack growth velocity is a function of temperature since that temperature affects both hydrogen
solubility and hydrogen transport to the crack tip.
A detailed update of the Dutton-Puls theory,
along with a response to challenges to the theory
by the group of Kim73 was recently released.74
The review by McRae supports the validity of the
Dutton and Puls models rather than the alternatives
promoted by Kim.
Recently, Colas et al.75 used high-energy synchrotron X-rays at the advanced photon source, to perform in situ characterization of hydride dissolution,
reprecipitation, and reorientation during thermal
cycles under load. Their results, from samples initially charged with hydrogen at concentrations up to
600 ppm, indicate that the reorientation occurred
above a threshold stress of 7580 MPa. In another
Unstable
crack
growth
Hydride
Plastic
enclave
dg
Hydride
r=L
r = li
r=l
Log crack velocity
Free
surface
65
Vc
Stable crack
growth
KIC
No crack
growth
rg
KH
Stress intensity factor (KI)
s
Figure 23 Crack and diffusion geometry assumed in
the DHC model of Puls. Reproduced from Puls, M. P.
J. Nucl. Mater. 2009, 393, 350367.
Figure 24 Schematic diagram of crack propagation by

DHC in hydrided Zircaloy. Reproduced from Delayed
hydride cracking in zirconium alloys in pressure tube
nuclear reactors. IAEA-TECDOC-1410; Nuclear Power
Technology Development Section, International Atomic
Energy Agency, Vienna, Austria, 2004.
66
recent study related to hydride reorientation, Daum

et al.76 found that the threshold stress is approximately
7580 MPa for both nonirradiated and high-burnup
stress-relieved Zry-4 fuel cladding cooled from
400 C. Within the uncertainty of the experiment,
the irradiation was not critical to setting the threshold
stress. Under ring compression at both room temperature and 150 C, Daum found that radial-hydride
precipitation embrittles Zry-4. Interestingly, for
nonirradiated Zircaloy-4, samples with lower hydrogen concentration (300 vs. 600 ppm) appeared to be
more susceptible to radial-hydride related embrittlement. In a separate work, Daum76 also showed that
failure is sensitive to hydride-rim thickness. Zircaloy-4
cladding tubes with a hydride-rim thickness >100 mm
(700 wt ppm total hydrogen) exhibited brittle behavior, while those with a thickness <90 mm (600 wt
ppm) remained ductile.
Many challenges remain to be addressed in understanding the corrosion and hydriding of Zr alloys in
nuclear environments. Although mechanistic understanding has been developed over the past decades,
still much needs to be understood, in particular, on
the role of alloy design on corrosion rate, hydrogen
pickup, and oxide transition. In addition, the behavior
of cladding under the more challenging conditions of
severe fuel duty associated with longer exposures,
higher temperatures, aggressive chemistry, and incidence of boiling needs to be studied.
References
1.
2.
3.
5.03.7 Summary and Outlook

The extensive research on the corrosion of zirconium alloys has resulted in an enormous flow of
information during several decades. On the basis
of this, a basic understanding of the processes leading to oxidation and hydriding of zirconium alloys
now exists.
1. Zirconium alloy fuel cladding undergoes corrosion when subjected to the reactor environment.
The corrosion is related to the oxidation of the
metal by coolant water and is associated with
hydrogen uptake into the cladding. The latter
phenomenon is the main contributor to in-reactor
degradation of cladding performance.
2. Uniform corrosion is alloy dependent and environment dependent. The higher fuel duty now
imposed on nuclear fuel can lead to accelerated
corrosion, which can limit fuel lifetime.
3. Corrosion is accelerated under irradiation relative
to out-of-pile results. The corrosion rates can
increase after a given exposure.
4. The hydrogen pickup fraction can vary from alloy
to alloy and for different environments and corrosion times. The hydrogen pickup mechanisms and
the influence of the alloy on the process are still
under study.
5. Modern alloys such as M5 and ZIRLO provide
much improved corrosion performance and show
the potential for significant benefits from careful
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in the Nuclear Industry, ASTM STP-1354, 2000;
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5.04 Corrosion and Stress Corrosion Cracking

of Ni-Base Alloys
S. Fyfitch
AREVA NP Inc., Lynchburg, VA, USA
5.04.1
Introduction
70
5.04.2
5.04.2.1
5.04.2.2
5.04.2.3
5.04.3
5.04.3.1
5.04.3.2
5.04.3.3
5.04.3.4
5.04.4
5.04.4.1
5.04.4.1.1
5.04.4.1.2
5.04.4.1.3
5.04.4.1.4
5.04.4.2
5.04.4.3
5.04.4.4
5.04.4.4.1
5.04.4.4.2
5.04.4.4.3
5.04.4.4.4
5.04.4.4.5
5.04.4.5
5.04.4.5.1
5.04.4.5.2
5.04.4.5.3
5.04.4.5.4
5.04.4.5.5
5.04.4.6
5.04.4.7
5.04.5
References
Ni-Base Alloy Use in PWRS/BWRS

Wrought NiCrFe Alloys
Age-Hardenable Ni-Base Alloys
Ni-Base Welding Alloys
General Corrosion
Water Chemistry
Flow Rates
Crevices
Mitigation
Stress Corrosion Cracking
Environmental Conditions
Temperature
Water chemistry
Sulfur intrusions
Electrochemical potential
Flow Rates
Crevices
Material Susceptibility Factors
Heat treatment
Microstructure
Grain size
Chemical composition
Product form
Stress
Operating stress
Residual stress
Surface effects
Weld geometry
Stress relief annealing
Irradiation
Mitigation
Outlook
70
70
72
73
73
75
75
75
75
75
77
77
77
80
81
81
82
82
82
83
84
84
85
85
86
86
87
87
87
88
90
90
90
Abbreviations
ASME
ASTM
B&PV
BWR
CEDM
CMTRs
American Society of Mechanical Engineers

American Society for Testing and Materials
Boiler and Pressure Vessel
Boiling water reactors
Control element drive mechanism
Certified material test reports
CRDM
ECP
EPRI
GMAW
GTAW
HAZ
IASCC
Control rod drive mechanism

Electrochemical potential
Electric Power Research Institute
Gas-metal-arc welding
Gas-tungsten-arc welding
Heat-affected zone
Irradiation-assisted stress corrosion
cracking
69
70
Corrosion and Stress Corrosion Cracking of Ni-Base Alloys
IGSCC
INCO
LM
LWR
MSE
NRC
PWR
PWSCC
RCS
RUBs
SAW
SCC
SEM
SMAW
TT
Intergranular stress corrosion cracking

International Nickel Company
Light microscopy
Light water reactor
Mechanical surface enhancement
Nuclear Regulatory Commission
Pressurized water reactors
Primary water stress corrosion cracking
Reactor coolant system
Reverse U-bends
Submerged-arc welding
Scanning electron microscope
Shielded-metal-arc welding
Thermal treatment
5.04.1 Introduction
Nickelchromiumiron alloys (i.e., nickel-base alloys)
are widely used in the power industry in both fossil
(e.g., coal and gas) power stations and light water
reactor (LWR) nuclear power stations (i.e., pressurized
and boiling water reactors (PWRs and BWRs)). As a
result, the service behavior of these alloys has been
extensively studied,1 especially their susceptibility to
corrosion and stress-induced corrosion phenomena.
The power industry is concerned with the occurrence
of such failure phenomena because of their effect on
the safety and availability of equipment.
Corrosion and, in particular, stress corrosion failures
are not new. The power industry is well acquainted
with stress corrosion cracking (SCC) of stainless steel
in BWR piping and nickel-base alloys in PWR steam
Table 1
generators and its effect on equipment availability.2

SCC of these austenitic alloys has been known for
more than 50 years.
5.04.2 Ni-Base Alloy Use in PWRS/

BWRS
5.04.2.1
Wrought NiCrFe Alloys
The wrought nickel-base alloys that are typically used

for nuclear applications are Alloy 600 and, more
recently, Alloy 690, which contain approximately
twice the chromium content. These materials are
used primarily for their inherent resistance to general
corrosion (i.e., oxidation resistance), strength at elevated temperatures, and a coefficient of thermal expansion very close to carbon and low-alloy steels. The
typical chemical composition and mechanical properties of these alloys are summarized in Tables 1 and 2,
respectively.
Both Alloy 600 and Alloy 690 are non-agehardenable, austenitic solid-solution strengthened
materials. No precipitation reaction is possible with
either alloy to increase strength; however, strength
can be increased by cold-working the material. They
are normally used in the annealed condition; however, a low-temperature heat treatment, or thermal
treatment (TT), is also generally used with these
alloys, which tends to improve the resistance to
SCC in primary water chemistry conditions, which
is typically known as primary water SCC (PWSCC)
(see later sections of this chapter). This improvement
is clearly shown to be more pronounced, at least for
Alloy 600 material, in crack initiation testing.3
Chemical composition of wrought nickel-base alloys used in nuclear applications
Alloying element
Alloy 690
Alloy 600
Alloy X-750
Alloy 718
Alloy 800
Ni Co
C
Mn
Fe
S
Si
Mo
Cu
Cr
Ti
Al
P
Nb Ta
Others
58.0 min.
0.04 max.
0.5 max.
7.011.0
0.015 max.
0.50 max.
0.50 max.
28.031.0
72.0 min.
0.15 max.
1.00 max.
6.0010.00
0.015 max.
0.50 max.
0.50 max.
14.017.0
70.0 min.
0.08 max.
1.00 max.
5.09.0
0.01 max.
0.50 max.
0.50 max.
14.017.0
2.25 2.75
0.401.0
0.701.20
50.055.0
0.08 max.
0.36 max.
Bal.
0.015 max.
0.35 max.
2.83.3
0.30 max.
17.021.0
0.651.15
0.200.80
0.015 max.
4.755.50
B 0.006 max.
3235
0.03 max.
0.41.0
Bal.
0.300.70
<0.75
20.023.0
<0.60
0.150.45
These alloys are widely used in LWRs. In BWRs,

applications include such locations as reactor vessel
nozzle safe ends, core support structures, and shroud
bolts. The PWR applications are typically within the
reactor coolant system (RCS) such as steam generator
tubing, penetrations and nozzles, control rod drive
mechanism (CRDM) and control element drive mechanism (CEDM) nozzles in reactor vessel heads, and
instrument nozzles in pressurizers and RCS piping, but
may also be found in selected non-Class 1 components
such as the Core Flood Tanks. In addition, Alloy 600
has also been used in a number of fastener applications.
Table 2
71
Figures 14 show typical applications of Alloy 600

material as used in the reactor coolant systems of the
four major BWR and PWR vendor designs.
Alloy 600 and 690 materials are available as plate,
barstock, tube/pipe, or forged material. The majority
of these materials were procured for the American
Society for Testing and Materials (ASTM)4 or American Society of Mechanical Engineers (ASME) Boiler
and Pressure Vessel (B&PV) Code5 specifications
(e.g., ASTM B 166 and B 167 or ASME SB-166 and
SB-167). Table 3 lists the various industry specifications that are used to procure these materials.
Typical room temperature mechanical properties of wrought nickel-base alloys used in nuclear applications
Mechanical property
Alloy 600
Alloy 690
Alloy X-750a
Alloy 718b
Alloy 800c
Yield strength, min. MPa (ksi)

Ultimate tensile strength, min. MPa (ksi)
Elongation, min. (%)
242 (35)
552 (80)
30
242 (35)
586 (85)
30
655 (95)
1103 (160)
20
1241 (180)
1034 (150)
10
334 (48)
572 (83)
30
Alloy X-750 HTH: Solution annealing at 1093 C (2000 F) and age-hardening at 704718 C (13001324 F).
Alloy 718: Solution annealing at 11001400 C (18322000 F) and age-hardening at 720 and 620 C (1328 and 1148 F).
c
Alloy 800: Solution annealing at 10381066 C (19001950 F) and age-hardening at 760 C (1400 F) for 10 h, furnace cool to 649 C
(1200 F), hold for 20 h.
b
Feedwater recirculation
inlet/outlet welds
RPV attachments/
brackets
Shroud support
structure
Courtesy GE nuclear
CRD in-core housing

instrumentation penetrations
Figure 1 Typical applications of Alloy 600 materials in the reactor coolant systems of a General Electric Design
boiling water reactor. RPV, Reactor Pressure Vessel.
72
Instrument and
vent penetrations
(both hot legs)
Decay
heat
line
weld
CRDM nozzles
Pressure
relief nozzle
safe ends/
welds (both
tanks)
PZR vent, spray,

and relief line
welds
PZR steam and
water instrument
penetrations
CRDM
motor
housings
Leak-off
monitor
lines
PZR heater
sleeves
and
diaphragm
plates
Core flood
tank
instrument
penetration
(both tanks)
PZR surge
nozzle weld
HPI/MU
nozzle
welds
(all cold legs)
Hot legsurge
nozzle
weld
Core flood
line welds
(both lines)
Core
guide
lugs
(ID)
Piping-RC pump
suction and
discharge welds
(all pumps)
RV bottom
head
instrument
penetrations
Primary drain
nozzles (both
SGs)
Instrument nozzles and

drain penetrations (all
cold legs)
SG nozzle dam
rings (both SGs)
Figure 2 Typical applications of Alloy 600 materials in the reactor coolant systems of a Babcock & Wilcox Design
pressurized water reactor. RV, Reactor Vessel; RC, Reactor Coolant; SG, Steam Generator; PZR, Pressurizer.
5.04.2.2
Age-Hardenable Ni-Base Alloys
Alloy X-750, a high-strength precipitation-hardening

alloy originally developed for gas turbines and the
aerospace industry, is widely used in internal applications for both BWR and PWR designs, such as fuel
assembly hold-down springs, control rod guide tube
support pins, jet pump beams, and reactor internals
structural bolting. This alloy is very similar in composition to Alloy 600, but contains additions of titanium and aluminum, which combine with nickel to
form the g0 precipitates, Ni3Al and Ni3 (Al, Ti), for
strengthening.6
Alloy 718 is another age-hardenable austenitic
nickel-base alloy, originally developed for the aerospace industry, that has seen much use in the nuclear
industry as a structural material due to its high strength
and corrosion resistance.7 A significant increase in
strength can be achieved by two precipitation reactions from solid solution involving g0 and g00 (Ni3Nb)
secondary phases within the austenitic matrix.8 The

addition of niobium sets this alloy apart from other
high-strength nickel-base alloys (e.g., Alloy X-750)
that are strengthened by g0 alone. Both the g0 and g00
precipitates are quite small and can only be resolved
with an SEM (scanning electron microscope) unless
gross over-aging has taken place. The microstructures
of the solution-annealed and age-hardened conditions
are indistinguishable with light microscopy (LM).
Alloy 718 has also been used extensively in PWR
primary coolant systems, predominantly for fuel assembly hardware.9 Alloy 718 is utilized for fuel assembly
hold-down springs, bolts, and spacer grids. It has been
shown to possess superior SCC initiation resistance
compared to Alloy X-750. Although Alloy 718 has
experienced some isolated failures in PWRs due to
fatigue/fretting cracking, it is considered highly resistant to intergranular SCC (IGSCC) initiation and
other forms of corrosion.
73
PZR
instrument
nozzles
PZR and RC pipe-surge
line connections
CEDM motor
housing
Spray nozzlepipe weld

Safety and
relief valve
nozzle-pipe
welds and/or
flanges
CEDM/ICI nozzles to
RPV head welds
RPV top head
vent nozzle
PZR heater
sleeves
RPV head
leak monitor
tubes (2)
Surge
nozzle-pipe
welds
Charging inlet
nozzles (2 cold
legs)
Instrument nozzles
(all hot and cold legs)
Safety injection and
SDC inlet nozzle
(all hot and cold legs)
Let-down and drain
nozzles (all hot and
cold legs)
Shutdown
cooling
inlet
nozzle
(all cold
legs)
Spray
nozzles
(2 cold legs)
Primary nozzle closure

rings and welds
(both SGs)
Bottom channel head
drain tube and welds
(both SGs)
Guide lugs
flow skirt
ICI nozzles-ICI guide
tubes (system 80 plants)
RCP suction
and discharge
(all cold legs)
Shutdown cooling outlet

nozzle (1 hot leg)
Figure 3 Typical applications of Alloy 600 materials in the reactor coolant systems of a Combustion Engineering
Design pressurized water reactor. RPV, Reactor Pressure Vessel; RC, Reactor Coolant; RCP, Reactor Coolant Pump;
SDC, Shutdown Cooling; PZR, Pressurizer.
In addition, a modified Alloy 800 material, with

carbide-forming elements added to limit the solid
solution carbon content, has been successfully used for
many years in Germany for steam generator tubing.
The typical chemical compositions, mechanical
properties, and industry procurement specifications
are provided in Tables 13.
5.04.2.3
Ni-Base Welding Alloys
Welding of nickelchromiumiron alloys is typically

performed using arc-welding processes such as gastungsten-arc welding (GTAW), shielded-metal-arc
welding (SMAW), and gas-metal-arc welding
(GMAW).7 Submerged-arc welding (SAW) may also
be used provided the welding flux is carefully selected.
Alloy 82, 182, and 132 are typical filler metals used to
join Alloy 600 components to carbon or low-alloy steel
vessels and other component items. These weld alloys
are also used as cladding in selected components
within the reactor coolant system. In addition, Alloy
52 and 152 (and newly developed variants such as
Alloy 52M and 152M) are filler metals that have
recently become the preferred materials used to join

Alloy 690 component items to carbon or low-alloy
steel vessels in the reactor coolant system.
Occasionally, there is a need for welded Alloy
X-750 items and the filler metals Alloy 82 or 69
(ERNiCrFe-8) were used during original fabrication.
The Alloy 69 material is no longer produced and
filler metal Alloy 718 is the currently recommended
material for welding.
The typical chemical compositions and industry
procurement specifications of these alloys are summarized in Tables 3 and 4.
5.04.3 General Corrosion

One of the main reasons that nickel-base alloys were
chosen for LWR applications is that they have the
ability to withstand a wide variety of severe operating
conditions involving corrosive environments, high
temperatures, high stresses, and combinations of these
factors. General corrosion can be defined as uniform
deterioration of a metal surface by chemical or
74
Spray nozzlepipe weld
Safety and relief

nozzle-pipe
welds
Head
vent pipe
CRDM
motor
housings
CRDM
nozzles
RPV
head
leak
monitor
tube
Surge nozzlepipe welds
Thermowells (all
hot and cold legs)
RV nozzle
pipe weld
(all hot and
cold legs)
SG nozzlepipe weld
(all hot and
cold legs)
Core support
block
Bottom-mounted
instrument nozzles
Bottom channel
head drain tube
and welds (all SGs)
Primary nozzle
closure rings and
welds (all SGs)
Figure 4 Typical applications of Alloy 600 materials in the reactor coolant systems of a Westinghouse Design pressurized
water reactor. RPV, Reactor Pressure Vessel; RV, Reactor Vessel; SG, Steam Generator.
Table 3
Typical nickel-base alloy specifications used in nuclear applications
ASME B&PV Code
ASTM Standard
Material
Product form
SB-163
SB-166
SB-167
SB-168
SB-637
SB-670
SFA 5.11
SFA 5.14
B 163
B 166
B 167
B 168
B 637
B 670
Alloys 600/690/800
Alloys 600/690
Alloys 600/690
Alloys 600/690
Alloys 718/X-750
Alloy 718
Alloys 182/152
Alloys 82/52
Seamless tubing
Rod and bar
Seamless pipe and tube
Plate, sheet, and strip
Rod, bar, and forgings
Plate, sheet, and strip
Covered welding electrodes
Bare welding rods and electrodes
electrochemical reaction with the environment. Nickel

has good resistance to corrosion in the normal atmosphere, in freshwaters, and in deaerated nonoxidizing
acids, and it has excellent resistance to corrosion by
caustic alkalies. The high nickel content of these alloys
gives them resistance to corrosion by many organic and
inorganic compounds and also makes them virtually
immune to chloride-ion SCC. Chromium additions

provide resistance to sulfur compounds and also provide resistance to oxidizing conditions at high temperatures or in corrosive solutions. Details of the
corrosion resistance in these types of environments
can be found elsewhere (i.e., see also Chapter 2.08,
Nickel Alloys: Properties and Characteristics).2,10
Table 4
75
Chemical composition of nickel-base welding alloys used in nuclear applications
Alloying
element
Alloy 52a
filler metal
Alloy 69
filler metal
Alloy 72
filler metal
Alloy 82
filler metal
Alloy 132
electrode
Alloy 152a
electrode
Alloy 182
electrode
Ni Co
C
Mn
Fe
S
Si
Mo
Cu
Cr
Ti
Al
P
Nb Ta
Al Ti
Zr
B
Others
Bal.
0.04 max.
1.0 max.
7.011.0
0.015 max.
0.50 max.
0.50 max.
0.30 max.
28.031.5
1.0 max.
1.10 max.
0.030 max.
0.10 max.
1.5 max.
0.50 max.
70.0 min.
0.08 max.
1.0 max.
5.09.0
0.015 max.
0.50 max.
0.50 max.
14.017.0
2.002.75
0.401.00
0.030 max.
0.701.20
55.0 max.
0.05
0.1 max.
0.2 max.
0.008 max.
0.1 max.
0.20 max.
44.0 max.
0.6 max.
67.0 min.
0.10 max.
2.53.5
3.0 max.
0.015 max.
0.50 max.
0.50 max.
18.022.0
0.75 max.
0.030 max.
2.03.0
0.50 max.
62.0 min
0.08 max
3.5 max
11.0 max
0.02 max
0.75 max
Bal.
0.05 max.
5.0 max.
7.012.0
0.015 max.
0.75 max.
0.50 max.
0.50 max.
28.031.5
0.50 max.
0.50 max.
0.030 max.
1.02.5
0.50 max.
59.0 min.
0.10 max.
5.09.5
10.0 max.
0.015 max.
1.0 max.
0.50 max.
13.017.0
1.0 max.
0.030 max.
1.02.5
0.50 max.
0.50 max
13.017.0
0.030 max.
1.54.0
0.50 max
Alloys 52M and 152M have controlled additions of boron and zirconium.
5.04.3.1
Water Chemistry
The water chemistry of LWRs is discussed in detail

in Chapter 5.02, Water Chemistry Control in LWRs.
Nickel-base alloys are essentially immune to general
corrosion in LWR environments due to the formation
of an adherent Cr-rich oxide on the surface.
5.04.3.2
Flow Rates
The inherent passivity of nickel-base alloys provides

them with excellent resistance to flow-assisted corrosion. They are able to withstand very high flow rates,
on the order of 18.3 m s1 (60 ft s1), without concern.
Corrosion rates in such flowing conditions for nickelbase materials are expected to be <2.5 mm year1
(<0.1 mil year1).11
5.04.3.3
Crevices
General corrosion of nickel-base alloys in crevices

is not anticipated to be of great concern in LWRs
because of the passive nature of these materials. Pitting
may occur occasionally in the presence of impurities,
which could lead to SCC (see Section 5.04.4.3),
particularly in the more oxidizing conditions of BWRs.
No failures in PWRs have been directly attributed to
creviced locations.
5.04.3.4
Mitigation
As general corrosion is minimal in LWR environments, mitigation is not really necessary. As noted
in this section on LWR Structural Materials, PWR

environments have reducing conditions and general
corrosion is not of concern. However, mitigation of
corrosion concerns in the more oxidizing environment of BWRs has been through the use of hydrogen
water chemistry (i.e., to make the environment more
reducing, similar to a PWR) and noble metal chemical
additions.12,13
5.04.4 Stress Corrosion Cracking

SCC of nickel-base alloys is an important age-related
phenomenon affecting LWRs. This type of failure
mechanism for nickel-base alloys typically occurs
intergranularly and is generally termed intergranular
stress corrosion cracking (IGSCC). In PWRs, IGSCC
is typically termed primary water stress corrosion
cracking (PWSCC). The occurrence of SCC of nickelbase alloys has been extensively studied since the first
reported observation of cracking in laboratory tests
using Alloy 600 in high-purity water by Coriou et al.14
in 1959. Over the last three decades, IGSCC has
been observed numerous times in LWRs and it has
affected both the safe and economic operation of
the reactors. In BWRs, cracking of nickel-base
components such as safe ends, shroud bolts, and access
hole covers has occurred; however, the predominant
failures have been identified in Alloy 182 welds. In
PWRs, PWSCC of Alloy 600 component items has
been observed in steam generators, pressurizers, and
76
CRDM nozzles, and most recently in Alloy 182 and

Alloy 82 welds. The mechanism of this cracking
phenomenon is not completely understood, and prediction of crack initiation time has proven to be
extremely difficult, if not impossible, due to the uncertainty of numerous variables (e.g., heat treatment and
residual stress). In this section, emphasis will be given to
the SCC of Alloy 600 materials in PWRs, given the fact
that it has been the most prevalent; however, as noted
above, BWR conditions are not immune to IGSCC of
nickel-base alloys.
It is known, however, that SCC of nickel-base materials occurs as a result of the following three factors:
susceptibility of the material
a tensile stress (including both operating and residual stress)
a corrosive environment
The synergistic effect of these three factors is
typically shown on a Venn-type of diagram (Figure 5).
As an example, the susceptibility of Alloy 600
material to PWSCC depends on several factors,
including the chemical composition, heat treatment
during manufacture of the material, heat treatment during fabrication of the component, and
operating parameters of the component. Chemical
composition and heat treatment are interrelated in
several ways. For example, one reason for annealing
Alloy 600 is to solutionize the carbon in the alloy.
As the material cools, chromium carbides precipitate from the solution at both intragranular and
intergranular locations. If the cooldown from the
Mechanical
Operational tensile stresses
residual tensile stress
SCC
Corrosive
Susceptible material
Chemical composition
microstructure
Electrochemical
corrosion potential
temperature
pH-value
Figure 5 Synergistic factors affecting stress corrosion

cracking of nickel-base materials.
anneal is sufficiently slow, a greater number of carbides

will precipitate at the grain boundaries (i.e., intergranularly) and the resistance to PWSCC will be
improved. Well-decorated grain boundaries are an
indication that an Alloy 600 material has received
proper heat treatment and that sufficient carbon
was available in the solution to combine with chromium. If adequate amounts of carbon and chromium
exist, but the anneal is not at a high enough temperature or sufficient time is not allowed to solutionize the
carbon, an adequate amount of carbon will not be
available to precipitate intergranularly as chromium
carbides, leading to minimal grain boundary decoration. Most precipitation occurs during cooldown
following annealing; however, stress relief treatments
can lead to additional precipitation. The primary goal
of stress relief, however, is to allow a local realignment
of highly strained regions to reduce internal stresses.
Carbon and chromium concentration gradients are
also reduced given the extended time at the temperature. Thus, if the anneal has not adequately solutionized carbon for chromium carbide precipitation at
the grain boundaries, stress relief treatment will not
reduce susceptibility to PWSCC.
Tensile stresses, resulting from both residual and
operating stresses, can be significant for some Alloy
600 component items. Operating stresses are produced from mechanical and thermal loading, while
residual stresses are generated as a result of fabrication, installation, and welding processes. Residual
stresses are more difficult to quantify than operating
stresses and, in many instances, are of a higher magnitude than operating stresses.
PWSCC is a thermally activated degradation
mechanism, that is, as the temperature increases, the
rate of PWSCC increases exponentially. Thus, the
hot leg temperature of the RCS creates a more
aggressive environment in which the Alloy 600 components must operate.
The cracking observed in PWRs to date is typically axially oriented (although circumferentially oriented cracks have been observed) and occurs in
an area, such as a weld heat-affected zone (HAZ),
that has high residual tensile stresses. In a cylindrically
shaped component (e.g., piping, vessel, and nozzles),
the circumferential stresses are inherently higher than
axial stresses. Thus, in a homogeneous material with no
initial flaws, cracking would be expected to occur
axially because of the higher circumferential stresses.
PWSCC has been the subject of much research
and analyses in recent years as a result of the many
failures that have been attributed to it. However,
(5070 F) temperature differences between hot and

cold legs are enough to significantly influence the
time to initiation and subsequent crack growth rate.
Temperature is generally believed to affect the
rate of SCC attack in accordance with an activation
model for thermally controlled processes (Arrhenius
equation), exp(Q/RT), where Q is the activation
energy, R is the ideal gas constant, and T is the
absolute temperature. The current consensus is that
the activation energy for crack initiation falls in the
range of 188230 kJ mol1 (4555 kcal mol1) and
many predictions are based on 210 kJ mol1 (50 kcal
mol1). There is also evidence that the activation
energy varies with material carbon content.15
a reliable crack initiation model has yet to be developed. PWSCC of Alloy 600 components in the RCS
can lead to through-wall cracking and thus leakage of
primary water. (Catastrophic failure is not expected as
circumferentially-oriented cracks do not occur
unless very high axial stresses are generated in the
component, e.g., from roll expansion methods.)
5.04.4.1
Environmental Conditions
The major environmental conditions affecting SCC

of nickel-base material in LWR environments appear
to be temperature, water chemistry (oxygen, hydrogen, lithium, boron, and sulfur content), and electrochemical potential (ECP). Each of these factors is
evaluated as follows.
5.04.4.1.2 Water chemistry
The water chemistry of LWRs can generally be

described as essentially pure water. PWRs primarily
include hydrogen, boron, and lithium to produce reducing conditions. BWRs primarily operate with low levels
of oxygen, but in recent times, hydrogen additions have
been introduced to limit the oxidizing potential of
the environment. Additional details are included in
Chapter 5.02, Water Chemistry Control in LWRs.
5.04.4.1.1 Temperature
By far, temperature is the single most significant

environmental factor influencing the initiation of
SCC in LWR environments. This is evidenced by
the fact that the vast majority of SCC of PWR steam
generator roll expansion transitions have occurred
on the hot leg side of the tube sheet. The 2839 C
MA + drawn
35 % area reduction
4000
SCC initiation time (h)
77
3000
2000
1000
Hydrogen
200 ppm B
0.7 ppm Li
hydrogen
500 ppm B
1.0 ppm Li
hydrogen
1100 ppm B
2.0 ppm Li
hydrogen
Water chemistry
Figure 6 Stress corrosion cracking initiation times for Alloy 600 steam generator tubing at 360 C (680 F). Stress
corrosion cracking initiation time as a function of primary water chemistry for as-drawn (35% area reduction) mill-annealed
tubing. Reproduced from Airey, G. P. The stress corrosion cracking performance of Inconel Alloy 600 in pure and primary
water environments. In Proceedings: 1983 EPRI Workshop on Primary-Side Stress Corrosion Cracking of PWR Steam
Generator Tubing; EPRI NP-5498, Project S3035, with permission from Electric Power Research Institute.
78
5.04.4.1.2.1 Hydrogen
The effect of dissolved hydrogen on SCC susceptibility of nickel-base alloys (e.g., Alloys 600 and
X-750) has been evaluated by numerous researchers.
Pathania and McIlree16 reviewed the influence of
hydrogen on PWSCC in 1987. At that time, the
emphasis of the work was on initiation at temperatures of 360 C (680 F) and above. The authors concluded that the susceptibility of Alloy 600 increased
when the amount of dissolved hydrogen increased.
Airey17 has shown that dissolved hydrogen increases
the rate of PWSCC of steam generator tubing in
autoclave tests at 360 C (680 F). An example of his
Temperature (C)
10-5
290
325
345
365
Crack growth rate (mm s-1)
4 pts
10-6
4 pts
Ave. of
4 pts
data, shown in Figure 6, shows that the SCC initiation time for pure water is decreased dramatically
when hydrogen is added. However, in the primary
water of PWRs, the effect of hydrogen appears to be a
function of the boron and lithium content. Bandy and
Van Rooyen18 have shown a similar effect with boron
alone versus pure water and primary water (Figure 7).
They showed that 83% of the specimens cracked in
pure water with hydrogen versus only 2% in pure
water without hydrogen.
More recently, Norring has reported on tests to
determine the effect of hydrogen overpressure in
330 C (626 F) water.19 Results of these tests, shown
in Figure 8(a), suggest that the rate of PWSCC
increases with increasing hydrogen overpressure.
The most recent update on the influence of
hydrogen on PWSCC was prepared by Cassagne
et al.20 in 1997. All the data seem to indicate that the
susceptibility of Alloy 600 decreases drastically for
low hydrogen values (<10 kPa (1.45 psi)) regardless of
temperature. For hydrogen partial pressure above
100 kPa (14.5 psi), a more progressive decrease in
susceptibility seems to occur between 360 and
400 C (680 and 752 F). Data are not available in
this range for lower temperatures. Between 10 and
100 kPa (1.45 and 14.5 psi), it appears that PWSCC
initiation is not greatly affected for all temperatures
between 400 and 310 C (752 and 590 F). At 290 C
(554 F), the influence of hydrogen cannot be
assessed because of a lack of data.
5.04.4.1.2.2
10-7
Flattened specs, I.E.
Cold worked, pure H2O
As received, pure H2O + H2
As received, pure H2O + H3BO3
As received, pure H2O
As received, (0.03 % C),
pure H2O
Primary H2O
10-8
1.75
1.70
1.65
1
T(K)
1.60
1.55
] 1000
Figure 7 Effect of hydrogen on Alloy 600 cracking in pure

and primary water environments. Reproduced from Bandy,
R.; Van Rooyan, D. Quantitative examination of stress
corrosion cracking of Alloy 600 in high temperature
water Work in 1983. In Proceedings: 1983 EPRI Workshop
on Primary-Side Stress Corrosion Cracking of PWR Steam
Generator Tubing; EPRI NP-5498, Project S3035, with
permission from Electric Power Research Institute.
Boron and lithium
Evaluations of boron and lithium on PWSCC of Alloy

600 have been performed by numerous investigators.
Norring et al.19 concluded that increasing the lithium
content from 2.4 to 3.5 ppm significantly decreased
the time to crack initiation (see Figure 8(b)).
The most complete evaluation was performed by
Ogawa et al.21. In these tests, hydrogen overpressure was
kept at a constant level of 30 cm3 kg1 H2O. The results
of this work are shown in Figures 9 and 10. It appears
that maintaining a constant pH of 7.17.3 (at 285 C
(545 F)) will produce a range of crack initiation times
(Figure 9) and that increasing the boron content
greater than 1200 ppm (at any lithium level) decreases
the crack initiation times (Figure 10). Therefore,
the beginning of cycle boron concentrations appears
to be the worst condition for PWSCC initiation. Maintaining a pH level of 7.3 (at 285 C (545 F)) also
appears to be better than a pH level of 7.1.
Follow-up tests were performed at high boron
concentrations with varying lithium concentrations
Temperature...........
329.9 C
329.6 C
Boron......................
1471 ppm
1441 ppm
Lithium....................
2.42 ppm
2.38 ppm
Hydrogen content...
13.1 ml kg-1
25.2 ml kg-1
7.0 kPa
13.6 kPa
7.354
7.351
Activity...
99
90
50
25
10
5
1
100 200
10
5
(a)
99
90
B&W 1700 F 7/8 (6A)
25
10
5
500 1000 2000 5000 10 000

Exposure time (h)
The influence of hydrogen on the tendency to PWSCC
Temperature...........
328.9 C
329.6 C
Boron......................
1241 ppm
1441 ppm
Lithium....................
3.54 ppm
2.38 ppm
Hydrogen content...
24.7 ml kg-1
25.2 ml kg-1
13.6 kPa
13.6 kPa
7.575
7.351
Activity...
pH...........................
B&W 1700 F 7/8 (6)
90
50
25
10
5
1
100 200
500 1000 2000 5000 10 000

Exposure time (h)
B&W 1700 F 3/4
90
50
25
10
5
1
100 200
99
Cracked specimens (%)
99
99
(b)
500 1000 2000 5000 10 000

Exposure time (h)
50
1
100 200
500 1000 2000 5000 10 000

Exposure time (h)
B&W 1700 F 3/4
25
B&W 1700 F 7/8 (6)
99
90
79
50
1
100 200
pH...........................
500 1000 2000 5000 10 000

Exposure time (h)
B&W 1700 F 7/8 (6A)
90
50
25
10
5
1
100 200
500 1000 2000 5000 10 000

Exposure time (h)
The influence of lithium on the tendency to PWSCC
Figure 8 Effect of hydrogen and lithium on time to stress corrosion cracking of Alloy 600 steam generator tubing.
Reproduced from Norring, K.; Rosborg, B., Engstrom, J., Svenson, J. Influence of LiOH and H2 on primary side IGSCC of
Alloy 600 steam generator tubes, Colloque International Fontevraud II, Sept 1014, 1990; Societe Francaise dEnergie
Nucleaire, Paris, France, 1990; pp 243249, with permission from Societe Francaise dEnergie Nucleaire.
80
Li (ppm)
4
1.7 1.6
1.5
1.4
1.3
1.2
1.1
1.0
0
6.3
6.4
6.5
6.6
6.7
6.8
6.9 7.0
pH 285 C
7.1
7.2
7.3
7.4
7.5
7.6
Figure 9 Isosusceptibility diagram for primary water stress corrosion cracking of Alloy 600 as a function of lithium and pH at
285 C (545 F). The numbers (1.0, 1.1, 1.2, . . .) represent the ratio of the percent intergranular fracture referenced to the
response at B:280/Li:2.0 ppm. Reproduced from Ogawa, N.; et al. Nucl. Eng. Des. 1996, 165, 171180.
Li (ppm)
1.7
1.6
1.5
1.4
1.3
1.2
1.1
1.0
0
2000
1500
1000
B (ppm)
500
Figure 10 Isosusceptibility diagram for primary water stress corrosion cracking of Alloy 600 as a function of lithium and
boron. The numbers (1.0, 1.1, 1.2, . . .) represent the ratio of the percent intergranular fracture referenced to the response at
B:280/Li:2.0 ppm. Reproduced from Ogawa, N.; et al. Nucl. Eng. Des. 1996, 165, 171180.
to simulate beginning of fuel cycle conditions. Ogawa

et al.22 report that there is little effect of lithium content from 2 to 10 ppm at boron concentrations greater
than 1200 ppm (see Figure 11) and PWSCC susceptibility at 1600 ppm boron (210 ppm lithium) was
higher than that at 500 or 280 ppm boron concentrations (with 2 ppm lithium).
5.04.4.1.3 Sulfur intrusions
Sulfur intrusions by themselves will not produce

SCC in nickel-base material; however, sulfate will
promote intergranular attack and intergranular SCC.
A sensitized material microstructure is much more
susceptible (in terms of initiation time) to this type of

attack, although all nickel-base materials will be
attacked by sulfate.
Andresen23 has shown that the time to failure
decreased by 23 orders of magnitude in constant
load tests between pure water and sulfate impurities
(conductivities ranging from 5 to 55 mS cm1 due to
sulfuric acid additions).
Bandy et al.24 have shown that sulfates are very
potent cracking agents for Alloy 600 materials. Temperature significantly accelerates the cracking and
most likely decreases the threshold stress for cracking
to occur.
81
11
(1.53)
10
1.5
(1.46)
Li (ppm)
5
1.4
4
1.3
1.2
1.1
1.0
1.1
1.2
0
2000
1500
1000
B (ppm)
500
Figure 11 Revised isosusceptibility diagram for primary water stress corrosion cracking of Alloy 600 as a function of lithium
and boron. The numbers (1.0, 1.1, 1.2, . . .) represent the ratio of the % intergranular fracture referenced to the response at
B:280/Li:2.0 ppm. Values in parentheses are extrapolated or interpolated from test result values. Reproduced from
Ogawa, N.; Nakashiba, T.; Yamada, M..; Umehara, R.; Okamoto, S.; Tsuruta, T. In Proceedings of the Eighth International
Symposium on Environmental Degradation of Materials in Nuclear Power Systems; American Nuclear Society: La Grange
Park, IL, 1997; pp 395401. Copyright 1997 by the American Nuclear Society, La Grange, IL, USA.
5.04.4.1.4 Electrochemical potential
100
PH2 = 0.005 MPa
IGSCC (%)
80
PH2 = 0.1 MPa
60
40
20
Alloy 600
350 C
0.01 m H3BO3 + 0.001 m LiOH soln
0
-1000
-300
0
(E )
Potential (mV) Corr
300
Figure 12 Effect of electrochemical potential on rate

of primary water stress corrosion cracking in
Alloy 600 material. Reproduced from Smialowka,
S. Hydrogen induced IGSCC of Alloy 600 in high
temperature aqueous environments. In Proceedings:
1987 EPRI Workshop on Mechanisms of Primary Water
Intergranular Stress Corrosion Cracking; EPRI
NP-5987SP, with permission from Electric Power
Research Institute.
SCC is also significantly affected by the ECP.

As shown in Figure 12 by the work of Smialowska,25
small changes in the ECP can have a large effect on SCC.
Test results have demonstrated that a crack growth
rate maximum, with respect to coolant hydrogen
variation, is observed in proximity to a key phase transition, the nickel (Ni) to nickel oxide (NiO) phase transition, as shown bya Pourbaixdiagram (see Figures 13 and
14).26,27 The SCC hydrogen dependency is fundamentally described by the extent that the alloys corrosion
potential deviates from the potential of the Ni/NiO
phase transition. This potential difference represents
the relative stability of the SCC controlling oxide films
(e.g., crack tip oxides are often of a NiO structure).
5.04.4.2
Flow Rates
Flow rates in LWRs do not appear to have any effect

on SCC susceptibility and no testing data are known
to be available.
82
Potentials typical of
deaerated environments
Oxide film and IGSCC

arrows indicate an increasing
sensitivity to cracking
RHE potential
Potential
Ni/Nio equilibrium
Potentials typical of environments

with dissolved hydrogen (10/30 bars)
No oxide film
no IGSCC
Neutral environments
Caustic environments
Stable Cr oxides
Cr very soluble
9/10
pH at 300/320 C
Figure 13 Effect of pH and potential on the surface films and sensitivity to stress corrosion cracking of Alloy 600 material.
Reproduced from Scott, P. M.; Le Calvar, M. In Proceedings of the Sixth International Symposium on Environmental
Degradation of Materials in Nuclear Power Systems; The Minerals, Metals, and Materials Society: Warrendale, PA, 1993;
pp 657667, with permission from The Minerals, Metals, and Materials Society.
5.04.4.3
Crevices
Nickel-base materials have been found to be very

susceptible to IGSCC in crevice areas of BWR applications, especially at welds where both weld-induced
sensitization and high residual stresses are present.
Stress corrosion crack initiation and growth of nickelbase materials in BWRs have been attributed to the
development of an acidic environment within crevices
because of the oxygen in normal BWR water chemistry, combined with high residual and applied stresses
resulting from the geometry and nearby welds. The
first widely reported occurrence of SCC of Alloy 600
material in BWRs was at the Duane Arnold unit in
1978.28 This occurred in the crevice area of a recirculation inlet nozzle safe end and was initiated in the
creviced area between the thermal sleeve and the safe
end. However, no known failures of nickel-base materials have been directly attributed to environmental
conditions within crevices in PWRs.
5.04.4.4
Material Susceptibility Factors
The PWSCC susceptibility of a particular heat of

Alloy 600 material is dependent upon a variety of
factors. The most important factors, based on results
from a number of investigators, appear to be material
microstructural features, chemical composition, and
manufacturing process (or product form). Each of
these has been evaluated below.
5.04.4.4.1 Heat treatment
Considerable research efforts have been made to

identify the mechanism responsible for PWSCC of
Alloy 600. These investigations, reviewed by Was,29
have shown that PWSCC is primarily dependent
on the heat treatment received by the material. For
instance, a heat treatment of mill-annealed (MA)
Alloy 600 in the temperature range 650750 C
(12001380 F) has been found to cause a drastic
improvement in the resistance to PWSCC. This has
83
1.50
O2
1.00
H2O
0.50
NiO2
1 ppb
V (SHE)
0.00
Acid
SO4
cracking
H2
1 atm
8.2 ppm
Ni3O4
Ni++
Ni
-0.50
NiO
Fe++
Fe
PWR
Secondary side
Primary side
Fe3O4
Fe
Caustic
cracking
PWSCC
-1.00
Ni(OH)3
Caustic
IGA
-1.50
-2.00
10
12
14
pH
Figure 14 Main domains of intergranular attack and stress corrosion cracking of Alloy 600 in aqueous solutions at
300 C (572 F) relative to the Pourbaix diagram for nickel. (Note the stability boundary for iron relative to its lowest
oxidation states is also shown to indicate that iron can be oxidized under all likely PWR primary and secondary conditions
whereas elemental nickel can be stable under certain PWR primary conditions depending on the corrosion potential
fixed by the hydrogen partial pressure.) Reproduced from Scott, P. M.; Combrade, P. In Proceedings of the Eighth
International Symposium on Environmental Degradation of Materials in Nuclear Power Systems; American Nuclear Society:
La Grange Park, IL,1997; pp 6573. Copyright 1997 by the American Nuclear Society, La Grange Park, IL, USA.
been termed thermal treatment (TT). Although the

exact mechanism of enhanced resistance to PWSCC
is unclear and still under debate, there is general
agreement that the chemical composition and structure of grain boundaries are of crucial importance.
In this connection, chromium depletion, segregation
of impurities to grain boundaries, intergranular carbides and their mechanical effect on stress concentrations, and grain boundary misorientation appear to
be essential to the corrosion behavior of the material.
Annealing temperature and time are critical to the
precipitation reactions that occur. The penultimate
and final anneals appear to be the most critical
for PWSCC resistance. Stiller et al.,30 Briant et al.,31
Hall and Briant,32 EPRI NP-507233 all agree that a
high-temperature final anneal, sufficient to solutionize all carbon precipitates, followed by a slow
enough cooling rate to precipitate copious carbides
on the grain boundaries (intergranular carbides) will
produce a reasonably PWSCC-resistant material.
Norring34 tested Alloy 600 reverse U-bends (RUBs)
in high-purity water containing hydrogen. The time
to crack initiation at 320 C (608 F) increased by a
factor of 8 when the annealing temperature was
increased from 925 C (1697 F) to 1025 C (1877 F).
5.04.4.4.2 Microstructure
The precipitation obtained in the final material

microstructure is dependent upon heat treatment
and chemical composition (mainly carbon, chromium,
84
titanium, and nitrogen content). During the cooling

that occurs after annealing, carbon combines with
chromium to form chromium carbides. In addition,
titanium carbides and titanium nitrides are formed.
These precipitate within the grains (intragranularly)
or at grain boundaries (intergranularly) depending
largely upon the temperature reached during annealing
and thermal treatments, the presence of prior precipitates (e.g., undissolved carbides), the time at temperature, the carbon content, and the cool down rate.
A study was conducted by the Electric Power
Research Institute (EPRI) in 1981 to evaluate carbide
dissolution and precipitation kinetics of Alloy 600.35
This study showed that final annealing temperatures
between 982 and 1010 C (1800 and 1850 F) (for
carbon contents between 0.02% and 0.048%) provide
a consistent thermal treatment response and an adequate precipitation of chromium carbides.
The most widely accepted hypothesis for the beneficial effect of intergranular carbides on PWSCC
resistance has been proposed by Bruemmer,36 who
suggests that grain boundary carbides promote crack
blunting due to their effectiveness as dislocation
sources. Another possible explanation proposed by
Smialowska25 is that Alloy 600 material passivates more
readily in the presence of grain boundary carbides.
Most recently, Fish et al.37 have proposed that intergranular carbides may improve passivity at the crack
tip by reducing the amount of carbon segregated along
the grain boundaries.
Whatever the mechanism, or mechanisms, involved,
there is general agreement that a microstructure with
copious intergranular carbides and few intragranular
carbides correlates with good resistance to PWSCC.
A range of intergranular and intragranular carbide
precipitation has been used by many investigators to
quantify PWSCC susceptibility.15 Scott et al.38 have
developed a range of material susceptibility indices,
based on minimum times to failure, for Alloy 600
material used in French steam generators. These factors
have also been used for CRDM nozzles.39,40
5.04.4.4.3 Grain size
Grain size can be related to yield strength and tensile

strength of Alloy 600 material by the general type of
HallPetch relationship.41 That is, a lower yield
strength material will typically have a larger grain
size. Data for PWSCC42 show that very small grain
sizes (typically ASTM grain size numbers >9) are
more prone to PWSCC than larger grain sizes (typically ASTM 48). Other data43 show that steam
generator tubing with a grain size number larger
than ASTM 6 is less susceptible to PWSCC. However, the effect of grain size is most likely a secondorder effect, while carbide precipitation tends to be
more important.
5.04.4.4.4 Chemical composition
The chemical composition of Alloy 600 has mainly

been correlated to PWSCC susceptibility in terms of
the carbon content. Many investigators have shown
that carbon contents near the high end of the typical
mill range (0.020.06 wt%) result in increased
PWSCC susceptibility. Electricite de France (EdF)
conducted a series of RUB specimen tests on steam
generator tubing, using a low mill anneal temperature
with carbon content ranging from 0.01 to 0.07 wt%.44
The tests were conducted in elevated temperature
pure water and primary water with hydrogen overpressure. These tests show that low carbon (<0.018%)
had the lowest PWSCC susceptibility. Pichon and
others45 have shown that carbon contents that are
relatively high (>0.063%) or very low (<0.012%)
are more susceptible to PWSCC.
The carbon content of Alloy 600 weld materials
(Alloys 182 and 82) has also been investigated by
several researchers.46,47 It appears that low carbon
contents (<0.02%) are most susceptible, medium
carbon contents (0.020.04%) are intermediate, and
high carbon contents (>0.04%) have the most resistance to PWSCC.
However, correlating the actual carbon content of
the material may not be the best approach. This is
also shown in the test data reported by Norring et al.34
A better approach may be to determine the available
carbon content. This would entail knowledge of the
titanium and nitrogen content of the heat of material.
If it is assumed that all the nitrogen is precipitated as
titanium nitrides (TiN), then the remaining titanium
can be assumed to react with the carbon in the
material. With these assumptions (which are thermodynamically reasonable), the remaining carbon would
be the available carbon amount to precipitate as
chromium carbides (M7C3 or M23C6 precipitates).
Unfortunately, titanium and nitrogen are not normally
reported in the certified material test reports (CMTRs);
thus, this approach cannot be used without archive
material or sampling of the heats in service.
Buisine et al.48 evaluated the PWSCC resistance of
nickel-based weld metals with various chromium
contents. The tests clearly demonstrated that weld
metals with 30% chromium were resistant to
PWSCC. The threshold for PWSCC resistance
appears to be between 22% and 30% chromium.
There have been discussions in the literature of

the role of chromium depletion along the grain boundaries (sensitization), as well as boron and phosphorous segregation along the grain boundaries.49 The
degree of sensitization is tied to the heat treatments
and there have been conflicting reports on the benefits
and disadvantages of sensitization. It has been shown
that a sensitized material is more susceptible to caustic
attack. In addition, boron and phosphorous may be
beneficial for retarding PWSCC, but the experimental
evidence is weak at present.
5.04.4.4.5 Product form
Alloy 600 component items in the RCS are fabricated

by press forging, hammer forging, hot rolling, and
forming and machining from bar stock in accordance
with ASME SB-166 or cold drawn and hot finished
tubing or piping in accordance with ASME SB-167.
In addition, it has been suggested that some ASME
SB-167 material was actually produced from SB-166
bar stock and recertified as SB-167 material. The
fabrication processes affect the material microstructure, yield strength, and hardness, which in turn
affect the PWSCC resistance of the material.
The PWSCC susceptibility of various product
forms has been evaluated to some degree. The most
susceptible product form appears to be cold worked
and low temperature MA steam generator tubing, as
evidenced by the vast majority of data available in the
literature. However, the other product forms (i.e.,
forgings, piping, and bar stock) have not been assessed
as extensively. One study, performed by Webb50
found differences in susceptibilities of cold-worked
and hot-worked materials with similar microstructures. The cold worked and annealed tubing was
more susceptible than hot worked and annealed
forging material. The different behavior remains
even when yield strength differences between the
materials are taken into account.
Another study on the relative susceptibility of
high and low yield strength bar and tubing, performed for EPRI,51 concluded that PWSCC susceptibility ranked in decreasing order as (1) high-yield
strength bar, (2) high-yield strength tubing, and
(3) low-yield strength bar. However, no low-yield
strength tubing was tested in this study.
Microstructural evaluation in the study described
above indicated that grain boundary carbide decoration is generally poor in bar products and better in
tubing products. However, the susceptibility of Alloy
600 material also depends on surface cold work due
to machining, grinding, and reaming. A material with
85
highly susceptible microstructure when subjected

to a large amount of cold work on the surface (i.e.,
reaming or grinding) becomes very susceptible to
PWSCC. Therefore, component items that were
machined from bar stock and with weld root grinding
should be considered highly susceptible to PWSCC.
A machined surface without reaming or grinding is
considered to have undergone moderate cold work
and somewhat less susceptible to PWSCC. The least
susceptible material is for cold drawn tubing with a
high mill-anneal temperature. This type of approach
has been adopted by Consumers Power Company
at the Palisades Nuclear Plant.52
The most recent work was performed by Briceno
et al.,53 who tested a variety of product forms.
Two groups of materials appear to exist, as shown in
Figure 15. The first group contains cold-worked
material, thick wall tube, and steam generator tubing;
whereas, the second group contains hot-worked thick
wall tubes. The forged bars showed higher crack initiation times than the tubes tested. Specimens made of
forged bars and hot-worked tube with similar grain
boundary carbide distributions (60%) and the same
grain size (ASTM 4.04.5) showed a significant difference in initiation times. The same tendency is seen
for a low density of intergranular carbides when coldworked tube and forged bar with the same grain size
were compared.
5.04.4.5
Stress
Laboratory tests and operating experience in PWRs

suggest that significant PWSCC should not occur
in Alloy 600 component items at stresses less than
about 242 MPa (35 ksi) for temperatures up to around
324 C (615 F). As operating design stresses permitted by the ASME B&PV Code are much less than
242 MPa (35 ksi), PWSCC failure would not be
expected to occur due to applied pressure and thermal loadings. This is supported by the fact that
essentially all PWSCC failures have occurred at
locations where (1) high residual stresses are produced during fabrication (e.g., pressurizer nozzle
J-groove welds), (2) high stresses are produced as
a result of strains induced during operation (e.g.,
steam generator-dented tube support plate intersections), or (3) high stresses are produced by geometric abnormalities (e.g., excessive steam generator
tube ovality).
The following paragraphs address the operating
and residual stresses that may act in RCS pressure
boundary component items.
86
Specimens cracked/specimens tested
1.0
0.8
0.6
FC no cracks
FB
FA
FX
V1V2
W1
W2 no cracks
GW
GV
0.4
0.2
0.0
0
Bar
Thick
wall
tube
S.G.
tube
1000
2000
3000
4000
Time (h)
5000
6000
7000
Heat
Working
method
Final thermal
treatment
YS (MPa)
after
forging
YS (MPa)
after
thermal
treatment
%C
FC
Forged bar
745 C/2 h (a.c)
428
413
0.021
FB
Forged bar
800 C/2 h (a.c)
491
489
0.021
FA
Forged bar
800 C/2 h (a.c)
550
412
0.024
FX
Hot worked
(*)
291
0.03
V1
Cold rolled 1000 C/3 min (w.c)
301.5
0.051
V2
Cold rolled 1000 C/3 min (w.c)
274
0.052
W1
Hot worked
980 C
320.6
0.081
W2
Hot worked
980 C
244.7
0.067
GVW
Cold worked 927 C/35 min (a.c)
393
0.04
GV
Cold worked 927 C/35 min (a.c)
389
0.038
( * ) no heat treatment after extrusion of the tube.

% C = Percentage carbon content
Figure 15 Stress corrosion cracking initiation time at 330 C (626 F) for up to 10 500 h. Reproduced from Briceno, D.;
Blazquez, F; Hernandez, F. In Proceedings of the Eighth International Symposium on Environmental Degradation of Materials
in Nuclear Power Systems; American Nuclear Society: La Grange Park, IL,1997; pp 249256. Copyright 1997 by the American
Nuclear Society, La Grange Park, IL, USA.
5.04.4.5.1 Operating stress
5.04.4.5.2 Residual stress
Operating stresses, on the order of 69138 MPa

(1020 ksi) in the hoop direction of J-groove, partial
penetration welds, as well as full penetration welds,
are anticipated in LWR component items. Stress
levels on this order are not high enough to cause
concern with SCC. Therefore, residual stresses must
be taken into account.
The magnitude and sign of residual stresses in most

typical RCS component items are considered to be a
function of (1) surface layer hardness produced by cold
working (e.g., rolling, machining, bending, or reaming)
and (2) residual stresses produced by welding.
Test data by Bandy and Van Rooyen (Figure 16)
indicate that the initiation time for PWSCC in
87
Fraction of yield strength (RT)
10
AR
CW
345 C (AR)
1.0
0.1
1
100
10
1000
Failure (days)
Figure 16 Correlation between stress and time to stress corrosion cracking for steam generator tubing tested in pure water
at 300 C (tfailure K Stressb, b 4). CW: cold work; AR: as-received. Reproduced from Bandy, R.; Van Rooyan D.
Quantitative examination of stress corrosion cracking of Alloy 600 in high temperature water Work in 1983. In Proceedings:
1983 EPRI Workshop on Primary-Side Stress Corrosion Cracking of PWR Steam Generator Tubing; EPRI NP-5498, Project
S3035, with permission from Electric Power Research Institute.
elevated temperature water varies inversely with the

fourth power of the applied stress.18 Test data by
Yonezawa et al.54 (Figure 17(a) and 17(b)) suggest
that the initiation time varies inversely with the sixth
or seventh power of the applied stress. In addition,
Figure 18 shows data from Yonezawa that suggest
that the absolute value of the stress raised to a
power is not the only significant factor. Other significant factors include the amount of cold work and the
ratio of the applied stress to the material yield
strength. In other words, the PWSCC initiation
time at a given applied stress level should increase
as the material strength is increased. Conversely, for
strain-controlled situations, such as at a J-groove
weld, where the residual stress is a fixed percentage
of the material yield strength, increasing the yield
strength can actually decrease the initiation time.
5.04.4.5.3 Surface effects
The residual stress in a component item is a function of the applied mechanical forces and the heat
input. Mechanical forces applied during cold work
tend to produce compressive residual stresses in
the surface layer. Conversely, heat input has the
potential to produce tensile residual stresses. Specifically, heat input causes expansion of the surface
layer yielding, if the thermal stresses exceed material yield strength and residual tensile stresses in
the surface layer upon cooling. This suggests that
high heat input operations such as drilling, turning,
or grinding have the potential to develop higher

tensile residual stresses than low heat input operations such as reaming. Note that these high tensile
residual stresses produced during machining are
limited to a few mils depth.
Berge et al.55 have shown, in crack initiation testing
performed in France, that the time to crack initiation with a base material tensile stress of 500 MPa
(72.5 ksi) is four times that of a material with a
cold-worked surface stress of 1000 MPa (145 ksi).
5.04.4.5.4 Weld geometry
The welding of small penetration nozzles into larger

vessel component items, by either partial penetration
or full penetration welds, can produce tensile stresses
in the nozzle. The magnitude of these stresses is
generally on the order of the yield strength of the
material. The cooling and subsequent shrinking of
the weld material pull the nozzle wall toward the
much stiffer component item to which it is welded.
This shrinkage results in residual tensile hoop stresses in the nozzle near the weld. This weld shrinkage
also results in axial bending of the nozzle. The magnitude of the bending stress, however, is typically
much lower than that of the hoop stress.
5.04.4.5.5 Stress relief annealing
The primary goal of stress relief heat treatment is to

allow a local realignment of highly strained regions
to reduce internal stresses. As mentioned above,
Stress measured by X-ray diffraction analysis on the

top of U-bend specimens (kgf mm-2)
88
100
90
s-7
80
70
60
Crack
50
0.2% Offset proof stress at room temperature: 3.3 kgf mm-2
40
102
103
Applied stress (kgf mm-2)
(a)
104
Stress corrosion cracking testing time (h)
Crack
No crack
s-6
70
60
50
40
30
20
0.2% offset proof stress at 360 C
10
0
(b)
102
103
104
Stress corrosion cracking testing time (h)
Figure 17 Correlation between stress and time to stress corrosion cracking for Alloy 600 steam generator tubing.
(a) Effect of stress on the stress corrosion cracking resistance of mill-annealed Alloy 600 at 360 C in high temperature
water. (b) Effect of stress on the stress corrosion cracking resistance of mill-annealed Alloy 600 at 360 C in high
temperature water, using constant load stress corrosion cracking test. Reproduced from Yonezawa, T.; Onimura, K.; Saito, I.;
Takamatsu, H. In Materials for Nuclear Reactor Core Applications; BNES: London, 1987; pp 7783, with permission from
British Nuclear Energy Society.
improvement to the intergranular carbide precipitation is also almost always a benefit.

The degree of stress relief is known to be a function of time and temperature. Available data from the
International Nickel Company (INCO) are given in
Figure 19.56 It can be seen that at a temperature of
482 C (900 F) for 4 h, 21% of the stress is relieved.
Also, at a temperature of 870 C (1600 F) for 4 h,
88% of the stress is relieved. It should be noted that
essentially all the stress relief occurs within 1 h at
the temperature of interest. Residual stresses are
generally reduced from values near the room temperature yield strength to values that are near zero stress.
5.04.4.6
Irradiation
Irradiation-assisted stress corrosion cracking

(IASCC) is an age-related degradation mechanism
where materials exposed to neutron radiation become
more susceptible to SCC with increasing fluence.57
IASCC, like PWSCC, is a distinctive subset of SCC.
Despite numerous investigations and research efforts,
89
Applied
stress
(kgf mm-2)
Material
Heat
treat
ment

testing time (h)
Applied
stress
-2
Frac- (kgf mm )
ture
0.80.2
Cold
working
1.0sO2
24
8%
tensile
strained
45
15%
tensile
strained
57
(2.793)
(2.713)
IGSCC
975 C 25%
0.07 annea- tensile
ling strained
72
(159)
(3.231)
IGSCC
C (%)
20%
cold
rolled
87
2.000 4.000 6.000 8.000 10.000 12.000 14.000
(1.717)
Fracture
2.000 4.000 6.000 8.000 10.000 12.000 14.000
9.505
(3.704)
(5.772)

testing time (h)
IGSCC
IGSCC
IGSCC
IGSCC
IGSCC
45
(12.8481)
IGSCC
(2.374)
(4.191)
57
IGSCC
No crack
Crack
Figure 18 Effect of applied stress to yield strength ratio on time to stress corrosion cracking for Alloy 600 steam
generator tubing. Effect of cold working on the stress corrosion cracking resistance for the same ratio of applied stress to
yield strength of mill-annealed Alloy 600 at 360 C in high temperature water. Reproduced from Yonezawa, T.; Onimura, K.;
Saito, I.; Takamatsu, H. In Materials for Nuclear Reactor Core Applications; BNES: London, 1987; pp 7783, with permission
from British Nuclear Energy Society.
30
482 C (900 F)
593 C (1100 F)
25
538 C (1000 F)
Residual stress (1000 psi)
649 C (1200 F)
20
15
704 C (1300 F)
10
760 C (1400 F)
5
871 C (1600 F)
2
Time (h)
Figure 19 Effect of heating time and temperature on residual stress of cold-drawn, annealed Alloy 600 rod.
Reproduced from Inconel Alloy 600, International Nickel Company: Huntington, WV, 1978, with permission from Special
Metal Corporation.
details of the IASCC mechanism remain hypothetical.5861 The current consensus is that IASCC results
from a synergistic effect of irradiation damage to the
material, water environment with possible radiolysis
effects, and a stress state. At present, interactions

between these variables have not adequately been
quantified and no primary IASCC controlling mechanism has been identified.
90
Nickel-base alloys, such as Alloy 600 and 690,

are not typically utilized in areas of high fluence
because of their high nickel content. Nickel will
become highly radioactive when exposed to neutron
radiation. No known IASCC-related studies have
been reported in the open literature for these alloys.
There are, however, some data available for Alloy
X-750 at low neutron fluence levels. Results obtained
from swelling capsule tests indicate that IASCC
resistance of Alloy X-750 is approximately the same
as Types 304 and 316 stainless steel.62,63 Some tensile
test data of small scale Alloy X-750 HTH Condition
bolts irradiated in a PWR to 1.4 1019 n cm2
(E > 1.0 MeV) performed without any failure up to
0.95% strain.64 Simulated BWR testing demonstrated
an irradiation-enhanced IGSCC susceptibility of
Alloy X-750 HTH Condition as a function of fluence
and boron content.65 Fluence at 1019 n cm2 versus
10141018 n cm2 (E > 1.0 MeV) showed an increase
in susceptibility.
Alloy 718 has an excellent record in PWR primary
water applications often at operating stresses close to or
exceeding the yield point that can be 1000
1100 MPa (145160 ksi). Alloy 718 is used in fuel applications where very high neutron fluxes are also experienced. The few failures that have occurred have been
attributed to a manufacturing defect that allowed components to enter service with preexisting intergranular
defects. Alloy 718 is known to be highly resistant to
crack initiation, but IGSCC will propagate rapidly in
PWR primary water from preexisting defects.
5.04.4.7
Mitigation
A number of techniques have been evaluated and are

available to delay or eliminate the occurrence of SCC
in LWRs. Many of the available and future mitigation
techniques were evaluated in a paper presented at a
conference held by the US Nuclear Regulatory Commission (NRC) in 2003.66 In general, these techniques
fall into three main categories:
1. Mechanical surface enhancement (MSE)
2. Environmental barriers or coatings
3. Chemical or electrochemical corrosion potential
(ECP) control
MSE techniques represent processes that reduce surface tensile residual stresses or induce compressive
surface stresses on a component item or weld. Examples of MSE techniques include shot peening and
electropolishing. Environmental barrier or coating
techniques represent processes that protect the
material surface from an aggressive environment.

Coating examples include nickel plating and weld
deposit overlays or inlays. Chemical or ECP control
techniques represent changes to the environment
that alter the corrosion process or produce corrosion
potentials outside the critical range for SCC. Examples of chemical or ECP control include zinc additions
to the reactor coolant and modified water chemistry
(e.g., hydrogen water chemistry and noble metal chemical additions to BWR coolant; variations in dissolved
hydrogen levels, lithium concentrations, and boron
concentrations for PWR coolant).
5.04.5 Outlook
Wrought nickel-base alloys and their weld metals
were originally used in LWRs due to the materials
inherent resistance to general corrosion in a number
of aggressive environments and because of a coefficient of thermal expansion that is very close to that of
low alloy and carbon steel. Over the last 40 years,
SCC has been observed in numerous component
items and associated welds, sometimes after relatively
long incubation times. The occurrence of SCC has
been responsible for significant downtime and
replacement power costs.
Nickel-base materials will continue to be used both
for repair and replacement activities in currently
operating nuclear units and in the next generation of
LWRs. Although the continued use of Alloy 600 material, for example, has essentially been eliminated in
LWRs, acceptance and use of the higher chromium
material, Alloy 690, is widely recognized by the industry. These higher chromium materials have been
shown to be highly resistant to SCC in laboratory
experiments and component repairs. Their use has
proven to be an effective decision, since replacements
have been free from cracking in operating reactors over
periods up to about 20 years. Improvements in the
weldability of the higher chromium weld metals (i.e.,
variants of Alloys 52 and 152) have been identified
through significant research and the results have been
put into application today.
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of the nickel based alloys susceptibility to PWSCC.
In Proceedings: 1992 EPRI Workshop on PWSCC of Alloy
600 in PWRs, EPRI TR-103345, Paper F6, Dec 1993.
Cattant, F. Metallurgical investigations performed on
CRDM nozzles removed from power plants.
In Proceedings: 1992 EPRI Workshop on PWSCC of Alloy
600 in PWRs, Dec 1993; EPRI TR-103345, Paper B5.
Park, H. B.; Kim, Y. H.; Lee, B. W.; Rheem, K. S. J. Nucl.
Mater. 1996, 231(3), 204212.
Proceedings: 1985 Workshop on Primary-side SCC of
PWR S/G Tubing; EPRI NP-5158, Project S3035, EPRI.
Shah, V. N.; Lowenstein, D. B.; Turner, A. P. L.; et al. Nucl.
Eng. Des. 1992, 134, 199215.
Majo, D. G.; Gelpi, A.; Dallery, D.; Rouillon, Y.; Van
Duysen, J. C.; Zacharie, G. Prediction of the in-service
behavior of Alloy 600 tubes used in steam generators of
pressurized water reactors. In Colloque International
Fontevraud II Sept 1014, 1990; Societe Francaise
dEnergie Nucleaire: Paris, France, 1990; pp 281290.
92
44. Pichon, C.; Boudot, R.; Benhamou, C.; Gelpi, A. Residual

life assessment of French PWR vessel head penetrations
through metallurgical analysis. In American Society of
Mechanical Engineers, Pressure Vessels and Piping
Division, 1994 Pressure Vessels and Piping Conference;
Service Experience and Reliability Improvement: Nuclear,
Fossil, and Petrochemical Plants, 1994; Vol. 288,
pp 4147.
45. Seman, D. J.; Webb, G. L.; Parrington, R. J. Primary water
stress corrosion cracking of Alloy 600 Effects of
processing parameters. In Proceedings: 1991 EPRI
Workshop on PWSCC of Alloy 600 in PWRs, EPRI
TR-100852, Paper E3, July 1992.
46. Mullen, J. V.; Parrington, R. J. Stress corrosion of Alloy
600 weld metal in primary water. In Proceedings: 1992
EPRI Workshop on PWSCC of Alloy 600 in PWRs, Dec
1993;EPRI TR-103345, Paper F3.
47. Buisine, D.; Vaillant, F.; Vidal, P.; Gimond, C. PWSCC
resistance of nickel based weld metals with various
chromium contents. In Proceedings: 1994 EPRI Workshop
on PWSCC of Alloy 600 in PWRs, EPRI TR-105406, Paper
D5, Aug 1995.
48. Airey, G. P. Metallography 1980, 13, 2141.
49. Webb, G. L.; Burke, M. G. In Proceedings of the Seventh
of Materials in Nuclear Power Systems; National
Association of Corrosion Engineers: Houston, TX, 1995.
50. Sarver, J. M.; Pathania, R.; Stuckey, K.; Fyfitch, S.;
Gelpi, A.; Foucault, M. PWSCC of Alloy 600 penetrations
(EPRI RP 3223). Presentation E1 in Proceedings: 1994
EPRI Workshop on PWSCC of Alloy 600 in PWRs, EPRI
TR-105406, Project 3223-1, Aug 1995.
51. Hoang, P. H. Primary water stress corrosion cracking
inspection ranking scheme for Alloy 600 components.
In Proceedings of the Sixth symposium: Current Issues
Related to Nuclear Power Plant Structure, Equipment and
Piping, Dec 46, 1996; available from N. Carolina State
University Center for Nuclear Power Plant Structures,
Equipment, and Piping: Raleigh, NC.
52. Briceno, D.; Blazquez, F.; Hernandez, F. In Proceedings of
the Eighth International Symposium on Environmental
Degradation of Materials in Nuclear Power Systems;
pp 249256.
53. Yonezawa, T.; Onimura, K.; Saito, I.; Takamatsu, H.
Materials for Nuclear Reactor Core Applications; BNES:
London, 1987; pp 7783.
54.
55.
56.
57.
58.
59.
60.
61.
62.
63.
64.
65.
Berge, P.; Buisine, D.; Gelpi, A. PWSCC effect of initial

surface preparation. In Proceedings: 1997 EPRI Workshop
on PWSCC of Alloy 600 in PWRs, EPRI TR-109138, paper
E5, Nov 1997.
Inconel Alloy 600, International Nickel Company:
Huntington, WV, 1978.
McNeil, M. B. Nucl. Eng. Des. 1998, 181, 5560.
Scott, P. A review of irradiation assisted stress corrosion
cracking of austenitic materials for PWR core internals.
Eurocorr, Framatome, France, Sept. 1996.
Nelson, J. L.; Andresen, P. L. In Proceedings of Fifth
Monterey, CA, Aug, 1991; American Nuclear Society:
Andresen, P. L.; Ford, F. P.; Murphy, S. M.; Perks, J. M.
In Proceedings of 4th International Symposium on
Systems Water Reactors, Jekyll Island, GA, Aug, 1989;
National Association of Corrosion Engineers: Houston, TX,
pp 1-831-121.
Hanninen, H.; Aho-Mantilla, I. In Proceedings of 3rd
Traverse City, MI, Aug 30Sept 3, 1987; The Minerals,
Metals, and Materials Society: Warrendale, PA, 1987;
pp 7792.
Scott, P. J. Nucl. Mater. 1994, 211, 101122.
Andresen, P. L. In Stress Corrosion Cracking Materials
Performance and Evaluation; Jones, R. H., Ed.;
American Society for Metals: Metals Park, OH, 1992;
pp 182210.
Materials Reliability Program: Stress Corrosion Cracking
of High Strength Reactor Vessel Internals Bolting in PWRs
(MRP-88); EPRI Report 1003206; 2003.
Bajaj, R.; Mills, W. J.; Lebo, M. R.; Hyatt, B. Z.; Burke, M.
G. In Proceedings of Seventh International Symposium on
SystemsWater Reactors; American Nuclear Society:
La Grange Park, IL, 1997.
Conference on Vessel Penetration Inspection, Crack
Growth and Repair (NUREG/CP-0191). Compiled by:
Mintz, T. S., Cullen, W. H., Sr.; US Nuclear Regulatory
Commission, Mar 2004.
5.05 Corrosion and Stress Corrosion Cracking of Austenitic

Stainless Steels
U. Ehrnsten
VTT Technical Research Centre of Finland, Espoo, Finland
5.05.1
Introduction to Austenitic Stainless Steels
5.05.1.1
5.05.1.2
5.05.1.3
5.05.2
5.05.2.1
5.05.2.1.1
5.05.2.1.2
5.05.2.1.3
5.05.2.1.4
5.05.2.1.5
5.05.2.2
5.05.2.3
5.05.3
5.05.4
References
Types, Mechanical Properties, and Microstructures

Welding
Components Made of Stainless Steels in BWRs and PWRs
Stress Corrosion Cracking
IGSCC in BWR Environment
Degree of sensitization
Deformation
Environment
Stress
Components at risk
IGSCC in PWR Environment
TGSCC in BWR and PWR Environments
Pitting Corrosion
Microbiologically Induced Corrosion
Abbreviations
BWR
CGR
ECP
EPR
HAZ
HWC
IGSCC
K
KISCC
LWR
MIC
NG
NMC
NMCA
NWC
PLEDGE
PWR
RBMK
SCC
TGSCC
VVER

Crack growth rate
Electrochemical corrosion potential
Electrochemical (potentiokinetic)
reactivation
Heat-affected zone
Stress intensity factor
Threshold stress intensity for SCC
Light water reactor
Microbiologically influenced corrosion
Nuclear grade
Nobel metal chemistry
Noble metals chemistry addition
Normal water chemistry
Plant life extension and diagnosis by
GE (General Electric)
Channel type graphite moderated
reactor
Transgranular stress corrosion cracking
Water-water energetic reactor
93
94
94
94
96
96
96
98
98
100
101
101
101
102
102
103
5.05.1 Introduction to Austenitic

Stainless Steels
Austenitic stainless steels have rendered their vast
use because of their good performance in corrosive
environments, in addition to their excellent ductility,
formability, toughness, and weldability. The good
corrosion resistance of austenitic stainless steels is
mainly due to chromium alloying, resulting in a protective, chromium-rich passive film on the material
in many environments. Molybdenum, used as an
alloying element in Type 316 stainless steels, further
increases the corrosion resistance. Chromium and
molybdenum are, however, both ferrite-forming elements, and to maintain a fully austenitic structure,
a balance between austenite-stabilizing elements
(C, N, Ni, Mn, and Co) and ferrite-stabilizing elements (Cr, Mo, Si, Ti, Nb, Al, V, and W) in solution
must be established.1 To compensate for the molybdenum addition in Type 316 stainless steels, the
amount of nickel is increased. In materials for nuclear
environments, the cobalt content is kept as low as
possible (<0.02%), because of its strong influence
on radioactivity buildup.
Stress corrosion cracking (SCC) is taken into account
in the design codes for light water reactors (LWRs,
93
94
Corrosion and Stress Corrosion Cracking of Austenitic Stainless Steels
i.e., boiling and pressurized water reactors (BWRs

and PWRs)) through a statement that SCC should not
occur.2 Intergranular stress corrosion cracking (IGSCC)
is still by far the largest damage mechanism for austenitic stainless steels in oxidizing BWR conditions, and
work on avoiding IGSCC is still going on.3,4 Several
factors affect IGSCC, one of them being sensitization.
Sensitization is a result of nucleation and growth of
chromium-rich carbides on grain boundaries, causing
grain boundary chromium depletion. Chromiumdepleted grain boundaries are prone to corrosion
and, in combination with a large enough stress and
suitable environment, to IGSCC. All measures to
prevent sensitization are therefore taken in all steps
of component manufacturing and plant operation.
Concerning the chemical composition, this can be
done by reducing the carbon content to levels below
0.03%, as is done in Types 316L, 316LN, and 316NG
stainless steels, where the carbon content is typically in the order of 0.02%. Since carbon is a
strengthening element, nitrogen is added to these
steels to still achieve good mechanical properties.
Nitrogen also reduces chromium-rich carbide formation, a concept that is utilized in the French RCCM
norms, which allow a carbon content of 0.035% in
their nitrogen-strengthened Type 316 stainless steel
with 0.08% N. The other approach to avoiding sensitization is to tie up the carbon into precipitates.
This is utilized in stabilized stainless steels, which
are of two main categories, titanium- and niobiumstabilized stainless steels, Type 321 and 347, respectively. To ensure that the carbon is tied into Ti(C,N)
or Nb(C,N) precipitates, a high enough stabilization
ratio, that is, Ti/C or Nb/C above 5 or 10, respectively, is specified.
Good corrosion resistance is ensured by restricting the amount of harmful elements, especially sulfur
and phosphorus, which may cause intergranular
corrosion when segregated to grain boundaries. Several standardized grain boundary corrosion tests,
such as the Strauss test5 and the electrochemical
potential reactivation (EPR) test,6 are employed routinely as part of acceptance tests for materials and
components.
5.05.1.1 Types, Mechanical Properties, and
Microstructures
The chemical compositions and mechanical properties of the most common stainless steels are presented
in Table 1 and the main mechanical properties are
summarized in Table 2.
In addition to compositional, mechanical, and corrosion resistance requirements, several other requirements are put on austenitic stainless steel materials
for nuclear components. These include, for example,
requirements on grain size. A small enough grain
size is needed to enable reliable nondestructive inspection requirements, using ultrasonic techniques. A common requirement is that the grain size must not exceed
ASTM number 4.0, which corresponds to an average
grain size of 90 mm. The grain size of stabilized stainless
steel components is typically smaller than this.
5.05.1.2
Welding
Stainless steels are generally welded with a slightly

over-alloyed filler metal to ensure good corrosion
resistance of the final joint. The weld shall contain
a small amount (>3% but <10%) of d-ferrite to
avoid solidification and liquation cracking.7 Welding
induces residual stresses, which together with the
operational stresses enhance crack initiation and
growth. The aim is, naturally, always to minimize
the residual stresses by a proper choice of welding
parameters, by securing a good fit between the parts
to be welded, etc. The use of a narrow-gap welding
technique has increased remarkably during the last
few decades. The narrow-gap welding method has
many advances as it results, for example, in a lower
level of residual stresses, a reduced weld volume, a
narrower heat-affected zone (HAZ) with lower risk of
sensitization, and less grain growth.8
5.05.1.3 Components Made of Stainless
Steels in BWRs and PWRs
Austenitic stainless steel is the main construction
material in nuclear power plants (NPPs) owing to
its good corrosion resistance, ease to manufacture different shapes, and good weldability. In BWRs, stainless
steels are used for piping and reactor pressure vessel
cladding and structures inside the pressure vessel,
including the core shroud (which separates the primary water upward flow through the core from the
downward flow in the annulus), the core plate (which
supports the bottom of the fuel), the top guide
(which aligns the top of the fuel bundles), the shroud
dome, the steam separators, etc. Austenitic stainless
steel is also largely used for other components such
as pumps, valves, shafts, sleeves, and in auxiliary systems such as water tanks.
The material choices for PWRs are essentially the
same. The steam generator (SG) tubes are made of
Chemical composition of common stainless steel alloys
Type
C (max.%)
Mn (max.%)
Si (max.%)
P (max.%)
S (max.%)
Cr
304
0.08
2.00
1.00
0.045
0.030
18.020.0
8.0010.5
304L
0.03
2.00
1.00
0.045
0.030
18.020.0
8.0012.0
304LN
0.03
2.00
1.00
0.045
0.03
18.020.0
8.0012.0
Z2CN19-10
316
0.035
0.08
2.00
2.00
1.00
1.00
0.040
0.045
0.030
0.030
18.520.0
16.018.0
9.010.0
10.014.0
2.003.00
316L
0.030
2.00
1.00
0.045
0.030
16.018.0
10.014.0
2.003.00
316LN
0.030
2.00
1.00
0.045
0.030
16.018.0
10.014.0
2.003.00
Z2CN18-12
321
0.038
0.08
2.00
2.00
1.00
1.00
0.040
0.045
0.030
0.030
17.018.2
17.019.0
11.512.5
9.0012.0
2.252.75
347
0.08
2.00
1.00
0.045
0.030
17.019.0
9.0013.0
Source: Wegst, C. E. Stahlschluessel Key to Steel; Stahlschluessel Wegst GmbH: Marbach, 1995.
a
The corresponding alloys according to the Swedish SS and the German DIN standards are also given.
Ni
Mo
Others
SS 2333/SS 2332
DIN 1.4301
SS 2352 DIN
1.4306
SS 2371 DIN
1.4311
0.100.16
0.08
SS 2343/SS 2347
DIN 1.4436/DIN
1.4401
SS 2348/SS 2353
DIN 1.4404/DIN
1.4435
SS 2375 DIN
1.4429
0.100.16
0.08
Corresponding
alloysa
5 C
min. Ti
10 C
min. Nb
SS 2337 DIN
1.4541
SS 2338 DIN
1.4550
Table 1
95
96
Table 2
Minimum room temperature mechanical properties of stainless steels (hot finished and/or annealed forging)
Type
Tensile strength
(min. MPa)
0.2% yield strength

(min. MPa)
Elongation
(min.%)
Reduction
in area
(min.%)
304
304L
304LN
Z2CN1910
316
316L
316LN
Z2CN1812
321
347
515
450
515
510
515
450
515
510
515
515
205
170
205
210
205
170
205
210
205
205
40
40
40
35
40
40
40
35
40
40
50
50
50
50
70
50
50
Source: Davis, J. ASM Specialty Handbook; ASM International: Materials Park, OH, 1994; ASM Standard A 240.
Ti-stabilized stainless steel in the Russian designed

Waterwater energetic reactors (VVERs), which are
PWRs with slightly different water chemistry and
horizontal instead of vertical SGs, as in Western
PWRs. The SG tubes in western PWRs are made
of nickel-based materials (Alloy 600, 690, or 800).
Further, both the SG vessel and the pressurizer are
clad with austenitic stainless steel.
5.05.2 Stress Corrosion Cracking

SCC is a failure mode caused by a combination of a
susceptible material, stresses, and an aggressive environment (Figure 1). There are two modes of SCC in
austenitic stainless steel, namely intergranular and
transgranular stress corrosion cracking (IGSCC and
TGSCC). IGSCC in austenitic stainless steel is the
major failure mode in BWRs, while it has not been
considered as a plausible failure mode in PWR primary water under normal operation conditions.
However, the number of IGSCC cases in PWRs has
increased by time, showing that PWRs are not totally
immune to IGSCC.
Most TGSCC cases are due to chloride-induced
SCC. TGSCC is rare in the primary system, and
the failure cases are typically observed in auxiliary
systems.
5.05.2.1
IGSCC in BWR Environment
In this section, the main factors affecting IGSCC in

BWR environment are reviewed, that is, degree of
sensitization, deformation, electrochemical corrosion
potential (ECP), water purity, and stress. Also several
Region of
potential stress
corrosion cracking
Stress
Environment
Material
susceptibility
Figure 1 The classic presentation of stress corrosion

cracking includes the three circles: material, environment,
and stress. Reproduced from General Electric Company.
Alternative Alloys for BWR Pipe Application; NP-2671-LD,
Final Report; San Jose, CA, 1982, with permission from
BWR Owners Group.
other parameters affect IGSCC susceptibility, but a

comprehensive description of these is out of the scope
of this chapter. Among these parameters are temperature, hydrogen, mechanisms related to localization
of deformation and to corrosion deformation interactions, such as effect of strain rate, subtle differences in
chemical composition, dynamic strain aging, dynamic
recovery, vacancy injection, selective dissolution, grain
boundary segregation, and relaxation.921
5.05.2.1.1 Degree of sensitization
Sensitization is the result of nucleation and growth of

chromium-rich carbides M23C6 at the grain boundaries, which results in a depletion of chromium at the
grain boundaries because of faster diffusion rate
along the grain boundaries compared to that within

the grain interior. Chromium-rich carbides form
within the temperature range of 500750 C, but
continue to grow down to much lower temperatures.
Sensitization can therefore occur as thermal sensitization during heat treatment and welding or as lowtemperature sensitization during long-time exposure
to LWR temperatures, below the chromium-rich carbide precipitation temperature.22 In the latter case,
the nucleation of carbides must have occurred previously, and the nucleated carbides grow during the
long-time exposure and deplete the grain boundaries
of chromium. The degree of sensitization is typically
measured using the EPR test, which is sensitive to the
area where the grain boundary chromium content is
below 15%, and is, thus, not a true measure of the

grain boundary chromium content.
The time for carbide precipitation increases as the
carbon level decreases as seen in Figure 2. Nitrogen
alloying delays carbide precipitation (Figure 3),
while deformation accelerates diffusion and precipitation. The obvious remedy to avoid sensitization
is, thus, to decrease the amount of free carbon, as
explained earlier, by reducing the carbon content, or
by tying carbon to Ti- or Nb-carbides and by
restricting the degree of deformation.
IGSCC in sensitized stainless steels occurs typically in the weld HAZ at a distance of 48 mm from
the fusion line, at the location where a high degree of
sensitization combined with high residual stresses
1000
1800
900
800
1400
316L (0.027% C)
316 (0.07% C)
Temperature (F)
Temperature (C)
1600
304 (0.053% C)
700
1200
600
1000
500
100
101
102
103
104
Time (min)
900
800
1832
0.069% N
0.145% N
0.247% N
1652
0.039% N
1472
700
1292
600
1112
500
0.01
0.1
10
Time (h)
100
1000
932
Precipitation temperature (F)
Precipitation temperature (C)
Figure 2 Timetemperatureprecipitation diagram for stainless steels with different carbon contents. Reproduced
from Shah, V. N.; MacDonald, P. E. Aging and Life Extension of Major Light Water Reactor Components; Elsevier:
Amsterdam, 1993.
1000
97
Figure 3 Effect of nitrogen on precipitation of M23C6 in a 0.05C17Cr13Ni5Mo stainless steel. Reproduced from
Peckner, D.; Bernstein, I. M. Handbook of Stainless Steels; McGraw-Hill: New York, 1977; pp. 4-354-53, pp 751757.
98
results in most severe conditions for IGSCC. The

typical location of IGSCC is different in nonsensitized stainless steels, where IGSCC occurs very close
to the fusion line, within the first few grains.
5.05.2.1.2 Deformation
Deformation increases the susceptibility of stainless

steels to IGSCC, in sensitized as well as in nonsensitized stainless steels, where the role of strain is decisive. Deformation occurs as bulk cold work from
rolling, bending, grinding, etc., as surface cold work
from machining, grinding, etc. and as weld shrinkage
from welding. Weld shrinkage can lead to up to 25%
equivalent room temperature strain in the weld HAZ
(Figure 4). The highest degree of deformation occurs
very close to the fusion boundary, and this is also the
location of observed IGSCC cracking in nonsensitized stainless steels pipes.2327 The importance of
cold deformation in IGSCC is shown in Figure 5.
Deformation is estimated to be the main affecting
parameter in 50% of all IGSCC cases covered in
the survey (including sensitized and nonsensitized
stainless steels). The effect of deformation has been
studied using bulk-deformed materials,2835 and the
results show a correlation between IGSCC crack
growth rate (CGR) and yield strength (Figure 6).
20
Various BWR stainless steel

weld HAZs
% Strain
15
10
10
15
20
25
30
35
Distance from weld fusion line (mm)

Figure 4 Deformation versus distance from the weld
fusion line in various stainless steel weld HAZs. Deformation
is expressed in terms of equivalent tensile strain at room
temperature, and results from weld shrinkage strains
during welding. Reproduced from Andresen, P. L.; et al.
In Corrosion 2000, NACE 55th Annual Conference,
Orlando, FL, Mar 2631, 2000; p 12, Paper No. 00203,
with permission from BWR Owners Group.
Much effort is nowadays put on deformation in

terms of restrictions on bulk and surface deformation
and on the development of sophisticated surface treatment procedures to remove surface cold work at critical locations.36,37 Application of narrow-gap welding
results both in a decrease in the degree of deformation
in the HAZ and in lower residual stresses. It should be
pointed out that some components, such as bolts, can
be made of intentionally cold-worked stainless steel to
increase the material strength.
5.05.2.1.3 Environment
As mentioned earlier, one of the main reasons for the

good behavior of austenitic stainless steels in LWR
conditions is the formation of a protective passive
film in high-temperature water (around 300 C).
The oxide film formed in high-temperature water
has a double-layered structure. The inner layer
grown on the metal surface consists of a chromium
spinel or magnetite and is covered by an outer layer
of magnetite or FeNi spinel precipitated from the
aqueous phase.38,39 The double-layered oxide structure forms so that faster diffusing elements pass
through the inner layer to the outer layer while the
slower diffusing elements, such as chromium, remain
in the inner layer and therefore the outer layer contains mainly of iron and the inner layer is enriched
with chromium. Although consensus is not yet reached
on the mechanistic details for corrosion and SCC in
LWR environments, breakage of the passive film is
generally considered to be of major importance
because of the fact that if the oxide film breaks, the
corrosion rate is high until passivation occurs.28,40,41
The CGR of IGSCC is highly dependent on the
oxidizing power of the environment, that is, the ECP
(Figure 7). The corrosion potential increases as the
oxygen content increases in the high-temperature
Cold work
Chemistry
Material
Nuclear grade
Ni-base alloy
Weld repair
Residual stresses
Sensitization
Figure 5 Cause of IGSCC in Swedish nuclear power

plants. Cold work is the biggest singular parameter affecting
IGSCC. Gott, K. Personal communication, April 2010.
99
1E 06
Very high
martensite
Unsensitized 304, 304L and 316L SS and A600

288 C high purity water, 2000 ppb O2
CT tests at 27.530 MPa m
Circles = High martensite SS
Triangles = Alloy 600
Predicted
response
Two sensitized points
for comparison
1E 07
Very low or no
martensite
Annealed cold worked
1E 08
0
100
200
300
400
500
Yield strength (MPa)
600
700
800
Figure 6 Effect of yield strength (and martensite content) on stress corrosion crack growth rate of unsensitized stainless
steels in oxygenated, high purity water. The predicted response is based on the PLEDGE model (plant life extension and
diagnosis by GE). Reproduced from Andresen, P. L.; et al. In Proceedings of 11th International Symposium on Environmental
Degradation of Materials in Nuclear Power Systems Water Reactors, Stevenson, WA, Aug 1114, 2003; American Nuclear
Society: La Grange Park, IL, 2003; p 435, with permission from BWR Owners Group.
water, but it is not a linear relationship, and small

changes in oxygen concentration can result in large
changes of ECP and CGR. Important to notice is
that the correlation between CGR and ECP is different for sensitized stainless steels and deformed, nonsensitized stainless steels, which show much higher
CGRs compared to sensitized materials at low potentials (although lower than at high ECP).
Two solutions to lower the ECP in BWRs have
been developed, that is, hydrogen water chemistry
(HWC) developed by General Electric and Asea
Brown Boveri, and noble metal chemistry addition
(NMCA, NobleChem), developed by General Electric. The ECP in a BWR recirculation circuit during
normal operation and using normal water chemistry
(NWC), that is, 200 ppb oxygen, is above 100 mVSHE.
The ECP is still higher in the core because of radiolytic decomposition of water forming hydrogen peroxide, H2O2. The ECP is remarkably lower in plants
using either HWC, where 40250 ppb hydrogen is
added to the feed water, or noble metal chemistry
(NMC), where a small amount of platinum is
added to the reactor water either at about 130 C
during startup or during full power operation
(OnLine NobleChem), creating an electrocatalytic
surface layer.42,43 The ECP of the buffered PWR
environment is in the lower range of the ECP curve,
that is, about 600 mVSHE. The trend, especially for
the US BWR fleet is toward HWC and NMCA. None
of the US BWR plants operates on NWC, and 75%

apply NMCA.44 The majority of the European BWRs
operate on NWC.
Water purity has a profound effect on both crack
initiation and CGR in oxidizing environments. The
main concerns are chlorides and sulfates for SCC and
additionally copper for pitting corrosion (although Cu
also has a synergistic effect on SCC). Sulfate and/or
chloride levels already in the ppb-range increase the
IGSCC susceptibility. Power plants monitor online the
conductivity, which is a mirror for water purity, and
analyze the amounts of impurities on regular basis
from grab samples. The conductivity of BWR primary
water of today has been reduced from a typical range
of about 0.4 mS cm1 in the 1970s to 0.10.2 mS cm1
(the conductivity of theoretically pure water is
0.056 mS cm1).
Dissolved oxygen is consumed inside cracks and
crevices, and the local ECP is reduced to low levels,
creating a potential gradient between the outer surface and the crack tip. This results in migration of
anions into the lower potential area, which results in
very high anion levels in the crack despite low levels
in the surrounding environment.45 Further, the local
environment in a crack can remain aggressive for a
long time after, for example, short periods of higher
impurity levels in the bulk environment.
It is not only the environment during steadystate operation that needs attention, but also the
100
Sensitized 304 stainless steel

30 MPa m, 288 C water
0.060.4 S cm1, 025 ppb SO4
SKI Round Robin Data
Filled triangle = Constant load
Open squares = Gentle cyclic
200 ppb O2
500 ppb O2
2000 ppb O2
1E-05
4 dpa
304SS
106
316L stainless steel
25 mm CT specimen
constant load
288 C water
Test conditions:
-2
0 C cm EPR
27.5 MPa m
200 ppb O2
20% CW
A600
316L (A14128, square)

304L (Grand Gulf, circle)
non-sensitized SS
50%RA 140C (black)
10%RA 140C (grey)
1E-07
42.5
28.3
14.2
mh1
20% CW A600
GE PLEDGE
predictions
30 MPa m
sens SS
0.5
2000 ppb O2
Ann. 304SS
200 ppb O2
0.25
1E-08
1E-06
107
108
0.1 S cm
Means from analysis of
120 L sens SS data
0.06 S cm1
0.06 S cm1
0.1
Predicted curves from

PLEDGE code for
typical range in ECP
GE PLEDGE predictions for

unsens. SS (upper curve for 20% CW)
1E-09
0.6 0.5 0.4 0.3 0.2 0.1 0.0 0.1 0.2
(a)
Corrosion potential (VSHE)
109
0.3 0.4
(b)
101
100
101
Solution conductivity (S cm1)
Figure 7 Summary of crack growth rates of sensitized stainless steels versus corrosion potential, ECP (a) (reproduced
from Andresen, P. L.; Morra, M. M. J. Nucl. Mater. 2008, 383(12), 97111) and for nonsensitized stainless steels versus
solution conductivity (b) (reproduced from Andresen, P. L. Corrosion 1988, 44(7), 450). The prediction curves for different
water conductivity levels are according to the PLEDGE model, with permission from BWR Owners Group. RA reduction
in area; CW cold work.
environment during shutdown, downtime periods,

and during startup. The possible role of these will
increase with plant age and amount of shutdowns and
startups.
5.05.2.1.4 Stress
The stresses causing IGSCC are a combination of

residual and operational stresses, although the first is
considered more decisive in IGSCC failures. This is
because operational stresses are kept low by design
and components are usually designed to operate
below 80% of their yield strength. The CGR of
intergranular stress corrosion cracks increases with
increasing stress intensity factor (K ) (Figure 8). The
effect of stress intensity on CGR varies depending on
the material and environment. Knowledge of the
dependency between K and CGR is very important
for structural integrity calculations, which are made
to show that flaws, either postulated or detected using
nondestructive inspections, are tolerable and do not
pose a safety risk. Huge efforts have been put on the
production of high-quality laboratory CGR data and
efforts are still going on. Approved relationships (i.e.,

agreement reached between national safety authority
and plant operators) are called disposition lines, and
examples of published lines are shown in Figure 8.
Several methods to mitigate IGSCC have been
applied over the years, such as last pass heat sink
welding, mechanical stress improvement, and weld
overlay cladding.46 All these aim at producing a compressive stress state in the HAZ. However, these
methods are usually applied as temporary remedies.
Measurement of residual stresses is an area of
increased focus nowadays, and lack of knowledge can
result in excessive under- or over-conservatism in
design and in structural integrity calculations. Also
other stress-related factors affect IGSCC, such as
vibratory loading, thermal loads from, for example,
stratification, as well as load cycles during shutdowns
and startups. Much effort was earlier put on defining
the KISCC; that is, the stress intensity, below which SCC
would not occur. With improved laboratory testing
techniques, lower and lower KISCC values have been
measured and a true threshold value may not exist.
101
1E 04
NRC 0313, BWR NWC
MD-01, BWR NWC
JSME, BWR NWC
JSME, BWR HWC
Crack growth rate (mm s )
1E 05
1E 06
1E 07
1E 08
1E 09
1E 10
1E 11
10
20
30
40
50
60
Stress intensity (MPa m)
70
80
90
Figure 8 Crack growth rate versus stress intensity according to dispositions lines for sensitized stainless steels in
normal water chemistry boiling water reactors environment. Compiled by author from NRC Generic Letter GL880011. NRC
Position on IGSCC in BWR Austenitic Stainless Steel Piping; January 25, 1988; http://www.nrc.org; Jansson, C.; Morin, U.
In Proceedings of 8th International Symposium on Environmental Degradation of Materials in Nuclear power Systems Water
Reactors, Amelia Island, FL, Aug 1014; American Nuclear Society: La Grange Park, IL, 1997;
pp 667674; Kobayashi, H.; Kashima, K. Int. J. Press. Vess. Pip. 2000, 77, 937944. JSME is the Japan Society of
Mechanical Engineers; NRC is the Nuclear Regulatory Commission.
5.05.2.1.5 Components at risk
The earliest incidents of SCC in BWRs occurred in

stainless steel fuel cladding, before zirconium alloys
were used.47 IGSCC plagued the BWRs in the 1970s
and caused a clear reduction in capacity factors. Cracking was first observed in the recirculation and water
cleanup systems in pipes with small diameter and later
also in larger diameter pipes. The material was mainly
Type 304 with a high carbon content of 0.6%. Owing
to large efforts to solve the problem, including the
development of Type 316NG, narrow-gap welding
technique, as well as low-potential water chemistries,
the number of IGSCC incidents has remarkably
reduced.3 In the late 1980s, cracking in Ti-stabilized
stainless steel piping was detected.4850 Robust mitigation measures, including adoption of narrow-gap
welding, change of material to Nb-stabilized stainless
steel with higher stabilization ratio requirements, and
reduction of the amount of welds, were applied in
Germany to solve the problem. Also from Russian
channel type graphite moderated reactors (RBMKs),
which operate under BWR-like conditions, numerous
IGSCC cases have been reported.51,52 In the 1990s,
the first cases with IGSCC in nonsensitized stainless
steels were reported in BWRs,23,25 first in pipings,
and later numerously in core shrouds.27 Deformation
(weld shrinkage in piping and surface grinding in
the core shrouds) is considered to be of major importance in these cases.

5.05.2.2
IGSCC in PWR Environment
PWRs operate at low corrosion potentials and very

low oxygen levels, <30 ppb. The risk of IGSCC
in austenitic stainless steels in nonoxidizing environment is, thus, much lower than in NWC BWR
environment.31,53 Incidences with IGSCC under nominal PWR conditions have not been reported. Oxygen
can, however, be enclosed in certain situations, such as
startups, and can lead to IGSCC in austenitic stainless
steels. Although the number of IGSCC cases in PWRs
is still very low, the number seems to be increasing.54,55
IGSCC has been observed in pressurizer heater
sleeves, canopy seals in the control rod drives, SG
safe-ends, etc. Laboratory tests on cold-worked stainless steels show that IGSCC is possible also in normal
PWR environment, indicating (although not generally accepted) that more IGSCC failures may occur in
the operating PWR plants with time.
5.05.2.3 TGSCC in BWR and PWR
Environments
Austenitic stainless steels are prone to TGSCC when
exposed to aggressive oxidizing water, for example,
102
containing chlorides, under sufficiently high stresses.

As chloride levels in BWR and PWR primary systems
are kept low, TGSCC is rare under normal operating
conditions. The exception is TGSCC from the secondary side in VVER SG tubes, manufactured of
Ti-stabilized stainless steels. Condenser leakages, frequently reported in VVERs, can result in chloride
contamination of the secondary water and eventually
in TGSCC in the SG tubes. Copper release from brass
condensers and crevices formed by iron deposits further enhance both TGSCC and pitting corrosion on
the secondary side of the SG tubes.
A risk of TGSCC exists at locations where (a slow)
buildup of aggressive conditions can occur. The risk
of TGSCC increases with plant age, as the buildup of
aggressive conditions can be very slow and can occur
at unknown (uninspected) locations. Known chloride
sources are old insulation and sealing materials (e.g.,
asbestos), leakage from cables, polymers, paints, concrete, etc. Wet insulation is the worst of these, as
the insulation provides crevice conditions in addition
to a chloride source. Strict regulations for expendables
(grease, cleaning agents, sealing materials, etc.) allowed
in NPPs are applied to reduce the risk of buildup of
aggressive conditions. All bare outer surfaces of austenitic stainless steel components, where humidity
may exist, can be at risk for TGSCC.
TGSCC has been reported in valves,56 for example, where the source for the chlorides is assumed to
be asbestos sealing used early in time and in water
tanks, where chlorides probably stem from humidity
and concentration buildup at the waterline. Stainless
steel bellows in the BWR reactor containment are, in
principle, at risk because of the high degree of cold
work in the bellows. However, no SCC has been
reported in these. New components can also be at
risk for TGSCC, if proper measures are not taken to
avoid contamination of components during transportation, storage, and installation.
TGSCC can occur in oxidizing concentrated boric
acid solutions although laboratory results are not fully
conclusive whether chloride is also needed or not.5658
is very often observed at same locations as TGSCC, but

pitting corrosion can also occur without SCC and vice
versa. The risk of pitting corrosion under normal BWR
conditions is extremely low. However, pitting corrosion
can occur in pressure boundary systems at locations
where (slow) buildup of aggressive local conditions can
occur. Such locations are, for example, areas with low
water flow, dead ends, and valves with sealing.
As pitting occurs only in oxidizing conditions, it is
not a plausible degradation mechanism in PWR primary water under nominal environmental conditions.
However, the environment may be oxidizing both
locally and/or temporarily because of startups, for
example. Different systems during shutdown may be
filled with air, and this may cause air pockets during
startup. The oxygen from air will then dissolve into
the primary water and local oxidizing conditions
temporarily emerge until the oxygen is consumed by
the oxidation of metal surfaces. The risk of pitting
corrosion (and TGSCC) is, however, highest in auxiliary systems, for example, at outer surfaces, where the
temperature is low enough for condensation to occur.
Thus, pitting corrosion can occur at nominally dry
locations. Accumulation of aggressive local conditions
is enhanced by crevices.
The sources of chlorides were listed earlier.
Sulfate sources have been introduced earlier, for
example, in molybdenum disulfide greases, but
since the harmful influence of this material was identified, it is not an allowed expendable material. Again,
copper can enter the system from copper-containing
structural components.
Pitting corrosion is seldom considered to pose a
safety problem, as the wall thicknesses of pressure
boundary components are usually large enough to
sustain pitting corrosion for long times without leakage. However, pitting corrosion is always an indication of a harmful environment existing at the location
and is often associated with the risk of TGSCC,
which can cause wall cracking in short time periods.
Pitting corrosion enhances the risk of SCC as the pits
increase the local stress concentration and thus act as
crack initiators. Observation of pitting corrosion shall
therefore not be omitted as insignificant.
5.05.3 Pitting Corrosion

Pitting corrosion occurrence has several similarities to
TGSCC, that is, it requires oxidizing conditions and
presence of water with harmful ions, such as chlorides,
fluorides, sulfates, and/or copper, but no stress is needed.
The Type 304 stainless steel is more prone to pitting
corrosion than Type 316 stainless steel. Pitting corrosion
5.05.4 Microbiologically Induced

Corrosion
A rather rare corrosion mode is microbiologically
induced corrosion, or nowadays, microbiologically influenced corrosion (MIC). MIC is normal
electrochemical corrosion where the microorganisms

either chemically or physically change the conditions
on the metal surface to be favorable to corrosion.59
MIC appears as localized corrosion rather than as
uniform corrosion, and in welds rather than in base
materials. Pitting corrosion in the weld metal can
cause preferential attack of either the austenite or
the ferrite phase of the weld metal. The microorganisms of interest in MIC are mostly bacteria and fungi.
The highest risk of MIC is at temperatures from 15
to 45 C and near neutral pH, that is, in the range
from 6 to 8. MIC has been observed in fire-fighting
systems, for example.
MIC is stopped with great difficulty once it is
established due to the high sustainability of the microorganisms involved. The quality of the water in all
phases of the lifetime of the equipment is, thus, very
important at locations with risk of MIC. Water of high
quality must be used, not only during normal operation,
but also during hydrotesting of the system, for example.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
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5.06 Corrosion and Environmentally-Assisted Cracking of

Carbon and Low-Alloy Steels
H.-P. Seifert
Paul Scherrer Institut, Villigen PSI, Switzerland
J. Hickling
Independent Technical Consultant, Prastio-Avdimou, Cyprus
D. Lister
University of New Brunswick, Fredericton, NB, Canada
5.06.1
Introduction
107
5.06.2
5.06.2.1
5.06.2.2
5.06.2.2.1
5.06.2.2.2
5.06.2.2.3
5.06.3
5.06.3.1
5.06.3.2
5.06.3.2.1
5.06.3.2.2
5.06.3.2.3
5.06.3.2.4
5.06.3.2.5
5.06.4
5.06.4.1
5.06.4.2
References
Uniform and Flow-Accelerated Corrosion

Uniform Corrosion
Flow-Accelerated Corrosion
Controlling factors
Mechanisms and models
Service experience and mitigating actions
Localized Corrosion and Environmentally Assisted Cracking
Pitting
Environmentally Assisted Cracking
Basic types of EAC and major factors of influence
Corrosion fatigue and strain-induced corrosion cracking
EAC mechanisms and models
Service experience and mitigation actions
Conclusions
Uniform and Flow-Accelerated Corrosion
Localized Corrosion and Environmentally Assisted Cracking
109
109
111
111
114
118
120
120
122
122
123
128
132
136
139
139
139
140
Abbreviations
AC
AGR
ANL
ASME
ASME BPV
ASME III
ASME XI
ASTM
BWR
BWRVIP
BWRVIP-60
Content of Cr, Mo and Cu in alloy in

EPRI CHECWORKS FAC-Code
Advanced gas-cooled reactor
Argonne National Laboratory, USA
American Society of Mechanical
Engineers
ASME Boiler and Pressure Vessel
Code
Section III of ASME BPV Code
Section XI of ASME BPV Code
American Society of Testing and
Materials Standards
Boiling Water Reactor Vessel and
Internals Program
Basis document for SCC
disposition lines for low-alloy
steels
CANDUW
CF
CRDM
CS
DCPD
DH
DL
DO
DSA
EAC
EC
ECP
ECPcrit
CANada Deuterium Uranium,

PHWR developed by Atomic Energy
of Canada Ltd.
Corrosion fatigue
Control rod drive mechanism
(housing)
Carbon steel
(Reversed) direct current potential
drop crack length measurement
method
Dissolved hydrogen (concentration)
Disposition line
Dissolved oxygen (concentration)
Dynamic strain ageing
Environmentally assisted cracking
Erosion corrosion
Critical cracking potential (e.g., for
SICC)
105
106
Corrosion and Environmentally-Assisted Cracking of Carbon and Low-Alloy Steels
EPRI
Electric Power Research Institute,

USA
F & A model EAC model for CS & LAS developed
by P. Ford and P. Andresen (GE GR)
FAC
Flow-accelerated corrosion
FRAD
Film rupture anodic dissolution EAC
mechanism
HAEAC
Hydrogen-assisted EAC
mechanism
HAZ
Heat-affected zone of weldment
HCF
High-cycle fatigue
HT
High temperature
HWC
JSME
Japanese Society of Mechanical
Engineers
LAS
Low-alloy steel
LCF
Low-cycle fatigue
LEFM
Linear elastic fracture mechanics
LWR
Light water reactor
MT
Mass transfer in EPRI
CHECWORKS FAC-Code
NDT
Nondestructive testing
NMCA
Noble metal chemical addition
NRC
Nuclear Regulatory Commission,
USA
NWC
Normal water chemistry
PHWR
Pressurized heavy water reactor
PWHT
Postweld heat treatment
PWR
PWSCC
Primary water stress corrosion
cracking (in PWRs)
QT
Quench and temper heat treatment
RPV
Reactor pressure vessel
SCC
SEM
SHE
Standard hydrogen electrode
SICC
Strain-induced corrosion cracking
SS
Stainless steel
SSR(T)
Slow strain rate (test)
SSY
Small-scale yielding
UTS
Ultimate tensile strength
VGB
German Association of Large Power
Plant Operators
YS
Yield strength
Ceq
Symbols
KI
KI,i
C
Cb
Concentration of Fe(II) species at

the oxidecoolant interface
Concentration of Fe(II) species in
the bulk coolant
CODLL
d
D
da/dN
da/dNAir
da/dNCF
da/dtAir
da/dNAir/
DtR
da/dtCF
da/dNCF/
DtR
da/dtSCC
da/dtSICC
dCODLL/dt
de/dt
de/dtcrit
dKI/dt
EA
Fen
G
h
kc
kd
Thermodynamic equilibrium
concentration of Fe(II) species
Crack-opening displacement at
load line in precracked fracture
mechanics specimen
Pipe diameter
Diffusivity
Crack advance per fatigue cycle
Crack advance per fatigue cycle in
air
Corrosion fatigue crack advance
per fatigue cycle in hightemperature water
Time-based fatigue crack growth
rate in air
Time-based corrosion fatigue
crack growth rate in hightemperature water
SCC crack growth rate
SICC crack growth rate
Crack-opening displacement rate
in slow rising load or displacement
test
Strain rate (sometimes locally at
crack-tip)
Critical strain rate (e.g., for SICC)
Stress intensity factor rate in slow
rising load or displacement test
Arrhenius activation energy of
thermally activated process
Environmental correction factors,
ratio of fatigue life in air at room
temperature to that in water at
service temperature
Geometry factor in EPRI
CHECWORKS FAC-Code
Mass transfer coefficient for Fe(II)
species from the oxidecoolant
interface to the bulk environment
by convection
Geometry factor in Siemens-KWU
WATHEC FAC-Code
Dissolution reaction rate constant
of magnetite at the oxidecoolant
interface
Stress intensity factor (LEFM)
Stress intensity factor at the onset
of SICC crack growth in slow rising
load tests with precracked fracture
mechanics specimens
KIJ
Stress intensity factor at the onset

of ductile crack growth
m
Paris law exponent for fatigue and
corrosion fatigue
n
Frequency exponent for corrosion
fatigue
pH log[H] pH value
R
Load ratio of minimum to
maximum load
Flow-accelerated corrosion rate
RFAC
Dissolution rate of magnetite at the
Rd
oxidecoolant interface
Formation rate of magnetite at the
Rg
metal/oxide interface
Mass transport rate of Fe(II)
Rm
species from the oxidecoolant
interface to the bulk environment
by convection
Re dur/m
Reynolds number
Sc m/( rD)
Schmidt number
Sh hd/D
Sherwood number
t
Time
T
Temperature
u
Coolant velocity
Z
Reduction of area in tensile test
[X]
Concentration of element/species
X in water or in alloy
a
Steam void fraction in EPRI
CHECWORKS FAC-Code
DC Ceq Cb Undersaturation in dissolved Fe(II)
species
Dd
Wall thinning
DK KI,max Stress intensity factor range of
KI,min
fatigue cycle
Upper DK threshold for corrosion
DKCF,H
fatigue
Lower DK threshold for corrosion
DKCF,L
fatigue
DK threshold for fatigue in air
DKth, Air
Decline time (down-ramp) of
DtD
fatigue cycle
Hold time at maximum load of
DtH
fatigue cycle
Rise time (up-ramp) of fatigue cycle
DtR
e
Mechanical strain
Critical strain (e.g., for SICC)
ecrit
k
Specific electrical conductivity
m
Viscosity of coolant
n
Loading frequency
Upper critical frequency for
ncrit,H
corrosion fatigue
ncrit,L
r
s
scrit
t
107
Lower critical frequency for

corrosion fatigue
Density
Mechanical stress
Critical stress (e.g., for SCC)
Fluid shear stress at pipe wall
5.06.1 Introduction
Carbon and low-alloy steels (CS & LAS, Table 1)
and their associated weld filler metals are widely
used for pressure vessels and piping in both the
primary and secondary coolant circuits of watercooled reactors (light water reactors (LWRs) and
CANDUs pressurized heavy water reactors
(PHWRs)), as well as in service water systems.1
The main reasons for the use of CS & LAS are
their combination of relatively low cost, good
mechanical strength and toughness properties in
thick sections (hardenability), and good weldability,
as well as their good stress corrosion cracking (SCC)
resistance in primary coolant environments. Compared with austenitic stainless steels and nickel-base
alloys, ferritic CS & LAS exhibit only moderate
corrosion and irradiation resistance. They also show
a ductile-to-brittle transition in toughness properties
at lower temperatures.
CS & LAS components in the primary circuit of
pressurized water reactors (PWRs) are clad (usually
with austenitic stainless steel) and thus do not generally come into direct contact with the reactor coolant.
This is also the case for the reactor pressure vessel
(RPV) in boiling water reactors (BWRs), although
the RPV head is sometimes left unclad and the cladding has been removed from the blend radius of many
RPV feedwater nozzles. In BWRs of German and of
newer General Electric designs, extensive use is also
made of unclad LAS and CS in both the feedwater and
steam lines, as well as in the condensate system. The
primary coolant piping in conventional CANDUs is
made exclusively of unclad CS. In secondary coolant
systems, the steam generator pressure vessel shell is
unclad, as are the feedwater, drain, and steam lines.
CS & LAS pressure-boundary components, in particular in the primary circuit such as the RPV, are
very critical systems with regard to plant safety and
lifetime (extension). Minimizing corrosion improves
plant availability and economics and is also fundamental for safe operation over extended periods of
5060 years.
108
Typical CS & LAS piping and pressure vessel materials in Western LWRs (US designation, according to Section II of ASME BPV Code)
Designation
Type
Product
form
Cmax
(%)
Mn
(%)
Pmax
(%)
Smax
(%)
Simin
(%)
Cumax
(%)
Nimax
(%)
Crmax
(%)
Momax
(%)
Vmax
(%)
YS25 C
(MPa)
Heat
treatment
Microstructure
SA 106 Gr. B
CS
CMn
Pipe drawn
0.30
0.29
1.06
0.035a
0.035a
0.10
0.40a
0.40b
0.40b
0.15b
0.08b
240
300400c
Normal.
Ferriticpearlitic
SA 333 Gr. 6
CS
CMn
Pipe drawn
0.30
0.29
1.06
0.025a
0.025a
0.10
240
300400c
Normal.
Ferriticpearlitic
SA 516 Gr. 70
CS
CMn
Vessel plate
0.27d
0.79
1.30
0.03a
0.035a
0.13
0.45
260
300400c
Normal.
Ferriticpearlitic
SA 533 B Cl.1
LAS
MnMoNi
(R)PV plates
0.25
1.07
1.62
0.12e
(0.35)
0.15e
(0.35)
0.13
0.45
0.10e
0.37
0.73
0.41
0.64
0.05
345
450550c
Q&T
Bainitic
SA 508 Gr. 3 Cl. 1
LAS
MnMoNi
(R)PV
forging
0.25
1.20
1.50
0.12e
(0.25)
0.15e
(0.25)
0.15
0.40
0.10e
0.40
1.00
0.25
0.45
0.60
0.05
345
450550c
Q&T
Bainitic
SA 508 Gr.2 Cl. 1
LAS
NiMoCr
(R)PV
forging
0.27
0.50
1.00
0.12e
(0.25)
0.15e
(0.25)
0.15
0.40
0.10e
0.50
1.00
0.25
0.45
0.55
0.70
0.05
345
450550c
Q&T
Bainitic
In modern steels, these values are less than 0.015%.

Combination shall not exceed 1.0%.
c
Typical range.
d
Carbon varies with thickness up to 0.31%.
e
Requirement for core belt region.
YS yield strength; Normal. normalized; Q & T quenched and tempered.
b
Table 1
Consideration of both uniform and flowaccelerated corrosion (FAC) behavior for all unclad
surfaces is important for corrosion product transport
and deposition (e.g., crud formation on fuel elements)
but together with the assessment of resistance to
localized corrosion phenomena such as pitting and
environmentally assisted cracking (EAC) is obviously also required for integrity reasons. In the case of
EAC, however, safety considerations furthermore
require that possible defects extending through the
cladding be taken into account, so that the susceptibility of the RPV must be assessed as if no cladding were
present. Sometimes, thick pads of Alloy 182 have been
welded directly onto the RPV to act as attachment
points for internal structures; the higher yield strength
of Alloy 182, the thicker section and its known SCC
susceptibility raise special concerns for these areas.
In such cases, it is possible that SCC or thermal fatigue
of the austenitic alloy will occur such that the crack
tip propagates to the interface between the austenitic
and ferritic alloys. Furthermore, leakage of coolant
from the primary circuit in PWRs poses a special
hazard for CS & LAS components, since the boric
acid it contains can concentrate and lead to uniform
corrosion, or wastage, of external surfaces.
This chapter covers both the uniform and localized corrosion behavior of CS & LAS pressureboundary components in the primary (BWR, PWR,
and CANDU) and secondary (PWR and CANDU)
coolant systems of Western reactors, whereby the
discussion is focused on relevant US nuclear codes
and rules together with material standards in this
area. Special emphasis in Sections 5.06.2 and 5.06.3
is placed on FAC and on EAC, both of which have
resulted in serious pipe ruptures (FAC) or leaks (EAC)
during both nuclear and fossil service in the past.
In Section 5.06.2, the uniform and boric acid
corrosion behavior of CS & LAS, as well as the nature
of the protective oxide film on these materials, are
summarized first, followed by a condensed review of
the FAC behavior of these steels. The major factors
controlling FAC, the underlying mechanism and predictive models, as well as the relevant service experience and possible mitigation actions are discussed.
After a brief overview of pitting in CS & LAS in the
first part of Section 5.06.3, crack initiation susceptibility conditions and crack growth behavior are discussed in detail for the different types of EAC and
compared with the relevant design codes and crack
growth disposition curves for CS & LAS. This is
followed by a review of the mechanistic understanding of EAC and of existing EAC models. LWR service
109
experience and mitigation actions with regard to

EAC are then summarized and compared with this
experimental and theoretical background knowledge.
Finally, Section 5.06.4 summarizes the major conclusions of this review.
5.06.2 Uniform and FlowAccelerated Corrosion

5.06.2.1
Uniform Corrosion
Uniform or general corrosion does not normally

cause a problem for the structural integrity of CS
or LAS components in nuclear coolant systems.
Corrosion rates in typical circuits are generally of
the order of a micrometer per year (1 mm year1) or
less higher than those of stainless steel or nickelbased alloys, for example, but quite acceptable.
Around 300 C, uniform corrosion rates of CS &
LAS are minimal at a slightly alkaline pH300 C of
66.5 (neutral high-purity water has a pH300 C of
5.7) and intermediate dissolved oxygen levels. Under
some shutdown conditions, however, LWR primary
coolant can be aggressive to these materials, in particular in conjunction with increased oxygen levels
(e.g., through oxygen ingress from air); below
100 C, corrosion rates may be high. Compact,
defect-free oxide films grown at higher temperatures
during service are kinetically quite stable at lower
temperatures and usually provide sufficient protection
against uniform corrosion during short shutdown periods. Nevertheless, reactor vessels and LAS piping in
PWRs are clad with stainless steel, which helps reduce
the build-up of crud on fuel and of radiation fields by
ensuring a high degree of water purity with a low level
of dissolved iron.
A particular concern in PWRs arises from the
leakage of borated coolant from joints such as gasketed flanges and its impingement on components
such as flange studs. Up to 2001, some 140 leaks had
been reported publicly.2 Solid boric acid at room
temperature and dilute, deaerated boric acid solutions regardless of temperature have little effect
on CS & LAS, but as the boric acid concentrates, corrosion rates up to about 1 mm year1 may be reached.
Aerated solutions can be much more aggressive,
with the attack increasing with acid concentration.
Note that as hot coolant escapes to the environment,
its boric acid content (which may be nominally
2000 ppm (1 ppm 1 mg kg1; 1 ppb 1 mg kg1) or
more as elemental boron) concentrates by evaporation.
At temperatures in the neighborhood of 100 C, which
110
are attained by surfaces impacted by coolant flashing

to steam, corrosion rates can reach 250 mm year1.2
In some situations, flow effects can exacerbate the
attack, as described in Section 5.06.2.2.
The resistance of CS and LAS to corrosion is
dependent upon the protective properties of the
oxide film. Environments such as boric acid that
dissolve or erode the oxide then promote corrosion.
The predominant oxide on CS and LAS in coolant
circuits operating above about 130 C is magnetite
Fe3O4. In deoxygenated alkaline water, the magnetite
forms a double layer that has been well characterized
in terms of materials performance in boiler systems at
temperatures of about 300 C.3 This morphology is
found on CS in CANDU primary circuits, and would
be found on pressure-vessel steel exposed to PWR
primary coolant in the absence of high-alloy cladding.
The layers are formed by the simple oxidation of
the steel by water:
Fe 2H2 O FeOH2 H2
I
The nascent hydrogen is absorbed by the metal and

diffuses to the exterior. Roughly half of the ferrous
species (often as the dissolved hydroxide depending
on the pH) are precipitated oxidatively at the metaloxide interface as small crystallites of magnetite, each
a few tens of nanometers across, also releasing hydrogen to the coolant:
3FeOH2 Fe3 O4 2H2 O H2
II
The precise fraction precipitated is determined by

the density of the oxide relative to that of the metal,
since the inner layer occupies the volume of metal
corroded.3 The remainder of the dissolved iron diffuses through the oxide to the bulk coolant and precipitates according to eqn [II] as an outer layer of
magnetite crystals, each several micrometers across,
again releasing hydrogen to the coolant. If metal
species other than those of iron originate from alloy
components elsewhere in a circulating system, they
may coprecipitate and modify the locally formed
magnetite. An example of double-layer formation is
shown in Figure 1.
The concentration of dissolved iron in the coolant
governs the oxide formation. If the coolant is significantly undersaturated in iron, the outer layer cannot
precipitate and the inner layer may even dissolve at
the oxidecoolant interface. In nonisothermal systems,
temperature gradients create solubility differences and
transport iron around the circuit, modifying the oxide
films accordingly (the same phenomenon transports
different oxides around circuits containing other
Coolant flow
Precipitation
Dissolution
Outer oxide
o/s interface
Inner oxide
m/o interface
Corroding metal
Figure 1 Schematic of double layer oxide formation on

carbon steel in high-temperature water.
materials, such as the nickel-base alloys in PWRs).

Thick films may also spall and release oxide particles
to be distributed by the coolant. In circuits connected
to the reactor core, oxide transport may create deposits
on the fuel, impeding heat transfer and leading to
increased radiation fields around out-of-core components (note that the nickel-base alloys and stainless
steel in PWRs can produce deposits derived from
nickel ferrite, NiFe2O4; on high-burnup fuel undergoing subcooled boiling, these can harbor boron from
the coolant and provoke shifts in the neutron flux, as
well as affect radiation fields).
Evolved hydrogen also affects magnetite solubility
(by the one-third power of the concentration as
indicated by eqn [II]). Such increased solubility at the
metaloxide interface has been invoked as the reason
for the lack of precipitation within pores as iron diffuses to the oxidecoolant interface.4 Magnetite films
formed on steel surfaces that are pressure boundaries,
where the hydrogen evolved by eqn [I] continuously
effuses through the metal, tend to have a more adherent inner layer of larger crystallites than those formed
on totally immersed surfaces such as test coupons,
where the evolved hydrogen can only diffuse through
the oxide to the bulk coolant once the metal becomes
saturated.5
Under neutral oxidizing conditions, magnetite is
still the predominant base oxide formed on steels.6
However, since dissolved oxygen becomes the oxidant rather than water, hydrogen generation is suppressed and the basic oxidation reactions become:
2Fe 2H2 O O2 2FeOH2
6FeOH2 O2 2Fe3 O4 6H2 O
III
IV
The oxide layers especially the outer one then

tend to contain the more-oxidized forms maghemite
and/or hematite (both of formula Fe2O3), particularly in BWR circuits.7 Under reactor coolant conditions, corrosion rates and oxide solubilities under
oxidizing conditions are generally substantially lower

than those under reducing conditions. At high oxygen
levels, however, the risk for pitting and EAC increase
significantly (see Section 5.06.3).
The forms of oxide that are thermodynamically
stable under various conditions in coolant circuits are
indicated by Pourbaix diagrams, which plot the equilibrium potentials of the oxidizingreducing reactions
against pH; the higher the potential, the more oxidizing the environment. For dissolved species, the equilibria and therefore the lines in the diagram are
dependent upon the concentration; when illustrating
corrosion situations, a concentration of 106 M or less
is often assumed. It should be borne in mind, therefore,
that such diagrams are mainly indicative in nature and
illustrate the possibilities of species formation without
taking account of reaction kinetics. Figure 2, adapted
from Beverskog and Puigdomenech,8 is an example for
species pertinent to steel at 310 C, where a species
concentration of 108 M is representative. The hydrogen line in the figure represents the equilibrium:
2H2 O 2e 2OH H2
5.06.2.2
V
Flow-Accelerated Corrosion
5.06.2.2.1 Controlling factors
Flow-accelerated (or -assisted) corrosion (FAC), sometimes called erosioncorrosion (EC) in older literature,
0
0.2
Fe2O3
0.4
Fe(OH)4
0.6
Fe3O4
E(v)
Fe(OH)+
Fe(OH)2
0.8
Hydr
ogen
line
Fe(OH)3
1
Fe
1.2
1.4
6.5
7.5
8
pH310 C
8.5
9.5
Figure 2 Pourbaix diagram for iron at 108 m at 310 C.

Reproduced from Beverskog, B.; Puigdomenech, I. Corros.
Sci. 1996; 38(12): 21212135.
111
is essentially the dissolution and erosion of the normally

protective oxide film on CS (or LAS with a Cr-content
< 0.2 wt%), exacerbated by fluid flow effects, resulting in excessive corrosion rates and substantial pipe wall
thinning. Nowadays, the term EC implies the involvement of a significant mechanical component as an abrasive (e.g., by dispersed solid particles in the liquid phase)
or cavitation-induced (mechanical) removal of surface
material; it should therefore be differentiated from FAC,
which is primarily caused by a flow-induced increase in
the mass transfer of dissolving and reacting (corrosive)
species at high-flow or highly turbulent locations,
although fluid shear stress on the oxide film at the
material surface may also make substantial contributions to the damage in some situations.
FAC is a pervasive problem in most types of
steam-raising system and has caused feedwater line
ruptures, occasionally with fatal consequences, in
both fossil and nuclear plants.9,10 In primary coolant
systems also, less serious (though costly) FAC occurs
chronically in the CS outlet feeders of conventional
CANDUs,11 and flow effects are implicated in the
corrosion of PWR pressure-vessel steel by borated
coolant leaking through cracked penetrations in the
RPV head.12 FAC thus occurs in the regions of high
turbulence in both single and two-phase flows, but
never in systems with dry steam.
FAC depends on hydrodynamics (mainly steam
quality, flow rate, fluid shear stress at the wall,
turbulence intensity, and mass transfer coefficient),
environmental factors (mainly temperature, pH,
dissolved oxygen, hydrogen, and iron concentrations)
and material parameters (metal composition Mo,
Cu and, in particular, Cr content).9 The critical
parameter combinations for the occurrence of FAC
in feedwater systems and the main parameter effects
are schematically summarized in Figure 3.
The conditions leading to increased FAC rates
are usually related to regions with turbulent flow, to
low electrochemical corrosion potentials ECP (i.e.,
to chemically reducing conditions), and to low iron
concentrations in the water (Figures 3 and 4).
Depending on the pH, the maximum FAC rates
occur at about 130 C in single-phase flow, and at
about 180 C in two-phase flow (in the latter, it is the
condition in the liquid layer at the steel surface that
controls the FAC rate, but this is difficult to measure
or predict). Note that FAC can still be a problem
at other temperatures, even though rates are lower.
For example, feeder FAC in CANDU primary coolants occurs at 300310 C at the core outlet, and FAC
is also significant in feedwater systems at the low
Log FAC rate
112
pH 7
Hydrodynamics
Hydrodynamics
Hydrodynamics
pH 9
Shear stress at surface

Flow rate
Turbulent intensity
Mass transfer coefficient
Flow
Critical conditions
for high FAC risk
in feedwater
150 C
Material
Environment
[Cr] in metal < 0.2%
Log FAC rate
Log FAC rate
pH 7
Low [Fe]
pH < 9.2
120 C < T < 180 C
[O2] < 240 ppb
pH 7
0.2% Cr
pH 9
40 ppb
Log FAC rate
pH 7
12 ppb
pH 9
Log FAC rate
pH 9
[Cr] in metal
130 C
pH 9
pH
[O2]
Figure 3 Critical parameter combinations for flow-accelerated corrosion (derived from Uchida, S. et al. In: Proceedings
of the 13th International Conference on Environmental Degradation of Materials in Nuclear Power Systems, CD-ROM.
Whistler, British Columbia, Canada, 1923 August, King, P., Allen, T., Busby, J., Eds.; Toronto, ON: The Canadian
Nuclear Society, 2007) and major parameter effects on flow-accelerated corrosion under feedwater conditions.
temperature of condensate extraction. Specific geometries like elbows, bends, protruding weld roots,
orifices, and valves cause local turbulence, which
significantly increases FAC rates at, or immediately
downstream of, the location concerned. Systems such
as the moisture-separator/reheater drain lines, where
steam has condensed and relatively iron-free water is
flowing, are particularly susceptible. In primary coolant systems, there is the desire to keep iron concentrations low to prevent crud build-up and radiation
transport problems, hence the frequent use of highalloy materials that are resistant to FAC as cladding.
However, it must be recognized that a recirculating
system will always tend toward equilibrium; in other
words, dissolved iron concentrations on average will
vary around solubility values, depending upon oxide
dissolution and precipitation kinetics, temperature
gradients around the circuit, and the capacity of
sinks such as the purification circuit.
Most studies of FAC have been performed under
feedwater conditions, which generate high rates of
attack that can reach several millimeters per year in
some situations. Neutral chemistry, low-oxygen conditions at about 140 C, as may be found in BWR
feedtrains, can give high FAC rates, so dual-cycle

PWRs or PHWRs routinely add an amine such as
ammonia to raise the pH in the secondary coolant
circuit. The actual pH employed depends upon the
materials of construction; for all-ferrous feedtrains,
a pH25 C from 9.3 to 9.6 is usually specified, but the
value is kept below 9.2 to avoid excessive corrosion of
copper-base alloys, if these are present. Also, to
achieve a more even distribution of additive around
the circuit, an amine (such as morpholine) with a
coefficient of distribution between the steam and
liquid phases closer to unity than that of ammonia
may be used.
Oxygen dissolved in the coolant is also a powerful
inhibitor of FAC; it has been added routinely to feedwater systems in BWRs and certain fossil boilers for
some time. Depending upon the rate of attack, levels
of oxygen from a few ppb to several tens of ppb are
sufficient to stifle FAC completely. Maintaining a
dissolved oxygen content >30 ppb, which raises
the corrosion potential ECP in the feedwater system above the Fe3O4/Fe2O3 phase boundary in the
Pourbaix diagram in Figure 2, is particularly crucial
in BWRs operating on hydrogen water chemistry
113
St37.2 (A414 Gr B-carbon steel)
Flow (kg h1)

983
491
15Mo3 (A161 Gr T10.5% Mo)
907
756
605
378
302
227
15NiCuMoNb5
13CrMo44 (A213 Gr T121% Cr, 0.5% Mo)
10CrMo910 (A213 Gr T222.2% Cr, 1% Mo)
3000
4.0
pH = 9.04
pH = 7.0
2.0
Increasing flow
Loss rate (mm year1)
3.0
1.0
Specific material wear rate (g cm2 h1)
1000
300
100
30
10
3.0
1.0
0.3
0
90
(a)
100 110 120 130 140 150 160 170

Temperature (C)
0.1
50
(b)
100
150
200
250
300
Temperature (C)
Figure 4 Effect of temperature, flow rate (a) (data from Bignold, G. J. et al. In: Proceedings of the International Specialists
Meeting on Erosion-Corrosion of Steels in High-Temperature Water and Wet Steam, Les Renardieres, France, 1112 May;
EDF: France, 1982) and material (b) (data from Heitmann, H. G.; Schub, P. In: Proceedings of the Third Meeting on Water
Chemistry of Nuclear Reactors, pp. 243252, Bournemouth, UK, October; British Nuclear Engineering Society (BNES):
London, UK, 1983) on single-phase flow-accelerated corrosion under different flow and chemistry conditions. Reproduced
from Dooley, R. B. Power Plant Chem 2008, 10(2), 6889.
(HWC) with high rates of hydrogen injection into the

feedwater. If HWC is combined with noble metal
chemical addition (NMCA), the FAC risk is reduced,
since much lower hydrogen injection rates are then
adequate to mitigate SCC in stainless steel recirculation piping and reactor internals. (Recombination of
hydrogen and oxygen to lower the ECP requires the
radiation fields present in the RPV.) Oxygen levels
significantly above 50 ppb may increase the risk
of strain-induced corrosion cracking and corrosion
fatigue in CS & LAS feedwater piping (see Section
5.06.3). Furthermore, the deliberate addition of oxygen
to feedwater systems in dual-cycle reactors may
pose problems, since residual oxygen entering the
steam generators can provoke SCC of the high-alloy
steam-generator tubes. Nevertheless, severe FAC of
components in the feed train of advanced gas-cooled

reactors (AGRs) has been successfully mitigated since
the early 1980s by oxygen additions.13
Material properties have a significant impact
on FAC rates, but typically the plant operator has
no control over this (unless a replacement of piping
is an option). Certain elements in the steel can act
to retard FAC, as mentioned earlier; for example,
chromium is particularly effective and a concentration of 0.1% in the metal reduces FAC in 180 C
ammoniated water and watersteam mixtures at
pH25 C 9 by about 70%.14 Moreover, under CANDU
primary coolant conditions of 310 C and pH25 C 10.5
(adjusted with lithium), increasing the chromium content of SA-106 Grade B CS from 0.019% to 0.33%
reduces FAC by about 50%.11
114
5.06.2.2.2 Mechanisms and models
As with uniform corrosion (discussed in Section

5.06.2.1), FAC is governed by the ability of the
oxide film to protect the metal. Magnetite forms on
the steel at the metaloxide interface and is degraded
at the oxidecoolant interface by fluid flow effects
and by dissolution according to the general equation
[VI] (which indicates the dependence of the dissolved
species on pH under reducing conditions and which is
equivalent to eqn [II] for b 2). The turbulence
in the coolant and the solubility of the magnetite
are then paramount in determining the severity of
the attack.
Fe3 O4 32 bH H2 3FeOHb 2b
4 3bH2 O
VI
with b 0, 1, 2, or 3.
Mass transfer is often assumed to control the
mechanism.15 This derives from the postulate that
the magnetite film attains a steady-state thickness as
it dissolves at the rate Rd at its outer surface in
coolant undersaturated in dissolved iron and forms
continuously at the metaloxide interface at the
same rate Rg. Since the magnetite formation at
the metaloxide interface accounts for only about
half of the corroded metal, the other half diffuses
through the magnetite to the oxidecoolant interface, and with the iron from the magnetite dissolution is transported to the bulk coolant at the rate Rm.
The FAC rate RFAC is thus twice the dissolution rate
Rd of the magnetite at the oxidecoolant interface.
This concept of two processes in series dissolution
Rd and mass transfer Rm leads to the equation for
the steady-state FAC rate RFAC dm/dt Rm 2Rd
with all the variables in equivalent units of iron per
unit surface and time.
1. Steady-state assumption for the serial process:
Rg Rd 0:5Rm
1
2. Dissolution rate of magnetite at the oxidecoolant

interface according to eqn [VI] (assuming firstorder kinetics):
Rd 0:5 dm=dt kd Ceq C
2
where kd is the dissolution reaction rate constant, C is

the concentration of Fe(II) species at the oxidecoolant
interface, and Ceq is their equilibrium concentration
according to eqn [VI], which corresponds to their
maximum solubility in the coolant.
3. Transport of Fe(II) species from the oxidecoolant

interface to the bulk environment by turbulent
mass transfer:
Rm h C Cb
3
where Cb is the concentration of Fe(II) species in the

bulk coolant and h is the mass transfer coefficient,
which is dependent on flow conditions and geometry.
From eqns [1][3] it follows that:
RFAC
h kd DC
0:5 h kd
4
where DC Ceq Cb is the undersaturation in

iron. Models of FAC are based on the principles
behind eqn [4]. We expect that kd strongly increases
with temperature according to an Arrhenius law
for a thermally activated process (although there are
no data to confirm this over the temperature ranges
of interest), whereas h only shows a moderate
increase through the temperature dependence of the
properties in eqn [6]. If mass transfer controls, h is
small compared with kd (h kd) and the equation
reverts to:
RFAC hDC
5
For a coolant of constant conditions containing little or

no dissolved iron (i.e., Cb 0), the driving force DC
approaches a constant value the solubility of the
oxide, Ceq and RFAC varies as the mass transfer
coefficient (which increases with increasing flow rate
and turbulence). The mass-transfer model then
implies that the effects of materials composition and
coolant chemistry on FAC rate are brought about by
their effects on oxide solubility (Figure 5). According
to eqn [VI], the saturation concentration or solubility
Ceq depends on temperature, pH and H2 concentration
by simple chemical equilibrium thermodynamics.
Accordingly, the effect of chromium in the steel
can be attributed to the relative stability of mixed
oxides containing chromium (iron chromite, FeCr2O4,
for example, is virtually insoluble in reducing coolant
and accounts for the protection afforded by stainless
steel and similar alloys). As corrosion proceeds and
the magnetite dissolves, chromium is not leached out
in concert but continually concentrates in the film. It
is interesting to note that the inhibition occurs immediately at the start of exposure and continues at about
the same level, suggesting that the mechanism is the
rapid formation at the metaloxide interface of a more
protective layer of oxide that is maintained throughout exposure.16 It appears that the higher the chromium content of the steel, the more protective that
100
NH3
(mg kg1) pH
0.1
80
Fe (g kg1)
60
8.75
0.2
8.90
0.3
9.00
0.5
9.20
1.0
9.40
2.0
9.60
300
350
40
20
0
0
50
100
150
200
250
Temperature ( C)
Figure 5 Solubility of magnetite/iron as a function of

temperature at various ammonia concentrations.
Reproduced from Dooley, R. B. Power Plant Chem 2008,
10(2), 6889.
oxide layer; hence, the immunity of stainless steel and

certain LAS like 13CrMo44 or 10CrMo910. These
observations cannot be fully explained with the DC
term in the simple mass-transfer model of eqn [5],
which would indicate an increasing inhibition with
time as the chromium concentrates in the film. One
mode of inhibition of FAC by additives in the coolant
may be via incorporation in the magnetite to make it
less soluble. From the experience with chromium,
whatever species is added should be available to affect
the metaloxide interface consistently, presumably by
being kept permanently in solution in the coolant.
So far, titanium has shown promise as a coolantborne inhibitor of FAC under CANDU primary coolant conditions. Its effectiveness has been attributed
to its ability to form a mixed oxide with iron
ulvospinel along with the magnetite that forms
on corroding CS.17 An in-plant demonstration of
titanium addition to a CANDU primary system is
described in Section 5.06.2.3.
The simple mass-transfer model also indicates
that temperature should affect FAC partly through
its influence on magnetite solubility. In ammoniated
115
water at pH25 C 9.0, there is a strong temperature

dependence and the maximum FAC rate occurs
between 130 and 140 C, depending on flow rate.18
The solubility of magnetite under the same conditions increases from the range 515 ppb at 25 C to
a maximum of about 30 ppb that persists over the
range 110150 C,9,19 while mass transfer coefficients
at the same mass flow should approximately double
between 25 and 140 C. Similarly, in neutral water, the
maximum attack for several materials occurs at about
150 C,20 while the magnetite solubility increases from
about 70 ppb at 25 C to a maximum of about 140 ppb
at 120130 C. The rough correspondence between
the temperatures of maximum FAC rate and of maximum magnetite solubility, as well as the effect of
temperature itself on solubility, indicate the strong
influence of oxide film dissolution on the FAC mechanism. It is likely that at low temperatures dissolution
rates of magnetite are low enough for kd to have an
effect through eqn [4] and lower the flow dependence
accordingly.18
The inhibiting effect of amines and high pH at
feedwater temperatures should also be realized
mainly through the solubility of magnetite. Thus, in
neutral water at 140 C, the solubility of magnetite is
about 119 ppb, but if the pH25 C is raised with ammonia to 9.2, the value falls to the range 1426 ppb.9,19
This would suggest that a reduction in FAC rate by a
factor of 8.54.5 might be expected from ammoniating the coolant to pH25 C 9.2; however, experiments
indicate a reduction by a factor of only about 2.16
It is also instructive to consider the mass transfer
implications of the model according to eqn [5]. Mass
transfer in pipe flow in aqueous systems can be
described via a correlation of the mass transfer coefficient h with dimensionless numbers:
h Sh
D D
ARe p Sc q
d
d
6
in which the Sherwood number, Sh (given by hd/D,

where d is the pipe diameter and D is the diffusivity),
characterizes mass transfer in terms of the flow (via the
Reynolds number, Re, given by dur/m, where u is the
coolant velocity, r is the density, and m is the viscosity)
and physical properties (via the Schmidt number, Sc,
given by m/(rD)); A, p, and q are constants.
Typically, experiments on mass transfer of dissolved species yield values between about 0.6 and
0.9 for the exponent p.21,22 Recent experiments in a
water loop on FAC under neutral conditions at
140 C, however, indicated that the FAC rate RFAC
correlated rather weakly with Re.1.2,23 An alternative
116
mass transfer analysis gave an excellent correlation

with fluid shear stress at the pipe wall, t:
Ru Pt
7
FAC rate Flow rate (mm year1m s1)
where P is a constant (see Figure 6). Thus, a steel

containing 0.019% chromium gave the correlation
RFACu 0.07t, while a steel containing 0.001% chromium in parallel experiments gave RFACu 0.18t,
where RFAC is in units of millimeters per year, u is
in meters per second, and t is in pascals.16
The predominance of mass transfer in developing
such correlations depends upon the dissolution rate
constant, kd in eqn [4], being large enough to make
the mass transfer coefficient, h, controlling. This
would seem to be valid under neutral chemistry conditions, where the solubility of magnetite is high, but
under high-pH conditions, where the solubility is
reduced, kd may be reduced also and its influence
may become significant. However, although recent
80
indications24 are that FAC in 140 C ammoniated

water at pH 9.2 is not correlated well by the simple
mass-transfer model leading to eqn [6], those experiments also indicated a greater dependence on flow
rate or shear stress, viz., t raised to the power 1.52.0.
This cannot be attributed to an increasing influence
of kd in eqn [4]; apparently, a different mechanism is
involved.
Surface texturing usually accompanies FAC. In
steamwater mixtures, tiger-striping is caused by
the streaming pattern of the liquid film on the surface, while in single-phase water, scalloping sculpts
the attacked surface with grooves, flutes, or shallow
depressions (Figure 7(a) and 7(b)). However, in
experiments in neutral water at 140 C, in which corrosion rates of several millimeters per year were seen
in tubular test sections, a low-chromium steel developed no scallops, even though it corroded at more than
twice the rate of a higher chromium steel that developed distinct scallop patterns.23 The scalloping that
was seen was approximately related to the pipe flow
via a characteristic scallop Reynolds number:
70
Resc 1:55
104 2:6
103
60
50
40
30
20
10
0
0
200
400
600
800
1000
1200
Shear stress (N m2)
Figure 6 Correlation for flow-accelerated corrosion at

140 C in neutral water: carbon steel with 0.019% Cr.
in which the characteristic dimension is the average

scallop spacing. While the scallops were formed by the
corrosion of the metal, it was significant that distinct
oxide forms developed and were related more to scallop crests than to valleys. Those forms, shown in
Figure 7(c), occurred over pearlite grains in the
metal and may be described as coral-like. They provide further confirmation of the importance of oxide
dissolution in the mechanism, since they are no doubt
formed by the different solubilities of the different
compositions of oxide overlaying the lamellae of
cementite and ferrite in the pearlite. As the magnetite
200 m
(a)
8
3 m
(b)
Diameter of piping
(c)
Figure 7 Surface texturing in flow-accelerated corrosion. (a) Scalloping or horseshoe pits in single-phase flow. (b) Tiger
striping in two-phase flow. (c) Coral-like oxide on carbon steel undergoing flow-accelerated corrosion in neutral water at
140 C. (a) and (b) courtesy of COMSY with permission of AREVA NP.
generally dissolves, that over the cementite lamellae is

less soluble and is left standing proud. It was noted in
the experiments that the coral oxide concentrated
about 50% more chromium than the surrounding
oxide on the ferrite grains, possibly because the underlying pearlite contained more chromium as carbide
associated with the cementite.
Loop studies using tubular test sections of the
material of interest16 under reactor feedwater conditions establish the basis for adding oxygen with minimal residual concentrations left at the end of piping
systems. At 140 C in neutral water, about 40 ppb of
dissolved oxygen are required to stifle FAC, whereas at
pH25 C 9.2 with ammonia, only 12 ppb are required.
The concentrations required for stifling are related to
the measured FAC rates and it is clear that as oxygen
is progressively added to the corroding system the
cathodic reaction of water being reduced to hydrogen
is replaced by oxygen reduction; at the stifling concentration, the oxygen sink disappears and with continuing
addition its concentration in the loop jumps sharply.
However, although there is an obvious relationship
between the FAC rate at stifling and the stoichiometric
flux of oxygen by mass transfer to the surface, a
straightforward linear correspondence may not apply.13
While several mechanistic models of FAC in feedwater systems based mostly on the principles behind
eqn [4] have been developed, empirical models have
been applied extensively for some time. In the 1980s, for
example, parametric studies at the laboratories of the
then Siemens-KWU led to the formulation of a correlation between pipe wall thinning Dd and the system
variables u (flow velocity), T (temperature), pH, O2
(oxygen concentration), M (materials composition
Cr, Mo, and Cu), and t (exposure time):
Dd kc f u; T ; pH; O2 ; M; t
9
where kc is a geometry factor. The correlation

was developed initially from data for single-phase
water flow, but was adapted to two-phase steam-water
flows, with the bulk velocity u substituted by the mean
velocity of the annular film of water covering the pipe
wall. The resulting computer code, WATHEC, was
restricted to steels with the content of Cr plus Mo less
than 5% and exposure times greater than 200 h. The
predictions of wall thinning for a large number of
situations were equal to or greater than the measured
values in 85% of the cases in other words, the code
was considered to be suitably conservative.25 Later, the
data management tool DASY was added to the code.
The EPRI-sponsored computer code CHECWORKS combined an empirical equation, which
117
had some basis in mechanisms such as that leading to

eqn [4], with a comprehensive data management
scheme.26 The data management includes analysis
of ultrasonic test data, calculation of critical wall
thickness for components at risk, and organization
of pertinent databases. The FAC rate RFAC is written
as a function of the system variables:
RFAC f T ; AC; MT; O2 ; pH; G; a
10
where T is temperature; AC is alloy content of Cr, Mo,

and Cu; MT is mass transfer; O2 is concentration of
dissolved oxygen; G is a geometry factor; and a is the
steam void fraction. The factors in eqn [10] are interrelated and the equation is nonlinear. While the absolute
predictions of RFAC in CHECWORKS are not generally of high precision, iterations incorporating plant
measurements can identify the locations of risk and
can rank components in the order of vulnerability.27
The FAC of CS is most pronounced under feedwater conditions, but it also occurs at higher temperatures in the primary coolant systems of PHWRs.
The phenomenon was identified in the late 1990s at
the Point Lepreau CANDU in New Brunswick,
Canada, where surfaces of affected outlet feeders of
CS were scalloped and the wall thinning rates plotted
against coolant velocity indicated a dependence on
the velocity raised to the power 1.5.28 Regions of
high turbulence, such as the tight-radius bends close
to the reactor face, were more severely affected.
It was also noted that the coolant at the core outlet
was unsaturated in dissolved iron, since it entered the
core at 265 C saturated after its passage through the
steam generators of nickel alloy and the inlet feeders
of CS; as its temperature rose in the fuel channels
the solubility at the high pH rose in concert (the
CANDU core contains no iron-bearing alloys, so it
cannot act as a source of dissolved iron).
Although the high-turbulence (and therefore highmass-transfer) regions are again the most affected in
primary coolant FAC, it is unlikely that the mechanism
in primary coolant is straightforward mass-transfer
control based on eqn [11]. First of all, the velocity
dependence is too high (the power of 1.5 rather than
0.60.9 as expected from correlations such as eqn [6]).
Second, measurements of the dissolution rate of magnetite under chemistry conditions close to those of
CANDU coolant29 have given a value of kd in eqn [4]
very much lower than the mass transfer coefficient h,
which would put the mechanism squarely under dissolution control with no velocity effect at all. The
alternative theory proposed is that dissolution of magnetite works in synergy with fluid shear stress at the
118
surface to degrade the oxide. Thus, the loosening of

the magnetite crystallites in the film makes them susceptible to removal by the fluid forces and as they are
eroded away the film becomes less protective. A mathematical model developed on this principle was able to
predict quite well the thinning of the walls of outlet
feeders at an operating plant in terms of the development of the oxide film, the pattern of attack around
representative bends, and the corrosion potential ECP
and velocity-dependence of FAC rate in individual
feeders.30 The model was adapted for predicting corrosion under conditions when the coolant is saturated in
dissolved iron and gave reasonable predictions of oxide
film growth and general corrosion in CANDU inlet
feeders, where corrosion rates are quite low.
It is probably more than a coincidence that FAC
under these primary coolant conditions, when magnetite solubility is low, seems not to be controlled directly
by mass transfer, while similar indications apply under
feedwater conditions at high pH, when solubilities
are also low. The parallel between the two situations
could be clarified if measurements of kd under feedwater conditions were available and the measurements
under primary coolant conditions were verified.
The high rate of general corrosion of CS caused
by aerated concentrated solutions of boric acid originating from leaking PWR coolant was described in
Section 5.06.2.1. Some of the studies that quantified
the attack were done with dynamic systems, such as
evaporating sprays, and it became clear that flow has
an effect.2 Of immediate concern is the corrosion of
RPV steel caused by borated coolant leaking through
cracked penetrations housing control rod drive
mechanisms. At the Davis Besse PWR in 2002, such
corrosion had threatened the integrity of the vessel.
The sequence of events that can lead to cavity formation next to a nozzle was postulated12 to be in three
phases: initially, slow seepage of coolant into the external annulus (crevice) in the head would be accompanied by low corrosion rates; next, when the crevice had
opened enough and the crack had lengthened to give
substantial leak rates, an evaporating coolant jet would
accelerate the attack through flow effects; finally, leakage into a cavity would create a turbulent evaporating
pool, extending the attack sideways.
An extensive testing program sponsored by the
Electric Power Research Institute (EPRI), Palo Alto,
California, investigated the phases of boric acid
attack at Davis Besse. The second phase, which experienced substantial flow effects, was simulated with
laboratory experiments in which a flashing jet of
borated coolant was directed onto a heated sample
of pressure-vessel steel and the damage assessed

in terms of system parameters notably, coolant
chemistry and flow rate.31 Volumetric (or massive)
metal loss was correlated with volumetric coolant
flow and seemed to behave differently from metal
penetration, which was correlated with jet velocity.
FAC was in evidence through miniature scallops in
the damage craters that formed around (but some
distance away from) the points of jet impact. Metal
loss rates attained about 3 cm3 year1 at a flow rate of
200 ml min1 with a boric acid concentration equivalent to 1500 ppm [B] and pH300 C of 6.9 adjusted with
lithium; the rate depended on the volumetric flow
in the jet raised to the power 0.84. Under the
same chemistry conditions, the penetration rate
reached 200 mm year1 at a jet velocity of 140 m s1
and the two were correlated via the velocity raised to
the power 4.3. It was notable that neither pH300 C nor
the boron concentration was the controlling chemistry parameter; rather, it was the ratio [B]/[Li].
5.06.2.2.3 Service experience and mitigating
actions
Many incidences of feedwater pipe thinning by FAC

from two-phase coolant were reported in the 1980s.
In 1985 March, a line downstream of a level control
valve for a feedwater heater at the Haddam Neck
PWR actually ruptured because of FAC induced by
flow-impingement. However, the first major incident
in a nuclear plant was the catastrophic pipe break at
the Surry Unit 2 PWR in December 1986, which led
to five deaths and several injuries. The 0.46 m diameter line thinned and ruptured at an elbow, 0.3 m from
a 0.6 m header, as a section of the pipe wall 0.6
1.2 m
was blown out. Until then, FAC by steamwater mixtures had been considered to be more serious than
FAC by single-phase coolant. Six months later, excessive thinning of a feedwater line was reported at the
Trojan plant and, in September 1988, Surry Unit 2
reported 20% wall loss in the suction line to a feedwater pump over a 1.2-year period.
Reports of serious thinning of feedwater piping
continued after the Surry incident, even though
plant inspections had generally become more rigorous
and chemistry control had tightened. In May 1990,
the Loviisa Unit 1 WWER (Eastern type PWR) in
Finland suffered a break in a 0.3 m diameter line in
the turbine hall, releasing about 50 m3 of steam and
water into the building, and in February 1993, a
similar incident occurred in Unit 2.
The latest major FAC incident in a nuclear plant
was the rupture of a feedwater line at the Mihama
Unit 3 PWR in 2004, which led to four deaths and

seven serious injuries.32 The thinning of the pipe wall
from 10 to 0.6 mm by FAC caused a large section to
peel back after rupture, allowing the coolant at
Figure 8 The ruptured feedwater line at Mihama-3.
140 C to flash to steam on release. The damaged

pipe is shown in Figure 8. Maximum thinning rates
were observed just downstream of an orifice plate,
where turbulence intensity was high. It should be
noted that chemistry had been maintained at high
pH with ethanolamine and that hydrazine was used to
scavenge oxygen. However, the location had not been
inspected since the plant start-up in 1976. The possibility of adding oxygen to the feedwater is being
considered and inspection procedures have been
revised extensively.
In 1997, at the Point Lepreau CANDU PHWR
in New Brunswick, Canada, the outlet feeder pipes
of CS that carry the heavy water coolant from the
core to the steam generators were found to be corroding excessively. The same problem has since then
been seen at all CANDUs in operation before 2000.
Figure 9 shows the arrangement of pipes at a reactor
face. The feeders are about 76 mm diameter and carry
119
2
5
8
10
1. Reactor outlet header

6. Calandria end shield face
2. Reactor inlet header
7. Tube spacers
3. Reactor outlet header
8. Support brackets
4. Reactor inlet header
9. Walkway
5. Feeder tube upper supports 10. End fittings
Figure 9 CANDU reactor face; cutaway view of feeder pipe arrangement, with permission from Atomic Energy of
Canada Limited.
120
coolant at velocities between about 12 and 22 m s1.

At the coolant temperature of 310 C and pH 10.6
(adjusted with lithium), the solubility of magnetite is
relatively low about 1.7 ppb and the FAC rates
accordingly attain only about 120 mm year1. The
attack is only a fraction of that observed under
feedwater conditions and has caused no safety issues,
but it means that feeder integrity may be lifelimiting and has necessitated replacements at some
reactors. Mitigating actions have been taken by
reducing the primary coolant alkalinity to the bottom of the recommended pH range, where the magnetite solubility is close to the minimum, while
plants in service since 2000 employ feeders with
a relatively high chromium content (0.3% in
contrast with the 0.02% in earlier reactors).
One trial of a coolant additive was made at the
Darlington Unit 3 900 MW CANDU in 2002,
when a titanium dioxide slurry was added to one
channel to give a concentration of ten or so microgram per kilogram at the outlet feeder33; significant
reductions in FAC rate were recorded, but it
was decided not to undertake the further development needed to proceed to the next stage of
full-plant addition. Meanwhile, feeder replacement
has become a manageable if costly operation at
severely affected plants.
The boric-acid corrosion at the Davis Besse PWR
in Ohio, which in 2002 was found to have a large
wastage cavity in the RPV head adjacent to a penetration housing a control rod drive mechanism, was
postulated to be partly due to FAC (see Figure 10).
About 2040 cm3 of the pressure-vessel steel had
corroded away and about 106 cm2 of stainless steel
cladding were exposed at the bottom. Substantial
quantities of solid boric acid had deposited close by.
Subsequent investigations12 determined that coolant
had leaked from a crack in the adjacent Alloy 600
nozzle into the surrounding annulus and in time
had widened it. The crack was an example of primary
water stress corrosion cracking (PWSCC), of which
numerous incidences have been recorded in PWRs.
No simple means of mitigation have been proposed
for existing plants, since the coolant boron level is
fixed by reactivity considerations. Long-term prevention entails avoiding operating with coolant
leaks (as is, in fact, the regulation in some jurisdictions), for example, through minimizing the possibility of PWSCC by using less-susceptible Alloy 690
material for the CRDM penetrations. In the meantime, more rigorous inspection regimes are being
implemented.
Figure 10 Cavity in the reactor pressure vessel head at the

Davis Besse pressurized water reactor.
5.06.3 Localized Corrosion and

5.06.3.1
Pitting
In CS & LAS, a shallow form of pitting can occur in

the complete absence of anionic water impurities as
the electrochemical corrosion potential (ECP) at the
steel surface is raised, for example, through oxygen
and other oxidizing species. Such corrosion pits often,
but not exclusively, initiate at MnS inclusions which
intersect the steel surface. Figure 11, originally compiled by Hickling, shows the critical boundaries
between uniform surface attack and shallow pitting
in high-purity water at low flow rates as a function of
temperature and dissolved oxygen level. The critical
oxygen concentration for pitting drops with decreasing temperature and is further reduced by a simultaneous mechanical straining of the surface, or by
increased sulfate and chloride impurity levels. Furthermore, pitting in CS & LAS is favored by high
steel sulfur contents and quasi-stagnant flow conditions. In the absence of impurities, increasing the flow
rate of water across the metal surface mitigates the
aforementioned form of pitting corrosion. Alkalization
shifts this boundary to much higher values, as does the

introduction of buffering and passivating species (e.g.,
on the secondary side of steam generators).3437
Some degree of pitting corrosion is inevitable
after long-term exposure of unclad CS & LAS surfaces to water in LWR systems and is not usually a
threat to either coolant purity or to structural integrity. Shallow pitting has been observed primarily in
specific piping systems with residual water because of
121
incomplete draining during nonoperational periods

(shutdown corrosion). This can be avoided by adequate wet or dry preservation techniques. If pitting
happens during normal plant operation at high temperatures, however, it indicates conditions under
which EAC may also occur (since this is controlled
by similar parameters, see Section 5.06.3.2) and can
even be directly implicated in the initiation of EAC
(Figure 12).
300
ck
ce
ta
at
ce
tin
fa
pit
ng
ur
tti
ls
ra
ne
Ge
Pi
ne
ra
ls
ur
fa
200
Ge
Temperature (C)
at
ta
ck
Pitting with
straining
Pitting
without
straining
100
SSRT
0
10
lzumiya, Tanno
Videm
Mizuno et al.
Ford
Coupon
specimens
1000
100
10 000
Dissolved oxygen content DO (ppb)

Figure 11 Boundaries between uniform corrosion and pitting attack in carbon and low-alloy steel in quasi-stagnant
high-temperature water. Compiled from The general and localized corrosion of carbon and low-alloy steels in
oxygenated high-temperature water. EPRI-NP-2853; EPRI: Palo Alto, CA, 1983; http://my.epri.com/; Electric Power
Research Institute. BWR environmental cracking margins for carbon steel piping. EPRI Report NP-2406; EPRI: Palo Alto, CA,
1982; http://my.epri.com/; Indig, M. et al. Rev Coat Corros 1982, 5, 173225; Videm, K. In Proceedings of the 7th
Scandinavian Corrosion Congress, Trondheim, Norway, May 2628, 1975; pp 444456.
(a)
20 mm
(b)
Acc.V Spot Magn

20.0 kV 5.9 1696x
20 mm
Det WD
SE 11.0 5/1;250C;HigN
Figure 12 Strain-induced corrosion cracks initiating from a corrosion pit or a (dissolved) MnS inclusion at the surface of a
low-alloy and carbon steel in high-temperature water in slow strain rate experiments. Adapted from Congleton, J. et al.
Corros. Sci. 1985, 25, 633650; Atkinson, J. D. et al. In Proceedings of the 13th International Conference on Environmental
Degradation of Materials in Nuclear Power Systems, Whistler, British Columbia, Canada, Aug 1923; King, P., Allen, T.,
Busby, J., Eds.; The Canadian Nuclear Society: Toronto, Canada, 2007; CD-ROM.
122
5.06.3.2 Environmentally Assisted

Cracking
5.06.3.2.1 Basic types of EAC and major
factors of influence
EAC is used here as a general term to cover the

full spectrum of corrosion cracking ranging from
stress corrosion cracking (SCC) under static load to
corrosion fatigue (CF) under cyclic loading conditions (Table 2).38,39 Strain-induced corrosion cracking (SICC) involving slow, dynamic straining with
localized plastic deformation of material, but where
obvious cyclic loading is either absent, or is restricted
to a limited number of infrequent events such plant
startup and shutdown, is increasingly used as an
appropriate term to describe the area of overlap
between SCC and CF.38,39
Under critical parameter combinations, EAC is
observed in all wrought and welded CS & LAS in
high-temperature water. The EAC crack path is
usually perpendicular to the direction of maximum
Table 2
tensile stress and transgranular in nature, with a

quasicleavage appearance showing a feathery morphology at high magnifications. The general fracture
appearance is similar for SCC, SICC, and even CF
(at least for strong environmental acceleration of
fatigue crack growth), thus confirming that EAC is
governed by the same basic process for all three
loading modes. In the case of cyclic loading at frequencies 103 Hz, the fracture surface also usually contains both ductile and brittle fatigue striations,
which are perpendicular to the local crack-growth
direction.38
EAC initiation and growth in CS & LAS are
governed by a complex interaction of environmental,
material, and loading parameters, and most influencing factors are both interrelated and synergistic. The
major parameters of influence, which have been
identified so far, are summarized in Table 3.38,39
The effect of these parameters on EAC initiation
and crack growth (including key thresholds) is
Basic types of EAC in CS & LAS and relevant nuclear codes
Mechanism
Environmentally assisted cracking (EAC)

CF
Corrosion fatigue
SICC
Strain-induced corrosion cracking
SCC
Type of loading
Cyclic: low-cycle, high-cycle
Static
LWR operation
condition
Characterization of
crack growth
Characterization of
crack initiation
Thermal fatigue, thermal

stratification, . . .
ASME XI
Code Case N-643 (PWR)
ASME III
Fen-approach
Slow monotonically rising or very

low-cycle
Start-up/shut-down, thermal
stratification
High-sulfur line of F & A model as
upper bound
Susceptibility conditions:
ECPcrit, de/dtcrit, ecrit
Transient-free, steady-state
power operation
BWRVIP-60 disposition lines
scrit
Source: Seifert, H. P.; Ritter, S. Research and service experience with environmentally-assisted cracking of carbon & low-alloy steels in
high-temperature water. SKI-Report 2005:60; SKI: Stockholm, Sweden, 2005; ISSN 1104-1374. http://www.stralsakerhetsmyndigheten.
se/.
Hickling, J. et al. PowerPlant Chem. 2005, 7, 3142.
Table 3
Major influencing factors for EAC in C & LAS
Environmental parameters
Material parameters
Loading parameters
Corrosion potential, dissolved oxygen

content
Temperature
S-content, morphology, size, spatial distribution

and chemical composition of MnS
2

Cl, SO2
4 , S , HS
Susceptibility to dynamic strain ageing,

Concentration of interstitial C and N
Hardness/yield stress if >350HV5/800 MPa
Frequency, loading or strain

rate
Level of load, KI, stress,
strain, DK
Type of loading
Flow rate
Residual stress
Source: Seifert, H. P.; Ritter, S. Research and service experience with environmentally-assisted cracking of carbon & low-alloy steels in hightemperature water. SKI-Report 2005:60; SKI: Stockholm, Sweden, 2005; ISSN 1104-1374. http://www.stralsakerhetsmyndigheten.se/.
Hickling, J. et al. PowerPlant Chem. 2005, 7, 3142.
discussed in detail in Seifert and Ritter38 and an

interpretation of their synergism is given both there
and in Section 5.06.3.2.4.
5.06.3.2.2 Corrosion fatigue and straininduced corrosion cracking
5.06.3.2.2.1 Initiation and susceptibility
conditions
Slow strain rate (SSR)38,40 and low-cycle fatigue

(LCF) tests4042 with smooth specimens have clearly
shown that CF and SICC can occur in CS & LAS in
oxygenated, high-purity, high-temperature water if
the following conjoint threshold conditions are
simultaneously satisfied:
Water temperature >150 C. In LCF experiments, susceptibility then increases with temperature up to 320 C. SSR tests, on the other hand,
usually indicate a maximum of susceptibility
between 200 and 270 C, depending on strain rate.
Corrosion potential > ECPcrit 200 mVSHE or
dissolved oxygen content >30 ppb. Above this
threshold, EAC susceptibility then generally
increases with increasing ECP/oxygen content,
but saturates at very high levels.
Loading which leads to (local) macroscopic strains
at the water-wetted surface above the elastic limit.
The susceptibility then increases strongly with the
degree of plastic strain. SSR experiments with
tapered specimens, and LCF tests with different
waveforms, indicate a minimum critical strain of
0.150.2%, which is in a similar range to typical
oxide film rupture strains on CS & LAS (0.05
0.2%) in high-temperature water.
Positive strain rates below 103 s1. The EAC
susceptibility then increases with decreasing strain
rate de/dt. In most LCF investigations, saturation
of the decrease in fatigue life is observed below
a strain rate of 105 s1, but SSR tests indicate a
maximum of susceptibility between 105 and
107 s1, depending on ECP and temperature.
EAC susceptibility increases with increasing steel
sulfur content and a lower threshold is often quoted
at 0.003 wt%, but experimental evidence for the
latter is weak. Distinct material susceptibility
to dynamic strain aging (DSA) in the critical
temperature/strain-rate range, or a low yield
stress, may also favor crack initiation by SICC.
If one or other of these conjoint threshold conditions
is not satisfied, SICC initiation is extremely unlikely
and no, or only a minor, environmental reduction of
123
fatigue life is observed in high-temperature water.

Furthermore, in high-purity water, a high flow rate
may completely suppress SICC susceptibility and significantly retard CF crack initiation (in particular,
for small strain amplitudes or slow strain rates) compared to quasi-stagnant conditions, since the risk for
the formation of an aggressive, occluded water chemistry within small surface defects is significantly
reduced by convection. Note, however, that high levels
of chloride or sulfate may extend the range of susceptibility to less severe conditions (e.g., to lower ECP and
strain levels).
The range of system conditions where EAC crack
growth from incipient cracks may occur is significantly extended compared to the initiation susceptibility conditions specified earlier. For example,
CF crack growth has been observed in high-purity
PWR water at ECPs below 500 mVSHE under certain cyclic loading conditions (102 to 10 Hz).38
Apart from local stress raisers such as welding
defects, which may help overcome the strain threshold
in the field, the effect of initial surface condition (surface roughness, cold work, residual stress, oxide film,
and preoxidation) on SICC and CF initiation is much
less pronounced than for (high-cycle) fatigue in air, or
with SCC of stainless steels or Ni-base alloys. SICC
cracks usually, but not exclusively, initiate at MnS
inclusions or corrosion pits.38,40,43,44 Pitting, particularly if occurring actively, therefore facilitates SICC
initiation (Figure 12). CF cracks, on the other hand,
initiate mainly along slip bands, carbide particles, or at
the ferritepearlite phase boundary, and less frequently
at micropits or MnS inclusions.4042 The effect of
pitting and MnS inclusions on CF initiation is thus
moderate, but may become more pronounced in the
case of deep, high-aspect-ratio pits, mild environmental conditions, or at small strain amplitudes.40
5.06.3.2.2.2 SICC initiation and crack growth from
incipient cracks
In high-purity water in the absence of any significant

fatigue contribution, CS & LAS show distinct SICC
susceptibility only in highly oxidizing environments.
For example, it is almost impossible to initiate relevant
SICC crack growth in precracked specimens in slow
rising-load tests with constant load rate at KI values
<70 MPa m1/2 in high-purity water at an ECP of
<100 mVSHE. Even under highly oxidizing conditions (ECP 50 mVSHE), KI values of 25 MPa m1/2
have to be exceeded to initiate SICC in slow, risingload experiments in high-purity water. A maximum
in SICC initiation susceptibility (i.e., a minimum in
124
(a)
101
102
60
103
SA 533 B Cl. 1, 0.018% S

288 C, 8 ppm O2 65 ppbSO24
106
50
107
45
108
40
35
30
107
109
106
105
104
103
Crack opening displacement rate dCODLL/dt (mm s )
(b)
108
50
40
109
30
Weld filler material, 0.007% S
dCODLL/dt = 24 106 mm s1
20
100
102
8 ppm O2, 65 ppp SO24
150
200
250
300
SICC crack growth rate (ms1)
55
100
Stress intensity factor at onset of

SICC crack growth Kl,i (MPam1/2)
60
SICC crack growth rate (m s1)
Stress intensity factor at onset of

SICC crack growth Kl,i (MPa m1/2)
Stress intensity factor rate dKl/dt (MPa m h1)

101
350
Temperature (C)
Figure 13 Effect of loading rate (a) and temperature (b) on Strain-induced corrosion cracking initiation and crack growth
from incipient cracks in oxygenated high-temperature water in a low-alloy steel reactor pressure vessel steel. Reproduced
from Seifert, H. P.; Ritter, S. J. Nucl. Mater. 2008, 378, 312326.
the KI,i value needed to initiate SICC) occurs at intermediate temperatures around 200250 C and at slow
loading rates (Figure 13). Furthermore, the SICC
initiation susceptibility is affected by environmental
and material parameters in a very similar way as in
SSR tests with smooth specimens.38,45
Under highly oxidizing conditions (ECP
50 mVSHE), SICC cracks can grow without any significant fatigue crack growth contribution and, in extreme
cases, SICC growth rates during plant transients with
severe thermal stratification can reach high values (up
to several hundreds of micrometers per event, or several millimeters per day). Under such circumstances,
SICC crack growth rates in both high-purity water and
water with increased sulfate or chloride levels are
comparable for all CS & LAS, independent of their
sulfur content. Once growth is initiated, crack velocities rise with increasing loading rates dKI/dt (and thus
crack-tip strain rates) and with increasing temperature
(Figure 13), at least up to 250 C.38,45
5.06.3.2.2.3 CF initiation and crack growth from
incipient cracks
Under cyclic loading, CS & LAS show a distinct

susceptibility to initiation of corrosion fatigue (CF)
from incipient cracks in all LWR environments.
However, environmental acceleration of fatigue
crack growth in these materials only occurs for
certain combinations of loading and environmental parameters. The cycle-based crack growth rate
da/dN then usually depends strongly on loading frequency and temperature, in contrast to fatigue in air,
and can achieve 10100 times higher values under
certain conditions (although the actual effects on
component integrity in the field are much less severe

than might appear at first glance from isothermal test
data). The combination of material, loading, and
environmental conditions, where strong environmental acceleration of fatigue crack growth (factor of
10) usually occurs, extends over a broad range in
the case of highly oxidizing BWR/NWC conditions,
but is restricted to a much narrower range at low
ECPs (Figures 14 and 15(a)), that is, in the case of
PWRs and of BWRs operating on HWC (with or
without NMCA (noble metal chemical addition)).
In contrast to SICC initiation, there is no threshold ECPcrit for CF in high-purity water, and material
parameters usually play a less pronounced role
(Figure 15(b)).46,47 The major parameters affecting
CF crack growth are shown in Table 4, and the
observed cracking behavior can be briefly summarized
as follows.38,47
Above an upper critical frequency ncrit,H of
1100 Hz and/or an upper DKCF,H threshold, environmental acceleration of fatigue crack growth disappears, because air fatigue crack growth rates are
higher than the maximum EAC rates for CS & LAS
in high-temperature water. These upper ncrit,H and
DKCF,H thresholds are shifted to lower values with
increasing DK and frequency, respectively, and do not
depend noticeably on environmental and material
parameters.
Strong environmental acceleration of fatigue
crack growth (factor of 10) in LWR environments
occurs with all CS & LAS below these upper thresholds for the combination of temperatures 100 C,
loading frequencies ncrit,L f (ECP, DK, . . .), and
DK values DKCF,L f (ECP, n, . . .). If one or more
125
102
0.4 or 8 ppm O2
+50 to + 200 mVSHE
0.2 ppm O2
0 mVSHE
ASME Xl air
104
103 102 101

Frequency n (Hz)
(a)
100
101
dK/dt , n
102
T = 288 C, R = 0.7 0.8, K = 14 22 MPa m1/2

SA 533 B Cl. 1 (0.018% S), 20 MnMoNi 5 5 (0.015% S)
105
101
we
< 0.005 ppm O2

500 mVSHE
100
Xl
ASME Xl Wet
101
102
101
ME
100
SA 533 B Cl. 1,0.0018% S

250 C, kout 0.07 S cm1
0.4 ppm O2
103
102
(b)
AS
101
da/dNCF (m cycle1)
da/dNCF (m cycle1)
102
ai
Xl
AS
Kl.max = 58 MPa m1/2

0.5 MPa m1/2h1
5 MPa m1/2h1
35 MPa m1/2h1
370 MPa m1/2h1
1
10
100
Stress intensity factor amplitude K (MPa m1/2)
(a)
106
SA 533 B Cl.1 (0.018 wt % S)

T = 274 288 C
108
1010
/d
t Air
1012
da
NWC, + 150 mVSHE

NWC, 100 mVSHE
HWC, 500 mVSHE
1012
1010
108
106
Fatigue crack growth rate in air da/dtAir (m s1)
Corrosion fatigue crack growth rate in

high-temperature water da/dtCF (m s1)
Corrosion fatigue crack growth rate

in high-temperature water da/dtCF (m s1)
Figure 14 Effect of electrochemical corrosion potential, loading frequency (a) and DK and loading rate (b) on corrosion
fatigue crack growth in low-alloy steel in high-temperature water and comparison with ASME XI Air and Wet, crack growth
rates. Reproduced from Seifert, H. P.; Ritter, S. Corros. Sci. 2008, 50, 18841899.
(b)
103
Superposition-model da/dtCF = da/dtENV + da/dtAir
105
107
109
1011
1013
1013
T = 240 288 C
0.4 8 ppm O2
<1 or 65 ppb SO42
n = 3E 6 to 8E 3 Hz
240 C
R = 0.20.8
288 C 250 C
K = 11 62 MPa m1/2
r
SA
533
B
Cl.1
(0.018% S)
i
t
20 MnMoNi 5 5 (0.004% S)
/d A
20 MnMoNi 5 5 (0.015% S)
da
1011
109
107
105
103
Figure 15 Corrosion fatigue crack growth in the time-domain as a function of electrochemical corrosion potential (ECP) for
a high-sulfur low-alloy steel (a) and as a function of material and loading parameters at high ECPs > 50 mVSHE (b).
Reproduced from Seifert, H. P.; Ritter, S. Corros. Sci. 2008, 50, 18841899.
of these threshold conditions are not satisfied, the

environmental effect is moderate (factor of 5), or
even absent altogether. When these conjoint threshold
conditions are simultaneously satisfied, the environmental acceleration of fatigue crack growth increases
with increasing temperature (sometimes with a maximum around 250 C) and decreasing loading frequency and DK values, often showing maximum
enhancement close to the lower thresholds.
The lower thresholds ncrit,L and DKCF,L depend on
material, environmental, and loading parameters (in
particular, ECP and DK or frequency see Figure 14
and Table 4). They can reach very low values of
106 Hz and of 2 MPa m1/2 (for load ratio R!1)
or 5 MPa m1/2 (R! 0) under highly oxidizing conditions (ECP 100 mVSHE). Below these lower
thresholds, the environmental acceleration of fatigue
crack growths drops to moderate values (factor of 5)
and the cycle-based crack growth rate da/dN becomes
independent of frequency. The DK-dependence is the
same as in air and the effect of temperature is usually
moderate. Such behavior is sometimes designated
as true corrosion fatigue and corresponds to the
low-sulfur curve of the Ford and Andresen model
(see Section 5.06.3.2.4; Ford and Andresen48 and
Ford49). Once conditions exceed these lower thresholds, the material behavior corresponds to the highsulfur curve of the model.
126
Table 4

Major parameter effects on CF crack growth with typical parameter values
Crack-tip environment
Low-sulfur, 0.1 ppm S2
High-sulfur, 15 ppm S2
Range
da/dtCF/dat/dtAir
n < ncrit,L
25
6 f(n)
m 3, that is, parallel to air curve
6f(n), that is, n 0
DKth, Air f(R)
ncrit,L n < ncrit,H 1 Hz

10100 (10 000)
n# ! da/dtCF/dat/dtAir"
m 12
n 0.50.6
n", R", ECP", SO2
4 ", S", DSA"! DKCF,L#
100 mVSHE: DKCF;L 25 MPa m1/2
500 mVSHE: DKCF,L 1030 MPa m1/2
ECP", SO2
4 ", S" DK" ! ncrit,L#
100 mVSHE: 1 E5 Hz to <1 E6 Hz
500 mVSHE: 1 E3 Hz to 1 E1 Hz
T > 100 C: T" ! da/dtCF"
EA 4050 kJ mol1
T# ! DKCF#
With minimum of DKCF at intermediate T?
da/dNCF BDKm
da/dNCF Ann
DKCF,L f(n, R, ECP, . . .)
ncrit,L f (DK, R, ECP, . . .)
No evidence for lower threshold for

low-sulfur behavior
Temperature
Moderate effect
Above 110 Hz, the environmental effects on crack growth disappear.

Source: Seifert, H. P.; Ritter, S. Research and service experience with environmentally-assisted cracking of carbon & low-alloy steels in
high-temperature water. SKI-Report 2005:60; SKI: Stockholm, Sweden, 2005; ISSN 1104-1374. http://www.stralsakerhetsmyndigheten.
se/; Seifert, H. P.; Ritter, S. Corros. Sci. 2008, 50, 18841899.
The water flow rate has little effect on CF crack

growth of long/deep cracks, in contrast to CF initiation and short-crack growth. In the latter cases, CF
effects can disappear entirely if flushing out of the
local crack-tip electrolyte occurs, but this is unrealistic for deep, semi-elliptical cracks.
5.06.3.2.2.4 Adequacy and conservatism of
fatigue design according to Section III of ASME
BPV Code in the context of environmental effects
Design against fatigue of CS & LAS primary pressureboundary components is often based on Section III of
the ASME BPV Code.50 It relies on the use of fatigue
curves and endurance limits, derived mainly from
strain-controlled LCF tests with small, smooth specimens in air at room temperature, which do not explicitly consider the possible effects of LWR environments.
The accumulated good service experience with
CS & LAS primary pressure-boundary components does not indicate any generic deficiencies in
the current fatigue design procedures arising from
lack of consideration of environmental effects (see
Section 5.06.3.2.5), even though laboratory investigations clearly reveal that the fatigue lives of CS &
LAS can be substantially reduced in LWR environments (Figure 16)38,41,42,51,52: Although the microstructures and cyclic-hardening behavior of CS &
LAS differ significantly, the effects of the environment on the fatigue life of all these steels are very
similar. The magnitude of the reduction in this
depends on temperature, strain rate, oxygen level in

the water (i.e., ECP), and sulfur content of the steel.
The decrease is significant only when four conditions
are satisfied simultaneously, that is, when the strain
amplitude, temperature, and dissolved oxygen content in the water are above certain threshold values
(0.15%, 150 C, 0.04 ppm) and the strain rate is
below a key threshold value (103 s1). Although
only a moderate decrease in life (by a factor of <2)
is observed if any one of the aforementioned threshold conditions is not satisfied, fatigue lives of CS &
LAS can be more than a factor of 20 lower in the
coolant environment than in air under certain environmental and loading conditions (Figure 16). Such
observations have thus raised some concern with
respect to the possibility of insufficient safety margins for the fatigue design of certain CS & LAS
pressure-boundary components.
Conservatism in the ASME Code fatigue evaluations may arise from (a) the fatigue evaluation procedures themselves and/or (b) the fatigue design
curves they use. Sources of conservatism in the procedures include the use of design transients that are
significantly more severe than those experienced in
service, conservative grouping of transients, and use
of simplified elasticplastic analyses that result in
higher stresses/strains. The design margins of 2 and
20 on stress and cycles, respectively, in the ASME III
design curve were intended to cover the effects of
some variables (e.g., surface finish, material
127
10.0
1.0
0.1
101
(a)
A533-Gr B low-alloy steel

288 C, ea 0.4%
150250 >250
0.050.2 >0.2
0.010.4 <0.01
0.006 0.006
Temp( C) :<150
DO (ppm) :0.05
Rate (%/s) :0.4
S (wt.%) :>0.006
Fatigue life (cycles)
Strain amplitude ea (%)
Carbon steel
Mean curve
RT air
ASME design curve

102
103
104
104
103
Air
Simulated PWR
0.7 ppm DO
102
105
105
106
Fatigue life (cycles)
(b)
104
103
102
101
100
Strain rate (%/s)
Figure 16 Comparison of fatigue initiation life of carbon steel in high-temperature water with ASME III mean and design
curves in air (a) and effect of strain rate and oxygen content on fatigue initiation life in low-alloy steel. Reproduced from US
NRC. Effect of LWR coolant environments on the fatigue life of reactor materials. NUREG/CR-6909; US NRC: Washington,
DC, 2007, http://www.nrc.gov/. Work performed by Argonne National Laboratory, managed and operated by UChicago
Argonne, LLC, for the US Department of Energy under Contract No. DE-AC02-06CH11357.
variability, load sequence, and size effects) that can

influence the fatigue life of components, but were not
actually investigated in the tests which provided the
original data for the curves. They were not intended to
cover the effects of LWR environments,38 but a recent,
detailed analysis41,42 revealed that the factors of 2 on
stress/strain and 20 on cycle number not only provide
appropriate margins for the intended factors but may
also contain excess conservatism that would partially
counteract reductions in fatigue life due to EAC.
Based on large research programs, methods have
been developed in the United States42 and in
Japan51,53 for incorporating the effects of LWR coolant environments into fatigue evaluations. Experimentally derived fatigue life correction factors Fen
(defined as the ratio of life in air at room temperature
to that in water at the service temperature) are used
to adjust component fatigue usage values for environmental effects. Such approaches have recently been
implemented in the Japanese JSME Code54 and the
new US NRC Regulatory Guide 1.207,55 which is to
apply to new plants.
The apparent discrepancy between isothermal
laboratory results (strong environmental effects) and
field experience (only a few CF incidents under very
specific circumstances, predominantly related to thermal transients) mainly arises from the large degree
of conservatism in the fatigue evaluation procedures
mentioned earlier. The significantly higher strains of
design transients may fully outweigh possible environmental effects for real plant transients. Furthermore,
one or more threshold conditions are often also not
satisfied for most transients. Even plant transients

with strong environmental effects (e.g., at slow strain
rates) are usually not very damaging with respect to
fatigue damage accumulation because of their small
strain amplitudes, together with the rather limited
number of cycles during the whole component lifetime. Finally, as discussed earlier, the turbulent flow
rate at most component surfaces significantly retards
corrosion fatigue crack initiation (in particular for
small strains and slow strain rates) compared to
the quasi-stagnant conditions used in most lab
investigations.38,41,42
fatigue flaw tolerance evaluations according to
Section XI of ASME BPV Code in the context of
environmental effects
Fatigue flaw tolerance evaluations in combination

with periodic in-service inspections are based on
Section XI of the ASME BPV Code. Article A-4300
in Appendix A of Section XI contains a set of reference fatigue crack growth rate da/dN curves for CS
& LAS in air (air curves) or in LWR coolant environments (wet curves).56 The current ASME XI wet
curves (Figure 17) are based on lab data obtained
prior to 1980. They depend explicitly on DK and load
ratio R, but not on other variables that are known to
be important in CF, such as loading frequency, ECP,
or steel sulfur content. The same curves are used for
different types of CS & LAS and for BWR/NWC,
BWR/HWC/NMCA, and PWR primary or secondary side conditions. System conditions (or thresholds)
100
101
102
101
trise = 14 s
R = 0.95
0.018% S
100
101
102
43 s
6 0
N 20
e
=
s
ca t ise
e r
od .65
C 0
=
R
HWC, 274/288 C
3
64 s
N- 14
e =
s
e
ca t ris
de 95
Co = 0.
R
rv
103
ME
AS X I W
et,
ME
R
XI
0
W
.65
et,
R
0.2
5
101
N-643, EAC-curve for S > 0.013 % S, R = 0.65, tR = 100 s

N-643, EAC-curve for S > 0.013 % S, R = 0.65, tR > 1 s
N-643, non-EAC curve, R = 0.65
ASME XI Wet, R = 0.65
ASME XI Air, R = 0.65
AS
da/dN (m per cycle)
102
da/dNCF (m per cycle)
128
ir
XI
AS
trise = 2002000 s
R = 0.30.7
0.0040.018% S
cu
AC
-E
on
N
103
104
1
10
100
1
10
100
(a)
(b)
Figure 17 ASME XI Air and Wet curves and Code Case N-643 for high and low-sulfur steels (a) and comparison of cyclic
corrosion fatigue crack growth rates under hydrogen water chemistry conditions for different loading conditions with the
corresponding curves (b). Reproduced from Seifert, H. P.; Ritter, S. Corros. Sci. 2008, 50, 18841899.
where environmental effects on fatigue crack growth

can be neglected or excluded are not defined in the
present ASME Section XI Code.38,47
A more specific Code Case N-64357 for fatigue
crack growth in CS & LAS exposed to PWR primary
environments has been developed since 2000 and
may be used as an alternative to the ASME XI wet
reference fatigue crack growth rate curves for this
specific environment (Figure 17). Depending on system conditions, the Code Case N-643 procedure
predicts either lower or higher crack growth rates
than the general Section XI approach. The main
advantage of this newer Code Case is that it contains
criteria for the onset/cessation of EAC and that it
better reflects the experimentally observed cracking
behavior in PWR environments, since it considers
steel sulfur and frequencyloading-rate effects to a
certain extent. However, this approach has not (yet)
found general acceptance, primarily because of the
difficulty of defining appropriate rise times for actual
plant transients and the complications involved in
including these in component analyses.
In a similar way to that discussed earlier for
fatigue life design, conservatism in fatigue flaw tolerance evaluations may arise from (a) the fatigue flaw
tolerance evaluation procedures themselves (e.g., by
the use of design transients) and/or (b) the fatigue
crack growth rate curves. As discussed in Seifert and
Ritter,38,47 the current ASME XI wet curves conservatively cover the CF crack growth rate laboratory data
under most combinations of loading, environmental,
and material parameters. Even under highly oxidizing
BWR/NWC conditions, they are only significantly
exceeded under some very specific (but plantrelevant) circumstances (Figures 14 and 17), which
have caused some isolated CF cracking incidents in

the past. The Section XI curves might therefore be
regarded as an adequate, general bounding approach
under most system conditions, but they do not
realistically describe and reflect the experimentally
observed CF crack growth behavior of CS & LAS in
oxygenated high-temperature water. The curves predict crack growth rates which are either significantly
too high (e.g., n 102 Hz and ECP < 200 mVSHE)
or too low (e.g., n 102 Hz and ECP > 0 mVSHE).
Furthermore, system conditions or thresholds (e.g.,
n > 1 Hz), where environmental effects on fatigue
crack growth can be neglected, or even excluded, are
not defined in ASME XI.
5.06.3.2.3 Stress corrosion cracking
5.06.3.2.3.1
conditions
Initiation and susceptibility
Table 5 shows an assessment scheme according to

Hickling,58 based on both laboratory and field experience, for SCC initiation susceptibility and crack
growth in CS & LAS at normal strength levels
under BWR/NWC conditions.
Initiation of propagating SCC cracks from
smooth, defect-free surfaces under static load in
high-purity water is only observed for the following
conjoint conditions: stresses at the water-wetted surface above the high-temperature yield strength,
quasi-stagnant flow conditions, and dissolved oxygen
contents 0.2 ppm. Furthermore, if complete exhaustion of low-temperature creep is allowed to occur
before the specimens are exposed to high-purity,
high-temperature water, no SCC is observed, thus
indicating nonclassical SCC behavior and confirming the importance of slow dynamic surface straining
Assessment scheme for SCC susceptibility of CS & LAS
O2 (ppm)
Operating medium: HT water or steam condensate with T > 170 C

Flow conditions
k (mS cm1)
Crack initiation by SCC?
Derivation
Crack growth by SCC?
Derivation
<0.2
<0.2
<0.2
Typical for reactor

Quasi-stagnant
Quasi-stagnant
Typical, that is, 0.1

0.2
Raised (e.g., by impurities)
1
1
2
Typical for reactor

Quasi-stagnant

0.2
0.20.4
Quasi-stagnant
0.4
Typical for reactor
0.4
Quasi-stagnant
<1 often (0.2)
0.4
Quasi-stagnant
No susceptibility
No susceptibility
Possibility cannot be excluded,
perhaps after incubation time
No susceptibility
Susceptibility is suppressed
through flow
1
2
3
0.20.4
0.20.4
No susceptibility
No susceptibility
For stress levels at the water-wetted surface in
the region of the HT yield pointa
No susceptibility
For stress levels at the water-wetted
surface > HT yield pointa
For stress levels at the water-wetted surface in
the region of the HT yield pointa
In general, no susceptibility (? at stress
levelsHT yield point)
For stress levels at the water-wetted surface
HT yield pointa
For stress levels at the water-wetted in the
region of the HT yield pointa
1
2
2
1, 3
2
2
a
Possibility cannot be excluded, perhaps after long incubation time.
1 from experiments in more aggressive environments; 2 from appropriate autoclave experiments; 3 no direct experimental evidence.
Source: Hickling, J.; Reitzner, U. VGB Kraftwerkstech. 1992, 72, 359367.
1
2
2
2
2
2
Table 5
129
under such conditions. Initiation of small nonpropagating SCC surface microcracks (surface
length < 15
grain diameter) at (MnS) inclusions
or corrosion pits may occur under less severe conditions than specified earlier. Furthermore, the possibility of SCC at stresses around the high-temperature
yield strength range cannot be excluded for very unfavorable parameter combinations.38,40,58
Since the primary design stresses are limited to
values below the yield strength and turbulent flow conditions prevail at most component locations, SCC initiation appears to be extremely unlikely under stationary,
transient-free, LWR power operation conditions, but
growth of a preexisting crack could occur under certain
conditions, as discussed in the next section.
5.06.3.2.3.2 SCC crack growth
Stress corrosion crack growth rate

da/dtscc (m s1)
In contrast to SICC and CF crack growth (and to the

behavior of austenitic stainless steels and nickel-base
alloys), CS & LAS reveal very low susceptibility to
sustained SCC crack growth up to high KI levels
in LWR environments at operating temperatures.
Such high KI-levels would correspond to rather
deep cracks in pressure-boundary components. In
laboratory tests with relatively small specimens,
no sustained SCC crack growth (or only very
slow (<0.6 mm year1), often localized propagation)
is observed up to KI values of 5060 MPa m1/2 in a
chloride-free BWR/NWC environment and up to
80100 MPa m1/2 in PWR or BWR/HWC/NMCA
environments. Above these KI thresholds, SCC growth
rates increase rapidly within a small KI-interval of
1020 MPa m1/2 and reach a plateau at high growth
rates of up to several meters per year.38,5961
(a)
106
T = 288 C, 0.004 0.018 % S
O2 = 200600 ppb, < 1 165 ppb SO42
2
108
1010
O2 = 8 ppm, <165 ppb SO4
Down-pointing arrows indicate continuous decay of SCC

with subsequent crack arrest within 1000 h
BWRVIP-60 SCC DL 1
1012
40
60
80
100
20
Stress intensity factor Kl (MPa m1/2)
The very low SCC crack growth susceptibility

at KI values below 50 MPa m1/2 is also confirmed by
long-term exposure of precracked specimens in
actual reactors,61,62 as well as by the field experience
with both unclad LAS components and with cracks
in claddings or dissimilar metal welds, where the
crack-tip extends to LAS at the fusion boundary
(see Section 5.06.3.2.5).
On the other hand, critical conditions for water
chemistry (e.g., chloride content > 5 ppb high ECP
> 0 mVSHE), for loading (e.g., ripple loading), or for
the material itself (e.g., hardness > 350 HV5 or high
DSA susceptibility at intermediate temperatures) can
result in sustained and relatively fast (>10 mm
year1) SCC for KI-values well below 60 MPa m1/2
(Figures 18 and 19). Such conditions, identified in
laboratory experiments, generally appear atypical
for current, optimized BWR power operation practice
with modern, properly fabricated CS & LAS pressureboundary components. Changing to HWC (i.e., low
ECP) always results some few hours later in a significant reduction of laboratory SCC crack growth rates
(by more than one order of magnitude even under
otherwise critical conditions).38,60
BWRVIP-60 SCC disposition lines
With regard to structural integrity, the possible

occurrence of SCC is usually more critical than CF,
since fatigue was considered in the original component design, whereas even very slow SCC growth
rates might result in relevant crack advance over
long operational periods. Within the framework
of the BWRVIP program of the Electric Power
Stress corrosion crack growth rate
da/dtscc (m s1)
130
(b)
106
108
T = 288 C, Weld HAZ,

350 HV5 + 0.022% S
T = 288 C, 460 HV5
T = 288 C, KI KIJ
1010
BWRVIP-60 SCC DL 1
1012
180 C < T < 270 C + high DSA

Base metal
Weld filler
Weld HAZ
20
40
60
80
100
Stress intensity factor Kl (MPa m1/2)
Figure 18 (a) Experimental confirmation of the conservative character of the BWRVIP-60 stress corrosion cracking
disposition line 1 for stationary, transient-free boiling water reactor power operation at 274288 C. (b) Constant load test
results with stress corrosion cracking growth rates above the BWRVIP-60 stress corrosion cracking disposition lines 1.
Reproduced from Seifert, H. P.; Ritter, S. J. Nucl. Mater. 2008, 372, 114131.
131
8.0 ppm DO
109
0.4 ppm DO
108
0.2 ppm DO
line
r SCC
sulfu
h
g
Hi
line
CC
S
r
fu
sul
wo
L
100 ppb Cl
50 ppb Cl
20 ppb Cl
15 ppb Cl, 250 C
10 ppb Cl
5 ppb Cl
on curv
e
+200 mVSHE
8 ppm DO
0.02 wt % S
1010
Transiti
SCC crack growth rate da/dtSCC (m s1)
107
1011
BWRVIP-60 SCC DL 2 for water chemistry transients

BWRVIP-60 SCC DL 1 for stationary power operation
101210
20
(a)
30
40
50
60
70
80
Stress intensity factor KI (MPa m)
90
100
Accelerated SCC crack growth (>10 mm year1) at KI < 60 MPa m
T = 274/288 C
NWC
200
0
Continuous operation
allowed
Prompt
shut-down
EPRI action
Level limit 3
400
EPRI action
Level limit 1
200
HWC
Corrosion potential ECP (mVSHE)
No SCC (<0.6 mm year1) at KI < 60 MPa m
600
1
(b)
10
Chloride content (ppb)
100
Figure 19 (a) Effect of chloride content on stress corrosion cracking crack growth in low-alloy steel in simulated boiling
water reactor/normal water chemistry environment and comparison with the BWRVIP-60 stress corrosion cracking
disposition lines and the F & A model. (b) Synergistic effect of electrochemical corrosion potential and chloride content on the
onset of fast stress corrosion cracking in low-alloy steel under simulated boiling water reactor conditions and comparison
with the typical conditions during stationary boiling water reactor power operation and Action Levels 1 and 3 of the EPRI BWR
water chemistry guidelines. Reproduced from Seifert, H. P.; Ritter, S. J. Nucl. Mater. 2008, 372, 114131.
Research Institute (EPRI), SCC disposition lines for

flaw tolerance evaluations (Figure 18) were developed in 1999 based on lab investigations and service
experience61 and later accepted by the US NRC as an
interim position. The BWRVIP-60 SCC disposition
line 1 applies to crack growth in LAS under static
loading and transient-free, stationary BWR/NWC or
HWC power operation conditions. On the other
hand, disposition line 2 (low-sulfur SCC line of
the Ford and Andresen model63) may be used for
estimating SCC crack growth during and 100 h after

transients in water chemistry (>EPRI action level 1
limit of EPRI BWR water chemistry guidelines64) or
load transients not covered by fatigue evaluation
procedures. These curves are currently undergoing
minor revisions.
The conservative character of the BWRVIP-60
disposition line 1 for SCC crack growth in CS &
LAS under NWC conditions has been confirmed
for temperatures in the range of 274288 C and
132
both base and weld filler/heat-affected zone (HAZ)

materials (Vickers hardness < 350 HV5, 0.02 wt% S)
if the water chemistry is maintained within current
BWR/NWC operational practice (<EPRI action
level 1 limit).38,60
In the case of NWC conditions, several results
clearly indicate, however, that line 1 may be slightly
exceeded at intermediate temperatures (180270 C)
in CS & LAS which show distinct susceptibility to
DSA. Not unexpectedly, sustained SCC with crack
growth rates significantly above line 1 is observed at
288 C if excessive hardness (350 HV5) is present in
the steel, for example, in bad weld HAZs. Furthermore, BWRVIP-60 disposition line 2 is significantly
exceeded for the case of ripple loading (R > 0.95) or
during chloride transients ( EPRI action level 1
limit), even at fairly low stress intensity values
around 30 MPa m1/2 (see Figure 19). On the other
hand, line 2 seems to cover even very severe sulfate
transients above the EPRI action level 3 limit.38,60
At low ECP, that is, in the case of BWR/HWC or
PWR conditions, line 1 appears conservatively to
cover the SCC crack growth in LAS, even under
the otherwise critical conditions mentioned earlier
for more oxidizing, environments.38,60
FRAD-EAC-mechanism
1
5.06.3.2.4 EAC mechanisms and models

5.06.3.2.4.1
EAC crack growth mechanism
For the case of EAC in CS & LAS in hightemperature water, the film rupture/anodic dissolution (FRAD), also referred to as slip dissolution/
oxidation, and hydrogen-assisted EAC (HAEAC)
cracking mechanisms have been proposed in the
literature (see Figure 20). Either of these may be
superimposed on pure mechanical fatigue.
In the FRAD mechanism, the protective oxide film
formed on CS & LAS in high-temperature water is
ruptured by plastic straining at the crack-tip. The
crack-tip then advances by anodic dissolution of the
bare metal matrix. Anodic dissolution is slowed down
and finally stopped by the nucleation and reformation
of the oxide film (repassivation). Thus, continued
crack advance will depend on a further oxide rupture
process due to the action of a strain rate at the cracktip. The crack propagation rate is controlled by both
anodic dissolution/repassivation kinetics and the frequency of oxide film rupture at the strained crack-tip.
The first part is governed by the chemical composition
of the local crack-tip electrolyte and the material. The
second part is determined by the fracture strain of
the oxide film and the crack-tip strain rate.63
Hydrogen-assisted EAC mechanism

syy
Crack surface covered by

an oxide film
Bare surface of metal

generated by oxide film rupture and
anodic dissolution of the metal
Elasticplastic
stress distribution
Acidic oxygen free water

Oxide layer
1
Void
8
8
3
MnS
MnS
Fe2+
4
1. Local anodic reaction
Repassivation: Oxide
nucleation and growth
ad
Fe Fe2+ + 2e
2. Hydrolysis and generation of H+
Fe2+ + H2O FeOH+ + +
3. Liquid phase transport
4. Local cathodic reaction
H+ + e H
MnS + 2H+ H2S + Mn2+
7
5. Hydrogen absorption
6. Hydrogen transport in lattice
7. Hydrogen trapping on inclusions
8. Hydrogen-induced cracking
9. Linkage of microcracks to
main fracture
Figure 20 Schematic illustrations of film rupture/anodic dissolution (left) and of hydrogen-assisted environmentally
assisted cracking mechanisms for carbon and low-alloy steel in high-temperature water. Adapted from Ford, F. P. J. Pressure
Vessel Technol. 1988, 110, 113128; Hanninen, H. et al. Corros. Sci. 1983, 23, 663679.
Oxide film rupturerepassivation events at the

strained crack-tip are also involved in the HAEAC
model, but here, hydrogen-induced microcrack formation ahead of the crack-tip and linkage of
these microcracks to the main crack are the prime
sources of EAC crack growth, and result in discontinuous crack propagation. The hydrolysis of metal
cations from anodic dissolution is an important
source of hydrogen, but in contrast to the FRADmechanism anodic dissolution does not contribute
significantly to crack advance. Hydrogen transport in
the electrolyte and in the metal lattice is believed to
be fast. Therefore, the generation of bare metal surface by film rupture and film reformation may be the
rate-controlling steps and explain the strain rate
dependence of EAC.65,66
The FRAD and HAEAC mechanisms may be
simultaneously active and controlled by the same
rate-limiting steps (e.g., oxide film rupture rate or
repassivation kinetics). Both mechanisms are able to
explain the observed, dominant effect of strain rate
and of MnS inclusions on EAC. The EAC behavior of
CS & LAS in high-temperature water can best
be rationalized by a superposition/combination of
the FRAD and HAEAC mechanisms. At lower temperatures (<100 C) and/or high yield strength/
hardness levels (>800 MPa/>350 HV5) and high
strain rates (>103 s1), hydrogen effects are more
HCl H2SO4
NaCl
Role of MnS inclusions
Sulfur-anions as HS, S2, and SO2

may signifi4
cantly retard repassivation after oxide film rupture
and therefore increase crack advance by anodic dissolution in the FRAD model.38,63 Retarded repassivation of the film-free surface and adsorbed HS, S2,
or H2S also increase hydrogen absorption into the
metal lattice and therefore favor HAEAC.38,65,66 Furthermore, the dissolution of MnS is a further potential source of hydrogen, and MnS inclusions in the
region of maximum hydrostatic stress ahead of the
crack-tip may act as strong hydrogen traps and thus
HAEAC microcrack initiation sites.38,65,66
The effects of steel sulfur content are synergistic
with environmental variables, such as (sulfur-) anionic
impurities in the bulk environment, ECP (dissolved
oxygen content), and flow rate (Figure 21).38,67 This is
believed to be due to the creation of a sulfur-rich
crack-tip environment responsible for EAC, which
arises both from the dissolution of MnS intersected
by the growing crack and by the transport of sulfuranions by migration/diffusion/convection within the
crack enclave.38
SSRT, 1106s1
hpw, 288 C
Low-flow autoclave
100
5.06.3.2.4.2
Filled symbols TGSCC

Open symbols no SCC
100
200
pronounced. At high temperatures (150 C) and/or

lower yield strength/hardness levels and slow strain
rates (<103 s1), anodic dissolution appears to
dominate.38
Pure water
Cl
SO42
Na2SO4
300
400
500
SCC
200
300
No SCC
400
A533-B A508 A533-B
0
(a)
133
100
200
300
400
Anion concentration (ppb)
500
A533-B
0.005 0.010 0.015 0.020 0.025
600
(b)
Sulfur content (wt.%)
Figure 21 Synergistic effect of electrochemical corrosion potential and sulfate anion concentration (a) and steel sulfur
content (b) on strain-induced corrosion cracking susceptibility of low-alloy steel in high-temperature water. Data obtained
from Sund, G.; Rosborg, B. The influence of impurities on the tendency to stress corrosion cracking of pressure vessel steel
A533-B in water at 288 C; Personal communication; 1991.
134
(which affect repassivation/pH/oxide film stability)

in the crack-tip environment. The onset and extent of
EAC is crucially dependent on simultaneously maintaining a slow, positive crack-tip strain rate and a
critical, local sulfur-anion activity of about 15 ppm
S2. If these two conjoint requirements are not met,
no SCC and SICC and only minor environmental
acceleration of fatigue crack growth are generally
observed. If the critical anion concentration is
exceeded, the EAC crack growth rate depends primarily on the crack-tip strain rate and increases with
increasing external strain rate up to an upper critical
limit of around 103102 s1 (Figure 23). Most
EAC thresholds, as well as phenomena involving
cessation or local retardation of crack growth, may
be directly attributed to this conjoint requirement
and thus to crack-tip environment chemistry and
crack growth rate/crack-tip strain rate, rather than
to overall loading parameters or bulk environmental
conditions per se. For example, suitable combinations
of different parameters may help exceed the critical
crack-tip sulfur-anion concentration, provided that
there is at least one source of sulfur (MnS inclusions
or sulfur anions in the bulk environment).38,63,69
These two local factors are governed by a system
of interrelated and synergistic corrosion parameters:
In general, the crack-tip strain rate increases with
increasing loading rate/frequency/level, crack growth
rate, yield strength, and DSA susceptibility. The
sulfur anion activity in the crack-tip environment
increases with increasing steel sulfur content, concentration of sulfur anions in the bulk environment outside the crack, crack growth rate (exposure of fresh,
dissolvable MnS by the growing crack), and corrosion
Under certain combinations of temperature (100

350 C) and strain rate (108102 s1), DSA may
synergistically interact with both mechanisms to
increase EAC susceptibility and provide an additional contribution to the crack growth process
(Figure 22). DSA may result in the occurrence of a
higher crack-tip strain/strain rate than for loading
outside the DSA range, or than in a material which
is not susceptible to DSA. The localization of plastic
deformation and increase in planar deformation from
DSA probably support mechanical rupture of the
oxide film and result in a reduction of the local
fracture toughness, thus favoring quasi-brittle crack
extension.38,68
The concentrations of free, interstitial nitrogen
and carbon (which mainly govern the DSA susceptibility in CS & LAS) might therefore be just as relevant for EAC susceptibility as the steel sulfur content,
and some data suggest that DSA may even overwhelm sulfur effects under certain conditions. DSA
generally results in an extension of the susceptibility
region and can affect the temperature and strain-rate
dependence of EAC. The most pronounced effects
of DSA on EAC38 are typically observed close to
crack growth thresholds (e.g., for SCC under static
load,60 or for CF close to critical frequencies under
cyclic load47).
5.06.3.2.4.4 Controlling factors for EAC crack
growth
As shown by lab testing, EAC growth from incipient

cracks is essentially governed by the crack-tip strain
rate and the activity of sulfur or chloride anions
108
80
90
20 MnMoNi 5 5, A, 0.004 % S
DO = 8 ppm, 65 ppb SO42
20 MnMoNi 5 5, A, 0.004 % S
SRL tests (8 ppm DO, 65 ppb SO42)
Tensile tests in air (DIN 50125)
70
SCC crack growth da/dtSCC (m s )
80
Open symbols: no SICC detected by DCPD (Kmax

)
I
75
60
70
50
65
40
Reduction of area Z (%)
Stress intensity factor at the onset of

SICC crack growth KI,i (MPa m1/2)
90
85
109 BWR VIP 60 DL K = 6075 MPa m1/2

I
80
1010
75
1011
70
1012
Reduction of area Z (%)
5.06.3.2.4.3 Role of dynamic strain ageing
65
30
100
(a)
150
200
250
Temperature ( C)
300
1013
60
350
(b)
50
100
150
200
250
300
60
350
Temperature ( C)
Figure 22 Coincidence of maximum of strain-induced corrosion cracking susceptibility in slow rising load tests (a) and
maximum in stress corrosion cracking growth rates in constant load experiments (b) with maximum in DSA susceptibility in
terms of temperature (and strain rate). (a) Reproduced from Seifert, H. P.; Ritter, S. J. Nucl. Mater. 2008, 378, 312326;
(b) reproduced from Seifert, H. P.; Ritter, S. J. Nucl. Mater. 2008, 372, 114131.
SA 533 B Cl. 1, C, 0.018% S, SICC

20 MnMoNi 5 5, A, 0.004% S, no SICC
20 MnMoNi 5 5, A, 0.004% S, SICC
107
108
6
Scatter band for dCODLL/dt =2 410
mm s1
8 ppm DO, + 150 mvSHE,288 C

dCODLL/dt = 24 106 mm s1
109
1010
135
DO = 8 ppm, <1or 65 ppb SO42, T = 288 C, 250 C, 200 C
106
SCC or SICC crack growth rate

da/dt scc or da/dtSICC (ms1)
SICC crack growth rate da/dtSICC (m s1)
100
200
300
Sulfate content (ppb)
106
Constant load
Very low-frequency cyclic load
107
Slow rising load

Linear fit of
95% prediction interval
108
109
1010
400
da/dtEAC (dCODLL/dt)0.8
Model: da/dtEAC = A . de/dtn
1011
109 108 107 106 105 104 103

Crack-opening displacement rate dCODLL/dt (mm s1)
Environmental component, +200 mvSHE

Mechanical component, air fatigue
106
Max. environm.
component
e
ur lin
ig
ue
-sulf
High
Shifted to
higher de/dt
10
10
with ECP , S
SO42 or Cl
108
rf
at
108
1012 10
10
(a)
DSA, YS de/dt for given loading conditions
fu
ul
-s
Ai
EAC crack growth rate (ms1)
104
lin
105
107
DO
DH [ppm]
21 0.79
8
0
0.4 0
HWC
+150 mVSHE
DO
DH
8.4 1.26
0 0.095
0 0.150
104
Crack-tip strain rate de/dt
102
100
(s1)
(b)
: NMCA
HWC
500 mVSHE T = 27428 C
low-alloy steel
109
F & A-model for NWC

F & A-model for HWC
PSI NWC curve
da/dtAir
1011
w
Lo
106
Corrosion fatigue crack growth rate in

high-temperature water da/dtCF (m s1)
Figure 23 Effect of sulfate content on strain-induced corrosion cracking crack growth in a low- and high-sulfur low-alloy
steel (left) and of crack mouth opening rate (as a measure for the crack-tip strain rate) on environmentally assisted cracking
crack growth rate under different loading conditions (right). Evidence for the described conjoint conditions and the important
role of crack-tip strain rate. Reproduced from Seifert, H. P.; Ritter, S. J. Nucl. Mater. 2008, 378, 312326.
High-sulfur line
Low-sulfur line
t Air
/d
da
1011
109
107
105
Figure 24 Basic environmentally assisted cracking crack growth curves of the F & A model (a) and good correlation of the
observed corrosion fatigue crack growth behavior under boiling water reactor/normal water chemistry and hydrogen water
chemistry or noble metal chemical addition conditions with the predictions of the F & A model (b). (a) Adapted from Ford, F. P.
J. Pressure Vessel Technol. 1988, 110, 113128 and (b) reproduced from Seifert, H. P.; Ritter, S. Corros. Sci. 2008, 50,
18841899.
potential/dissolved oxygen content (enhanced migration of sulfur anions toward the crack-tip).38
5.06.3.2.4.5 Ford & Andresen EAC model
The mixed mechanisticphenomenological Ford and

Andresen model (Figure 24) is the sole quantitative
approach for CS & LAS and is based on the FRAD
mechanism.48,49,63,69,70 In the case of corrosion
fatigue, a linear superposition of fatigue and EAC
crack growth is assumed. In this model, EAC crack
growth is controlled by the crack-tip strain rate
de/dCT and the sulfur-anion activity cCT in the
crack-tip electrolyte. The EAC crack growth rate
da/dtEAC increases with increasing crack-tip strain
rate de/dCT according to a power law and saturates

above a critical strain rate of 103102 s1 (continuous dissolution at a crack tip free of protective
oxide).
The exponent of this power law relationship
is dependent on the sulfide-anion activity in the
crack-tip environment. Above a sulfide concentration
of 0.02 ppm (low-sulfur threshold), the formation of
a new oxide layer is increasingly delayed by increasing sulfide content, which thus leads to a larger
increment of crack advance by anodic dissolution
per oxide-rupture event. Above a sulfide content of
2 ppm (high-sulfur threshold), the sulfide effect on
repassivation saturates. Based on this experimentally
136
derived relationship, lower and upper limiting EAC

crack growth curves for CS & LAS (Figure 24) were
defined (so-called low- and high-sulfur EAC lines).
A critical, high sulfur-anion content of 2 ppm S2
has to be maintained in the crack-tip electrolyte to
sustain fast, high-sulfur EAC crack growth rates, otherwise the crack growth rates quickly drop down to
low-sulfur crack growth rates.48,49,63,69,70
The sulfur-anion concentration in the crack-tip
environment from dissolution of MnS inclusions is
assumed to be proportional to the steel sulfur content
and the crack growth rate itself (intersection of the
crack with new, dissolvable MnS inclusions) and to
increase exponentially with the potential gradient/
ECP (based on crevice experiments and modeling).
Similarly, the degree to which sulfur anions are
enriched in the crack-tip environment depends on
how much they tend to migrate there from the bulk
environment. It is thus proportional to their concentration and increases exponentially with potential
gradient/ECP.48,49,63,69,70
The Ford and Andresen model correctly predicts
most experimentally observed EAC data trends for
CS & LAS over a wide range of conditions.38 Furthermore, it has also been successfully applied to
predict LCF initiation.70 It therefore has good potential for data analysis and the definition of disposition
lines. The high-sulfur line of the model conservatively covers almost all EAC crack growth rate data.
Recent results indicate, however, that the transition
curve between the low- and high-sulfur CF lines
might be nonconservative under highly oxidizing
BWR/NWC conditions (ECP > 0 mVSHE) and very
low loading frequencies (<104 Hz),47 possibly as a
result of DSA (which is not considered in the model).
Furthermore, the model predicts much too high
SCC crack growth rates at KI levels < 60 MPa m1/2
in high-purity water.38 This is related to the cracktip strain rate formulation for static loading conditions,
which was originally derived for stainless steels and is
generally unsatisfactory when applied at these lower
KI levels.38 In addition, the model does not explain the
unexpectedly strong effect of relatively low chloride
levels on SCC crack growth rates (see Figure 19).
5.06.3.2.5 Service experience and
mitigation actions
5.06.3.2.5.1 Service experience
The accumulated operating experience with CS &

LAS pressure-boundary components in the primary
and secondary coolant circuits of LWRs is very good
worldwide. Use of the current fatigue design and

evaluation codes (ASME III and XI) has been generally successful in preventing fatigue cracks and failures in CS & LAS components and therefore the
limited (and nonspecific) consideration of EAC
in these codes would at first sight seem to be
adequate under most operating circumstances, or
even (fortuitously) conservative. However, isolated
instances of EAC have occurred under specific circumstances and these always involved several unfavorable factors. EAC has occurred particularly in
BWR service, most often in CS & LAS piping, less
frequently in vessels, and very rarely in the clad RPV.
EAC cracking has been observed in wrought, weld
filler, and weld HAZ materials and has been transgranular in nature. In BWRs, steam and feedwater
piping as well as condensate systems and RPV
feedwater nozzles have been affected (Figure 25).
In the secondary circuit of PWRs, cracking has
been observed in feedwater piping/tanks and heat
exchangers, feedwater nozzles of PWR steam generators, and steam generator girth welds. EAC damage was usually detected during in-service inspection
and seldom led to through-wall penetrations with
leakage.1,38,39,46,63,7174
These EAC incidents have been clearly associated
with an oxidizing environment (usually due to dissolved oxygen), severe dynamic straining (due to
global and local thermal stratification/striping, or
due to thermal and pressurization cycles during plant
transients), and either high local stresses (around or
above the high-temperature yield strength) or high
secondary/residual stress (due, e.g., to welding defects,
pipe bends in conjunction with inadequate pipe supports or restraints, and localized post-weld treatment).
Most PWR cracking incidents involved aerated feedwater under specific start-up operating conditions (no
application of nitrogen blankets in condensate storage
tanks) or at special locations (e.g., locations with air
present during shutdown), where the normally low
contents of oxygen and low ECP during operation
cannot be assumed upon startup. The fact that cracking frequently occurred in BWR lines with stagnant
steam or nondegassed condensate, but not in comparable lines carrying flowing steam, is another indication that oxygen concentration and ECP are crucial
parameters with respect to the occurrence of EAC,
since such conditions are known to encourage
the formation of a condensate film rich in dissolved
oxygen. Thermal hydraulics (thermal stratification/
striping phenomena) and local stress raisers played
a key role and were often more important than water
5 mm
(a)
(c)
(b)
Feed water pipe
Weld root
5 mm
137
5 mm
RPVnozzle
(d)
200 mm
Figure 25 (a) Circumferential strain-induced corrosion cracking crack at the feedwater pipe to reactor pressure vessel
nozzle weld of a German boiling water reactor originating form a weld root notch due to severe thermal stratification during
plant start-up and hot stand-by at low feedwater flow rates. Reproduced from Hickling, J.; Blind, D. Nucl. Eng. Des. 1986, 91,
305330. (b) Crack interruptions markings on a strain-induced corrosion cracking fracture surface indicating intermittent
crack growth during plant transients. Reproduced from Hickling, J.; Blind, D. Nucl. Eng. Des. 1986, 91, 305330. (c) Formation
of multiple, semielliptical strain-induced corrosion cracking cracks at a circumferential weld between a straight seamless pipe
and a valve casing in a boiling water reactor. Reproduced from Hickling, J.; Blind, D. Nucl. Eng. Des. 1986, 91, 305330.
(d) Corrosion fatigue cracks in carbon steel instrumentation line at the main steam pipe of a pressurized water reactor
originating from corrosion pits with intermittent corrosion during shutdown and subsequent reinitiation of cracking during
plant transients. Reproduced from Roth, A. et al. In Proceedings of the 12th International Conference on Environmental
Degradation of Materials in Nuclear Power System Water Reactors, Snowbird, Salt Lake City, UT, Aug 1418; Todd, R. A.,
King, P. J., Nelson, L., Eds.; The Minerals, Metals and Materials Society: Warrendale, PA, 2005; pp 795802.
chemistry or material aspects. These cases were

attributed either to SICC or CF. Cracking incidents
with a major or relevant contribution of SCC to the
total crack advance in properly manufactured and
heat-treated CS & LAS primary pressure-boundary
components have not been observed. In fact, longterm exposure and reinspection of unclad components, such as BWR feedwater nozzle radii or vessel
heads, and several cracking incidents in dissimilar
metal welds (e.g., in core shroud support welds,
where crack-tips in the susceptible Alloy 182 weld
metal arrested in the interface region to the adjacent
LAS) confirm the generally excellent resistance of
CS & LAS to SCC in reactor coolant.38,39,72,73
Cracks often initiated from water-wetted geometric discontinuities (e.g., welding defects) and/or in
regions with stagnant flow or creviced geometry.
In several cases, EAC cracks preferentially initiated

from corrosion pits (Figure 25) and corrosion during
shutdown periods (pitting and sometimes corrosion
products (rust) close to the water line as a possible
source of anionic impurities during startup) can be
a further contributing factor. In general, crack initiation
has been more affected by high-frequency, high-cycle
fatigue, for example, due to local thermal stratification
or thermal striping loads which were limited to nearsurface regions. Crack propagation was often dominated by LCF from slower and less frequent transients,
for example, due to more global thermal stratification
or to operational power transients.38,39,72,73
Several incidents were related to unanticipated
sources of thermal stress cycles in critical locations.
In many cases, fabrication or design deficiencies
(e.g., welding defects) favored local plastification of
138
the water-wetted material surface and sometimes

resulted in an increased loading level (from residual
stress) or increased EAC susceptibility of the material
(e.g., excessive hardness of weld HAZs and distinct
DSA susceptibility of weld metal). Reoccurrence of
this kind of cracking can be avoided by improved
design of the components and/or fabrication procedures, as well as by better quality control during
the manufacturing process, and in some cases by
optimized operational procedures.38,39,7274
5.06.3.2.5.2 Critical components and operational

conditions
Special attention should be paid to components which

are likely to undergo significant (localized) mechanical
loading, or which are exposed to increased oxygen
levels in the coolant, higher conductivities, and/or
quasi-stagnant flow conditions during operation.
Critical components, for example, are piping carrying nearly stagnant steam, or nondegassed condensate, during normal reactor operation (e.g., in systems
which are used only intermittently), feedwater nozzles and adjacent sections of horizontal piping (if
thermal stratification can occur) and thin-walled piping, and pipe bends in conjunction with inadequate
pipe supports or restraints. Operational transients
associated with thermal stratification and thus high
secondary strains (e.g., start-up, hot stand-by, or slow,
but relevant pressure and temperature changes)
should receive attention, in particular, if they occur
with a sufficiently high frequency.38
5.06.3.2.5.3 Possible mitigation actions and
countermeasures
Apart from good design, the common EAC mitigation

strategy is, firstly, to exclude large preexisting defects
by nondestructive examination and quality assurance
measures during fabrication and installation of components and, secondly, to avoid during operation
those water chemistry and stress or strain combinations which could lead to either EAC crack initiation
or to accelerated crack growth. This procedure
should be complemented by periodic, nondestructive, in-service inspection of critical component locations. In summary, EAC risks can be minimized by38:
Selection of suitable materials, for example, lowsulfur steel (<0.003 wt% S) with low EAC and
DSA susceptibility and optimized high toughness
(! larger critical crack size).
Selection of suitable manufacturing and fabrication practices to avoid welding defects and HAZs
with high hardness (350 HV5) and to reduce residual stress (e.g., stress relief heat treatment and
narrow gap welding).
Improved design to reduce regions of high local
stresses (by increased wall thickness, by internal
flush grinding of joints and optimization of welding
technology, avoidance of discontinuities and constraints, optimized pipe supports, etc.).
Reduction of the number and severity of thermal
and pressurization cycles (thermal-stratification
during hot stand-by, startup/shutdown), for example, by optimized operating procedures and/or by
improved design of the affected component (thermal sleeves for feedwater nozzles, feedwater spargers, etc.).
Avoidance of near-stagnant operating conditions
(including in crevices or dead-legs) and reduction
in dissolved oxygen levels (e.g., by inert gas shielding of make-up water, modification of startup procedures to allow venting of piping, improvement of
drainage in horizontal lines, etc.).
Maintenance of adequate water chemistry control
with regard to anionic impurities (EPRI or VGB
guidelines) and application of HWC/NMCA to
reduce the ECP in BWRs.
5.06.3.2.5.4 Service experience vs. experimental

and theoretical background knowledge
Plant-operating experience fits well to the accumulated

experimental/mechanistic background knowledge on
EAC and pitting behavior for CS & LAS components
exposed to high-temperature water. Both show the
same qualitative parameter trends, for example, for
dissolved oxygen (ECP), flow rate, and strain. They
confirm the high SCC resistance of CS & LAS under
static loading conditions (steady-state power operation) and clearly reveal that slow, positive (tensile)
straining with associated (localized) plastic yielding
and sufficiently oxidizing conditions are essential for
EAC initiation in high-purity, high-temperature water.
Since primary design stresses are generally limited to
values below the elastic limit, thermal-hydraulics (e.g.,
thermal stratification) and local stress raisers have
therefore played a key role for SICC/CF in the field
and were generally more important than material or
water chemistry aspects. EAC cracks often initiated
from corrosion pits and pitting of LAS is strongly
favored under oxidizing conditions, especially at low
and intermediate temperatures, and by slow, dynamic
straining. Quasi-stagnant or low-flow conditions promote EAC initiation by the formation of an aggressive, occluded water chemistry at the base of the pit
(or within small surface defects), as well as by the

enrichment of oxygen in steam condensate.38,39,72,73
By taking the exact boundary conditions in laboratory tests and in the field into account, no major
discrepancy between operating experience and experimental trends is found. The few EAC cracking incidents in the field can be rationalized by the identified
susceptibility conditions and by EAC flaw tolerance
evaluations. The apparently higher cracking frequency in lab tests may be explained by the beneficial
effect of a turbulent flow rate in the field (which is
characteristic for most component locations) upon
EAC initiation, the large degree of conservatism
in the fatigue evaluation procedures, and the conjoint
threshold conditions for the onset of EAC with
regard to ECP (or dissolved oxygen), strain rate,
strain, and temperature. In general, for most transients/component locations, one or more threshold
conditions are not satisfied. The threshold strain
and stress for SICC/CF and SCC initiation, in particular, are seldom exceeded in the case of good
operational practice and the absence of design or
fabrication deficiencies.38,39,7173
5.06.4 Conclusions
5.06.4.1 Uniform and Flow-Accelerated
Corrosion
Uniform corrosion of CS and LAS poses no significant threat to the integrity of coolant systems under
normal operating conditions; the typical corrosion
rates of less than 1 mm year1 or so are manageable.
A significant drawback of the material is the rather
thick corrosion-product layer that develops in hightemperature water double-layered magnetite in
alkaline, reducing conditions (such as PWR or
CANDU primary coolants) but with an admixture
of oxidized species such as maghemite or hematite in
neutral, oxidizing conditions (such as BWR coolant).
The fouling and contamination of reactor circuits
from the release of such oxides by spalling in high
flows, as well as by dissolution as a result of solubility
gradients, is minimized by careful chemistry control.
Similarly, although the material in contact with PWR
primary coolant is mainly stainless steel or nickelbased alloy, the transport of nickel-ferrite corrosion
products is minimized by continuous control of alkalinity. The reactor circuit in BWRs exposes mainly
stainless steel to the coolant, but depending upon
the chosen operating chemistry (NWC, HWC,
HWC/NMCA) the chief source of corrosion
139
products (CS/LAS in the feedtrain) can be controlled

by the addition of metal ions to the feedwater so as to
give an optimum ratio of Fe/Ni and minimize radiation field buildup. CANDUs have unclad CS in the
primary circuit and operate at constant high pH;
although this controls activity transport, general fouling of the circuit from corrosion products released
from FAC can create thermohydraulic problems.
Some CANDUs have had to clean components in
the primary system in order to restore optimum
operating conditions.
The stainless-steel cladding in PWR primary circuits prevents corrosion of the LAS base material,
especially under shutdown conditions. However,
leaks at high temperature can allow the boric acid
in the coolant to concentrate on unclad external surfaces and, together with oxygen from the atmosphere,
can provoke highly corrosive situations. Flow effects
can exacerbate such attack. Rigorous surveillance
regimes are required to avoid damage to components
such as flanges, valve fittings and especially, the
pressure-vessel head in the vicinity of leaking penetrations. Corrosion of unclad CS & LAS in PWR
secondary systems is prevented by chemistry control
during HT-operation, but additional measures (e.g.,
nitrogen blanketing) are required during shutdown.
FAC of CS in reactor systems is most damaging in
feedwater circuits, where the solubility of normally
protective oxide films is high, dissolved iron is low,
and turbulence is intense. Chronic FAC of feeders in
the CANDU primary circuit occurs through similar
mechanisms, although the oxide solubility is low at
the constant high pH and temperature of the coolant.
Depending upon the circumstances, oxide solubility
can be controlled to some extent by adjusting the
chemistry with pH additives (such as ammonia)
and/or adding oxygen (as is done in various feedwater circuits) or even by replacing components with
higher-Cr material. Commercial software is available
to pinpoint likely vulnerable areas, give some indications of possible rates of attack, and manage databases. However, rigorous surveillance of vulnerable
components, for example, where high coolant turbulence is induced, is still necessary to avoid catastrophic pipe failures.
5.06.4.2 Localized Corrosion and
In CS & LAS, a shallow form of pitting can occur in
the complete absence of anionic water impurities as
the corrosion potential (ECP) is raised, for example,
140
through oxygen and other oxidizing species. Some

degree of pitting corrosion is inevitable after longterm exposure of unclad CS & LAS surfaces to water
in LWR systems and is not usually a threat to either
coolant purity or to structural integrity. Shallow
pitting has been observed primarily in specific piping
systems with residual water because of incomplete
draining during nonoperational periods (shutdown
corrosion). This can be avoided by adequate wet or
dry preservation techniques.
Laboratory investigations have revealed significant effects of simulated reactor environments on
fatigue crack initiation/growth, as well as the possibility of SCC crack growth under certain critical
combinations of environmental, material, and loading
parameters. During the last three decades, the major
factors of influence and EAC susceptibility conditions have been clearly identified. The effects of
most parameters on EAC initiation and growth are
adequately known with acceptable reproducibility
and reasonably understood by mechanistic models.
Tools for incorporating environmental effects into
ASME III fatigue design curves have been developed/qualified, but not yet widely adopted. The
BWRVIP-60 SCC disposition lines and ASME XI
reference fatigue crack growth curves are usually
conservative and adequate under most PWR and
BWR operational circumstances, but there is nevertheless valuable potential for the reduction of undue
conservatism and the need for improvements to eliminate some specific inadequacies.
The operating experience of CS & LAS primary
pressure-boundary components in LWRs is very good
worldwide. However, isolated instances of EAC have
occurred, particularly in BWR service, most often in
piping and more rarely in the RPV itself. Oxidizing
conditions (usually dissolved oxygen) and relevant plastic straining were always involved. These cases were
attributed either to SICC or CF and can be rationalized
by the experimental/mechanistic background knowledge. Both service experience and appropriate laboratory experiments confirm the high resistance of CS
& LAS to SCC under static loading conditions (representative of steady-state power operation) and
clearly reveal that slow, positive (tensile) straining,
with associated (localized) plastic yielding and sufficiently oxidizing conditions, are usually necessary
for EAC initiation in high-temperature water. Based
on the above, different remedial and mitigation
actions have been qualified and successfully applied
to further reduce the low EAC cracking frequency
in the field.
In spite of the absence of SCC in operating reactors, several unfavorable, critical parameter combinations have been identified in the laboratory, which
can lead to sustained, fast SCC, with crack growth
rates well above the BWRVIP-60 SCC disposition
lines. Most of them appear atypical for current
BWR plant operation with properly manufactured
CS & LAS components, but some further clarification is required, in particular, with regard to
improved quantification of the boundaries/thresholds for the transition from very low to high SCC
crack growth rates. In this context, research should be
focused on the effects of chloride transients and DSA/
yield strength on the SCC crack growth behavior of
CS & LAS (including weld and HAZ materials) under
BWR/NWC conditions, as well as on the behavior of
Alloy 182-LAS dissimilar metal weld joints. Additionally, the mitigation effect of HWC/NMCA should be
confirmed under these critical conditions.
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1987; 11891200, Vol. III. pp 11891200.
70. Electric Power Research Institute. Environmentally
assisted fatigue crack initiation in low-alloy steels
A review of the literature and the ASME Code
requirements, EPRI TR-102765; EPRI: Palo Alto, CA,
1993; http://my.epri.com/.
71. Hickling, J.; Blind, D. Nucl. Eng. Des. 1986, 91, 305330.
72. Roth, A.; et al. Crack initiation due to environmentallyassisted cracking in carbon and low-alloy steels exposed
to high-temperature water Part 2: Overview and
assessment of operating experience. Workshop on
Detection, Avoidance, Mechanisms, Modeling, and
Prediction of SCC Initiation in Water-Cooled Nuclear
Reactor Plants, CD-ROM, Beaune, Burgundy, France,
Sept 712, 2008.
73. Roth, A.; Hickling, J. In Proceedings of the 13th
Materials in Nuclear Power Systems, CD-ROM, Whistler,
British Columbia, Canada, Aug 1923; The Canadian
Nuclear Society: Toronto, Canada, 2007.
74. Roth, A.; et al. In Proceedings of the 12th International
Conference on Environmental Degradation of Materials
in Nuclear Power System Water Reactors, Snowbird,
Salt Lake City, UT, Aug 1418; Todd, R. A., King, P. J.,
Nelson, L., Eds.; The Minerals, Metals and Materials
Society: Warrendale, PA, 2005; pp 795802.
5.07
Performance of Aluminum in Research Reactors
K. Farrell
Formerly of Oak Ridge National Laboratory, Oak Ridge, TN, USA
5.07.1
5.07.2
5.07.2.1
5.07.3
5.07.3.1
5.07.3.2
5.07.4
5.07.5
5.07.6
5.07.6.1
5.07.6.2
5.07.6.2.1
5.07.6.2.2
5.07.6.2.3
5.07.7
5.07.7.1
5.07.7.2
5.07.7.3
5.07.7.4
5.07.8
References
Introduction
Typical Applications
History of Aluminum Applications in Research Reactors
Properties of Aluminum
Practical Characteristics
Alloy Types, Temper Designations, and Tensile Properties
Fuel Elements
Corrosion
Radiation Effects
Basics
Microstructures
Fluence
Temperature
Transmutation products
Property Changes
Swelling
Mechanical Properties
Effects of Neutron Spectrum
Radiation Softening, Creep, and Stress Relaxation
Conclusion
Abbreviations
AIME
ANL
ANSI
ASM
ASTM
ATR
CRC
CTE
EBR-II
Emod
ETR
GR
HEU
HFIR
HPRR
IAEA
INL
IRV-M2
American Institute of Mining,

Metallurgical, and Petroleum Engineers
Argonne National Laboratory
American National Standards Institute
American Society for Metals
American Society for Testing Materials
Advanced Test Reactor
Chemical Rubber Company
Coefficient of thermal expansion
Experimental Breeder Reactor-II
Modulus of elasticity
Experimental test reactor
Graphite Reactor
Highly enriched uranium
High Flux Isotope Reactor
High performance research reactor
International Atomic Energy Authority
Idaho National Laboratory
Acronym for a recent Russian research
reactor
LANL
LEU
MTR
OPAL
ORNL
ORR
PIE
PIREX
RERTR
RR
SNF
STP
TRIGA
TEM
UTS
VPH
YS
144
144
144
145
146
147
149
153
158
158
159
160
161
161
166
166
166
169
170
173
173
Los Alamos National Laboratory

Low enriched uranium
Specifically, MTR is the Materials Testing
Reactor at Idaho National Laboratory.
Also used generically for materials test
reactors
Open Pool Australian Light water reactor
Oak Ridge National Laboratory
Oak Ridge Research Reactor
Post irradiation examination
Proton Irradiation Experiment facility
Reduced enrichment for research and
test reactors
Research reactor
Spent nuclear fuel
Special Technical Publication
Test, research, isotopes, general atomic
Transmission electron microscopy
Ultimate tensile stress
Vickers pyramid hardness
Yield stress
143
144
5.07.1 Introduction
Aluminum alloys are generally too weak or have
temperature limitations that preclude their use in
reactors built to produce electricity, high-temperature
process heat, or marine propulsion. But in the milder
conditions in most research reactors (RRs) where
bulk water coolant temperatures are usually <100 C,
aluminum alloys are quite comfortable and are universally employed and have greatly contributed to
the success and longevity of the reactors. RRs are
those whose principal function is to generate neutrons for purposes of nuclear education and training,
production of medical and industrial isotopes, neutron activation analyses, neutron scattering studies,
and even semiconductor doping, neutron radiography, and food preservation treatments. RRs are also
employed to study basic radiation effects in materials
and as test beds for evaluating candidate structural materials and fuels/assemblies for power reactors. RRs come in many shapes, sizes, and types.
For descriptions of the various classes of RRs, see
http://www.world-nuclear.org/ and West.1 They are
generally low power, typically about a few kilowatts,
thermal, but range up to about 250 MW. According to
the recently updated list2 of worldwide RRs published
by the IAEA, a total of 674 RRs have been built in
57 countries, of which 234 are still operational, and
7 are planned or under construction. Two new ones
are OPAL, the 20 MW Open Pool Australian Light
water-cooled reactor, which opened at Lucas Heights,
Sydney, in April 2007, and the Russian 4 MW pooltype IRV-M2 commissioned in 2008.
This chapter is a review, more a tutorial, of the
behavior of aluminum alloys in water-cooled RRs.
It is a somewhat personal view, based on American
experience in the area. Because that experience
has been adopted in many countries and is still
influencing the current state of the art, this chapter
should be of interest outside the borders of the
United States.
5.07.2 Typical Applications

Aluminum is the material of choice for construction of many components in low-temperature
water-cooled-and-moderated RRs. Typical applications are the reactor tanks in open-pool reactors;
containment vessels in some sealed reactors; core
grids; pedestals; neutron beam tubes; cold neutron
source moderator vessels; shrouds to direct and
separate water flows; shuttles (rabbits) and aluminum filler powder used to convey isotope target
materials and test materials rapidly in and out of
the reactor via aluminum hydraulic and pneumatic
tubes; sheaths and finned tubing for stationary longterm isotope target rods; cladding for control plates/
rods; cladding and liners for reflector materials; cladding and thermal conduction filler for fuel rods/
plates; and temporary plugs for closing idle irradiation
facilities in and around the core. Applications outside
the reactor per se are in-pool tool extension arms;
transfer gates between pool sections; restraint baskets
in some shipping casks; support beams for pool covers;
and hot cells manipulator arms.
5.07.2.1 History of Aluminum
Applications in Research Reactors
Aluminum was at the forefront of the development
of nuclear technology. It has the distinction of being
the first nonfissile, non-neutron absorber class metal
used in the worlds first continuously operating
nuclear reactor, the X-10 Graphite Reactor at Oak
Ridge, TN. The Graphite Reactor became critical
on 4 November 1943, <1 year after Fermis demonstration of a self-sustaining nuclear fission chain in
the graphite pile at the University of Chicago on
2 December 1942. In Fermis experiment, the only
metals in the pile were natural uranium and the
cadmium-coated control rods. The pieces of natural
uranium (238U containing about 0.7 at.% 235U) and
uranium oxide were bare, placed in shallow depressions carved into the upper faces of the graphite slabs,
and cooled by convection of ambient air. The power
level was about 2 kW. The X-10 Graphite Reactor
pile3 was much bigger than the Chicago pile and
was designed to operate at 1 MW thermal power,
later upgraded to 4 MW. It was built to produce
pilot plant quantities of plutonium isotopes. The
Chicago pile had no shielding; the Graphite Reactor
was shielded by a 2.2-m thickness of high-density
concrete. Aluminum made its debut in the Graphite Reactor as fuel cladding to protect the highly
chemically reactive uranium from contamination
by air and graphite during the higher power and
longer fissioning periods and to safeguard it from
attack by water during subsequent radioactive decay
in underwater storage. In addition, it trapped the
more copious volatile radiation products resulting
from the longer irradiation exposures. These
aluminumclad pieces of natural uranium, called
slugs, were the forerunners of metalclad fuel
elements. A slug was made by placing a solid cylinder

of uranium in a thimble-shaped aluminum can
25 mm diameter 100 mm long with a 0.75 mm
wall. A flat Al end cap was added, and the assembly
was passed through a die to force the can walls tightly
around the fuel. Surplus wall material was cut off
above the cap, and the cap was welded all around its
edge. These slugs were pushed end to end into the
reactor via round horizontal holes through the concrete face, which were aligned with 44 mm square
holes cut through the full 7.3 m width of the cubic
array of graphite blocks. The square holes were oriented on edge such that the slugs occupied the lower
corner, allowing cooling spaces around the slugs.
Cooling was simple: two large fans at the rear of the
pile sucked ambient air through the holes around the
slugs and discharged it up a tall chimney. The slugs
exited the pile at the rear face and were channeled into
a deep water canal where they were held until shipped
to hot cells for processing to extract the plutonium.
Some early problems4 were encountered in the slugs,
including faulty welds and blisters and formation of
an intermetallic UAl3 phase by interdiffusion at the
UAl interface, especially in the high-temperature
regions in the center of the reactor. The blistering
was attributed to fast-growing gas bubbles in the UAl3
phase. These problems were overcome by better
welding practice and the development of bonded
slugs as described next.
The next phase of exploitation of aluminum was
in the B reactor at the Hanford site in Washington
State, which went critical on 27 September 1944.
The B reactor was a scaled-up production model
of the Graphite Reactor designed to operate at
250 MW. At such power, forced air cooling would
have been inadequate. So the horizontal holes
were replaced with aluminum tubes in which
aluminumclad uranium slugs were cooled with
flowing water from the Columbia River. To improve
the transfer of heat from the uranium to the cladding, the spaces between them were filled with a low
melting Al12% Si eutectic alloy by melting the
eutectic in situ. A bonus of this treatment was that
it killed the formation of the UAl3 phase and associated blistering, presumably due to an inhibiting
effect of the silicon. The successes of these upgrades
established aluminum as a suitable material for use
in combined conditions of intensive irradiation and
a flowing aqueous environment. Aluminum became
more firmly entrenched in RRs with the development of advanced fuel elements, as described in
Section 5.07.4.
145
Before concluding the present subsection, another

lesser-known first for aluminum deserves mention.
It has particular relevance to the nuclear power
industry. It is not widely known that aluminum was
involved in the earliest demonstration of electricity
produced from steam made by boiling water in a
nuclear reactor. Normally, the heat from nuclear
fission in RRs is discarded, not used to produce
electricity. However, in August 1948, two staff members at the X-10 Graphite Reactor, Mansel Ramsey
and Charles Cagle, placed an aluminum can containing ten aluminumclad uranium slugs and some
water in a normally unused side channel of the reactor where it was exposed to reactor neutrons. The
trapped heat generated in the slugs boiled the water.
Steam from the process was piped to a small model
steam engine, rated at 1/1000 hp (0.75 W), which
rotated an armature mounted between the poles
of a permanent magnet. Sufficient electricity was
generated to light a flashlight bulb. The thermal
efficiency was estimated to be 2%. The Graphite
Reactor is now a National Historic Landmark and is
open to the public. A commemorative plaque and a
replica of the steam engine and coupled dynamo
from Ramsey and Cagles pioneering boiling water
power reactor are displayed in a small showcase
in the reactor lobby. The official first production
of nuclear electricity is credited to the lighting of
another bulb on December 1951 at the Experimental
Breeder Reactor-I, Arco, Idaho, now the Idaho
National Laboratory.
5.07.3 Properties of Aluminum

Heat removal and reduced generation of heat
are major considerations in the popularity of aluminum in RRs. Most of the energy released from controlled nuclear fission appears as heat. Much of the
heat, >80%, arises in the fuel from nuclear fissions.
However, a significant portion, 520%, is produced
in the nonfissile materials in the core and its surroundings by bombardment with particles emanating
from the fission reactions and from decay of fission
products. For power reactors, the heat is essential to
generate the electrical output. In the case of RRs, the
heat is a nuisance product; and the goals are to
minimize heat generation from the nonfissile materials in the system and to get rid of it from those
materials and from the fuel as fast as possible.
Hence, structural materials that create the least heat
and/or conduct it away the fastest are the most
146
favored for RRs. In this regard, aluminum is outstanding. Generally, heat production is greater with
increasing material density and with decreasing
specific heat. It is increased by high cross-sections
for neutron absorption and scattering, which also
reduce reactor efficiency by stealing neutrons from
participation in fission processes. Heat removal rate
is larger with higher thermal conductivity. Therefore, construction materials with low density, high
specific heat, high thermal conductivity, and low
nuclear cross-sections offer the best prospects for
minimizing heat generation and maximizing heat
removal. In Table 1, the relevant properties for
aluminum are compared with those of other cladding and structural materials used in power reactors
and for uranium. All values are for room temperature or 100 C. The scatter in values for a given
parameter and material is due in part to sensitivity
to chemical composition and heat treatment, etc.
These variations do not mask the large differences
between Al and the other materials. The density of
Al is 1/21/3 of those of the other cladding materials, and only 1/7 that of U. Its specific heat capacity
is twice as high as the other materials. And its
thermal conductivity is 510 times greater than
the values for the other materials. Additionally,
its neutron capture and scattering cross-sections are
much smaller than those of the other materials, except
for nuclear-grade Zr. In that respect, it should
be remembered that in the early days when Al was
establishing its foothold in nuclear technology commercial Zr was contaminated with up to 3% of the
strong neutron absorber Hf. It was also inordinately
expensive.
Table 1
5.07.3.1
Practical Characteristics
Having attractive physical properties for reactor use

is of no merit if those properties cannot be exploited
in a practical manner. The commercial and economic
attributes of aluminum that encourage its deployment in RRs are: It is ductile, plentiful, cheap, and
light weight. It is castable, machineable, and weldable, and it can be shaped readily by conventional
processes of rolling, forging, extrusion, drawing, and
cupping. It has good aqueous corrosion resistance due
to near-insolubility in water and formation of a passive, self-restoring surface film of hydrated aluminum
oxide. It is nonmagnetic and nonsparking. Although
aluminum is inherently weak, it can be strengthened
by cold work, solid solution hardening, and precipitation treatments. It has an fcc crystal structure and
no crystallographic phase changes. Its crystal structure is near isotropic, ensuring that it will not suffer
damaging directional thermal expansion and radiation growth like those exhibited by graphite and the
hexagonal metals Mg and Zr. It does not form stable
embrittling hydride phase(s) as Ti and Zr do. At low
temperatures, it has no ductile-to-brittle transition.
On the contrary, it is somewhat special in that at
cryogenic temperatures, where it gains strength, it
often gains ductility too. This combination of no
hydride phase, outstanding low temperature properties, and low neutron cross-sections make aluminum
the prime material for building cold neutron sources.
Another attractive feature is that pure aluminum has
no long-lived radioisotopes. The major source of
immediate radioactivity is from decay of 24Na produced via 27Al(n,a)24Na, decaying by g-emission
Relevant properties of reactor materials
Material
Aluminum
Zirconium
Austenitic steel
Ferritic steel
Uranium
Density
(kg m3)
2700
6490
8000
7900
1900
Specific heat
(J kg1 K1)
887963
254285
377565
440494
111167
Thermal
conductivity
(W m1 K1)
160230
840
1121
1742
1128
Melting
point ( C)
660
1852
1425
1525
1132
Emod (GPa)
70
8898
190201
200210
176208
CTE, lin.
(106 K1)
23
5.7
16
12
13.9
Nuclear
cross-section
(barns)
sabs
ss
0.23
0.19
3.0
2.5
7.6
1.5
6.4
10
11
8.9
Sources: Matos, J. E.; Snelgrove J. L. Selected Thermal Properties and Uranium Density Relations for Alloy, Aluminide, Oxide, and Silicide
Fuels; IAEA- TECDOC-643, International Atomic Energy Agency, Vienna, 1992; pp 119, article Appendix I-1.1 in Research reactor core
conversion guidebook Volume 4; Fuels (Appendices IK). Lide, D. R., Ed. CRC Handbook of Chemistry and Physics, 86th ed.;
Taylor & Francis: Boca Raton, FL, 20052006; Gale, W. F.; Totemeier, T. C., Eds. Smithells Metals Reference Book, 8th ed.; Elsevier and
ASM International, Amsterdam and Materials Park, OH, 2004; Cverna, F., Ed. ASM Ready Reference: Thermal Properties of Metals;
ASM International: Materials Park, OH, 2002.
with a half-life of 15 h. In alloys, long-lived radioactivity arises from decay of isotopes produced from
alloying elements and residual impurity elements
present in the aluminum, primarily 65Zn, 51Cr, 59Fe,
with half-lives of 250, 28, and 45 days respectively.
So if low residual radioactivity is an objective it can
be met to a large extent by avoiding alloys containing
significant quantities of Zn, Cr, and Fe.
Aluminum is not without its shortcomings. It has a
low elastic modulus and low melting temperature.
The former means that in their annealed conditions
aluminum alloys have low strengths compared with
annealed austenitic steels, Zr, and bcc metals. However, aluminum can be hardened by various treatments
as described in Section 5.07.3.2. However, the low
melting temperature of 660 C imposes operating
temperature limits of 100150 C, which are homologous temperatures of 0.40.45Tm where lattice
vacancies are mobile and can invoke susceptibility
to creep and stress relaxation. Even without imposed
stresses, the strength condition of prehardened alloys
can become compromised at temperatures above
150 C because of the possibility of thermal overaging
as described in Section 5.07.3.2 Aluminum has poor
abrasion resistance. It can be sensitive to localized
galvanic and pitting corrosion. It is prone to liquid
metal embrittlement, particularly Hg. Difficulties
may be encountered in obtaining leak-tight fusion
welded joints for hi-tech applications, mainly due
to porosities resulting from solidification shrinkage
(volumetric change) and dissolved gases, in particular,
hydrogen.5 In addition, aluminum does not undergo a
color change on heating, and during manual welding
may melt abruptly without warning, allowing overheating that can cause excessive sagging and dropthrough of the weld bead. The advent of a solid-state
joining process, namely friction-stir welding,6 has
largely overcome those welding troubles.
5.07.3.2 Alloy Types, Temper
Designations, and Tensile Properties
There is no universally embraced international standard system for defining the types and conditions
of aluminum alloys. The International Standards
Organization does have classifications for aluminum
and its alloys, but most countries adhere to their
own systems. The system followed in the United
States of America is ANSI H35.1-1990, instituted
by the American National Standards Institute and
supported by the Aluminum Association and ASM
International. The ANSI system and the US alloys
147
covered by it are described in reference,7 which is an

excellent source of aluminum data; it includes a short
list of alloys for other nations and their national
designations. The ANSI system is used herein. In its
entirety, it is a morass. Here, it is outlined just to the
extent that is necessary to provide an uninformed
reader with enough details to understand the nomenclature and the various processing treatments and the
upper service temperature limits those treatments
impose for maintaining stability of the processed
materials.
The system has two classifications, one for
wrought alloys and one for cast alloys. Only the
wrought alloy classification is described here. Briefly,
it is an eight-character code consisting of two groups
of four characters separated by a hyphen. The first
four characters are all numerals and they identify the
alloy group by chemical composition. There are eight
aluminum alloy groups. The first digit of the first alloy
group is 1, which represents alloys with a minimum of
99.00 wt% aluminum. In this group, the major foreign
elements are Fe and Si, which are really residues from
the aluminum extraction process and will be found to
various degrees in all aluminum alloys. The next three
digits in the group identify specific alloys in the same
series, and the group as a whole is denoted the 1xxx
series, often vocalized as the one-thousand series.
The other seven alloy series are 2xxx (major alloying
element, Cu), 3xxx (Mn), 4xxx (Si), 5xxx (Mg), 6xxx
(Mg Si), 7xxx (Zn), and 8xxx (other element).
An upper case X preceding the series identifier
numeral indicates an experimental alloy.
The second group of four characters in the eightcharacter designation represents the temper condition, that is, the heat treatment or degree of cold
work. The first character of the four-character temper condition is an upper case letter representing a
type of treatment. The other three characters are digits
indicating variations within the treatment. There are
many temper treatments. Only the three treatments
most likely to be encountered in RR materials are
described here. They are O for the fully annealed
condition, H for a strain-hardened condition, and
T for a precipitation-hardened condition. The
O condition is attained by annealing the material at
about 340 C then slowly cooling it. There are no
specified variations of the O condition. The H temper
is more complex. The first digit after the H is a 1, 2,
or 3. H1 signifies strain-hardened only. H2 is strainhardened and partially annealed. H3 is strain-hardened
and stabilized by a low temperature heat treatment.
The second digit, that is, the one following the H1,
148
H2, or H3 designation is a number between 1 and

8 and is the degree of reduction in thickness or crosssectional area given to the alloy in its fully annealed
condition to bring it to the desired strength level.
Level 8 corresponds to a maximum reduction of
about 75%. Level 1 represents approximately oneeighth of 75%, 2 is two-eighths, and so on. The third
digit, if used, implies a variation of the two-digit
temper. Partial annealing for the H2 condition is
applied to products that are strained beyond the
desired final amounts and are then brought back
to the needed strength level by the partial anneal.
Stabilization heat treatment for the H3 condition
is applied to those products that, unless stabilized,
would gradually age-soften at room temperature.
Partial annealing also inhibits age softening. This
tendency for softening of some cold-worked aluminum alloys at room temperature is important
because such recovery requires the involvement of
mobile lattice vacancies and/or self-interstitial
atoms that promote climb and rearrangement of the
cold work dislocations. It indicates the occurrence of
atomic movement at room temperature, which, as we
shall see shortly, is a factor affecting the development of radiation damage in aluminum.
In addition to hardening by cold work, aluminum
can be strengthened by solid solution treatment
and by precipitation hardening. Only two alloying
elements, Mg and Li, have sufficient solubility
(several %) at room temperature to provide significant solid solution strengthening. AlLi alloys are
not recommended for reactor use because natural
Li contains about 7.5% 6Li, which has a large crosssection for transmutation to 3H and 4He, both of
which can be highly detrimental to aluminum.
So the only solid solution-hardened alloys available
for reactor use are the 5xxx (AlMg) series. Other
metallic elements, principally Cu, Si, and Zn, have
little or no solubility in aluminum at room temperature but are modestly soluble at higher temperatures
near the melting point. This latitude permits considerable strengthening of such alloys by quenching-andaging, also known as precipitation hardening. The
ANSI designations for the precipitation-hardened
T conditions comprise ten subdivisions, T1T10.
For all T treatments, the alloy is heated to a temperature of 500540 C to dissolve segregated alloying
elements, followed by a rapid quench into cold water,
which gives an unstable supersaturated solid solution.
Precipitation is achieved by allowing the material to
sit at room temperature for periods of weeks called
natural aging (tempers T1T4) or by artificial
aging at temperatures of 160190 C for times of

624 h (tempers T5T10). Flattening or straightening treatments may be applied before or after the
aging treatment and are indicated by numbers in
the third and fourth character positions. The temper
conditions for aluminum alloys most often encountered in RRs are T4, T6, and T651. A T651
condition indicates a material that has been artificially aged then subjected to a light stretching
operation insufficient to change its mechanical
properties from those of the T6 condition. Of the
precipitation-hardened alloys, the 6xxx series hardened by precipitates of Mg2Si is by far the most
popular for RR service. The 6061 alloy in its T6
and T651 conditions has been approved for service as a class 1 nuclear components material under
the Boiler and Pressure Vessel Code of the American Society of Mechanical Engineers, Case N-519.8
Two types of precipitation-hardenable wrought
aluminum alloys, the 2xxx series (AlCu) and the
7xxx series (AlZn), both of which can be heat
treated to greater strengths than the 6xxx alloys,
are not usually found in nuclear reactors. Some
2xxx alloys are prone to aqueous pitting corrosion
or may release Cu ions to the coolant that could
be deleterious to other materials in the reactor
such as stainless steel. The 7xxx series alloys
have too low ductility and are the most difficult to
weld. Their high zinc contents will cause high
radioactivity.
Unlike the cold-worked 1xxx alloys that can
undergo recovery at room temperature, the
precipitation-hardened alloys are thermally stable
at temperatures up to about 150 C provided they
have been given appropriate natural or artificial
aging treatments. However, exposure to higher temperatures will cause overaging and associated reduction in mechanical strength. This softening is
illustrated in Figure 1 for 6061-T6 alloy after heating
to various temperatures for various times and testing
at room temperature.9 It can be seen that softening is
promoted by both time and temperature. For times
up to 1 h, softening commences at about 200 C and
is substantial but incomplete at about 370 C. For
a longer exposure of 1000 h, the softening begins
around the aging temperature, indicated by the
down-pointing arrow, and is essentially complete at
temperatures between 260 and 300 C. The data in
Figure 1 are for specimens reheated without load.
If reheating occurs under loads sufficient to induce
creep and stress relaxation, the softening temperatures are pushed downward.
149
350
Softening effects of reheating temperature and time on room temperature
properties of 6061-T6Al (originally aged 18 h at 160 C)
300
200
1000 h
30 min
6 min
150
50
100
Elong., 1000 h
25
Elongation
50
Elong., 6 and 30 min
100
200
Reheat temperature (C)
% Elongation
0.2% yield stress (MPa)
YS
250
0
400
300
Figure 1 Softening effects of reheating temperature and time on room temperature properties of 6061-T6 aluminum
(originally aged 18 h at 160 C). Data from Structural Alloys Handbook, 1989 ed., Vol. 3, Battelle Memorial Institute, Columbus,
OH, 1989; p. 14.
Table 2
Example alloys and their room temperature tensile properties
Alloy
Composition (wt%)
YS (MPa)
UTS (MPa)
Elongation (%)
1100-O
4032-T6
5052-H34
6061-T651
<1 (Fe Si)

12.2Si, 1Ni
2.5Mg, 0.25Cr
1Mg, 0.6Si, 0.28Cu, 0.2Cr
35
320
210
280
90
380
260
310
40
9
16
17
Source: Aluminum Standards and Data, 10th ed.; The Aluminum Association: Washington, DC, 1990.
Table 2 gives typical tensile properties of various

Al alloys employed in RRs. The weak 1100-O alloy
is simply annealed commercial purity aluminum with
no deliberate alloy additions; it is hardenable to an
H condition by cold work if so desired. The 4032
alloy is a eutectic composition of Si in aluminum that
has been solution-treated and aged to create finely
divided precipitates of Si; this alloy is used principally as a filler wire to improve the weldability of
aluminum alloys. The 5052 alloy is a solid solution
alloy of 2.5% Mg with a small amount of Cr added to
control grain size and strengthen the grain boundaries. The particular 5052 alloy in the table has been
work hardened to a 4/8, or half-hard, condition
before stabilization. The 6061-T651 alloy has been
solution treated and artificially hardened by precipitates of Mg2Si phase and its precursors, then given a
mild stretching treatment.
5.07.4 Fuel Elements

The most crucial and demanding applications of
aluminum in RRs are in the fuel elements. There it
is used inside the fuel element as a thermal conduction matrix in which a dispersion of fuel particles is
embedded and as a cladding material that protects
the fuel from corrosive attack by the cooling water,
retains fission products, and transfers heat from the
fuel and matrix to the coolant. As RRs matured,
considerable improvements were made in the fuel
elements. Most fuel in RRs is no longer unalloyed,
metallic a-phase uranium whose orthorhombic crystal structure is prone to severe radiation growth and
swelling leading to distortion and cracking. It has
been ousted by more stable and more isotropic uranium compounds that can also better accommodate
fission gases with minimum swelling. The most
150
common ones are U3O8, UAlx, where x can be 2, 3, or 4

but is usually considered10 to be a mixture of 3 and 4,
and U3Si2. There is also a hydride fuel, UZrH1.6,
which is used exclusively in the open-pool TRIGA
(test, research, isotopes, General Atomic) types where
the fuel is in the form of slugs comprised of particles of
U dispersed in the ZrH1.6 phase (see Chapter 3.12,
UraniumZirconium Hydride Fuel). Originally, the
TRIGA slugs were sheathed in aluminum, which has
now been replaced with stainless steel or nickel alloy.
However, TRIGA reactors still contain other aluminum components.
There is no outstandingly superior aluminum
cladding alloy. The most common aluminum cladding
alloys are 1100 and the stronger 6061. Other alloys
have been investigated in neutron irradiations,11
namely 5052; X800N, where N is 1, 2, or 3 and
whose compositions are Al1Ni1Fe; and two sintered aluminum powder alloys, M257 and M470,
which were fabricated by ball milling flake powder
of 1100Al in air until it contained a dispersion of 6%
and 10% Al2O3, respectively, then consolidating by
pressing, sintering, and hot rolling. The Mxxx alloys
were deemed to be no better than 1100 and 6061
types. They are more difficult and expensive to
make and harder to weld than regular melted-type
alloys. In Europe, particularly in France, two preferred
alloys are AlFeNi, a relative of X8001 with the composition 1Fe1Ni1Mg, and AG3-NET, a 5xxx-type
with 2.53.0Mg and low residuals. The greatest
concern for cladding is its corrosion behavior (see
Section 5.07.5).
A feature of RR fuels is that they are much more
highly enriched in 235U than those in power reactors:
1293% versus about 2.5%. Drivers for raising the
235
U levels were extended fuel cycles; the growing
demands for industrial and medical isotopes, particularly 99Mo the parent of the all-important medical
diagnostics tool 99mTc; and the need for higher neutron fluxes for increased production of the heavy,
transuranic isotopes. The use of highly enriched
uranium (HEU) meant higher heat generation and
required improved means of removing the heat. The
solution was the development of dispersion fuels
in which particles of the enriched fuel were distributed
in a matrix of thermal conductor material, all compressed together in sealed aluminum cans. The
thermal conductor is aluminum powder, usually a
1xxx-type, often atomized powder of better than
99.5% purity and particle size <100 mesh (150 mm
maximum, 2348 mm mean). Atomized powder particles are denser, pour more easily than milled flake
powders, and have less low conductivity surface oxide

per unit volume. The aluminum matrix may occupy
more than 50 vol% of the fuel/aluminum mixture.
A huge advance in fuel element morphology and
heat removal efficiency took place when Eugene
Wigner designed his thin, curved fuel plates for the
high flux Materials Testing Reactor (MTR) built at
Arco, Idaho. A thin plate has a number of advantages
over cylindrical slugs. The rolling treatment used to
produce the plates from a fuel slab, or from a dispersion of fuel particles in aluminum matrix powder,
sandwiched between two aluminum cladding sheets
gives superior mutual contact of cladding, matrix, and
fuel for improved heat transfer paths to the cladding.
The much larger surface-to-volume ratio of plates
provides more efficient heat transfer to the coolant,
thus permitting higher fuel loadings per unit volume.
The benefit of a curved fuel plate is that any buckling
and bowing in the plate due to irradiation will be
focused in the direction of the radius of curvature.
Thus, in a fuel element comprised of a stack of
curved plates restrained at their edges and separated
from each other by cooling channels of the same
width as the thickness of the plates, any such distortions will be accommodated cooperatively in the
radial direction without unacceptable narrowing of
the cooling channels. An MTR fuel element contained
18 plates each about 72 mm wide and about 727 mm
long bent to a curvature of 140 mm radius in the width
direction. The plate thickness was 1.27 mm including a
minimum cladding thickness of 0.25 mm on each face.
The plate edges were brazed into sturdy side panels
to seal the plate edges and impart rigidity to the
assembly. The water gap was 1.27 mm. The cladding
and side panels were made from 1100Al; the Al
brazing alloy contained about 13% Si.12 This assembly was then enclosed in a long, rectangular aluminum box fitted with end fixtures for remote handling.
The end fixtures were castings of Al7% Si. The
reactor core was built from groups of such elements
assembled upright in rectangular arrays held together
by aluminum grid plates. Refueling was done from
the top, and any element could be replaced by a box
of the same size containing a reactor experiment or
materials for isotope production, or a beryllium
reflector or a control rod. These MTR-type boxed
fuel elements in open grid core arrangements performed very well and became very common for RRs.
To satisfy demands for higher power densities and
more sophisticated tailoring of local neutron fluxes,
the next advancement in aluminumclad fuel elements
was the development of upright, annular
elements using curved fuel plates in which the fuel

particles may be required to be graded in concentration across the thickness and width. Beryllium reflectors surrounding the annulus direct neutrons from
the fuel back to the hollow center, or trap, of the
annulus where reactor experiments and isotope targets are placed. The Be also creates additional neutrons from (n, 2n) reactions. Vertical holes
bored through the reflector allow passage of cooling
water and house irradiation experiments. Two highperformance beryllium-reflected reactors using annular fuel elements are the High Flux Isotope Reactor
(HFIR) at Oak Ridge National Laboratory (ORNL),
rated at 100 MW thermal and currently running at
85 MW, and the Advanced Test Reactor (ATR) at
Idaho National Laboratory, rated at 250 MW but
lately operating at 100125 MW. The cores of these
reactors are of uncommon designs and deserve comment. The ATR core13 is 1.22 m diameter and 1.22 m
high. It contains a continuous serpentine-like wall of
fuel elements looped around nine flux traps each
about 120 mm diameter arrayed in a square 3 3
grid. In plan view, the wall forms the shape of a
four-leaf clover. It fully embraces the central flux
trap and the four corner ones. The other four traps
lie just outside the wall; each is tucked in between the
junctions of two leaves and is about half wrapped by
the wall. At each corner lobe, there are four shim
control cylinders just outside the wall and six shim
rods at the neck of the wall inside the cloverleaf.
These controls allow each of the four lobes to be
run at different power levels simultaneously, as
needed by the experiments in the traps. The remainder of the space in the core is occupied by blocks of
Be reflector containing numerous experiment holes.
The wall is built14,15 from 40 individual wedgeshaped fuel elements, each containing 19 curved
fuel plates. The cross-sectional area of an element is
a 45 sector of a circular annulus. Its outer arc, plate
#19, has a radius of 137 mm and an arc length of
100.9 mm. Its inner arc, plate #1, has a radius of
77 mm and an arc length of 54.1 mm. The 19 fuel
plates are attached by roll-swaging to 6061-T6Al side
panels 64.6 mm wide 1257 mm long. Within the
elements, the curved plates are concentric with the
circumferences of the traps. The plates are 1.27 mm
thick except for #1 and #19, which are thicker. The
water gap is 1.98 mm. The ATR fuel is UAlx enriched
with 235U to 93%, dispersed in a matrix of Al powder
and clad with 0.38 mm thick 6061-OAl.
The HFIR core16 is more compact, about the size
of a small trash can, into which are packed 540 fuel
151
plates in quite a different arrangement than in the

ATR. The core diameter is 435 mm and it is 791 mm
tall. It has a single central flux trap, 129 mm diameter.
The fuel is granules of U3O8 enriched with 235U to
93% and embedded in Al powder. The cladding is
6061Al. The core consists of two concentric annular
arrays of involute-curved fuel plates, as shown in the
sketch of a radial segment in Figure 2. The black
region in the fuel plates is the fuel dispersed in its
Al matrix; the white area is Al filler. There are 369
plates in the outer annulus and 171 in the inner
annulus. The plates are 610 mm high with widths for
the inner and outer annulus plates of 94 and 81 mm,
respectively, before bending. The plate thickness and
coolant gaps are 1.27 mm, as in the MTR-type elements. The two annuli are fabricated separately and
are united when loaded into the reactor. In addition to
the unique radial-like orientation of the fuel plates, the
fuel particles are uniquely distributed in the plates. To
minimize the radial peak-to-average power density
ratio, the thickness of the compacted fuel mix is varied
along the arc of the involute curve as seen in Figure 2.
This shaped region is backed by filler Al containing
no fuel particles. For the inner annulus, the filler
powder backing the shaped fuel region contains
Al filler
Al + 41 wt% U3O8
1.27 mm
Coolant
channel
Outer
annulus
sidewalls
Al + 30 wt% U3O8
Al filler +
B4C poison
1.27 mm
Figure 2 Horizontal section through a small segment

of the HFIR core showing fuel plate curvatures and
fuel distributions in the plates. Modified from
Binford, F.T.; Cramer, E. N. The High Flux Isotope
Reactor; A Functional Description, Vol 1B, Illustrations;
ORNL-3572 (Rev.2); Oak Ridge National Laboratory:
Oak Ridge, TN, 1968.
152
particles of B4C burnable poison. Two concentric

cylindrical control plates clad in Al are located immediately surrounding the core. Outside the control
plates are four concentric cylindrical Be reflectors.
Because beryllium generates copious quantities of
helium and tritium from neutron irradiation, it tends
to swell and crack, particularly at the faces of its high
neutron flux regions. To retain chips spalled from
these surfaces, the reflector and any penetrations in it
are clad with aluminum. Four horizontal 6061Al beam
tubes and numerous vertical holes penetrate the
reflector.
Like most dispersion-type fuel plates, the HFIR
and ATR plates are fabricated by what is called
a picture frame technique. This utilizes powder metallurgy methods to disperse the fuel particles uniformly in the Al matrix and press the mixture into
a hard rectangular compact. The rigid compact is
placed in a window of the same size cut in an Al
slab or frame, which is usually the same alloy as the
cladding. Sheets of cladding material are welded to
the top and bottom faces of the filled frame and the
assembly is hot rolled through a large reduction in
thickness to ensure that the cladding is fully bonded
to the fuel charge and the frame. After verifying the
location of the fuel charge, the rolled plate is cold
rolled to flatten it and bring it to the specification
thickness. It is then given a final anneal at 500 C
to reveal any blisters and rolling defects in the
cladding surfaces. After verifying the location of the
fuel region, the plates are blanked to finished size in
a press.
Of course, it is not as simple as that. Strict quality
assurance standards have to be met, and at every stage
in the operation, there are numerous inspections
and rigorous sizing and confirmation tests. To reproducibly obtain the graded fuel distributions in the
HIFR plates, a special procedure was developed.17,18
A custom-designed contoured auxiliary die plate
is mounted over the cavity of the powder press to
facilitate mounding of the fuel/matrix powder mix in
a semicylindrical hump. Another auxiliary die plate is
added to allow filler powder to be leveled on top
of the humped fuel charge. This duplex charge is
withdrawn into the press cavity, the auxiliary dies
are removed, the rectangular punch is inserted into
the die mouth and pressure applied, and the charge
is consolidated in a single cold pressing operation.
The HFIR fuel plates are bent to the desired involute
shape in an elastomer-faced punch and die press.
They are welded into the cylindrical inner and outer
sidewalls of the fuel elements. The sidewalls are
machined from extruded-type 6061 aluminum tubing

in the T6511 temper. Twenty-seven equally spaced
circumferential weld grooves are turned on one face
of each sidewall, and slots are milled at prescribed
depths and angles on the other face of the wall. The
weld grooves intrude a short way into the slots.
The fuel plates are slid into the slots and properly
spaced with the aid of temporary Teflon separators.
The plates are machine welded in place through the
grooves. A 4043Al weld filler wire and an argon shield
gas are used. End fixtures machined from 6061Al
tubing are welded to the ends of the elements, and
final machining and inspection are conducted.
These multiplate fuel elements are a testimonial
to designer ingenuity and superb fabrication skills,
and the versatility of aluminum. Manufacturing these
fuel elements is not only painstaking but also expensive. In year 2007, each HFIR element cost $1 M.19
It is replaced after its regular lifetime operating
cycle of 26 days. With so much effort and cost
invested in it, a rejected element is a severe financial
loss. The specifications and acceptance standards are
so high that the chances of producing a fuel element
completely free of specification violations are very
low. The first 30 000 fuel plates suffered a rejection
rate of 12%, and of the first 45 fuel assemblies, only
4 inner elements passed the final inspection.20 However, the degrees of severity of the violations were
all minor or were correctable. With waivers, all 45
elements were accepted and gave exemplary service.
After operation of the first 60 fuel cores at the
full design power level of 100 MW, 4 of them were
autopsied.21 No significant faults were found. The
in-reactor performance of these complex aluminumbased fuel elements has been incredible, surpassing all
expectations.
Development of RR fuels and fuel plates is
continuing. Concerns over the possibilities of nuclear
weapons proliferation and terrorism led to establishment of the Reduced Enrichment for Research and
Test Reactor (RERTR) program at Argonne National
Laboratory.22 The goal of RERTR is to eliminate
the use of highly enriched uranium (HEU) in RRs
by converting to the use of low enriched uranium
(LEU). HEU is defined as uranium that has the
fraction of the fissile isotope 235U greater than 20%,
LEU is less than 20%. Historically, RRs have used
enrichment levels of 235U up to 93%. RERTR
is intended to be achieved without impairing the
safety and performance of the reactors and/or jeopardizing the production of important isotopes,
and at minimum cost for changes in fuel elements.
In some RRs with modest uranium enrichment and

low power levels the RERTR LEU goal was met by
diluting the fuel with natural uranium. For many of
the high performance RRs (HPRRs) that must retain
their 235U levels and cannot tolerate the burden of
added 238U without excessive operational penalty, the
RERTR dilution can be achieved by replacing the
HEU fuel with LEU compounds or alloys containing
higher fractions of U. To that end, the initial focus of
RERTR was on the development of uranium silicide
fuels, U3Si and U3Si2, dispersed in aluminum and
clad with aluminum.23,24 While this move has been
successful for many RRs it is not sufficient for the
most demanding HPRRs. For them, attention has
turned away from dispersion fuels to monolithic alloy
fuels where higher U densities are attainable. The goal
is to develop fuel plates built from foils of LEU alloy,
250500 mm thick, clad with aluminum.19,2527 In
order to prevent buckling and cracking of the foil
during multiple rolling and recrystallization treatments and to inhibit radiation growth and warping,
there must be just enough alloying metal in the
U to stabilize it in its isotropic g-phase. Several
alloying metals are suitable, but the field of contenders has been reduced to the UMo system. A 90%
LEU-10% Mo alloy currently holds the best prospects. Some serious hurdles are recognized. Interdiffusion between the cladding and the fuel foil during
annealing and in-reactor exposure encourages the
formation of reaction layers of uraniumaluminum
compound(s) with low thermal conductivity and low
resistance to growth of fission gas bubbles. Such
layers threaten the integrity of the fuel/cladding
interface. Development of these layers is retarded
by additions of Zr or Ti to the fuel, or Si in the
cladding. When Si is incorporated in the cladding, it
is found to segregate at the fuel/cladding interface,
acting like a diffusion barrier. Thin film diffusion
barriers of Si, Zr, and ZrN applied directly to the
surfaces of the fuel foil by co-rolling and thermal
spraying have done well in reactor tests. The current
hot roll bonding processes used for attaching cladding to dispersion fuel plates may not be fully
adaptable to barrier-coated foil fuels. Other bonding
methods such as hot isostatic pressing are under
investigation. For HFIR plates, where the foils must
be tapered in both width and length and have involute shapes, fitting and bonding diffusion films and
cladding to the fuel foil on a mass production scale
is a challenge. Hot roll bonding will not work
because the foil and the cladding will not deform
to the same extent and will result in nonuniformly
153
thick cladding, and shear deformation during rolling

may damage the diffusion barrier. It is recommended19 that the tapered foil, bent to its involute
shape and with an adherent diffusion barrier, should
be prepared separately then sandwiched in shaped
recesses in two full-length clamshells of cladding
of appropriate thickness and bonded over all mating
surfaces. Alternatively, if the clamshells can be made
from a two-ply Al sheet, like the commercial OneSide Alclad, the inner layer of, say, 1100Al, could
contain the ingredients for a diffusion barrier. The
hot isostatic pressing route may then allow bonding
and barrier filming in a single operation and in batch
mode. If burnable poison cannot be incorporated in
the fuel foil, it may be possible to accommodate it
in the inner cladding layer with the diffusion barrier
components.
The corrosion behavior of the Al cladding on alloy
foil fuel elements will need to be explored thoroughly. A penetration of the cladding will probably
be more serious than one in current dispersion fuel
plates because the alloy fuel will likely be more reactive and soluble in water than the dispersant-type
intermetallic and refractory fuels.
5.07.5 Corrosion
Metallic corrosion, the removal of metal atoms from
the metal surface by the electrochemical action of
the environment, has many forms: uniform, galvanic,
pitting, grain boundary, crevice, etc. Uniform corrosion and pitting are the types of most interest to RRs.
The greatest worry is the aluminum fuel cladding
where the environmental conditions are most aggressive and where an unexpectedly high corrosion rate
might breach the cladding and allow release of highly
radioactive fission products throughout the water
system. Pitting corrosion is the major form of attack
on the cladding of spent fuel elements during longterm storage in water basins.28 Herein, the focus is on
uniform corrosion of cladding.
Aluminum is a very reactive metal. In dry air,
it combines with oxygen to form an adhesive,
self-healing Al2O3 film that retards further oxidation
at the metal surface. Such films are usually quite thin,
tens of nanometers, usually described as amorphous.
Films formed in moist air and water are much thicker,
1 mm or more. The water-formed reaction films developed on aluminum cladding are variously described
as hydrated oxides and hydroxides, and oxidehydrates, and they are generically referred to as
154
oxide films. In HPRRs, the films grown on the fuel

cladding may be 2050 mm thick.29,30 The most common corrosion products28,30 reported on aluminum
cladding are boehmite, a crystalline monohydrated
aluminum oxide, Al2O3H2O, and bayerite, a crystalline trihydrated oxide, Al2O33H2O. At temperatures
below about 77 C, the boehmite phase is formed
preferentially but may transform to bayerite with
continued immersion. At temperatures above 77 C
and below 100 C, a pseudoboehmite structure
grows, which may age to other hydrated oxide forms
or retain its pseudoboehmite structure. Between 100
and 400 C, crystalline boehmite will form. A gelatinous boehmite is the chemical precursor of both of the
crystalline hydroxides.30 The mature hydroxides are
normally white color but other hues have been
reported and may stem from absorption of Fe, Cr, Ni,
or other metal ions leached from steels in the reactors
or in the corrosion test loops.
The corrosion film is both the reaction product
and the medium through which the corrosion process
occurs. Whether corrosion is governed by ingress of
O and OH ions through the film to the metal surface
or by egress of Al ions to the film/water interface,
it is expected to be diffusion controlled. Thus, all else
being equal, an increase in film thickness should
lower the corrosion rate by increasing the diffusion
length, and vice versa. Therefore, the corrosion rate
should be parabolic with time and have an Arrheniustype dependence on temperature. Moreover, ideally,
if all the corroded metal was retained in the corrosion film, if the chemical composition and physical
structure of the film were constant throughout
the thickness, and if all of the film was retained
on the metal, the film thickness would be proportional
to the amount of metal corroded. Alas, such ideality
does not prevail. The corrosion process is confounded by a number of interacting factors, including
the following: there is a one-sided heat flux on the
cladding; the corrosion film is a thermal insulator
compared with the Al cladding, so the temperature
of the film will increase with thickness; the film may
not be of uniform composition and/or structure;
the film is soluble to some extent in water, and its
solubility is strongly susceptible to the pH of the water,
which is related to water composition; the film is
subject to erosion in flowing water and to spontaneous
spallation above some uncertain thickness, about
50 mm in one case.31 And to further complicate the
situation, there is wide variation in the ways the corrosion tests are conducted and in the parameters that
are measured.
The tests may be carried out in open cups, closed

autoclaves, vented autoclaves, closed loops, bypass
loops, or on used fuel plates. Evaporation or consumption of the water may require that it will need
to be periodically replaced or its volume readjusted.
Except in in-reactor tests and loop test systems with
bypass monitoring and adjustment of the water, the
chemistry of the water may change substantially during the test. Few corrosion rates for cladding materials are measured directly. They are usually derived
from measurements of the thickness of the corrosion
film. A thickness measurement gives the thickness of
the film adhering to the substrate at the time of the
measurement. It will not include film that has been
dissolved and/or eroded away. On a spent fuel element, it may include film that has formed in a storage
pool over time periods much longer than it experienced in-reactor, and with no forced cooling. During
preparation for post irradiation examination (PIE) in
a hot cell, the spent element is no longer fully
immersed. It gets hot and has to be periodically
sprayed with water to cool it. It has been opined21
that the resultant steaming and thermal cycling may
cause more corrosion than in-reactor operation and
underwater storage. There is no guarantee that the
density and the composition of the film will be invariant through the film thickness. On the contrary, multilayer films are more common than not. Almost all
films have a thin, monolithic base in contact with the
Al surface, presumably associated with the ubiquitous
air-formed Al2O3 film. On top of this base, there may
be one to three distinct layers. Some films contain
pores or are cracked. Only the films on irradiated fuel
elements have been exposed to the effects of neutron
irradiation and radiolysis of the water. The way in
which the film thickness is measured may be questionable, too. At least six different methods are used,
viz.: (1) Scaled measurements by optical or scanning
electron microscopy of metallographically polished
and etched cross-sections of the corroded test piece;
(2) micrometer measurements of the thickness of the
test piece before corrosion and after the corrosion
product is removed by electrolytic polishing until the
shiny metal is seen; (3) weight gains of coupons with
film in place; (4) weight losses of coupons after
removal of the film; (5) acoustic and eddy current
measurements with instruments calibrated against
accepted standard films; and (6) temperature increases
measured with thermocouples attached to the noncorroding back surface of the test piece during the test,
and related to spot film thicknesses measured metallographically after the test.
A neglected aspect of film measurements is that

almost all of the measurements have been made on
specimens that, deliberately or unavoidably, were
dried at room temperature or at 100 C32 before the
measurement was attempted, or before the measuring
instrument was calibrated. Until recently, nobody
seems to have determined whether such drying treatments will shrink, spall, crack, or otherwise alter the
bulk film. The gelatinous surface layer that precedes
the crystalline corrosion films will almost certainly
be altered during dehydration. It is not uncommon
for test coupons to be dried, weighed, and placed
back in the test for the next exposure period, and
so on until the termination of the campaign. That
was the method used in one seminal laboratory test
study.33 The first periods in the full exposure sequence were the shortest ones, 1 or 2 days, and they
always showed the largest weight gains, usually
6090% of the total weight gained during the full
duration of the test, which was about 22 days. Weight
gains after the first period were linear with time and
were relatively minor. That is not parabolic corrosion
behavior. The abrupt change in weight gain indicates
that something happened during the first interruption of the test that set the scene for a sudden switch
from an initial rapid corrosion rate to a subsequent
constant low rate. Likely, the first drying treatment
irreversibly altered the structure and permeability of
the hydrated film. Recent autoclave tests34 on AlFeNi
alloy reinforce that suspicion. It was demonstrated
that during a 34-day test, interruptions made every
7 days to remove, dry, weigh, descale, dry, reweigh,
and replace the test piece in the autoclave with
refreshed water for the next exposure period had
serious consequences to the corrosion kinetics. Without interruptions, the inner and outer oxide layers
were twice as thick, the weight gain was 26% higher,
and the amount of metal removed from the substrate
was 23% higher.
Some efforts have been made to correlate film
thicknesses with corrosion rates.3133 Tests made
under controlled conditions in a corrosion loop31
found that the thickness of the boehmite film on
1100, 6061, and X8001 alloys was about 1.4 times
the depth of penetration into the aluminum regardless of changes in test parameters that changed the
film thickness, as long as there was no stripping or
spallation of the film. Using a literature value for the
density of boehmite, it was estimated that about 70%
of the corroded Al remained in the adherent film and
about 30% was lost to the coolant. When spallation
did occur, which was usually above a film thickness of
155
50 mm, the 1100 and 6061 alloys always showed localized attack of the aluminum under the spalled area,
whereas the X8001 alloy showed only uniform attack
under all conditions. This correlation was for a
closed, single set of data. It should not be considered
representative of all data and situations. Other data
by some of the same authors,32 where the principal
variables were temperature and flow rate, showed
that the ratio of corrosion product retained to the
weight of metal corroded ranged from a high of 0.54
at a low temperature of 170 C and flow rate of
6.19.5 m s1 to a low of 0.08 at 290 C and 29 at
32.6 m s1. Another source29 quotes a retention level
of 5080% of the oxide on the cladding surface, but it
may be citing Griess et al.31 In general, the relationship between film thickness and corrosion rate is not
well established.
Film thicknesses from laboratory tests31,3538 display power law growth with exposure time, but the
time exponents, preexponential factors, and activation energies differ from one experimenter to another
and may be applicable only to the particular set of
data from which they were determined. Nevertheless,
the laboratory tests have established that the corrosion films are sensitive to a number of interacting
factors. They include the temperature and surface
condition of the cladding; the heat flux density on
the cladding; and the temperature, pH, flow rate, and
purity of the water. In RRs, water purity is controlled
by filtration and ion exchange systems; it is also
linked to pH. With regard to pH, the films will
dissolve if the water is strongly acidic (pH < 4.5)
or strongly alkaline (pH > 8.5); films are most stable in the range 5.06.5, the closer to 5.0 the better.
The pH of reactor water and spent fuel storage pool
water tends to converge toward the desired range
by carbonic and nitric acids formed from CO2 and
N absorbed from air. It can be maintained close
to 5.0 by controlled additions of nitric acid. The
strongest increase in film growth is from increase in
temperature, and the controlling temperature is that
at the hydroxide/water interface.31 To lesser extents,
increased heat flux density and water flow rate
will raise the film growth rate. For the alloys 1100,
6061, and X8001, which all corroded alike until spallation occurred,31 the rate of oxide formation at a
heat flux of 1.58 MW m2 was about half of that at
3.136.31 MW m2, other conditions being the same.
At coolant flow rates in the range 7.613.7 m s1, the
rate of accumulation of the corrosion product was
the same for all three alloys. Corrosion rates measured
on the insides of 1100Al production tubes39 were
156
found to be unchanged by water velocities in the range

0.3055.58 m s1. Reduced water temperatures will
reduce the film growth rate.
Despite differences in strengths, compositions,
and microstructures, the alloys 1100, 6061, and X8001
all seem to have similar corrosion behavior under
similar conditions.31,32 Spalling tends to introduce
local attack in 1100 and 6061 but not in X8001.31
The AlFeNi alloy shows good performance at
temperatures up to 250 C in autoclave tests35 and
in-reactor exposures40 at temperatures below 120 C,
but it has not been tested under high heat fluxes.
AG3-NET cladding on U3Si2 dispersion fuel plates
undergoing in-reactor tests failed41 at a heat flux of
5.5 MW m2. The cladding was swollen and breeched
by a combination of a very thick corrosion film and
subfilm intergranular corrosion. Cross-section X-ray
spectroscopy analyses showed that oxygen had penetrated intergranularly all the way through the cladding to the meat. The corroded cladding was
interesting in other ways. The outer oxide layer was
monolithic and was exceptionally thick, 100 mm.
Directly beneath it was a region about 80 mm thick
containing many round 30 mm size pores. Below the
porous region, the grain boundaries were enriched in
Mg and oxygen. The plates were intended to reach a
temperature of about 180200 C at the exterior surface of the cladding and 220240 C in the fuel.
Temperatures estimated from the thick corrosion
layers were >300 C for the water/corrosion film
interface and >400 C for the fuel meat. The AG3NET alloy has a history of intergranular cracking in
beam tubes and other structures in the Reacteur Haut
Flux at the Institut Laue-Langevin in France.
Although that cracking occurred at high fluences,
the irradiation temperatures were low. Such low temperature intergranular cracking is a sign of pending
weakness in the alloy and does not bode well for
applications at higher temperatures as in fuel
cladding.
The influences of neutron flux and radiolysis of
water are unclear. These parameters are omnipresent
in RRs and we might imagine them to strongly affect
aqueous corrosion of fuel cladding by damaging
the cladding and its corrosion film and by altering
the activity of the water. One researcher42 writes that
reports of neutron flux effects on the hydroxide films
are few and there is disagreement; he claims that
the opinion of most (Russian) researchers is that
neutron irradiation decreases, rather than increases,
the corrosion rate. Effects of radiolysis are uncertain.
According to Golosov,42 one Russian authority argues
that radiolysis may either accelerate corrosion by

facilitating cathodic processes or reduce corrosion
by promoting anodic passivation. Data from laboratory
corrosion loop tests without radiation fields seem to be
fairly compatible with data from irradiated fuel elements in terms of oxide thicknesses, compositions,
and pH effects. There are no outlandish differences
that would immediately draw attention to radiation
effects. At least, none that has been strong enough to
insist that loop tests should be repeated in irradiation
fields. A similar conclusion was reached for aqueous
corrosion of aluminum process tubes in production
reactors.39 Therefore, irradiation effects must be
modest at worst. However, there are some troubling
reports that seem to indicate large effects of irradiation fields in nonreactor conditions. Sindelar et al.43
studied 6061Al coupons exposed to moist air at 150
and 200 C, with and without exposure to a 60Co g
source at 1.8 106 R h1. Weight gains and film
thicknesses were measured. The corrosion product
was patches of loosely aggregated, randomly oriented
1 mm size boehmite crystals sitting on a thin monolithic base layer, even at 100% relative humidity
where the product was permanently under a film of
water. g-Irradiation seemed to double the weight
gains and increase the film thicknesses by a factor of
10. There was substantial surface blistering of the
base layer, attributed to hydrogen gas. The paper
provided no details of the experimental conditions.
Enquiries to the authors produced a lengthier publication44 with the missing details. Those details cast
grave doubt on the conclusions drawn from Sindelar
et al.43 In particular, the experiments with the g-field
were made under radically different conditions
than those without the field. Specimens for the
g-irradiations were sealed in small stainless steel
cans of just 78 ml and each can represented an uninterrupted test for a given exposure period of 1, 4, 8,
and 12 weeks. The tests without the g-field were made
in stainless steel autoclaves of volume 37 850 ml for
15 unequal exposure periods totaling about 30 weeks.
At the end of each period, the specimens were
removed, dried, weighed, and replaced in the autoclave with a new charge of water. In light of the
effects of interruptions described in Wintergerst
et al.,34 the effects of g-irradiation described in
Sindelar et al.43 and Lam et al.44 are inconclusive.
In the other work,45 Al coupons of undeclared composition and condition were exposed to static brackish water of pH 89, at undisclosed temperature
for periods of up to 30 days, with and without low
dose irradiations with neutrons from a 252Cf source
(1010 n m2 s1) and, separately, g-rays from a 60Co

source at 15 Sv h1 (1.6 104 R h1). Corrosion was
determined from weight losses. It was not stated
whether the specimens were recycled from one period
to the next. The neutrons and the g-rays had the same
effects and to the same degree; they promoted formation of a grayish layer on the specimen surfaces; they
reduced the weight losses by 2530%; and they almost
eliminated severe pitting corrosion displayed by the
unirradiated specimens. None of these three reports
mentioned whether radiation heating was a factor.
The laboratory loop tests have verified the expectation that the corrosion film is a thermal insulator compared with the Al cladding, and they have provided31
a thermal conductivity value of 2.25 W m1 K for
boehmite, which is a factor of 70100 less than Al.
However, it is not always ascertained whether a particular film is boehmite or bayerite or a mix of both.
No thermal conductivity value is available for bayerite. When insulating films build on the Al cladding
of heat sources like the fuel and long-term heavy
isotope targets, the temperatures of the sources and
their claddings or containers will rise. This temperature rise will increase the corrosion rate and
the growth rates and dissolution rates of the corrosion
films. In HPRRs, a side effect of an increase in cladding temperature by the adherent corrosion product
is the threat of plate buckling.31 As described earlier,
the strengths of the cladding and Al fuel matrix can
be decreased significantly by tens of degrees increases
in temperature, and creep rates will increase. If an
insulating corrosion film increases the temperature
gradients between the center thickness of the fuel
plate and the surface of the film, and between the
fuel-loaded portions of the fuel plates and their cooler
frames, the plates may distort. If the distortion is not in
phase from one plate to the next, it might perturb the
coolant flow and accelerate the temperature changes.
Griess et al.31 envisaged that the insulation provided by
the corrosion-product film might be more of a limitation on the use of aluminumclad fuel elements in
high flux reactors than is corrosion damage per se and,
in the worst case, may lead to burnout of parts of the
fuel plates. Fortunately, that prophecy has not been
fulfilled. Serious plate distortion has not been a widespread issue. One case of plate distortion is described
in Shaber and Hofman.30 Plate buckling found in some
MTR elements12 was blamed on new design changes.
It is recommended30 that new fuel elements
should be prefilmed with a hydroxide film to reduce
the rate of in-reactor buildup of the corrosion layer.
Tests32 with 1100, 5154, 6061, and X8001 alloys at flow
157
rates in the range 6.120.4 m s1 found that preexposure of the test pieces to water at 250300 C for 24 h
in an autoclave caused a significant improvement in
corrosion resistance, but not at higher flow rates. The
ATR elements are pretreated30 by immersing them in
water for 48 h at 180 C and pH 5.0. In the early days
of HFIR operation, the new fuel elements were often
stored in the reactor pool water for up to 3 months
before being placed into service. This immersion
resulted in the formation of a rather thick, gelatinous,
corrosion product film on the element surfaces.21 In
an attempt to avoid that condition, some of the elements were pretreated by boiling them in deionized
water for 24 h to produce a thin, boehmite film on the
surfaces of the elements before they were placed into
service. When the pretreated elements were used, the
coolant flow rate was found to gradually decrease
and the pressure drop across the elements gradually
increased during the reactor fuel cycle. No significant
damage was caused. Changes in coolant flow rate
and pressure drop were not observed when the reactor was operated with non-pretreated fuel elements.
Metallographic examinations of cross-sections of
the spent fuel plates revealed much thicker corrosion
films on the pretreated plates. Pretreatment of the
HFIR fuel elements was discontinued. Most RRs do
not practice pretreatment of their fuel elements. It is
proposed here that because of the seemingly large
effects of dehydration on retarding subsequent film
growth as discussed earlier, at least one in-reactor
trial should be made of a prefilmed fuel plate with
a dehydration step or a low temperature baking
treatment added. A drying treatment might also be
worthwhile for a newly spent fuel element before it
enters pond storage.
What we really need to learn from corrosion measurements and film thickness data is the thickness of
uncorroded Al cladding remaining on the fuel element at the end of reactor service, and whether that
thickness will be sufficient to continue to seal the
spent fuel through further corrosion expected during
cool-down storage in water basins. That is, we need
reliable corrosion rates pertinent to the particular
application. Corrosion product thickness data are
invaluable in identifying and characterizing the
major factors governing corrosion and the interplay
between them, but they are meaningless to corrosion
rates if a reproducible relationship between film
thickness and corrosion rate is not established. We
need predictability. To that end, efforts are underway
to derive predictive models for film thicknesses40,46
and corrosion rates.42 These models are in their
158
infancy. Because they lack a large body of consistent

data to draw on, the authors must make many assumptions, fittings, and correlations to derive constants,
correction factors, adjustment factors, and augmentation factors. With so much flexibility built into
the prediction equations, it is not surprising that the
authors can find good correlations with selected data
from measurements made on spent fuel cladding.
This is not intended as a criticism of the modelers;
it is a reflection of the paucity of input data. Reliable
modeling is essential. But it needs reliable input data.
Data obtained from recycled test coupons should
either be excluded from the models or modeled as a
separate category. To be generically applicable, film
thickness models and corrosion rate models should
attempt to merge in a complementary manner.
In low power RRs where convective flow is
sufficient to take care of cooling and water quality
is adequately controlled, problems from corrosion
films formed on the aluminum cladding and on other
aluminum components elsewhere in the reactor are
uncommon. In HPRRs, the most prominent corrosion
problems were those in the early days of operation that
caused a milky turbidity of the coolant and a white
deposit and increase in surface radioactivity on all
surfaces exposed to the coolant. The turbidity was
identified as a fine suspension of boehmite, and the
g-radioactivity was consistent with decay of 24Na, both
effects attributable to corrosion/erosion of the fuel
cladding. The turbidity is created by increase in the
cladding temperature due to the warming effects of
the hydroxide film. In turn, the temperature of the
coolant in immediate contact with the film is raised.
This increases the solubility of aluminum oxide in the
immediate volume of coolant. When this small volume
moves on and merges with the cooler bulk coolant,
the solubility falls and much of the dissolved film is
released as a particulate suspension. Particles of film
washed directly into the coolant by erosion of the
cladding due to the high coolant flow rate contribute
to the turbidity. Since turbidity ensues when the concentration of aluminum in the bulk water exceeds the
solubility of the aluminum oxide, turbidity problems
are brought under control by tuning demineralization
treatments to remove dissolved aluminum from the
bulk water and by reducing the degree of dissolution
through adjustments in pH to between 5.1 and 5.4
where aluminum oxides have minimum solubility.
In-reactor pitting corrosion and galvanic corrosion have not been serious problems. Pitting of Al,
which is encouraged by the presence of ions of Cu,
halides, and bicarbonates, is more serious in storage
pools where poorer water chemistry and nearly stagnant water conditions may exist, but diligent monitoring and control of water chemistry can mitigate
these concerns. Intergranular corrosion has not been
a problem in RRs, but it could become an issue at
high irradiation temperatures as evidenced by the
AG3-NET cladding described earlier.
Overall, aluminum cladding has given very good
service in water-cooled RRs and continues to do so.
The major variables influencing the corrosion process
(es) and corrosion products are fairly well identified
except for effects of irradiation. More data from spent
fuel elements are needed to guide and refine models
for predicting film thicknesses and corrosion rates.
5.07.6 Radiation Effects

5.07.6.1
Basics
As in other metals, irradiation of Al with neutrons or

charged particles introduces lattice vacancies, selfinterstitial atoms, and transmutation products that
evolve into radiation damage microstructure, which
causes swelling, radiation hardening, and loss of ductility. Radiation damage effects in aluminum differ
from those in most other metals in two respects. One
is that the radiation damage is affected strongly by a
solid transmutation product, silicon, discussed more
in Section 5.07.6.2.3. The other is that Al is much
more tolerant of radiation effects than most other
metals. At least, it is for irradiations conducted at
ambient temperatures. Neutron irradiation of Al
at temperatures between 25 and 100 C does not
induce detectable radiation hardening until the fast
neutron fluence exceeds about 1 1024 n m2, whereas
in Fe and Zr, radiation hardening is detectable at
fluences two to three orders of magnitude less than
that.47 Moreover, even when Al is radiation hardened
at 25100 C, it still retains significant ductility when
compared with considerably reduced ductilities in Fe
and Zr. This delayed display of radiation hardening
exists despite the fact that the number of atomic
displacements per atom in Al are about twice as
many as in other metals at the same fast fluence,
which is brought about by the lower displacement
threshold energy for Al. The larger part of Als better
tolerance of radiation damage is owed to its low
melting temperature, which makes its homologous
temperature high compared with those for Fe and Zr.
At room temperature, the homologous temperature
of aluminum is 0.32Tm, versus 0.175 for austenitic
steel, 0.17 for ferritic steel, and 0.26 for a-Zr if
referred to the a ! b-transition temperature of about

860 C, or 0.14 if referred to the m.p. of b-Zr, 1852 C.
In general, noticeable thermally induced movement
of lattice vacancies will occur in metals at homologous temperatures above about 0.3Tm. Because of that
movement at room temperature in Al, there will be a
greater loss of radiation-produced vacancies and of
interstitials to mutual recombination, resulting in less
nucleation of the point defect clusters that are the
seeds of damage microstructure, hence less radiation
hardening.
A feature of radiation damage in polycrystals is
the absence of point defect damage microstructure at
grain boundaries and other incoherent interfaces.
Point defect clusters and voids do not develop on
the boundaries, and damage-free zones are formed
on each side of a grain boundary. This denuding may
be difficult to see in many high melting point metals
irradiated at temperatures below 100 C because
the zones are narrow. In Al, the high Tm allows
development of wide and conspicuous denuded
zones. Incoherent interfaces are comprised of structural dislocation networks and high equilibrium
concentrations of vacancies that make the boundaries deep sinks for absorption and recombination of
freely migrating point defects. They are pulled in
from the near regions of the butting grains, leaving a
volume of matrix straddling the boundary that is
diminished in radiation-produced point defects.
Due to the greater mobility of the interstitials and
the bias of dislocations for absorption of interstitials,
the zone deprived of interstitials is wider than that
for the vacancies. This creates an unbalanced concentration of vacancies at the rim of the denuded
zone. Therefore, vacancy clusters are encouraged to
form in that rim and they become more numerous
and/or larger than those in the grain matrix. Impurities and transmutation products are also drawn
into the grain boundary, but they are not annihilated
there; they accumulate. If they are largely insoluble,
as H, He, and Si are in Al, they will precipitate and
grow there, the gases as bubbles and the Si as particles
or films. Within the grains, the gases will stabilize
embryo clusters of vacancies and facilitate their
growth into voids as long as there is an excess of
vacancies. Some of the Si will attach itself to the
voids. Grown-in dislocations in the grain interiors
are also sinks for point defects.
Diffusion and binding of freely migrating point
defects and solute atoms are important for understanding and analyzing radiation effects. Some useful
parameters for pure Al are:48,49
159
The threshold energy for atomic displacements is

25 eV compared with 40 eV or more for most other
metals.
The self-diffusion rate, Dsd A(Qsd/kT), where A is a
constant and the activation energy Qsd is the sum
of the formation energy of a vacancy, Evf , and the
migration energy of the vacancy, Evm .
For temperatures between 298 and 580 K, A is
1.6E 5 m2 s1 and Qsd is 1.3 eV.
For temperatures between 570 and 923 K, A is
2.0E 4 m2 s1 and Qsd is 1.48 eV.
Evf 0.6 eV.
Evm 0.7 to 0.88 eV, deduced from Evm Qsd Evf .
Eif the formation energy of an aluminum interstitial atom, >3 eV.
Eim the migration energy of an aluminum interstitial atom, 0.1 eV.
Evb-s the binding energy between a vacancy and a
solute atom and is considered to be <0.1 eV for Ag,
Cu, Mg, Zn, and Si.
Eib-s the binding energy between an aluminum interstitial atom and a solute atom. No
values are available, but for the solute to reduce
b
needs to
radiation damage microstructure Eis
m
m
b
E
E
.
be >Ev i
vs
Solutes that seem to reduce radiation damage structure most strongly at concentrations of 100 appm
are Cr, Cu, Mn, Ti, V which have the largest negative
lattice misfits, defined as (a-a0)/fa0, where a0 is the
lattice parameter of pure Al, a is the lattice parameter
of the alloy, and f is the atomic fraction of solute.
No relationship is found between degree of radiation damage and thermal diffusion rates of solutes.
5.07.6.2
Microstructures
Examples of the damage microstructure in highpurity Al irradiated to a fast neutron dose of

3.5 1024 n m2 at 50 C are presented in Figure 3.
The two photographs are not the same field. The
one on the left shows typical radiation-produced
dislocation loops. Some of the smaller spots are
particles of radiation-produced Si. The other photograph is tilted to put the dislocations out of contrast and reveal the voids more clearly; they are
facetted. The loops and voids are of order 30 nm
diameter. In ferritic steel, austenitic stainless steel,
and Zircaloy-4 alloys irradiated under similar
temperature and neutron fluence conditions as in
Figure 3, the radiation damage microstructure
is resolvable as 12 nm black dots.47 The loops in
Figure 3 are not faulted. Nobody has reported
160
(a)
0.1 mm
(b)
0.1 mm
Figure 3 Dislocation loops (a) and voids (b) in high-purity aluminum after irradiation at 50 C to a fluence of
3.5 1024 n m2 (E > 0.1 MeV).
faulted loops or stacking fault tetrahedra in neutron-irradiated Al, presumably because the
very high stacking fault energy (SFE) of Al,50,51
about 160200 mJ m2, would inhibit faulting. Yet
faulted loops, and multilayered loops, are formed in
aluminum during electron bombardment in a highvoltage electron microscope52 and in thin foils that
are water-quenched from temperatures near the
melting point then aged.53 The occurrence of faulting in these cases is increased with increasing aging
temperature and impurity level. It is possible that
the SFE may have been reduced by contamination
occurring through the foil surfaces.
5.07.6.2.1 Fluence
Experiments54 made to establish the minimum fast

neutron fluence for the onset of visible radiation
damage microstructure in high-purity Al foils irradiated at <60 C indicate a threshold in the vicinity
of 3 1023 n m2, E > 1 MeV. The specimens were in
two conditions, annealed and cold worked, and were
of three thicknesses, 100 nm, 12.7 mm, and 76.2 mm.
None of the 100 nm foils showed damage structure
for exposures up to 5 1022 n m2. At a fluence of
3 1023 n m2, the 12.7 and 76.2 mm foils, both
annealed and cold worked, showed many small
loops, about 25 nm size in low concentration and
spotty distribution. After a dose of 1.6 1024 n m2,
the loop concentration was higher, but there was little
or no change in size. At both of these doses, the
annealed specimens contained loosely tangled
dislocation lines at higher density than is characteristic of well-annealed high-purity Al. These dislocations were kinked, and some of them that moved
while under observation in transmission electron
microscopy (TEM) examination were seen to have
been pinned at the loops. In annealed specimens, the

grain boundaries had well-defined denuded regions
about 0.35 mm wide on each side at a dose of
1.3 1024 n m2, and in the regions next to the
denuded zones many of the loops were large and
there were dislocation segments among them. Some
of these segments spanned the denuded zones. These
denuded regions are wider than the 100 nm thick foils
in which no radiation damage was found, suggesting
that the radiation point defects had migrated from
those foils. For cold-worked specimens, nothing
was said about the cold work dislocations. It is quite
possible that considerable recovery of the coldworked dislocation structure occurred before and
during irradiation. At grain boundaries in the coldworked material after irradiation to 6 1023 n m2,
a few loops and some dislocation segments are present within a distance of about 0.35 mm from the
boundary. In the adjoining regions, loops and dislocation segments are present in high concentrations, and
many of the loops are large, >0.1 mm, and they encircle smaller loops or are kinked by smaller loops.
Evidently, the dislocation segments are portions of
growing loops. The tangled dislocation lines in the
annealed specimens at the lower doses probably arose
from growth of the earliest loops. No radiation voids
were seen in these experiments. It was speculated that
the loops were vacancy-type, growing from collapse of
vacancy clusters produced by the irradiation. French
studies55,56 have corroborated and enlarged on the
heterogeneous nature of evolution of early damage
microstructure and the roles of dislocations in Al.
With increasing fluence at constant irradiation
temperature, the loops evolve into dislocation lines,
and voids and Si precipitates arise, which increase in
concentrations and sizes. The voids are larger and
161
0.1 mm
Figure 4 Denuded grain boundary and associated void

enhanced regions in 49 purity aluminum after irradiation at
50 C to a fluence of 3.4 1026 n m2 (E > 0.1 MeV).
less numerous than the Si precipitates. The voids are

facetted and so are the larger particles of Si. Most,
if not all, of the voids have a facetted Si particle
attached to the outside of one facet of the void.
The majority of the Si particles are not attached to
voids. The grain boundary denuded regions are not
enlarged, but the voids at their rims are exaggerated,
as illustrated in Figure 4. An unpleasant potential
consequence of these sheets of large voids is that
in the event of an unexpected overload, they may
provide paths for premature failure by a tearingalong-the-dotted-line-type separation.
Raising the irradiation temperature coarsens the

damage microstructure and decreases the degree
of radiation hardening for a given dose. At 150 C,
Figure 5, the dislocation structure almost disappears;
there are fewer voids, but they are larger than
at 50 C and are strongly facetted, and many of
them are very much elongated.57 Particles of
radiation-produced Si are attached to one face of a
void, usually at the narrow end of elongated voids.
Freestanding Si particles are likewise facetted and
elongated, some in ribbon shapes. The denuded
regions straddling grain boundaries are wider, about
1 mm each side. For annealed materials irradiated at
temperatures above 150 C, certainly above 200 C,
no dislocation-type radiation damage microstructure
or voids are produced; coarse Si particles are seen. In
cold rolled pure Al, some large cavities remained58
after irradiation at 220 C. During postirradiation
annealing59 removal of damage microstructure was
slowed by impurity content and by higher doses. For
1 h anneals of 1100Al, void swelling began recovery at
200 C and was almost complete at 300 C where gas
1 mm
Figure 5 Voids in high-purity aluminum irradiated at

150 C to a dose of 2 1025 n m2 (E > 0.1 MeV). Right:
Preinjected with 3 appm He. Reproduced from Farrell, K.;
Wolfenden, A.; King, R. T. Radiat. Eff. 1971, 8, 107114, with
permission from Taylor and Francis.
bubble swelling intervened. Void ripening preceded

void elimination. Si precipitates ripened and were
prevalent on grain boundaries.
5.07.6.2.3 Transmutation products
The gases helium and hydrogen produced from (n, a)

and (n, p) reactions of fast neutrons with lattice atoms
considerably affect the development and effects of
radiation damage structure by encouraging the nucleation of voids, dislocation loops, and bubbles.57,60,61
Helium is insoluble in Al. It binds strongly with
vacancies and has very limited mobility. Hydrogen
is almost insoluble at ambient temperatures, becoming more soluble with increasing temperature. In the
lattice, it is mobile even at room temperature. The
degree of promotion of voids and loops by the gases
decreases with increasing irradiation temperature,
and the promotion of bubbles increases. In the righthand micrograph of Figure 5, it is evident that even
for a high irradiation temperature of 150 C, the
presence of just 3 appm He implanted at room temperature has boosted nucleation of voids. The string
of voids in the field is not on a grain boundary. It
probably marks the position of a grown-in dislocation
present during implantation that has climbed away
during irradiation. At higher irradiation temperatures58 or during postirradiation anneals,59 the gases
form bubbles. The levels of helium and hydrogen
produced in Al are not widely different from those
in other metals. For the purpose of comparison we
can use the production rate tables of Gabriel et al.62
162
to estimate the levels of He and H produced in Al,

Fe, and Zr during a 1-year exposure in the high flux
peripheral target positions of the HFIR core. There,
on the horizontal mid-plane at current operating
conditions, the annual fast neutron fluence will be
2.4 1026 n m2, E > 0.11 MeV, and the thermal fluence will be 4.5 1026 n m2. In Al, this fast fluence
will generate gas concentrations of 11 appm He and
63 appm H, and in Fe there will be 5 appm He
and 95 appm H. In Zr, which is noted for its low
cross-sections, only about 0.25 appm He and 5 appm H
would be produced. The atomic displacement levels
for the three metals can also be calculated. They are
36 dpa for Al, 18 dpa for Fe, and 17 dpa for Zr.
The larger dpa level in Al is due primarily to its low
effective displacement energy, 25 eV versus 40 eV for
Fe and Zr.
There are three interesting reactions with thermal
neutrons that produce gases from the foreign elements Li, B, and Ni, which may be present in some
Al alloys. The spatial distributions of gases from these
sources are each different. Lithium has high solubility in Al and generates a uniform distribution of
gases. Boron and Ni are insoluble and they produce
localized concentrations of gas. Lithium is not a common impurity in Al, but there is a commercial series
of AlLi alloys developed for their lightweight highstrength properties. Laboratory-made AlLi alloys
have been used to study radiation hardening, helium
embrittlement, and swelling.63,64 Natural Li contains
7.5% of the 6Li isotope, which has a capture crosssection of about 950b and decomposes to He and
tritium via the reactions 6Li nth ! 7Li ! 4He 3H.
The present writer65 made an Al0.052 wt% Li
alloy using 69 high-purity Al and Li enriched to
98% with 6Li, and irradiated it to a dose of
5.5 1025 n m2, E < 0.0253 eV and 2.2 1025 n m2,
E > 0.1 MeV at 55 C. About 9599% of the 6Li was
burnt up to produce about 2200 appm each of He and
tritium. The atomic displacement level was about
3 dpa, not including any displacements from the
recoiled gases. The effects of these high levels of
gases were striking, see Figure 6. The insert is an
enlarged view of the matrix cavities. Compared with
irradiated pure Al control specimens, the concentrations of matrix cavities were increased 1000-fold,
and their sizes decreased tenfold; dislocation densities
were increased tenfold. Most grain boundaries were
crammed with large bubbles, many so interconnected
that it was difficult to obtain thinned foils for TEM
examination because the grain boundaries were eaten
away before much thinning of the grain interiors
0.1 mm
1 mm
Figure 6 Modification of void structure by very high

helium and tritium levels from burnup of 6Li. Reproduced
from Farrell K.; Houston J. T. Combined Effects of
Displacement Damage and High Gas Content in Aluminum,
ORNL-TM-5395; Oak Ridge National Laboratory: Oak
Ridge, TN, May 1976. Also available in Proceedings of
International Conference on Radiation Effects and Tritium
Technology for Fusion Reactors, Gatlinburg, TN, Oct. 13,
1975, U.S. Department of Commerce CONF-750989,
Mar 1976; pp. II-209II-233.
occurred. The grain boundary in Figure 6 is one

with a low concentration of bubbles. Hardness measurements gave a Vickers pyramid hardness (VPH) of
137 MPa for the annealed, unirradiated Al and the
alloy, and 382 and 902 MPa for the irradiated specimens. In bend tests made in air and liquid nitrogen
(LN), the unirradiated materials and the irradiated
pure Al were bent through full circles without rupture. The irradiated alloy broke with an audible crack
and with no detectable plastic strain. Fracture was
accompanied by release of tritium. The fracture surfaces displayed 100% intergranular failure. These
are incredible hardening and embrittling effects of
the gases. Electron microcopy examination of carbon
replicas taken from the fracture surfaces showed huge
irregular interconnected bubble cavities. Failure
occurred by plastic tearing of the small areas of intact
grain boundaries between the cavities. Postirradiation
annealing treatments caused the appearance of a coarse
distribution of large facetted matrix cavities superimposed on the small matrix cavities, and with
no denuding of the surrounding small cavities. These
enlarged cavities were frequently associated with large
silicon particles that grew concurrently during the
anneals. An anneal at 500 C showed incipient disintegration of the specimens and TEM foils could not
be obtained. It was postulated that the large cavities

grown during annealing were tritium bubbles.
Al often contains trace quantities of B in the
form of small B4C inclusions. Natural B contains
19.8% 10B, which has a large neutron capture
cross-section of 3835b, producing Li and He via
10
B nth ! 11B ! 7Li 4He. The range of the
recoiled He atoms is about 5 mm, and the He is
segregated in a well-defined band in a halo around
the parent inclusion. The larger Li atom has a smaller
range and is soluble; it forms a diffuse halo. At low
irradiation temperatures and low doses, the halos are
very prominent because of heavy decoration with
dislocation loops. As the dose increases, the loops
grow and move off leaving dense halos of voids, especially for the He halo. The writer has seen hundreds of
these halos. Most of them were circular or near circular, with an occasional cigar shape, depending on the
shape of the mother particle. Most were isolated
randomly, but some were in groups or were strung
in chains on a grain boundary. One is illustrated in
Figure 7. This particular halo is slightly squashed,
following the elliptical contour of the central particle.
The dark region of the outer halo is actually filled
with small cavities, resolvable at higher magnification. Where a halo intercepts a grain boundary the
voids seem to disappear, but during annealing they
become visible as bubbles on the boundary that grow
1 mm
Figure 7 Damage halos around a suspected B4C particle

in 1100-OAl irradiated to 2.9 1026 n m2 at about 55 C.
163
faster than those elsewhere in the halo. Such highly

heterogeneous distributions of transmutant gas have
been perceived more as a novelty than as a possible
threat to the integrity of the host material. This
attitude may be unwarranted. A highly localized concentration of helium in a patch on a grain boundary
could be a prime site for premature helium embrittlement at stresses and temperatures below the ranges
for normal helium embrittlement elsewhere in the
specimen. A spongy helium halo that intercepts the
surface of Al cladding may provide a potential site
for initiation of local corrosion. For these reasons, it
might not be a good idea to consider placing particles
of B4C burnable poison in single-layer cladding on
monolithic LEU fuel plates; a better location would
be in the inner layer of a two-layer cladding.
Some of those considerations apply to He produced from Ni in Al. It comes from the 59Ni isotope,
which is not found in natural Ni. The 59Ni must
first be created from 58Ni that comprises 68.1% of
natural Ni. The two-step process66 to yield the He is
58
Ni nth ! 59Ni; 59Ni nth ! 56Fe 4He. Helium
generation via this route does not scale linearly with
time. It is slow to start while the 59Ni accrues, then
it increases as the square of the fluence. It is favored
by long-term exposures or strongly thermalized neutron spectra. Only trace quantities of Ni are found
in most Al alloys except the X8001 and AlFeNi-type
alloys, which contain a nominal 1 wt% Ni. These
alloys were developed for cladding because early
laboratory corrosion tests indicated they might have
better corrosion resistance than existing cladding
alloys. Trials of the X8001 have not shown superior
performance. The alloying elements in X8001 are
insoluble in the solid alloy and form intermetallic
inclusions that are malleable and become deformed
and extended into stringers during unidirectional
rolling and extrusion processing. The helium atoms
formed from the Ni in the stringers are recoilimplanted into the near-matrix regions surrounding
the stringers where they accelerate local formation of
voids and dislocations. The recoiled 56Fe atoms cause
extra dpa locally.67 These He-enriched regions are
not as obvious as those around B4C inclusions. They
are indicated by higher concentrations of voids, and
the emergence of more numerous He bubbles during
postirradiation annealing. This localized damage
offers an explanation of a hitherto inexplicable puzzle found in the corrosion response of X8001 alloy.
A characteristic of extruded X8001 tubes undergoing
aqueous corrosion in reactors is that smooth shallow
troughs or discontinuous ruts lying in the direction of
164
the tube axis are created in the corroded surfaces.68

Such troughs have not been reported in laboratory
corrosion tests of X8001. It is suggested here that the
troughs are stringer beds left when the Ni-rich stringers are eased out of the surface by selective corrosion/erosion of the more highly damaged He-rich
matrix at the stringers.
Localized enhancement of He at Ni-rich stringers
is also believed to play a major role in the occurrence
of axial cracking of the X8001 cladding on HFIR
long-term isotope target rods.69,70 The target material is a cylindrical compact of actinide oxides in
an Al powder matrix, 6.3 mm diameter 14.5 mm
long, each jacketed in 1100Al. The meat contains
about 10% porosity to accommodate fission gases.
A target rod consists of 35 jacketed capsules stacked
in a tube of X8001 alloy that is hydrostatically compressed around them to form the outer cladding. The
tubes are made by extrusion and have six equally
spaced longitudinal fins. Before the target slugs are
loaded into the tubes, most of the fins are machined
off, leaving short lengths of fins at several locations
along the active length of the rod. The loaded target
rod is slid into an X8001 tubular sheath with hexagonal ends, known as a hex can. The groups of remnant
fins along the length of the rod act as spacers that
centralize the rod in the hex can and maintain
an annular water-cooling channel around the rod.
A bundle of 31 sheathed target rods just fills the
vertical HFIR trap. Cooling water flows inside and
outside the hex cans. Cracks were found in the mid
length, high flux regions of the target rods during a
search for the source of a-contamination detected in
the exiting coolant. Investigation showed that the
cracks were intergranular and were oriented in the
length of the rods at locations where the fins had been
removed. Lengths were up to 66 mm. The cracks
originated in the target rod cladding, but some of
the larger ones had penetrated the 1100Al jackets of
the target slugs. There was no evidence that corrosion
was involved. The hex cans were not cracked. The
exposure history of the rods is that they were first
irradiated for about 1 year in the D2O environment of
the C reactor at Savannah River Nuclear Laboratory
at a temperature of 20 C. They were returned to
ORNL and inserted in the HFIR at 46 C where,
during their fifth fuel cycle, the a-leak was detected.
The summed fluences were 6.9 1026 n m2, thermal, and 1.2 1026 n m2, E > 0.82 MeV. The conclusion from the investigation was that gas swelling of
the target meat had imposed a hoop stress on the
radiation-damaged cladding that had become too stiff
to undergo plastic flow and had cracked instead.

Rupture tests on unirradiated lengths of the cladding
tubes by internal pressure caused failure along the
machined-off fin lines, indicating the lines were weak
regions in the tubes. A possible solution to the cracking problem was to decrease the swelling-related
hoop stresses on the cladding by raising the pore
volume in the target meat from the then current
10% level to 20% and 25%. Trials were successful,
and the cracking no longer occurs. The questions of
why the cracks were located only on the fin lines and
why it was intergranular were not answered, but were
pursued.71 The intergranular nature of the fractures
made helium embrittlement a suspect. However, calculations of helium levels from the 27Al(n, a) reaction
with fast neutrons had given 7 appm, which was
considered inadequate for helium embrittlement at
the low irradiation temperatures experienced by the
rods. But supposing it was occurring, why did it favor
the fin lines? Metallographic and TEM examinations
of pieces of unirradiated cladding tubing showed that
the extrusion process had stretched the inclusion
particles into stringers and forced sheets of them
into the fins from which they extended back into
the tube wall. Removal of the fins left behind an
aggregation of stringers protruding into the tube
wall. Ergo the weakened regions along the fin lines
seen in the rupture tests of the unirradiated tubing.
When the enhanced production of helium from Ni by
thermal neutron capture was announced,66 a connection between aggregates of Ni-rich stringers and
helium embrittlement was discerned. Irradiated pieces
of high-purity Al, 1100Al, and a X8001 hex can were
sent to a specialist laboratory for helium analyses. For
a common thermal fluence of 1 1026 n m2, the
results were 1.8, 4.8, and 9.5 appm, respectively. After
a fluence of 3 1026 n m2, the corresponding
values were 7.2, 18.1, and 145. A piece of hex can
irradiated to 5.8 1026 n m2 yielded 220 appm.
A piece of 6061Al at 13.8 1026 n m2 gave 47 appm,
much less than the hex can at 5.8 1026 n m2. These
results leave no doubt that the presence of Ni in Al
irradiated to high thermal neutron fluences greatly
boosts the helium levels. And since the He will
remain close to the Ni particles, there must be very
large concentrations around the stringers. Any grain
boundaries overlapped by those local helium clouds
will be prime candidates for helium embrittlement
cracking under the influence of hoop stresses. Hence,
the intergranular cracking at the fin lines.
In most metals, the gaseous transmutation products
play a larger role in the development and effects of
165
radiation damage structure than do the nongaseous

transmutants, one reason being that most construction
metals do not produce much nongaseous transmutants. Al is different. Depending on the degree of
thermalization of the neutron spectrum, Al can produce large quantities of silicon from the two-step reaction 27Al nth ! 28Al g; 28Al ! 28Si b. A rough
guide to the quantity expected annually in the HFIR
PTP spectrum can be obtained by multiplying the
thermal neutron fluence by 230mb, the standard thermal neutron (0.0235 eV, 2200 m s1) absorption crosssection for Al. The result is 1.035 at.% Si (1.073 wt%).
The Si is insoluble in Al at temperatures below about
350 C and is usually manifest as a precipitate of
elemental Si.72 This precipitate makes a substantial
contribution to radiation damage in Al, and is the
dominant hardening agent at high thermal neutron
fluences. There is one outstanding qualifier to that
generalization. In the 5xxx-type AlMg solid solution
series, the free Mg atoms dissolved in the Al will react
with the atoms of transmutant Si to form a precipitate
of Mg2Si.73 Thus, a 5xxx series alloy will be converted
to a 6xxx-like alloy.7376 Figure 8 shows the Mg2Si
microstructure formed in irradiated 5052-O alloy.
Because this precipitate occurred at a temperature
below the usual 160 C aging temperature used to
obtain the T6 tempered condition in 6061Al, the
Mg2Si precipitate developed in the 5000 alloy is finer
than in the 6061-T6 alloy. The microstructure of
heavily irradiated 6061-T6 alloy is illustrated in
Figure 9. Since there are usually larger quantities of
Mg in the 5xxx alloys than in the 6xxx alloys, a greater
volume of Mg2Si can be created in the former 5xxx
alloys. Hence, irradiated 5xxx alloys will undergo radiation hardening and precipitation hardening simultaneously, and their overall hardening rate will be larger
than in other Al alloys exposed to the same neutron
fluence. Note that there are no voids in Figure 8.
Sparsely distributed voids are found75 at a higher
fluence of 1.8 1027 n m2. At half of that dose, the
6061-T6 alloy contains many more voids, Figure 9.
The association of the transmutant Si with voids is
interesting. We saw earlier that voids and particles of
Si become visible in the microstructure at about the
same dose. The voids are larger and fewer than the Si
particles. A Si particle is usually attached to one facet
of a void, and that particle is larger than its unattached brethren in the matrix. It is also facetted.
As irradiation continues, a change occurs in the
void-Si relationship. The voids lose their facetted
shape and become rounded.77 They are completely
covered with a thin coating consisting of mostly Si
100 nm
200
000
220
020
Figure 8 Precipitates of Mg2Si and excess Si in formerly

5052-OAl irradiated to 5.7 1026 n m2 at 55 C.
Reproduced from Farrell, K. J. Nucl. Mater. 1981, 97, 3343,
with permission from Elsevier.
0.1 mm
Figure 9 Voids with background precipitate of

radiation-produced silicon and silicon-decorated original
Mg2Si precipitates in 6061-T6Al irradiated to 1027 n m2
at 55 C.
166
0.1 mm
Figure 10 Si particles and Si-coated voids on a
carbon extraction replica from 1100-OAl irradiated to
1.4 1027 n m2 (E > 0.1 MeV) and 2.3 1027 n m2
(E < 0.025 eV) at 55 C. Reproduced from Farrell, K.;
Bentley, J.; Braski, D. N. Scripta Metall. 1977, 11,
243248.
with some Al. The coating is noncrystalline and flexible. The unattached Si particles in the matrix are also
rounded but are crystalline. The coated voids jut out of
the thinned edge of the hole in TEM foils and can be
lifted from the matrix on carbon extraction replicas.
Figure 10 is an example. The larger features with the
dark rims are the coated voids. Four of them have
partially collapsed without breaking, indicating a
highly ductile coating. Many of the Si particles seem
to have a layered structure. The AlSi system is a
simple eutectic; there are no compounds. It is suspected
that the small amount of Al found in the void coatings
may be from the Al matrix that was not completely
dissolved from the voids during the electrolytic
extraction process. Silicon is obviously involved in
void formation and growth but its specific role is
unclear.
5.07.7 Property Changes

5.07.7.1
Swelling
Radiation swelling is the increase in volume arising

by accumulation of voids from excess vacancies and
by formation of gas bubbles. For Al, there are also
small swelling contributions from build-up of particles of transmuted Si and, in 5xxx alloys, Mg2Si,
which have densities of 2329 and 1990 kg m3,
respectively.78 Gas bubble swelling is not an issue
for Al in RRs because the temperature is too low,
except perhaps in fuel cladding where some pores
found in the cladding may have been formed by the

accumulation of hydrogen. Swelling can be measured
from dimensional changes. More often it is determined from changes in immersion density values.
Swelling in various Al alloys is shown in Figure 11.
These alloys were all irradiated in the core of the
HFIR and they make the most comprehensive and
consistent set of swelling data.79 For reference, the
dotted line is estimated for the swelling from Si alone.
It is evident that the unirradiated chemical compositions and microstructures have major effects on the
degree of radiation swelling. The purest grades, sixnines and four-nines, show swelling earliest in dose
and swell at the highest rates with dose. The rates
decrease above a dose of about 1 1025 n m2.
Swelling in the two-nines grade (1100-O) requires
significantly higher doses, but the swelling rate is
unchanged. The 6061-T6 alloy, with its inherent
Mg2Si phase, starts swelling appreciatively later in
dose than the 1100-O. This is traceable to reduced
nucleation of voids, but its swelling rate is about the
same as the other alloys. The greatest resistance is
in the 5052-O alloy. There, the swelling is less than
for the Si alone. In this alloy, much of the early
swelling is not due to voids; it is caused by the silicon
and the new Mg2Si phase and by the increase in the
original density of the matrix, r0, as Mg is drawn
from solution to create the Mg2Si.
The effects of prior cold work on swelling in
Al agree in general that the presence of cold work
dislocation structure decreases the overall void
swelling but the reduction is not massive; concurrence
of dislocation recovery confuses the details.8083
5.07.7.2
Mechanical Properties
The major consequences of radiation damage structures on the mechanical properties of Al alloys are
radiation hardening and associated loss in ductility.
There are too many data from too many sources
to be described in detail here. A good source of
compiled data, including the sparse information on
fracture toughness and weldments, is Marchbanks.84
For 6061Al in particular, see Farrell.85 Strengthening and loss of ductility are demonstrated best
in tensile properties. In Figure 12 we can directly
compare the changes in strength and ductility of
different alloys irradiated and tested under the
same conditions.79 The most striking feature is the
relatively rapid hardening displayed by the 5052-O
alloy. As explained earlier, this is caused by the
combined effects of radiation damage and in-reactor
wt % Si 0.1
dpa 0.1
10
10
10
100
6-9
4-9
2-9 (1100-O)
6061-T6
5052-O
( ri )
Ti = 328 K (0.35 Tm)

1
6061-T6
Swelling
rori
167
1100-O
5052-O
0.1
Pure aluminum
28
Si
0.01
1024
1025
1026
Fluence (n m-2 > 0.1 MeV)
1027
Figure 11 Radiation-induced swelling in various Al alloys as a function of fast fluence. Reproduced from Farrell, K.
In Proceedings of the Conference on Dimensional Stability and Mechanical Behaviour of Irradiated Metals and Alloys,
Brighton, Apr 1113, 1983; British Nuclear Energy Society: London, 1983; Vol. 1, pp 7376, with permission from British
Nuclear Energy Society (now The Nuclear Institute).
formation of a fine precipitate of Mg2Si. In contrast,

the 6061-T6 alloy, which contains Mg2Si before
irradiation, begins radiation hardening at about the
same fluence as the 1100-OAl, and hardens thereafter at the same rate. The 1100-O alloy contains no
Mg2Si before or after irradiation. From which we
deduce that preexisting Mg2Si precipitates play no
role in radiation hardening. This is an interesting
conclusion. It contradicts the expectation that the
precipitates would diminish the degree of radiation
hardening in 6061-T6Al by promoting the recombination of freely migrating vacancies and interstitials.
Perhaps that expectation is wrong. But it seems
satisfactory for explaining the delayed swelling in
the 6061-T6 alloy, where nucleation of voids is
retarded, perhaps until the transmutant gases enable
achievement of critical size cavity nuclei. Alternatively, maybe the radiation-produced Si dominates
the hardening process. It is a mystery. The fluence
for the onset of radiation hardening in the weak
49Al is about one order of magnitude less than in
the other alloys, and the subsequent rate of hardening is less than for the others. Here, again, we invoke
the recombination argument. This higher purity
material contains less solutes and inclusions. Thus
there is less trapping and annihilation of freely
migrating point defects, hence more point defect
clusters are formed in the early stages of irradiation.
It is suspected that the reduced rate of hardening is
connected with dynamic recovery of deformation
during the tensile test. It was pointed out in Section
5.07.3.2 that recovery from cold work occurs readily
in high-purity Al at room temperature. Loss in
uniform elongation in all of the alloys is concomitant with increase in strength . . . to a point. At a
fluence of about 1026 n m2 the ductility reaches a
plateau of 35% even though the strength continues
to rise. The 1100-OAl has the least ductility in the
plateau region and displays an intergranular-like
fracture mode that may be caused by tearing and
void interconnection in the void-rich regions lying
alongside the grain boundaries.
600
Stress (MPa)
500
Tirr = 328 K
Ttest = 323 K
.
~ 10-4 S-1
'
168
UTS
0.2% FS
400
300
6061-T6
200
5052-O
100
1100-O
4-9AI
0
Uniform elongation (%)
40
30
20
4-9AI
5052-O
1100-O
10
6061-T6
0
1023
1024
1025
1026
1027
-2
Fluence (n m > 0.1 MeV)

Figure 12 Radiation-induced changes in room temperature tensile properties of various Al alloys. Reproduced from
Farrell, K. In Proceedings of the Conference on Dimensional Stability and Mechanical Behaviour of Irradiated Metals and
Alloys, Brighton, Apr 1113, 1983; British Nuclear Energy Society: London, 1983; Vol. 1, pp 7376, with permission from
British Nuclear Energy Society (now The Nuclear Institute).
Irradiated metals undergoing plastic deformation

are prone to strain localization, seen as dislocation
channels swept free of point defect clusters. Such
channeling coincides with changes in the tensile test
curve, notably introduction of a sharp yield point
and a reduction in the slope of the strain-hardening
portion of the curve. In severe cases, a yield point
drop occurs that leads directly into prompt necking.
Dislocation channeling has not been reported for
neutron-irradiated Al. Nor do the tensile curves for
neutron-irradiated Al display sharp yield points and
pronounced decreases in work hardening rate. The
reason for this apparent resistance to channeling in
Al is not known. Al is not immune to channeling.

It occurs in unirradiated quenched-and-aged Al.
When high-purity Al crystals are quenched from
near the melting point into water at room temperature or into iced brine, then aged at room temperature for 14 days or at 60 C for 2 h, there is
a considerable increase in yield stress (YS) and large
decrease in strain hardening rate.86,87 Such quenchaging treatment produces many small vacancy clusters. Yielding occurs abruptly, and large widely
spaced slip bands appear on the specimen surfaces,
forming mirror images from one surface to the
opposite surface. TEM examination87 reveals that
A5 AI, ~35% CW, 77 K (0.08 Tm)
400
~1 1023 n m-2, E > 1 MeV
Stress (MPa)
300
~5 1021 n m-2
7.5 1021 n m-2, then

held 60 h at room
temperature before
test at 77 K
200
Unirradiated
100
Unirradiated,
tested 293 K
0
0
10
20
30
40
Elongation (%)
Figure 13 Tensile curves of pure Al irradiated and tested

at cryogenic temperatures, showing recovery at room
temperature. Reproduced from Bochirol, L.; Brauns, P.;
Claudet, G. Prog. Refrigeration Sci. Technol. 1973, 1,
643650, with permission from International Institute of
Refrigeration, AVI Publishing Company.
the slip bands are dislocation channels prominently

displayed against the background of undisturbed
vacancy clusters remaining in the matrix between
the channels. Another way to induce a sharp yield
point and reduced strain hardening rate in Al is to
irradiate and tensile test at cryogenic temperature.
Figure 13 gives tensile curves for an A5 alloy
(>99.95% Al) in the half-hard, H24 (35% cold
worked), condition after neutron irradiation and testing at 77 K in LN.88 A curve for an unirradiated
specimen tested at room temperature is included as
a reference condition. Note that this unirradiated
specimen has only 14% elongation, in keeping with
its cold-worked condition. When tested in LN the
unirradiated material is not only stronger it is much
more ductile, with an elongation of 44%. This is an
example of the enhancement of ductility at low temperature mentioned in Section 5.07.3.1. Irradiation
to 5 1021 n m2 in LN further increases the YS,
and although the elongation falls a little, it is still
larger than at room temperature; moreover, the initial
part of the strain hardening curve to about 8% elongation is steeper than that for the unirradiated specimen, indicating no irradiation-induced dislocation
channeling. However, the reduced slope after 8%
elongation and prior to onset of necking in the irradiated specimen signals possible late entry of channeling. Note that for this dose at room temperature
there would be no discernible radiation damage
structure and no change in tensile properties. In
the LN specimen irradiated to the higher fluence
169
of 1 1023 n m2 intervention of channeling is

more likely. There, very steep initial strain hardening
passes though a peak at 1% elongation and plunges
into prompt necking. Even greater strengthening and
more exaggerated prompt necking is found for both
cold-worked and annealed specimens when the irradiation and testing are done at 27 K in liquid neon.88
The deformation modes were not determined for
these specimens. Identification of the deformation
mode would have required TEM examinations of
specimens cut from the gauge sections of the specimens and would probably not have revealed the
channeling because the specimens would undergo
rapid recovery from radiation hardening when they
are brought up to room temperature. Such recovery
is illustrated by the curve for the specimen irradiated
to 1 1022 n m2 then held at room temperature
for 60 h before testing in LN. Almost complete recovery has occurred, indicating elimination of the point
defect clusters needed to provide background contrast for detection of dislocation channels. The good
result of this recovery is that it relieves the stored
energy built up by accumulation of the radiation
damage microstructure at the cryogenic temperature.
Advantage is taken of this recovery process in Al cold
neutron sources by performing periodic in situ room
temperature anneals on them. These anneals do not
erase the transmutation products. Residual hardening
from the gaseous products will be negligible but
the accumulating Si, whose levels will be high due
to the highly thermalized neutron spectrum at the
cold source, will give increasing retained hardening as it forms precipitates at room temperature.
For cold source vessels constructed from 5xxx alloys,
the transmutation-produced Si will react with dissolved Mg at room temperature to create naturally
aged fine precipitates of Mg2Si, with greater hardening effects than from Si alone.
5.07.7.3
Effects of Neutron Spectrum
When tensile data for irradiated Al from different

reactors or from different regions of a single reactor
are compiled in a single traditional plot of property
versus fast neutron fluence, there tends to be a large
scatter in the data, particularly at the higher fluences.
It was noted89 that the scatter was reduced somewhat
if the plot was made in terms of thermal fluence.
This improvement was attributed to a spectral effect
involving the production of Si precipitates by the
thermal neutrons and their modification by fast neutrons. That explanation has since been taken a little
170
wt% silicon
0.1
0.01
10
Tensile strength (MPa)
800
6061-T6 aluminum . grouping by fth/ft ratio
700
20
Unirradiated
HFIR target
HFBR surveillance
HFBR V15
HFBR CRDF
600
500
21
21
21
8 5-81-3
22
400
5
1.3
.57
53
0.5
300
200
0
1023
1024
1025
1026
Thermal fluence (n m- 2)
1027
1028
Tensile strength (MPa)
800
20
700
21
600
21
21
5-8
8
500
5
22
400
5
1-3
1.3
.57
.53
0.5
300
200
0
1023
1024
1025
1026
1027
1028
Fast fluence, E > 0.1 MeV (n m- 2)
Figure 14 Radiation-induced strengthening of 6061-T6Al discriminated by thermal and fast fluence. Reproduced from
Farrell, K. In Proceedings of Materials Research Society Symposium on Microstructure of Irradiated Materials, 1995; Vol. 373,
pp 165170, with permission from Materials Research Society.
farther.90 Figure 14 presents tensile strength data

for the 6061-T6 alloy irradiated in two reactors,
the HFIR and the High Flux Beam Reactor (HFBR),
at 5065 C. The same strength data are plotted
against thermal fluence in the upper box and against
fast fluence in the lower box. Ignoring for the
moment the lines in the plots, it is evident that at
fluences above 1 1025 n m2 the data points are
more scattered when plotted against fast fluence. The
HFIR specimens were all irradiated at the same
location where the ratio of thermal-to-fast flux, th/
f, was narrow, 1.72.3. The HFBR was cooled and
moderated by heavy water, and the HFBR specimens
were taken from regions with th/f values between
0.5 and 22. When the data are discriminated by th/
f as indicated by the lines labeled with the large
numerals, a pattern of dependence on th/f
emerges. The trend is the same in both boxes but
the separation is clearer in the fast fluence plot. It is
evident that when irradiation is conducted in a hard
spectrum, th/f 0.5, there is little increase in
strength, even at high fluence. As the spectrum softens, th/f ! 21, the specimens harden. This
response is obviously due to greater generation of
silicon precipitates in the more thermalized spectra.
TEM examinations of the more heavily irradiated

specimens showed that the dominant microstructural
feature introduced by the irradiation in both reactors
was particles of Si. They were more numerous and
smaller in the softer spectrum, in agreement with
the strengthening trend. After eliminating possible
contributions from differences in damage rates, irradiation temperatures, and exposure times, it was concluded that the spectrum controls the ripening
behavior of the Si precipitates, which determines the
degree of strengthening. A hard spectrum causes more
sputtering of the precipitates and more transport of
the sputtered atoms, resulting in greater ripening of
the precipitates and less strengthening per unit Si
level or unit fluence.
5.07.7.4 Radiation Softening, Creep, and
Stress Relaxation
There are some highly contentious reports of radiation softening of Al alloys that demand some discussion. These are not claims of minor softening such as
a decline in the strain-hardening region of a tensile
curve. They are full-blown changes from an agehardened or cold-worked condition to a dead soft,
annealed state. And they occur in specimens that are

not carrying a load. The softening is usually interpreted as being due to destruction of dislocation
tangles and precipitate particles through dynamic
atomic displacements created by fast neutrons. It is
the present writers opinion that they are actually
unintended instances of thermal softening by radiation heating, which can happen very easily and
quickly in Al if adequate precautions are not taken
to ensure adequate cooling during irradiation. In each
of these reports, the specimens were irradiated in
sealed cans with external water cooling and no
means of measuring the internal temperature. Using
sealed cans is an invitation to radiation heating of the
contents unless very strict actions are taken to ensure
satisfactory heat removal. In the first91 of these
reports, disks of 2024-O, 2024-T3, 1100, and sintered
Al powder of undeclared Al2O3 content were placed
in aluminum cans evacuated and back filled with
helium. The cans were irradiated in the MTR for
60 days to fast neutron doses of 3 1022, 2 1023, and
8.5 1023 n m2 at estimated temperatures of 100,
119, and 138 C, respectively. Hardness tests on the
2024-T3 disks showed: unirradiated control, Hv 170;
3 1022 178; 2 1023 68; 8.5 1023 60, indicating a pronounced change from the age-hardened-T3
condition to a fully softened condition. The hardnesses
of the 1100 and the sintered aluminum powder alloy
were unchanged by the irradiations. This softening of
2024-T3 alloy conflicts with tensile and hardness
data92 for a 2024-T3 or -T4 alloy irradiated to doses
between 2 1023and 1.3 1026 n m2 that show no
change in properties to a dose of 1.2 1024 n m2,
above which there is hardening. These latter data
were for specimens that were irradiated in direct
contact with flowing water to minimize nuclear heating. The writer has also tested tensile specimens
of 2024-T351Al that were irradiated in contact
with flowing water; there was no change in properties
for fluences between 4 1021 and 1 1024 n m2,
beyond which hardening was displayed.93
The second softening claim94 was made for tensile
specimens of Al3Mg in a cold-worked condition
(degree of work not given), and 6061-T6 bombarded
with 600800 MeV protons in the Los Alamos Meson
Physics Facility (LAMPF). Annealed specimens of
the two alloys were included for reference. Assemblies of seven specimens laid side-by-side were sealed
in envelopes made from 0.13 mm thick foil of 1100Al.
Sixteen packages were stacked with gaps between
them to allow cooling water to flow though at a
rate of 1 l s1 and pressure of 17 bar (1700 kPa) to
171
ensure good contact of the foil with the specimens.

The beam spot size was 50 mm, the average current
was 574 mA, and the exposure period was 750 h.
Displacement damage up to about 0.2 dpa was created by the direct impact of the protons and by highenergy neutrons spalled from surrounding materials
and the nearby beam stop. No Si was generated.
Helium and hydrogen contents were 67 and
275 appm. From the beam parameters, it can be seen
that the power input was about 200 MW m2, which
is about 20 times larger than the heat fluxes reached
on fuel cladding. The irradiation temperature for the
LAMPF specimens was estimated to be 4050 C,
certainly not exceeding 100 C. Postirradiation tests
revealed that the yield strengths of the cold-worked
Al3Mg and 6061-T6 specimens were reduced
by 7080% and the ultimate strengths by 4065%,
which placed them at the same strength levels as
those for unirradiated annealed specimens of the
alloys. The irradiated annealed alloys did not
undergo irradiation hardening; they actually softened
by 1020%. Metallographic studies and TEM examinations of the formerly cold-worked Al3Mg alloy94,95
showed that recrystallization had occurred. At a dose
of only 0.1 dpa, the tightly packed dislocation cell
structure was gone, replaced by very loosely tangled
dislocations, and the grains were now equiaxed.
In the former 6061-T6 alloy, there were no longer
any Mg2Si precipitates. In the irradiated annealed
Al3Mg specimens, there were gas bubbles on the
grain boundaries. These microstructural changes are
very much like those found for thermal anneals or
high temperature irradiations; they require sustained,
long range, high-intensity diffusion of vacancies and
solutes. Usually, irradiation with energetic particles
does not create or support such condition unless
radiation heating occurs. Under adequate temperature control, radiation enhanced diffusion is highly
local and sporadic and is rapidly quenched. Normally, radiation attrition of precipitates results in
precipitate atoms being recoiled into the adjacent
matrix and there forming new satellite particles of
the mother phase or a new phase. A situation of total
elimination, with no reappearance of the precipitate
by aging, is more typical of a high-temperature solution anneal and a slow cool. Nevertheless, the authors
attributed these extreme changes in microstructure
to the absence of transmutation-produced Si which
stabilizes radiation damage microstructure in regular
neutron irradiations, and to the different nature
of the damage produced by high-energy protons,
this despite efforts they and others were making
172
at the time to promote such irradiations as a substitute

for slower neutron irradiations. They were unable to
account for the disagreement with an earlier 600 MeV
proton irradiation of a solution-treated AlMgSi
alloy similar to 6061 at 150 C in the Swiss PIREX
facility, which induced precipitation of a high density
of Mg2Si precipitates.96 Strangely, they gave no consideration to the possibility that they might have
overestimated the cooling efficiency of their irradiation experiment in LAMPF. It should have been the
prime consideration because at that time LAMPF
was undergoing changes to make it suitable for materials irradiations. None had been performed there
previously. The changes were incomplete but the
experiment was made anyway. It was a pseudo atest. Since then, improvements have been made to
the facility and many materials irradiations have been
conducted that simulate reactor irradiations. Later
irradiations of 6061-T6 in LAMPF97,98 have not
encountered the softening found in the inaugural
proton irradiation.
The third softening claim99,100 was again for
a cold-worked, nominal Al3Mg alloy and for a
precipitation hardened AlMgSi (6061-type) alloy.
Tensile specimens and annealed companion specimens were irradiated to fast fluences of 8.7 1021
and 2.5 1022 n m2 in the wet channels of the
Egyptian Nuclear Research Reactor. The responses
of the materials to both of these fluences were almost
identical and are confusing. The AlMgSi alloy in two
different age-hardened conditions and its as-received
cold rolled condition displayed large decreases
in hardness, YS, and ultimate tensile stress (UTS).
The Al3Mg alloy in its as-received cold rolled condition showed large reduction in hardness and relatively small reductions in YS and UTS. In a partially
annealed condition (1 h at 240 C) its hardness was
reduced 30% but its YS and UTS were increased by
55% and 27%. In the fully annealed state (1 h at
400 C) the hardness was decreased by 5%, the YS
was increased by a whopping 380%, and the UTS rose
by 97%. Although no microstructural studies were
made, the authors concluded that the observed softening was due to removal of cold work dislocations
and dissolution of Mg2Si precipitates as seen in
Lohmann et al.94 and Singh et al.95 The conclusion
that Mg2Si precipitates are unstable in a neutron flux
is at odds with the well-established fact that the precipitates persist to very high fluences in 6061-T6
specimens that are properly cooled during irradiation,
and they are actually generated by the irradiation in
AlMg solid solution alloys. The unusually large
hardening caused in the partially and fully annealed

Al3Mg specimens was not discussed. It was ascertained from the lead author that the specimens had
been irradiated in sealed cans. It was conveyed to the
author that ongoing experiments at ORNL with
6061-T6 were not finding any signs of radiation
softening at fluences similar to those in his experiments. Some years later, he published a third paper101
on the AlMgSi alloy in four conditions: Cold rolled;
annealed; naturally age hardened; and artificially age
hardened. The specimens were wrapped in Al foil
and were packed in aluminum powder in sealed Al
cans. The fast neutron fluence was 3.7 1022 n m2,
somewhat higher than his previous irradiations.
Hardness and tensile tests revealed no softening of
the cold-worked and age-hardened specimens. The
annealed specimens displayed a 23% increase in
Vickers hardness and a 111% increase in yield
strength. This radical departure from the previous
softening results was not credited to better cooling
of the specimens during irradiation. Rather, the newfound nonsoftening of the prehardened materials was
attributed to the longer irradiation exposure. It was
explained that the prehardened alloys actually did go
through a full softening process in the region of
1 1022 n m2 as before, by the mechanism of
radiation-induced dissolution of the cold work dislocations and Mg2Si precipitates. This removal of
these strong point defect sinks allowed irradiation
damage microstructure to build up as irradiation
continued. At the exposure of 3.7 1022 n m2 sufficient damage microstructure had formed to restore
the strengths of the softened materials to their former
values.
These claims of radiation softening, controversial
as they are, do serve a useful purpose. They highlight
the previously discussed temperature sensitivity of
cold-worked and age-hardened aluminum. Moreover,
they send a message that in the event of an unplanned
temperature excursion on such materials they should
be examined carefully to ensure that they still meet
the strength requirements for the application.
Radiation creep and stress relaxation are timedependent plastic deformation processes driven by
applied external stresses or by stored internal stress.
They can be accelerated by point defects from atomic
displacement events. The few data that exist for
radiation creep in aluminum are confusing and inconclusive. Details are available in Farrell.85 Creep can
lead to failure if the load is continuously applied.
Strain from stress relaxation ceases once the load is
relaxed. There are at least two cases81,102 of stress
relaxation in Al reactor components. Both were

found in retired reactor components that had entered
service in cold-worked conditions, one 1100Al and
the other precipitation-hardened 6063Al. During service they had been continuously in direct contact
with the coolant water, so thermal interference was
not involved. Some softening occurred due to partial
recovery of the cold work structure at low doses,
followed by radiation hardening at higher doses.
Complete softening to an annealed level did not
occur during irradiation.
5.07.8 Conclusion
Aluminum and its alloys have contributed immensely
to development of water-cooled RRs and to our
understanding of radiation effects in metals. They
continue to do so.
10.
11.
12.
13.
14.
15.
16.
Acknowledgments
During preparation of this chapter, interactions with
present and former Oak Ridge National Laboratory
personnel, S. A. David, R. D. Godfrey, S. J. Pawel, J. D.
Sease, and R. E. Stoller were sincerely appreciated.
Opinions and conclusions in this chapter are solely
the responsibility of the writer.
17.
18.
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Ismail, Z. H.; Mohammed, H. G. Scripta Metall. 1989, 23,
20672072.
Ismail, Z. H. Radiat. Eff. Defects Solids 1990, 112,
105110.
Ismail, Z. H.; Birt, B. J. Nucl. Mater. 1995, 218,
289292.
Munitz, A.; Shtechman, A.; Cotler, C.; Talianker, M.;
Dahan, S. J. Nucl. Mater. 1998, 252, 7988.
5.08
Irradiation Assisted Stress Corrosion Cracking
P. L. Andresen
GE Global Research Center, Schenectady, NY, USA
G. S. Was
University of Michigan, Ann Arbor, MI, USA
5.08.1
Introduction
177
5.08.2
5.08.2.1
5.08.2.2
5.08.3
5.08.3.1
5.08.3.2
5.08.4
5.08.4.1
5.08.4.2
5.08.4.2.1
5.08.4.2.2
5.08.4.2.3
5.08.4.3
5.08.5
References
Irradiation Effects on SCC: Laboratory and Plant Data

Individual Effects of Radiation on IASCC
Service Experience
Irradiation Effects on Water Chemistry
Radiolysis and Its Effect on Corrosion Potential
Effects of Corrosion Potential on IASCC
Irradiation Effects on Microchemistry and Microstructure
Radiation-Induced Segregation
Microstructure, Radiation Hardening, and Deformation
Irradiated microstructure
Radiation hardening
Deformation mode
Radiation Creep and Stress Relaxation
Summary
180
180
183
187
187
189
190
190
194
194
196
198
201
202
202
Abbreviations
AES
AGR
BWR
CT
CW
DPA
FEGSTEM
FWHM
HWC
HWR
IASCC
IGSCC
NWC
PWR
RIS
RH
SCC
SFE
SGHWR
SS
SSRT
STEM
Auger electron spectroscopy

Advanced gas cooled-reactor
Compact type (specimen)
Cold work
Displacements per atom
Field emission gun TEM
Full-width half-max (for profiles)
Hydrogen water chemistry (in BWRs)
Heavy water reactor
Irradiation-assisted stress corrosion
cracking
Normal water chemistry (in BWRs)
Radiation-induced segregation
Radiation hardening
Stacking fault energy
Steam generating heavy water reactor
Stainless steel
Slow strain rate test
Scanning transmission electron
microscopy
TEM
TG

Transgranular
5.08.1 Introduction
Nuclear power accounts for about 17% of the worlds
electricity production, and the rapid expansion in
nuclear power throughout the world will necessitate
that they operate with high reliability and safety.
Stress corrosion cracking (SCC) has occurred in all
water cooled reactors, including boiling-water reactors (BWRs) and pressurized-water reactors (PWRs),
with a greater incidence in unirradiated, out-of-core
components, especially between 1970 and 1990. As
these materials, component designs, and water chemistries have improved, an increasing percentage of
cracking problems has occurred in irradiated components. While irradiation-assisted stress corrosion
cracking (IASCC) has been observed since early
plant operation, increasing operating time and fluence has led to an increased incidence of cracking.
Setting aside zircaloy fuel cladding and pressure
vessel steels, most irradiated core components consist
of austenitic stainless steels and nickel-base alloys
177
178
exposed to environments that span oxygenated to

hydrogenated water at 270340 C. The core of a
nuclear reactor is an extreme environment consisting
of high-temperature water, imposed stresses and
strains, and an intense radiation field that affects
the water chemistry, stress, and microstructure of
the core materials (Figure 1). For background, the
reader is referred to Chapter 1.03, RadiationInduced Effects on Microstructure; Chapter 1.05,
Radiation-Induced Effects on Material Properties
of Ceramics (Mechanical and Dimensional), and
Chapter 1.07, Radiation Damage Using Ion Beams
for more detailed treatments of radiation effects on
materials. Initially, the affected components were primarily small components (bolts, springs, etc.) or components designed for replacement (fuel rods, control
blades, or instrumentation tubes). However, in the
last 20 years, IASCC has been observed in structural
components (e.g., PWR baffle bolts and BWR core
shrouds and top guides).
Extensive literature exists for SCC under unirradiated conditions, and the basic factors and dependencies are well defined and reasonably well
modeled for austenitic stainless steel and nickel alloys
(e.g., Alloys 600 and its weld metals).19 A complete
consensus on the underlying mechanism of cracking
has not emerged although the well-behaved continuum in crack growth rate response versus material/
composition (including from stainless steels to nickel
Solution renewal
rate to crack-tip
Stress
f Anionic
transport
Oxide rupture
rate at
crack-tip
Environment
Microstructure
g-field
Crack tip f [A], pH
Passivation rate
at crack-tip
Grain boundary denudation
Hardening
Relaxation
N-fluence
Segregation
Figure 1 Schematic of the primary engineering

parameters that effect stress corrosion cracking stress,
microstructure, and environment and the underlying crack
tip processes that control stress corrosion cracking. The
primary ways in which radiation affects stress corrosion
cracking is also shown: segregation, hardening, relaxation,
and radiolysis. Radiolysis can increase the corrosion
potential, which in turn increases the potential gradient
() and the crack tip potential , anion concentration
[A], and pH.
alloys), water chemistry, temperature, and radiation

suggests that a common crack growth mechanism is
operative.813
Our understanding has evolved from the view that
SCC occurs under very specific and unique conditions
to the view that a continuum in response exists.813 With
steady improvement in laboratory and plant detection
of SCC, it is clear that SCC occurs under a wide range
of conditions and also at a wide range of growth rates.
Figures 2 and 3 show examples of the effect of environment (corrosion potential and water purity), material
condition (sensitized vs. cold-worked), and stress (stress
intensity factor) on SCC growth rates; the solid curves
are the predicted response.8,9,12,13 SCC occurs even at
low corrosion potential (Figure 2), and thus the behavior in BWRs and PWRs is linked, with the primary
differences being dissolved H2, temperature, and the
dissolved ion chemistry (B and Li are added to PWR
primary water; see Chapter 5.02, Water Chemistry
Control in LWRs).810,14 Of these, temperature has a
universal effect, variations in dissolved H2 are particularly important in nickel alloys, and B/Li has little or
no effect in deaerated water.9,14
Early plant (Figure 4) and laboratory (Figure 5)
observations showed that the same basic dependencies
existed for unirradiated and irradiated stainless steels,
and that increasing fluence produces a well-behaved
increase in SCC susceptibility (Figure 6). Figure 4
shows a strong effect of water purity for both unirradiated and irradiated BWR components, and Figure 5
shows a very similar response to corrosion potential to
that in Figure 2. Thus, it was proposed that radiation
enhances SCC primarily in four ways: segregation,
hardening, relaxation, and radiolysis (Figure 1). The
neutron fluence where these processes have an effect is
shown in Figure 7, along with the current end-of-life
fluence for various BWR and PWR components. The
primary radiation effects on materials operate in a
similar range of fluences, and thus their individual
contributions can be difficult to distinguish. An example of their interaction in altering SCC growth rate is
shown in the prediction of cracking of a weld in a BWR
core shroud (Figure 8) in which the individual effects
are plotted along with the resulting crack length versus
time. While many of the enhancements in SCC susceptibility from irradiation dose (neutron fluence)
have been well established, it remains possible that
additional factors will emerge at high fluences (e.g.,
>30 displacements per atom (dpa)).
Intergranular (IG) SCC is promoted in austenitic stainless steels above a threshold fluence
179
1.0E05
1
25 mm CT specimen
Furnace sensitized; 15 C cm2
288 C water
; 0.10.3 mS cm1
Constant load
; 25 Ksi in1/2
42.5 in h1
107
10
1.0E06
11
106

30 MPa m1/2, 288 C water
0.060.4 S cm1, 025 ppb SO4
filled triangle = constant load
open squares = gentle cyclic
14
14.2 in h1
Theoretical
curves
S cm1
0.3
0.2
0.1
108
200 ppb O2
500 ppb O2
2000 ppb O2
304 Stainless steel
3 7
4
Screened round robin data

- highest quality data
- corrected corr. potential
- growth rates corrected
to 30 MPa m1/2
42.5
28.3
14.2
1
in h
1.0E07
GE pledge
predictions
30 MPa m1/2
0.5
2000 ppb O2
Ann. 304SS
200 ppb O2
0.25
1.0E08
0.1
12
0.06 S cm1
Hydrogen water
chemistry
Normal water
chemistry
(ex-core)
600
400
200
0
+200
Corrosion potential (mVshe)
+400
30 MPa m1/2
1.0E09
0.6 0.5 0.4 0.3 0.2 0.1 0 0.1
Corrosion potential (Vshe)
1.0E05
30 MPa m1/2, 288 C water
0.060.4 S cm1, 025 ppb SO4
SKI round robin data
filled triangle = constant load
open squares = gentle cyclic
200 ppb O2
500 ppb O2
2000 ppb O2
109
0.06 S cm
Industry mean
0.2
0.3
0.4
4 dpa
304SS
1.0E06
316L (A14128, square)
304L (Grand gulf, circle)
nonsensitized SS
50% RA 140 C (black)
10% RA 140 C (gray)
1.0E07
20% CW
A600
42.5
28.3
14.2
in h1
20% CW A600
GE pledge
predictions
30 MPa m1/2
Sens SS
0.5
2000 ppb O2
Ann. 304SS
200 ppb O2
0.25
1.0E08
0.1
0.1 S cm
Means from analysis of
120 lit. sens SS data
0.06 S cm1
0.06 S cm1
GE pledge predictions for

Unsens. SS (upper curve for 20% CW)
1.0E09
0.6 0.5 0.4 0.3 0.2 0.1 0 0.1
Corrosion potential (Vshe)
0.2
0.3
0.4
Figure 2 Stress corrosion cracking growth rate versus corrosion potential for stainless steels tested in high-purity water
at 288 C containing 2000 ppb O2 and 953000 ppb H2. Dissolved O2 strongly influences corrosion potential, which in turn
affects crack chemistry and growth rate of sensitized stainless steels (two graphs at left) as well as cold-worked stainless
steels and Alloy 600 (large rectangular symbols on right graph) and irradiated stainless steel (large triangular symbols).
Cold-worked or irradiated materials have an elevated yield strength, which causes an increase in growth rate at both low
and high potential. RA, Reduction in area; CW, Cold work.
180
105
Stress intensity (ksi in1/2)

6 8 10
20 30 40 60 80
103
Sens. 304 stainless steel
288 C water
104
107
NRC disposition
line
105
*
108
Theory
15 C cm2, 50 mVshe
0.5 ms cm1
Theory
2
15 C cm , 50 mVshe
0.2 ms cm1
109
106
Theory
15 C cm2, 200 500 mVshe
0.2 ms cm1
1010
Crack growth rate (in h1)
106
107
8 10
20 30 40 60 80
Stress intensity (MPa m1/2)
Figure 3 Effect of stress intensity factor on stress

corrosion cracking growth rate for sensitized stainless steel
exposed in various water chemistries at 288 C.
(Figures 5 and 6). This occurs in oxygenated (e.g.,

BWR) water above 25 1020 n cm2 (E > 1 MeV),
which corresponds to about 0.30.7 dpa, and depends
on the stress, water chemistry (especially, sulfate and
chloride), and other factors. Attempts to reproduce the
same level of IG cracking in inert environments have
been unsuccessful, confirming that it is an environmental cracking phenomenon, not simply a change in
the mechanical properties and response of the material
in an inert environment.
Cracking in hydrogenated water (i.e., BWR hydrogen water chemistry (HWC) or PWR water) is typically observed at roughly a 4 higher fluence than in
oxidizing water, with IASCC enhanced at elevated
temperature (Figure 9). For both BWR and PWR
conditions, the same basic dependencies exist for
unirradiated and irradiated materials.
It is important to distinguish the results of different
kinds of SCC testing. Crack-growth testing typically
uses fracture mechanics specimens, commonly a compact type (CT) specimen. It has the significant
advantage of continuous, online monitoring of crack

length versus time, usually by employing an electric
current, potential drop technique. It can provide a
resolution of about 1 mm and can accurately characterize the inherent resistance to crack advance (i.e., beyond
the ill-defined initiation stage) as well as the dependencies on corrosion potential, stress intensity factor,
etc. Smooth specimen tests, whether by constant load,
constant displacement, or slow strain rate (SSR), are
simpler tests to perform, but represent some combination of initiation and growth. SSR tests impose failure
and can overstate or understate the SCC susceptibility.
Constant load or displacement tests generally require
periodic interruption for examination, and initiation
can be microscopic cracks or complete failure.
Work over the last 25 years has enabled many aspects
of IASCC phenomenology to be explained and predicted on the basis of the experience with intergranular
stress corrosion cracking (IGSCC) of nonirradiated
stainless steel in high-temperature water environments.
This continuum approach has successfully accounted
for radiation effects on water chemistry and its influence on electrochemical corrosion potential. However,
all radiation-induced microstructural and microchemical changes that promote IASCC are neither fully
known nor fully reproducible in similar materials.
Well-controlled data from well-characterized irradiated
materials remain insufficient due to the inherent experimental difficulties and financial limitations. Many of
the important metallurgical, mechanical, and environmental aspects that are believed to play a role in the
cracking process are illustrated in Figure 1. Only persistent material changes are required for IASCC to
occur, but in-core processes such as radiation creep
and radiolysis also have an important effect on IASCC.
5.08.2 Irradiation Effects on SCC:

Laboratory and Plant Data
5.08.2.1 Individual Effects of Radiation
on IASCC
IASCC can be categorized into radiation effects on the
water chemistry (radiolysis) and on the material/stress,
and the accepted definition of IASCC encompasses
cases where either factor is dominant (low-fluence
materials tested in water undergoing radiolysis, or preirradiated materials tested without an active radiation
flux). Radiation dose rate in rads/h is often used in
radiolysis, and in neutrons per square centimeter
(n cm2) or displacements per atom in materials.
In light water reactors (LWRs), 1 dpa corresponds
Frequency of SCC initiation

increases dramatically with
increasing conductivity
0.2
Best fit
1.2
1.0
0.8
0.6
Threshold
conductivity for
SCC initiation
increases as level
of sensitization
decreases
Low carbon SS
High carbon SS
Nonsensitized
low carbon SS
0.2
0
0
0.2
(b)
1.0
0.9
Sensitized
high carbon SS
0.4
0.6
Plant average conductivity (ms cm1)
0.4
0.6
0.8
Frequency of IGSCC
initiation increases
with plant conductivity
0.7
0.6
0.5
0.4
* Experienced
substantial high
conductivity
excursions not
reflected in
average value
0.3
0.2
0.1
0
(c)
181
1.4
Upper bound
0.4
% with IGSCC/on-line months
(a)
1.5
1.4
1.3
1.2
1.1
1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0
% with IGSCC/on-line months
% with IGSCC/on-line month
0.1
0.2
0.3
0.4
0.5
0.6
0.7
Figure 4 The effects of average plant water purity shown in field correlations of the core component cracking behavior for
(a) stainless steel intermediate and source range monitor dry tubes, (b) creviced stainless steel safe ends, and (c) creviced
Inconel 600 shroud head bolts, which also shows the predicted response versus conductivity. Adapted from Brown, K. S.;
Gordon, G. M. In Proceedings of 3rd Environmental Degradation of Materials in Nuclear Power Systems Water Reactors;
The American Institute of Mining, Metallurgical, and Petroleum Engineers (AIME): New York, NY, 1988; pp 243248.
to 7 1020 n cm2 when counting neutrons with

E > 1 MeV, or 1.5 1021 n cm2 for E > 0.1 MeV.
The primary effects of radiation on materials8,1522
include microcompositional effects (grain boundary
chemistry) and microstructural changes (formation of
dislocation loops, voids, precipitates, and the resulting changes hardening and deformation mode). In
terms of their effect on IASCC, the primary effects
of radiation are the following:
Radiolysis of water, in which a variety of short- and
long-lived radicals and species are produced.
There is no evidence that the specific species
formed are important, and indeed their effect on
cracking appears to be fully captured by their overall effect on the corrosion potential of the material.
Radiation-induced segregation (RIS), which produces an enrichment in some species (e.g., Ni and
Si) at grain boundaries and other defect sinks, and a
depletion in other species (e.g., Cr). Even though the
distance over which RIS occurs is very limited (a few
nanometers), studies of unirradiated materials have

shown that the narrow profiles can affect SCC.23,24
Radiation hardening (RH), which results from radiation damage and the creation of vacancy and interstitial loops, which impede dislocation motion. Once
a few dislocations move along a given slip plane, they
clear the channel of most of these barriers, and
subsequent dislocation occurs primarily in these
channels.
Radiation creep relaxation, which reduces constant displacement stresses such as in bolts or associated with weld residual stress. During active
irradiation, radiation creep can promote dynamic
strain, and thereby SCC.
Swelling, which occurs to a limited extent at temperatures above 300 C, but can be sufficient to
produce reloading of components such as PWR
baffle former bolts. Swelling occurs differently in
different materials, and is delayed in cold-worked
materials. Stresses due to swelling are balanced by
182
Data of Jacobs( ) and Kodama( )

Postirrad. SSRT 23 107 s1 288 C
Comm. purity 304SS( ) and 316SS( )
42 ppm O2-satd vs.
0.02 ppm O2
100
80
100
40
42
ppm O2
60
%IGSCC
% IGSCC fracture
Data shifted right by Init. grain boundary Cr enrichment
0.2
0.02
0.05
fC, Vshe
20
0.4
0
1019
0.2
0.2
1020
1021
Neutron fluence (n cm2 ) (E > 1 MeV)
1022
Percentage of spot welds inspected with IGSCC
Figure 5 Dependence of irradiation-assisted stress corrosion cracking on fast neutron fluence as measured in slow strain
rate tests at 3.7 107 s1 on preirradiated type 304 stainless steel in 288 C water. The effect of corrosion potential via
changes in dissolved oxygen is shown at a fluence of 2 1021 n cm2. Reproduced from Jacobs, A. J.; Hale, D. A.; Siegler, M.
Unpublished Data on SCC of Irradiated SS in 288 C Water and Inert Gas; GE Nuclear Energy: San Jose, CA, 1986.
SSRT, Slow strain rate test.
PWR control
BWR core BWR end rod failures
(IASCC)
component
of life
failures
(IASCC)
100
80
1020
BWR creviced control blade sheath

60
Threshold fluence for IGSCC
5 1020 n cm2
40
0.1
0
0
0.2
0.4
0.6
0.8
1.2
1.4
Neutron fluence (n cm2 1021) (E > 1 MeV)
Figure 6 Dependence of irradiation-assisted stress

corrosion cracking on fast neutron fluence for creviced control
blade sheath in high-conductivity boiling-water reactors.
Reproduced from Gordon, G. M.; Brown, K. S. In Proceedings
of 4th International Conference on Environmental Degradation
NACE: Houston, TX, 1990; pp 14-4614-62.
radiation creep relaxation, but the resulting stress

can be sufficient to cause IASCC.
Other microstructural changes, such as precipitation or dissolution of phases in materials. While
there is no clear evidence that such changes affect
IASCC response, this may only reflect the limited
PWR end
of life
PWR life
extension
1021
1022
1023
Neutron fluence (n cm2) (E >1 MeV)
Irradiation dose (dpa)
1
10
Significant changes
in grain boundary
composition, alloy
strength, and ductility
20
PWR baffle
bolt failures
(IASCC)
100
Onset of significant
void swelling
and possible
embrittlement
Figure 7 Neutron fluence effects on irradiation-assisted

stress corrosion cracking susceptibility of type 304SS
in boiling-water reactor environments. Reproduced
from Bruemmer, S. M.; Simonen, E. P.; Scott, P. M.;
Andresen, P. L.; Was, G. S.; Nelson, J. L. J. Nucl. Mater.
1999, 274, 299314.
characterization and IASCC studies that has been

performed on high fluence materials.
The individual (segregation, hardening, and creep,
Figure 10) and composite (SCC, Figures 59) effects
of radiation increase with dose in much the same
manner, which makes the isolation of, and attribution
to, individual contributions difficult. The dislocation
loop microstructure is closely tied to radiation
30
20
30
25
Effect of
rad segregation
20
Effect of rad hardening
15
10
Depth
10
Stress intensity (K)
Effect of stress relaxation

0
0
100
200
300
Time (month)
Fraction of IG cracking area
40
In PWR primary water

CW316, 340 C
CW316, 325 C
CW316, 290 C
Type 304, 325 C
*
*
1.0E + 20
20
Loop line
length
SCC
15
10
1.0E + 21
1.0E + 22
Fluence (n cm2) (E > 0.1 MeV)
CP-304SS
3.2 MeV protons
360 C
0
0
3
Dose (dpa)
Figure 10 Schematic diagram showing the dose

dependence of key irradiated microstructure features
(radiation-induced segregation and dislocation
microstructure) and radiation hardening along with stress
corrosion cracking susceptibility. Reproduced from
Was, G. S. In Proceedings of 11th International
in Nuclear Power Systems Water Reactors; American
Nuclear Society (ANS): La Grange Park, IL, 2004;
pp 965985.
irradiation. Subsequent sections focus on the possible

mechanisms by which water chemistry, RIS, microstructure, hardening, deformation mode, and irradiation creep individually or on concert may affect
IASCC.
* Specimen broke at the pin hole
20
Cr
Cr depletion
100
60
25
0
500
400
Figure 8 Predicted effect of radiation segregation,

radiation hardening, and radiation creep relaxation on a
boiling-water reactor core shroud, where the through-wall
weld residual stress profile is the primary source of
stress. Less aggressive water chemistry (corrosion
potential and water purity) would result in less crack
advance early in life, which would give a greater
opportunity for radiation creep relaxation. The leak depth
is the wall thickness of the shroud. While radiation
hardening continues to increase the yield strength, its effect
on crack growth is reduced (see Figure 21(a)). EPR,
Electrochemical potentiokinetic repassivation (a test for
sensitization).
80
Hardness
Arbitrary units
Crack depth (mm)
Leak depth
38.1-mm thick 304SS, two-sided weld

0.75 Vshe, 0.15 S cm1
EPR0 = 10.8 C cm2 (0.050% C)
Flux = 3 1019 n cm2 year
K, segregation, hardening, or relaxation
40
30
183
1.0E + 23
Figure 9 Percentage intergranular stress corrosion

cracking versus fluence for cold-worked type 316 stainless
steel tested at various temperatures. Despite the low
potential environment of pressurized-water reactor primary
water, at high fluence (especially at higher temperature)
there is significant susceptibility to stress corrosion
cracking.
hardening and both increase with dose until saturation occurs by 5 dpa. RIS also increases with dose
and tends to saturate by 5 dpa. Although dependent
on both metallurgical and environmental parameters,
IASCC generally occurs at doses between 0.5 dpa (for
BWRs) and 23 dpa (for PWRs), which encompasses
the steeply rising portion of the curves in Figure 4
that describe the changes in materials properties with
5.08.2.2
Service Experience
The IASCC service experience extends over 50 years,

and the early observations projected an accurate view
of the important characteristics and dependencies,
and pointed to the assisted nature of radiation in
enhancing SCC. As with other forms of SCC, early
observations suggested that a growing incidence with
time and neutron fluence should be expected.
IASCC was first reported in the early
1960s7,8,1522,2536 and involved intergranular cracking of stainless steel fuel cladding, with the initiation of multiple cracks occurring from the water side.
By contrast, mostly ductile, transgranular cracking
was observed in postirradiation mechanical tests
performed in inert environments at various strain
rates and temperatures. Grain boundary carbide
184
precipitation was rarely observed although preexisting thermal sensitization was present in some cases.
A correlation between time-to-failure and stress level
was reported, with failure occurring first in thinwalled rods with small fuel-to-cladding gaps, where
fuel swelling strains were the largest. The highest
incidence of cracking occurred in peak heat flux
regions, corresponding to the highest fluence and
the greatest fuelcladding interaction (highest stresses and strains.) Similar stainless steel cladding in
PWR service exhibited fewer instances of intergranular failure. At that time, off-chemistry conditions or
stress rupture were often considered to be the cause
of PWR failures.
In the last 30 years, a growing number of other
stainless steel (and nickel alloy) core components
have exhibited IASCC, including neutron source
holders in 1976 and control rod absorber tubes in
1978. Instrument dry tubes and control blade handles
and sheaths, Figure 5, which are subject to very low
stresses, are also cracked, generally in creviced locations and at higher fluences.15,18,20,37,38 These initial
failures in the most susceptible components were
Table 1
followed by more numerous incidents of IASCC in

the past 20 years, perhaps most notably in BWR core
shrouds8,15,16,39 and PWR baffle bolts.19,40,41
A summary of reported failures of reactor internal
components is listed in Table 1 and demonstrates
that IASCC is not confined to a particular reactor
design, material, component, or water chemistry. For
example, stainless steel fuel cladding failures were
reported years ago in commercial PWRs and in PWR
test reactors.15,22,25,2936,42 At the West Milton PWR
test loop, intergranular failure of vacuum-annealed
type 304 stainless steel fuel cladding was observed31
in 316 C ammoniated water (pH 10) when the cladding was stressed above yield. Similarly, IASCC was
observed in creviced stainless steel fuel element ferrules in the Winfrith steam generating heavy water
reactor (SGHWR),43,44 a 100 MWe plant in which
light water is boiled in pressure tubes, where the coolant chemistry is similar to other boiling-water reactor
designs. The 20% Cr25% NiNb stainless steel differs from type 304 primarily in Ni and Nb content, as
well as in its lower sulfur (0.006%) and phosphorus
(0.005%) contents. The ferrules were designed for
Irradiation-assisted stress corrosion cracking service experience
Component
Material
Reactor type
Possible sources of stress
Fuel cladding
Fuel cladding
Fuel claddinga
Fuel cladding ferrules
Neutron source holders
Instrument dry tubes
Control rod absorber tubes
Fuel bundle cap screws
Control rod follower rivets
Control blade handle
Control blade sheath
Control blades
Plate type control blade
Various boltsb
Steam separator dryer boltsb
Shroud head boltsb
Various bolts
Guide tube support pins
Jet pump beams
Various springs
Various springs
Baffle former bolts
Core shroud
Top guide
304SS
304SS
20% Cr25% NiNb
20% Cr25% NiNb
304SS
304SS
304/304L/316L SS
304SS
304SS
304SS
304SS
304SS
304SS
A-286
A-286
600
X-750
X-750
X-750
X-750
718
316SS cold work
304/316/347/L SS
304SS
BWR
PWR
AGR
SGHWR
BWR
BWR
BWR
BWR
BWR
BWR
BWR
PWR
BWR
PWR and BWR
BWR
BWR
BWR and PWR
PWR
BWR
BWR and PWR
PWR
PWR
BWR
BWR
Fuel swelling
Fuel swelling
Fuel swelling
Fabrication
Welding and Be swelling
Fabrication
B4C swelling
Fabrication
Fabrication
Low stress
Low stress
Low stress
Low stress
Service
Service
Service
Service
Service
Service
Service
Service
Torque, differential swelling
Weld residual stress
Low stress (bending)
Cracking in AGR fuel occurred during storage in spent fuel pond.

Cracking of core internal occurs away from high neutron and gamma fluxes.
AGR, Advanced gas-cooled reactor
b
a 5-year exposure during which the peak fast neutron

flux is 23 1013 n cm2 s (E > 1.5 MeV), yielding a
peak fluence over 5 years of 35 1021 n cm2.
The similarity of IASCC in BWRs and PWRs was
also noted in swelling tube tests performed in the
core44,45 on a variety of commercial and high-purity
heats of types 304, 316, and 348 stainless steel and
Alloys X-750, 718, and 625. Swelling was controlled
by varying the mix of Al2O3 and B4C within the
tubes; the latter swells as neutrons transmute B to
He. Nominally identical strings of specimens were
inserted into the core in place of fuel rods.
Historically, the oxidizing potential in a PWR
core is lower than in BWRs, but in the last decade,
most BWRs employ an electrocatalytic technology
called NobleChem(4648) to create a low corrosion
potential. Some early investigators attributed PWR
cracking to low ductility stress rupture (of course,
this mechanism would apply equally to BWRs).
A few laboratory studies reported small amounts of
intergranular cracking of irradiated stainless steels in
SSR tests in 300 C inert environments49 although
in many related experiments50,51 no intergranular
failure was found. Small amounts of intergranular
cracking in inert tensile tests are not surprising, and
since the early 1990s, the plant and laboratory
IASCC data show that cracking is environmentally
assisted and follows a well-behaved continuum in
response over ranges in fluence, corrosion potential,
temperature, stress, etc.8,1517
Factors that distinguish PWRs from BWRs
include their higher operating temperature, 10
higher maximum neutron fluence in core structural
components, higher hydrogen fugacity, and borated
lithiated water chemistry (including the possibility of
localized boiling and thermal concentration cells in
crevices from gamma heating, which could lead to
aggressive local chemistries). The possible role of RIS
of Si may be especially important in accounting for
the limited difference in SCC response at high
potential (BWR) versus low potential (PWR) at
high fluence.52,53
Brown and Gordon37,38 (Figure 4) accumulated
and analyzed data for cracking in Alloy 600 shroud
head bolts (first observed in 1986) as well as stainless
steel safe ends (first observed in 1984) and in-core
instrumentation tubes (first observed in 1984) with a
focus on components that were creviced, a factor
known to exacerbate cracking.7,37,38 The highest radiation exposure occurred for the intermediate range
and source range monitor (IRM/SRM) dry tubes,
which contain flux monitors housed in thin-walled,
185
annealed stainless steel tubes. Cracking initiated

in the crevice between the spring housing tube
and the guide plug at fluences between 0.5 and
1.0 1022 n cm2 (E > 1 MeV). Wedging stresses
from the thick oxide observed in the crevice were
implicated, since other (applied and residual) stresses
were negligible. The primary variable from plant
to plant is the average coolant conductivity, which
correlates strongly with cracking incidence
(Figure 4(a)4(c)). Each point in Figure 4 represents
inspection results for one BWR plant, and data are
normalized using reactor operating time (i.e., percentage of components with intergranular cracks
divided by the online exposure time). The scatter in
Figure 4(a) was attributed to variations in fluence
and specific ion chemistry, as well as limitations in
the resolution of underwater visual inspection. Scatter can also result from short-term excursions in
conductivity, which is not adequately reflected in
the average, as identified in Figure 4(c).
Correlations between IASCC and conductivity
were also reported for cracking in shroud head bolts
(Figure 4(c)) and creviced safe ends (Figure 4(b)).
The strong influence of conductivity on cracking of
stainless steel has also been shown in laboratory tests
and plant recirculation piping, where predictive
modeling8,12,13,15,54,55 has been compared to field
data on the operational time required to achieve a
detectable crack (typically, 10% of the wall thickness). Preliminary prediction of the shroud head bolt
cracking response8 also provides reasonable agreement with observation (Figure 4(c)).
High-strength, nickel-base alloy components15,22
have also experienced IASCC (Table 1), with many
incidents in lower radiation flux regions (e.g., where
the end-of-life fluence is below 5 1019 n cm2)
such as cracking of Inconel X-750 jet pump beams
in BWRs. Inconel X-750 cracking has also occurred
extensively in PWR fuel hold-down springs, which
attain an end-of-life fluence of 110 1021 n cm2; it
is proposed that cracking has been aggravated by
vibrational stresses (corrosion fatigue). The effects of
irradiation on IASCC in high-strength, precipitationhardened nickel-base alloy components as well as in
stainless steels have not been characterized.
BWR core shrouds8,15,16,39 and PWR baffle
bolts40,41 are the two most common examples of
IASCC although susceptibility clearly exists in
other areas, such as control blade components, fuel
components, the BWR top guide, etc. SCC in the
BWR core shroud occurs almost exclusively near the
welds (both circumferential and vertical), and
186
initiation is observed from both the inside (ID) and

outside (OD) surfaces (the shroud separates the
upward core flow from the downward recirculation
flow that occurs in the annulus between the shroud
and the pressure vessel). This large-diameter welded
pipe has little active (DP) loading, and its susceptibility arises primarily from weld residual stresses and
weld shrinkage strains.5658 Cracking is observed in
both low fluence and moderate fluence areas, and the
extent of the enhancement in SCC susceptibility by
irradiation is limited because, while RH and RIS
occur, radiation creep also relaxes the weld residual
stress. SCC predictions for a BWR core shroud that
account for the damaging effect of RIS and RH and
the beneficial effect of radiation creep relaxation are
shown in Figure 8 and illustrate the complexity of
the interactions of these phenomena in the evolution
of cracking. Predictions also indicate that, if SCC
does not nucleate early in life (e.g., below 0.5 dpa),
for example, from high coolant impurity levels or
severe surface grinding, susceptibility tends to
decrease with fluence in the shroud welds because
of radiation-induced creep relaxation (although
many shroud welds are in very low flux areas).
The last decade has also seen extensive failures of
PWR baffle bolts40,41 although large plant-to-plant
and heat-to-heat differences are observed. Most baffle bolts are fabricated from type 316 stainless steel
cold-worked to 15% to increase their yield
strength. The complex baffle former structure exists
in a PWR because their fuel does not have a surrounding channel, so the baffle former structure
must conform closely to the geometry of the fuel to
provide well-distributed water flow. The baffle former plates are usually made from annealed material,
typically type 304 stainless steel. Because of their
proximity to the fuel, very high fluences can develop
up to 80 by the end of the original design life. The
high gamma flux produces significant heating in the
components, in some instances estimated at 40 C,
especially in designs where the PWR coolant does
not have good access to the bolt shank. While the
heat-to-heat variations are not understood, it is clear
that plants that load-follow (and therefore undergo
power level changes and thermal cycles) are much
more prone to baffle bolt cracking. Another aggravant
is the thermal gradient and possible boiling (resulting
in altered water chemistry) in the shank area of the
bolt if the coolant access is restricted. However, primary factors must be the very sizeable stress relaxation that occurs early in life (e.g., during the first
5 dpa), followed by preferential radiation swelling of

the annealed baffle plates over the cold-worked baffle
bolts, which will cause reloading. The dynamic equilibrium between swelling and radiation creep, which
determines the reloading stress in the bolt, is likely a
complex function of many parameters, including
local neutron flux, temperature, baffle plate geometry, and composition.
The number of IASCC incidents continues to
grow, and there can be no question that many LWR
components are susceptible. Strategies to mitigate
IASCC (e.g., NobleChem(4648)) and manage
IASCC (e.g., by showing some IASCC could be tolerated, installing mechanical restraints to mitigate
the impact of IASCC in BWR shrouds, or selectively
inspect and replace baffle bolts) have been successful.
IASCC field experience has led to the following
trends and correlations:
Intergranular cracks associated with radiation
effects on solution-annealed stainless steel were
once thought to occur only at fluences above
0.3 1021 n cm2. But significant intergranular
cracking in BWR core shrouds (which do not have
thermal sensitization) occurs over a broad range
of fluences, showing that a true fluence threshold
does not exist.15,16 The observations of SCC in unirradiated, unsensitized stainless steel (with or without
cold work) also undermine the concept of a threshold fluence below which no SCC occurs. This also
holds for thresholds in corrosion potential, water
impurities, temperature, etc.8,54,59,60
SCC susceptibility is affected by fluence in a complex fashion. SCC in BWR shrouds and PWR
baffle bolts does not always correlate strongly
with fluence, and one important reason for this is
that radiation creep produces relaxation of the
stresses from welding and in bolts. The need to
account for many changing factors is necessary in
interpreting and predicting SCC.
Most early incidents involved high stresses or
dynamic strains, but cracking has since been
observed at quite low stresses at high fluences
and longer operating exposure. Laboratory and
field data indicate that IASCC occurs at stresses
below 20% of the irradiated yield stress, and at
stress intensities below 10 MPa m1/2.
Extensive laboratory and field data show that corrosion potential is a very important parameter, with
its effect being consistent from low to high fluence,
except in some high fluence materials and/or

under high stress intensity factor conditions. Materials prone to high radiation-induced changes in
grain boundary Si level may exhibit a very limited
effect of corrosion potential.52,53 There is no evidence of threshold potential, and indeed irradiated
materials exhibit IASCC in deaerated water.
Impurities, especially chloride and sulfate, strongly
affect IASCC in BWR water (Figure 4). As noted
by Brown and Gordon,37 this correlation applies
equally to low and high flux regions and to stainless
steels (Figure 4(a) and 4(b)) and nickel-base alloys
(Figure 4(b)). Indeed, the correlation closely parallels that from out of core.8,12,13,15,38,54,55 At higher
levels, the same impurities can affect SCC in
PWRs. Similarly, if high corrosion potential conditions form in the PWR primary (where B and Li are
present), high growth rates can result.9,14
Crevices exacerbate cracking primarily due to
their ability to create a more aggressive crevice
chemistry from the gradient in corrosion potential
(in BWRs) or in temperature (most relevant to
PWRs). Crevices can also produce stress and strain
concentration.
Cold-working often exacerbates cracking (especially abusive surface grinding), although it can
also delay the onset of some radiation effects.
Temperature has an important effect on IASCC,
enhancing both crack initiation and growth rate.
Preexisting grain-boundary carbides or chromium
depletion is not required for susceptibility
although furnace-sensitized stainless steels are
clearly highly susceptible to cracking in-core. Cr
depletion will develop or be magnified by irradiation, and increase IASCC susceptibility, although
its effect is most pronounced in pH-shifted environments, as can develop when potential or thermal
gradients exist. The role of N, S, P, and other grainboundary segregants is less clear.
IASCC is enhanced at a fluence that is dependent
on applied stress and strain, corrosion potential,
solution conductivity, crevice geometry, etc. At
sufficiently high conductivities, cracking has been
observed in solution-annealed stainless steel in
the field (Figure 6(a) and 6(b))37 and in the laboratory.8,12,13,15,54,55 Thus, while convenient in
a practical engineering sense, the concept of a
threshold fluence (or stress, corrosion potential,
etc.) is scientifically misleading8,52,59,60; cracking
susceptibility and morphology are properly considered an interdependent continuum over many
relevant parameters.
187
5.08.3 Irradiation Effects on Water

Chemistry
5.08.3.1 Radiolysis and Its Effect on
Corrosion Potential
SCC susceptibility is fundamentally influenced by
corrosion potential, not by the oxidant and reductant
concentrations per se.8,15,61 The lower H2 concentration in BWRs distinguishes BWRs from PWRs
because it permits the radiolytic formation of oxidants. Above 500 ppb (5.6 cm3 kg1) H2, radiolytic
formation of oxidants is effectively suppressed, and
the corrosion potential remains close to its thermodynamic minimum (which is a function of temperature, H2 fugacity, and pH). BWRs cannot achieve this
H2 level in the core because H2 partitions to the
steam phase, which begins to form about a quarter
of the way up the fuel rods. Thus, this section is
primarily relevant to BWRs.
Radiolysis and the presence of oxidizing species
require that many sequential and nonlinear dependencies that must be considered, for example, radiation flux produces oxidizing and reducing species,
the corrosion potential is controlled by multiple
reactions of these species, the crack chemistry is
nonlinearly dependent on the corrosion potential
and the dissolved ions present, and the SCC growth
rate is a nonlinear function of the crack chemistry.8,61 The relationship between radiation flux and
SCC cannot easily be determined empirically, but
rather requires a fundamental understanding of each
subprocess.
Water is decomposed by ionizing radiation into
various primary species6265 including both radicals
(e.g., e
aq, H, OH, HO2) and molecules (e.g., H2O2, H2,
O2), which can be oxidizing (e.g., O2, H2O2, HO2) or
reducing (e.g., e
aq, H, H2). The predominant species
that are stable after a few seconds are H2O2 and H2,
with O2 forming primarily from the decomposition of
H2O2. Because H2 partitions to the steam phase and
H2O2 is not volatile, 87% of the water that is
recirculated in a BWR (1114% of the core
flow becomes steam) is oxidant rich. H2 is introduced
in the feed water, which mixes with the recirculated
water near the top of the annulus (the region of
downflow between the core shroud and pressure
vessel).
The concentrations of radiolytic species are
roughly proportional to the square root of the radiation flux in pure water. The radiation energy versus
intensity spectrum influences the concentration of
0.4
0.3
Corrosion potential (VSHE)
each radiolytic species, which is described in terms of

a yield, or G value (molecules produced per 100 eV
absorbed by water). In LWRs, the G values for most
species are within a factor of 3 for fast neutron
versus gamma radiation. Despite this similarity, the
influence of fast neutron radiation is much stronger
than gamma radiation primarily because the energy
deposition rate, or mean linear energy transfer
(LET), is greater (40 eV nm1 for fast neutrons versus
0.01 eV nm1 for gamma radiation63). Also, the neutron flux in LWRs (e.g., 1.03 109 Rad h1 core
average and 1.68 109 Rad h1 peak in a BWR4 of
51 W cm3 power density) is also higher than the
gamma flux (0.34 109 Rad h1). Indeed, the moderate gamma levels present in the downcomer in the
outside annulus of a BWR core actually promote
recombination of hydrogen and various oxidants.62,65
This is a key element in the effectiveness of HWC,
and BWRs that have a wider annulus and lower
gamma flux near the pressure vessel respond less to
a given H2 addition. The contribution of thermal
neutrons and beta particles to radiolysis is small
in LWRs.
As in many electrochemical processes, the
integrated effects of various oxidants and reductants
on environmental cracking is best described via
changes in corrosion potential, which controls the
thermodynamics and influences the kinetics of most
reactions. Since electrochemical potentials are logarithmically dependent on local oxidant, reductant,
and ionic concentrations (via the Nernst relationship,
o RT/nF ln [products/reactants], where is
electrochemical potential, R is the gas constant, T is
temperature in kelvin, n is the number of moles, and F
is Faradays constant), radiation-induced increases in
concentration of various species by many orders of
magnitude may have comparatively small effects on
the corrosion potential in hot water. Further, corrosion potentials are mixed potentials involving a balance of anodic and cathodic reactions on the metal
surface. At low oxidant concentrations, the rapid drop
in corrosion potential to 0.5 Vshe (Figure 11(a))
results from mass-transport-limited kinetics of oxidants to the metal surface.
The relationship between dissolved oxygen and
corrosion potential in hot water as a function of
radiation type and flux is shown in Figure 11(a),
in which the connected points represent data
obtained in controlled radiation on/off experiments.
The data from these latter experiments are shown in
Figure 11(b) in terms of a radiation-induced shift in
potential. The curves in Figure 11(a) represent the
2 points, 200 ppb H2O2

1 point, 31ppb Cu2+
0.2
0.1
0
0.1
200 ppb H2
H2Wc
BWR top core n + g
Proton rad. = BWR peak
1
30200 MGy h g
0.2
0.3
1
0.32 MGy h g
Pt, various rad levels
0.4
0.5
Open symbol = no radiation

Lines indicate paired data (e.g., g on/off)
Band of data for unirradiated conditions
0.6
0.7
100
(a)
101
102
103
104
0.3
0.2
Dfc with radiation (VSHE)
188
0.1
200 ppb H2O2
0
0.1
200 ppb H2
2 points
0.2
Proton, ECP in crevice

BWR top core n + g
Proton rad. = BWR peak
30200 MGy h1g
0.32 MGy h1g
Pt, various rad levels
0.3
<100
(b)
102
101
103
104
Figure 11 (a) Effect of radiation on the corrosion

potential of type 304 stainless steel in water at 288 C.
The curves denote the range of typical values in the
unirradiated corrosion potential data (reproduced from
Andresen, P. L.; Ford, F. P.; Higgins, J. P.; et al.
In Proceedings of ICONE-4 Conference; ASME
International: New York, NY, 1996). (b) Effect of radiation
on the shift in corrosion potential from the value under
unirradiated conditions for type 304 stainless steel in water
at 288 C. With the exception of the boiling-water reactor
measurements, all data were obtained in controlled
radiation on/off experiments (reproduced from
Andresen, P. L.; Ford, F. P.; Higgins, J. P.; et al.
In Proceedings of ICONE-4 Conference; ASME
International: New York, NY, 1996). Curves in (b) show the
trends in the proton-irradiated data, where the effects of
radiation (on/off and over a range of fluxes) were evaluated
for a variety of dissolved O2 and H2 concentrations under
otherwise identical conditions. H2Wc, Hydrogen Water
chemistry.
scatter band for the data obtained under unirradiated

conditions. Similar scatter also exists in the irradiated
corrosion potential data in Figure 11(a) and comprises contributions from both real effects and experimental error. High radiation flux experiments were
performed by Taylor66 and Andresen et al.67 using

multiple, fundamentally different types of radiationhardened reference electrodes. In-reactor measurements have also been performed by Indig68,69 using
multiple, radiation-qualified silver chloride reference
electrodes.
Figure 11(a) and 11(b) show that little, if any,
elevation in corrosion potential results from irradiation sources that do not include neutrons or simulate
their contribution (e.g., using high-energy protons67).
Some studies using gamma radiation15,66 showed a
significant decrease in corrosion potential, especially
in the intermediate (e.g., 10200 ppb) range of dissolved oxygen. This is consistent with enhanced
recombination of oxidizing and reducing species,
which occurs in the downcomer region of BWRs.65
In instances where neutrons or protons have been
used, a consistent, significant elevation in corrosion
potential is observed. This is more pronounced at low
dissolved oxygen concentrations with no dissolved
hydrogen (Figure 11(b)), where increases of over
0.25 V occur. At higher inlet oxygen concentrations
(e.g., 200 ppb), the data still show a significant
shift (typically 0.1 to 0.15 V) in corrosion potential for radiation conditions representative of peak
LWR core fluxes (Figure 11(b)); less increase is
observed for inlet oxygen concentrations associated,
for example, with air saturation (8.8 ppm O2) or
oxygen saturation (42 ppm O2 at STP). A similar
elevation in corrosion potential is observed for
additions of hydrogen peroxide (200 ppb H2O2,
Figure 11(a)), which suggests that H2O2 may be a
major factor in increasing the corrosion potential
under irradiated conditions.
In-core, in situ measurements in BWRs show that
the corrosion potential, which is 0.2 to 0.25 Vshe
in normal water chemistry (NWC), can be decreased
by >0.5 V by sufficient additions of dissolved hydrogen in a BWR.69 This is corroborated by other measurements67 (Figure 11(b)), which show very little
radiation-induced elevation in corrosion potential
when the fully deaerated inlet water contains moderate dissolved hydrogen (>200 ppb H2, 0 ppb O2). At
high H2 levels, the core becomes reducing, and the
small concentration of 16N (transmuted from 16O)
changes from soluble NO
3 to volatile NOx and
NH3, causing a large increase in radiation level in
the steam lines and turbine.
The effect of radiation on the corrosion potential
within a crack or crevice has also been of interest,
with the possibility that a net oxidizing environment
in the crack could be created that could elevate the
189
corrosion potential above the potential at the crack

mouth. In the absence of radiation, measurements in
high-temperature water in artificial crevices (e.g.,
tubing),70,71 at the tip of growing cracks,72 and of
short crack growth behavior73 show that the corrosion potential remains low (i.e., 0.5 0.1 Vshe in
pure water at 288 C) for all bulk oxygen concentrations, indicating that complete oxygen consumption
occurs within the crack. Measurements of radiation
effects in crevices67 show that the elevation in corrosion potential is limited to <0.05 V (c < 0.45 Vshe)
in-core; this is consistent with interpretation of available corrosion potential data on free surfaces.8,15,16
These small changes will not significantly affect the
0.75 V (0.25 Vshe (near mouth) minus 0.5 Vshe (in
crack)) potential difference in the crack under irradiated normal BWR water chemistry conditions. The
potential difference, along with other factors, controls the enhancement mechanism that can lead to
an increased anion activity and altered pH at the
crack tip.12,13,54,55
5.08.3.2 Effects of Corrosion Potential
on IASCC
Preirradiated stainless steels were evaluated in
SSR tests50,74 in hot water using additions of oxygen
and/or hydrogen peroxide to elevate the corrosion
potential to simulate the effect of radiation. Jacobs
et al.50 showed that IASCC in stainless steel irradiated
to 3 1021 n cm2 was strongly affected by dissolved oxygen (and, by inference, corrosion potential)
(Figure 5(b)). Ljungberg74 also evaluated preirradiated materials in SSR tests and observed decreasing
average crack growth rates with decreasing corrosion
potential. Less IASCC occurs at low corrosion potential, but crack growth rate tests (discussed later) and
other tests confirm that IASCC does not vanish at
low corrosion potential (Figures 5 and 9).
Continuously monitored fracture mechanics
specimens were installed in the recirculation piping
and core of the Nine Mile Point Unit 1 BWR.
Furnace-sensitized type 304 stainless steel specimens
in both locations showed higher growth rates in
the core, where the corrosion potential was higher
(Figure 12). Specimens of annealed type 304 and
304L stainless steel showed growth after different
fluences but, once growth initiated, the growth rates
at a given fluence were identical. The delay time
(fluence) and differences in delay time were attributed to the need to transition from a transgranular
fatigue precrack to IG SCC.
190
104
100
Furnace sensitized 304 st. st.
27.5 MPa m1/2
Crack length (mm)
100
Nine Mile Point 1 BWR

DCB specimens for monitoring SCC
96
94
Incore
Observed
Theory
Nine Mile Point 1 BWR

DCB specimens for
monitoring SCC
C304SEN, thermally
27.5 MPa m1/2
sensitized 304
C304ST, solution
treated 304
102
92
90
Crack length (mm)
98
98
96
94
C304L, low
carbon 304
92
90
88
88
86
Recirculation line
86
84
84
0
(a)
500
1000 1500 2000 2500 3000 3500 4000

Time (h)
2000
4000
6000
8000
10 000
12 000
Time (h)
(b)
Figure 12 Data for fracture mechanics specimens of type 304 stainless steel exposed in the high flux region of the
core and in the recirculation line of the Nine Mile Point Unit 1 BWR. All specimens were precracked and
wedge loaded to an initial stress intensity factor of 27.5 MPa m1/2. (a) Comparison of predicted and observed crack length
versus time for furnace-sensitized type 304 stainless steel specimens in the core and recirculation line. (b) Crack
length versus time for one furnace-sensitized and two annealed specimens of type 304 stainless steel in the core. Adapted
from Andresen, P. L.; Ford, F. P.; Murphy, S. M.; Perks, J. M. In Proceedings of 4th International Symposium on
Environmental Degradation of Materials in Nuclear Power Systems Water Reactors; Cubicciotti, D., Theus, G. J., Eds.;
NACE: Houston, TX, 1990; pp 183; Andresen, P. L.; Ford, F. P. In Proceedings of 7th International Symposium on
Environmental Degradation of Materials in Nuclear Power Systems Water Reactors; NACE: Houston, TX, 1995;
pp 893908; Was, G. S.; Andresen, P. L. Corrosion 2007, 63(1), 1945; Andresen, P. L.; Ford, F. P. In Corrosion/89; NACE:
Houston, TX, 1989; Paper no. 497; Andresen, P. L.; Ford, F. P. International Cooperative Group on Irradiation Assisted
Stress Corrosion Cracking (ICG-IASCC) Minutes, Apr 1989.
Figures 2 and 13 present the first laboratory SCC

growth rate testing ever performed on irradiated
(4 dpa) type 304SS, which was well behaved at high
corrosion potential and showed a large change in
growth rate at lower corrosion potential. One evolving concern for high-fluence stainless steels is the
prospect of a major loss of the effect of corrosion
potential and stress intensity factor, as has been
observed in unirradiated alloys possessing high
Si.52,53 The detrimental effect of Si is likely associated
with its ability to oxidize at all LWR-relevant potentials, coupled with its relatively high solubility in hot
water (i.e., it does not form a protective oxide like
Cr2O3 or Fe/Ni oxides/spinels).
These data are compared with other irradiated
and unirradiated data in Figure 2 based on simultaneous measurements of corrosion potential and crack
growth rate in fracture mechanics specimens; the
accompanying curves represent model predictions.8,13,15,16,54,55,75,76 Clearly, the in situ data compare favorably with the spectrum of unirradiated
data, and data obtained on a fracture mechanics
specimen of furnace-sensitized type 304 stainless
steel using high-energy proton irradiation to simulate the mix of neutron and gamma radiation present
in power reactors.
5.08.4 Irradiation Effects on

Microchemistry and Microstructure
5.08.4.1
Radiation-Induced Segregation
RIS describes the redistribution of major alloying

elements and impurity elements at point defect
sinks.7787 Because IASCC is intergranular, the sinks
of greatest interest are the grain boundaries. RIS is
driven by the flux of radiation-produced defects to
sinks and is therefore fundamentally different from
thermal segregation or elemental depletion due to
grain boundary precipitation. Vacancies and interstitials are the basic defects produced by irradiation and
can reach concentrations that are orders of magnitude higher than those at thermal equilibrium, resulting in large increases in diffusion rates. If the relative
participation of alloying elements in the defect fluxes
is not the same as their relative concentration in the
alloy, then a net transport of the constituents to or
from the grain boundary will occur (Figure 14). This
unequal participation of solutes in the vacancy and/
or interstitial fluxes to sinks results in either enrichment or depletion of an alloying element at the grain
boundary. The species that diffuse more slowly by the
vacancy diffusion mechanism are enriched, and the
faster diffusers become depleted.
191
250
12.59
2.7 108 mm s1
12.53
150
To 0 ppb O2@1508 h
Crack length (mm)
12.55
1.3 106
mm s1
12.51
12.49
100
Constant K
200
12.57
50
CT#2 - irradiated 304SS, 4 dpa

21 MPa m1/2, 220 ppb O2, 288 C, 20 ppb SO4
12.47
12.45
1475
0
1495
1515
1535
1555
1575
1595
Time (h)
Figure 13 Crack length versus time for Type 304 stainless steel irradiated to 4 dpa and tested in at 21 MPa m1/2 in water at
288 C. A large reduction in crack growth rate is observed as the dissolved O2 and corrosion potential are decreased.
Reproduced from reproduced from Andresen, P. L.; Ford, F. P.; Higgins, J. P.; et al. In Proceedings of ICONE-4 Conference;
ASME International: New York, NY, 1996.
Cv
Ci
Jv
JA
Ji
JB
JB
(a)
JA
(b)
CB
CA0,B
CA
(c)
Figure 14 Schematic illustration of radiation-induced
segregation in a binary 50A50B system showing (a) the
development of the vacancy concentration profile by the flow
of vacancies to the grain boundary balanced by a equal and
opposite flow of A and B atoms, but not necessarily in equal
numbers, (b) the development of the interstitial concentration
profile by the flow of interstitials to the grain boundary
balanced by a equal and flow of A and B atoms migrating as
interstitials, but not necessarily in equal numbers, and (c) the
resulting concentration profiles for A and B. Reproduced
from Was, G. S. Fundamentals of Radiation Materials
Science: Metals and Alloys; Springer: Berlin, 2007.
Enrichment and depletion can also occur by association of the solute with the interstitial flux. The undersized species will enrich, and the oversized species will
deplete.80 The magnitude of the buildup/depletion
is dependent upon several factors such as whether
a constituent migrates more rapidly by one defect
mechanism or another, the binding energy between
solutes and defects, the dose, dose rate, and the temperature. RIS profiles are also characterized by their
narrowness, often confined to within 510 nm of the
grain boundary, as shown in Figure 15 for an irradiated stainless steel.
Segregation is a strong function of irradiation
temperature, dose, and dose rate (Figure 16). Segregation peaks at intermediate temperatures since a
lack of mobility suppresses the process at low temperatures, and back-diffusion of segregants minimizes
segregation at high temperature (where defect concentrations approach their thermal equilibrium
values). For a given dose, a lower dose rate results in
a greater amount of segregation. At high dose rates, the
high defect population results in increased recombination which reduces the number of defects that are able
to diffuse to the grain boundary. Figure 16 shows the
interplay between temperature and dose rate for an
austenitic stainless steel. RIS occurs in the intermediate temperature range, and this range rises along the
192
18
4
JEOL 2010F
0.75 nm probe
16
14
12
10
8
Ni
Si
P
0
6
20
15 10 5
0
5
10 15
Distance from grain boundary (nm)
20
Figure 15 Compositional profiles across grain

boundaries obtained by dedicated scanning transmission
electron microscopy from a low-strain, high-purity 348
stainless steel swelling tube specimen irradiated to
3.4 1021 n cm2 in water at 288 C in a boiling-water
reactor. Composition profiles were measured using
a field-emission gun scanning transmission electron
microscope. Reproduced from Jacobs, A. J.;
Clausing, R. E.; Miller, M. K.; Shepherd, C. M. In
Proceedings of 4th International Symposium on
Systems Water Reactors; Cubicciotti, D., Ed.; NACE:
Houston, TX, 1990; pp 1421.
temperature scale with increasing dose rate to compensate for the higher recombination rate.
In FeCrNi alloys, the vacancy exchange
(inverse Kirkendall) mechanism successfully explains
the observed major element segregation.84,85 Studies
have shown that nickel segregates to grain boundaries
while chromium and iron deplete. The directions of
segregation are consistent with an atomic volume
effect in which the subsized solute migrates preferentially with the interstitial flux, and the oversized
solute participates preferentially in the vacancy flux.
The results are also consistent with the diffusivity of
the solutes in FeCrNi, in which Ni is the slow
diffuser, Cr is the fast diffuser, and Fe is intermediate.
In commercial austenitic stainless steels, chromium
depletes at grain boundaries and nickel enriches,
while iron can either deplete or enrich according to
the magnitude of the diffusion coefficient relative to
the other solutes.88
RIS increases with neutron dose in LWRs and
saturates after several (5) displacements per atom
in the 300 C temperature range. Figure 17 shows
grain boundary chromium depletion for austenitic
Homologous temperature (T/Tm)
5
Cr
Si or P concentration (wt%)
Cr or Ni concentration (wt%)
20
1105
0.8
0.7
Back diffusion
of vacancies
933
0.6
761
589
0.5
0.4
Radiation-induced
segregation
416
LWR
0.3 peak flux region
0.2
0.1
108
244
Recombination of
vacancies and interstitials
107
106
105
104
1
Radiation flux (dpa s )
72
Temperature for g stainless steel (C)
22
101
103
Figure 16 Dependence of radiation-induced segregation

on homologous temperature and dose rate for austenitic
stainless steels.
stainless steels as a function of dose.8997 As the slowest diffusing element, nickel becomes enriched at the
grain boundary. Since iron depletes in 304 and 316
stainless steels, the nickel enrichment makes up for
both chromium and iron depletion and can reach
very high levels up to 30 wt%.
Minor alloying elements and impurities also segregate and have been implicated in the IASCC process.
Mn and Mo strongly deplete at the grain boundary
under irradiation,98 but neither is believed to be a
significant factor in IASCC. Minor alloying or impurity
elements such as Si and P also segregate under irradiation. Silicon strongly enriches at the grain boundary
to as much as ten times the bulk (0.72.0 at.%) composition in the alloy99 and can be important in IASCC.
Phosphorus is present at much lower concentrations
and is only modestly enriched at the grain boundary
because of irradiation.83,98 Phosphorus tends to
segregate to the grain boundary following thermal
treatment, which reduces the amount of additional
segregation to the grain boundary during irradiation,
making the contribution due to irradiation difficult to
detect.98 Undersized solutes such as C, B, and N should
also segregate, but there is little evidence of RIS,
due in part to the difficulty of measurement. Another
potential segregant is helium, produced by the transmutation of 10B. The mobility of He is low at LWR core
temperatures, but the opportunity for accumulation
at the grain boundary is increased by segregation of
B to the boundary. Overall, the behavior of these minor
elements under irradiation is not well understood.
Fast neutron fluence (E > 1 MeV) 1025 n m2

Grain boundary Cr concentration (wt%)
26
8
304 (82)
304 (13)
304 (91)
304 (92)
304 (93)
316 (82)
316 (94)
348 (91)
24
22
20
10
12
14
HP 304 (95)
CP 304 (95)
CP 316 (95)
CP 304 (17)
CP 316 (17)
HP 316 (17)
CP 304 Protons 96
CP 316 Protons 96
18
16
14
12
10
0
10
Dose (dpa)
15
20
Figure 17 Dose dependence of grain boundary

chromium concentration for several 300-series austenitic
stainless steels irradiated at a temperature of about 300 C.
Adapted from Asano, K.; Fukuya, K.; Nakata, K.; Kodama, M.
Systems Water Reactors; Cubicciotti, D., Simonen, E. P.,
Gold, R. E. Eds.; American Nuclear Society (ANS):
LaGrange, IL, 1992; p 838; Jacobs, A. In Proceedings of 7th
Materials in Nuclear Power Systems Water Reactors;
NACE: Houston, TX, 1995; p 1021; Jacobs, A. J.;
Wozadlo, G. P.; Nakata, K.; et al. In Proceedings of 6th
Materials in Nuclear Power Systems Water Reactors;
Gold, R. E., Simonen, E. P., Eds.; The Minerals, Metals, and
Materials Society (TMS): Warrendale, PA, 1993; p 597;
Kenik, E. A. J. Nucl. Mater. 1992, 187, 239; Nakahigashi, S.;
Kodama, M.; Fukuya, K.; et al. J. Nucl. Mater. 1992,
179181, 1061; Jacobs, A. J.; Clausing, R. E.; Miller, M. K.;
Shepherd, C. M. In Proceedings of 4th International
Nuclear Power Systems Water Reactors; Cubicciotti, D.,
Ed.; NACE: Houston, TX, 1990; pp 1421; Walmsley, J.;
Spellward, P.; Fisher, S.; Jenssen, A. In Proceedings of 7th
International Symposium on Environment Degradation of
Materials in Nuclear Power SystemWater Reactors;
NACE: Houston, TX, 1997; p 985; Was, G. S.; Busby, J. T.;
Gan, J.; et al. J. Nucl. Mater. 2002, 300, 198.
Oversize solutes can affect the microchemistry or

microstructure of the alloy, thereby altering the
IASCC susceptibility. They are believed to affect
RIS by acting as vacancy traps, thereby increasing
the effective recombination of vacancies and interstitials and thus reducing RIS. Kato et al.100 conducted
electron irradiations of several stainless steels at temperatures of 400500 C up to 10 dpa. Results showed
that some solutes (Zr and Hf) consistently produced a
large suppression of radiation-induced chromium
193
depletion, while others resulted in less suppression

or suppression at only certain temperatures. Fournier
et al.101 conducted irradiation of 316 containing Hf or
Pt using 3-MeV protons (400 C) and 5-MeV Ni ions
(500 C). Ni irradiations showed little effect of the
oversize impurity in reducing grain boundary chromium depletion (Cr depletion increased in the case
of Hf), but proton irradiation showed a significant
suppression of RIS of chromium at low dose (2.5 dpa)
with the effect diminishing at higher (5.0 dpa) dose.
Pt had a smaller effect on Cr. Ti and Nb similarly
produced little change in the grain boundary chromium concentration after irradiation with 3.2-MeV
protons to 5.5 dpa at 360 C. In Zr-doped 304SS,
there were no consistent results of suppression of
grain boundary chromium after 3.2-MeV proton irradiation to 1.0 dpa at 400 C.102 Neutron irradiation at
very low dose (0.5 dpa) shows a small effect of Ti and
Nb on grain boundary Cr.103 In all, the data on the
effect of oversize solutes on RIS of chromium are
inconsistent.
RIS is understandably implicated in IASCC of
stainless steels, especially in oxidizing environments,
in part because of the effect of thermal sensitization
in extensive data from lab and plant operational
experience.1520,37,38,104,105 As shown in Figure 17,
grain boundary chromium depletion during irradiation can be severe. Figure 18(a) shows a correlation
between grain boundary chromium level and IGSCC
susceptibility in stainless steels where the grain
boundary depletion is due to thermal sensitization.106
Much data have been accumulated to support the
role of chromium depletion as an agent in IGSCC
of austenitic alloys in oxidizing conditions. Numerous studies show that, as the grain boundary chromium level decreases, intergranular SCC increases.
Typical chromium-depleted zone widths are of the
order 100300 nm full width at half-maximum
(FWHM), providing a significant volume of depleted
material adjacent to the grain boundary.
Figure 18(b) shows a similar correlation between
grain boundary chromium level and IASCC susceptibility as measured by the percentage IG cracking
on the fracture surface during SSR experiments.
A major difference between Cr depletion profiles
resulting from RIS and those due to precipitation
reactions is that the width of the RIS profiles can
be as much as 2 orders of magnitude smaller, typically 510 nm. There is large scatter in the data
that makes a direct correlation difficult to support,
and differences in testing conditions undoubtedly
contribute.
194
%IGSCC in slow strain rate test
100
80
60
e = 2 107 S1
= 1 106 S1
40
Alloy 600
SSR tests,
23 C sulfuric
acid
20
Type 304SS
SSR tests, 288 C
8 ppm O2 water
0
4
(a)
6
8
10
12
14
16
18
20
Minimum grain boundary chromium concentration (wt%)
100
HP 316 SS with single

solute additions108
3xx SS17
80
%IG
60
40
20
0
10
(b)
12
14
16
18
20
Grain boundary Cr content (wt%)
irradiation. However, it should be noted that these

alloys were not irradiated, and this difference may be
important in the relevance of such experiments to
IASCC. Using 1.55% Si stainless steels of both
standard (e.g., 304L) base composition and synthetic
irradiated grain boundary composition, Andresen has
observed significantly increased growth rates, reduction in the benefit of lowering corrosion potential,
and very little effect of stress intensity factor between
27 and 13 ksi in1/2.
The data on impurity segregation effects on
IASCC remain inconclusive. Extensive experiments
have been conducted to isolate the effect of particular
impurities such as S, P, C, N, and B in IASCC, but
none have yielded unambiguous results. Sulfur has not
been found to segregate under irradiation, and, while
P thermally segregates to a significant extent, irradiation-induced P segregation is small in comparison. C,
N, and B cannot be measured in STEM; N and B are
very difficult to identify in AES; and C is a common
contaminant. Overall, it has been a challenge to establish a link between impurity element segregation and
IASCC in austenitic stainless steels.
22
Figure 18 Effect of grain boundary Cr content on

intergranular stress corrosion cracking for (a) sensitized
stainless steel and Alloy 600 and (b) irradiated stainless
steels. Slow-strain-rate tests are tests in which the
specimen is monotonically strained versus time.
Reproduced from Bruemmer, S. M.; Was, G. S. J. Nucl.
Mater. 1994, 216, 348.
Among the minor alloy elements, only Si is known

to segregate to high levels, and Si segregation is
correlated with IASCC. Experiments by Busby
et al.107,108 on a high-purity 316 base alloy doped
with 1 wt% Si showed severe IASCC in NWC and
in primary water after irradiation to 5.5 dpa at 360 C.
STEM measurements of grain boundary Si confirm
levels up to 6 wt%. Past studies comparing Auger
electron spectroscopy (AES) and scanning transmission electron microscopy (STEM) results have shown
that the actual concentration of Si at the grain boundary plane may be as high as 1520 wt%. Though the
electron beam probe in STEM is very small, the
measurement underpredicts the concentration at
the grain boundary by a factor of 2 to 3. Yonezawa
et al.109112 and Li et al.113 have provided extensive
evidence to show that increased Si in stainless steel
results in increased IGSCC in alloys tailored to imitate the composition of grain boundaries under
5.08.4.2 Microstructure, Radiation

Hardening, and Deformation
5.08.4.2.1 Irradiated microstructure
The microstructure of austenitic stainless steels

under irradiation changes rapidly at LWR service
temperatures. Point defect clusters (called black dot
damage when electron optics could not resolve the
details) begin to form at very low dose, dislocation
loops and network dislocation densities evolve with
dose over several displacements per atom, and the
possibility exists for the formation and growth of
He-filled bubbles, voids, and precipitates in core
components in locations exposed to higher dose and
temperatures.114120 Below 300 C, the microstructure is dominated by small clusters and dislocation
loops. Near 300 C, the microstructure contains
larger faulted loops plus network dislocations from
loop unfaulting and cavities at higher doses.
The primary defect structures in LWRs are
vacancy and interstitial clusters and Frank dislocation
loops. The clusters are formed during the collapse of
the damage cascade associated with primary and secondary atom collisions after an interaction with a
high-energy particle. The larger, faulted dislocation
loops nucleate and grow as a result of the high mobility of interstitials. The loop population grows in size
and number density until absorption of vacancies and
interstitials equalize, at which point the population

has saturated. Figure 19 shows the evolution of loop
density and loop size as a function of irradiation dose
during LWR irradiation at 280 C. Note that saturation of loop number density occurs very quickly,
by 1 dpa, while loop size continues to evolve up
to 5 dpa. The specific number density and size are
dependent on irradiation conditions and alloying elements, but the loop size rarely exceeds 20 nm and
densities are of the order of 1 1023 m3.
The hardening process and IASCC susceptibility
are influenced by small defects. The traditional view
that small defect clusters are predominantly faulted
interstitial loops and vacancy clusters121 may be inaccurate. Analysis of recent postirradiation annealing
experiments by Busby et al.122 and Simonen et al.123
suggests that there are at least two types of defects
with different annealing characteristics: vacancy and
interstitial faulted loops, each with different annealing
kinetics. The step change in hardness as a function
of annealing time suggests that the density of vacancy
loops is perhaps much higher than previously believed,
and higher than the density of interstitial loops.122
Above 300 C, voids and bubbles may begin to
form, aided by the increased mobility of point defects
at the higher temperature. The dislocation structure
will evolve into a network structure as larger Frank
loops unfault. The reduction in the sink strength
of the dislocation loops aids in the growth of voids
and bubbles. While their size and number density
increase with temperature, the dislocation microstructure continues to be the dominant microstructure component over the temperature range expected
for LWR components (<350 C).
Loop density (m3)
11
1023
Loop density
1022
Loop size
10
9
8
7
1021
1020
0
Type 304SS heats

Type 316SS heats
1
3
4
5
6
Irradiation dose (dpa)
5
7
Average loop diameter (nm)
12
Figure 19 Measured change in density and size of

interstitial loops as a function of dose during light water
reactors irradiation of 300-series stainless steels at
275290 C. Reproduced from Bruemmer, S. M.; Simonen,
E. P.; Scott, P. M.; Andresen, P. L.; Was, G. S.; Nelson, J. L.
J. Nucl. Mater. 1999, 274, 299.
195
Irradiation can also accelerate or retard the

growth of second phases, modify existing phases, or
produce new phases, although these processes are
more pronounced above 400 C. In stainless steels,
the principal second phase is chromium carbides,
which are stable under irradiation. In high-strength
Ni-base alloys, the second phases can undergo several types of transformations: g0 can dissolve, g00 can
dissolve and reprecipitate, and Laves phase can
become amorphous. A key factor in phase formation
in austenitic stainless steels under LWR operating
conditions is RIS, which can induce the formation
of phases by exceeding the local solubility limit. Was
et al.124 irradiated a high-purity stainless steel containing 1 wt% Si with 3.2-MeV protons to 5.5 dpa at
360 C. They observed the formation of g0 (Ni3Si) in
the matrix but not on the grain boundary, which is
puzzling since the concentration of both Si and Ni is
higher in the boundary. This was also observed in a
similar alloy irradiated with neutrons to 7 dpa at
300 C.125 g0 is a coherent precipitate that can significantly strengthen the matrix and has the potential to
alter the deformation behavior in the unirradiated
and irradiated conditions.
Oversize solutes can also affect the irradiated
microstructure by mechanisms similar to RIS. Proton
and nickel ion irradiations show that the addition of
Hf to a 316SS-base alloy increased loop density,
decreased loop size, and eliminated voids.101 Platinum addition to 316SS resulted in no change in loop
density and a small increase in loop size, but
increased void size and density. The good agreement
between proton and Ni ion irradiation results indicates that the major effect of the oversized solute is
not due to the cascade (where there are large differences between proton and nickel ion irradiation),
but rather is due to the post-cascade defect partitioning to the microstructure evolution. Electron
irradiation experiments by Watanabe et al.126 and
proton irradiation experiments by Was et al.124
showed that stainless steel with Ti additions had
slightly lower dislocation loop densities and larger
sizes compared to the base alloy. Nb increased only
the loop size. In contrast to the base alloy, neither
the Ti nor the Nb-doped alloys formed voids under
the conditions tested. Zirconium addition to 304SS
resulted in reduced hardness, decreased loop density, and no change in loop size in proton irradiation
to 1.0 dpa at 400 C and compared to the base
alloy.127 Zirconium-containing samples also had a
lower void density with no change in void size as
compared to the base alloy.
196
5.08.4.2.2 Radiation hardening
1200
1000
Yield strength (MPa)
The dislocation loop microstructure formed during

irradiation hardens the alloy, which correlates with
increased SCC susceptibility. Under an applied
stress, dislocation network interacts elastically with
the dislocation loops, producing an increase in the
yield strength of the alloy, which can be detected in
tensile tests or indentation hardness measurements.
This is accompanied by a decrease in elongation,
which is affected more than reduction in area because
necking occurs relatively early in most tensile tests of
irradiated stainless steel. Fracture toughness also
decreases with fluence.
The increase in yield strength with dose in 300
series stainless steels irradiated around 300 C is
shown in Figure 20. The yield strength can reach
values up to five times the unirradiated value by about
5 dpa, and its increase follows a square root dependence on dose. Both the source hardening model128
and the dispersed barrier hardening model129 provide reasonable correlations between hardening
and the dislocation loop microstructure. In the dispersed barrier hardening model, the increase in hardness is proportional to (Nloop dloop)1/2, where Nloop
is the loop number density and dloop is the loop
diameter.
Deformation changes dramatically with radiation.
Homogeneous deformation at low dose is replaced by
heterogeneous deformation at higher doses as the
defect microstructure begins to impede the motion
of dislocations. Plasticity becomes localized to narrow channels that have been cleared of defects by
preceding dislocations, providing a preferred path for
subsequent dislocation motion. The channels are
very narrow (<100 nm) and closely spaced (<1 mm)
and typically run the full length of a grain, terminating at the grain boundaries.130 Dislocation channeling
can cause localized necking and a sharp reduction in
uniform elongation.131
Hardening has been cited as a key factor in IASCC
susceptibility. Figures 2 and 21(a) show that increasing cold work and yield strength increases the crack
growth rate in nonsensitized austenitic stainless steel
tested in 288 C BWR NWC.132 This dependence
carries over to irradiated material. Figure 21(b)
shows a correlation between yield strength and susceptibility to IASCC in SSR tests although the correlation is complicated by other radiation-induced
changes, especially RIS. The correlation is better at
high values of yield strength (>800 MPa) and at very
low values (<400 MPa), with more scatter at intermediate values (400800 MPa).
800
600
400
200
0
4
6
Dose (dpa)
10
Figure 20 Irradiation dose effects on measured

tensile yield strength for several 300-series stainless
steels, irradiated and tested at a temperature of about
300 C. Adapted from Singh, B. N.; Foreman, A. J. E.;
Trinkaus, H. J. Nucl. Mater. 1997, 249, 103; Seeger,
A. In Proceedings of 2nd United Nations International
Conference on the Peaceful Uses of Atomic Energy;
United Nations: New York, NY, 1958; Vol. 6, p 250;
Bruemmer, S. M.; Cole, J.; Carter, R.; Was, G. S. In
Power Systems Water Reactors; Gold, R. E.,
Simonen, E. P. The Minerals, Metals, and Materials Society
(TMS): Warrendale, PA, 1993; p 537; Bloom, E. E.
In Radiation Damage in Metals; Peterson, N. L.,
Harkness, S. D., Eds.; ASM International: Materials Park,
OH, 1975; p 295.
Hardening alone is not sufficient to explain

IASCC. Annealing experiments tracked the change
in hardness and dislocation loop microstructure versus annealing condition.133 Figure 22 shows the
change in hardness and the change in the dislocation
loop line length (Navg davg) along with the change
in IASCC susceptibility in SSR tests as annealing
progresses.120,134,135 Except for very short annealing
times, the loop line length and the hardness closely
track each other, as expected if the loop structure is
controlling the hardening. At very small values of
(Dt)1/2, the hardening remains flat before decreased
with annealing time. While both hardening and
cracking are reduced with increased annealing, the
behavior of the hardness does not fully explain the
response.
Busby et al.122 postulated that the removal of very
small defects at short annealing times may account
for the IASCC behavior. Short times at high temperature (500 C) may preferentially remove the small
107
108
10
100
Stress corrosion cracking,
nonsensitized austenitic stainless steels
in simulated BWR water 288 C
HP 316SS with single

solute additions 108
3xxSS 17
80
304, 1.4301
347, 1.4550
321, 1.4541
316Ti, 1.4571
60
% IG
Stress corrosion cracking growth

rate, a/t, (m s1)
106
197
40
1010
20
1011
Intergranular
1012
0
(a)
200
increasing fraction of transgranular SCC
400 600 800 1000 1200 1400 1600

Yield strength, Rp0.2 (MPa)
(b)
0
200
400
600
800
1000
Yield stress (MPa)
Percentage of as-irradiated feature

remaining after heat treatment
Figure 21 Effect of yield strength on intergranular stress corrosion cracking. (a) Crack growth rate of cold-worked,
unirradiated 300-series stainless steels tested in 288 C simulated boiling-water reactor (reproduced from Speidel, M. O.;
Magdowski, R. In Proceedings of 9th International Symposium on Environmental Degradation of Materials in Nuclear
Power Systems Water Reactors; Ford, F. P., Bruemmer, S. M., Was, G. S., Eds.; The Minerals, Metals & Materials
Society: Warrendale, PA, 1999; p 325) and (b) percentage intergranular stress corrosion cracking in slow strain rate
tests on 300-series stainless steels where hardening is by irradiation (adapted from Bruemmer, S. M.; Simonen, E. P.;
Scott, P. M.; Andresen, P. L.; Was, G. S.; Nelson, J. L. J. Nucl. Mater. 1999, 274, 299; Busby, J. T.; Kenik, E. A.; Was, G. S.
J. Nucl. Mater. (in press)).
120
RIS
100
IASCC
Hardness
Loop line length
RIS
80
60
40
Hardness
and loop
line length
IASCC
20
0
0
0.0005 0.001 0.0015 0.002 0.0025 0.003

Iron diffusion distance, (DFet)1/2, (cm)
Figure 22 Removal of radiation-induced segregation

and dislocation microstructure as measured by loop line
length and hardness with extent of annealing as
measured by (Dt)1/2 for iron, where D is the diffusivity of
Fe and t is time. This relationship accounts for annealing
at different times and temperatures. The effect on
irradiation-assisted stress corrosion cracking in slow
strain rates is also shown. Adapted from Busby, J. T.;
Was, G. S.; Kenik, E. A. J. Nucl. Mater. 2002, 302, 20;
Edwards, D. J.; Simonen, E. P.; Garner, F. A.;
Greenwood, L. R.; Oliver, B. M.; Bruemmer, S. M. J. Nucl.
Mater. 2000, 317, 32; Katsura, S.; Ishiyama, Y.; Yokota, N.;
et al. In Corrosion/98; NACE: Houston, TX, 1998;
Paper no. 132; Jacobs, A.; Wozadlo, G. P.; Gordon, G. M.
Corrosion 1995, 51, 10, 731.
defect clusters either by annihilation or by spontaneous dissociation. The dislocation loops may absorb
the free vacancies and interstitials, thus adding to
their line length. The loss of the small defect clusters
will be offset by the growth of Frank loops producing
no net change in measured hardness or yield strength.
Despite a lack of hardness change, this process may
alter the deformation mode at the local level by
removing the small obstacles to dislocation motion,
thus changing the character of localized deformation.
Hash et al.136 showed that hardening is not the sole
factor in IASCC, by testing a series of samples of
commercial purity 304SS with nominally the same
hardness but with different contributions from cold
work and proton irradiation. At the extremes were a
sample that was cold-rolled to a 35% reduction in
thickness and no irradiation and one with 1.67 dpa
irradiation and no cold work. Three samples had
varying amounts of cold work (10, 20, and 25%) and
corresponding amounts of irradiation dose (0.55,
0.25, and 0.09 dpa) to give a hardness level that was
within 5% over all samples. SCC susceptibility was
measured by the amount of IG cracking in an SSR
test in 288 C BWR NWC. IASCC susceptibility was
not constant, as would be expected if hardness were
the only factor, with cracking observed in only the
two highest dose samples (0.55 dpa with 10% cold
198
work and 1.67 dpa with no cold work), irrespective of

their hardness, Figure 23. The amount of cracking in
the lower dose sample was higher than in a companion sample at the same dose but without cold work,
indicating that cold work can enhance the IASCC
susceptibility. These results also suggest that RH may
promote crack initiation, as it does crack growth.
Combined with the annealing results, they suggest
that other factors besides the hardness level and yield
strength such as RIS and deformation mode play a
role in the IASCC process.
5.08.4.2.3 Deformation mode
Results of IASCC experiments on proton-irradiated

samples over a wide range of doses and alloys have
consistently showed that high Ni alloys have high
IASCC resistance in SSR tests. In particular, Ni concentrations >18 wt% are highly resistant to IASCC
compared to 304SS with 8 wt% Ni. Kodama et al.137
showed that there is a good, but not perfect, correlation between Ni equivalent and IASCC. Notable
exceptions are alloy 800138 and a Fe20Cr25Ni
1Nb alloy used in AGR that experienced IGSCC.139
Ni may affect IASCC directly through a change in
composition or indirectly by changing the slip character. Higher nickel content in stainless steel increases
the stacking fault energy (SFE) significantly, producing a change in slip from planar to wavy. Swan et al.140
studied the effect of SFE on slip behavior using a
series of Fe18CrxNi alloys where 8<x<23. He
showed that for the 8% Ni alloy, the slip was entirely
planar and, as Ni increases, the cross-slip increases. By
20% Ni, there was no evidence of planar slip and the
deformation microstructure consisted of a web of
Dose (dpa)
0.09
0.25
0.55
dislocation tangles, which is evidence of wavy slip in

a high SFE material. Figure 24 shows that planar slip
yields greater dislocation interaction with grain
boundaries than does a wavy slip.
SFE has been linked to SCC resistance in stainless
steels by Thompson and Bernstein, who found that
increasing SFE correlates well with increased reduction in area and decreased SCC susceptibility.141 The
IASCC susceptibility of several irradiated stainless
steels is plotted as a function of SFE in Figure 25
and shows that there is a good correlation between
SFE and IASCC using Rhodes142 and Schramms143
correlations for SFE. These correlations differ in the
elements included and the weights given in terms of
nickel equivalent (NiEq), but are unable to account
for some minor elements and therefore may deviate
substantially from the true SFE in some cases. There
is much scatter in the Ni equivalent plots, similar to
that shown in the IGSCC dependence on grain
boundary Cr and yield strength. One potential source
of the scatter is the inherent variability in initiationdominated phenomena. Another is that, while grain
boundary Cr and yield strength are measured, NiEq
and SFE are generally calculated and with considerable uncertainty. So they may be useful in identifying
transitions in behavior, but are not as reliable
quantitatively.
Microstructure can also influence the deformation
mode. Farrell et al.144 conducted neutron irradiation
of 316 stainless steel at temperatures between 65
and 100 C to doses of <1 dpa, and then characterized the deformation behavior. With increasing dose,
the propensity for dislocation channeling increased
(Figure 26). The volume of material occupied by
channels increases rapidly with dose and saturates
1.67
Extent
of IG
cracking
1mm
1mm
Low SFE planar
Cold work 35%
25%
20%
10%
High SFE wavy slip
0%
Figure 23 Degree of irradiation-assisted stress corrosion

cracking in Type 304 stainless steel samples with the same
hardness but with different combinations of hardening by
cold work and irradiation using 3.2-MeV protons at 360 C.
Reprinted, with permission, from 21st International
Symposium on Effects of Radiation on Materials,
copyright ASTM International, 100 Barr Harbor Drive,
West Conshohocken, PA 19428.
Grain boundary
Grain boundary
Figure 24 Micrographs and corresponding schematic

illustrations of planar and wavy slip in the vicinity of a grain
boundary (micrographs from Swann140).
at <0.5 dpa. These data show that the defect microstructure created by irradiation can induce planar
deformation in the form of narrow dislocation
channels.
The importance of slip localization in IASCC may
be in the way in which the dislocations interact with
the grain boundary. In planar slip, well-defined and
separated slip bands or dislocation channels (for irradiated materials) transmit dislocations during plastic
deformation. These slip bands or channels terminate
at grain boundaries where dislocations are fed into
the grain boundary region versus forming a tangled
dislocation network within the grain. In the more
traditional view of dislocation infusion into grain
boundaries, the pileup of dislocations in the intersecting channel creates progressively higher stresses
at the grain boundary at the head of the pileup. If the
stress exceeds a critical value, separation of the grain
boundary could occur according to a Stroh (wedge)
cracking type of mechanism.145 This cracking process
could occur regardless of the environment and may
in fact be the mechanism that occurs in some of the
IG cracking observed in very highly irradiated steels
in inert environment.131 At lower fluences, the stress
at the grain boundary may promote rupture of the
oxide film, leading to exposure of the metal to the
solution and subsequent corrosion and IASCC.
Alternatively, deformation could occur in the
boundary plane, which would rupture the oxide
film and promote IASCC. Alexandreanu146 showed
that dislocation absorption by grain boundaries in
100
IGSCC (%)
80
60
SFE = 1.2 + 1.4% Ni + 0.6% Cr
+ 17.7% Mn 44.7% Si
Rhodes and Thompson142
40
20
0
0
(a)
50
100
Stacking fault energy (mJ m2)
150
100
IGSCC (%)
80
60
SFE = 53 + 6.2% Ni + 0.7% Cr
+ 3.2% Mn + 9.3% Mo
Schramm and Reed143
40
20
0
0
(b)
50
100
150
Stacking fault energy (mJ m2)
200
Figure 25 Irradiation-assisted stress corrosion cracking

susceptibility as measured by percentage IG cracking as a
function of stacking fault energy determined using
(a) Rhodes correlation (reproduced from Rhodes, C. G.;
Thompson, A. W. Met. Trans. 1977, 8A, 1901) and
(b) Schramms correlation (reproduced from Schramm, R. E.;
Reed, R. P. Met. Trans. A 1975, 6A, 1345).
0.3
1015
ND (cm2)
0.15
1014
Channel area
0.1
ORNL NERI
316 SS
Neutron irradiated
0.05
0
0.5
1
Dose (dpa)
1.5
0.04
0.03
0.02
0.01
Channel area (nm2 nm2)
0.2
0.05
Strain hardening exponent (n)
0.25
Strain hardening
exponent (n)
1013
0
199
Figure 26 Variation in dislocation channel area, dislocation loop line length, and strain hardening exponent as a function of
dose for neutron-irradiated 316SS. ND is the product of the number density and diameter of Frank dislocation loops.
Reproduced from Farrell, K.; Byun, T. S.; Hashimoto, N. Mapping flow localization processes in deformation of irradiated
reactor structural alloys, Report ORNL/TM-2002/66; Oak Ridge National Laboratory, July 2002.
200
nickel-base alloys leads to deformation in the grain

boundary, usually by boundary sliding, and promotes
IGSCC. He observed random grain boundaries
exhibited more sliding, and boundaries where sliding
occurred were four times more susceptible to IGSCC
in primary water at 360 C than boundaries that did
not slide. This same process could explain how dislocation injection into grain boundaries by planar slip
or dislocation channeling can result in IASCC.
The concept that slip planarity controls the deformation mode and IASCC is consistent with observations of IASCC in 304 and 316SS. 316SS has, in some
cases83 been shown to be more resistant to IASCC
than is 304SS, which is consistent with its higher SFE.
Observations by Bailat et al.147 on neutron-irradiated
samples and by Busby et al.148 on proton-irradiated
samples show clear dislocation channel patterns on
the surface of 304SS samples that cracked in SSR
tests but an absence of those patterns on the 316SS
samples that did not crack. In addition, SSR tests on
high Ni alloys (with SFE of 40 mJ m2) showed no
IG cracking and also no dislocation channeling.
Further support for the influence of slip planarity
on IASCC comes from the annealing studies cited

earlier. On samples that underwent either a short,
low-temperature anneal or were tested in the asirradiated condition, IG cracking was accompanied
by a high density of dislocation slip bands on the
surface of 65 mm2. Annealing at 500 C for
45 min resulted in the elimination of IG cracking
and a reduction in the surface slip band density
to 25 mm2.
In the annealing experiments described earlier,
hardening by irradiation was much more effective in
initiating IGSCC than was cold work, where the
dislocation structure will likely be more cellular
than planar. Bruemmer et al.149 showed a correlation
between slip band intersection with the walls of a
growing crack and the accompanying steps on the
oxide on the walls. Figure 27(a) shows a TEM
micrograph of SCC in a cold-worked 316 stainless
steel baffle bolt. The slip bands intersect the walls of
the narrow crack at 45 to the crack growth direction.
The slip bandcrack wall intersections are also coincident with steps in the oxide as shown schematically
in Figure 27(b). This suggests that the flow of
Metal
m/o interface
Oxide
100 nm
Crack wall
oxide growth
Crack
Grain boundary
deformation
by dislocation
Figure 27 Micrograph of (a) deformation bands intersecting a crack in a baffle bolt (reproduced from Thomas, L. E.;
Bruemmer, S. M. In Proceedings of 9th International Symposium on Environmental Degradation of Materials in Nuclear Power
Systems Water Reactors; Ford, F. P., Bruemmer, S. M., Was, G. S., Eds.; Metallurgical Society of the American Institute of
Mining, Metallurgical, and Petroleum Engineers (AIME): Warrendale, PA, 1999; p 41). (b) A schematic of the role that the
deformation bands may be playing in irradiation-assisted stress corrosion cracking.
250
200
Stress (MPa)
dislocations along the slip steps and into the grain

boundary may have been responsible for discontinuous growth of the crack along the grain boundary.
Thus, low SFE and irradiation can both lead to
planar or localized deformation, which terminate at
grain boundaries, which must be accommodated by
the grain boundary. This results in shear strain that
can rupture the oxide film and promote the initiation
of intergranular cracks.
150
100
50
5.08.4.3 Radiation Creep and Stress

Relaxation
0
0
5
10
Displacement level (dpa)
15
Figure 28 The effects of radiation-induced creep on load

relaxation of stainless steel at 288 C. Reprinted, with
permission, from 16th International Symposium on Effects
of Radiation on Materials, copyright ASTM International, 100
Barr Harbor Drive, West Conshohocken, PA 19428.
1.0
0.9
Fraction of stress remaining
At LWR temperatures, radiation creep results from

diffusion of the radiation-produced vacancies and
interstitial atoms to dislocations, enhancing the
climb-to-glide process that controls time-dependent
deformation. Radiation creep can be both beneficial
and detrimental. Benefits accrue from relaxation of
constant displacement stresses, for example, weld
residual stress and in loaded bolts and springs. However, under these conditions and more so under
constant load conditions radiation creep also
induces elevated creep rates, including grain boundary sliding, that help initiate and sustain SCC.
Figures 28 and 29 show examples of load relaxation under constant displacement conditions, a process that is quite reproducible over a wide range of
materials and loading modes, and generally produces sizeable (>50%) load relaxation within a few
displacements per atom. Thus, for example, in areas
of the BWR shroud that receive a moderate neutron
flux, if SCC initiation does not occur early in life
(e.g., by 1 dpa), the relaxation in residual stress
should diminish the likelihood of cracking later in
life. Because the effect of relaxation is significant, it
tends to offset the detrimental effects of RIS and
RH. Thus, it is not surprising that the incidence of
SCC in BWR shroud welds, where the neutron flux
can vary by 2 orders of magnitude because of the
varying proximity of the fuel, does not show a strong
correlation with fluence.
Radiation creep relaxation also affects PWR baffle
bolts, which are subject to large variations in fluence
and temperature.40,41 Baffle bolts in high flux regions
can accumulate more than 3 dpa year1, and thus the
preload will rapidly decrease during the first several
years. Thus, SCC probably initiates early in life
(before significant radiation creep relaxation occurs)
or later in life when reloading occurs from differential swelling in the (annealed) baffle plates relative to
the (cold-worked) baffle bolts.
201
Preload
23.6 N
36.5 N
0.7
0.5
Walters -1977
370 C, EBR-II
X-750 springs
0.3
2
3
Neutron dose (dpa)
Figure 29 Radiation creep relaxation of X-750 springs at

370 C. Reproduced from Walters, L. C., Ruther, W. E.
J. Nucl. Mater. 1977, 68, 324.
While difficult to prove, the elevated and sustained

deformation rates associated with radiation creep can
only accentuate susceptibility to SCC. Estimates of
crack tip deformation rates15 indicate the radiation
creep is not a large contributor in actively growing
cracks, but rather it is expected to promote crack
initiation and to sustain crack growth (or promote
crack reinitiation, if an existing crack does arrest).
202
It is obviously very important to factor radiation

creep relaxation into initial component design and
subsequent SCC analysis. Its impact is large, and it
occurs in the same fluence range as RIS and RH.
5.08.5 Summary
Cracking of in-core reactor components exposed to
both irradiation and high-temperature water supports the significant role of irradiation in intergranular SCC. The effects of irradiation on SCC occur
through changes in the water chemistry and in the
alloy microstructure. It is the persistent radiation
effects on the microstructure that are responsible
for the threshold-like behavior of IASCC. The principal effect of irradiation on water chemistry is
through radiolysis, which, below 500 ppb dissolved
H2, can increase the corrosion potential from the
formation of radiolytic species (radicals and molecules that are oxidizing and reducing). High corrosion potentials strongly correlate with severity of
cracking in both laboratory tests of preirradiated
specimens and in core components in operating
power reactors.
Irradiation causes a significant change in local
composition near grain boundaries and other defect
sinks. The enrichment of nickel and silicon, and the
depletion of chromium, may affect the susceptibility
to IASCC. Irradiation also alters the microstructure,
and, under LWR conditions, faulted dislocation loops
represent the primary irradiation-induced microstructure defect. The loops impede the motion of
dislocations, resulting in an increase in the yield
strength by factor of up to 5. RH correlates with
IASCC propensity, and also induces highly localized
deformation in the form of dislocation channels,
which could contribute to IASCC. Irradiation also
induces creep that can relax macroscopic stresses
and can also enhance local dynamic deformation.
Other factors, such as swelling and formation of
new phases, may accentuate IASCC at high fluence.
With the many effects of irradiation, which overlap
spatially and temporally, more work is needed to
identify the mechanism(s) of IASCC and develop a
comprehensive prediction methodology.
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5.09
Material Performance in Lead and Lead-bismuth Alloy
K. Kikuchi
Ibaraki University, Ibaraki, Japan
5.09.1
Recent Lead-Alloy Activity
207
5.09.2
5.09.2.1
5.09.3
5.09.4
5.09.5
5.09.6
5.09.7
5.09.8
References
Utilization of LA
The Conceptual Models of ADS and MYRRHA
FerriticMartensitic Steels
Surface Treatment to F/M and Austenitic Steels
Oxide Dispersion-Strengthened Steel
Austenitic Stainless Steels
Precipitation Formation
Outlook
209
209
210
213
214
215
216
217
218
Abbreviations
ADS
AFM
BEM
DBTT
EB
EDX
F/M steel
GESA
GIF
ICP
LA
LBE
LFR
LINAC
MA
MEGAPIE
MFM
MYRRHA
ODS
OECD/NEA
SEM
WDX
Accelerator-driven nuclear
transmutation system
Atomic force microscopy
Backscattered electron microscope
Ductile-to-brittle transition
temperature
Electron beam
Energy-dispersed X-ray analyzer
Ferriticmartensitic steel
Gepulste Elektronenstrahlanlage
Generation IV International Forum
Inductive-coupled plasma atomic
emission spectrometer
Lead alloy
Leadbismuth eutectics
Liquid-metal-cooled fast reactor
Linear accelerator
Minor actinides
MEGA-watt Pilot Experiment
Magnetic force microscopy
Multipurpose hybrid research
reactor for high-tech applications
Oxide dispersion-strengthened steel
The Organisation for Economic
Co-operation and Development/
The Nuclear Energy Agency
Scanning electron microscopy
Wave-dispersed X-ray analyzer
5.09.1 Recent Lead-Alloy Activity

A brief justification for the utilization of lead or lead
bismuth for use as a coolant in nuclear energy systems was given in 2001 by Sekimoto.1 When the
possibility of the utilization of nuclear energy was
discovered, it was expected to be a primary energy
source in the future. Fast reactors can utilize the
entire energy content of natural uranium. The selection of a coolant was an important item for designing
fast reactors. The neutron slowing-down caused by
the coolant should be minimized. This is first made
possible by decreasing the average atomic density of
the coolant in the reactor core, and second by
employing a nuclide with a large mass number as
the coolant, whose neutron moderating power is
low. A liquid metal is considered the best coolant
for using the second method. Initially, liquid mercury
was employed but it was not successful in either the
United States or Russia. Since then, several liquid
metals were considered, including lead alloys (LA),
and finally, sodium was selected. However, public
concern about the safety of sodium has increased
following sodium leakage incidents, so the development and deployment of fast reactors on more than a
prototype scale has not occurred.
In the last 10 years, the study of the utilization of
LA including leadbismuth eutectics (LBE) has been
ongoing for application to nuclear waste transmutation
systems and leadbismuth cooled nuclear reactors.
207
208
LBE is a candidate material for a spallation target and a

reactor coolant. In the accelerator-driven nuclear
transmutation system (ADS), LBE is a candidate for
both the subcritical-reactor coolant and the spallation
neutron source target. In addition, the lead or lead
bismuth-cooled fast reactor (LFR) is one of the four
reactor types investigated in Generation IV systems
proposed by the Generation IV International Forum
(GIF). A LBE-cooled Long-Life Safety Simple Small
Portable Proliferation-Resistant Reactor has also been
proposed.2
As a result of the investigations on LA, comprehensive literature has been published. The Working
Group on LBE of the OECD/NEA Nuclear Science
Committee3 published a handbook and review
reports on LA technology. The material properties
of lead and leadbismuth are discussed in detail in
Chapter 2.14, Properties of Liquid Metal Coolants.
As part of the development of advanced nuclear
systems, including ADS proposed for high-level
radioactive waste transmutation and Generation IV
reactors, heavy liquid metals such as lead or LBE
were investigated as reactor core coolant and spallation targets. Heavy liquid metals were also being
envisaged as target materials for high-power neutron
spallation sources. The objective of the handbook is
to collate and publish properties and experimental
results on lead and LBE in a consistent format in
order to provide designers with a single source of
qualified properties and data and to guide subsequent
development efforts. The handbook covers liquid
lead and LBE properties, material compatibility and
testing issues, key aspects of the thermal-hydraulic
and system technologies, existing test facilities, and
open issues and perspectives.
Zhang and Li4 reviewed the studies on fundamental issues in LBE corrosion. They included phase
diagrams, thermodynamics, physical properties, corrosion mechanisms, oxygen control, experimental
results, and corrosion results. Some recommendations were proposed for future studies: precipitation
and deposition of corrosion products; oxygen transport; oxide formation and kinetics in LA; coolant
hydrodynamic effects; steel composition, microstructure, and surface effects; and corrosion models. These
are key areas for future research.
Fazio et al.5 characterized corrosion property for
ferriticmartensitic (F/M) steels and austenitic steels
in stagnant LA on the basis of the results of corrosion
tests. This report briefly summarized the current
status on LA activities. At a temperature below
450 C, adequate oxygen activities in the liquid
metal steels form an oxide layer that behaves as a

corrosion barrier. In the temperature range above
500 C, corrosion protection because of the oxide
scales seems to fail. A mixed corrosion mechanism
has been observed, where both oxide scale formation
and dissolution of the steel elements occurred. However, in this high-temperature range, it has been
demonstrated that the corrosion resistance of structural materials can be enhanced by coating the steel
with FeAl alloys. Experiments performed in flowing
LA (mostly LBE) confirm that the corrosion mechanism of the steels depends on the oxygen content in
LA. At relatively low oxygen concentration, the corrosion mechanism changes from oxidation to dissolution of the steel elements. The experimental activity
also extends up to temperatures of 750 C for oxide
dispersion-strengthened (ODS) alloys and their
welded variants in Pb. The use of materials at higher
temperatures will also require investigation of creep
rupture.
MEGAPIE was the MEGA-watt Pilot Experiment
done at Paul Scherrer Institut (PSI) in 2006 for
developing a LBE spallation target. The MEGAPIE
project was started as an essential step toward demonstrating the feasibility of coupling a high power accelerator, a spallation target, and a subcritical core
assembly. The project was expected to furnish important results regarding safe treatment of components
that had come into contact with leadbismuth.6 The
design data was obtained and the operational mode
was confirmed.7 Corrosion rates were estimated
experimentally at 400 C for a LBE flow rate of
1 m s1 and 2.2 m s1 where the oxygen content in
the LBE was <107 wt%. No protective oxide layer
was produced on the steel surface. This oxygen content has been considered representative of the
MEGAPIE conditions, as no oxygen control and
monitoring system is anticipated to be used in the
target. The estimated corrosion rates, 4086 mm
year1, indicate that in the given testing conditions,
the corrosion resistance of the steel does not represent a critical issue, especially since LBE temperature
is expected to be lower (320 C). The goals of the
experiment were fully accomplished8: 4 months of
reliable and essentially uninterrupted operation
(beam trips and short beam interruptions permitted)
at a power level as high as the accelerator was able to
deliver (about 0.75 MW) excellent performance of
the target and the dedicated ancillary systems, the
proof of functionality of advanced proton beam safety
devices, and, last but not least, a superb neutronic
efficiency delivering about 80% more neutrons for
the users compared to the previously operated leadcannelloni target. Verification of performance will be
scheduled in the postirradiation experiment.
material usage in design studies. The material temperature at contact with LBE is slightly <500 C in the
spallation reaction area and <550 C in the fuel core
area under normal conditions.
Figure 1 shows the ADS concept. A superconducting linear accelerator (LINAC) is connected
with a subcritical fast reactor. A high-energy proton
beam is injected into the core of the reactor. Spallation reactions produce a number of neutrons from
the leadbismuth nuclei, which are then used to
transmute minor actinides (MA). The interface
between the beam duct and lead bismuth is called
the beam window. For example, a tank type reactor
with 800 MW thermal power and LBE-coolant and
spallation target was proposed.1113 The proton beam
energy was set at 1.5 GeV. The beam current varied
between 10 and 20 mA according to criticality swings.
In the steady-state condition, as the beam window
material generates heat by spallation reactions and is
cooled by flowing LBE. A temperature difference is
established between the LBE, the material in contact
with the LBE, and the material on the other side of
the window, with the temperatures being 400, 450,
and 500 C, respectively. As the MA core cladding
material is gamma heated and the fuel adds to the
radiation heat, temperatures reach, for example, a
maximum of 500, 550, and 600 C. The maximum
average velocity in the particular flow channel of
LBE is 1.8 and 2.0 m s1, at the window and in the
MA core region, respectively.
Figure 2 shows the conceptual model of MYRRHA consisting of an inner vessel, guard vessel,
5.09.2 Utilization of LA
5.09.2.1 The Conceptual Models of ADS
and MYRRHA
Recent activity on materials research and development in LA, especially LBE, aims at realizing ADS,
MEGAPIE, LFR, and MYRRHA (multipurpose
hybrid research reactor for high-tech applications).9,10
It is valuable to know each specific environment for
Liq.He
RF
ADS
Injector
RFQ
DTL
Superconducting LINAC
Beam duct
P
Beam
window
Beam
window
MA
PbBi (Am,Cm)
n
MA
Subcritical reactor
PbBi
209
Spallation reaction
Figure 1 The conceptual model of accelerator-driven

nuclear transmutation system with beam window.
11
10
1. Inner vessel
2. Guard vessel
3. Cooling tubes
4. Cover
5. Diaphragm
6. Spallation loop
7. Subcritical core
5
8
12
11
8
9
10
11
3
13
2
1
12
8. Primary pumps
9. Primary heat exchangers
10. Emergency heat exchangers
11. In-vessel fuel transfer machine
12. In-vessel fuel storage
13. Coolant conditioning system
Figure 2 The conceptual model of subcritical reactor in multipurpose hybrid research reactor for high-tech applications.
Courtesy of J Bosch. ADS Candidate Materials Compatibility with Liquid Metal in a Neutron Irradiation Environment, Doctoral
Thesis, ISBN 978-90-8578-241-4, 2008; 7.
210
cooling tubes, spallation loops, primary heat exchangers, and so on, but without a beam window.15 In this
system, a high-energy proton beam with an energy of
600 MeV is injected directly into the free surface
of the leadbismuth in the subcritical reactor core.
The MYRRHA project aims to serve as a basis for
the European experimental ADS. In the first stage,
the project focuses mainly on demonstrating the ADS
concept, safety research of subcritical systems, and on
nuclear waste transmutation studies. Subsequently,
MYRRHA will be used as a fast spectrum irradiation
facility dedicated to research on structural materials,
nuclear fuel, liquid metal technology, and associated
aspects on the one hand and as a radioisotope production facility on the other. The system consists of a
proton accelerator that supplies a 600 MeV 34 mA
proton beam to a LBE spallation target, delivering the
primary neutrons, which in turn couples to a LBEcooled subcritical fast core. The structural materials for
MYRRHA need to withstand temperatures ranging
between 200 and 550 C (normal operating temperature between 300 and 450 C) under high spallation
neutron flux and contact with liquid LBE. It is clear
that the candidate materials need to fulfill challenging
requirements such as high thermal conductivity, high
heat resistance, low thermal expansion, low ductileto-brittle transition temperature (DBTT) shift, sufficient strength at elevated temperatures with limited
loss of ductility and toughness, low swelling rate, high
creep resistance, and good corrosion resistance.14
Studies of LA for developing ADS are also reported
from the points of view of conceptual ideas16,17 and
related facility.18
5.09.3 FerriticMartensitic Steels

One method of using materials such as F/M and
austenitic stainless steels in LA is to keep an oxide
layer on the surface of the base metal in contact with
LA by controlling the oxygen concentration in the
LA.1921 Too little oxygen in LA will lead to dissolution of the protective iron oxide. Excess oxygen solution in the LA will lead to the production of lead
oxide that could plug the cooling tubes. Theory predicts that an adequate oxygen concentration in LA
exists between, for example, 106 and 104 wt% in
the temperature region of 400 and 700 C. An alternative method is to add anticorrosion elements such
as Al to the surface, which leads to a protective oxide
that guards base metals, as mentioned in the section
on surface treatment.
The oxide scale is not a simple structure but

consists of duplex layers: magnetite Fe3O4 near the
LA side and spinel (FeCr)3O4 near the base metal.
The original surface exits at the interface between
the magnetite and spinel but not at the front surface
of the magnetite near the LA. An early question
was how the oxide layers on the surface of the base
metal grew.
Martinelli et al.2224 reported a global study on the
oxidation process of Fe9Cr1Mo martensitic steel
(T91) in static LBE. The isotope tracer oxygen-18 was
employed in the corrosion test. Also, the mass balance
of Fe and Cr was investigated theoretically. They
explained the FeCr spinel growth rate mechanism as
follows: The oxidation reaction can occur because of
the presence of nano-channels. Nano-channel formation is achieved by the dissociative/perforative growth
in the magnetite. The nano-channel allows a fast diffusion of oxygen to the T91/spinel interface. Oxygen
cannot diffuse in the oxide lattice because its rate is
insufficient for FeCr spinel formation, but is instead
transported via short cut diffusion paths. Even if oxygen
diffusion in grain boundaries could be possible, oxygen
would likely diffuse inside nano-channels. The nanochannels are, in some cases, called lead nano-channels
because of the results of the LBE oxidation tests. Liquid
metal does not penetrate evenly in the oxide scales;
only lead penetrations are observed. Nevertheless, in
pure bismuth oxidation tests, bismuth penetrations are
also observed in the scales. On the other hand, the iron
diffusion from T91 to the magnetite/PbBi interface
leads to vacancy formation at the T91/FeCr spinel
interface. Because of the presence of chromium atoms,
these vacancies can accumulate to form nano-cavities
at the T91/FeCr spinel interface. This accumulation
is quasi complete; very few cavities are annihilated
on the T91/oxide interface. The FeCr spinel grows
inside the nanocavity until it is completely filled.
At that moment, the oxygen can no longer reach the
T91 alloy and the oxidation reaction interrupts itself.
The formed FeCr spinel thickness then becomes
equal to the consumed T91 thickness because of
this self-regulation process, as shown in Figure 3.
In this process, the limiting step of the FeCr spinel
growth rate is thus the iron diffusion across the oxide
scale.
A key issue in maintaining structural integrity is to
maintain high performance of the welded materials.
The corrosion properties between the base metal
and the weldment were investigated.25 The materials
tested were F/M steel F82H26 and the electron beam
(EB) welding of F82H. The chemical composition
Oxygen
Nano-channel
211
Nano-channel
LBE
LBE
Oxide
Iron
Oxide
Original metal
surface
Nano cavity
Newly formed oxide
Figure 3 Self-regulation of the FeCr spinel growth.
of F82H is 8Cr2W0.2VTabal/Fe (wt%). Oxygen

concentration was controlled to (24) 105 mass %.
Welded materials were prepared with a bead-onplate weldment with a 15 mm depth of melting.
F82H steel was welded after preheating at 300 C,
heat-treated at 300 C for 2 h, and then annealed at
750 C for 2 h for stress relief. Figure 4 shows optical
microscope observation of cross-section for F82H
specimens and an impinging-flow simulation around
the specimen. It was observed that the welded metal
of F82H revealed a coarse martensitic structure in
comparison with the fine microstructure in the nonwelded region because of melting and resolidification
in the welding process. The corrosion depth in F82H
was limited near the surface of the material. A failure
of the outside layer in the duplex corrosion layers was
observed. The heat-affected zone showed that the
martensitic structure became fine because of the
rapid heating and cooling during the welding process.
Regardless of the difference in microstructures, the
corrosion layer showed no apparent difference. The
growth of the corrosion depth, defined by the layers
of magnetite and spinel, followed a parabolic law,
where diffusion controls the process. The result of
the flow simulation of LBE impingement indicated
that the velocity varied from 0 to 1 m s1 near the
specimen surface. At higher temperatures, for example, above 500 C, the internal oxide layer or diffusion zone was clearly identified. Furukawa et al.27
observed three layers, consisting of the duplex layers
mentioned earlier and a diffusion zone in the base
metal beneath the spinel layer in the static LBE
test at 500 and 550 C under the oxygen control
to 106 wt% for high Cr steel (10.54Cr1.75W
MnMoV) with heat treatment: 1070 C, 100 min aircooled; 770 C, 440 min air-cooled.
Tan and Allen tested high Cr steel material in the
DELTA loop, at Los Alamos National Laboratory
(LANL). The material tested was HCM12A, procured from Sumitomo Metal Industries, Ltd., with
composition provided by the supplier: 10.83Cr

1.89W1.02Cu0.64Mn0.39Ni0.30Mo0.27Si0.19V
0.11C0.063N0.054Nb0.016P0.002S0.001Al3.1
105 B, and balance/Fe (wt%).28 The chemical composition and heat treatment of this material are slightly
different from those used in the experiment by
Furukawa and Muller. HCM12A is one of the thirdgeneration 12Cr ferritic steels with tempered martensite,29 which was originally developed for heavy section
components such as headers and steam pipes for use
at temperatures up to 620 C and pressures up to
34 MPa30 with good resistance to thermal shocks.31
The HCM12A was received after being annealed at
1050 C and tempered at 770 C.28 They compared the
oxide layer to the porous magnetite layer on the supercritical water exposed sample at 600 C, 667 h. Temperatures at both conditions were different. It was
found that detachment of most of the magnetite nonprotective layer occurred on the LBE-exposed sample
at 530 C600 h earlier in time than models developed
by Zhang and Li. From a technical experimental point
of view, it is the issue how to detect the original surface
of base metal in order to evaluate the oxide thickness.
A thin yttrium coating layer will help to detect it in the
LBE corrosion test.
At temperatures above 600 C, the oxide layer grew
thinner with increasing temperature, which suggests
that around this temperature, a change occurred in
the mechanism of oxidation. At 570 C, FeO-wustite
is formed. Compared with magnetite, wustite has a
lower standard free energy of formation, which ensures
its stable existence at low oxygen potential. In fact, the
layer was formed in the region between magnetite
and base metal. Also in this temperature range that is
beyond the point of oxidation mechanism change, dissolution attack was observed at several points, and the
number of such points increased with prolongation of
run duration. The observations would suggest lowering
the maximum processing temperature in LBE applications from the point of view of the static LBE test.27
212
Welded zone
Heat-affected
zone
Tip
1 mm
(a)
1 mm
(b)
Oxide layer
20 m
Oxide layer
20 m
(d)
(c)
Oxide layer
Oxide layer
PbBi
(e)
(f)
STAR
Specimen
PROSTAR 3.10
Velocity magnitude
M/S
Local MX = 1.089
Local MN = 0.7602E-03
*Presentation grid*
1.089
1.012
0.9338
0.8560
0.7783
0.7005
0.6228
0.5450
0.4673
0.3895
0.3118
0.2340
0.1563
0.7851E01
0.7603E03
LBE flow
Y
x
z
(g)
Figure 4 Optical microscope observation of cross-section for F82H specimens and an impinging-flow simulation around
the specimen. (a) Macro structure, including welded zone and heat-affected zone, (b) macro structure at the specimen
end where leadbismuth eutectics impinges from the right hand side indicated with an arrow, (c) micro structure of welded
zone tested at 450 C for 1000 h, (d) micro structure of tip region tested at 450 C for 1000 h, (e) cross-section of tip
region tested at 450 C for 3000 h, (f) cross-section of tip region tested at 500 C for 1000 h, and (g) simulated flow profile
of leadbismuth eutectics around the specimen.
Hosemann et al. attempted nano-scale characterization of HT-9 (11.95Cr1Mo0.6Mn0.57Ni

0.5W0.4Si0.33Vbal/Fe (wt%)) by using atomic
force microscopy (AFM), using a function of magnetic force microscopy (MFM) and C-AFM. C-AFM
is a contact mode electrical characterization technique that involves applying a voltage typically
between the conductive AFM tip and the sample
while monitoring variations in the local electrical
properties in a range of picoamperes to microamperes. The HT-9 tube was tested at 550 C in flowing
LBE under 106 wt% oxygen for 3000 h.32 It was
found that the oxide consists of at least four different
layers with different grain structures and therefore
conductivity/magnetic properties. The outer layers
seem to be Fe3O4 and have good conductivity, while
the inner layer is Cr enriched and has lower conductivity or is insulating. This is in agreement with the
literature where Cr additions lower the conductivity
of Fe3O4. The outer layer can be divided into two
distinct areas based on a change in grain structure.
The inner oxide layers adopt the grain structure from
the bulk steel. High pore density within these layers
suggests that these are fast diffusion paths allowing Fe
diffusion outward and O diffusion inward. The LBE
corrosion experiment in the DELTA Loop on T91,
HT-9, and EP823 conducted for 600 h at 535 C
showed multilayer oxides on the tested materials.
The wave-dispersed X-ray analyzer (WDX) measurements on the cross-sections revealed two Cr and Fe
containing oxide layers and no Fe3O4 layer. It appears
that the main difference between observed oxide
layers is the Fe content and the microstructure.
Nano-indentation tests across the oxide layers
were performed.33 The results showed lower values
of E-modulus in these oxide layers than that of the
bulk steel layers and higher hardness values for the
oxides than that of the bulk steel. The inner oxide
layer is softer than the outer oxide layer. This might
be due to the fact that the inner oxide layer has higher
porosity than the outer layer.
Yamaki and Kikuchi34 conducted a mechanical
test of oxide scales. The beam window at the boundary of the high-energy proton beam and reactor core,
as shown in Figure 1, is loaded by thermal stress
and buckling load in the deep LBE of the reactor.35
The specimen was a ring made from the F/M steel
pipe, HCM12A. The inner surface of the pipe had
been exposed to flowing LBE during the loop operation at 400500 C for 5500 h under an oxygen concentration in the range from 1 105 to 5 105 wt%.
Apparently, the oxide layer had a duplex structure.
Possibly they were outside the magnetite and inner
213
side spinel. Figure 5 shows the results of the ring

compression test. The HCM12A ring was compressed by 50% and unloaded. Near position A,
cracking occurred because of excess strain to the
spinel layer rather than the Fe3O4 layer. This was
caused by the fact that the Youngs modulus of
FeCr spinel layer was lower than that of Fe3O4
layer by 10% with the same hardness in both layers.
Near position E, the oxide layer was spalled off
from the boundary between the base metal and the
spinel.
F/M steels can guard the base metal by forming a
spinel oxide layer. The formation mechanism is controlled by the iron diffusion rating. The magnetite
oxide layer is not protected against contact with
LBE. Under the tensile stresses, excess strains will
spall off the oxide layer from the interface between
the base metal and the spinel layer. Over 570 C, the
oxide formation mechanism is changed by the formation of wustite.
5.09.4 Surface Treatment to F/M

and Austenitic Steels
Muller et al. demonstrated that the effect of Al-alloying
into the surface of the base metal was the F/M
steel OPTIFER IVc (10Cr0.58Mn0.56C0.40W
0.28Vbal/Fe (wt%)) using electron pulse treatment,
GESA (Gepulste Elektronenstrahlanlage).36,37 There
was no corrosion attack visible in any part of the
alloyed portion after 1500 h exposure to liquid lead
at 550 C with 8 106 at.% oxygen. The alumina
layer that must have formed at the surface during
oxidation in lead might be very thin and could not be
detected. Only the unalloyed part of the surface was
covered with thick oxide scales. The results also
suggested that the FeCr spinel layer ends at the
original specimen surface. This surface treatment
had a similar result when applied to an austenitic
steel base metal 1.4970(16.5Cr13.8Ni1.91Mn
0.81SiMoTibal/Fe (wt%)).
Weisenburger et al. examined T91 tubes with
modified FeCrAlY coatings in LBE. These coatings
are often used for turbine blade protection.38 The
coating had an average thickness of 30 mm after application by a plasma spray method and was remelted
using the pulsed large area GESA EB to gain a dense
coating layer and to improve the bonding between
the coating and the bulk material. They intended to
simulate a cladding materials environment by using a
pressurized tube type specimen. The results showed
214
Load
Load
Delamination
Initial
diameter
(48 mm)
Final
diameter
(24 mm)
Specimen
Flat plate
(a)
d width
Crack
Base metal
d interval
(b)
10 mm
A
B C
F
H G
27.5 mm
(e)
Oxide scales
10 mm
(c)
Base metal
No oxide scale
B
C
100 mm
(f)
E
(d)
Figure 5 The ring compression test. (a) HCM12A ring model before compression, (b) the ring model after compression
by 50%, (c) the ring after unloading, (d) simulation of maximum principal strain distribution induced at loading, (e) the
cross-section near position A, and (f) the cross-section near position E.
that the tangential wall stress of about 112.5 MPa

induced by an internal tube pressure of 15 MPa
increased the Fe diffusion and led to enhanced magnetite scale growth. Coated specimens, however, have
no magnetite layer. This is another advantage of the
coating. Energy-dispersed X-ray analyzer (EDX) line
scans of the cross-section of the coated T91 tube
specimen after 2000 h exposure to LBE at 600 C
show that the top oxide scale must consist mainly of
alumina followed by a thin layer enriched in Cr.
These layers protect the steel not only from LBE
attack but also from oxygen diffusion into the coating
and bulk material. The coating process needs some
improvement to avoid coating regions with aluminum concentrations below 4 wt%; otherwise, the
oxide layer will grow in the same manner as the
original material. Steels with 815 wt% Al alloyed
into the surface suffer no corrosion attack for all
experimental temperatures and exposure times.39
Technical concerns about surface treatment are the
effect of cyclic loading on the low cycle fatigue
endurance in air and LBE. Low cycle fatigue tests
were conducted in LBE containing 106 wt% dissolved oxygen with T91 steel at 550 C. T91 was
employed in two modifications, one in the as-received

state and the other after alloying FeCrAlY into the
surface by pulsed EB treatment (GESA process).
Tests were carried out with symmetrical cycling
(R 1) with a frequency of 0.5 Hz and a total elongation Det/2 between 0.3% and 2%. No fatigue effects
from LBE could be detected. Results in air and LBE
showed similar behavior. Additionally, no difference
was observed between surface treated and nontreated
T91 specimens.14
A melting process of coating materials enhances
bonding between the coating and the bulk materials.
Heat deposition because of a pulsed EB exposure
successfully demonstrated that remelted alumina or
FeCrAlY coating was effective in protecting the base
metal property from LBE attack.
5.09.5 Oxide DispersionStrengthened Steel

Takaya et al.40 investigated the corrosion resistance of
ODS steels with 03.5 wt% Al and 13.717.3 wt% Cr,
at 550 and 650 C for up to 3000 h in stagnant LBE
containing 106 and 108 wt% oxygen. The ODS

steels were manufactured by hot extrusion of mechanically alloyed powders at 1150 C, and consolidated
bars were annealed by 60 min of heat treatment at
1150 C, followed by air cooling. Chemical compositions of ODS materials are (13.717.3) Cr(1.93.5)
Al(0.340.36)Y2O3TiSiMnbal/Fe (wt%). Protective Al oxide scales formed on the surfaces of the
ODS steels with 3.5 wt% Al and 1417 wt% Cr, and
no dissolution attack was seen in any of the cases.
Addition of Al is very effective in improving the
corrosion resistance of ODS steels in LBE. On the
other hand, the ODS steel with 16 wt% Cr and no Al
showed no corrosion resistance, except in the case of
exposure to LBE with 106 wt% oxygen at 650 C.
Thus, the corrosion resistance of ODS steels in LBE
may not be improved solely by increasing Cr
concentration.
There is additional data reported by Hosemann
et al. on ODS alloys in LBE. Specimens were exposed
to flowing LBE in the DELTA Loop at LANL
at 535 C for 200 and 600 h. The oxygen content
in the LBE was about 106 wt%. The detailed
manufacturing process was not disclosed. Conclusively,
PM2000, which has a chemical composition of 20Cr
5.5Al0.5Y2O30.5Tibal/Fe (wt%), showed a very
dense, thin, and protective oxide layer because of its
higher Al content. The compositions of the oxide layers
found on the Al alloyed materials change with depth.
Elements are oxidized based on the amount of oxygen
available for oxidation and the free energy of the oxide.
It appears that at least 5.5 wt% Al in the alloy is
necessary to form a protective Al-enriched oxide.41
The oxide scale has a duplex structure below 500 C.
Over 500 C, a diffusion zone in the base metal is
apparently observed. The oxide layer appears to consist
of three layers, that is, the duplex layers plus the diffusion zones. The oxide scale does become unstable. The
outer magnetite layer is prone to be spalled off in the
flowing LA. In such an environment, the Al coating is
found to be effective in enhancing corrosion resistance.
Remelting processes, for example, by GESA EB exposure, make a good Al layer. The disadvantage of the
coating method is the disintegration or cracking due to
an uncontrolled process. This cracking could be attributed to the local reduction of Al content. The ODS
alloy is developed for cladding materials. Materials
development is progressing in the direction of highCr Al-ODS alloys. The recommended Al composition
in ODS alloys varied from 3.5 to 5.5. An adequate
amount of Al will balance the corrosion resistance and
mechanical strength. Excess Al will reduce mechanical
215
strength. The reason why the Al enrichment in Febase steel improves corrosion resistance in LA will be
determined in future investigations.
ODS steel aims at enhancing the strength of
material applicable to the cladding materials of a
fast reactor. The addition of Al to ODS improves
corrosion resistance in LBE at the fuel cladding
temperatures. On the other hand, the excess addition of aluminum reduces the strength of materials.
An optimization is needed to balance the two factors at around 5%.
5.09.6 Austenitic Stainless Steels

Austenitic stainless steels are candidate materials for
the spallation target window in ADS. In MEGAPIE,
however, F/M steel, T91, was used for the beam
window in flowing LA, and this was acceptable for a
limited duration (4 months). The lifetime of the beam
window of the T91 liquid PbBi container in the
MEGAPIE target was summarized based on the present knowledge of LBE corrosion, embrittlement, and
radiation effects in the relevant condition.42 It was
suggested that the lower bound of the lifetime of the
T91 beam window was determined when the steel
became brittle at the lowest operation temperature,
230 C, with a safety margin of 30%. Evaluation
using the DBTT data and fracture toughness values
of T91 specimens tested in LBE, a dose limit of about
6 dpa, corresponding to 2.4Ah proton charge to be
received by the target in about 20 weeks in the normal operation condition, was set.
In the ADS design, for example, the beam window
material will produce about 1000 appm (3He 4He)
a year by 1.5 GeV proton beam bombardment in the
reactor core for austenitic stainless steel, Japanese
Primary Candidate Alloy (JPCA), and F/M steel,
F82H.43 The helium production of 1000 appm He
suggests that the DBTT will increase by 400
500 C.44 This increase will set the design temperature at the beam window at 450500 C. The use of
a F/M steel may lead to a brittle fracture, and those
materials should be avoided in operations for
extended times. Therefore, austenitic steel is the
candidate material. The production of hydrogen and
helium in JPCA was slightly larger, 34%, than
that of F82H because of the addition of nickel and
boron. JPCA, in which the chemical composition
is 0.50Si1.77Mn0.027P0.005S15.60Ni14.22
Cr2.28Mo0.24Ti0.0031B0.0039Nbal/Fe (wt%),
was developed to reduce the helium embrittlement
216
of austenitic steel for first wall and blanket structural components in fusion reactors.45 The optimized
JPCA material is manufactured by vacuum induction
melting, vacuum arc melting, and solution-annealing
at 1100 C for 1 h. The TiC precipitates within the
matrix and on the grain boundaries serve as trapping
centers for the helium produced during neutron irradiation. However, dissolution of the MC precipitates
initiates the onset of helium embrittlement as well as
high swelling during high fluence neutron irradiation. The improved stability of the MC precipitates,
which formed in the matrix during irradiation, prevents loss of ductility at 500 C and below.
The corrosion properties of an austenitic stainless
steel at low temperature demonstrated good endurance for material usage in LBE during a short time,
approximately at 300 and 470 C for 3000 h for 1.4970
austenitic stainless steel,46 and at 420 C for 2000 h
for 1.4970 austenitic stainless steel and 316L at an
oxygen concentration of 106 wt%.47 No dissolution
was seen in the aforementioned results. A thin oxide
scale may protect the material from attack in LBE.
As demonstrated in Figure 4, a corrosion test
under impinging flow was also conducted on JPCA
and its EB welded bar at an oxygen concentration of
24 105 wt%.48 The EB welded metal of JPCA
exhibited a dendritic structure 1 mm in width, but a
heat-affected zone was not visible. Scanning electron
microscopy (SEM) observation showed no corrosion
layer for the specimens tested at 450 C and 1000 h.
1600
1400
1200
1000
800
600
400
200
1200
1000
800
600
400
200
2000
But at 3000 h, a thin corrosion layer could be

observed at 12 mm in depth. For the weld joint, the
depth of the corrosion layer as well as corrosion
morphology showed the same results as with the
parent material. The results of X-ray diffraction analyses showed how the oxide layer developed at 450
and 500 C. Figure 6 shows X-ray diffraction analyses of the JPCA specimens under the conditions of
1000 h at 450 C (top, JPCA-1), 1000 h at 500 C
(middle, JPCA-2), and 3000 h at 450 C (bottom,
JPCA-3). Oxidation of the JPCA at 450 C progressed in the same manner as at 500 C.
5.09.7 Precipitation Formation

The dissolution of Ni, Cr, and Fe from structural
materials into LA was studied. Saturated solubility
of Ni in LA is calculated to be a couple of wt% at
450500 C.20 Corrosionerosion tests have been conducted at the JLBL-1 facility of the Japan Atomic
Energy Agency (JAEA). The main circulating loop
was made of SS316 austenitic stainless steel, and consisted of the specimens at high and low temperatures,
filters, a surge tank, a cooler, an electromagnetic flow
meter, a surface-level meter, thermocouples, and a
drain tank.49 The loop was operated at a maximum
temperature of 450 C with a temperature difference
of 50100 C and average flow velocity of 1 m s1. The
oxygen concentration was estimated to be 107 wt%,
Cr0.19, Fe0.70, Ni0.11
Bi
M3O4
JPCA-1
JPCA-2
JPCA-3
1500
1000
500
0
10.0
20.0
30.0
40.0
50.0
60.0
70.0
80.0
90.0
100.0
Figure 6 X-ray diffraction analyses of JPCA specimens under the condition of 1000 h at 450 C (top, JPCA-1), 1000 h
at 500 C (middle, JPCA-2), and 3000 h at 450 C (bottom, JPCA-3).
according to measurements using an oxygen probe.

The testing specimen tube is a cold-drawn seamless
type SS316, which was produced as a tubing form with
13.8 mm outer diameter, 2 mm thickness, and 40 cm
length. The tube was solution-heat treated at 1080 C
for 1.5 min and then cooled rapidly. Figure 7 shows
both the EDX analyses of the low-temperature specimen after corrosionerosion testing for the 3000 h
and the SEM image of an unused specimen. The surface of unused specimen was characterized by the creviced structure. This feature resulted from the acid
washing in the manufacturing process during material
preparation. It was found that precipitated materials
existed with the solidified LBE on the tube. The precipitation consists mainly of Fe and Cr as measured
using energy dispersive X-ray analyses and apparently
looks crystalline. The quantitative analyses by means of
a focused-ion beam, X-rays, and Transmission Electron
Microscope (TEM) showed that the weight concentration ratio was roughly Fe:Cr = 9:1, for example. Nickel
was not found in the crystals or in the solidified LBE.
The precipitations occur in the leadbismuth including
impurities dissolved from SS316 at the high temperature portion of the test.
Zhang and Li4,50 calculated the corrosion/precipitation rate for iron using a kinetic corrosion model
and the temperature profile for the JLBL-1 loop.
They reported that the observed deposition zones in
the JLBL-1 loop could be exactly predicted using the
nonisothermal and multimodular corrosion model.
The predicted corrosion rate is about 0.050.08 mm
per 3000 h if the diffusion coefficient is selected as
SEM
BEM
Fe
Cr
217
3.9 109 m2 s1. This agrees well with the experimental results of 0.030.1 mm.
Ni-rich precipitation was found in the JLBL-1
loop after a total operation time of 9000 h was
achieved. Figure 8 shows Ni-rich precipitates in an
SEM (low magnitude) and laser microscope (high
magnitude) images on the surface of solidified
LBE.51 The solubility of Ni is higher than that of
Fe and Cr, around a couple of wt% in the temperature range of 350450 C. For the measurement of
Ni in LBE, an inductive-coupled plasma atomic
emission spectrometer (ICP, ULTIMA2) was used
for analyses. It was found that the Ni concentration
was below 0.1 wt%. In addition, Ni-rich precipitates
were found not only at the high temperature part but
also at the low temperature part, and on the surface of
residual LBE as well. This was not the case for FeCr
precipitates; they were only found at the low temperature part. The driving force for FeCr precipitates
was concluded to be a difference of the saturation
concentration at different temperatures. It can be
assumed that the Ni-rich precipitates formed on the
surface of the residual LBE during a cooling period,
although the precipitation rate is not known for the
establishment of such a Ni-rich structure.
5.09.8 Outlook
For the use of LA as coolant and spallation target,
it is important that the compilations and databases
of material properties are extended to include
Unused specimen
surface
50 m
20 m
500 m
Ni
Pb
Bi
Figure 7 Energy-dispersed X-ray analyzer analyses of

low-temperature specimen after corrosionerosion test at
JLBL-1 and scanning electron microscopy image of unused
specimen.
Figure 8 Ni-rich precipitates of scanning electron

microscopy (low magnitude) and laser microscope (high
magnitude) on the surface of solidified leadbismuth eutectics.
High magnification image is taken by laser microscope.
Reproduced from Kikuchi, K.; Saito, S.; Hamaguchi, D.;
Tezuka, M. J. Nucl. Mater. 2010, 398, 104108.
218
the mechanical properties of structural materials

in LA, such as the effect of temperature and strain
rate,52 fracture toughness,25,53 weldment,54 and liquid
metal embrittlement.55 They are essential to the
design work for the concepts of the ADS systems.
Erosioncorrosion of materials in flowing LA
should be considered along with details of the flow
profile. It was recognized that magnetite in the oxide
layer is eliminated in the steady-state flowing LA.
There is evidence of erosion detected in the expanded
flow channel of the JLBL-1 test specimen. The eroded
part of the specimen coincides with regions in flowing
LA, such as secondary flow or vortex flow.
In the last decade, research projects for ADS, LFR,
MEGAPIE, and MYRRHA were launched. To design
the conceptual model of the real spallation target, the
performance of neutronics, reactor physics, and thermal hydraulics has been studied along with the performances of materials in leadbismuth or lead. For
the materials bombarded by high-energy particles,
such as proton beams, the surface coating or surface
treatment, defect formation mechanism including not
only corrosion but also the synergetic effect of irradiation field, must be understood. For the materials
applicable to the cladding of fuel rod, FeAl alloys
seem to be effective in the use of LA, but optimum Al
concentration must be determined.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
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Kondo, T. J. Nucl. Mater. 1986, 141143, 620.
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5.10
Material Performance in Molten Salts
V. Ignatiev and A. Surenkov

National Research Centre, Kurchatov Institute, Moscow, Russian Federation
5.10.1
Introduction: Brief Review of Different Related Applications
221
5.10.2
5.10.2.1
5.10.2.2
5.10.3
5.10.3.1
5.10.3.1.1
5.10.3.1.2
5.10.3.1.3
5.10.4
5.10.5
5.10.6
References
Choice of Fuel and Coolant Salts for Different Applications

Chemical Compatibility of Materials with Molten-Salt Fluorides
Preparative Chemistry and Salt Purification
Developments in Materials for Different Reactor Systems
Molten-Salt Reactor
Metallic materials for primary and secondary circuits
Graphite for the core
Materials for molten-salt fuel reprocessing system
Advanced High-Temperature Reactor
Liquid-Salt-Cooled Fast Reactor
Secondary Circuit Coolants
223
226
228
229
229
230
241
242
243
246
247
249
Abbreviations
AHTR
Advanced High-Temperature
reactor cooled by molten salts
ARE
Aircraft Reactor Experiment
CNRS
Centre de la National Recherche
Scientifique, France
dpa
Displacements per atom
FLIBE
Molten LiF-BeF2 salt mixture
FLINABE
Molten LiF-NaF-BeF2 salt mixture
Hastelloy N or Ni-Mo alloy developed for MSR
INOR-8
at ORNL
HTR
High-Temperature Reactor cooled
by helium
HX
Heat Exchanger
IGC
InterGranular Cracks
IHX
Intermediate Heat Exchanger
KI
Kurchatov Institute, Russia
LSFR
Liquid Salt-cooled Fast Reactor
LWR
Light Water Reactor
MA
Minor Actinides
MC
(U,Pu)C Metal Carbide fuel form
MOSART
Molten Salt Actinide Recycler &
Transmuter
MOX
(U,Pu)O2 Mixed Oxide fuel
MSBR
Molten Salt Breeder Reactor
MSFR
Molten Salt Fast Reactor
MSR
Molten Salt Reactor
MSRE
Molten Salt Reactor Experiment
MWe
Megawatts electrical
MWt
NCL
NFC
NPP
ODS
ORNL
RE
REDOX
RW
SFR
SNF
TRU
UOX
VHTR
Megawatts thermal
Natural Convection Loop
Nuclear Fuel Cycle
Nuclear Power Plant
Oxide Dispersion-strengthened
Steels
Oak Ridge National Laboratory,
USA
Rare Earth elements
Electrochemical reduction
oxidation
Radioactive Wastes
Sodium-cooled Fast Reactor
Spent Nuclear Fuel
TRans-Uranium elements
UO2 Uranium Oxide fuel
Very High-Temperature Reactor
5.10.1 Introduction: Brief Review of

Different Related Applications
In the last few years, there has been a significantly
increased interest in the use of high-temperature
molten salts as coolants and fuels in nuclear power
and fuel cycle systems.15 The potential utility of a
fluid-fueled reactor that can operate at a high temperature, but with a low-pressure system, has been
recognized for a long time. One of the attractive
221
222
features of the molten-salt system is the variety of

reactor types that can be considered to cover a range
of applications. Molten salts offer very attractive
characteristics as coolants, with respect to heat transport and heat transfer properties at high temperatures. The molten-salt system has the usual benefits
attributed to fluid-fuel systems. The principal advantages over solid-fuel element systems are (1) a high
negative temperature coefficient of reactivity; (2) lack
of radiation damage that can limit fuel burnup; (3) the
possibility of continuous fission-product removal;
(4) the avoidance of the expense of fabricating new
fuel elements; and (5) the possibility of adding makeup fuel as needed, which precludes the need for
providing excess reactivity. Indeed, fuel can be processed in an online mode or in batches in order to
retrieve fission products and then reintroduced into
the reactor (fuel in liquid form during the whole cycle).
Molten fluoride salts were first developed for
nuclear systems as a homogeneous fluid fuel. In this
application, salt served as both fuel and primary
coolant at temperatures 700 C. Secondary coolant
salts were also developed that contained no fissile and
fertile materials. In the 1970s, because power cycle
temperatures were limited by the existing steam system technology, the potential for use of molten salts
at extreme temperatures was not fully explored.
Today, much higher temperatures (>700 C) are of
interest for a number of important applications.
For 60 years, nitrate salts at lower temperatures
have been used as coolants on a large industrial scale
in heat transport systems in the chemical industry;
thus, a large experience base exists for salt-base heat
transport systems.68 However, because these salts
decompose at 600 C, highly stable salts are required at higher temperatures. Most of the research
on high-temperature molten-salt coolants has focused
on fluoride salts because of their chemical stability and
relatively noncorrosive behavior. Chloride salts are a
second option, but the technology is less well developed.9,10 As is true for most other coolants, corrosion
behavior is determined primarily by the impurities in
the coolant and not the coolant itself. While largescale testing has taken place, including the use of such
salts in test reactors, there is only limited industrial
experience.
In the 1950s and 1960s, the US Oak Ridge
National Laboratory (ORNL) investigated moltensalt reactors (MSRs), in which the fuel was dissolved
in the fluoride coolant, for aircraft nuclear propulsion
and breeder reactors.11 Two test reactors were
built at ORNL: the Aircraft Reactor Experiment
(ARE)1214 and the Molten Salt Reactor Experiment

(MSRE).15 The favorable experience gained from the
8 MWt MSRE test reactor operated from 1965 to
1969 led to the design of a 1000 MWe molten-salt
breeder reactor (MSBR) with a core graphite moderator, thermal spectrum, and thoriumuranium fuel
cycle.16,17 In the MSBR design, fuel salt temperature
at the core outlet was 704 C. The research and
development effort, combined with the MSRE and
a large number of natural and forced convection loop
tests, provided a significant basis for demonstrating
the viability of the MSR concept.
Since the 1970s, with other countries, including
Japan, Russia, and France, the United States placed
additional emphasis on the MSR concept development.1822 Recent MSR developments in Russia
on the 1000 MWe molten-salt actinide recycler
and transmuter (MOSART)1 and in France on the
1000 MWe nonmoderated thorium molten-salt reactor (MSFR)4,5 address the concept of large power
units with a fast neutron spectrum in the core. Compared to the MSBR, core outlet temperature is
increased to 720 C for MOSART and 750 C for the
MSFR. The first concept aims to be used as efficient
burners of transuranic (TRU) waste from spent UOX
and MOX light water reactor (LWR) fuel without any
uranium and thorium support. The second one has a
breeding capability when using the thorium fuel
cycle. Studies of the fast-spectrum MSFR also indicated that good breeding ratios could be obtained, but
high power densities would be required to avoid
excessive fissile inventories. Adequate power densities
appeared difficult to achieve without novel heat
removal methods. Earlier proposals for fast-spectrum
MSRs used chloride salts.9 However, chloride
salts have three major drawbacks: (1) a need for isotopically separated chlorine to avoid high-cross-section
nuclides; (2) the activation product 36Cl, which presents significant challenges to waste management
because of its mobility in the environment; and
(3) the more corrosive characteristics of chloride systems relative to fluoride systems.
Today, in addition to the different MSR systems,
other advanced concepts that use the molten-salt
technology are being studied, including the advanced
high-temperature reactor (AHTR) and the liquidsalt-cooled fast reactor (LSFR).
The AHTR uses clean molten salts as the coolant
and the same coated particle fuel encapsulated in
graphite as high-temperature gas-cooled reactors,
such as the very high-temperature reactor (VHTR).
The fuel cycle characteristics are essentially identical
to those of the VHTR. This concept was originally

proposed in the 1980s by the RRC-Kurchatov Institute in Russia,19 but most of the recent work is being
conducted in the United States.23 The AHTR is a
longer-term high-temperature reactor option with
potentially superior economics due to the properties
of the salt coolant. Also, better heat transport characteristics of salts compared to helium enable power
levels up to 4000 MWt with passive safety systems.
The AHTR can be built in larger sizes or as very
compact modular reactors, it operates at lower pressure, and the equipment is smaller because of the
superior heat transfer capabilities of liquid-salt coolants compared to helium.
A newer concept is the LSFR, which is being
investigated in the United States and France.24 Liquid
salts offer three potential advantages compared to
sodium: (1) molten fluoride salts are transparent and
have heat transport properties similar to those of
water; however, their boiling points exceed 1200 C;
(2) smaller equipment size because of the higher volumetric heat capacity of the salts; and (3) no chemical
reactions between the reactor, intermediate loop, and
power cycle coolants. There is experience with this type
of system because the ARE at ORNL used a sodiumcooled intermediate loop. The basic design of an LSFR
is similar to that of a sodium-cooled fast reactor
(SFR), except that a clean salt replaces the sodium
and the reactor operates at higher temperatures with
the potential for higher thermal efficiency. Molten-salt
fluoride-based coolants allow fast-reactor coolant
outlet temperatures to be increased from 500550 C
(sodium) to 700750 C, with a corresponding increase
in plant efficiency from 42% to 50%.
To identify salts that produce acceptable voiding
(meaning thermal expansion) response, chlorides are
also explored as salts for the LSFR, though one has to
consider the 36Cl production either by neutron capture on 35Cl or (n, 2n) reaction on 37Cl. Recent MSR
developments in the United States on the 2400 MWt
liquid-salt-cooled, flexible-conversion-ratio reactor
address the concept with a core power density of
130 kW l1 and a maximum cladding temperature
of 650 C.25
Based on technical considerations, LSFRs may
have significantly lower capital costs than SFRs;
thus, there is an incentive to examine the feasibility
of an LSFR. There are fundamental challenges to
this new reactor concept, such as development of
high-temperature clads that are corrosion resistant
in the salt environment, can operate at high temperatures, and can withstand high neutron radiation levels.
223
There are multiple industrial uses for hightemperature heat at temperatures from 700 to
950 C.2 There is a growing interest in using hightemperature reactors to supply this heat because of
the increasing prices for natural gas and concerns
about greenhouse gas emissions. Such applications
require high-temperature heat transport systems to
move heat from high-temperature nuclear reactors
(gas-cooled or liquid-salt-cooled) to the customer.
There are several economic incentives to develop
liquid-salt heat transport systems rather than using
helium for these applications: (1) the pipe crosssections are less than one-twentieth of that of helium
because of the high volumetric heat capacity of
liquid salts; (2) salt systems can operate at atmospheric pressure; (3) better heat transfer characteristics of the salt reduce the size of heat exchangers; and
(4) molten-salt pumps operate at much higher temperatures to provide heat in a narrow temperature
interval, compared to compressors that circulate
helium in a VHTR.19 For most of these applications,
the transport distances will exceed a kilometer.
Finally, it should be noted that fuel refining and
reprocessing in systems using molten chlorides/
fluorides and liquid metals (Bi, Zn, Cd, Pb, Sn, etc.)
is a promising method to solve the actinide and
fission product partitioning task for advanced fuels.
These approaches are considered as basic for reprocessing metal, nitride, and MSR fuels.2,4,17,19
As can be seen from the considerations above,
there are several potential applications of molten
salts for future nuclear power. There is great flexibility in the use of molten-salt concepts for nuclear
power in liquid-fuel and solid-fuel reactors, heat
transfer loops, or fuel-processing units.
5.10.2 Choice of Fuel and Coolant

Salts for Different Applications
Selection of salt coolant composition strongly
depends on the specific design application: fluid
fuel (burner or breeder), primary (LSFR or AHTR)
or secondary coolant, heat transport fluid, etc. In
choosing a fuel salt for a given fluid-fuel reactor
design, the following criteria are applied26:
Low neutron cross-section for the solvent
components
Thermal stability of the salt components
Low vapor pressure
Radiation stability
224
Adequate solubility of fuel (including TRU waste)

and fission-product components
Adequate heat transfer and hydrodynamic
properties
Chemical compatibility with container and moderator materials
Low fuel and processing costs
At temperatures up to 1000 C, molten fluorides
exhibit low vapor pressure (1 atm) and relatively
benign chemical reactivity with air and moisture.
Molten fluorides also trap most fission products
(including Cs and I) as very stable fluorides, and thus
act as an additional barrier to accidental fission product
release. Fluorides of metals other than U, Pu, or Th are
used as diluents and to keep the melting point low
enough for practical use. Consideration of nuclear
properties alone leads one to prefer as diluents the
fluorides of Be, Bi, 7Li, Pb, Zr, Na, and Ca, in that
order. Salts that contain easily reducible cations (Bi3
and Pb2, see Table 1) were rejected because they
would not be stable in nickel- or iron-base alloys of
construction.
Three basic salt systems (see Table 2)2733 exhibit
usefully low melting points (between 315 and 565 C)
and also have the potential for neutronic viability
and material compatibility with alloys: (1) alkali fluoride salts, (2) ZrF4-containing salts, and (3) BeF2containing salts. An inspection of the behavior of
the phase diagrams for these systems reveals a
considerable range of compositions in which the salt
will be completely molten with concentrations of
UF4 or ThF4 > 10 mol% at 500 C and >20 mol%
Table 1
Thermodynamic properties of fluorides
Compound
(solid state)
DGf,1000
(kJ mol1)
Compound
(solid state)
DGf,1000
(kJ mol1)
LiF
NaF
KF
BeF2
ThF4
UF3
ZrF4
UF4
522
468
460
447
422
397
393
389
AlF3
VF2
TiF2
CrF2
FeF2
HF
NiF2
CF4
372
347
339
314
280
276
230
130
Source: Novikov, V. M.; Ignatiev, V. V.; Fedulov, V. I.; Cherednikov,

V. N. Molten Salt Reactors: Perspectives and Problems;
Energoatomizdat: Moscow, USSR, 1990; Ignatiev, V. V.; Novikov,
V. M.; Surenkov, A. I.; Fedulov, V. I. The state of the problem on
materials as applied to molten-salt reactor: Problems and ways of
solution, Preprint IAE-5678/11; Institute of Atomic Energy:
Moscow, USSR, 1993; Williams, D. F.; et al. Assessment of
candidate molten salt coolants for the advanced high-temperature
reactor, ORNL/TM-2006/12; ORNL: Oak Ridge, TN, 2006.
at 560 C.27 Trivalent plutonium and minor actinides

are the only stable species in the various molten
fluoride salts. Tetravalent plutonium could transiently exist if the salt redox potential is high enough.
Solubility of PuF4 by analogy of ZrF4, UF4, and ThF4
should be relatively high. But for practical purposes
(stability of potential container material), the salt
redox potential should be low enough and correspond to the stability area of Pu (III). PuF3 solubility
is maximum in pure LiF, NaF, or KF and decreases
with the addition of BeF2 and ThF4.2833 The solubility decrease is more for BeF2 addition, because
PuF3 is not soluble in pure BeF2. As can be seen
from Table 2 (column 1), the LiFPuF3 system is
characterized by a eutectic point with 20 mol% of
PuF3 at 743 C.28 The calculated solubility of PuF3
in the matrix of LiFNaFKF (43.914.241.9) at
T 600 C has been found to be 19.3 mol%.5
Adequate solubility of PuF3 at 600 C in burner
(>2 mol%) and breeder fast-spectrum concepts
(34 mol%) can also be achieved using 7LiF(NaF)
BeF2 (column 3) and LiF(BeF2)ThF4 (column 4)
systems solvent (see Table 2), respectively. The lanthanide trifluorides are also only moderately soluble
in BeF2- and ThF4-containing mixtures. If more than
one such trifluoride (including UF3) is present, they
crystallize to form a solid, made up of all the trifluorides, on cooling of the saturated melt so that, in effect,
all the LnF3 and AnF3 act essentially as a single
element. If so, the total (An Ln) trifluorides in the
end-of-life reactor might possibly exceed their combined solubility.
Melts of these fluorides have satisfactory values of
heat capacity, thermal conductivity, and viscosity
over a temperature range of 5501000 C and provide
an efficient removal of heat when they are used as the
coolant over a wide range of compositions. (See also
Chapter 3.13, Molten Salt Reactor Fuel and Coolant). Transport properties of molten-salt coolants
ensure highly efficient cooling with natural circulation; the saltwall heat transfer coefficient is close to
the same as that for water. The thermal diffusivity of
the salt is 300 times smaller than that of sodium.
Therefore, all other things being equal, the characteristic solidification time for a volume of the fluoride
melt is 300 times longer than that of sodium.2
A particular disadvantage of ZrF4-containing (more
than 25 mol%) melts is its condensable vapor, which is
predominantly ZrF4.26 The snow that would form
could block vent lines and cause problems in pumps
that circulate the fuel. Note also that the use of Zr
instead of sodium in the basic solvent will lead to
225
Table 2
Molar compositions, melting temperatures ( C),27 and solubility of plutonium trifluoride (mol%) at 600 C in
different molten fluoride salts considered as candidates for the fuel and the coolant circuits in MSR concepts
Alkali-metal fluorides
LiFPuF3
(8020)
743 C28
LiFKF
(5050)
492 C
LiFRbF
(4456)
470 C
LiFNaFKF
(46.511.542)
454 C
19.35
LiFNaFRbF
(42652)
435 C
ZrF4-containing
BeF2 containing
ThF4 containing
Fluoroborates
LiFZrF4
(5149)
509 C
NaFZrF4
(59.540.5)
500 C
1.831
LiFNaFZrF4
(422929)
460 C
LiFNaFZrF4
(263737)
436 C
NaFRbFZrF4
(332443)
420 C
NaFKFZF4
(104842)
385 C
KFZrF4
(5842)
390 C
LiFBeF2
(7327)
530 C
2.032
LiFNaFBeF2
(155827)
479 C
2.032,33
LiFBeF2
(6634)
458 C
0.532,33
LiFBeF2ZrF4
(64.530.55)
428 C
NaFBeF2
(5743)
340 C
0.332
LiFNaFBeF2
(313138)
315 C
0.432
LiFThF4
(7822)
565 C
4.229
LiFBeF2ThF4
(75520)
560 C
3.129
LiFBeF2ThF4
(711613)
499 C
1.530
LiFBeF2ThF4
(642016)
460 C
1.229
LiFBeF2ThF4
(4751.51.5)
360 C
KFKBF4
(2575)
460 C
RbFRbBF4
(3169)
442 C
NaFNaBF4
(892)
384 C
increased generation of long-lived activation products

in the system. Potassium-containing salts are usually
excluded from consideration as a primary coolant
because of the relatively large parasitic capture crosssection of potassium. However, potassium-containing
salts are commonly used in nonnuclear applications
and serve as a useful frame of reference (e.g., LiF
NaFKF). This leaves 7LiF, NaF, and BeF2 as preferred
major constituents. For reasons of neutron economy at
ORNL, the preferred solvents for prior ThU MSR
concepts have been LiF and BeF2, with the lithium
enriched to 99.995 in the 7Li isotope. It has recently
been indicated that this well-studied BeF2-containing
solvent mixture needs further consideration, in view of
the current knowledge on beryllium toxicity.4
Unlike the MSR, AHTR and LSFR use solid fuel
and a clean liquid salt as a coolant (i.e., a coolant with
no dissolved fissile materials or fission products). For
the MSR, a major constraint was the requirement for
high solubility of fissile materials and fission products

in the salt; a second was suitable for salt reprocessing.
For AHTR and LSFR, these requirements do not exist.
The requirements mainly include (1) a good coolant,
(2) low coolant freezing points, and (3) applicationspecific requirements. As a result, a wider choice of
fluoride salts can be considered. For a fast reactor,
it is also desirable to avoid low-Z materials that can
degrade the neutron spectrum. In all cases, binary or
more complex fluoride salt mixtures are preferred
because the melting points of fluoride salt mixtures
are much lower than those for single-component salts.
According to recent ORNL recommendations,26
the following two types of salts should be studied for
AHTR and LSFR primary circuits in the future:
Salts that have been shown in the past to support
the least corrosion (e.g., salts containing BeF2 and
ZrF4 in the concentration range 2540 mol%);
226
Salts that provide the opportunity for controlling

corrosion by establishing a very reducing salt
environment (e.g., alkali fluoride (LiFNaFKF)
mixtures and BeF2-containing salts).
Alternatively, the 2400 MWt liquid-salt-cooled,
flexible-conversion-ratio reactor25 was designed, utilizing as a primary coolant the ternary chloride salt
30NaCl20KCl50MgCl2 (in mol%) with maximum
cladding temperatures under 650 C. The selected
chloride base salt has high melting points (396 C
for the reference salt vs. 98 C for sodium). Claim is
made that the materials used in the fuel, core, and
vessel should be the same as those in the sodium
and lead reactor designs but at temperatures required
corrosion behavior for mentioned above materials
in chloride salts is not clear yet (see details in
Section 5.10.6 Secondary Circuit Coolants, Table 7).
For applications that use molten salt outside a neutron field, additional salts may be considered. Candidate
coolants can include salts deemed unsuitable as a
primary coolant but judged as acceptable for use in a
heat transfer loop. Familiar oxygen-containing salts
(nitrates, sulfates, and carbonates) are excluded from
consideration because they do not possess the necessary thermochemical stability at high temperatures
(>600 C). These salts are also incompatible with
the use of carbon materials because they decompose
at high temperatures to release oxygen, which rapidly
reacts with the available carbon.
The screening criteria for selecting secondary salt
coolants require that the elements constituting the
coolant must form compounds that (1) have chemical
stability at required temperatures, (2) melt at useful
temperatures and are not volatile, and (3) are compatible with high-temperature alloys, graphite, and
ceramics.
In addition to the fluoride salts considered (see
Table 2), two families of salts fulfill these three basic
requirements: (a) alkali fluoroborates and (b) chloride
salts. For both salt systems, there are material problems, particularly at the high end of the temperature
range. The chemical stability of chloride salt mixtures
seems not as good as for fluorides, though exclusion of
oxygen and nitrogen is important. Sulfur from 35Cl
and some fission products are potential precipitating
species. Processing could be carried out, at some cost
in external holdup. High-temperature processing has
the potential benefits of being close-coupled, of
reducing inventory, and of conserving 37Cl.
Finally, a heat transport fluid is envisaged for the
coupling of a reactor with a chemical plant, for
example, for hydrogen production.34 Typical salts

considered are LiFNaFKF, KClMgCl2, and KF
KBF4. The ternary LiFNaFKF mixture provides
superior heat transfer, KClMgCl2 has the potential
to be a very low-cost salt, and KFKBF4 may provide
a useful barrier to isolate tritium from the hydrogen
plant. Also, the ternary eutectic 9LiCl63KCl
28MgCl2 (in mol%) with melting point of 402 C
appears to be the best compromise between raw
material cost, performance, and melting point.
As will be shown in the next sections, molten salts,
first of all fluorides, are well suited for use at elevated
temperatures as (a) fluid-fuel, (b) in-core coolant in
a solid-fuel reactor, and (c) secondary coolant to
transport nuclear heat at low pressures to a distant
location. Materials are the greatest challenge for all
high-temperature molten-salt nuclear applications.
Current materials allow operation at 700750 C and
may be extended to higher temperatures. Operating
temperatures much above 800 C will require significantly improved materials. There are strong incentives
to increase the temperature to reach the full potential
of the molten-salt-related systems for efficient electric
and thermochemical hydrogen production. In this
chapter, we review the relevant studies on materials
performance in molten salts.
5.10.2.1 Chemical Compatibility of
Materials with Molten-Salt Fluorides
For any high-temperature application, corrosion of the
metallic container alloy is the primary concern. Unlike
the more conventional oxidizing media, the products of
oxidation of metals by fluoride and chloride melts tend
to be completely soluble in the corroding media.3538
Owing to their solubility in the corroding media,
passivation is precluded and the corrosion rate depends
on other factors, including3946 oxidants, thermal gradients, salt flow rate, and galvanic coupling.
The general rule to ensure that the materials of
construction are compatible (noble) with respect to
the salt is that the difference in the Gibbs free energy
of formation between the salt and the container
material should be >80 kJ mol1 K1. The corrosion
strategy is the same as that used in SFR, where the
materials of construction are noble relative to metallic sodium. Many additional factors will influence the
corrosion of alloys in contact with salts, but it is
useful to keep in mind that the fundamental thermodynamic driving force for corrosion appears to be
slightly greater in chloride systems than in fluoride
systems. This treatment ignores a number of
important salt solution effects, especially for salt

mixtures that exhibit large deviations from ideal
thermodynamic behavior. Additional study in the
laboratory will be needed to understand whether
chloride salts are fundamentally more corrosive
toward alloys than fluorides, and whether corrosion
control strategies can be devised that can be used
with, or favor, chloride salt systems.34
As mentioned above, design of a practicable
MSR system demands the selection of salt constituents that are not appreciably reduced by available
structural metals and alloys whose components
Mo, Ni, Nb, Fe, and Cr can be in near equilibrium
with the salt (see Table 1). Equilibrium concentrations for these components will strongly depend
on the solvent system. Examination of the free energies of formation for the various alloy components
shows that chromium is the most active metal components. Therefore, any oxidative attachment to
these alloys should be expected to show selective
attack on the chromium. Stainless steels, having
more chromium than Ni-base alloys developed
within MSR programs, are more susceptible to corrosion by fluoride melts, but can be considered for
some applications.
Chemical reaction of the fluoride with moisture
can form metal oxides that have much higher melting
points and therefore appear as insoluble components
at operating temperatures.39,40 Reactions of uranium
tetrafluoride with moisture result in the formation of
the insoluble oxide:
UF4 2H2 O $ UO2 4HF
1
The most direct method to avoid fuel oxide formation is through the addition of ZrF4, which reacts in a
similar way with water vapor:
ZrF4 2H2 O $ ZrO2 4HF
2
The net reaction would be

ZrF4 UO2 $ ZrO2 UF4
3
Oxide films on the metal are dissolved by the following reactions:

2NiO ZrF4 ! 2NiF2 ZrO2
4
NiO BeF2 ! NiF2 BeO
5
2NiO UF4 ! NiF2 UO2
6
227
Other corrosion reactions are possible with solvent

components if they have not been purified well
before utilization:
Cr NiF2 ! CrF2 Ni
7
Cr 2HF ! CrF2 H2
8
These reactions will proceed essentially to completion at all temperatures within the circuit. Accordingly, such reactions can lead (if the system is poorly
cleaned) to rapid initial corrosion. However, these
reactions do not give a sustained corrosive attack.
The impurity reactions can be minimized by maintaining low impurity concentrations in the salt and on
the alloy surfaces.
Reaction of UF4 with structural metals (M) may
have an equilibrium constant which is strongly temperature dependent; hence, when the salt is forced to
circulate through a temperature gradient, a possible
mechanism exists for mass transfer and continued
attack:
2UF4 M $ 2UF3 MF2
9
This reaction is of significance mainly in the case of

alloys containing relatively large amounts of chromium. Corrosion proceeds by the selective oxidation
of Cr at the hotter loop surfaces, with reduction and
deposition of chromium at the cooler loop surfaces.
In some solvents (Li,Na,K,U/F, for example), the
equilibrium constant for reaction [9] with Cr changes
sufficiently as a function of temperature to cause the
formation of dendritic chromium crystals in the cold
zone.38 For Li,Be,U/F mixtures, the temperature
dependence of the mass transfer reaction is small,
and the equilibrium is satisfied at reactor temperature
conditions without the formation of crystalline chromium. Of course, in the case of a coolant salt with no
fuel component, reaction [9] would not be a factor.
Redox processes responsible for attack by molten
fluoride mixtures on the alloys result in selective
oxidation of the contained chromium. This removal
of chromium from the alloy occurs primarily in
regions of highest temperature and results in the
formation of discrete voids in the alloy.35 These
voids are not, in general, confined to the grain boundaries in the metal, but are relatively uniformly
distributed throughout the alloy surface in contact
with the melt. The rate of corrosion has been
measured and was found to be controlled by the
rate at which chromium diffuses to the surfaces
undergoing attack.41
228
Graphite does not react with molten fluoride mixtures of the type to be used in the MSR concepts
considered above (after carbon, borides and nitrides
appear to be the most compatible nonmetallic materials). Available thermodynamic data suggest that the
most likely reaction:
4UF4 C $ CF4 4UF3
10
should come to equilibrium at CF4 pressures

<101 Pa. CF4 concentrations over graphitesalt
systems maintained for long periods at elevated
temperatures have been shown to be below the limit
of detection (<1 ppm) of this compound by mass
spectrometry. Moreover, graphite has been used as
a container material for many NaFZrF4UF4,
LiFBeF2UF4, and other salt mixtures at ORNL
and the RRC-Kurchatov Institute, with no evidence
of chemical instability.47
In an MSR, reactions such as [11] and the later
[12] were prevented by careful control of the solution
redox chemistry, which was accomplished by setting
the UF4/UF3 ratio at approximately (5060)/1:
UF4 Cr $ UF3 CrF2
11
UF3 2C $ UC2 3UF4
12
Additions of metallic Be to the fuel salt lead to

reduction of the UF4 via
2UF4 Be0 $ 2UF3 BeF2
13
The significance of redox control to the MOSART

system with uranium-free fuel is that in some cases,
where the fuel is, for example, PuF3, the Pu(III)/Pu
(IV) redox couple is too oxidizing to present a satisfactory redox-buffered system. In this case, as was
proposed by ORNL, redox control could be accomplished by including an HF/H2 mixture to the inert
cover gas sparge, which will not only set the redox
potential, but will also serve as the redox indicator if
the exit HF/H2 stream is analyzed relative to inlet.48
In principle, avoiding corrosion in an MSR or in
fuel-processing units with metallic components is
significantly more challenging than avoiding corrosion in clean salt coolant applications (heat transport
loops, AHTR and LSFR). In an MSR, the dissolved
uranium and other such species in the fuel salt result
in the presence of additional corrosion mechanisms
that can limit the useful service temperature of
an alloy. In clean salt applications, these types of
corrosion mechanisms can be reduced or eliminated
by (1) using purified salts that do not contain chemical species that can transport chromium and other
alloy constituents or (2) operating under chemically

reducing conditions. Under chemically reducing
conditions, chromium fluoride has an extremely low
solubility, which limits chromium transport.
The interaction of trace amounts of oxides, air,
or moisture (either in the salt or cover gas) with
fluoroborates often controls alloy corrosion, but
these chemical interactions are complex and are not
completely understood. For the secondary coolant
NaFNaBF4, corrosion is mainly determined by the
selective yield of Cr from the alloy through the
following reactions45:
H2 O NaBF4 $ NaBF3 OH HF
NaBF3 OH $ NaBF2 O HF
6HF 6NaF Cr $ 2Na3 CrF6 3H2
14
The hydrolysis of BF3 in the presence of any moisture in the cover gas above the salt is rapid and
generates HF which is intensely corrosive to the
system, especially when it is absorbed into molten
salt. Some of the actual oxygen- and hydrogencontaining species that result from hydrolysis of BF3
in the salt have been identified. However, understanding of this chemistry is not complete,49 and
more work is needed before preparative chemistry
and online purification requirements can be defined
with confidence. The behavior of hydrogen- and
oxygen-containing species in fluoroborates is also
important because it provides a means to sequester
tritium in the salt, and thus an intermediate fluoroborate loop could serve as an effective tritium barrier.
The species that is likely responsible for holding
tritium in the salt was identified by Maya,50 and an
engineering-scale experimental program was conducted that proved the effectiveness of sodium fluoroborate in sequestering tritium.51
5.10.2.2 Preparative Chemistry and Salt
Purification
Molten-salt use typically begins with the acquisition
of raw components that are combined to produce a
mixture that has the desired properties when melted.
However, most suppliers of halide salts do not provide materials that can be used directly. The major
impurities that must be removed to prevent severe
corrosion of the container metal are moisture/oxide
contaminants. Once removed, these salts must be kept
from atmospheric contamination by handling and
storage in sealed containers. During the US MSR
program, considerable effort was devoted to salt purification by HF/H2 sparging of the molten salt, which
is described in numerous reports.5255 In addition to
removing moisture/oxide impurities, the purification
also removes other halide contaminants such as chloride and sulfur. Sulfur is usually present in the form
of sulfate and is reduced to sulfide ion, which is swept
out as H2S in the sparging operation. Methods were
also developed to ensure the purity of the reagents
used to purify the salts and clean the container surfaces used for corrosion testing. Another means of
purification that can be performed after sparging
involves simply reducing the salt with a constituent
active metal such as an alkali metal, beryllium, or
zirconium. While such active metals will remove
oxidizing impurities such as HF, moisture, or hydroxide, they will not affect the other halide contaminants
that influence sulfur removal. Therefore, it seems
inevitable that the HF/H2 sparging operation, either
by itself or followed by a reducing (active metal)
treatment, will be a necessity. Although a great deal
of effort can be devoted to purify the molten-salt
mixture in the manner described above, it is primarily useful in producing materials for research purposes, without the possibility of interference from
extraneous impurities.
Removal of oxygen-containing impurities from
chloride and fluoroborate salts is considerably more
difficult because the fluoride ion more readily displaces oxygen from most compounds than does the
chloride ion and because borate and hydroxyborate
impurities are difficult to remove by fluorination
with HF.
Nearly all of the chloride salts prepared for corrosion studies have had relatively high levels of oxygencontaining impurities. The typical salt preparation
for these studies involved treatment of reagent chlorides by drying the solid salt under vacuum, followed
by prolonged treatment with dry HCl gas, and finishing with an inert gas purge of HCl from the salt. This
treatment is not effective in removing the last portion
of bound oxygen from the salt. Depending on the salt
composition, oxygen contents of up to a few percent
(in wt%) may remain. A more effective method for
removing oxygen is needed to investigate the basic
corrosion mechanism in pure chloride salts; otherwise, the effects of oxygen-containing species will
dominate the apparent corrosion response. The use
of carbochlorination has been recommended56 for the
removal of oxygen and it has been claimed that salts
with very low oxygen content (3 ppm) can be produced by this method.57
229
A similar type of purification improvement is

needed for fluoroborates. Previous treatments with
HF and BF3 (to avoid loss of BF3 from the melt) were
not as effective as desired. There is also a need for
accurate analytical methods for the determination of
oxygen in melts and, in certain cases, it is necessary to
identify the oxygen-containing species (oxide type,
hydroxyl, etc).
5.10.3 Developments in Materials for

Different Reactor Systems
5.10.3.1
Molten-Salt Reactor
When considering an MSR, the materials required

fall into three main categories: (1) metallic components for primary and secondary circuits, (2) graphite
in the core, and (3) materials for molten-salt fuel
reprocessing systems.
The metallic material used in constructing the
primary circuit of an MSR will operate at temperatures up to 700750 C. The outside of the primary
circuit will be exposed to nitrogen containing sufficient air from inleakage to make it oxidizing to the
metal. No metallic structural members will be located
in the highest flux. The inside of the circuit, depending on design, will be exposed to salt-containing
fission products and will receive maximum fast and
thermal fluencies of about 12 1020 and 58 1021
neutrons cm2, respectively. The operating lifetime of
a reactor will be in the range of 3050 years, with an
80% load factor. Thus, the metal must have moderate
oxidation resistance, must resist corrosion by the salt,
and must not be subject to severe embrittlement by
neutrons.49 The material must be fabricable into
many products (plate, piping, tubing, and forgings)
and capable of being formed and welded both under
well-controlled shop conditions and in the field.
The primary circuit involves numerous structural
shapes ranging from a few centimeters thick to tubing
having wall thicknesses <1 mm. These shapes must be
fabricated and joined, primarily by welding, into an
integral engineering structure. Thus, the activities
required for development of material for the primary
circuits will suffice for secondary circuits if supplemented by information on the compatibility of the
material with the coolant salt.
Graphite is the principal material other than salt
in the core of the reference breeder reactor design
with a thermal spectrum and thorium fuel cycle.16,17
In nonmoderated MSR concepts (e.g., MOSART1
and MSFR4), graphite is used only as a reflector.
230
The graphite core and reflector structures will operate in a fuel salt environment over a range of
temperatures from 500 up to 800 C. In any MSR
design, graphite is, of course, subject to radiation
damage. There are two overriding requirements in
the graphite in MSRs, namely, that both molten salt
and xenon be excluded from open pore volume. Any
significant penetration of the graphite by the fuelbearing salt would generate a local spot, leading
to enhanced radiation damage to the graphite and
perhaps local boiling of the salt. This requires that
the graphite be free of gross structural defects
and that the pore structure be largely confined to
diameters <106 m.49 135Xe will diffuse into graphite and affect the neutron balance. This requires
graphites of very low permeability, for example,
108 cm2 s1. The requirements of purity and impermeability to salt are easily met by high-quality, finegrained graphite, and the main problems arise from
the requirement of stability against radiation-induced
distortion.58
Material selection for molten-salt fuel reprocessing systems depends, of course, upon the nature of
the chosen process and the design of the equipment
to implement the process. For MSRs,58 the key operations in fuel reprocessing are (1) removal of uranium
from the fuel stream for immediate return to the
reactor, (2) removal of 233Pa and fission product zirconium from the fuel for isolation and decay of 233Pa
outside the neutron flux, and (3) removal of rareearth, alkali-metal, and alkaline-earth fission products from the fuel solvent before its return, along
with the actinides, to the reactor. Such a processing
plant will present a variety of corrosive environments.
The most severe ones are (a) the presence of molten
salt along with gaseous mixtures of F2 and UF6 at
500 C and that with absorbed UF6, so the average
valence of uranium is near 4.5 (UF4.5) at temperatures
near 550 C and (b) the presence of molten salts
(either molten fluorides or molten LiCl) and molten
alloys containing bismuth, lithium, thorium, and
other metals at temperatures near 650 C as well as
HFH2 mixtures and molten fluorides, along with
bismuth in some cases, at 550650 C. High radiation
and contamination levels will require that the processing plant be contained and have strict environmental
control. If the components are constructed of reactive
materials, such as molybdenum, tantalum, or graphite, the environment must be an inert gas or a vacuum
to prevent deterioration of the structural material.
Obviously, materials capable of long-term service
under these conditions must be provided.
The main developments necessary to do this

within the above-mentioned categories are described
below.
5.10.3.1.1 Metallic materials for primary and
secondary circuits
An extremely large body of literature exists on the

corrosion of metal alloys by molten fluorides. Much
of this work was done at ORNL and involved either
thermal convection or forced convection flow loops.
To select the alloy best suited to this application, an
extensive program of corrosion tests was carried out
on the available commercial nickel-base alloys and
austenitic stainless steels.26,3438
5.10.3.1.1.1 Development status of nickel-base
alloys in ORNL
These tests were performed in a temperature gradient system with various fluoride media and different
temperatures (maximum temperature and temperature gradient). Chromium, which is added to most
alloys for high-temperature oxidation resistance, is
quite soluble in molten fluoride salts. Metallurgical
examination of the surveillance specimens showed
corrosion to be associated with outward diffusion of
Cr through the alloy. It was concluded that the chromium content should be maintained as low as reasonably possible to keep appropriate air oxidation
properties. Corrosion rate is marked by initial rapid
attack associated with dissolution of Cr and is largely
driven by impurities in the salt.26,3438 This is followed by a period of slower, linear corrosion rate
behavior, which is controlled by a mass transfer
mechanism dictated by thermal gradients and flow
conditions. Minor impurities in the salt can enhance
corrosion by several orders of magnitude and must be
kept to a minimum. Dissolution can be mitigated by a
chemical control of the redox in salts, for example, by
small additions of elements such as Be. Corrosion
increased dramatically as the temperature was
increased and is coupled to plate-out in the relatively
cooler regions of the system, particularly in situations
where high flow is involved.
The nuclear power aircraft application for which
MSRs were originally developed required that the
fuel salt operate at around 850 C. Inconel 600, out
of which the Na,Zr,U/F ARE test reactor was built,
was not strong enough and corroded too rapidly at
the design temperature for long-term use.1214 The
existing alloys were screened for corrosion resistance
at this temperature and only two were found to be
satisfactory: Hastelloy B (Ni28% Mo5% Fe) and
Hastelloy W (Ni25% Mo5% Cr5% Fe). However, both aged at service temperature and became
quite brittle due to formation of NiMo intermetallic
compounds.38 On the other hand, Hastelloy B, in
which chromium is replaced with molybdenum,
shows excellent compatibility with fluoride salts at
temperatures in excess of 1000 C. Unfortunately,
Hastelloy B cannot be used as a structural material
in high-temperature systems because of its agehardening characteristics, poor fabrication ability,
and oxidation resistance. Tests performed at 815 C
especially showed Ni-base alloys to be superior to
Fe-base alloys. This led to the development of a
tailored Ni-base alloy, called INOR-8 or Hastelloy
N (see Table 3), with a composition of Ni16%
Mo7% Cr5% Fe0.05% C.35 The alloy contained
16% molybdenum for strengthening and chromium
sufficient to impart moderate oxidation resistance in
air, but not enough to lead to high corrosion rates
in salt. Hastelloy N has excellent corrosion resistance
to molten fluoride salts at temperatures considerably
above those expected in MSR service; further (see
Table 4), the resultant maximum corrosion rate of
Hastelloy N measured in extensive Li,Be,Th,U/F
loop testing at reactor operating temperatures was
below 5 mm year1.4246 Higher redox potential set
in the system Li,Be,Th,U/F made the salt more oxidizing. At ORNL, the dependence of corrosion versus flow rate was tested in the range of velocities from
1 to 6 m s1. It was reported that the influence of
231
the flow rate was significant only during the first

10003000 h. Later, the corrosion rates, as well as
their difference, decreased.43
The mechanical properties of Hastelloy N at
operating temperatures are superior to those of
many stainless steels and are virtually unaffected by
long-time exposure to salts. The material is structurally stable in the operating temperature range, and
the oxidation rate is <2 mils in 100 000 h. No difficulty is encountered in fabricating standard shapes
when the commercial practices established for
nickel-base alloys are used. Tubing, plates, bars, forgings, and castings of Hastelloy N have been made
successfully by several major metal manufacturing companies, and some of these companies are
prepared to supply it on a commercial basis. Welding
procedures have been established, and a good history
of reliability of welds exists. The material has been
found to be easily weldable with a rod of the same
composition. Inconel is, of course, an alternate choice
for the primary circuit structural material, and much
information is available on its compatibility with
molten salts and sodium. Although probably adequate, Inconel does not have the degree of flexibility
that Hastelloy N has in corrosion resistance to different salt systems, and its lower strength at reactor
operating temperatures would require heavier structural components.
Hastelloy N alloy was the sole structural material
used in the Li,Be,Zr,U/F MSRE and contributed
Table 3
Chemical composition of the nickelmolybdenum alloys (mass %)
Element
Hastelloy N
(INOR-8)
Ti-modified Hastelloy N
197258
Nb-modified Hastelloy
197658
HN80M-VI
HN80MTY
(EK-50)
MONICR
Ni
Cr
Mo
Ti
Fe
Mn
Nb
Si
Al
W
Cu
Co
Ce
Zr
B
S
P
C
Base
7.52
16.28
0.26
3.97
0.52
0.5
0.26
0.06
0.02
0.07
<0.01
0.004
0.007
0.05
Base
68
1113
2
0.1
0.150.25
02
0.1
0.001
0.01
0.01
0.05
Base
68
1113
0.1
0.150.25
12
0.1
0.001
0.01
0.01
0.05
Base
7.61
12.2
0.001
0.28
0.22
1.48
0.040
0.038
0.21
0.12
0.003
0.003
0.008
0.002
0.002
0.02
Base
6.81
13.2
0.93
0.15
0.013
0.01
0.040
1.12
0.072
0.020
0.003
0.003
0.003
0.001
0.002
0.025
Base
6.85
15.8
0.026
2.27
0.037
<0.01
0.13
0.02
0.16
0.016
0.03
<0.003
0.075
<0.003
0.003
0.003
0.014
The elements were neither added to the melt nor determined.
232
Test loop
NCL-1255
Summary of ORNL loop corrosion tests for fuel fluoride salts

Structural
material
NCL-16
Hastelloy
N 2% Nb
Hastelloy N
MSRE
Hastelloy N
mod. Ti 0.5
Hastelloy N
NCL-15A
NCL-18
Hastelloy N
Hastelloy N
NCL-21A
Hastelloy N
NCL-23
Hastelloy N,
mod. 1% Nb
Inconel 601
NCL-24
FCL-2b
Hastelloy N,
mod. 3.4% Nb
Hastelloy N
Hastelloy N
mod. 1% Nb
Molten salt (mol%)
Fluid test conditions
Corrosion rate
(mm year1)
Circulation mode
Tmax ( C)
Natural convection
704
90
80 439
Natural convection
V = 2.5 cm s1
704
170
28 000
660
1.0
65LiF29.1BeF25.0
ZrF40.9UF4
66LiF34BeF2
73LiF2BeF25ThF4
68LiF20BeF11.7ThF
0.3UF4
71.7LiF16BeF212ThF4
0.3UF4
U4/U3
104
Fuel circuit
654
22
21 800
675
700
654
0.5
0.9
8.0
Coolant circuit
Natural convection
Natural convection
580
677
704
35
55
170
26 100
35 400
11 600
580
677
704
no
1.5
1.2
Natural convection
704
138
10 009
704
3.5
1004
704
3.7
71.7LiF16BeF212ThF4
0.3UF4
U4/U3
40
68LiF20BeF11.7ThF
0.3UF4
71.7LiF16BeF212ThF4
0.3UF4
U4/U3
100
Natural convection
704
138
721
704
34
V 1 cm s1
Natural convection
704
138
1500
704
2.5
Forced convection
704
138
4309
704
2.6
2242
704
0.4
70LiF23BeF25ZrF41UF4
1ThF4
66.5LiF34BeF20.5UF4
Tmax ( C)
Specim.
temperature ( C)
V 1 cm s1
V 2.55m s1
Exposure (h)
Source: Koger, J. W. Alloy compatibility with LiFBeF2 salts containing ThF4 and UF4, ORNL-TM-4286; ORNL: Oak Ridge, TN, 1972; Keiser, J. R.; et al. Salt corrosion studies, ORNL-5078; ORNL:
Oak Ridge, TN, 1975; pp 9197; Keiser, J. R. Compatibility studies of potential molten-salt breeder reactor materials in molten fluoride salts, ORNL-TM-5783; ORNL: Oak Ridge, TN, 1977.
Table 4
significantly to the success of the experiment.15,16

Less severe corrosion attack (<20 mm year1) was
seen for the Hastelloy N in contact with the MSRE
fuel salt at temperatures up to 704 C for 3 years
(26 000 h). The most striking observation is the
almost complete absence of corrosion for Hastelloy
N during the 3-year exposure to the MSRE coolant
Li,Be/F salt (see Table 4).
Two main problems of Hastelloy N requiring
further study were observed during the construction
and operation of the MSRE. The first was that the
Hastelloy N used for the MSRE was subject to a
kind of radiation hardening, due to accumulation of
helium at grain boundaries.59,60 Later, it was found
that modified alloys with fine carbide precipitates
within the grains would hold the helium and avoid
this migration to the grain boundaries. Nevertheless,
it is still desirable to design well-blanketed reactors
in which the exposure of the reactor vessel wall to
fast neutron radiation is limited. The second problem was the discovery of tiny cracks on the inside
surface of the Hastelloy N piping for the MSRE. It
was found that these cracks were caused by the
fission product tellurium.61,62 Later work showed
that tellurium attack could be controlled by keeping
the fuel under reducing conditions.6365 This is done
by adjustment of the chemistry so that about 2% of
the uranium is in the form of UF3, as opposed to
UF4. This can be controlled rather easily now that
good analytical methods have been developed. If the
UF3 to UF4 ratio becomes too low, it can be raised
by the addition of some beryllium metal, which, as
it dissolves, will rob some of the fluoride ions from
the uranium.
When the ORNL studies were terminated in early
1973, considerable progress had been made in finding
solutions to both problems.58 Since the two problems
were discovered a few years apart, the research on
them appears to have proceeded independently.
However, the work must be brought together for the
production of a single material resistant to both problems. It was found that the carbide precipitate that
normally occurs in Hastelloy N could be modified to
obtain resistance to embrittlement by helium. The
presence of 16% molybdenum and 0.5% silicon led
to the formation of coarse carbide that was of little
benefit. Reduction of the molybdenum concentration
to 12% and the silicon content to 0.1% and the
addition of a reactive carbide former such as titanium
led to the formation of a fine carbide precipitate and
an alloy with good resistance to embrittlement by
helium. The desired level of titanium was about
233
2%, and the phenomenon was confirmed by numerous small laboratories and commercial melts by 1972.
Because the intergranular embrittlement of Hastelloy N by tellurium was noted in 1970, ORNLs
understanding of the phenomenon was not very
advanced at the conclusion of the program in 1973.
Numerous parts of the MSRE were examined, and all
surfaces exposed to fuel salt formed shallow intergranular cracks (IGC) when strained. Some laboratory experiments had been performed in which
Hastelloy N specimens were exposed to low partial
pressures of tellurium metal vapor and, when
strained, formed IGC very similar to those noted in
parts from the MSRE. Several findings indicated that
tellurium was the likely cause of the intergranular
embrittlement, and the selective diffusion of tellurium along the grain boundaries of Hastelloy N was
demonstrated experimentally. One in-reactor fuel
capsule was operated in which the grain boundaries
of Hastelloy N were embrittled and those of Inconel
601 (Ni, 22% Cr, 12% Fe) were not. These findings
were in agreement with laboratory experiments in
which these same metals were exposed to low partial
pressures of tellurium metal vapor. Thus, at the close
of the program in early 1973, tellurium had been
identified as the likely cause of intergranular embrittlement, and several laboratory and in-reactor methods were devised for studying the phenomenon.
Experimental results had been obtained that showed
variations in sensitivity to embrittlement of various
metals and offered encouragement that a structural
material could be found that resisted embrittlement
by tellurium.
The alloy composition favored at the close of the
ORNL program in 1973 is given in Table 3 with the
composition of standard Hastelloy N. The reasoning at
that time was that the 2% titanium addition would
impart good resistance to irradiation embrittlement
and the 02% niobium addition would impart good
resistance to intergranular tellurium embrittlement.
Neither of these chemical additions was expected to
cause problems with respect to fabrication and welding.
When the ORNL program was restarted in 1974,
top priority was given to the tellurium-embrittlement
problem.6366 A small piece of Hastelloy N foil from
the MSRE had been preserved for further study.
Tellurium was found in abundance, and no other
fission product was present in detectable quantities.
This showed even more positively that tellurium was
responsible for the embrittlement.
Considerable effort was spent in seeking better
methods of exposing test specimens to tellurium.
234
Cracking parameter (frequency (cm1) average

depth (m))
175
150
Tellurium penetration (mm)
125
100
75
500 hr
200 hr
50 hr
25
100 hr
50
0
0
10
15
20
Square root of time (h)
25
Figure 1 Tellurium penetration versus time for Hastelloy

N exposed at 700 C to LiFBeF2ThF4 (721612 mol%)
containing Cr3Te4. Data obtained by Atomic Energy Station
(AES). Reproduced from Keiser, J. R. Status of
telluriumHastelloy N studies in molten fluoride salts,
ORNL-TM-6002; ORNL: Oak Ridge, TN, 1977.
The most representative experimental system developed for exposing metal specimens to tellurium
involved suspending the specimens in a stirred vessel
of salt with granules of Cr3Te4 and Cr5Te6 lying at the
bottom of the salt. Tellurium, at a very low partial
pressure, was in equilibrium with the Cr3Te4 and
Cr5Te6, and exposure of Hastelloy N specimens to
this mixture resulted in crack severities similar to
those noted in samples from the MSRE (see Figure 1).
As a result of these studies,65,66 it was found that
Hastelloy N exposed in salt-containing metal tellurides, such as LixTe and CryTex, undergoes grain
boundary embrittlement similar to that observed
in the MSRE. The embrittlement is a function of
the chemical activity of tellurium associated with the
telluride. Controlling the oxidation potential of
the salt coupled with the presence of chromium ions
in the salt appears to be an effective means of limiting
tellurium embrittlement of Hastelloy N. The degree of
embrittlement can be reduced by alloying additions
to the Hastelloy N. The addition of 12 mass %
Nb significantly reduces embrittlement, but small
900
Reducing
Oxidizing
600
300
10
20
40 70 100
200
400
Salt oxidation potential (U(IV)/U(III))
Figure 2 Cracking behavior of Hastelloy N exposed for

260 h at 700 C to molten-salt breeder reactor fuel salt
containing Cr3Te4 and Cr5Te6. Reproduced from
Mc Coy, H. E.; et al. Status of materials development for
molten-salt reactors, ORNL-TM-5920; ORNL: Oak Ridge,
TN, 1978.
additions of titanium or additions of up to 15 at.%

Cr do not affect embrittlement. It was found that if
the U(IV)/U(III) ratio in fuel salt is kept below about
60, embrittlement is essentially prevented when
CrTel.266 is used as the source of tellurium (see
Figure 2). However, further studies are needed to
assess the effects of longer exposure times and measure the interaction parameters for chromium and
tellurium under varying salt oxidation potentials.
Studies of irradiation embrittlement and intergranular tellurium embrittlement have progressed
to the point where suitable options are available.
Postirradiation creep properties were acceptable for
Hastelloy N modified with 2% Ti, 14% Nb, or
about 1% each of Nb and Ti. The 2%-Ti-modified
alloy was made into a number of products, and some
problems with cracking during annealing were
encountered. The other alloys were only fabricated
into 1/2-in.-thick plates and 1/4-in.-diameter rods,
and no problems were encountered. All alloys had
excellent weldability. There are no obvious reasons
why all of these alloys cannot be fabricated after
development of suitable scale-up techniques.
The resistance of all of these alloys to irradiation
embrittlement depends upon the formation of a fine
dispersion of MC-type carbide particles. These particles act as sites for trapping He and prevent it from
reaching the grain boundaries where it is embrittling.
235
8000
8926
2500 h
Crack frequency (number cm1) 3 crack depth (m)
These alloys would be annealed after fabrication into

basic structural shapes and the fine carbides would
precipitate during service in the temperature range
from 500 to 650 C. If the service temperature exceeds this range significantly, the carbides begin to
coarsen, and the resistance to irradiation embrittlement diminishes. Although some heated specimens of
the 2%-Ti-modified alloys and 34%-Nb-modified
alloys had acceptable properties after irradiation at
760 C, it is very questionable whether these alloys
can realistically be viewed for service temperatures
above 650 C.
One very important development related to intergranular embrittlement by tellurium was a number of
experimental methods for exposing test metals to
tellurium under fairly realistic conditions. The use
of metal tellurides, which produce low partial pressures of tellurium at 700 C, as sources of tellurium
provided experimental ease and flexibility. The inreactor fuel capsules also proved to be very effective
experiments for exposing metals to tellurium and
other fission products. The observation that the
severity of cracking in standard Hastelloy N was
influenced by the oxidation state of the salts adds
the further experimental complexity that the oxidation state must be known and controllable in all
experiments involving tellurium.
It is unfortunate that Ti-modified alloys were
developed so far because of their good resistance to
irradiation embrittlement before it was learned that
the titanium addition, even in conjunction with Nb,
resulted in alloys that were embrittled by Te as badly
as standard Hastelloy N. However, this situation was
due to the time spread of almost 6 years between
discoveries of the two problems and could not be
prevented. The addition of 12% Nb to Hastelloy
N resulted in alloys with improved resistance to IGC
by tellurium, but that did not totally resist cracking.
Samples of these alloys were exposed to Te-containing environments for more than 6500 h at 700 C with
very favorable results (see Figure 3). However, cyclic
tests where crack propagation is measured in the
presence of Te will be required to clarify whether
the Nb-modified alloys have adequate resistance to
Te. The mechanism of improved cracking resistance
due to the presence of Nb in the alloy is not known,
but it is hypothesized that Nb forms surface reaction
layers with the Te in preference to its diffusion into
the metal along grain boundaries.
Screening experiments with various alloys elucidated some other possibilities. Nickel-base alloys
containing 23% Cr (Inconel 601) resisted cracking,
7000
6000
1000 h
5000
4000
250 h
3000
2000
1000
2
3
Nb content (%)
Figure 3 Variations of severity of cracking with Nb

content. Samples were exposed for the indicated times to
salt-containing Cr3Te4 and Cr5Te6 at 700 C. Reproduced
from Mc Coy, H. E.; et al. Status of materials development
for molten-salt reactors, ORNL-TM-5920; ORNL: Oak
Ridge, TN, 1978.
whereas alloys containing 15% Cr (Inconel 600, Hastelloy S, and Cr-modified Hastelloy N) cracked as
badly as standard Hastelloy N. However, it is questionable whether the corrosion rate of alloys containing 23% Cr would be acceptable in salt. Type 304
stainless steel and several other iron-base alloys were
observed to resist intergranular embrittlement, but
these alloys also have questionable corrosion resistance in fuel salts. Alloys containing appreciable
quantities of chromium are attacked by molten salts,
mainly by the removal of chromium from hot-leg
sections through reaction with UF4, if present, and
with other oxidizing impurities in the salt. The
removal of chromium is accompanied by the formation of subsurface voids in the metal. The depth of
void formation depends strongly on the operating
temperatures of the system and on the composition
of the salt mixture. If 300 series stainless steels are
exposed to uranium-fueled salt under the same
closed system conditions, the corrosion is manifested
in surface voids of decreased Cr content to a depth of
236
6070 mm at 600650 C. Data on corrosion rates

obtained in experiments with molten Li,Be,Th,U/F
mixtures for 304SS and 316SS at ORNL42 as well as
later at the RRC-Kurchatov Institute19 for the Russianmade austenitic steels 12H18N10T (Fe18% Cr10%
Ni1% Ti0.12% C) and AP-164 (Fe15% Cr24%
Ni1.5% Ti4% W0.08% C) agree well with each
other.
It is possible that a salt can be made adequately
reducing to allow iron-base alloys to be used. This
possibility must be pursued experimentally, because
thermodynamic and kinetic data are not available to
allow analytical determination.
The discoveries that cracking severity was influenced by the oxidation state of the salt and that the
salt could be made sufficiently reducing to prevent
cracking in standard Hastelloy N opened many
doors. Thus, alloys containing Ti could be used to
take advantage of their excellent resistance to irradiation damage if they were protected from cracking by
Te. Even standard Hastelloy N could be used in part
of the system where the neutron flux was very low.
The research toward finding a material for constructing an MSR that has adequate resistance to
irradiation embrittlement and IGC by tellurium has
progressed. ORNL findings suggest very strongly
that an MSR could be constructed of 12%-Nbmodified Hastelloy N and operated very satisfactorily at 650 C.
5.10.3.1.1.2 Progress on NiMo alloy
development at RRC-Kurchatov Institute
In Russia, materials testing for the ThU MSR were

started at the RRC-Kurchatov Institute in 1976.19,20,47
It was substantiated by data accumulated in the
ORNL MSR program on nickel-base alloys for
UF4-containing salts. The Ni-base alloy HN80MT
was chosen as a base. Its composition (in wt%)
is Ni6.9% Cr0.02% C1.6% Ti12.2% Mo2.6%
Nb. The development and optimization of the
HN80MT alloy was envisaged to be performed in
two directions: improvement of alloy resistance to
selective chromium corrosion and increase in alloy
resistance to tellurium intergranular corrosion and
cracking.
About 70 differently alloyed specimens of
HN80MT were tested. Among alloying elements
were W, Nb, Re, V, Al, Mn, and Cu. The main finding
was that alloying by aluminum with a decrease of
titanium to 0.5% revealed significant improvement
in both the corrosion and mechanical properties of
the alloy. Chromium corrosion and intergranular
corrosion reached the minimum value at an aluminum content in the alloy of 2.5%. Irradiation effect
on corrosion activity of fuels was also studied. It was
shown that there was no radiation-induced corrosion
at least up to a power density of 10 W/cm3 in a
molten LiFBeF2ThF4UF4 mixture.
A subsequent radiation study of 13 alloy modifications was conducted. Specimens (in nitrogen atmosphere) were exposed to the reactor neutron field up
to the fluency of 3 1020 neutrons cm2. Mechanical
properties of alloys were studied at temperatures of
20, 400, and 650 C for nonirradiated and irradiated
specimens. The best postirradiation properties were
shown for alloys modified by Ti, Al, and V.
Lastly, corrosion under the stressed condition was
studied. It is known that tensile strain promotes an
opening of intergranular boundaries and thus boosts
intergranular corrosion and creates the prerequisites
for IGC. The studies did not reveal any dependence
of intergranular corrosion on the stress up to the
value 240 MPa, that is, 0.8 of a tensile yield of the
material and 5 times higher than typical stresses in
Li,Be,Th,U/F MSR designs.
The results of the combined investigation of
mechanical, corrosion, and radiation properties of various alloys of HN80MT permitted the RRC-Kurchatov
Institute to suggest the Ti- and Al-modified alloy as an
optimum container material for the MSR design. This
alloy, named HN80MTY (or EK-50), has the composition given in Table 3.
In the thermal convection loop operated with the
molten Li,Be,Th,U/F salt system, the HN80MTY
alloy specimens have shown a maximum corrosion
rate of 6 mm year1 (see Table 5) as for the
HN80MT alloy it was two times lower.20,67 The corrosion was accompanied by selective leaching of
chromium into the molten salt, which was evidenced
by the 10-fold increase in its concentration for 500 h
of exposure. Similar oxidizing conditions, characterized by the same content of Fe and Ni impurities in
the salt, existed in testing a standard Hastelloy
N alloy on the NCL-21A loop (see Table 4) operated
with a molten Li,Be,Th,U/F salt system at ORNL.46
For the NCL-21A loop, the uniform corrosion rate
of Hastelloy N specimens was about 5 mm year1.
However, in the NCL-21A loop, the maximum temperature was somewhat lower (704 C) than in the
RRC-Kurchatov Institute experiments (750 C), and
in addition, fission products, including Te, were not
added into the circuit.
A comparison with corrosion data obtained
at ORNL43,46 indicates that the HN80MT and
Table 5
Summary of Russian loop corrosion tests for fluoride salts
Loop
Salt (mol%)
Specimen material
Tmax ( C)
Solaris
46.5LiF11.5NaF42KF
620
KI C1
KI C2
KI C3
KI F1
KI F2
KI M1
KURS-2
VNIITF
92NaBF48NaF
KI T1
LiFNaFBeF2 + Cr3Te4
12H18N10T
HN80MT
12H18H10T
AP-164
HN80MT
HN80MT
HN80MTY
12H18N10T
12H18N10T
HN80MT
HN80MTY
MONICR
HN80MT
HN80MTY
MONICR
71.7LiF16BeF2
12ThF40.3UF4 + Te
66LiF34BeF2 + UF4
66LiF34BeF2 + UF4
LiFNaFBeF2 + PuF3
DT ( C)
237
Duration (h)
Corrosion rate
(mm year1)
20
3500
630
630
630
750
750
630
750
700
100
100
100
70
70
100
250
100
1000
1000
1000
1000
1000
500
750
1600
700
10
400
50
22
250
50
12
3.0
6.0
20
25
5
5
19
3
3
15
AP-164 alloy with a composition of Fe2225% Ni1416% Cr45% W0.51% Mn1.41.8Ti0.6% Si0.08% C0.035% P and
12H18N10T stainless steel with a composition of Fe1113% Ni1719% Cr2% Mn0.60.8% Ti0.8% Si0.12% C0.035% P.
Source: Novikov, V. M.; Ignatiev, V. V.; Fedulov, V. I.; Cherednikov, V. N. Molten Salt Reactors: Perspectives and Problems;
Energoatomizdat: Moscow, USSR, 1990; Ignatiev, V. V.; Novikov, V. M.; Surenkov, A. I.; Fedulov, V. I. The state of the problem on
materials as applied to molten-salt reactor: Problems and ways of solution, Preprint IAE-5678/11; Institute of Atomic Energy: Moscow,
USSR, 1993.
HN80MTY resistance is higher than that of the

standard Hastelloy N. This conclusion is confirmed by the microphotographs of HN80MT and
HN80MTY alloy specimens after corrosion tests.
Physical metallurgy studies were done on longitudinal metallographic sections of specimens subjected
to tensile tests (see Figures 4 and 5).
Under static conditions at T 600 C, there is
only a slight tendency of HN80MT to IGC, and
corrosion defects are observed along grain boundaries at a depth of 2030 mm. With an increase of
temperature to 750 C, the defect depth increases to
60 mm. Transition to loop tests at T 750 C show
even more expressed IGC (see Figure 4). Massive
defects in the material along the grain boundaries at
full depth and further cracking over boundaries of the
following grains were found. The defect area reached
130 mm. The alloy resistance to IGC was estimated
from a parameter K, which is equal to the product of
the number of cracks on a 1-cm length of a longitudinal section of specimens subjected to tensile strain
multiplied by an average crack depth in micrometers.
The estimated value for the parameter K in these
conditions (ampoule isothermal tests at T 750 C)
amounts to 1300 pc mm cm1. For the HN80MT
alloy, this value is more than 5 times lower than that
of a standard Hastelloy N alloy subjected to similar
testing conditions.66
Therefore, the maximum operating temperature

for HN80MT alloy in a reactor should be reduced
at least to 700 C, and rigorous control of oxidation
reduction potential of the fuel salt is necessary.
A completely different picture was observed in testing HN80MTY alloy specimens. No IGC traces
were found, both in static tests under stress conditions (at 650800 C up to 245 MPa) and in thermal
convection loops up to T 750 C.20,67 The thermal convection tests show that corrosion proceeds
uniformly along the entire grain volume, giving rise
to a small porous layer near the material surface in
contact with the fuel salt at the depth of 1530 mm
(see Figure 5). Thus, choosing effective alloying
additions can solve the problem of IGC for nickel
alloys in fuel salts containing fission products.
The corrosion and other characteristics of the
developed HN80MTY alloy makes it possible to
consider it as a promising structural material for
ThU MSRs with a maximum working temperature
of 750800 C.20
The weldability of the alloy, however, needs
improvement. To suppress crack formation during
welding, the metal penetration regime was set up
and maximum heat removal from the welded joint
was ensured. These measures made it possible to
increase significantly the characteristics of the
welded joints. The manufacturing of a heat exchanger
238
(a)
(b)
(c)
(d)
Figure 4 Microphotographs of the NiMo alloy specimen surface layer (enlargement 100) after 500 h exposure to tellurium
containing melt 71.7LiF16BeF212ThF40.3UF4. (a) HN80MT isothermal tests, Texposure 600 C; (b) HN80MT isothermal
tests, Texposure 750 C; (c) HN80MT nonisothermal tests in loop, Texposure 750 C; (d) standard Hastelloy N isothermal
tests, Texposure 700 C. Reproduced from Ignatiev, V. V.; Novikov, V. M.; Surenkov, A. I.; Fedulov, V. I. The state of the
problem on materials as applied to molten-salt reactor: Problems and ways of solution, Preprint IAE-5678/11; Institute of
Atomic Energy: Moscow, USSR, 1993.
(a)
(b)
Figure 5 Microphotographs of HN80MTY alloy specimens surface layer (enlargement 100) after 500 h exposure to the
tellurium containing melt 71.7LiF16BeF212ThF40.3UF4. (a) Isothermal tests, Texposure 750 C and (b) nonisothermal tests
in loop, Texposure 750 C. Reproduced from Ignatiev, V. V.; Novikov, V. M.; Surenkov, A. I.; Fedulov, V. I. The state of the
problem on materials as applied to molten-salt reactor: Problems and ways of solution, Preprint IAE-5678/11; Institute of
Atomic Energy: Moscow, USSR, 1993.
confirmed once more that the HN80MTY alloy is

technologically effective both in hot and cold process
stages.19
In a recent study, the central focus of the corrosion
studies was the compatibility of Ni-base alloys with a
molten Li,Na,Be/F salt system as applied to the
primary circuit of MOSART fuelled with different
compositions of actinide trifluorides from LWR spent
fuel without UTh support.6870 Prior ORNL
examinations71 of Inconel in natural convection

loops, which circulated molten 24LiF53NaF
23BeF2 and 34LiF49NaF15BeF2 (mol%) mixtures
with an excess of free fluoride ion content, revealed no
evidence of attack in either the hot or cold areas
of the loop. However, a microscopic examination of
specimens removed from the cooler coil did reveal the
presence of a small amount of metallic deposit. These
studies (see Table 5) included (1) compatibility tests
Table 6
Nickelmolybdenum alloys mechanical properties
Alloy
HN80M-VI
HN80MTY (EK-50)
MONICR
239
Specimens in the delivery condition, T 20 C
Specimens after the corrosion tests, T 20 C
s0.2 (kg mm2)
sB (kg mm2)
d (%)
s0.2 (kg mm2)
sB (kg mm2)
d (%)
110.4
110.1
112.7
40.3
39.6
119
121.7
122.3
73.5
70.0
10.9
10.6
9.1
57.2
54.0
50.0
52.5
50.5
75.0
78.5
75.3
103.9
90.0
89.5
39.6
40.3
39.6
38.5
36.3
36.3
120.0
103.0
101.1
76.9
73.4
76.0
67.5
62.5
65.0
28.0
22.4
22.4
56.0
55.0
55.2
53
39
38
between NiMo alloys and molten 15LiF58NaF

27BeF2 (mol%) salt in a natural convection loop
with a measurement of redox potential; (2) the effect
of PuF3 addition in molten 15LiF58NaF27BeF2
(mol%) salt on compatibility with NiMo alloys; and
(3) Te corrosion for molten 15LiF58NaF27BeF2
(mol%) salt and NiMo alloys in stressed and
unloaded conditions with measurement of the redox
potential. Three Hastelloy N-type modified alloys,
particularly HN80M-VI with 1.5% Nb, HN80MTY
with 1% Al, and MONICR68 with about 2% Fe, were
chosen for the study in the corrosion facilities (see
Tables 3 and 6).
Results of a 1200 h loop corrosion experiment69
with online redox potential measurement demonstrated that high-temperature operations with molten
15LiF58NaF27BeF2 (mol%) salt are feasible using
carefully purified molten salts and loop internals.
In the established interval of salt redox potential,
1.251.33 V relative to a Be reference electrode, corrosion is characterized by uniform loss of weight with
low rate from sample surfaces. Under such exposure,
the salt contained less than (in mass %): Ni 0.004;
Fe 0.002; Cr 0.002. Specimens of HN80M-VI and
HN80MTY alloys from the hot leg of the loop
exposed at temperatures from 620 to 695 C showed
a uniform corrosion rate from 2 to 5 mm year1. For
the MONICR alloy, this value was up to 20 mm year1
(see Figure 6).
No significant change in corrosion behavior of
material samples was found in the melt due to the
presence of 0.5 mol% PuF3 addition in 15LiF
58NaF27BeF2 (mol%) salt. Specimens of HN80MVI from the loop exposed during 400 h at 650 C
showed a uniform corrosion rate of about 6 mm year1.
Under such exposure, the salt contained about
(in mass %): Ni 0.008; Fe 0.002; Cr 0.002. No
traces of IGC were found for any specimen after loop
54
51
53
tests, even in the melt with PuF3 addition. Data from

chemical analysis of the specimens surface layer
showed a decrease in chromium content by 1020 mm.
Tellurium IGC testing of the NiMo alloys,69,70
without and under mechanical load (80 MPa), for
the 15LiF58NaF27BeF2 (mol%) melt under
dynamic and static conditions was carried out at
700 C with exposure times of 100, 250, and 400 h at
1.2 V system redox potential. Under stress exposure to
tellurium in the 15LiF58NaF27BeF2 melt, the
depth of cracks for MONICR specimens reached
220 mm (K > 10 000 pC mm cm1). For HN80M-VI
specimens tested without stress, rather low IGC intensity was observed (K 690 pC mm cm1). However,
under stress, the intensity of the HN80M-VI alloy
cracking increased more than twice and the crack
depth reached 125 mm. HN80MTY alloy is the most
resistant to tellurium IGC of the NiMo alloys studied.
The intensity of its cracking under stress is K 880 pC
mm cm1 (twice as low as that of HN80M-VI alloy).
The effect on the resistance to tellurium corrosion
of Nb, Al, Ti, Re, and Mn doping agents added
to the HN80M-type alloy was also studied in the Li,
Na,Be/F facility at the RRC-Kurchatov Institute.70 It
was shown that both Re and Y additions only slightly
increased the alloys resistance to tellurium cracking.
The alloy doped with Nb alone significantly increased
IGC resistance. Addition of Mn gave a significant
increase in alloy resistance to tellurium IGC. Therefore, testing of alloys with various compositions of
doping elements to enhance the alloys resistance to
tellurium IGC should be continued in a thermal
convection loop with long exposure times.
Finally, as can be seen from the considerations
above, new findings in the developments of NiMo
alloys for MSRs with fuel salt temperatures up
to 750 C shift the emphasis from alloys modified
with titanium and rare earths to those modified with
240
9
8
7
6
HN80M-VI
5
4
3
2
1
(a)
100 mm
0
0
10
20
30
40
50
10
20
30
40
50
8
7
6
5
HN80M-VI
4
3
2
1
(b)
60 mm
0
7
6
5
HN80MTY
4
3
2
1
(c)
100 mm
0
10
20
30
40
8
7
6
5
4
MONICR
3
2
1
(d)
100 mm
0
0
10
20
30
40
50
60
Figure 6 Chromium distribution (mass %) versus depth of the surface layer (mm) of specimens after corrosion tests in
the loop: (a) quenched HN80M-VI, Texposure = 690 C; (b) hot deformed HN80M-VI, Texposure = 670 C; (c) quenched
HN80MTY, Texposure = 620 C; and (d) MONICR in the Scoda delivery state, Texposure = 690 C. Reproduced from
Ignatiev, V. V.; et al. Nucl. Technol. 2008, 164(1), 130142.
niobium at ORNL58 and aluminum at the RRCKurchatov Institute.19 Subsequent steps for this
type of metallic materials development must involve
(1) irradiation, corrosion, tellurium exposure, mechanical property, and fabrication tests to finalize the
composition for scale up; (2) procurement of large
commercial heats of the reference alloy; (3) mechanical
property and corrosion tests of at least 10 000 h duration; and (4) development of design methods and rules
needed to design a reactor (breeder or burner) to be
built of the modified alloy.
5.10.3.1.1.3 Alternative approaches
Certainly, some less mature approaches are possible

and could be of interest for new MSR concepts.
For example, NiWCr alloys have been recently proposed by Centre National de la Recherche Scientifique
(CNRS) in France for their high potential to corrosion resistance for very high-temperature operation
(>750 C).5 Temperatures >850 C would require the
use of new solutions such as refractory alloys or
graphite. Included in further evaluation should also
be the assessment of (1) new proposed solvent systems
(e.g., Li,Th/F), (2) increased fuel salt outlet temperatures >750 C, and (3) lower salt redox potentials
from the point of view of establishing potentials that
must be maintained to avoid IGC for Ni-base alloys.
5.10.3.1.2 Graphite for the core
Extensive prior work has demonstrated that graphite

is compatible with molten fluoride salts (these are
fundamental properties and are not particularly
dependent on manufacturing). Much of the experience and data obtained in the gas-cooled reactor
programs is directly applicable to MSRs. In particular, the limited lifetime of graphite resulted from
neutron-induced damage. (See also Chapter 4.10,
Radiation Effects in Graphite).
By the time the MSBR program at ORNL was
cancelled in early 1973, the dimensional changes of
graphite during irradiation had been studied for a
number of years.49,58 These changes depend largely
on the degree of crystalline isotropy, but the volume
changes fall into a rather consistent pattern. There is
first a period of densification during which the volume decreases, and then a period of swelling in which
the volume increases. The first period is of concern
only because of the dimensional changes that occur,
and the second period is of concern because of the
dimensional changes and the formation of cracks.
The formation of cracks would eventually allow salt
to penetrate the graphite. The damage rate increases
241
with increasing temperature, and hence, the graphite

section size should be kept small enough to prevent
temperatures in the graphite from exceeding those in
the salt by a wide margin.
For fast neutron fluences greater than about
3 1022 neutrons cm2 (En > 50 keV), the rate of
graphite expansion becomes quite rapid, and it
appears that this represents an upper limit to acceptable exposure of the graphite (L Pm
200, where
L is the moderator lifetime in full-power years and Pm
is the maximum core power density in W cm3). For
example, in the MSBR design, the maximum power
density is about 70 W cm3 and the useful graphite
life would be about 34 years at full power.16,17
It was further required that the graphite be surfacesealed to prevent penetration of xenon into the graphite. Since replacement of the graphite would require
considerable downtime, there was a strong incentive to
increase the fluence limit of the graphite. A considerable part of the ORNL graphite program was spent in
irradiating commercial graphites and samples of special graphites with potentially improved irradiation
resistance. The approach taken to sealing the graphite
was surface sealing with pyrocarbon. Because of the
neutronic requirements, other substances could not be
introduced in sufficient quantity to seal the surface.
Fission product gases, notably 135Xe, will diffuse into
graphite with some effect on neutron balance (poison
fraction for uncoated graphite is about 0.010.02). It is
desirable, especially for high flux cores, to hold Xe
poisoning to the lowest possible level (poison fraction
of 0.005). This requires graphites of very low permeability, for example, 108 cm2 s1. The pyrolytic sealing
work at ORNL was only partially successful. It was
found that extreme care had to be taken to seal the
material before irradiation. During irradiation, the
injected pyrocarbon actually caused expansion to
begin at lower fluences than those at which it would
occur in the absence of the coating. Thus, the coating
task was faced with a number of challenges.
The most detailed creep data exist on the US and
German graphites for the HTR plant designs.49 But
these graphites, because of their coarse granularity
and large pore size, are unsatisfactory for molten-salt
applications. Fine-grained, isotropic, molded, or isostatically pressed, high-strength graphite suitable for
core support structures (e.g., Carbone USA grade 2020
or Toyo Tanso grade IG-11058 and Russian-made GSP
type graphite19) is available today. Past experience has
also demonstrated techniques for accommodating any
radiation-induced dimensional changes in the graphite
reactor vessel insulation. Development of sealing
242
techniques should continue both with the pulseimpregnation technique and isotropic pyrolytic coatings applied at somewhat higher temperatures.
With relaxed requirements for breeding performance in the new wave of MSR concepts relative
to the MSBR, the requirements for graphite would
be diminished.58 First, the lower gas permeability
requirements mean that graphite damage limits can
be raised. Second, if the salt flow rate through the
core is decreased from the turbulent regime down to
laminar one, the salt film at the graphite surface may
offer sufficient resistance to xenon diffusion so that it
will not be necessary to seal the graphite. Finally, the
peak neutron flux at the graphite location can be
reduced to levels such that the graphite will last for
the lifetime of the reactor. As noted above, the lifetime criterion adopted for the breeder was that the
allowable fluence would be about 3 1022 neutrons
cm2. This was estimated to be the fluence at which
the structure in advanced graphites would contain
sufficient cracks to be permeable to xenon.
Experience has shown that, even at volume changes
of about 10%, the graphite is not cracked but is uniformly dilated. For some nonbreeder devices where
xenon permeability will not be of concern, the limit
will be established by the formation of cracks sufficiently large for salt intrusion. It is likely that current
technology graphites could be used to 3 1022 neutrons cm2 and that improved graphites with a limit of
4 1022 neutrons cm2 could be developed. Also, early
efforts show promise that graphites with improved
dimensional stability can be developed.
Finally, for nonmoderated MSR concepts (e.g.,
MSFR and MOSART) with a graphite reflector,
there is no strong requirement on gas permeability
(108 cm2 s1), but molten salt should be excluded
from the open pore volume (pore structure < 106 m).
The last requirement can be met by currently available
commercial graphite (See also Chapter 4.10, Radiation Effects in Graphite).
5.10.3.1.3 Materials for molten-salt fuel
reprocessing system
For most established MSR concepts, processes

involving (1) removal of uranium from fuel salt by
fluorination and (2) selective extraction of transuranium elements and fission products from fuel salt into
liquid bismuth are considered the most promising
methods available. The material considerations below
are oriented in these directions.
Nickel or nickel-base alloys can be used for the
construction of fluorinators and containment of F2,
UF6, and HF, though these metals would require

protection by a frozen layer of fuel solvent over
areas where contamination of the molten stream by
the otherwise inevitable corrosion products would be
severe. Many years of experience in fabrication and
joining of such alloys have been accumulated17,49 in
the construction of reactors and associated engineering hardware. The corrosion of L nickel (low-carbon
nickel with: 99.36% Ni; 0.02% C; 0.26% Fe; 0.06%
Cu; 0.26% Mn; 0.04% Si; 0.001% S) and its alloys in
the severe environment represented by fluorination
of UF6 from molten salts has been studied in some
detail.72 Most of the data were obtained during operation of two plant-scale fluorinators constructed of
L nickel at temperatures ranging from 540 to 730 C.
A number of corrosion specimens (20 different materials) were located in the fluorinators. Several specimens, including INOR-1, had lower rates of
maximum corrosive attack than L nickel.72,73
Nevertheless, L nickel, protected where necessary
by frozen salt, is the preferred material for the
fluorinationUF6 absorption system since the other
alloys would contribute volatile fluorides of chromium and molybdenum to the gaseous UF6.
Absorption of UF6 in molten salts containing UF4 is
proposed as the initial step in fuel reconstitution for
many ThU MSR concepts. The resulting solution,
containing a significant concentration of UF5, is quite
corrosive. In principle, and perhaps in practice, the
frozen salt protective layer could be used with vessels
of nickel. It has been shown74,75 that gold is a satisfactory container in small-scale experiments, and plans to
use this expensive, but easily fabricable, metal in engineering-scale tests have been described.76
Most of the essential separations required of the
processing plant are accomplished by selectively
extracting species from salt streams into bismuth
lithium alloys or vice versa. Moreover, no satisfactory
alternative to the selective extraction metal transfer
process for removal of rare-earth fission products has
been identified (reductive extraction from moltensalt fluoride mixtures into lithiumbismuth alloys).58
These extractions pose difficult materials problems.
Materials for containment of bismuth and its alloys
are known, as are materials for containment of molten
salts. Unfortunately, the two groups have few common members.
Carbon steels are not really satisfactory long-term
containers for molten fluorides.77,78 Nickel-base alloys
are known17,49 to be inadequate containers for bismuth.
Corrosion studies79,80 showed molybdenum to
resist attack by bismuth and to have no appreciable
mass transfer at 500700 C for periods up to

10 000 h. Moreover, molybdenum is known to have
excellent resistance to molten fluorides.17,49 The external environment could be inert gas, but the problems in fabricating molybdenum are huge.
The resistance of tantalum and its alloys to molten
fluorides has long been questioned, but no definitive
tests had been made when previous surveys were
written.17,49 Further tests are obviously necessary,
but continued satisfactory operation of the Ta16%
W loop with fuel salts must be considered encouraging. Pure tantalum and some of its alloys with
tungsten (in particular, T-111 alloy: 8% W, 2% Hf,
balance Ta) have been shown to be usefully compatible with molten bismuth and bismuthlithium alloys.
Tantalum is easy to fabricate, but the external environment must be a high vacuum.58
Graphite, which has excellent compatibility with
fuel salt, also shows promise for the containment
of bismuth. Compatibility tests to date have shown
no evidence of chemical interaction between graphite and bismuth containing up to 3 wt% (50 at.%)
lithium. However, the largest open pores of most
commercially available polycrystalline graphites
are penetrated to some extent by liquid bismuth.
Capsule tests81 of three commercial graphites (ATJ,
AXF-5QBG, and Graphitite A) were conducted for
500 h at 700 C using both high-purity bismuth and
bismuth3 mass % lithium. Although penetration by
pure bismuth was negligible, the addition of lithium to
the bismuth appeared to increase the depth of permeation and presumably altered the wetting characteristics of the bismuth. Limited penetration of graphite
by bismuth solutions may be tolerable. If not, several
approaches have the potential for decreasing the
extent to which a porous graphite is penetrated
by bismuth and bismuthlithium alloys. Two wellestablished approaches are multiple impregnations
with liquid hydrocarbons, which are then carbonized
and/or graphitized, and pyrocarbon coatings. Graphite
can be adequately protected at the outside with an inert
gas, but it is difficult to fabricate into complex shapes.
As the chemistry of the processing system is engineered further through pilot plants, the precise type
of hardware needed will be better defined. Significant
additional research and development will necessarily
be concerned with detailed tests of material compatibility and studies of welding, brazing, and other joining techniques, as well as joint design. Facilities for
static testing, operation of thermal convection loop
assemblies, and fabrication and operation of forced
convection (pumped) loops will be required, along
243
with sophisticated equipment for welding, brazing,

etc., under carefully controlled atmospheres. Such
facilities have been used routinely in the past and
involve little, if any, additional development.
5.10.4 Advanced High-Temperature

Reactor
When considering materials performance in the
AHTR,82 the materials can be classified into three
main categories: (1) graphite and C/C composites,
(2) low-pressure reactor vessel materials, and
(3) high-temperature metallic components.
The graphite core, reflector and vessel insulation,
and C/C composite core supports and control rods
will operate in a molten-salt environment over a range
of temperatures from 500 to 1100 C or higher (peak
temperature being selected as a trade-off between
reactor thermal inertia, thermal blanket system performance, and material properties). It is anticipated that,
for the AHTR, properly designed and manufactured
C/C composite structures will demonstrate similarly
good properties in the presence of molten fluoride
salts and better mechanical properties.
The reactor vessel materials3 must be capable for
operation at 500 C and may need to withstand
temperature excursions to 800 C for 100 h under
accident conditions. The vessel must demonstrate
adequate strength and creep resistance (long-term
and short-term), good thermal-aging properties,
low-irradiation degradation, fabricability, good corrosion resistance, and the ability to develop and
maintain a high-emissivity surface in air. As previously noted, nickel-base alloys demonstrate good
corrosion resistance to molten salts. Therefore,
ORNL proposed82 that stable, high-strength, hightemperature materials, such as 9Cr1MoV, be
coated with a high-nickel coat for the reactor vessel
application. Should the vessel be required to withstand excessive off normal temperatures, base materials such as 304L, 316L, 347, Alloy 800H, or HT
may be appropriate. In addition, monolithic materials with adequate corrosion resistance to molten
fluoride salts and high-temperature strength may
include Alloy 800H or HT, Hastelloy N, and Haynes
242. Performance of the suggested materials needs to
be evaluated, especially at higher temperatures. Further, the ability to develop and maintain a highemissivity layer on the surface of the vessel exposed
to argon or air must be demonstrated, but this is not
considered a major barrier.
244
High-temperature metallic or composite materials

are needed for use up to 1000 C in the presence of
molten fluoride salts on one side and an insulation
system in contact with air on the other side. Piping
and heat exchangers are examples for the latter conditions. Pumps and other components submerged below
the primary salt pool will need to survive higher temperatures for short times or be replaceable at reasonable expense. The metallic materials used in these
environments must demonstrate adequate strength
(long-term and short-term), good thermal-aging properties, low-irradiation degradation, fabricability, and
good corrosion resistance. Based on material maturity
and the need for high nickel for fluoride corrosion
resistance, stable, high-strength, high-temperature
metallic materials such as Inconel 617, Haynes 230,
Alloy 800H, Hastelloy X or XR, VDM 602CA, and
HP modified with a coating with high-nickel content
could be possible candidates for detailed evaluation.3,26
Should higher temperature alloys be required, Haynes
214, cast Ni-base superalloys (for pumps), and ODS
MA 754 are possible candidates. Recent experience
suggests that, should the oxidation potential of the
salt be made very reducing, it may be possible to
use ODS MA 956 (an iron-base alloy). These monolithic materials will require more testing and data
development. For composite materials, liquid-siliconimpregnated (LSI) composites, with chemical vapor
deposition carbon coatings, may be promising for use
for pumps, piping, and heat exchangers.3 LSI composites have several potentially attractive features, including the ability to maintain nearly full mechanical
strength to temperatures approaching 1400 C, inexpensive and commercially available fabrication materials, and the capability for simple machining and
joining of carboncarbon performs, allowing the fabrication of highly complex component geometries.
As already discussed, corrosion activity of molten
salts is dependent upon the major salt constituents
and impurities in the salt. The coolant salt can be
prepared and maintained in such a way that impurities do not control the corrosion response. It is
expected that coolant salts can be used at significantly higher temperatures than were established in
the MSR design because of the different corrosion
characteristics of a clean salt coolant versus a molten
salt-containing actinides and fission product fluorides. A wider range of material options also exists.
The presence of uranium dissolved in the salt was
always found to accelerate corrosion, and there exist
additional methods to prevent corrosion when uranium is not present in the salt.
The equilibrium level of dissolved chromium has

been measured for fuel salts, but not for coolant
salts.8385 Although information on fuel salts is not
directly applicable to coolants, it is expected that fuel
solvents that experience minimal corrosion would
also be better coolants.26 Review of dissolved chromium levels for various fuel salts again reveals that
the molten 46.5LiF11.5NaF42KF (in mol%) mixture stands somewhat apart from the other salts as it
sustains a higher degree of corrosion. It also appears
that there is some benefit in avoiding a very acidic
(high ZrF4 or BeF2 content) system and that a salt
mixture that has a nearly complete coordination shell
(2:1 ratio of alkali halide to Zr or Be and heavier
alkali salt) has the least potential for supporting
corrosion based on temperature sensitivities. This
approach is a significant oversimplification, as the
identity of the various species is very important. For
example, the saturating species that contain chromium are different for each of these salts.
Although <10% of all corrosion testing was
done with salts that were free of uranium, this
small fraction amounts to a significant body of
work because of the extensive test program carried
out. The results of testing for uranium-free salts
reveals that Hastelloy N (INOR-8), just as it is for
fuel salts (see previous section), is a superior choice
(rather than Inconel or stainless steels) for coolant
salts. The corrosion is so intense and the duration
so short for most Inconel tests that it is hard to make
a judgment about which salt is the least susceptible
to corrosion.
For Hastelloy N loops at temperatures up to
700 C, the corrosion is so minor that it is hard to
sort out corrosion effects due to the salt composition.
Again, a molten 46.5LiF11.5NaF42KF (in mol%)
mixture is among the worst. Some additional Inconel
loop tests86,87 were conducted with special fuel salt
mixtures in which the ZrF4 and BeF2 concentrations
were varied in an attempt to select the best composition. However, these tests were somewhat inconclusive because of the short test duration (500 h) and
impurity effects. Within the resolution of these tests,
the following trends were verified: very basic (FLiNaK) and very acidic (LiFZrF4) salts showed the
worst performance.26
Corrosion tests of Hastelloy N, Hastelloy X,
Haynes-230, Inconel-617, and Incoloy-800H at a
high temperature of 850 C were performed at the
US University of Wisconsin-Madison in a molten
46.5LiF11.5NaF42KF (in mol%) mixture, with
the goal of ranking alloy suitability for the AHTR
core.88 In particular, an attempt was made to simulate

material performance in the corrosion system with a
primary salt coolant, metal reactor vessel, and graphite fuel materials. The isothermal tests were performed for 500 h in sealed graphite crucibles under
an argon cover gas, without any redox measurement
and control strategy. Certainly, graphite crucibles
may accelerate the corrosion process by promoting
the formation of carbide phases on the walls of the
test crucibles, but they did not alter the basic corrosion mechanism. Corrosion was noted to occur predominantly by release of Cr from the alloys, an effect
that was particularly pronounced at the grain boundaries of these alloys. Mass loss due to corrosion generally correlated with the initial Cr content of the
alloys, and was consistent with the Cr content
measured in the salts after corrosion tests. The corrosion attack was more severe for Hastelloy N (6.3%
Cr), where Cr depletion up to depths of about 50 mm
was observed. Hastelloy X (21.3% Cr) exhibited grain
boundary attack up to depths of at least 300 mm below
the surface. Inconel-617 (22.1% Cr) was uniformly
depleted in Cr up to depths of about 100 mm from the
surface and experienced dramatic grain boundary
corrosion throughout the thickness of the sample.
Similar attack was observed for Haynes-230 (22.5%
Cr); however, the surface of Haynes-230 exhibited a
Ni-enriched layer. For Haynes-230, W-rich precipitates were observed at the grain boundaries due to the
relatively high W content of this alloy, demonstrating
that W, like Mo, is resistant to attack from molten
fluoride salt. The fundamental reason why Haynes230 experienced more weight loss than the other
high Cr-containing alloys needs further investigation.
Two Cr-free alloys, Ni-201 and Nb1Zr, were also
tested. Ni-201, a nearly pure Ni alloy with minor
alloying additions, exhibited good resistance to corrosion, whereas Nb1Zr alloy exhibited extensive
corrosion attack.
At various periods at ORNL, control of the
oxidationreduction state of the salt was explored as
a means to minimize corrosion. However, it was not
practical, because strong reductants either reduced
zirconium or uranium in the salt to a metal that
plated on the alloy wall or resulted in some other
undesirable phase segregation. During the MSRE
operation, periodic adjustment of the U(III)/U(IV)
ratio was effective in limiting corrosion in the fuel
circuit. Keiser89 also explored the possibility of using
metallic beryllium to reduce corrosion in stainless
steel containing a LiFBeF2 salt, where the oxidation potential of the salt could be lowered by
245
buffering with metallic beryllium without concerns

for disproportionation of uranium trifluoride; the
corrosion rate was decreased at 650 C from 8 to
2 mm year1.
This treatment was effective only as long as the
metallic beryllium was immersed in the salt. There
was little, if any, buffering capacity in this salt to
maintain the reducing environment throughout the
melt. Del Cul et al.90 have identified and tested candidate agents that could be used as redox buffers to
maintain a reducing environment in the coolant circuit. None of these redox-control strategies has been
developed to the extent that we can rely on them for a
definite salt selection. However, some useful observations can be made in this regard. For a lower temperature system (<750 C), it appears that Hastelloy N is
fully capable of serving as a containment alloy without the need for a sophisticated redox strategy. Even
an alkali fluoride, such as a molten 46.5LiF11.5NaF
42KF (in mol%) mixture, could be suitable. For
temperatures in excess of 750 C and for alloys that
contain more chromium (as most higher temperature
alloys do), it appears that a reducing salt will be
needed to minimize corrosion. Inconel without the
benefit of a reducing environment was found to be
unsuitable for long-term use. Only a mildly reducing environment is possible with a ZrF4-containing
salt, since a strongly reducing redox potential would
reduce ZrF4 itself. Much more reducing systems
can be devised with either LiFNaFKF- or BeF2containing salts. Some very important material compatibility issues will have to be explored in order
to use a highly reducing salt at these higher temperatures because events such as carbide formation and
carburization/decarburization of the alloy (not discussed in the report) become a significant threat.
Should low-chromium/chromium-free alloys or suitable clad systems be devised as a container, these
problems with salt selection will largely disappear.
However, in the absence of this solution, ORNL has
considered two strategies: (1) select a salt that should
support the minimum level of corrosion in the
absence of a highly reducing environment (some
ZrF4 salts, BeF2-containing salts) or (2) select a salt
with a large redox window that can be maintained
in a highly reducing state (LiFNaFKF- or BeF2containing salts). Given the expense and difficulty
of carrying out development work with berylliumcontaining salts, ORNL proposed to explore the
most promising ZrF4 salts without strong reductants
and to explore LiFNaFKF with strong reductants and/or redox buffers.26
246
5.10.5 Liquid-Salt-Cooled Fast

Reactor
There are no metallic components in the reference
MSR core. While Hastelloy N or another nickel-base
alloy is suitable for the reactor vessel, heat exchangers, pumps, main circulation pipes, drain tanks, and
other equipment, it may not be suitable for LSFR incore components (structure and fuel cladding), which
will be subjected to higher temperatures and receive
large fast neutron fluences in the core. The metal incore components are likely to be the primary technical challenge for an LSFR, given the requirements for
higher temperature service, resistance to neutron
radiation damage, and corrosion resistance to liquid
salts. The use of binary metallic materials (either clad
or coated) may be desirable for some applications
(including the reactor vessel), in order to confer
appropriate strength and corrosion resistance.
Generally, practical metal systems are based on
(1) nickel-, (2) iron-, or (3) molybdenum-base alloys.3
The nickel-base alloys for high-temperature service in molten-salt coolants (but not as in-core components) have been evaluated as part of the AHTR
research and development activities (see previous
section). Some of these alloys are known to have
excellent chemical compatibility with molten saltcoolants; however, there is mixed experience with
the irradiation performance of nickel alloys. For
a UK Prototype Fast Reactor experience91,92 with
PE-16 irradiation performance, a nickel alloy (17Cr,
43Ni, 3Mo, 2.5Ti, 34Fe Al, in mass %) was good,
but at lower temperatures than required for LSFRs.
At the same time, many nickel-base super alloys have
poor radiation stability (grain boundary embrittlement). The potential of nickel-base alloys at the
higher temperatures for use in an LSFR core spectrum is not well understood. The strength of many
nickel alloys is a consequence of nickelsilicon precipitates. In irradiation fields, these precipitates can
dissolve, with the silicon migrating to the grain boundaries and causing the alloy to weaken. For these alloys,
it may be feasible to overcome this difficulty by the
development of oxide-dispersion-system (ODS) nickel
alloys. However, only very limited work has been done
on these systems.
The iron-base alloys have good radiation resistance. The primary LSFR concern associated with
iron alloys is their long-term high-temperature corrosion resistance. Some of these alloys are known to
have excellent chemical compatibility with moltensalt coolants.
For example, static corrosion tests87 were performed recently in molten 46.5LiF11.5NaF42KF
and 66LiF34BeF2 (in mol%) mixtures at 500 and
600 C for 1000 h. The purpose was to study the
corrosion characteristics of reduced-activation ferritic steels, JLF-1 (8.92Cr2W) in the molten salts.
The concentration of HF in the melts was measured
by the slurry pH titration method before and after
exposure. The HF concentration determined the
fluoridation potential. The corrosion was mainly
caused by dissolution of iron and chromium in the
melts due to fluoridation and/or electrochemical
corrosion. The corrosion depth of the specimens at
600 C, which was obtained from the weight losses,
was 0.637 mm in 66LiF34BeF2 melt and 6.73 mm in
46.5LiF11.5NaF42KF melt. The corrosion rate of
SS304 and SS316L steels in 66LiF34BeF2 melt after
1000 h exposure at 600 C was estimated as 10.6 and
5.4 mm year1, respectively.
Russian experience20 with molten-salt fluorides
and AP-164 iron-base alloy (1416 Cr, 2225 Ni,
0.51 Mn, 45 W, 1.41.8 Ti, 0.08 C, in mass %)
was good, but also at lower temperatures (630 C)
than required for LSFRs (700750 C).
To overcome the temperature limitations on ironbase systems, there has been significant developmental work on ODS iron alloys for fast reactors.93 These
alloys contain rare-earth oxides, such as yttrium
oxide, that enable iron alloys to maintain strength at
up to 80% of their melting point versus 50% for
traditional alloys. The limited corrosion testing of
iron-base alloys in molten fluoride salt coolants indicates the potential for corrosion-resistant iron-base
systems. However, more corrosion testing will be
required to expand upper operating temperature to
700750 C before gaining more confidence in such
an approach.
Molybdenum alloys are compatible with molten
salts and have good thermophysical properties.94
Molybdenum has a very high melting point
(2600 C), high thermal conductivity, and moderate
thermal neutron cross-section (2.65 barns). However,
isotopically separated molybdenum,94 with its very
low nuclear cross-section, is an option. There are
significant challenges with molybdenum alloys:
(1) such alloys are difficult to weld, (2) the fracture
toughness is somewhat low with concerns about radiation embrittlement, and (3) high-temperature oxidizing conditions must be avoided because MoO3 has
a melting temperature of 795 C. The potential oxidation should not be a significant concern for an
LSFR because the molten-salt mixture (such as
sodium) will be subjected to chemically reducing

conditions. The fracture toughness is a primary concern at lower temperatures. Radiation damage is
temperature dependent and is minimized by operating at higher temperatures in the range from 650 to
1000 C. Molybdenum-base alloys may ultimately
allow the construction of a very high-temperature
LSFR and is a class of materials where higher temperatures improve material properties.
5.10.6 Secondary Circuit Coolants

In the secondary circuits of an MSR, AHTR, LSFR,
or SFR, the main difference compared to the primary
one for the container metal will be the absence of
fission products and uranium in the coolant salt and
the much lower neutron fluences. This material must
have moderate oxidation resistance and must resist
corrosion by salt not containing fission products or
uranium. The corrosion for molten fluoride salts was
discussed in detail in previous sections. Very little
corrosion data are available for nuclear application of
molten-salt mixtures, including nitrate, chloride, and
fluoroborate salts, than for molten fluoride salts,
especially for temperatures above 600 C.
A nitrate mixture of 60NaN0340KNO3 (in
mass %) has been proposed for use in the intermediate circuit of SFRs and LSFRs.2 This molten-salt
mixture is attractive for such applications because
of its high heat capacity, its low reactivity in the
event of a leak to air or steam, and the low operating
pressures required for its use. However, the feasibility
of such a system depends partly on the compatibility
of the salt with candidate structural alloys. Alloy 800
and types 304, 304L, and 316SS were exposed in a
natural convection loop filled with molten NaNO3
KNO3 salt in the temperature range 375600 C for
more than 4500 h.7 The weight change data for the
alloys indicated that (1) the metal in the oxide film
constituted most of the metal loss; (2) the corrosion
rate, in general, increased with temperature; and
(3) although the greatest metal loss corresponded
to a penetration rate of 25 mm year1, the rate was
<13 mm year1 in most cases. Spallation had a significant effect on metal loss at intermediate temperatures
in the type 304L stainless steel loop. Metallographic
examinations showed no evidence of intergranular
attack. The exposure resulted in the growth of thin
oxide films on significant cold-leg deposits. Weight
change data further confirmed the absence of thermal
gradient mass transport processes in these draw salt
247
systems. Raising the maximum temperature of the

type 316SS loop from 595 to 620 C dramatically
increased the corrosion rate, and it appears that
600 C may be the limiting temperature for use of
such alloys in draw salt.
Material corrosion resistance for the SFR intermediate circuit containing 56LiCl44LiOH (in mol%)
was studied in Russia.20 The corrosion facility was
constructed according to a three-loop scheme. The
first circuit was filled with sodium to a maximum
temperature of 530 C. The second (intermediate)
circuit was filled with a molten 56LiCl44LiOH
mixture, which was heated from sodium to a maximum temperature of 490 C. The last circuit with a
steam generator was cooled down to 430 C. The loop
structural material was stainless steel 10H18N10T,
with the exception of the sodium-salt heat exchanger
and steam generator, which were made of a perlite
10H2M steel. Specimens of 10H2M (Fe2% Cr1%
Mo0.1% C), 10H18N10T, H9MFB (Fe9% Cr1%
Mo1% V1% Nb), 08H14MF (Fe14% Cr1%
Mo1% V0.08% C), 10H14GMFB (Fe14%
Cr1% Mn1% Mo1% V1% Nb), and
10H14N5MF (Fe14% Cr5% Ni1% Mo1% V)
steels for corrosion tests were inserted correspondingly in the hot and cold legs of the loops. The
specimen in the molten-salt loop was held for a little
over 2000 h. The highest corrosion resistance was
displayed by steels 10H18N10T and 10H14GFB,
and the least by 10H2M. The 10H18N10T steel
uniform corrosion rate in the molten 56LiCl
44LiOH mixture was 50 mm year1. The metallographic study also determined that 10H18N10T
steel corrosion had an intergranular character (crack
depth up to 60 mm year1). However, it should be
noted here that according to chemical analysis data,
the initial salt composition contained about 1% H2O.
Also, corrosion product deposits were found in some
local sections of the molten-salt loop.
For the purpose of comparison, the most relevant
corrosion results for chloride salts are displayed in
Table 7.95 These results do not conform to any
expected or predictable trends. For example, the
effect of chromium content in the alloy does not
seem to be an important factor, and the effect of
temperature is not clear. Unexpected variability in
the tests very likely reflects variation in the purity of
the starting materials and the degree to which impurities were excluded from the loop during operation.
The corrosion rates are rather high for these salts at a
relatively low temperature (550 C). These rates
are similar to those experienced with fluoride salts
248
Table 7
Loopa

Summary of Brookhaven loop corrosion tests for chloride salts
Loop material
%CrNiMo in Fe alloy
Duration (h)
Tests with LiClKCl eutectic salt

TCL-F
347SS
17.51.40.2
5500
TCL-L1
410SS
12.40.20.1
2200
TCL-L3
2.25Cr1Mo
2.2501
697
Tests with 30NaCl20KCl50MgCl2 eutectic salt (mol%)
TCL-L5
347SS
17.511.40.2
2467
TCL-L6
410SS
12.40.20.1
3971
FCL-M1
347SS
17.511.40.2
1034
FCL-M2
347SS
17.511.40.2
656
Tmax ( C)
DT ( C)
Corrosion rate (mm year1)
575
570
550
155
160
150
12
50
Highb
500
494
520
515
45
42
0
0
93
79
31
256
TCL refers to thermal convection loop, FCL refers to a forced convection loop.
No specimen corrosion depth was reported, but salt analysis showed 0.11% iron.
Source: Susskind, H.; et al. Corrosion studies for a fused salt-liquid metal extraction process for the liquid metal fuel reactor, BNL-585;
Brookhaven National Laboratory: Brookhaven, NY, 1960
b
Table 8
Summary of Hastelloy N corrosion loops with
8NaF92NaBF4 salt at ORNL
Loop
Duration
(h)
Tmax
( C)
DT
( C)
Corrosion rate
(mm year1)
NCL-13A
NCL-14
NCL-17
NCL-20
FCL-1
FCL-2
30.627
39.202
24.865
19.928
17.000
5.300
607
607
607
688
621
621
125
150
100
250
167
167
16
13
24
24
29
23
Source: Bamberger, C. E.; Baes, C. F. Corrosion of Hastelloy

N by fluoroborate melts, ORNL-4832; ORNL: Oak Ridge, TN,
1973; pp 4445.
in contact with stainless steels and Inconel at

800 C and are much higher than those experienced with Hastelloy N in contact with fluoride
salts at temperatures as high as 815 C.
The corrosion database for fluoroborates is shown
in Table 8.45 Improvement in fluoroborate salt purity
during the MSBR program was responsible for a
steadily decreasing level of corrosion in tests. For
NaFNaBF4 secondary coolant, ORNL data45 in
thermal corrosion loops containing Hastelloy
N specimens lie in the interval of 520 mm year1
and are determined mostly by the degree of salt
purification. These data are in good agreement with
later RRC-Kurchatov Institute corrosion studies20 for
Russian nickel-base alloy of the HN80MT type (about
1015 mm year1 at 600 C). The ORNL experience
reveals that the coolant fluoroborate salt absorbs moisture quite readily with attendant generalized corrosion.
On occasions when leaks developed, the corrosion rate
had increased and then decreased as the impurities
were exhausted. During these periods of high corrosion, all components of the alloy were removed uniformly from the hot leg and deposited in the cold leg.
Crystals of Na3CrF6 deposited in the cold regions as its
solubility was exceeded.
In summing up the results of work on secondary
circuit coolants, it should be emphasized that, among
the presently known high-temperature energy carriers with operating temperatures ranging from 300
to 550 C, the most promising for practical utilization
is nitratenitrite molten-salt mixtures. As for the
range of higher operating temperatures >700 C,
there are some alternatives with different maturity.
The database exists for fluoride-containing tests in
the 800900 C temperature range with both Inconel
and Hastelloy N (INOR-8) alloys. No experience
exists with loop corrosion tests using chlorides or
fluoroborates at temperatures approaching the levels
anticipated in the loop that transports heat from the
AHTR or VHTR nuclear plant to the hydrogen
production plant. There is a need to demonstrate
and recommend an improved method for purification
of chloride and fluoroborate salts to be used in corrosion tests.26,34 This new method should become a
purification standard to be used in conjunction with
corrosion tests. High-temperature corrosion tests
with properly purified chloride salts should be conducted to confirm the possibility of using chloride
and fluoroborate salts in the loop that will transport
heat from the AHTR or VHTR nuclear plant to the
hydrogen production plant. These tests should
include both batch exposures and loop tests and will
probably also require the innovative use of redox
buffers to minimize corrosion.26,34
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5.11
Material Performance in Helium-Cooled Systems
R. Wright and J. Wright

Idaho National Laboratory, Idaho Falls, ID, USA
C. Cabet
Commissariat a lEnergie Atomique, Gif-sur-Yvette, France
5.11.1
Introduction
252
5.11.2
5.11.3
5.11.3.1
5.11.3.2
5.11.3.3
5.11.3.4
5.11.3.5
5.11.3.6
5.11.3.7
5.11.3.8
5.11.4
5.11.4.1
5.11.4.2
5.11.4.3
5.11.4.4
5.11.4.5
5.11.5
5.11.5.1
5.11.5.2
5.11.5.3
5.11.6
5.11.7
5.11.8
5.11.9
5.11.10
References
Experience with VHTR Systems

Comparison of IHX Concepts
Shell-and-Tube
Plate and Fin
Etched Plate
Microchannel Heat Exchangers
Plate-Stamped Heat Exchanger
Foam IHX
Capillary IHX
Ceramic IHX
Heat Exchanger Alloys
Regulatory Issues
Alloy 617 (52Ni22Cr13Co9Mo)
Alloy 230 (57Ni22Cr14W2MoLa)
Alloy 800H (42Fe33Ni21Cr)
Alloy X (47Ni22Cr9Mo18Fe)
Welding
Base Metal Preparation and Filler Metal Selection
Preheating, Interpass Temperatures, and Postweld Heat Treatment
Nontraditional Joining Methods
Control Rod Materials
Core Barrel Materials
Environmental Effects of VHTR Atmospheres on Materials
Aging Effects
Summary
252
254
254
255
255
256
256
257
257
257
257
259
259
262
263
264
264
265
265
265
266
269
269
273
275
276
Abbreviations
AGCNR
AVR
DLOC
GE
GMAW
GTAW
HE
HTGRs
HTR-10
Advanced gas-cooled nuclear reactor

Arbeitsgemeinschaft Versuchsreaktor
Depressurized loss of coolant
General Electric
Gas-metal-arc welding
Gas-tungsten-arc welding
Heat exchanger
High-temperature gas reactors
High-temperature reactor-10MWth
in China
HTTR
IHX
INL
NGNP
ODIN
ORNL
PBMR
PCHE
PCS
High-temperature engineering test

reactor in Japan
Intermediate heat exchanger
Next generation nuclear plant
Online Data & Information Network
Pebble bed modular reactor
Printed circuit heat exchanger, Heatrics
Division Ltd.
Power conversion system
251
252
PFHE
PSHE
RCS
RCSS
RSS
SMAW
THTR
VHTR
Plate and fin heat exchanger

Plate stamped heat exchanger
Reactivity control system
Reactor control and shutdown system
Reserve shutdown system
Shielded metal arc welding
Thorium Hochtemperatur Reaktor
Very high-temperature reactor
5.11.1 Introduction
Over the past decade, there has been renewed interest in very high-temperature reactor (VHTR) technology. This type of reactor is of interest because
of a number of unique characteristics, including passive safety, electricity production on a more modest
scale compared to light water plants that might be
more compatible with the electrical distribution system in developing countries, and very high outlet
temperature that can be used for process heat or
hydrogen production. The relative value of electricity production or process heat applications varies
considerably with world economic conditions. Currently, it appears that steam for process heat and
hydrogen production will drive development of this
technology rather than electricity production.
There are currently two operating VHTR prototypes, the high-temperature engineering test reactor
(HTTR) in Japan and the high-temperature reactor
(HTR-10) in China. The HTTR is a 30 MWt (megawatts thermal output) prismatic core reactor and the
HTR-10 is a 10 MWt pebble bed prototype reactor.
Both the operating reactors are designed to investigate
electricity production with the VHTR technology;
however, each program has parallel activities to
develop process heat and hydrogen production as well.
The challenges for high-temperature materials are
not significantly different for either prismatic or pebble
bed reactor designs. Interest in specific applications for
VHTR technology is evolving rapidly. It appears that
the most significant immediate interest is in a reactor
with an outlet temperature on the order of 750 C with
a steam generator for either electricity generation or
process heat. This technology would use a relatively
mature conventional steam generator technology and
is expected to present lower technical risk. Higher
outlet temperatures using a heat exchanger between
the primary helium coolant and a secondary gas are
viewed to be higher risk development projects that
offer the opportunity for outlet temperatures from
850 to 950 C for hydrogen production by thermochemical processes or higher temperature process
heat for industrial applications. The material issues
associated with reactor internals are not affected significantly by the reactor outlet temperature; however,
heat exchangers operating at the higher outlet temperatures represent significantly different issues compared to steam generators. The focus of this chapter is
on higher outlet temperature systems because of the
development challenges.
The next generation nuclear plant (NGNP) being
developed in the United States is one particular
VHTR concept that is under very active development
and is typical of the development around the world.
This reactor is being developed to produce hydrogen
as well as electricity. Conceptual designs call for a gascooled reactor with an outlet temperature greater than
the 850 C required to efficiently operate the hydrogen
generation plant, with a maximum of 950 C. While the
design concepts are not yet final, it is highly probable
that helium will be the primary coolant in the reactor.
The primary material in the core will be graphite, and
the prime candidates for high-temperature metallic
components are the nickel-based alloys Alloy 617 or
Alloy 230. An artists representation of one concept
for the reactor and power conversion vessel and the
associated hydrogen generation plants is shown in
Figure 1. In this representation, a heat exchanger
carries most of the reactor thermal output to a secondary circuit that powers a turbine for electricity generation. An additional heat exchanger takes 10% of the
thermal energy of the reactor and diverts it as process
heat to the hydrogen production plant.
The most critical metallic component in the
VHTR system is the intermediate heat exchanger
(IHX). This heat exchanger will operate at a reactor
outlet temperature of up to 950 C. In addition, the
reactor system is intended to have a license period of
60 years. The combination of very high-temperature
operation and long duration of service restricts material choices for the heat exchanger to a small number
of coarse-grained solid-solution strengthened alloys
that provide stability and creep resistance and have
high chromium content for environmental resistance.
5.11.2 Experience with VHTR

Systems
Very early in the development of nuclear power for
electricity generation or process heat, the concept of an
inert gas-cooled, high-temperature reactor was explored.
253
Power
conversion unit
Intercooler
Generator
Turbine
Low-pressure
compressor
Primary
heat rejection
High-pressure
compressor
Recuperator
Commercial
power
Blower
Power for
electrolysis
Pump
Heat
exchanger
Pebble-bed or
prismatic reactor
Blower
Heat
exchanger
Hydrogen production
(electrolysis)
Hydrogen
Hydrogen production
(thermochemical)
Hydrogen
Heat
exchanger
Figure 1 An artists conception of a very high-temperature gas-cooled reactor and associated hydrogen production plants.
Table 1
Design characteristics of VHTRs that have been built and operated
Country of origin
Thermal power MWt

Net electric power MWe
Maximum core outlet temp ( C)
Helium pressure MPa
Steam temp ( C)
Reactor type
Vessel material
Date of operation
Dragon
AVR
Peach bottom
Ft. St. Vrain
THTR-300
HTTR
OECD/Britain
Germany
USA
USA
Germany
Japan
21.5
750
2.0
Sleeve
Steel
19641975
46
13
950
1.1
505
Pebble
Steel
1966
115
40
725
2.25
538
Sleeve
Steel
1967
842
330
775
4.8
538
Block
PCRVa
19791989
750
300
750
3.9
530
Pebble
PCRV
1985
30
10
950
4
Prism
Steel
1997
a
Prestressed concrete reactor vessel.
Source: Simon, R. A.; Capp, P. D. Operating experience with the dragon high temperature reactor experiment. In Proceedings of the
Conference on High Temperature Reactors, Petten, NL, Apr 2224, 2002; pp 16.
Burnette, R. D.; Baldwin, N. L. Specialists Meeting on Coolant Chemistry, Plate-Out and Decontamination in Gas Cooled Reactors,
Juelich, FRG, Dec 1980; International Atomic Energy Agency, 1980; pp 132137.
Shaw, E. N. History of the Dragon Project Europes Nuclear Power Experiment; Pergamon: New York, 1983.
Baumer, B.; et al. AVR Experimental High-Temperature Reactor; 21 Years of Successful Operation for a Future Energy Technology;
Association of German Engineers (VDI), The Society for Energy Technologies: Dusseldorf, Germany, 1990.
Baumer, R.; Kalinowski, I. Energy 1991, 16(1/2), 5970.
Brey, H. L. Energy 1991, 16(1/2), 4758.
Fuller, C. H. Design Requirements, Operation and Maintenance of Gas-Cooled Reactors, San Diego, CA, Sept 2123, 1988;
International Atomic Energy Agency, 1989; pp 5561.
The Peach Bottom reactor in the United States and

the European Dragon project were among the first
to seriously address the technical issues associated
with high-temperature environmental interaction
between the cooling gas and metallic components.13
Proposals for a VHTR with an outlet temperature of
1000 C or above were put forward in the late 1970s.
The Arbeitsgemeinschaft Versuchsreaktor (AVR) was

the first experimental pebble bed reactor. A commercial demonstration scale pebble bed, the Thorium
Hochtemperatur Reaktor (THTR), was developed
based on AVR experience. A summary of important
design characteristics for gas-cooled VHTRs that
have been operated to date are given in Table 1.17
254
The HTTR in Japan is the only one of the reactors

listed in the table that is still in operation. The HTR-10
is not included in the table since there is no extensive
operating experience with this reactor as yet.
Operating experience with these reactors has
shown that the primary helium coolant tends to contain H2O, H2, N2 as well as carbon-containing compounds CO, CO2, and CH4 at concentrations of a few
parts per million. Impurities are introduced through
adsorption on the fuel, leaks into the coolant, and
lubricants from components like the helium circulators. In the reactors that are currently under consideration, the gas pressure is typically between 5 and
7 MPa. The coolant is circulated at high velocity,
reaching velocities over 100 m s1 in some designs.
5.11.3 Comparison of IHX Concepts

The IHX design for the VHTR will be influenced
by a number of interrelated considerations, including
the required separation distance between the reactor
and the hydrogen production or other process heat
plant, the heat losses from the intermediate loop piping, the operating pressure, the working fluid in the
secondary loop, and the target efficiency of the hydrogen or process heat plant. The required separation
distance will affect the intermediate loop piping size,
the intermediate loop pumping requirements, and the
piping heat losses to the environment. The intermediate loop pressure is critical; a low pressure will produce
a high pressure differential between the primary and
secondary sides of the IHX and high stress on the IHX.
A high intermediate loop pressure will produce a high
pressure differential across the intermediate loop pipe
walls and within the hydrogen production or process
heat equipment. Pressure drops within the IHX affect
the pumping power requirements, which also depend
on the intermediate loop working fluid, and the fluid
temperature and pressure, and will have an effect on
the overall VHTR cycle efficiency.
The IHX may be arranged in parallel or in series
with the VHTR power conversion system (PCS). In a
serial arrangement, the total primary system flow
(reactor outlet gas) passes through the IHX. The
IHX receives gas of the highest possible temperature
for delivery to the hydrogen production process (with
slightly cooler gas going to the PCS), and must be
large enough to handle the full primary flow.
A parallel configuration splits the reactor outlet gas
flow, with only a portion entering the IHX for the
hydrogen or process heat plant, and the remainder of
primary flow going to a direct cycle power generation

turbine. This results in the smallest possible IHX and
the highest overall electrical power efficiency but
lower process heat efficiency because of the cooler
gas reaching that process.
Specific IHX designs under consideration include
countercurrent tube and shell, plate and fin, involute
heat exchangers, microchannel heat exchangers, and
the printed circuit heat exchanger (PCHE). The
design has a significant influence on the required
material properties. Tube-and-shell designs have the
advantage of technological maturity, use heavy gauge
materials, and are fabricated using conventional fusion
welding methods. For the most simple tube-and-shell
configuration, it has been estimated that 13 tons of
high-temperature alloy is required per megawatt of
heat transfer capability; helical designs can reduce
this value to about 1.2 tons MW1. Compact heat
exchanger designs have the potential for greater heat
transfer efficiency; it is estimated that some of these
designs will require only 0.2 tons of alloy per MW. The
compact designs are much less technologically mature
and increase the demands on material performance.
Some compact designs have wall thicknesses of less
that 1mm which places a premium on corrosion resistance and have significant stress concentrations that
will lead to increased demand for creep resistance.
In addition, several of these design concepts require
diffusion bonding of multiple sheets of material or
brazing in complex geometries. Neither of these joining methods has been used yet in nuclear applications,
and nondestructive inspection methods have not been
well developed.
5.11.3.1
Shell-and-Tube
A shell-and-tube heat exchanger is the most common

type of heat exchanger. It consists of a number of
tubes (often finned) placed inside a volume (shell).
One of the fluids runs through the tubes while the
second fluid runs across and along the tubes to be
heated. In one variation of this concept, the heat
transport fluid will flow on the shell side, allowing
the tubes to contain the catalysts necessary for hydrogen production. In the simple configurations, the tube
axis is parallel to that of the shell. The VHTR IHXproposed design features the tubes arranged in a
helical configuration. This type of arrangement
increases efficiency because of increased surface
area and reduces the size, providing the potential to
decrease the cost of materials. Tube-and-shell heat
exchangers represent relatively mature technology
that has been widely commercialized in both nuclear

and fossil energy systems. A helical design was extensively tested for the AVR reactor program and a
similar system is in use in the HTTR in Japan.
5.11.3.2
Plate and Fin
The plate and fin heat exchanger (PFHE) transfers

heat between two fluids by directing flow through
baffles so that the fluids are separated by metal
plates with very large surface areas. The fluids spread
out over the plate, which facilitates the fastest possible transfer of heat. This design has a major advantage
over a conventional heat exchanger because the size
of the heat exchanger is less for a comparable heat

transfer capability. However, the candidate heat
exchanger materials have relatively low thermal conductivities and will reduce the efficiency of a finned
structure. Brazing is typically used to join the fins to
the plate. Brazed plate heat exchangers are used in
many industrial applications, although usually at low
or even cryogenic temperatures. Although brazed
products have been developed for high-temperature
aerospace applications, the strength and creep
properties of brazed joints in an IHX for a hightemperature reactor are of great concern.
The unit cell heat exchanger is a typical modular
plate-fin design that is being developed by Brayton
Energy. An example is shown in Figure 2. Many of
these individual unit cells would be grouped into
larger heat exchanger assemblies. Integration of the
modules within the vessel and with the interfacing
piping is critical. Offset fin plate heat exchangers
have very large heat transfer area density and effective countercurrent flow.
5.11.3.3
(a)
(b)
Figure 2 Unit cell heat exchanger (a) primary side plate,
(b) the unit cell showing countercurrent flow.
255
Etched Plate
Etched plate heat exchangers are diffusion-bonded,

highly compact heat exchangers that can achieve a
thermal effectiveness of over 98% in a single unit.
Compact heat exchangers are four to six times smaller
and lighter than conventional shell-and-tube heat
exchangers of the equivalent heat transfer capability
(Figure 3). The small size gives the compact diffusionbonded heat exchangers significant benefits over conventional heat exchangers across a range of industries.
They are well established in the oil production, petrochemical, and refining industries. In addition, they
are suitable for a range of corrosive and high-purity
Figure 3 The diffusion-bonded heat exchanger in the

foreground undertakes the same thermal duty, at the same
pressure drop, as the stack of three shell-and-tube
exchangers behind.
256
Hot channel
Cold channel
Figure 4 Printed circuit heat exchanger configuration for the model.
streams and are particularly advantageous when

space is limited and weight is critical.
The most widely commercialized etched plate
heat exchanger is a PCHE developed by Heatric
Division of Meggitt (UK) Ltd. PCHE consists of
metal plates on the surface of which millimeter-scale
semicircular fluid-flow channels are photochemically
milled, using a process analogous to that used for the
manufacture of electronic printed circuit boards.
The plates are then stacked and diffusion-bonded
together to fabricate a heat exchanger core shown
schematically in Figure 4. Heatric reports pressure
capability in excess of 70 MPa and the ability to
withstand temperatures ranging up to 900 C.
Note that the channels are straight in this schematic, but in reality they have a zigzag configuration.
Flow distributors can be integrated into plates or
welded outside the core, depending on the design.
The channel diameter, plate thickness, channel
angles, and other attributes can be varied, so each
PCHE is custom-built to fit a specified task. Channel
dimensions are generally between 3 and 0.2 mm and
the thickness of the web of material left after milling
is typically less than 1 mm.8 The current fabrication
limits are 1.5 m 0.6 m plates and 0.6 m stack height.
The diffusion-bonded blocks made from several hundred individual sheets are modular and multiple
blocks can be welded together to form larger units.
5.11.3.4
Microchannel Heat Exchangers
Microchannel heat exchangers, produced, for example, by Velocys, also feature a compact design similar
to the etched plate design; however, the manufacturing
process is somewhat different. They are constructed
from diffusion-bonded corrugated sheets rather than
30
Figure 5 Plate-stamped heat exchanger concept.
etched plates. The layers of corrugated sheet form

many small-diameter channels that result in a high
surface area/volume ratio and a high heat transfer
coefficient.
5.11.3.5
Plate-Stamped Heat Exchanger
The plate-stamped heat exchanger (PSHE) concept

consists of a set of modules, each being composed of a
stacking of plates stamped with corrugated channels.
The plates are stacked in such a way as to cross the
channels of two consecutive plates and therefore to
allow the different channels to communicate through
the width of the plate as shown on the left in the
figure. A general view of a plate is shown in Figure 5.
Assembly of the plates into an IHX module is
accomplished by welding only on the edges of the
plates. No joining is performed in the active part of
the plates, which gives the module relatively good
flexibility. Therefore, this concept is thought to
accommodate the thermal stresses better than the
other concepts of plate IHXs. The location of the
welded joints is also favorable to inspection, even if
257
this remains a difficult question. The joining processes which seem to be the most relevant are laser
or electron beam welding due to the capability to
perform narrow-gap joints and to avoid the overlapping of the welds of two consecutive plates. It should
also be noted that the thickness of the PSHE plates
is the largest among the metallic plate types IHX
(1.5 mm), which means that it is the most favorable
concept with respect to corrosion life. These reasons
suggest that the PSHE concept may be the most
promising among the plate IHXs.
reaches very high values, which increases the complexity of manufacturing, notably as assembly by
narrow gap welding is required. Demonstration of
the elements necessary for successful implementation of the technology is mainly based on technological feasibility tests like demonstration of individual
tube to tube-plate welds by laser techniques. The
results confirm the feasibility for limited thickness of
the plate (a small mock-up is shown in Figure 7).
5.11.3.6
The development of IHXs made of ceramics is still at

the research stage. Ceramic heat exchangers under
development are either tubular or plate IHXs (mostly
PFHE for the ceramic plate IHXs). Tube-and-shell heat
exchangers based on SiC composite tubes have been
developed for fossil energy applications for example.
Joining the fiber-reinforced composite tubes to tube
sheets and accommodating thermal expansion are
the dominant technical challenges. Their resistance to
aggressive environment is remarkable and they can
operate at very high temperatures, >1000 C. Small
monolithic compact designs have been developed
from silicon carbide and silicon nitride through conventional ceramic forming and firing routes. In addition to technical issues, the cost of ceramic tubes of
sufficient size for a VHTR IHX remains problematic.
Table 2 provides a summary-level comparison of
the significant attributes of the different IHX concept
alternatives.
Foam IHX
The foam IHX concept is based on stacking plates

separated by metallic foam. The barrier between the
fluids is constituted by the separated plates and the
fluids flow through the foam (see Figure 6). It is a
new technology for heat exchanger application for
which very high efficiency has been claimed. Several
concerns have been identified regarding this type of
IHX concept. The pressure losses induced by the
foam are particularly high. Loss of small fragments
of the foam is hardly avoidable and the geometry of
the foam leads to an increased risk of clogging by
graphite dust.
5.11.3.7
Capillary IHX
A concept with thread tubes between two tube-plates

with external shell including bellows has been investigated. The diameter of the tubes is 23 mm. This kind
of heat exchangers is currently being developed on an
industrial scale. The small size of the tubes allows a
sharp reduction in size and mass, but some difficulties
arise at the same time, including the concern that
the vibration risk is increased so that the supporting
system needs to be very robust. The number of tubes
Figure 6 Foam heat exchanger concept.
5.11.3.8
Ceramic IHX
5.11.4 Heat Exchanger Alloys

The desire for higher temperature operation resulted
in the evolution of the materials under consideration,
from stainless steels to iron-based high-temperature
258
Figure 7 Capillary heat exchanger mock-up.
Table 2
Comparison of IHX concept alternatives
PCHE
PFHE
PSHE
Tubular IHX
Maturity
Stress behavior
Sensitivity to
corrosion
Compactness
Numerous developments
in conventional industry
High stress levels. 5 years

lifetime seems very challenging
High stress levels. 5 years
lifetime seems very challenging
Challenging but best stress
accommodation among
the plate IHXs
Limit of state of the art
Sensitive
26 MW m3
Very sensitive
24 MW m3
Sensitive
35 MW m3
Better than plates

but still sensitive
Very sensitive (loss
of fragments risk)
Very sensitive
0.4 MW m3
Foam IHX
Industrial components in
operation
R&D
No results
Capillary IHX
Industrial developments
No results
Ceramic IHX
R&D
Difficult design because of

fragile behavior
alloys to nickel-based alloys (see Chapter 2.08, Nickel

Alloys: Properties and Characteristics). An extensive
German program in the 1980s carried out exhaustive
studies of the corrosion behavior of the iron-based
Alloy 800H for control rods and nickel-based Alloy 617
for structural applications.912 The Japanese HTTR
program extensively studied Alloy X and developed a
variation known as XR with improved properties for
some applications, while retaining Alloy 800H for the
control rods.13 Compositions of these candidate alloys
are given in Table 3.1316 Based on creep resistance
above 850 C, the leading candidate alloys for VHTRs
are Alloy 617 and Alloy 230.
A common characteristic of the alloys that have
been put in service in high-temperature gas-cooled
Resistant
Comparable to
other plate IHXs
Better than
classical tubular
IHX
Comparable to
other plate IHXs
reactors is that they rely primarily on the formation

of a tenacious chromia scale for long-term protection
from environmental interaction with the gas-cooling
environment.9,10,12,17 The alloys are also primarily
solid-solution strengthened with carbides on the
grain boundaries to stabilize the microstructure and
enhance the creep resistance. Sustaining such a protective surface oxide requires sufficient oxygen partial pressure. The primary coolant gas of choice for
VHTRs is helium. Although the helium is nominally
pure and thus considered to be inert, there are inevitably impurities at the parts per million by volume (ppm)
levels in the coolant in operating high-temperature
reactors. Although at low levels, the impurities can
significantly affect the performance of materials,
259
Table 3
Compositions of potential high-temperature alloys for VHTR (compositions in wt%)
Alloy
Ni
Fe
Cr
Co
Mo
Al
Alloy 617
UNS N06617
Alloy 230
UNS N06230
Alloy 800H
UNS N08810
Alloy X
UNS N06002
44.5
2024
1015
810
0.81.5
Bal
2024
13
0.20.5
3035
39.5
1923
Bal
1720
20.523
810
0.1
0.6
0.050.15 1
1315
0.150.6
0.52.5
Ti
0.21
Si
Mn
1
0.050.15 0.250.75 0.31

0.150.6
0.050.1
0.03
0.050.15 <1
<1
Source: Incoloy Alloy 800H & 800HT, product sheet, Special Metals, 2004.
Inconel 230, UNS N06230, product sheet, Special Metals, 2004.
Inconel 617, UNS N06617, product sheet, Special Metals, 2005.
Tanaka, R.; Kondo, T. Nucl. Technol. 1984, 66(1), 7587.
depending on the chemistry of the particular alloy,

the concentration of impurities, and the temperature
at which the alloy can be oxidized, carburized, or
decarburized. Several reviews of the behavior of
metallic alloys for control rods, core internals, and
heat exchangers in the reactor helium environment
are available.912,17
Regardless of the IHX design, material selection
for this component is critical. The material must be
available in the appropriate product forms both
plate and sheet, weldable and suitable for use at
800 C or above. The majority of materials research
and development programs in support of hightemperature gas reactors (HTGRs) were conducted
from the 1960s to the early 1980s. The thrust of these
programs was to develop a database on materials for
application in steam-cycle and process-nuclear-heatbased HTGRs. Less work has been done on materials
with emphasis on direct and/or indirect gas-turbinebased HTGRs. The available material property data
were reviewed in detail, and an assessment of relevant factors was made including thermal expansion,
thermal conductivity, tensile, creep, fatigue, creep
fatigue, and toughness properties for the candidate
alloys. Thermal aging effects on the mechanical
properties and performance of the alloys in helium
containing a wide range of impurity concentrations
are also considered.17 The assessment includes four
primary candidate alloys for the IHX: Alloy 617,
Alloy 230, Alloy 800H, and Alloy X.
5.11.4.1
Regulatory Issues
The IHX will form part of the pressure boundary for

the VHTR and material selection and design will be
subject to regulatory requirements. In the United
States, the design will be guided by Section III of
the ASME Boiler and Pressure Vessel (B&PV) Code.

This section specifies materials and design data for
components in nuclear systems. Subsection NH of
the Code, which specifies materials and design parameters for materials that will undergo inelastic deformation, includes only a very few materials. The
temperature limits for Subsection NH Code materials,
other than bolting, at 300 000 h are listed in Table 4.
The maximum temperatures at which fatigue curves
are provided are also listed. Note that of the materials
under consideration for VHTR service, only Alloy
800H is currently contained in the appropriate section of the ASME Code and the service temperature
is limited to 760 C. Any VHTR design that has an
intended IHX service above this temperature will
require extension of the Code to include additional
materials, or at a minimum, extension of the use of
Alloy 800H to higher temperatures. Other regulatory
systems are in use internationally; however, it is generally true that additional materials and expanded
databases are required before a new VHTR design
can be finalized and licensed.
5.11.4.2
Alloy 617 (52Ni22Cr13Co9Mo)
Alloy 617, also designated as Inconel 617, UNS

N06617, or W. Nr. 2.4663a, was initially developed
for high-temperature applications above 800 C. It is
often considered for use in aircraft and land-based
gas turbines, chemical manufacturing components,
metallurgical processing facilities, and power generation structures. The alloy was also considered and
investigated for the HTGR programs in the United
States and Germany in the late 1970s and early 1980s.
The high Ni and Cr contents provide the alloy
with high resistance to a variety of reducing and
oxidizing environments. In addition, the Al also
260
forms the intermetallic compound g0 -(Ni3Al) over a

range of temperatures, which results in precipitation
strengthening on top of the solid-solution strengthening imparted by the Co and Mo. Strengthening is
also derived from M23C6, M6C, Ti(C, N), and other
precipitates when in appropriate sizes, distributions,
and volume fractions.
Table 4
Materials specified in NH for elevated temperature service in nuclear applications
NH code materials
(other than bolting)
304 stainless steels

(UNS S30400,
S30409)
316 stainless steel
(UNS S31600,
S31609)
Alloy 800H
(UNS N08810)
2 1/4Cr 1Mo steel,
annealed condition
(UNS K21590)
Grade 91 steel
(UNS K90901)c
Maximum
temperature ( C)
For stress allowables
S0, Smt, St, Sr up to
300 000 ha
For
fatigue
curves
816
704
816
704
760
760
593b
593
649
538
The primary stress limits are very low at 300 000 h and the
maximum temperature limit.
b
Temperatures up to 649 C (1200 F) are allowed up to 1000 h.
c
The specifications for Grade 91 steel covered by subsection
NH are SA-182 (forgings), SA-213 (small tube), SA-335
(small pipe), and SA-387 (plate). The forging size for SA-182 is not
to exceed 4540 kg.
Table 5
Investigator
Observations and predictions of which precipitates

form in Alloy 617 at given temperature ranges have not
been consistent. A comprehensive review of the precipitates in Alloy 617 has been performed by Ren.18,19
Additional reviews can be found in Natesan et al.20
However, it is clear from the reviews that the kinetics
of the precipitation and coarsening processes are
important in determining the effects of aging on
properties. The g0 intermetallic is generally too fine
to be observed in optical microscopy.
Other phases that have been identified include
CrMo(C, N) and TiN,21 M12C and a possible Laves
phase,22 and a Ni2(MoCr).23 A summary of observations is given in Table 5. The apparent trend is that
in the temperature range of interest to the VHTR
IHX, precipitates may form at initial exposure and
the alloy may become stronger, but most of the precipitates will be dissolved after long-term exposure,
and the alloy will depend on solid-solution strengthening in the long run. The most recent information
on precipitation in Alloy 617 upon aging is shown in
the TTT diagram in Figure 8. The influence of
aging on the mechanical properties of the alloys
under consideration for IHX applications is discussed
in the section on environmental effects.
The grain size also plays an important role in
the strength of the alloy. For general applications, a
grain size of 45 mm or coarser is typically preferred,
but it has been shown that creep strength increases
with increasing grain size, so microstructures of
100200 mm grain size are often produced. A tradeoff exists, however, when fatigue is an issue, since
finer grain sizes are preferred for fatigue resistance.
In addition, for compact IHX, the thin sheet form
Prediction and observations of second-phase precipitates in Alloy 617

M23C6
M6C
g0
Stable
Form
wt < 5% persist to
Thermocalc
prediction
T 800 C
T 780 C
T 650 C
(ORNL)
Observation in material aged for 10 000 h and less
T 1093 C
Not observed
Small wt% persist to
Mankins21
and
T 760 C
Kimball24
1000 C
1000 C
Not reported
Kihara25
Observed
Observed
5501000 C
Kirchhofer22
Observation in material aged for much longer than 10 000 h at 482871 C
Observed
Observed
Observed at 482, 538, &
Wu23
also
593 C, not at 704 C
for 43 000 h and
observed
longer, nor 870 C
eta-MC
after long time
Ti(C,N)
wt >10% 600
800 C
Not reported
Not observed
Not observed
Not observed
Not observed
Not reported
4001000 C
Not observed
TiN observed
261
1100
Temperature (C)
1000
Limited
formation
900
Ti (C, N) + M6C + M23C6 +
800
Fine M4C + y M23C6 + start
700
start extended
end
600
500
Ti (C, N) + M4C
400
0.1
Ti (C, N) + M4C+ M20C4

10
100
Time (h)
1000
10 000
100 000
Ti(C, N) + Coarse M6C + M23C6 +
Ti (C, N) + M4C4 + M4C + 5
Ti (C, N) + M4C + Coarse/Fine M6C +
Ti (C, N) + M4C4 + M4C + 5
Ti (C, N) + M23C4 + M6 + + Ni2/(Mo,Cr)

Figure 8 Time-temperature-transformation (T-T-T) diagram for precipitation of phases in Alloy 617 upon aging.
restricts development of large grain size. Whether the

grains will significantly coarsen after the dissolution
of certain grain boundary precipitates at long-term
exposure is not clear.
The existing mechanical property database for
Alloy 617 is extensive (Table 6). This alloy has adequate creep strength at temperatures above 870 C,
good cyclic oxidation and carburization resistance,
and good weldability. It also has lower thermal
expansion than most austenitic stainless steels and
high thermal conductivity relative to the other candidates. It retains toughness after long-time exposure
at elevated temperatures and does not form intermetallic or Laves phases that can cause embrittlement.
Preliminary testing described later indicates that
Alloy 617 has the best carburization resistance of
the four alloys.
During early development, Alloy 617 was systematically studied by Huntington Alloys, Inc. for
applications in gas turbines, nitric acid production
catalyst-grids, heat-treating baskets, Mo refinement
reduction boats, etc. When Alloy 617 was considered
for the HTGR, it was extensively investigated
by Huntington, Oak Ridge National Laboratory
(ORNL), and General Electric (GE). The Huntington
data were used to develop ASME B&PV Code qualification, including the 1980s draft Code Case for the
HTGR and applications covered by (nonnuclear)
Section I and Section VIII Division 1. Alloy 617 is
not currently qualified for use in ASME Code

Section III, although it is allowed in Section I and
Section VIII, Division 1 (nonnuclear service). Efforts
to gain the approval from the ASME Code committees
for nuclear service were stopped when interest in
VHTR technology waned in the 1990s.
Both the ORNL-HTGR and GE-HTGR studies
generated data from Alloy 617 that had been aged
and/or tested in simulated HTGR helium. The
helium impurities were the same as those considered
for the VHTR system but the concentrations were
different. Unfortunately, only processed data still
exist; all original test curves needed for certain modeling efforts are irretrievable. Alloy 617 was also
extensively investigated in Germany for its HTGR
and other programs. The data generated were collected in the Online Data & Information Network
(ODIN). Original test curves, if not all, are stored in
the ODIN. However, the strain measurements of creep
test curves were not all conducted with fine resolution
and may not all be ideal for constitutive equation
development. The aging effects on Alloy 617 are summarized in Ren and Swindeman.18 The development
in modeling creep behavior of Alloy 617 is summarized in Swindeman et al.24
It is believed that creepfatigue will be the most
significant failure mechanism for materials in the
IHX. Creepfatigue damage results from cyclic loads
superimposed on materials subjected to temperatures
262
Table 6
Summary of testing done on Alloy 617
Research organization
Number of heats
Number of samples
Test type
Temperature ( C)
Huntington alloys
13 1 wire
ORNLa
4 plate 1 wire
GEa
1 plate 1 bar
Germany
Not specified
Honeywell aerospace
Gen IV programb
Not specified
Not specified
179
249
73
51
25
1
36
7
40
302
1947
29
261
Tensile
Creep
Tensile
Creep
Charpy
Tensile after creep
Creep
Creepfatigue
Fatigue
Tensile
Creep
Creep crack growth
Low cycle fatigue
Not specified
Creepfatigue
251093
5931093
24871
593871
24
RT after 871
7501100
950
850, 950
RT-1000
5001000
7001000
<5001000
80
800, 1000
Some tests exposed to HTGR environment.

Air, pure helium and vacuum environments.
5.11.4.3
Alloy 230 (57Ni22Cr14W2MoLa)
Alloy 230, also designated as Haynes 230, UNS

N06230, or W. Nr. 2.4733, is a newer alloy than
Alloy 617. In addition to outstanding resistance to
oxidizing environments, Alloy 230 has good weldability and fabricability. It also has a lower thermal
expansion coefficient than Alloy 617; it appears that
thermal expansion has an inverse correlation with Ni
content. Alloy 230 has a higher tensile strength than
Alloy 617 up to 800 C, but above that the difference is
105
Cycles to failure (Nf)
and loads that will induce creep damage under monotonic loading. Recent creepfatigue data for Alloy 617
and Alloy 230 are shown in Figures 9 and 10 for
tests that involved fully reversed cyclic loading at
total strain ranges of 0.3% and 1% with varying
hold time during the tensile portion of the cycle at
800 and 1000 C. The plots show the reduction in
cycles to failure with increasing tensile hold time
under creep loading conditions. It can be seen that
in general, increased hold time results in decreased
cycles to failure. At 800 C, the two alloys have
similar behavior; however, at 1000 C, Alloy 617
appears to have somewhat higher cycles to failure
compared to Alloy 230. A limited number of tests
have been carried out on specimens that contain
weldments and it has been found that the cycles to
failure in specimens containing a fusion weld is
reduced. In these specimens, the cracking is typically in the weld metal and not in the heat-affected
zone or at the weldbase metal interface.
Alloy 617 0.3% total strain

Alloy 617CCA 0.3% total strain
104
1000
No hold
100
10
100
1000
Hold time (s)

Figure 9 Effect of hold time on cycles to failure in
creepfatigue at 800 C.
insignificant. It appears that Alloy 617 has slightly

better creep properties than Alloy 230. Alloy 230
has a better thermal fatigue crack initiation resistance
but a worse thermal cycling resistance compared to
Alloy 617.
The Ni base and high Cr content impart resistance
to high-temperature corrosion in various environments, and oxidation resistance is further enhanced
by the microaddition of the rare earth element La.
Compared to Alloy 617, Alloy 230 has a high W
concentration which replaces much of the Co in
105
Cycles to failure (Nf)
No hold

Alloy 6171.0% total strain
104
103
102
10
100
1000
Hold time (s)
10 000
Figure 10 Effect of hold time on cycles to failure in

creepfatigue at 1000 C.
Alloy 617. The W and Mo in conjunction with C are

largely responsible for the strength of the alloy, and its
relatively high B content in comparison to that in Alloy
617 can be controlled to achieve optimized creep resistance. Usually, B acts as an electron donor; it can affect
the grain boundary energy and help improve ductility.
In Ni-based alloys, B also segregates to grain boundaries and helps to slow grain boundary diffusion, thus
reducing the creep process. On the other hand, excess
boron in a neutron field could also lead to embrittlement due to transmuted He, although irradiation is not
a factor for IHX applications.
In the solution-annealed condition in which this
alloy is typically supplied, the grain size is typically
>45 mm with large carbide precipitates rich in W,
presumably of the M6C type. After aging, Alloy 230
typically exhibits M6C and M23C6 precipitates. After
aging for 1000 h at 850 C, very small carbide precipitates rich in Cr and M23C6 were observed along
the grain boundaries. No grain coarsening was
observed.25 Creep strength is believed to be brought
about by solid-solution strengthening, low stacking
fault energy, and precipitation of M23C6 carbides on
glide dislocations.26,27 However, a negative impact
of M23C6 on room temperature ductility was also
reported. After aging at 871 C for 8000 h, the room
temperature tensile elongation of Alloy 230 decreased from 50% to 35%, with a precipitation of
M23C6 observed in microstructural examination, but
an additional 8000 h of aging did not further decrease
263
ductility.26 Significant microstructural changes were

also observed after thermal aging in air for 10 000 h
at temperatures ranging from 750 to 1050 C. After
the 750 C aging, coarser intergranular precipitation
of M23C6 and coarse and blocky intra- and intergranular precipitates of M6C were observed. After
the 8501050 C aging, the M6C carbides were irregular in shape. After aging at 1050 C, the secondary
intragranular M23C6 appeared to have dissolved.
A decrease in toughness and ductility coincided with
the appearance of the intragranular M23C6 and reached
a minimum after the aging at 850 C. The toughness
and ductility recovered after the aging at 1050 C.28
There is less characterization of Alloy 230 compared to Alloy 617. The major known large-scale
study was tensile and creep tests by Haynes International. Creep times ranged from 15.3 to 28 391 h. Like
Alloy 617, Alloy 230 is not currently qualified for use
in ASME Code Section III, although it is allowed in
Section VIII, Division 1 (for nonnuclear service). At
present, the database for Alloy 230 is significantly
smaller than that for Alloy 617 and a much larger
effort is required to develop an Alloy 230 Code Case
for elevated temperature application. Some recent
data on environmental effects of exposure to prototypical VHTR chemistries are given in the following
sections and creepfatigue properties are included
in Figures 9 and 10.
5.11.4.4
Alloy 800H (42Fe33Ni21Cr)
This alloy is the only iron-based alloy under consideration, although it has a solid-solution strengthened
austenitic structure like the other three alloys. Upon
aging, precipitates can form and somewhat reduce
the tensile and creep ductility. Alloy 800H has the
lowest creep rupture strength and the lowest resistance to oxidation of the four alloys. There is an
additional variant of this alloy, 800HT, that has a
composition similar to that of 800H, but has an additional specification for coarse grain size. The majority
of material that is currently available in this alloy
series is Alloy 800HT, which also meets the specification for Alloy 800H.
Among the four candidate materials, Alloy 800H
is the only one that is Code qualified for use in
nuclear systems, but only for temperatures up to
760 C and a maximum service time of 300 000 h.
Alloy 800H was the primary high-temperature alloy
used in the German HTGR programs and an enormous amount of data were obtained. However, only
very limited data from the German HTGR programs
264
are currently available on the mechanical properties

of this alloy beyond 800 C, especially in impure
helium environments.
5.11.5 Welding
All of the solid-solution alloys that have been mentioned are readily welded using conventional fusion
welding methods. Alloys 617 and 230 are described in
more detail later as prototypical of these materials.
Alloy 617 has excellent weldability. Alloy 617 filler
metal is used for gas-tungsten-arc (GTAW) and gasmetal-arc welding (GMAW). The composition of the
filler metal matches that of the base metal, and deposited weld metal is comparable to the wrought alloy in
strength and corrosion resistance.29 Alloy 230 is also
readily welded by GTAW and GMAW. Shielded
metal-arc welding (SMAW) and resistance welding
techniques can also be used. Submerged-arc welding
Stress (MPa)
Alloy X has the best oxidation resistance of the four

alloys, although its carburization resistance is the
worst. Above 700 C, Alloy X can form embrittling
phases that result in property degradation. The creep
rupture strength is not as good as Alloy 617 or 230.
The limitations of this alloy will be similar to the
draft code case for Alloy 617 in terms of grain size,
product form, and limitations on service time.
A limited database exists for Alloy X for conditions typical of a VHTR, but the high-temperature
scaling in Hastelloy X has been less than optimal. As a
result, a modified version, Alloy XR, has been developed in Japan; however, the United States has little
access to Alloy XR material, either for evaluation or
for ASME Code qualification. Japanese are currently
using Alloy XR in a heat exchanger in the HTTR at
temperatures of 850950 C. The material is codified
in Japan for nuclear use, which would likely accelerate code acceptance in ASME. An extensive environmental database and HTGR experience exist.
However, the database may be limited to large grain
material, similar to the Alloy 617 draft code case.
Also, similar to the Alloy 617 draft code case, Alloy
XR may have issues with weldments that need to be
addressed. It is uncertain if this alloy is readily available as a commercial product.
Figures 1114 compare the creep rupture
strength, oxidation behavior, carburization behavior,
and allowable stress for the four alloys, respectively.
Alloy X
60
Alloy 230
50
Alloy 617
40
30
20
10
0
1
1000
100
Time to rupture (h)
10
10 000
100 000
Figure 11 Creep rupture strength at 962 C in air.
Thickness (mm)
Alloy X (47Ni22Cr9Mo18Fe)
Alloy 800H
70
20
10
0
10
20
30
40
50
60
70
80
90
Alloy 800H
Alloy 617
Oxide scale
Alloy 230
Affected zone
Alloy X
Internal oxide
Figure 12 Schematic representation of isothermal

oxidation behavior after 800 h exposure at 950 C in helium
environment.
24
Normalized weight gain
5.11.4.5
80
Alloy X
19
Alloy 230
Alloy 617
14
9
4
1
200
400
600
800
1000
1200
Exposure time (h)

Figure 13 Mass change as a function of time in H25.5%
CH44.5% CO2 carburizing environment at 1000 C.
is not recommended, as this process is characterized

by high heat input to the base metal and slow cooling
of the weld. These factors can increase weld restraint
and promote cracking. The as-welded properties of
these alloys are given in Table 7.30 The welds exhibit
room temperature strength that matches or is slightly
265
better than the base metal, but a considerable decrease

in ductility is observed at elevated temperatures, as
shown in Table 8.
alloy, HASTELLOY S alloy, or HASTELLOY W

alloy welding products may all be considered, depending upon the particular case.29,30
5.11.5.1 Base Metal Preparation and Filler

Metal Selection
5.11.5.2 Preheating, Interpass

Temperatures, and Postweld Heat
Treatment
Prior to any welding operation, the welding surface

and adjacent regions should be thoroughly cleaned
with an appropriate solvent. All greases, oils, corrosion products, and other foreign matter should be
completely removed. It is preferable, but not necessary, that the alloy be in the solution-annealed condition when welded.30
Alloys 617 and 230-W (AWS A5.14,
ERNiCrWMo-1) filler wire are recommended for
joining Alloy 617 and 230, respectively, by GTAW
or GMAW. The filler metals are not specifically
designed for nuclear application. For dissimilar
metal joining of Alloy 230 to nickel-, cobalt-, or
iron-based materials, 230-W filler wire, Alloy 556
Preheat is not required, generally room temperature

(typical shop conditions) is adequate. Interpass temperature should be maintained below 93 C. Auxiliary
cooling methods may be used between weld passes, as
needed, providing that such methods do not introduce contaminants. Postweld heat treatment is not
generally required either. Table 9 shows the nominal
welding parameters based on welding conditions
used in the Haynes International laboratories and
should serve as a guide for performing typical
GTAW and GMAW operations on Alloy 230. All
processes used 230-W filler wire.30
5.11.5.3
Maximum allowable stress (MPa)
250
Alloy X
Alloy 230
200
Alloy 617
Alloy 800H
150
100
50
0
0
200
400
600
800
1000
Temperature ( C)
Figure 14 Allowable stress for heat exchanger materials
for plate, sheet, and strip forms from the ASME boiler and
pressure vessel code Section VIII.
Table 7
Nontraditional Joining Methods
As noted earlier in the description of IHX designs,

several of the compact heat exchanger design concepts will require the joining of sheet product to be
either diffusion bonding or brazing. Diffusion bonding of these alloys is relatively well developed
because of applications in aerospace systems that
require this fabrication method. The etch plate compact design fabricated from austenitic stainless steel
has been commercialized for petrochemical applications, and limited diffusion bonding studies have
been completed using Alloy 617. Characterization
of diffusion-bonded stacks of sheet indicates that
mechanical properties comparable to base metal can
be achieved at room temperature. The details of diffusion bonding parameters are considered proprietary
by the IHX vendors, and it is not clear whether
temperatures sufficiently high to cause carbide dissolution and/or grain growth is a matter of concern.
Room-temperature tensile properties of joints in as-welded condition
Alloy
Specimen
Yield strength (0.2%

offset) (MPa)
Tensile strength
(MPa)
Elongation
(%)
Reduction of area
(%)
61729
GMAWa
GTAWb
GMAWc
510
542
490
761
823
785
43.3
37.3
48.2
42.0
38.3
23030
a
Alloy Filler Metal 617. Average of ten tests.

Alloy Filler Metal 617. Average of 17 tests.
Alloy 230-W filler wire.
b
c
266
Table 8
Tensile properties of 230 base and weld metals

23 C
GMAW deposit weld metal

Cold-rolled and 1232 C solution annealed (sheet)
Hot-rolled and 1232 C solution annealed (plate)
Vacuum investment castings (as-cast)
538 C
871 C
UTS
YS
EL
UTS
YS
EL
UTS
YS
EL
785
838
840
615
490
422
375
325
48.2
47.2
47.7
37.8
610
699
690
450
435
303
251
230
34.8
53.7
54.6
38.2
310
308
315
285
275
234
242
185
45.4
75.0
99.5
19.0
Source: HAYNESW 230W Alloy. Haynes International, Inc. Publication H-3000H, 2004.
Table 9
Weld parameters for Alloy 230
Welding method
GMAW
Configuration (mm)
Thickness > 2.3 1.1

dia. wire
Technique
Stringer bead or
slight weave
100130a
1821
4.34.8
12.719.1
203356
Torch, 50
Ar-25% He
Current (A)
Voltage (V)
Feed rate (m min1)
Stick-out (mm)
Travel speed (mm min1)
Gas flow (l min1)
Gas
GTAW
Auto
Manual
Square butt joints 1.0/1.6/3.2

thick, 1.6 electrode with
45 included shape
No filler metal added
50/80/120b
8.0/8.5/9.5
V or U groove, >3.6 thick, 3.6 dia.

wire, 3.6 electrode with 30
included shape
Stringer bead interpass
T < 100 C
120 root, 140150 fillb
1114
10/12/12
Shield, 14.2 backing, 4.7
Argon
102152
Shield, 14.216.5 backup, 4.7
Argon
DCEP, torch flow CFPH.

DCEN.
Source: HaynesW 230W Alloy, Haynes International High-Temperature Alloys.
b
Very little information on brazing these alloys is

available. A general concern is that low melting
point braze materials could result in poor elevated
temperature properties in structures fabricated by
these methods.
5.11.6 Control Rod Materials

The pebble bed modular reactor (PBMR) is the most
complete recent design for a VHTR. The reactor was
designed to operate at about 400 MWt and primarily
to produce electricity. Recent changes in the global
economic climate have caused reconsideration of the
design for a VHTR in South Africa; however, the
analysis that went into the design and selection of
materials for the control rods is illustrative of the
most recent analysis of these issues. A schematic of
the PBMR core is shown in Figure 15. The design
outlet gas temperature for the PBMR was 900 C; the
core was designed to be 11m high and 3.7 m in
diameter, and the annulus filled with about 452 000

60-mm-diameter fuel pebbles.31
The PBMR builds on the German experience of
the AVR and THTR; however, it will use a direct
cycle to produce power rather than a steam generator,
and it will have an annular core configuration with a
solid graphite central reflector. The annular core
produces several advantages: it shifts the peak power
radially outward, thus enabling significantly higher
output; it enhances the fuel safety margin; and, by
increasing the neutron flux in the outer graphite
reflector, it increases the effectiveness of the control
and shutdown systems.32
The reactor control and shutdown system (RCSS)
has two components: the reactivity control system
(RCS) and the reserve shutdown system (RSS). The
RCS consists of 12 control rods and 12 shutdown rods,
located in the outer reflector.33 They are evenly spaced
around the core and at a radial distance of about 70mm
from the inner surface of the reflector (see Figure 16).34
During normal operation, the control rods, which
Reactor pressure
Core barrel
Top
Side
Cold gas riser

Center
Pebble bed
Bottom
Inlet
Inl
Hot gas
Outlet
Figure 15 Schematic of the pebble bed modular reactor

(PBMR) annular pebble bed reactor. Reproduced from
Kriel, W. Material selection: High-temperature metallic
materials. Slides, Sept 2122, 2005.
Core barrel
267
penetrate a maximum distance of 1.5m into the core,34

are used for minor reactivity adjustments to keep the
reactor critical, provide reactivity compensation for
xenon poisoning effects during load following effects,35
and allow for some excess reactivity so that the reactor
may continue operation for some time if no fuel is being
loaded.36 They are also used for hot shutdown purposes.33 The reactor power is actually adjusted by regulating the mass flow rate of the gas inside the primary
circuit rather than by adjusting the control rods.32,33
During scram, the additional 12 shutdown rods are
lowered to the bottom of the active core. In the event
of a loss of electrical power, insertion of the rods is by
gravity. The first set of control rods will drop, and later
the shutdown rods will drop, should the need arise.
The RSS consists of eight storage containers of
10-mm-diameter small absorber spheres containing
B4C that can be fed by gravity into eight channels in the
central reflector. The RSS serves as both the secondary
shutdown system and the cold shutdown system. It
must be activated in addition to the RCSS to bring
the PBMR to a cold shutdown condition (100 C).
The control rod design is similar to that of previous metal control rods. A schematic is shown in
Figure 17. A number of annular B4C rings are
encased between two tubes of Alloy 800H, to form a
section about a meter long. One unique feature is that
Reactor pressure
vessel
Side reflector
barrel
Reactor
inlet pipes
Annular core
Reactor
outlet pipe
Center reflector
Gas riser
channels
Small absorber
sphere channels
Control rod
Figure 16 Top view of the PBMR core, showing the location of the control rod channels, fuel pebbles, small absorber
sphere channels, and other features. Reproduced from PBMR. Data and boundary conditions to be used in VSOP, TINTE,
and MCNP PBMR 400 MW ( Th) reactor models.
268
Control rod drive

mechanism
RCS chain
Control rod segment
Control rod link
Secondary shock absorber
Figure 17 Schematic of the control rod assembly in the

PBMR. Reproduced from Broom, N.; Smit, K. PBMR Design
Methodology. Slides, Oak Ridge, TN, 12th April 2005.
the inner tube is much thinner than the outer tube.

These sections are mechanically linked to form an
articulated control rod several meters long. One difference from past designs (e.g., the AVR) is that the
control rod is suspended from the drive mechanism
by a chain, rather than a cable. A secondary shock
absorber is in place in the channel below the control
rod to protect it and the core structure in the event of
a chain failure. Additional shock absorbers within the
drive mechanism dampen the impact load on the
control rod drives during scram.33 A control rod
guide tube (not shown in Figure 16) connects the
control rod drive mechanism to the core structure to
guide the control rod into the core.37
During normal operation, the temperature of the
control rods is estimated to be from about 650 to
700 C,38,39 and the temperature resulting from a
depressurized loss of coolant (DLOC) event is estimated to be only 850 C.39 The end-of-life fast fluence
is reported as 2 1022 (E > 0.1 MeV),38 and the thermal
fluence is reported as 5 1021 n cm2.39 The secondary

shock absorbers have an operating temperature of
900 C; during DLOC, they can be subjected to temperatures of up to 1100 C for short periods. Under
these conditions, the use of Alloy 800H was justified
by the PBMR program because the high-temperature
strength and creep resistance are sufficiently qualified for long-term normal operation at 700 C, and
limited operation above 850 C under abnormal
events can be tolerated according to available data.
The response of Alloy 800H to neutron irradiation
at the temperatures expected in the control rod sleeves
is not well characterized. The PBMR design notes that
the irradiation response has been characterized to high
levels of fast fluence at lower temperatures and Alloy
800H control rods have had extensive qualification and
service in previous German VHTR programs. Limited
data from older VHTR programs on irradiation effects
in Alloy 800H at temperatures above 600 C suggest
that helium embrittlement from (n, a) reactions associated with thermal neutrons is the predominant
degradation mechanism. Recent work has examined
property changes associated with irradiation to
1.45 dpa at temperatures of 580 and 660 C.40,41 Significant strengthening was observed along with a sharp
decrease in ductility. Material irradiated at 660 C and
subsequently tensile tested at 700 C showed tensile
elongation of less than 0.5%. The mechanisms of
embrittlement are not yet completely clear and irradiation experiments to higher fluence at higher temperature will likely be required to examine this issue.
The PBMR design includes specialized equipment
to remove and replace the control rods, as well as
storage for used control rods. The RCSS will be
inspected every 6 years during the scheduled maintenance outage, and repaired as necessary. These
outages are planned to last 3050 days, depending on
the other maintenance scheduled, with the exception
of a 180-day shutdown after 24 years to replace the
core reflector.34,42
Eventually, it is hoped that a VHTR similar in
design to the PBMR reactor can run with an outlet
temperature of 1000 C or even higher. In this case,
carbon fiber-reinforced carbon composites (Cf/C)
or silicon carbide fiber-reinforced silicon carbide
composites (SiCf/SiC) must be considered for the
more challenging temperatures of the control rods.39
Experience with irradiation of SiCf/SiC composites
for nuclear fusion applications suggests that these
materials have superior resistance to property degradation from neutron irradiation as well as resistance
to higher temperatures and could potentially have
lifetimes comparable to the life of the plant. As with

ceramic IHXs, application of these advanced materials
in a nuclear system would require considerable further development and cooperation with appropriate
standards and regulatory organizations.
5.11.7 Core Barrel Materials

Another evidently important metallic internal structure shown in Figures 15 and 16 is the core barrel.
The function of the core barrel is to mechanically
contain the shape of the graphite blocks making up
the core and to channel the flow of the primary
coolant. Although schematics in Figures 15 and 16
are specific to a pebble bed design, the core barrel is
essentially identical in design and function for a
prismatic design as well. The temperatures, neutron
fluence, and mechanical loads on the core barrel are
moderate and the PBMR design, for example, proposed the use of Type 316 stainless steel for this
application. Alloy 800H is also a leading candidate
for the core barrel material. Although the demands
on the material are modest in terms of mechanical
loading and neutron irradiation, it is a very large
structure (8 m high by 3.5 m diameter and 50 mm
in thickness) that will need to be fabricated on site by
welding in most cases. Both Type 316 stainless steel
and Alloy 800H are available in the required size and
are readily fabricated.
5.11.8 Environmental Effects of

VHTR Atmospheres on Materials
All the high-temperature reactor systems operated to
date had extensive gas cleanup systems associated with
the helium coolant flow. These systems are intended to
keep the total impurity levels in the helium below
typically 10 ppm. Particularly in the early reactors,
where the fuel was either not intended to contain the
fission products or was ineffective in this function,
the cleanup systems were also intended to capture
radionuclides.1,3 Capture of tritium that is produced
(at least in part) by transmutation of lithium impurities
in the graphite remains an important function of the
cleanup system. In the AVR and THTR reactors,
active control was maintained on the H2O and CO
concentrations to reduce oxidation of the graphite
reflectors, and the other impurities were routinely
found to reach acceptable steady-state levels without
active control.47,43,44 It has been noted that the
269
cleanup systems may play a secondary role in maintaining gas chemistry, with the massive amount of
graphite at high temperature present in all of the
reactor designs playing a dominant role.1
Molecular sieves are effective in capturing most of
the gaseous impurities; however, they have difficulty
capturing H2 and CO. To resolve this problem, the
gas stream is passed over a bed of CuO that oxidizes
the H2 to H2O and CO to CO2 upstream of the
molecular sieve where these gases are effectively
removed. The Peach Bottom plant attempted the
use of heated Ti getters for hydrogen and tritium;
however, these were not effective and oxidation of the
H2 prior to removal is now accepted practice.2 In a
typical plant, up to about 20% of the gas stream is
diverted to the cleanup system each hour.
Table 10 shows the impurity levels reported for
steady-state operation for several of the VHTRs.1,2,43,44
As shown in the table, at steady state, all of the reactors
for which operating data are available had similar levels
of impurities. Some caution should be exercised when
comparing the data for different plants, since, in some
cases, there are varying values reported in different
publications for the same plant. This may be associated
with conversion from partial pressure of impurities
(the preferred units for corrosion studies) to ppm by
volume (the typical units used for comparison of one
plant to another). Several plants have undergone extensive postmortem analysis of the core internals and heat
exchangers.1,2 There are reports of some oxidation and
at least one report of massive deposition of carbon on
the internals, as discussed in more detail in the following paragraphs; however, there have been no problems
with failure of components on the primary side associated with environmental effects.
There have been a large number of experimental
studies and modeling of the effect of VHTR
helium on the high-temperature alloys listed in
Table 3.1012,16,17,4554 Depending on the specific
proposed application, different model chemistries
have been developed, and the testing has focused on
these. Several of the model impurity chemistries are
shown in Table 11.4552,54 Comparison of the values
in Table 11 with actual operating experience suggests that the model chemistries tend to have higher
impurity levels of some species than those found in
operating reactors. This is notable for H2 in particular.
It is not clear why these particular values were chosen;
however, it can be noted that several of the proposed
applications were for process heat for coal gasification, and there was concern that hydrogen would
diffuse from the process plant into the primary
270
Table 10
Impurities reported in the helium coolant during steady-state operation of VHTRs (in ppm)
Dragon
Peach bottom
Fort St. Vrain
AVR
THTR
H2O
H2
CO
CO2
CH4
O2
N2
0.1
0.5
1
0.15
<0.01
0.1
10
7
9
0.8
0.05
0.5
3
45
0.4
0.02
<0.05
1
0.25
0.2
0.1
1.0
0.1
1
0.1
0.1
0.05
0.5
22
0.1
Source: Simon, R. A.; Capp, P. D. Operating experience with the dragon high temperature reactor experiment. In Proceedings of the
Conference on High Temperature Reactors, Petten, NL, Apr 2224, 2002; pp 16.
Burnette, R. D.; Baldwin, N. L. Specialists Meeting on Coolant Chemistry, Plate-Out and Decontamination in Gas Cooled Reactors,
Juelich, FRG, Dec 1980; International Atomic Energy Agency, 1980; pp 132137.
Nieder, R. Specialists Meeting on Coolant Chemistry, Plate-Out and Decontamination in Gas Cooled Reactors, Juelich, FRG, Dec 1980;
Nieder, R.; Stroter, W. VGB Kraftwerstech. 1988, 68, 671676.
Table 11
Model impurity chemistries used in environmental testing programs (compositions in ppm). HHT, PNP were
used for German nuclear process heat projects
HHT
PNP
AGCNR
JAERI B
H2O
H2
CO
0.75
0.75
1
0.5
250
250
200
100
20
7
20
50
CO2
CH4
0.1
1
25
10
10
2.5
O2
N2
5
<2.5
<2.5
<2.5
AGCNR was a German VHTR, and JAERI B composition was extensively studied in development of the HTTR.
Source: Nieder, R. Specialists Meeting on Coolant Chemistry, Plate-Out and Decontamination in Gas Cooled Reactors, Juelich, FRG, Dec
1980; International Atomic Energy Agency, 1980; pp 144152.
Nieder, R.; Stroter, W. VGB Kraftwerstech. 1988, 68, 671676.
Bates, H. G. A. Nucl. Technol. 1984, 66(2), 415428.
Brenner, K. G. E.; Graham, L. W. Nucl. Technol. 1984, 66(2), 404414.
Christ, H. J.; et al. Mater. Sci. Eng. 1987, 87, 161168.
Christ, H. J.; et al. Oxid. Metals 1988, 30, 2751.
Christ, H. J.; et al. Oxid. Metals 1988, 30, 126.
Fujioka, J.; et al. Nucl. Technol. 1984, 66(1), 175185.
Inouye, H. Nucl. Technol. 1984, 66, 392403.
coolant circuit.45 Note that N2, at concentrations

similar to those listed in Table 10, has never been
found to contribute significantly to environmental
interactions with nickel-based alloys.48,49
Interplay between the alloy surface, temperature,
and gas composition determines whether corrosive
oxidation, carburization, or decarburization occur.
The corrosion mechanisms of particular significance
to mechanical stability are carburization and decarburization. Carburization is associated with lowtemperature embrittlement, and decarburization is
linked to reduced creep rupture strength. Ideally, a
continuous self-healing, impermeable passivating oxide
layer is needed to establish the most corrosion-resistant
alloy. In the case of Alloy 617, the chromia layer
(Cr2O3) is the most important barrier to the effects
of corrosive reactor gases.
As noted earlier, of the existing materials, Alloy
617 is the leading candidate for use in the VHTR
heat exchangers because it has the highest creep

strength of the solid-solution alloys under consideration for temperatures above 850 C. Evaluation
of this alloy for VHTRs began in the early 1980s,
with the most comprehensive work done by Brenner
and Graham,46 Christ et al.,4749 Graham,51 and
Quadakkers and Schuster.54 Alloy 230 is under consideration as an alternative to Alloy 617 because it
has equivalent creep properties and may suffer from
less internal oxidation.
Based upon the work of Quadakkers and others,
assessments of Alloy 617 stability at various gas concentrations and temperatures can be displayed graphically. Quadakkers used a diagram of the type
shown in Figure 18 to display the results of the
stability calculations for the nickelchromium
alloy.4749,54 Five conditions are represented within
the diagram: I strong reduction (decarburization
without a surface oxide); II decarburization (with

3CO2Cr Cr2 O3 3C
PCO
CO pressure for this equilibrium
CrnCm
log ac
III
I
II
III
The measured steady-state conditions (AGCNR gas

composition) determine where the alloy sits within
the modified chromium diagram; hence, the steadystate carbon activity (acss ) and the steady-state oxygen
pressure (POss2 ) are tentatively calculated with the
following equations (provided the kinetics of methane splitting is low compared to the water vapor
dissociation on the alloy surface):
Cr2O3
IV
V
271
P*CO
Cr metal
ss1=2
log Po2
Figure 18 Modified chromium stability diagram at a given
temperature; Zone III is preferred for optimal chromia layer
protection against corrosion.
a porous oxide); III stable external oxide (with

stable internal carbides); IV mixed surface oxide
and carbide layers (with internal carburization); and
V strong internal and external carburization. Zone III
was determined to be the area of highest stability; an
environment that is oxidizing and slightly carburizing.
For a heat exchanger operating at temperatures of
900 C and assuming standard gas composition,
called AGCNR helium and shown in Table 11,
Alloy 617 would be in zone III, for example.
The diagram describing alloy stability was based
on the most relevant species involved in the corrosion
process, namely chromium. Identifying which form
Cr2O3 chromium carbide or chromium metal is
most stable in a particular environment will determine the ultimate fate of the alloy.55 It is important to
note that the gas chemistries found in operating reactors and used in the previous test programs are not in
thermodynamic equilibrium. A steady-state gas composition is reached at any temperature based on
kinetic considerations. As is shown later, the concentrations of H2O and CO largely determine the partial
pressure of oxygen and the activity of carbon, respectively. The important features of the diagram are
critical carbon activation (ac ), critical partial pressure
of oxygen (PO 2 ), and the critical partial pressure of

carbon monoxide (PCO
). At a given temperature,
these parameters are calculated from the following
thermodynamic reactions:
ac
23Cr 6C Cr23 C6
metal carbide equilibrium activity
PO 2
Cr2 O3 2Cr 1:5O2

disassociation pressure of chromia
II
ss
=PO2
acss CO C0:5O2 acss K PCO
IV
POss2 H2 OH2 O POss2 KPH2 O =PH2 2

1PCH4 =PH2 O 1=100
A chromium activity of 0.75 was assumed at the Alloy

617 surface.48,49
At very high temperatures, there is a critical temperature above which the oxide layer is unstable and
CO evolution will occur. This critical temperature
represents the maximum application temperature for
the alloy. The results of an experiment for Alloy 230
showing oxide instability and CO evolution are given
in Figure 19 for a specimen that was held at a constant
temperature of 900 C to establish a surface oxide before
rapidly increasing the temperature to 1000 C. The
chemical reaction that gives rise to CO evolution is
2Cr2 O3 Cr23 C6 6CO 27Cr
VI
It is also significant to note the rapid rate at which

the reaction occurs, indicating that significant
changes in surface condition of this alloy can occur
in a few hours.
The reaction [VI] (also known as the microclimate
reaction) suggests that degradation of the protective
oxide on the surface of the IHX alloys under consideration can be suppressed by increasing the partial
pressure of CO. Figure 20 shows the upper temperature for oxide stability as a function of CO partial
pressure for both Alloy 617 and Alloy 230.
The onset of reaction [VI] occurs at a particular
temperature, TA, when the CO concentration is no
longer sufficient to drive the reaction from right to
left. It results in eventual total loss of either chromium
oxide or carbide, depending on concentration, then
in complete carburization or decarburization of the
alloy, depending on the gas composition. This degradation mechanism is considered in the stability diagrams developed using the approach of Quadakkers

, and it has been discussed extensively by
as PCO
Brenner and Graham,46 Christ et al.,4749 and Graham.51
40
1000
Partial pressure (mbar)
35
T(C)
800
CO
30
PCO(mbar)
PCH4(mbar)
25
600
P(CO)inlet
20
400
15
Temperature (C)
272
CH4
200
10
5104
1105
2105
1.5105
Time (s)
Figure 19 Experimental determination of oxide instability (as evidenced by CO evolution) for Alloy 230 in He with 200 ppm
H2, 21 ppm CO, 19 ppm CH4, and 0.5 ppm H2O.
1275
1250
Fit a(Cr) = 0.72
TA In K
1225
1200
1175
Alloy 230
Alloy 617
Alloy 617 after(20)
1150
1125
0
3
P(CO) ln Pa
Figure 20 The critical temperature for oxide instability for Alloy 617 and Alloy 230 as a function of CO partial pressure.
At the temperature TA, the reaction will go to completion, and as a result, this temperature represents a
maximum use temperature for the particular alloy for
a given gas composition. Experimental results for this
reaction are shown for Alloys 617 and 230.
A shortcoming of the stability diagram approach
presented earlier is that it does not account for the
fact that Cr2O3 becomes volatile at a temperature
above about 950 C.56 There may be sufficient oxygen partial pressure to form the oxide as predicted
from the modified stability diagram; however, it will
not be protective because of the vapor pressure of

the oxide. Most laboratory studies have been at
very low flow rates to more closely approach thermodynamic equilibrium for fundamental studies
of corrosion mechanisms. It has been noted that
these conditions may not be representative of reactor systems, where very high gas velocities are
likely, for example, 75100 m s1 at the outlet of the
VHTR.48,49 With very low levels of impurities,
this increases the possibility that impurities will be
depleted during the experiments and may give rise
to anomalously low values for Cr2O3 vaporization in

test systems compared to reactor operation.4649,51,52
Micrographs of cross-sections from Alloy 617 and
Alloy 230 plate material after exposure to heliumcontaining impurities that resulted in decarburizing
atmosphere at 1000 C are shown in Figure 21(a)
and 21(b), respectively. The microstructures are
largely as anticipated. Alloy 617 shows a relatively
thick chromium oxide scale with significant formation
of grain boundary aluminum oxides. Alloy 230 shows
less surface oxidation and notably reduced tendency
for formation of grain boundary oxides. A decarburization region is also apparent for both alloys; the
decarburized region is particularly notable in Alloy
230 shown in Figure 21. Internal oxidation may be
of particular concern in alloy selection for compact
heat exchangers where very thin material sections may
be encountered.
Carburization of Alloy 617 has been examined in
previous work and the results shown in Figure 22 for
this alloy after exposure to carburizing conditions at
1000 C are largely consistent with behavior reported
in the literature. For the conditions examined, here
there is little formation of a surface oxide scale.
Carbon uptake in the material is manifested by
increased grain boundary carbide precipitate volume
fraction. The behavior of Alloy 230 is markedly different from that of Alloy 617. While there is little
evidence of scale formation, there is a very large
volume fraction of carbide formation in the alloy
that heavily decorates both grain and twin boundaries. This large volume fraction of carbides was
found through the entire thickness of the 3 mm
thick coupon after 500 h at 1000 C. A micrograph
from the center of an Alloy 230 coupon is shown in
Figure 23.
To investigate the effect of environmental interaction on the mechanical properties of the heat
exchanger alloys, Alloy 617 specimens that were carburized at 900 (1000 h) and 1000 C (500 h) as well as
companion specimens that were oxidized at 900 C
(1000 h) were tested. Representative room temperature stressstrain curves for the materials exposed at
900 C are shown in Figure 24. It is clear from the
figure that the heavily carburized specimen (IN 617-2)
has higher flow strength compared to the oxidized
specimen (IN 617-7), but considerably reduced ductility. Room temperature tensile results for the material carburized at 1000 C are essentially identical to
those for material carburized at 900 C. Tensile testing the carburized Alloy 617 at 800 C showed
increased reduction in area to about 4%; the oxidized
273
(a)
(b)
50.00 m
Figure 21 Optical micrographs of cross-sections through

(a) Alloy 617 and (b) Alloy 230 after 500 h at 1000 C under
decarburizing conditions.
material had greater than 50% reduction in area in

tension at 800 C. Tensile tests of Alloy 230 with
extensive carburization also indicated nil ductility at
room temperature and less than 1% tensile elongation at 800 C.
5.11.9 Aging Effects

In addition to decreased ductility from carburization,
aging will cause precipitation of carbides and other
phases in the temperature range of interest for heat
exchanger applications. The alloys with higher aluminum, such as Alloy 617, have a significant volume
fraction of Ni3Al (g0 ) formed at some aging temperatures. This phase increases the strength and results in
reduced ductility and impact properties. A TTT
diagram for Alloy 617 illustrating the region of
274
(a)
50.00 mm
50.00 m
Figure 23 Optical micrograph of carbides in the center

of the Alloy 230 coupon after carburizing exposure at 1000 C.
(b)
50.00 mm
Figure 22 Optical micrographs of cross-sections

through (a) Alloy 617 and (b) Alloy 230 after 1000 h at
1000 C under carburizing conditions.
stability of the g0 is shown in Figure 8. The most

rapid precipitation of additional phases occurs at a
temperature of 750 C, which is somewhat below the
expected maximum operating temperature of the
IHX. The effect of thermal aging on impact properties
of Alloy 617 is shown in Figure 25 for an aging time of
1000 h. Absorption of energy from impact testing
drops considerably for these aging treatments compared to the solution-annealed material.
The room temperature tensile ductility of Alloy
800H has been found to be essentially unchanged by
aging in air at 800 C for 30 000 h. In contrast, Alloy X
showed a drop in room temperature tensile elongation from 45% to 10% for similar aging treatment.
While the ductility of Alloys 617 and X decreases
significantly after aging conditions, both retain substantial ductility. Addition of degradation in properties
from carburization in the VHTR atmosphere could, of
course, be a cause for further concern.
Stress (Mpa)
% strain vs stress (MPa)

900
850
800
750
700
650
600
550
500
450
400
350
300
250
200
150
100
50
0
IN617-7
IN617-2
10
15
% strain
20
25
30
Figure 24 Room temperature tensile stressstrain curves

for Alloy 617 that has been oxidized (IN617-7) and
carburized (IN617-2) at 900 C for 1000 h.
Microstructures of Alloys X and 800H after 500 h

exposure to oxidizing conditions illustrate the differences in precipitation between the two alloys upon
aging. The grain size of heat-treated Alloy X is 35 mm
and precipitation within the grains is heavy as shown
in Figure 26. Several carbide populations coexist: fine
dark carbides which form stringers at twin boundaries
and round grayish carbides are within the grains; large
round white carbides (Mo rich, M6C) are formed at
grain boundaries.
Alloy 800H microstructure shown in Figure 27
after oxidizing exposure at 750 C exhibits large
and regular grains and lesser amounts of quite
275
Impact toughness (J) at RT
350
617 unaged
617 1000 h aged
300
250
200
150
100
50
//
0
500
600
700
800
900
Aging temperature (C)
1000
Figure 25 Room temperature impact energy for Alloy 617

after aging at various temperatures for 1000 h.
homogeneous precipitation compared to Alloy

X, except for some stringers of carbides along the
rolling direction.
The more pronounced precipitation in Alloy X
compared to Alloy 800H and the resulting decrease
in ductility for Alloy X would suggest that Alloy
800H might be the preferred alloy for use in this
temperature range. Note, however, that the oxidation
resistance of Alloy X is higher compared to Alloy
800X in terms of external as well as internal oxidation. For compact heat exchanger designs where thin
sections are a concern, the limited internal oxidation
might favor selection of Alloy X. Limited internal
oxidation is a particularly attractive attribute if it
can be shown that further reduction of ductility due
to carburization is not a significant probability.
Although aged materials retain ductility at
operating temperatures, embrittlement from aging
or environmental effects is an issue in some circumstances. Reduced ductility and impact properties of
any of the alloys are of concern during startup from
ambient temperature after an outage, for example,
because stresses from thermal gradients may be
large in this circumstance.
5.11.10 Summary
Although designs for very high-temperature nuclear
reactors are continuing, enough is known from system requirements and past experience to make reasonable material choices for the most highly
challenged systems, the heat exchanger and control
rod sleeves. Due to the high anticipated service temperature and the requirement for minimal change in
100 m
Figure 26 Microstructure of Alloy X after 672 h at 750 C
under oxidizing conditions.
100 m
Figure 27 Microstructure of Alloy 800H after 672 h
exposure at 750 C under oxidizing conditions.
material behavior for service lives up to 60 years, the

material choices are limited to face center cubic
solid-solution alloys. Compact heat exchanger designs
are especially demanding due to small section sizes.
The number of candidate alloys is further constrained by the necessity of selecting materials that
are sufficiently mature to be acceptable to regulators
for licensing the plant. The leading candidate alloy
for IHX application at outlet temperatures in excess
of 850 C is Alloy 617. Alloys 230, 800H, X, and XR
are also viable candidates for some applications.
Only Alloy 800H is currently in the US nuclear
design code and for temperatures limited to 760 C.
Additional material property characterization will be
required to allow application of Alloy 800H at higher
temperatures and to design with the other candidate
276
alloys. The need for additional data is apparent for

design under any regulator around the world. Characterization of the creep and creepfatigue properties for long times and under prototypical VHTR
atmospheres will be required. For compact heat
exchanger designs, joining methods that have not
typically been used in nuclear service, including
diffusion bonding and brazing, will need to be extensively studied and the properties of resulting structures characterized. Development of nondestructive
inspection methods for the complex IHX geometries
envisioned for VHTR systems is an urgent need.
Environmental resistance of the candidate alloys
has been extensively studied and is generally understood. Coolant chemistry has to remain in an acceptable domain which favors passive oxidation over
carburization or decarburization which affects the
alloy microstructure and properties. Additional
work remains to validate the understanding of environmental resistance and aging behavior of the materials, particularly at the highest temperatures.
The temperature and stress to which control rod
sleeves will be subjected under normal operating
conditions and for different accident scenarios have
not yet been fully understood. The best current
thinking is that control rod sleeves made of Alloy
800H will have sufficient properties to operate safely.
Irradiation-induced changes in mechanical properties of this alloy are not understood, and additional
testing may also be necessary to determine if the
lifetime of the sleeves will be adequate. Further
development and testing of composite control rod
sleeves, either carbon fiber or silicon carbide fiber, is
desirable to demonstrate operation at higher temperatures and for increasing the service life.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
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5.12
Material Performance in Supercritical Water
T. R. Allen, Y. Chen, X. Ren, K. Sridharan, and L. Tan

University of Wisconsin, Madison, WI, USA
G. S. Was and E. West

University of Michigan, Ann Arbor, MI, USA
D. Guzonas
Atomic Energy of Canada Limited (AECL), Deep River, ON, Canada
5.12.1
Introduction
280
5.12.1.1
5.12.2
5.12.2.1
5.12.2.1.1
5.12.2.1.2
5.12.2.1.3
5.12.2.1.4
5.12.2.1.5
5.12.2.2
5.12.2.2.1
5.12.2.2.2
5.12.2.2.3
5.12.2.3
5.12.2.3.1
5.12.2.3.2
5.12.2.4
5.12.3
5.12.3.1
5.12.3.1.1
5.12.3.1.2
5.12.3.1.3
5.12.3.1.4
5.12.3.1.5
5.12.3.2
5.12.3.2.1
5.12.3.2.2
5.12.3.2.3
5.12.3.2.4
5.12.3.3
5.12.3.4
5.12.3.5
References
Experimental Issues
Corrosion in SCW
Effect of Alloy Class
Ferriticmartensitic steels
Austenitic stainless steels
Ni-based alloys
Zr-based alloys
Ti-based alloys
Oxide Structures
Ferriticmartensitic steels
Austenitic steels
Ni-based alloys
Surface Composition Modification
Effect of grain size refinement
Effect of grain boundary structure optimization
Summary of Corrosion in SCW
Stress Corrosion Cracking in SCW
Temperature
Microstructure
Water chemistry
Pressure/dielectric constant
Irradiation
Nickel-Based Alloys
Alloy
Temperature
Water chemistry
Irradiation
FerriticMartensitic Alloys
Other Alloys
Summary of SCC Behavior in SCW
283
286
286
288
292
294
295
296
296
296
296
298
300
301
302
305
305
309
309
311
311
313
313
315
315
317
318
319
320
322
322
322
Abbreviations
AECL
AOA
AR
ASTM
Atomic Energy of Canada Limited

Axial offset anomaly
As received condition
American Society for Testing and
Materials
BWR
CANDU
CERT
CGR
CIPS
CLSBs

Canada Deuterium Uranium
Constant extension rate tensile
Crack growth rate
Crud-induced power shifts
Coincidence site lattice boundaries
279
280
CLT
DCPD
EBSD
ECAP
ECP
EDX or EDS
F/M
FFTF
GBE
GenIV
IGSCC
JPCA
LWR
ODS
OT
PHWR
PWR
RBMK
RHAB
SAM
SCC
SCW
SCWO
SCWR
SEM
TEM
TGSCC
XPS
XRD
Constant load tensile

DC potential drop
Electron backscatter diffraction
Equal channel angular processing
Energy dispersive X-ray
spectroscopy
Ferritic-martensitic steels
Fast Flux Test Facility
Grain boundary engineering
Generation IV
Intergranular stress corrosion
cracking
Japanese Prime Candidate Alloy
Light water reactor
Oxide dispersion strengthened
Oxygenated treatment
Pressurized heavy water reactor
Reactor Bolshoy Moshchnosty
Kanalny
Random high angle boundaries
Scanning auger microscopy
Supercritical water
Supercritical water oxidation
Supercritical water-cooled reactor
Transgranular stress corrosion
cracking
X-ray photoelectron spectroscopy
X-ray diffraction
5.12.1 Introduction
The Generation IV (Gen IV) advanced reactor initiative
is pushing nuclear reactor technology to completely
new performance requirements, as a result of

higher temperatures and process efficiency

longer lifetimes and higher neutron fluxes
challenges in materials technologies
novel technologies introduced for reactor fuel and
fuel cycles
One promising Gen IV concept is the supercritical

water-cooled reactor (SCWR). The idea of using a
supercritical water (SCW) coolant in a water-cooled
reactor dates back to the 1960s,1,2 although no such
reactor was ever built. More recently, two types of
SCWR concept have evolved from existing light

water reactor (LWR) and pressurized heavy water
reactor (PHWR) designs: (1) a number of designs35
consisting of a large reactor pressure vessel containing the reactor core (fueled) heat source, analogous to
conventional pressurized water reactor (PWR) and
boiling water reactor (BWR) designs, and (2) designs
with distributed pressure tubes or channels containing fuel bundles, analogous to conventional CANDU
(CANDU, Canada Deuterium Uranium, is a registered trademark of Atomic Energy of Canada Limited
(AECL)) and RBMK (Reactor Bolshoy Moshchnosty
Kanalny) nuclear reactors.6 The balance-of-plant is
typically a direct-cycle design, and the out-of-core
portions of both concepts are similar to existing fossilfired generators.
The SCWR will have core outlet temperatures
well above the thermodynamic critical point of water
(374 C, 22.1 MPa); the reference design for the
SCWR7,8 calls for an operating pressure of 25 MPa
and an outlet water temperature of up to 620 C. Peak
fuel cladding temperatures could be as high as 850 C
in some designs (e.g., Chow and Khartabil9). Figure 1
illustrates the proposed operating conditions of an
SCWR, as well as the operating ranges of existing
reactor designs, fossil-fired SCW power plants, and
supercritical water oxidation (SCWO) processes.
Operation in the SCW regime gives the SCWR many
advantages compared to the state-of-the-art LWRs and
PHWRs, including the use of a single-phase coolant
with high enthalpy, a direct, once-through steam cycle
that enables the elimination of components, such as
steam generators and steam separators and dryers, a
low coolant mass inventory resulting in smaller components, a much higher efficiency (45% vs. 33% in
current LWRs), and nearly 50 years of industrial experience from thermal-power stations with a SCW cycle.
Besides the design concept itself, the most important technical issues are likely to be the identification of
materials for in-core and out-of-core components and
the identification of appropriate coolant chemistry. As
noted, there is significant industry experience with the
use of SCW in nonnuclear power generation,10,11 with
about 268 944 MWe (462 units) of installed capacity in
coal-fired SCW power plants worldwide11 as of 2004.
However, a nuclear reactor core is significantly different from a fossil-fired boiler; Figure 2 illustrates the
scale differences between core components in an
SCWR and the corresponding components in a fossilfired SCW power plant. A fossil-fired boiler contains a
large number of relatively thick-walled (612 mm
thickness) fire tubes that circulate water on the inside.
281
70
60
Supercritical
Pressure (MPa)
50
Liquid
40
SCWO region
SCFP region
30
SCWR core
20
PWR core
10
0
100
Critical
point
CANDU core
BWR core
200
300
Possible peak
cladding
temperature
Steam
400
500
600
Temperature (C)
700
800
900
Figure 1 The temperaturepressure phase diagram of water showing the critical point and the supercritical regime. The
operational regions of present boiling water reactor and pressurized water reactor plants, as well as supercritical fossil-fired
boilers, are presented along with the design area of supercritical water-cooled reactors. The large area covered by
supercritical water oxidation processes is fully in the supercritical water region. Adapted from Heikinheimo, L.; Guzonas, D.;
Fazio, C. GENIV materials and chemistry research Common issues with the SCWR concept. 4th International Symposium
on Supercritical Water-Cooled Reactors, Heidelberg, Germany, Mar 811, 2009.
The wall thickness for the fuel cladding in the reference SCWR design is 0.63 mm (but may be as low as
0.4 mm12) and the wall thickness for the water rods is
0.40 mm. These very thin-walled components provide
little margin for corrosion in an SCWR core, where
the consequences of failure are significant. Oxide
films of several hundred micrometer thickness are
not unusual for fossil-fired plant boiler tubes, but are
unacceptable for an SCWR water rod or fuel cladding.
In addition to oxide films formed on fuel cladding
surfaces by corrosion of the base metal, the deposition
of corrosion products released from corrosion of outof-core components onto fuel cladding surfaces could
result in (1) overheating of the cladding surface or
underdeposit corrosion, leading to fuel failures, (2)
changes in reactivity in the core (crud-induced power
shifts (CIPS), also known as axial offset anomaly
(AOA)), and (3) increased radiation fields on out-ofcore piping. It is important to note that, with respect
to corrosion product deposition, corrosion rates of
out-of-core materials that may be acceptable for
fossil-fired SCW plants may not be acceptable for an
SCWR.13
In addition to the operating experience and
research in support of fossil-fired SCW plants, a
large amount of data on materials degradation in
SCW was acquired in the development of SCWO
processes. While the chemistry conditions in these
tests are generally not of direct relevance to an

SCWR, typically being acidic with high concentrations of aggressive species such as chloride, these data
do provide some insights into the key parameters
affecting corrosion phenomena in SCW.14 However,
in spite of information available from current reactor
designs, modern boiler technologies, and research in
support of SCWO, significant gaps still exist in our
understanding of the corrosion properties of materials under proposed SCWR operating conditions.
There is a strong interplay between coolant chemistry and materials selection in any water-cooled
nuclear power plant system. As noted, the SCW coolant in both the pressure vessel and pressure tube
concepts lies in both the liquid and supercritical fluid
areas of the TP phase diagram (Figure 1). The coolant passes through the critical point at some location
in the reactor core. The corrosivity of SCW varies
widely depending upon the values of properties, such
as density, ion product, and dielectric constant, as well
as on the nature of any solutes present (impurities,
dissolved oxygen) and their concentrations.14 At the
low density (100 kg/m3) expected at the core outlet
of an SCWR, SCW is a nonpolar solvent capable of
dissolving gases such as oxygen to complete miscibility. While the solubility of ionic species is expected to
be extremely low under these conditions, the formation of neutral complexes increases with temperature
282
Column 2 Column 5
Column 9
Column 13
Row 13
Coolant
Fuel rod/clad
Water duct
(5 6)
Water rod
Assembly duct
Row 1
(a)
Central instrumentation rod
04-GA50011-02
Fuel rod outer diameter = 12 mm

Clad wall thickness = 0.4 0.6 mm
Fire tube outer diameter = 50 mm

Tube wall thickness =10 mm
(b)
Water rod outer diameter = 40 mm (square)

Water rod wall thickness = 0.4 mm
Figure 2 (a) A 1/8 assembly model of the 21 21 supercritical water-cooled reactor fuel assembly and (b) comparison of
typical fossil boiler tube dimensions to fuel rod and water rod dimensions in the reference supercritical water-cooled reactor
design. Part (a) reproduced from Feasibility Study of Supercritical Light Water Cooled Reactors for Electric Power Production;
Final Report, DE-FG07-02SF22533, INEEL/EXT-04-02539, Jan 2005.
and can become important under near-critical and

supercritical conditions. It has been suggested that
the most important temperature region is from 300
to 450 C; over this temperature range, the properties
of water change markedly, and solvent compressibility
effects exert a huge influence on solvation. With the
exception of a few recent studies (see Wesolowski
et al.15), the thermochemistry of neutral hydrolyzed
metal species is poorly understood, even at temperatures well below the critical point.
In current water-cooled reactor designs, degradation of system components is minimized by selecting
and then controlling a set of chemistry parameters
that together reduce the aggressiveness of the coolant
to the specific alloys used in the system. Chemistry

performance requirements are set by the sometimes
conflicting desires to minimize corrosion (general
and localized), minimize corrosion product and activity transport, optimize thermal performance, and
maximize system lifetime. The primary requirement
of chemistry control is to reduce degradation rates
such that design lifetimes are achievable for the
entire system. Although fossil-fired SCW plants
have used a variety of water chemistries,16,17 to date,
most experimental work on SCWR materials has
been carried out using a limited subset of these water
chemistries, namely, low-conductivity, neutral-pH
water, low-conductivity, neutral-pH water with added
oxygen (508000 ppb) (this encompasses the oxygenated treatment (OT) commonly used in fossil-fired
SCW plants, in which a low concentration of oxygen
(50150 ppm) is added to the boiler feedwater to reduce
corrosion of mainly carbon steel components), and
hydrogen water chemistry (H2 concentration 30 cm3
kg1 water). Additional testing under a wider range of
water chemistries, developed based on a deeper understanding of SCW chemistry, may prove beneficial.
In addition to the water chemistry issues discussed
earlier, which, with the exception of activity transport,
are common to both nuclear and fossil-fired SCW
power plants, reactor in-core components must also
contend with the effects of irradiation on water chemistry and alloy microstructure. Water radiolysis can
increase the concentrations of oxygen and other oxidizing species (e.g., OH, H2O2, and HO2/O
2 ), raising
the corrosion potential and increasing susceptibility to
processes such as stress corrosion cracking (SCC).
While current PWRs and PHWRs limit the formation
of oxidizing species in-core by ensuring the presence of
excess hydrogen at concentrations sufficient to chemically lower the net production of oxidizing species by
radiolysis, the existing data are insufficient to determine whether this strategy would be effective in an
SCWR. Coupled with the high solubility of oxygen in
SCW, uncontrolled radiolysis could lead to very oxidizing coolant conditions in-core and immediately
downstream of the core.
Water chemistry experiments at very high temperatures and pressures, especially beyond the critical point of water, are difficult to perform, and
advances in this area will require a combination of
computer simulations and experiments. Water in a
reactor core is subject not only to extreme conditions
of high temperature and pressure, but also to an
intense flux of ionizing radiations (energetic neutrons,
g-rays, recoil protons, and heavy ions), making its
radiolysis difficult to determine experimentally. Currently, the limited experimental data available on
SCW radiolysis (see, e.g., Bartels et al.,18 Meesungnoen
et al.,19 Pommeret,20 Katsumura21) have shown that
virtually no free radical reaction rates follow an
Arrhenius law. As a result, rate constants for key
reactions cannot be extrapolated from data measured
at subcritical temperatures and must be measured.
Once sufficient data exist to predict the corrosion
potential, laboratory experiments can be carried out
to more accurately simulate environmental conditions expected for the core of an SCWR. Ultimately,
model predictions and out-of-core test data will need
to be validated against experimental data obtained
283
from in-reactor test loops.22 As direct measurement

of the electrochemical corrosion potential (ECP) of a
test specimen in an in-core SCW loop is not possible
with existing technologies, such testing will also
require development of a reference electrode that
can withstand the SCW environment.
For in-core components, perhaps the most challenging problem is the role of irradiation on microstructure
and how these changes affect SCC. Irradiation-assisted
SCC has been a generic problem in LWRs of all
types and covering many austenitic and nickel-based
alloys.23,24
This chapter reviews the current understanding of
the response of candidate materials for SCWR systems, focusing on the corrosion and SCC response,
and highlights the design trade-offs associated with
certain alloy systems. With the exception of the
effect of irradiation on SCC, the important issues of
radiation response and radiolysis are not addressed in
this review. For an overview of corrosion and SCC
in light water-cooled reactors, see Chapter 5.03,
Corrosion of Zirconium Alloys; Chapter 5.04,
Corrosion and Stress Corrosion Cracking of
Ni-Base Alloys; Chapter 5.05, Corrosion and
Stress Corrosion Cracking of Austenitic Stainless
Steels; and Chapter 5.08, Irradiation Assisted
Stress Corrosion Cracking.
5.12.1.1
Experimental Issues
Performing corrosion experiments at elevated temperatures and pressures below the critical point is
challenging, and becomes even more so under supercritical conditions. For example, material selection for
autoclaves and loop piping is complicated by the fact
that corrosion rates of these materials under SCW
conditions are often similar to those of the materials
under investigation. Electrochemical methods, often
employed for corrosion studies at subcritical temperatures, become difficult or impossible at the low ionic
conductivities of low-density SCW.25 Tests using irradiated materials or simulated radiolysis conditions,
required for the development of an SCWR, significantly increase the experimental challenges.
Key experimental variables affecting corrosion in
SCW identified to date are temperature, water density
(pressure), dissolved oxygen concentration, water
conductivity, and surface preparation. The effect of
solution pH has not been studied for the SCWR,
although some fossil-fired SCW plant water chemistries are slightly alkaline. Tests have been performed
at temperatures ranging from below the critical
temperature up to 650 C. Test durations have ranged

from 24 to 3000 h. After exposure to SCW, test
specimens have been characterized using techniques
ranging from weight change measurements to various
surface analytical methods such as scanning electron
microscopy (SEM), energy dispersive X-ray spectroscopy (EDX or EDS), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS),
Raman spectroscopy, and scanning Auger microscopy (SAM).
Corrosion experiments in SCW can be performed
in static autoclaves and capsules, and refreshed autoclaves and loops, complicating the comparison of data
from various research groups. Loops can be either
recirculating, in which a major amount of the loop
water is circulated through the loop circuit without
purification (a side-stream purification system is often
used to reduce impurity concentrations) or oncethrough, which includes loops that cool and purify
all of the water to remove ionic impurities prior to its
reintroduction to the test section. Static autoclaves are
relatively simple to operate, but significant, and possibly unrepresentative, concentrations of dissolved corrosion products can build up in the autoclave as a
result of the corrosion of both the test specimens and
the autoclave body in SCW. Figure 3 shows the results

of experiments carried out in Hastelloy C and Alloy
625 autoclaves, in which the autoclave body itself acted
as the test specimen.26 The concentrations of various
metals in the solutions before and after exposure to
SCW conditions were measured. The data show that
significant amounts of Ni, Mo, and W were released
into solution. These dissolved species can deposit onto
other system surfaces, such as test specimens, by precipitation or direct incorporation into the growing
corrosion film. Daigo et al.27 have shown that chromium released from the autoclave body by corrosion
can migrate to the surfaces of test specimens in the
autoclave, leading to improved corrosion resistance
of the test alloy. (Tests were carried out at 400 C
and 30 MPa in 0.01 M H2SO4 and 0.025 M oxygen
(800 ppm) for the development of SCWO processes.)
It was proposed that the observed reduction in corrosion rate was due to (1) changes in the solubility of
Cr2O3 due to temperature gradients in the loop and
(2) the possible formation of soluble Cr6+ species
under the highly oxidizing conditions of these tests.
The buildup of corrosion products can be minimized
using a refreshed autoclave or a once-through loop.
Once-through loops maintain constant, well-controlled
Elemental concentration (ng mL-1)
3500
45
40
3000
35
2500
30
2000
25
1500
20
15
1000
10
500
Percent of element in alloy
284
0
Cr
Mn
Fe
Ni
Zr Nb + Ta Mo
Element
Blank concentration
Alloy %
0
Sn
Water sample after

280 h exposure in
hastelloy C autoclave
Figure 3 Concentrations of various metals in solution after 280-h exposure of a Hastelloy C autoclave containing
deionized water at 450 C. The concentrations of various elements in the alloy and the concentrations in the water before
the test are also shown. Reproduced from Guzonas, D.; Tremaine, P.; Brosseau, F. Predicting activity transport in a
supercritical water cooled pressure tube reactor. 4th International Symposium on Supercritical Water-Cooled Reactors,
Heidelberg, Germany, Mar 811, 2009.
chemistry conditions ideal for studying mechanistic

effects, but these conditions may also be unrepresentative of those expected in a real plant, because the
coolant in an operating SCWR will likely have some
measurable concentration of impurities, especially
metal ions, which could alter the dissolution of surface films and therefore change the corrosion rate.
A recirculating loop with sidestream purification is a
good compromise, allowing both good chemistry control and controlled corrosion product transport. It is
important that the experimenter be aware of both the
advantages and potential shortcomings of a particular
test facility when planning an experiment, and ensure
that all the required test parameters are identified and
controlled. In all types of test facilities, characterization of water samples during and after the tests, and/or
measurement of the solution conductivity before and
after the test specimens, can provide some insight into
the release of metal ions into solution.
Under SCW conditions, the solvent density can be
varied by changing either the temperature at constant
pressure or the pressure at constant temperature.
The former case is more relevant to an SCWR. At the
relatively low pressures of interest for an SCWR, the
widest variation in density can be achieved at temperatures just above the critical temperature. Figure 4 illustrates the variation in density that can be achieved as a
function of temperature at a pressure of 25 MPa. It
should be noted that at this pressure, the variation in
density above 450 C is small, so that experiments carried out above this temperature can be considered to be
at constant density (about 100 kg m3).
As in any corrosion testing, care must be taken to

avoid galvanic coupling between corrosion coupons
and the test section or autoclave; the coupon holder
should be constructed of an insulating material.
This can be a challenge in SCW, as many ceramics,
including ZrO2, can dissolve at very high temperatures. The concerns about galvanic effects are mitigated to some extent at higher temperatures because
of the low ionic conductivity of SCW under typical
test conditions.
The surface treatment of corrosion coupons prior
to exposure to SCW has received only limited attention in recent investigations, although the effect has
been known for decades. For example, Ruther et al.28
reported that surface preparations that left a strainfree surface resulted in much higher corrosion in
superheated steam than surface preparations that
severely work the surface. This effect was attributed
to higher chromium diffusivity for mechanically
worked surfaces. Thus, care must be taken to assess
the surface preparation methods used when comparing results from different research groups.
Weight gain is commonly used as a measure of the
extent of corrosion, but the results are generally only
semiquantitative because (1) some of the metal
released from the base metal by corrosion can enter
the test solution rather than remain in the oxide, (2)
corrosion products from other sources in the test
system can deposit on the surface, and (3) spalling
of the oxide can occur. Measuring the weight loss
obtained by removing the oxide film from the test
coupon surface by descaling (e.g., ASTM G 1-03)
800
Tcritical
700
Density (kg m-3)
600
500
400
300
200
100
0
300
350
400
285
450
500
Temperature (C)
550
600
650
Figure 4 Dependence of the density of supercritical water on temperature at a constant pressure of 25 MPa.
286
provides a better measure of the corrosion rate,

but finding a suitable descaling method for an alloy
can be challenging.
5.12.2 Corrosion in SCW

The worldwide programs to study corrosion (see
Chapter 5.01, Corrosion and Compatibility for an
overview of corrosion in nuclear systems) in SCW
have examined many material classes, including
ferriticmartensitic (F/M) steels, austenitic steels,
Ni-based alloys, Zr-based alloys, and Ti-based
alloys2993 (see Chapter 2.07, Zirconium Alloys:
Properties and Characteristics; Chapter 2.08,
Nickel Alloys: Properties and Characteristics; and
Chapter 2.09, Properties of Austenitic Steels for
Nuclear Reactor Applications for descriptions of
each alloy class). When data from the fossil-fired
SCW industry and programs to develop SCWO systems are considered, some corrosion data relevant to
the development of an SCWR exist for at least 90
alloys, although there are few alloys for which a good
understanding of the corrosion mechanism exists.
Table 1 lists the types of materials tested and the
test conditions from programs to measure corrosion
in SCW; of the five classes listed, most of the work has
focused on the first three. Test temperatures have
ranged from subcritical up to 650 C, with dissolved
oxygen concentrations ranging from <10 ppb to
8000 ppb. Tests have been performed with durations
Table 1
ranging from 24 to 3000 h. It should be noted

that in spite of the experimental issues raised in
Section 5.12.1, in most cases, there is reasonable
agreement in the corrosion data for the same alloy
obtained under the same test conditions in different
laboratories within the estimated experimental error.
Some specific alloys have multiple designations. For
example, HCM12A and T122 have the same composition as do NF616 and T92. In the figures that follow,
the alloy designation used is the same as that used in
the original reference. Table 1 can be used to crossreference alloys with multiple designations.
5.12.2.1
Effect of Alloy Class
The corrosion response in SCW is a strong function

of alloy class, as illustrated in Figures 5 and 6, which
show data from corrosion tests performed for up to
3000 h at 500 C in SCW, with a dissolved oxygen
concentration of 25 ppb at the test section inlet. Of
the three classes of materials included in the figures,
oxidation occurs most rapidly for F/M steels and is
slowest for the nickel-based alloys. Within each alloy
class, there are certain alloys with better oxidation
resistance. From a strictly general corrosion mitigation
viewpoint, improvements in oxidation resistance are
most critical in the F/M steels, as a high oxidation rate
would remove too much of the base metal in a thinnedwalled reactor component like the fuel cladding.
Generally, temperature was found to have the
greatest influence on oxidation/corrosion of the
Summary of experiments on corrosion in pure supercritical water
Alloy class
Alloy
Temp.
( C)
Water chemistry
Exposure
time (h)
Austenitic
stainless steel
304, 304L, 316, 316L, 316 + Zr, 310,

310S, 310 + Zr, 347H, Sanicro28, D9,
800H, AL6XN, Carpenter 20C B3,
Nitronic-50, PNC1520, alloy 1.4970
600, 625, 690, 718, 825, C22, B2, C276,
MAT21, MC
290650
Deaerated (<10 ppb) to

8000 ppb dissolved oxygen
1003000
290600
1003000
T91, T91a, T91b, HCM12A (T122),

HCM12, HT-9 (12Cr1Mo1WVNb),
NF616 (T92), MA956, 2.25Cr1Mo
(T11), P2
9Cr, 12Cr, F/M, 316, Inconel, Hastelloy
G-30, 19Cr, 14Cr4Al, 16Cr4Al,
19Cr4Al, 22Cr4Al
Zr, ZrNb, ZrFeCr, ZrCrFe,
ZrCuMo, Zr-2, Zr-4
Ti3Al2.5V, Ti6Al4V, Ti
15Mo5Zr3Al, Ti15V3Al3Sn3Cr
290650

8000 ppb dissolved oxygen,
<0.1 mS cm1
<0.1 mS cm1
360600
25 ppb
2003000
400500
Deaerated (<10 ppb dissolved

oxygen), <0.1 mS cm1
0.1 mS cm1
<2880
Nickel-based
Ferritic
martensitic
Oxide dispersion
strengthened
Zirconium-based
Titanium-based
290550
1003000
500
287
8
3000 h 500 C, 25 ppb
7
Weight gain (mg cm-2)
Ferritic
martensitic
5
4
3
2 Ni-based
Austenitic
1
0
625
NF709
800H
316
D9
ODS
NF616 HCM12A T91
Alloy
Figure 5 Comparison of weight gain for various alloys exposed to supercritical water at 500 C for 3000 h. The oxide
dispersion strengthened alloy is the 9Cr oxide dispersion strengthened alloy listed in Table 1.
5
500 C, 25 ppb
NF616
316
0
625
-1
500
1000
1500
2000
Time (h)
2500
3000
3500
Figure 6 Comparison of weight gain for various alloys exposed to supercritical water at 500 C for up to 3000 h. NF616
represents a typical ferriticmartensitic steel, 316 stainless steel represents a typical austenitic steel, and Alloy 625 represents
a typical nickel-based alloy.
materials (Figure 7). With an increase of exposure

temperature, the weight gain associated with oxidation typically increases significantly. While corrosion
studies performed in support of the development
of SCWO systems suggested a maximum in the
corrosion rate at temperatures around the critical

point, where the water density decreases significantly,12 most measurements of the corrosion rate
under SCWR conditions do not clearly show this
effect. As noted in Section 5.12.1, between about
288
10
1026 h
HCM12A
D9
625
0
Pseudo critical point
-2
350
400
450
500
550
Temperature (C)
600
650
Figure 7 Comparison of weight gain for various alloys exposed to supercritical water at temperatures from 360 to 600 C for
1026 h. HCM12A represents a typical ferriticmartensitic steel, D9 stainless steel represents a typical austenitic steel, and
Alloy 625 represents a typical nickel-based alloy.
300 and 450 C, the properties of water change dramatically. At higher water densities (and higher dielectric constants), an electrochemical mechanism based
on the formation and dissolution of a surface film is
expected to dominate.94,95 Below some threshold water
density, it has been proposed that the dominant mechanism changes to one based on the molecular interactions of the metal with oxygen and/or water and the
transport of cation and anion defects in the oxide. For
example, Betova et al.96 concluded that at temperatures of up to 500 C, the oxidation of stainless steels
proceeds in a manner analogous to that in high-temperature subcritical water, whereas at higher temperatures, the oxidation kinetics seems to be closer
to that in water vapor. Yi et al.85 concluded that
corrosion in SCW was similar to that in gaseous
conditions, where oxide formation occurs without
metal dissolution.
5.12.2.1.1 Ferriticmartensitic steels
As seen in Figure 8, the bulk chromium concentration

in F/M alloys has a significant effect on oxidation
response, with higher bulk chromium concentrations
leading to reduced weight gain. T91, a 9 wt% Cr alloy,
has the worst oxidation response as reflected by the
largest weight gain. The newer alloys, HCM12A and
NF616, perform slightly better and have similar oxidation responses.
The 9Cr oxide dispersion strengthened (ODS)
alloy has the best oxidation response of the F/M
alloys studied, even though it has a lower bulk chromium concentration. The 9Cr ODS alloy has two
significant microstructural differences compared to
conventional F/M steels. It contains distributed
nanosized YTiO particles91 and is composed of
fine equiaxed ferritic grains about 1 mm in size.50
The typical effects of time and temperature on oxide
growth in F/M steels are shown in Figure 9, using 9Cr
ODS, NF616, and HCM12A as examples. The time
exponents, n, obtained by fitting the weight gain data
using the generalized equation W = kptn, which is usually employed to evaluate high-temperature oxidation
kinetics, are also summarized in Figure 9. In the equation, W is the weight change of the steel (mg cm2), kp
is a rate constant, and t is the exposure time (h). The
oxide growth kinetics vary between parabolic and cubic
rate laws, and the oxide growth rate increases significantly with temperature and tends to follow a parabolic
growth rate at higher temperatures.
Figure 10 shows a TEM image of the morphology
of grains and grain boundaries in the internal oxidation layer of the 9Cr ODS alloy after the corrosion
tests, as well as EDS analyses, indicating the presence
of yttrium in selected areas.43 Yttrium was enriched
in oxide ribbons that formed along the oxidemetal
grain boundary regions in the internal oxidation
layer. Formation of these ribbons reduced the cation
flux in these regions, resulting in depletion of iron
cations in the (FeCr)3O4 and the gradual decrease of
scale density with the increase of exposure time.
289
6
500 C, 25 ppb
T91
HCM12A
NF616
9Cr ODS
3
1
HT9
0
0
500
1000
1500
2000
Time (h)
2500
3000
3500
4000
Figure 8 Comparison of weight gain for various ferriticmartensitic alloys exposed to supercritical water at 500 C for up to
3000 h. HT9 and HCM12A are 12 wt% Cr alloys. T91 and NF616 are 9 wt% Cr alloys.
14
600 C
500 C
360 C
HCM12A
HCM12A
HCM12A
NF616
NF616
NF616
9Cr ODS
9Cr ODS
9Cr ODS
Weight change (mg cm-2)
12
n = 0.42
10
n = 0.37
n = 0.39
8
6
4
n = 0.39
n = 0.38
n = 0.25
2
0
-2
0
200
400
600
800
Exposure time (h)
1000
1200
Figure 9 Weight change as a function of exposure time for ferriticmartensitic steels 9Cr oxide dispersion strengthened,
HCM12A, and NF616 in 500 and 600 C supercritical water and 360 C subcritical water with an inlet-dissolved oxygen
content of 25 ppb. Reproduced from Chen, Y.; Sridharan, K.; Allen, T. R. J. Nucl. Mater. 2007, 371, 118128.
The strong effect of temperature on the general

corrosion of F/M alloys is seen in the weight gain
data for HCM12A in Figure 7. Weight gain from
oxidation increases with increasing temperature
from 360 to 600 C. Yi et al.85 reported a weight loss
for T91 exposed to 370 C water for 200 h at 25 MPa

with <10 ppb dissolved oxygen, and Hwang et al.73
reported weight losses for T91, T92, and T122 in
deaerated SCW at 370 C and 25 MPa. As noted
above, there may be a change in corrosion mechanism
290
100 nm
(a)
Cr-K
Counts
2200
O-K
Fe-K
Counts
(b)
0.000
20
19
18
17
16
15
14
13
12
11
10
9
8
7
6
5
4
3
2
1
0
0.000
keV
20.480
Y-K
2.000
4.000
6.000
8.000
10.000
12.000
14.000
16.000
18.000
keV
Figure 10 (a) Transmission electron microscopy image shows the morphology of grains and grain boundaries in the
internal oxidation layer formed in the oxidized 9Cr oxide dispersion strengthened alloy and (b) X-ray spectra showing the
presence of yttrium in ribbon along grain boundary. Reproduced from Chen, Y.; Sridharan, K.; Allen, T. R.; Ukai, S. J. Nucl.
Mater. 2006, 359(12), 5058.
291
0.22
HCM12A
500 C
168236 h
Weight gain (mg cm-2 day-1)
0.20
0.18
0.16
0.14
0.12
10
1000
100
104
Oxygen (ppb)
Figure 11 Weight gain as a function of temperature for HCM12A exposed to low oxygen concentration supercritical
water for 1026 h. Data are compiled from two different institutions. Reproduced from Was, G. S.; Ampornrat, P.;
Gupta, G.; et al. J. Nucl. Mater. 2007, 371, 176201.
as the density decreases above the critical point. The

observed weight losses suggest that most of the metal
released by corrosion dissolves into the solution phase.
As the SCWR coolant will pass through the critical
point in the SCWR core, additional studies of corrosion
near the critical point would be helpful in determining
whether a corrosion maximum exists in this region.
Regardless of the uncertainties in corrosion behavior
near the critical point, all studies of F/M alloys show
very high corrosion rates at high temperatures relative
to the austenitic and Ni-based alloys.
Dissolved oxygen concentration influences the
oxidation behavior, as shown in Figure 11, which presents data from test systems with flowing refreshed
water. For HCM12A, the weight gain at 500 C
decreases with increasing dissolved oxygen concentration between 10 and 300 ppb. At much higher dissolved
oxygen concentrations (2000 ppb), the weight gain
increases considerably above that experienced between
10 and 300 ppb.
This dependence of oxidation on dissolved oxygen concentration is exploited in the fossil-fired
energy industry. Combined water chemistry control
in fossil-fired power plants97,98 involves addition of
small amounts of oxygen to the feedwater to enhance
the formation of hematite crystals between the magnetite grains, thus reducing the oxidation rate, perhaps by reducing the diffusion of oxygen through the
multiphase film. In studies examining F/M materials
for use in SCWRs, significant hematite crystals have

not been found between the magnetite grains at
10300 ppb oxygen, where oxidation is the slowest.
Figure 12 compares weight gain results at 25
and 8000 ppb for T91. Starting around 500 h, the
weight gain for 25 ppb exposure appears to be greater
than that from 8000 ppb exposure. This trend is
the opposite of that seen for HCM12A, where high
oxygen concentrations led to large oxide growth.
However, in Figure 12, the data come from two
different research groups using different experimental methods; the 8000 ppb data are from a static
autoclave and the 25 ppb data from a flowing system.
The corrosion rate in the static autoclave may
become lower at longer exposure times because
the test solution becomes saturated with corrosion
products, inhibiting their further release into the
solution.
Figure 13 demonstrates the effects of both temperature and time on the corrosion of HCM12A.
Similar to the data in Figure 7, weight gain for
HCM12A in deaerated water is seen to be a strong
function of temperature. This figure combines the
measurements from two different institutions,
showing consistency for nominally similar conditions. Figure 14 shows similar trends for T92 (also
known as NF616) in nondeaerated (8000 ppb) SCW.
Oxidation of T92 is also a strong function of temperature. The weight gain data for 500 C and 8000 ppb
292
6
T91 500 C
5
25 ppb oxygen
4
2
Nondeaerated (8000 ppb)
1
500
500
1500
2000
Time (h)
1000
2500
3000
3500
Figure 12 Weight gain on T91 exposed to supercritical water at 25 and 8000 ppb at 500 C. The 8000 ppb data are from
a static autoclave and the 25 ppb data from a flowing system. Nondeaerated data displayed in green are from KAERI.
Reproduced from Jang, J.; Han, C. H.; Lee, B. H.; Yi, Y. S.; Hwang, S. S. Corrosion behavior of 9Cr F/M steels in supercritical
water. Proceeding of ICAPP05, Seoul, Korea, 2005; Paper no. 5136. Two symbols are shown as KAERI tested two different
heats of alloy T91. Test results displayed in red are from the University of Wisconsin. Copyright 2005 by the American Nuclear
Society, La Grange Park, Illinois.
10
HCM12A <10 to 25 ppb

600 C
500 C
2
500 C
400 C
2
500
360 C
500
1000
1500
2000
Time (h)
2500
3000
3500
Figure 13 Weight gain as a function of time for HCM12A exposed to deaerated water at 360, 400, 500, and 600 C. Test results
displayed in red are from the University of Wisconsin and test results displayed in blue are from the University of Michigan.
Data from Ampornrat, P.; Bahn, C. B.; Was, G. S. Proceedings of the 12th International Conference on Environmental Degradation
of Materials in Nuclear Power Systems Water Reactors; The Minerals, Materials and Metals Society, 2005; p 1387.
is compared with data for 500 C and 25 ppb. In contrast

to HCM12A (Figure 10) and similar to T91, T92
undergoes a larger weight gain at lower dissolved
oxygen concentration.
5.12.2.1.2 Austenitic stainless steels
Figure 15 demonstrates that variability in oxidation

response also occurs among austenitic stainless steels
of different composition. Of the three alloys shown,
293
4
T92 (NF616)
3.5
550 C
3
2.5
2
500 C
25 ppb
1.5
500 C 8000 ppb
400 C
350 C
0.5
0
0
100
200
300
400
500
600
700
800
Time (h)
Figure 14 Weight gain as a function of time for T92 (also known as NF616) exposed to 8000 ppb water at temperatures
ranging from 350 to 550 C (8000 ppb data from KAERI displayed as green points are adapted from Jang et al.62 and
compared to data taken at 500 C and 25 ppb dissolved oxygen from the University of Wisconsin.
6
600 C
316
4
D9
1
800H
0
200
400
600
800
1000
1200
Time (h)
Figure 15 Weight gain as a function of time for austenitic stainless steels, D9, 316, and Alloy 800H, exposed to low oxygen
concentration supercritical water at 600 C.
weight gain is greatest for 316 stainless steel. The weight

gain for Alloy 800H is less than that for the other alloys,
but erratic. This erratic weight gain is associated with
spallation of the oxide. Guzonas et al.26 reported weight
change data for the austenitic alloys Carpenter 20CB3,
Nitronic-50, and AL6XN after exposure to SCW
at 450 C for 483 h at 23 MPa. Carpenter 20CB3 lost

weight, while the other two alloys gained weight.
As with the F/M alloys, temperature has a strong
effect on oxide growth for austenitic steels. This is
demonstrated in Figure 16, which shows significantly
greater weight gains in 316 stainless steel with
294
316 stainless steel exposed at 500 C shows a slightly

greater weight gain from oxidation at higher dissolved oxygen concentrations (2000 ppb vs. 25 ppb).
At 550 C, the samples exposed to deaerated water
(<10 ppb dissolved oxygen) show significantly greater
weight gain from oxidation than samples exposed to
8000 ppb.
increasing temperature. The measured activation

energies are around 210 kJ mol1 for the stainless
steels (210 kJ mol1 for 304 stainless steel and 214 kJ
mol1 for 316L stainless steel), corresponding to cation diffusion through the oxide as the rate-limiting
step.81
The effect of dissolved oxygen concentration
on the oxidation of austenitic steels does not demonstrate a clear trend as evidenced by Figure 17.
5.12.2.1.3 Ni-based alloys
As shown in Figure 5, Ni-based materials show relatively little oxidation compared to F/M and austenitic
steels. As an example, Figure 18 shows that the weight
gain for Alloy 625 is small and does not change significantly with time for material exposed at 500 and
600 C. The Ni-based alloys were the only class of
alloys to show increasing weight gain (retained oxide)
at temperatures below the critical point (360 C),
where the density of the water is greater than just
above the critical point.
As with other alloys, weight gain due to oxidation
increases with temperature, as demonstrated in
Figure 19. The measured activation energies are 140 kJ
mol1 for the Ni-based alloys (134 kJ mol1 for Alloy
690 and 142 kJ mol1 for Alloy 625), corresponding to
cation diffusion through the oxide as the rate-limiting
step.81 At low temperatures (400 C), Alloy 625 exhibits a weight loss due to pitting. In Ni-based materials,
the weight change for shorter durations is determined
1.4
485 h
1.2
316 stainless steel

<10 ppb oxygen
1.0
0.8
0.6
0.4
419 h
0.2
575 h
0
400
578 h
450
500
Temperature (C)
550
Figure 16 Effect of temperature on the oxide growth of

316 stainless steel in deaerated water for roughly 500 h.
Reproduced from Was, G. S.; Teysseyre, S.; Jiao, Z.
Corrosion 2006, 62(11), 9891005.
0.07
316L < 10 ppb
Weight gain (mg cm-2 day-1)
0.06
0.05
316 and 316L
0.04
0.03
316 2000 ppb
0.02
0.01
316L 8000 ppb
316 25 ppb
0
250
300
350
400
450
500
550
600
Temperature (C)
Figure 17 Weight gain rate as a function of temperature for 316L exposed in <10 ppb dissolved oxygen (blue circles), 316L
exposed in 8000 ppb dissolved oxygen (green diamonds), 316 exposed in 25 ppb dissolved oxygen (red triangles), and
316 exposed in 2000 ppb dissolved oxygen (black squares). Data for exposure in 2000 ppb and less from Was et al.37
Data at 8000 ppb from Kasahara.60
by both the weight loss from pitting and the weight

gain from general oxidation. As a result, the actual
weight gain may be underestimated. Nevertheless,
experimental evaluation of layer thickness showed
that this class of alloys exhibits the lowest oxide layer
thickness.
0.3
360 C
625
0.25
0.2
0.15
0.1
600 C
0.05
0
-0.05
500 C
0
200
400
600
Time (h)
800
1000
1200
Figure 18 Weight gain as a function of time for Alloy 625

exposed to low oxygen concentration supercritical water at
360, 500, and 600 C. Adapted from Was, G. S.; Allen, T. R.
Time, temperature, and dissolved oxygen dependence of
oxidation of austenitic and ferriticmartensitic alloys in
supercritical water. Proceedings of ICAPP05;
Paper no. 5690; Ren, X.; Sridharan, K.; Allen, T. R.
Corrosion 2007, 63, 603.
295
5.12.2.1.4 Zr-based alloys
Zirconium-based alloys have been considered for incore SCWR applications (fuel cladding in all designs,
pressure tubes in a pressure tube design) because of
their good neutron economy, although current commercial alloys lack the high-temperature strength for
load-bearing application at SCW temperatures. The
CANDU SCWR design retains the use of zirconium
alloy pressure tubes by using an insulated fuel channel design9; in this design, the pressure tube, which
forms the in-core pressure boundary, operates at
about the moderator temperature (80 C), where the
mechanical strength is higher and the corrosion rate
is lower. The zirconium alloy Excel,99 a Canadian
zirconium-base alloy with nominal composition of
Zr3.5Sn0.8Nb0.8Mo, has been chosen for this
application.
Alloys investigated for use as an SCWR fuel cladding in international programs include Zircaloy-2,
Zircaloy-4, zirconium, and model alloys including
ZrNb, ZrFeCr, and ZrCuMo.34,52,69,77,92 Initial
studies of Zircaloy-2 and Zircaloy-4 showed extremely high oxidation, suggesting that zirconiumbased alloys would be unacceptable for use at the
temperatures required in an SCWR core. Further
studies of model alloys52,92 have indicated that optimized compositions can reduce the oxidation rate to
levels less than that of F/M steels, although still
higher than that of austenitic steels. Oxidation results
0.03
0.025
485 h
Alloy 625
<10 ppb oxygen
0.02
0.015
0.01
578 h
419 h
0.005
575 h
0
-0.005
-0.01
400
450
500
550
Temperature (C)
Figure 19 Weight gain as a function of temperature for Alloy 625. Reproduced from Was, G. S.; Teysseyre, S.; Jiao, Z.
Corrosion 2006, 62(11), 9891005.
296
2.5
500 C, <10 ppb O2
Processed at 580 C
1.5
Processed at 720 C
0.5
500
1000
1500
2000
2500
3000
3500
4000
Time (h)
Figure 20 Weight gain results for Zr0.4Fe0.2Cr alloys exposed to supercritical water at 500 C. The two datasets
represent materials processed at two different temperatures before exposure. Graphic produced from the data in
Motta et al.92
for one set of the model ZrFeCr alloys are shown

in Figure 20.
5.12.2.1.5 Ti-based alloys
Japanese programs have studied the corrosion of

Ti-based alloys in SCW. Alloys examined include
Ti15Mo5Zr3Al, Ti3Al2.5V, Ti6Al4V, and
Ti15V3Al3Sn3Cr.65 These Ti-based alloys were
exposed in static autoclaves with 8000 ppb dissolved
oxygen for 500 h at temperatures of 290, 380, and
550 C. Little difference was noted in the weight
gain of samples exposed at 290 and 380 C. Weight
gain of the samples exposed at 550 C was significantly higher than that of samples exposed at lower
temperatures. At 550 C, the Ti15V3Al3Sn3Cr
and Ti15Mo5Zr3Al alloys had roughly a factor of
three lower weight gain than the Ti3Al2.5V and
Ti6Al4V alloys. The weight gain at 550 C for
Ti15V3Al3Sn3Cr is similar to the weight gain
experienced by 304 stainless steel exposed at the
same temperature and <10 ppb dissolved oxygen.
5.12.2.2
Oxide Structures
5.12.2.2.1 Ferriticmartensitic steels
The oxide formed on a F/M steel exposed under

low (ppb) dissolved oxygen concentration consists of
two layers plus an internal oxidation layer.48 Examples
of oxide layer growth on F/M steels are shown in

Figure 21. A diagram of the process is shown in
Figure 22.100 All F/M steels form thick, but stable,
surface oxide layers. The scale consists of a layered
structure with an outer Fe3O4 layer, an inner
(FeCr)3O4 layer with the spinel structure, and an
innermost internal oxidation layer. (Spinel refers to a
2
class of compounds of general formulation A2+B3+
2 O4
that crystallize in the cubic (isometric) crystal system.
The oxygen anions are arranged in a cubic closepacked lattice and the cations A and B occupy some
or all of the octahedral and tetrahedral sites in the
lattice. Magnetite and nickel ferrite are examples of
iron oxides having the (inverse) spinel structure.) The
outer Fe3O4 layer predominantly consists of coarse
columnar grains and the inner (FeCr)3O4 layer is
composed of very fine equiaxed grains. Depending
on the steel, the thickness of the internal oxidation
zone was observed to vary significantly. None of the
F/M steels tested showed any indication of oxide
scale spallation at exposures of up to 3000 h for all
temperatures tested (290650 C, see Table 1).
5.12.2.2.2 Austenitic steels
Most examinations of oxidation layers formed on

austenitic alloys exposed to SCW reveal that the
oxide scale has a layered structure consisting of an
outer magnetite or mixed magnetitehematite layer
297
9Cr ODS
15 kV 3000
8 mm
15 kV 3000
8 mm
15 kV 3000
8 mm
15 kV 3000
8 mm
HCM12A
Figure 21 Top figure is a cross-section of the oxide formed on NF616 exposed at 500 C for 1026 h. Bottom figure is a
comparison of HCM12A and 9Cr oxide dispersion strengthened alloy exposed at 500 C in 25 ppb dissolved oxygen for
1026 h. 9Cr oxide dispersion strengthened alloy has a thinner and less porous oxide.
Atomic concentration (at.%)
100
2 mm
O
Cr
Fe
80
60
40
20
0
0
Outward
growth
10
15
20
Distance (mm)
25
30
35
Inward
growth
Fe2/3+,
eCr3+, e-
Diffusion
Diffusion
zone
Bulk FeCr
alloy
O2-
SCW
Fe3O4
FeCr
spinel
Fe
Figure 22 Typical cross-section for the oxide formed on a ferriticmartensitic steel exposed to 25 ppb supercritical water.
The upper left image is a scanning electron micrograph of the oxide cross-section. Between points 1 and 2 is the outer
magnetite layer. Between points 2 and 3 is the inner spinel layer. To the right of point 3 is the diffusion layer and the bulk metal.
298
5 mm
Figure 23 Cross-section morphology of the D9 stainless steel after exposure to supercritical water with 25 ppb of inlet
oxygen content at 500 C for 505 h.
scale, in which the oxide grains display preferential

orientations imposed by the original austenite grain
orientations.101
5.12.2.2.3 Ni-based alloys
20 m
20 m
20 m
Figure 24 Cross-sectional morphologies of the oxide

layers formed after exposure to supercritical water with an
inlet-dissolved oxygen content of 25 ppb at 600 C: (a) 316
stainless steel for 1000 h, (b) D9 stainless steel for 1000 h,
and (c) NF709 for 667 h.
and an inner (Fe, Cr, Ni, M)3O4 (M: other minor

elements) layer with the spinel structure. In some
cases, particularly at higher temperatures, bulk
microstructure rather than bulk composition was
observed to promote changes in the multilayered
structures and significantly alter the corrosion behavior of the alloys.
Figure 23 shows that the oxide layer formed on
the 15Cr15Ni austenitic D9 stainless steel exhibits a
nodular structure with an uneven surface after exposure at 500 C.101 The spacing of these nodules is in
the range of 510 mm, which is comparable to the size
of the austenitic grains in the D9 stainless steel.
At 600 C, a dual-layered structure was observed
on 316 stainless steel, as shown in Figure 24(a). For
the 15Cr15Ni D9 stainless steel, an additional continuous Cr2O3 layer was observed to form between
the spinel layer and the base alloy.47 Thereafter, D9
stainless steel showed much lower weight gain than
even the more highly alloyed NF709 after exposure
to 600 C SCW, implying good corrosion resistance
to the SCW environment. For the 20Cr25Ni alloy,
NF709, the near-surface austenite grains were readily oxidized intragranularly to form the inner oxide
The oxides found on Ni-based alloys are thin compared

to those found on the other alloy classes; Guzonas26
reported oxide thicknesses of about 50 nm on Alloy 625
and Alloy 690 after 483-h exposure to SCW at 450 C
and 23 MPa. The surface morphologies of the Ni-based
alloys, Alloys 625 and 718, after exposure to SCW at
500 C for about 500 h are shown in Figure 25. For Alloy
625, the oxide layer consisted of oxide particles with a
typical size of about 1 mm on a uniform oxide layer
composed of very fine oxide particles in the size range
of tens of nanometers. This particle size was verified
by high magnification imaging, which is not shown
here. Pits with varying diameters were also observed on
the sample surface. Similarly, Alloy 718 exhibited oxidation, consisting of oxide particles on a uniform oxide
layer, which leads to weight gain, and local pitting,
which leads to weight loss during SCW exposure.
For Alloy 625, increasing the SCW test temperature to 600 C resulted in the formation of a uniform
oxide surface with fine particulates, while the grain
boundaries were outlined by a topographically elevated oxide, as shown in Figure 26(a). Gray-scale
EDS mapping images for oxygen, chromium, and
nickel shown in Figure 26(b), 26(c), and 26(d),
respectively, indicate that grain boundaries on the
oxide surface were enriched in oxygen and chromium, whereas nickel was depleted. These results
indicate that grain boundaries are the primary paths
for cation migration in these corrosion regimes.47
There were no identifiable X-ray diffraction
(XRD) peaks corresponding to oxide from Alloy
625 at 500 C for 505 h because the oxide layer
formed was too thin. However, at 600 C for 1026 h,
three types of oxide products were identified on
Alloy 625. The major phase was a spinel phase with
a stoichiometry of Ni(Fe,Cr)2O4, and the other two
oxides were identified as Cr1.3Fe0.7O3 and NiO.47
(a)
299
(b)
Pitting in Alloy 625
Oxidation in Alloy 625
(c)
10 mm
(d)
Oxidation in Alloy 718
Pitting in Alloy 718
Figure 25 Morphological features of surface corrosion for Alloy 625 and 718 samples after exposure to supercritical water
with an inlet-dissolved oxygen content of 25 ppb at 500 C for 500 h. Reproduced from Ren, X.; Sridharan, K.; Allen, T. R.
Corrosion 2007, 63, 603.
15
25 mm
(a)
Cr K
(c)
65535
28
133
25 mm
OK
25 mm
(b)
Ni K
(d)
75
20
130
25 mm
Figure 26 Intergranular corrosion observed in Alloy 625 after exposure to supercritical water at 600 C for 1026 h. Scanning
electron microscope image is shown in (a) and energy dispersive X-ray spectroscopy mapping images of Cr, Ni, and O are
shown in (b), (c), and (d). Reproduced from Ren, X.; Sridharan, K.; Allen, T. R. Corrosion 2007, 63, 603.
Guzonas et al.26 reported Raman spectra from the

oxides formed on Alloy 625 and Alloy 690 after
exposure to SCW at 450 C for 483 h. The Raman
spectra suggested that the oxide on these alloys was
mainly NiFe2O4; the spectrum obtained from the

Alloy 690 surface showed an additional, unidentified
band. Auger electron spectroscopy of the surface of
Alloy 625 shows a duplex oxide structure after
300
80
In625 at 500 C for 500 h
14
Oxygen
60
Nickel
50
40
Chromium
30
20
600 C
600 C
10
8
6
4
Molybdenum
2
10
0
0
80
12
9
Sputter time (min)
15
18
In625 at 600 C for 1026 h
70
Atomic concentration (%)
NF616
AR
500 C
500 C
Y
12
Weight gain (mg cm2)
Atomic concentration (%)
70
60
Nickel
Oxygen
50
40
Chromium
30
20
Molybdenum
10
200
400
600
Time (h)
800
1000
Figure 28 Weight change data as a function of exposure

time for as-received (AR) and Y-coated ferritic steel Alloy
NF616 after exposure to supercritical water with an
inlet-dissolved oxygen concentration of 25 ppb at 500 and
600 C for up to 1000 h. Other ferriticmartensitic steel
samples exhibit comparable trends before/after coating
with a 250 nm yttrium layer. Adapted from Tan, L.;
Machut, M. T.; Sridharan, K.; Allen, T. R. J. Nucl. Mater.
2007, 371, 171175; Chen, Y.; Sridharan, K.; Allen,
T. R. In 13th Environmental Degradation of Materials in
Nuclear Power Systems 2007; Allen, T. R., Busby, J. T.,
King, P. J., Eds.; Canadian Nuclear Society, 2007.
Iron
0
0
10
20
30
Sputter time (min)
40
Figure 27 Chemical composition versus depth profiles as

determined by Auger electron spectroscopy for Alloy 625
after exposure to supercritical water with an inlet-dissolved
oxygen content of 25 ppb at (a) 500 C for about 500 h and
(b) at 600 C for 1026 h. Reproduced from Ren, X.;
Sridharan, K.; Allen, T. R. Corrosion 2007, 63, 603.
exposure to SCW at both 500 and 600 C.47 The

oxide consisted of a nickel/iron-rich outer layer and
a chromium-rich inner spinel layer, as indicated in
Figure 27. Moreover, a diffusion layer existed
between the oxide layer and the base alloy, where
the chemical compositions of all elements gradually
changed from that of the oxide to the bulk alloy
concentration.
5.12.2.3
Surface Composition Modification
In an attempt to mitigate the high oxidation rates

seen in the F/M alloys, modification of the surface
composition was investigated. Shown in Figure 28 as
an example, coating a thin yttrium film on the surface
of the F/M steel samples significantly mitigated the
corrosion rate in SCW environments.49,51 Figure 29

shows the cross-sectional view and EDS mapping of
the Y-coated 9Cr ODS alloy after exposure to SCW
at 500 C.
In comparison with the oxide structure for uncoated 9Cr ODS alloy (Figure 21), a yttrium-rich
layer formed on the Y-surface-treated 9Cr ODS alloy.
This layer was observed to divide the magnetite layer
into two parts.49,51 The yttrium, shown in the elemental mapping (Figure 29(c)), is mostly concentrated in one central layer, indicating that this layer
formed in the initial stages of exposure because of the
high thermodynamic stability of Y-based oxide, and
was subsequently driven outward because of the
growth of the fine Fe3O4 grains underneath. XRD
analyses have indicated that yttrium is predominantly present in the form of a YFeO3 phase.51
The yttrium layer converted to a discrete YFeO3
particulate layer, and this layer bisected the magnetite
layer into two regions with distinct morphologies.
The outer magnetite layer was porous, while the inner
magnetite layer was fine grained. The YFeO3 particulates acted as effective local diffusion barriers for cation
diffusion; however, the interparticulate regions provided
adequate diffusion paths for cations to promote the
formation of a fully developed oxide layer.
4 mm
(a)
100
Atomic concentration (at. %)
80
60
O
Cr
Fe
40
20
0
5
Y
W
4
3
2
1
0
0
10
(b)
15
20
25
30
Distance (mm)
Cr
Fe
301
5.12.2.3.1 Effect of grain size refinement
Grain boundaries are fast diffusion pathways. Since

diffusion is critical to oxide growth, one possible way
to influence oxidation rates is to change the grain
size. This has two potential offsetting effects. Smaller
grains allow oxide-forming elements, like chromium,
to quickly diffuse to the surface and form protective
oxides. On the contrary, smaller grains can allow
oxygen to more rapidly enter the bulk metal and
form an oxide. This is not desired. Typically, the
amounts of protective oxide-forming elements, like
chromium, in the bulk metal determine whether
smaller grains are beneficial to mitigating oxidation.
A smaller grain size was obtained on T91, using
equal channel angular processing (ECAP) and shot
peening. Before the grain refinement treatments, the
grain size was 5 mm. Following treatment, as shown in
Figure 30, the ECAP material had an average grain
size of 1.25 mm. In the affected near-surface region,
the shot-peened material had an average grain size
of 0.93 mm.
Figure 31 shows that weight gain is reduced by both
ECAP and shot-peening treatments. The reduction
in weight gain is roughly 30%. As demonstrated in
Figure 32 for the shot-peened material, the spinel
layer is thinnest in those regions where the bulk
metal grains are smallest, providing indications that
smaller grains in the bulk metal can lead to a more
protective oxide. Figure 33 provides an additional
example of improvement in oxidation resistance
through grain refinement. The data in Figure 33
0.12
(c)
Figure 29 (a) Cross-sectional scanning electron
microscopy image of the Y-coated 9Cr oxide dispersion
strengthened ferritic steel after exposure to supercritical
water at 500 C with an inlet-dissolved oxygen
concentration of 25 ppb for 667 h, (b) corresponding energy
dispersive X-ray spectroscopy elemental composition
profile across the oxide thickness, and (c) energy dispersive
X-ray spectroscopy mapping showing the elemental
distribution of O, Cr, Fe, and Y. Reproduced from Chen, Y.;
Sridharan, K.; Ukai, S.; Allen, T. Effect of yttrium thin film
surface modification on corrosion layers formed on C rods
steel in supercritical water. In 13th International Conference
on Environmental Degradation of Materials in Nuclear Power
Systems, Vancouver, Canada, August 2007.
Area fraction
0.10
0.08
0.06
0.04
ECAPed avg = 1.25
0.02
Shot-peened avg = 0.93
0.00
0
3
2
Grain size (m)
Figure 30 Comparison of grain size for T91 produced by

equal channel angular processing and shot-peening
processes. Both treatments lead to substantial grain
refinement. Ren, X.; Sridharan, K.; Allen, T. R. Mater. Corros.
2010, 61(9), 748755. Copyright Wiley-VCH Verlag GmbH &
Co. KGaA. Reproduced with permission.
302
6
TP1 500 C, 25 ppb
As-received
Nanograined
Shot peened
3
0
0
500
1000
1500
2000
2500
3000
3500
4000
Time (h)
Figure 31 Comparison of weight gain for T91 in three different metallurgical conditions exposed to supercritical water at
500 C for times up to 3000 h.
near-surface region significantly reduces the oxidation rate by 60% in Alloy 800H.
5.12.2.3.2 Effect of grain boundary structure
optimization
15 m
Figure 32 Example of changing oxide thickness with local
grain size in T91 exposed to supercritical water at 500 C.
The spinel layer (black) is thinnest in regions where the bulk
metal grains (right side of figure) are the smallest. Ren, X.;
Sridharan, K.; Allen, T. R. Mater. Corros. 2010, 61(9),
748755. Copyright Wiley-VCH Verlag GmbH & Co. KGaA.
Reproduced with permission.
are for an austenitic steel, Alloy 800H. After shot

peening, the surface grain size of the Alloy 800H
was around 15 nm. During exposure to SCW, the
grain size grew to 180 nm. As with T91, shot peening and the subsequent grain size reduction in the
Given that grain size significantly affects the oxidation response in both F/M and austenitic alloys,
studies were performed to determine whether changing the character of the grain boundary distributions
is important. Grain boundary engineering (GBE) was
applied to Alloy 800H by means of one cycle of
thermomechanical processing, followed by annealing
to improve the spallation resistance of the protective
oxide layer.38,53,102,103
Weight change measurement and SEM evaluations after SCW corrosion tests showed that extensive
oxide spallation occurred in the as-received samples, but
not in the GBE-treated samples (Figures 34 and 35).
To explain this distinct difference, cross-sections of
the samples were examined using electron backscatter diffraction (EBSD). Figure 36 shows the EBSD
maps illustrating the distribution of phases and strain
in the as-received sample (Figure 36(a) and 36(b))
and the GBE-treated sample (Figure 36(c) and 36(d))
after exposure to SCW at 500 C for 505 h and 690 h.
As shown in these figures, austenite (fcc structure),
magnetite, FeCr spinel, and hematite were identified
for both types of samples. Magnetite and FeCr spinel
are not distinguishable by EBSD because of their
identical crystal structure, but EDS analysis showed
303
0.8
Alloy 800H 500 C, 25 ppb
0.7
As received
0.6
0.5
0.4
0.3
0.2
0.1
0
Shot peened
500
1000
1500
2000
Time (h)
2500
3000
3500
Figure 33 Comparison of weight gain for Alloy 800H in large- and small-grained metallurgical conditions exposed to
supercritical water at 500 C for times up to 3000 h.
0.5
800 H
0.4
TM processed
Annealed (1 mm)
Annealed (600 grit)
500 C
25 ppb
0.3
0.2
0.1
0.0
0.1
0
200
400
600
800
1000
1200
Time (h)
Figure 34 Weight gain versus time for Alloy 800H exposed at 500 C. TM refers to thermomechanically processed
condition. Annealed samples were polished to 1 mm and 600 grit finish prior to exposure. TM samples were polished to 1 mm
finish prior to exposure.
that the inner layer is an FeCr spinel phase and the

outer layer is magnetite. Comparing Figure 36(a) with
36(c), it can be seen that the GBE-treated sample
showed a higher fraction of hematite mixed with a
smaller amount of magnetite in the outer layer, and
an inner layer of a spinel phase mixed with phases
identified as austenite.
The strain distribution shown in Figure 36(b)

is presented by the local average misorientation
between each EBSD data point measurement and
its neighbors, excluding any higher angle boundaries
(>5 ). This figure indicates that for the as-received
sample, there is a strain accumulation close to the
FeCr spinelmagnetite interface (the interface
304
(a) AR: 500 C/3-week
(b) GBE: 500 C/4-week
Exfoliated
Compact and
continuous
2000 m
Retained oxide
2000 m
(c) AR: 600 C/6-week
(d) GBE: 600 C/6-week
Exfoliated
Compact and
continuous
Hematite
200 m
200 m
Figure 35 Plan view images indicate that spallation of the oxide was significant in as-received Alloy 800H, but not in the
grain boundary-engineered Alloy 800H. Reproduced from Tan, L.; Sridharan, K.; Allen, T. R.; Nanstad, R. K.; McClintock, D. A.
J. Nucl. Mater. 2008, 374, 270280.
fcc
(c) GBE
(phase)
(b) AR
(strain)
fcc
(d) GBE
(strain)
fcc + S
(a) AR
(phase)
M
H
2 mm
2 mm
Inner
Outer
2 mm
2 mm
Inner
Outer
Inner
Outer
Inner
Outer
Figure 36 Electron backscatter diffraction maps of cross-sections of oxide layer formed on Alloy 800H samples,
demonstrating the phase and strain (0 5 average misorientation) distribution: (a, b) as-received (AR) samples exposed to
supercritical water with an inlet-dissolved oxygen content of 25 ppb at 500 C for 3 weeks and (c, d) grain boundary
engineering-treated samples exposed to supercritical water at 500 C for 4 weeks. The labels fcc, S, M, and H denote
phases with face-centered cubic structure, such as the substrate austenite, spinel [(Fe,Cr)3O4], magnetite [Fe3O4], and
hematite [Fe2O3], respectively. The specimen layout during electron backscatter diffraction analysis is schematically
shown beside the electron backscatter diffraction maps, with the direction of TD [010] and RD parallel to oxide growth
and oxide surface, respectively. Adapted from Tan, L.; Sridharan, K.; Allen, T. R.; Nanstad, R. K.; McClintock, D. A.
J. Nucl. Mater. 2008, 374, 270280.
between the inner and the outer layers). The

strain distribution shown in Figure 36(d) for
the GBE-treated sample is relatively uniform in the
oxide scale.
By integrating the strain intensity along the

direction parallel to the FeCr spinelmagnetite
interface, relative strain intensity as a function of
the location across the oxide scale was obtained and
305
1.0
Strain intensity (normalized)
+
0.8
AR
GBE
0.6
0.4
0.2
Metal Inner oxide Outer oxide
0
3
4
Distance (mm)
Figure 37 Normalized strain intensity across the oxide scale on the as-received and the grain boundary engineeringtreated Alloy 800H samples. The two lines are aligned at the innerouter oxide interface. Reproduced from Tan, L.;
Sridharan, K.; Allen, T. R.; Nanstad, R. K.; McClintock, D. A. J. Nucl. Mater. 2008, 374, 270280.
is shown in Figure 37. These data clearly show that

there is a sharper strain change at the FeCr spinel
magnetite interface in the as-received sample
compared to the GBE-treated sample. The strain
change between the inner or outer oxide layers was
significantly reduced after GBE treatment. This is
believed to be attributable to the increased population of low energy coincidence site lattice boundaries (CLSBs) for the GBE-treated samples,104,105
and results in lower levels of oxide spallation for
the GBE-treated alloy.
5.12.2.4
Summary of Corrosion in SCW
1. All F/M steels exhibited a dual-layered oxide

structure after exposure to SCW, composed of an
outer Fe3O4 magnetite layer and inner FeCrO
spinel layer.
2. Oxide growth, as measured by weight gain of the
samples, increased dramatically with temperature.
3. The 12Cr F/M steels exhibited a lower weight
gain compared to those containing 9% Cr, with
the exception of 9Cr ODS alloy, which showed a
lower weight gain than all the F/M steels tested.
TEM examination of the oxidized layer in the 9Cr
ODS alloy indicated segregation of yttrium to the
grain boundary area in the internal oxidation layer,
which may retard outward cation diffusion.
4. For austenitic alloys, the weight gain and oxide
thickness were substantially lower than for F/M
steels. Weight change measurements and SEM
cross-sectional examination showed that the

oxide layer in these alloys is susceptible to spallation. In some of these alloys, an innermost Cr2O3
layer was also observed.
5. In terms of weight gain, the Ni-based alloys
showed the best performance, but these alloys
also exhibited some pitting that may numerically
offset some of the weight gain from oxidation.
6. Surface modification approaches, such as yttrium
surface treatment, can reduce the oxidation kinetics
and hold promise, particularly for ferritic steels.
7. Grain refinement techniques, such as ECAP and
shot peening, lowered the oxide growth rate in both
F/M and austenitic alloys. GBE reduced the tendency for oxide spallation in austenitic alloys, and
strain measurements across the oxide layer showed
a more gradual change in strain distribution for
the GBE-treated samples, which may be in part
responsible for the reduced spallation.
5.12.3 Stress Corrosion Cracking in

SCW
This section reviews the current understanding of
SCC behavior of candidate materials for SCWR systems. With the exception of the effect of irradiation
on SCC, the important issues of radiation response
and radiolysis are not addressed in this review. In
general, the data reviewed here are distinct from the
body of literature covered by SCWO experiments;
306
however, most of the data reported below on the

effects of water chemistry and of density or dielectric
constant are from the SCWO literature.
In support of the SCWR program, corrosion and
SCC have been studied in pure SCW in austenitic
stainless steels, Ni-based alloys, F/M steels, and Tibased alloys. Test temperatures have ranged from 288
to 732 C. Dissolved oxygen concentration has ranged
from <10 ppb to 8000 ppb. The effects of chemical
additions have been examined in the context of the
development of SCWO systems, specifically the
effects of addition of H2SO4, HCl, H2O2, and NaCl.
Additionally, the effects of system pressure and dielectric constant on SCC resistance have been studied.
SCC experiments in SCW include constant extension rate tensile (CERT) tests, constant load tensile
(CLT) tests, and crack growth rate (CGR) tests.
A total of four alloy systems have been investigated
for their SCC response in varying levels of detail:
austenitic stainless steels (nine alloys), nickel-based
alloys (eight alloys), F/M steels (six alloys), and one
titanium and one F/M ODS alloy. Intergranular
stress corrosion cracking (IGSCC) has been found
in all but the titanium alloy system, which exhibited
transgranular stress corrosion cracking (TGSCC).
The alloy systems, specific alloys and range of test
conditions are summarized in Table 2.
The existing database is characterized by a large
number of alloys and parameters, yet experiments
were conducted by relatively few investigators and
laboratories. The selections of the reference alloy
condition (sensitized vs. unsensitized) and the reference water chemistry (deaerated vs. 8000 ppb dissolved oxygen) tend to be specific to the laboratory
in which the experiments were conducted. The result
is that there exist few instances in which data can be
compared between laboratories because of the inherent differences in experimental conditions. As such,
the following results and their interpretation are
compromised somewhat by the lack of a systematic
approach across the various laboratories and investigators conducting the experiments.
An issue of particular importance in the determination of SCC susceptibility is the way in which this
susceptibility is measured. Two different measures
are presented in the literature. One is based on the
amount of intergranular cracking (%IG) of the fracture surface following failure, and the other is based
on the quantification of cracks on the sample surface
(density, length, length/unit area, depth). Tsuchiya
et al.,61,106,109 Fujisawa et al.,110 and Saito107 use the
%IG on the fracture surface as a measure of SCC
susceptibility. Was and coworkers84,111,122 use crack

depth and crack density on the gauge surface as an
indicator of the IGSCC susceptibility. Unfortunately,
these measures are not always in agreement.
As described later, results often show that extensive IG cracking occurred in multiple locations in the
gauge section, but very little was observable on the
fracture surfaces. This is likely due to two principal
factors: obscuring of the fracture mode by severe
oxidation following fracture, and the poor statistical
probability of the fracture surface capturing the
extent of IG cracking. It has been shown in many
studies that ductile alloys that fail by IG fracture in
service (e.g., Alloy 600 in primary water) often exhibit
only small amounts of IG cracking in CERT tests.127
Because CERT tests are typically conducted at a high
strain rate relative to the growth rate of a stress
corrosion crack, the plastic strain tends to outrun
the IG cracks that have initiated, resulting in a largely
ductile fracture mode. For example, a rough measure
of the CGR can be obtained by dividing the maximum crack depth by the time of the test. For 304
stainless steel tested in 400 C deaerated SCW,111 this
value falls between 1.0 108 mm s1 (400 C) and
3.2 107 mm s1 (550 C). So, even the fastest CGR
is still an order of magnitude below the extension rate
(7 106 mm s1) imposed by the test. As an aside,
these CGRs are similar to those experienced by 304
stainless steel in BWRs under low-potential conditions.128 In these cases, the fracture surfaces are
largely ductile, but the samples display significant
IG cracking on the surfaces, but with little depth
penetration. As such, a better measure of cracking is
obtained through analysis of the gauge section and
the cross-section of the tensile bars. Cracking severity, as measured by the crack length per unit area
(crack density crack length on the gauge surface),
incorporates both the density and length of the
cracks. Further, crack length measured on the gauge
surface correlates well with crack depth measured in
cross-section. This agreement is supported by extensive work by Santarini,129 who showed through successive crack sectioning that there is a functional
relationship between crack length and crack depth
in CERT samples.
While the significance of cracking on the gauge
surface is not yet understood, the degree of IG cracking is known to depend on the strain rate in CERT
tests, and at lower strain rates, the amount of IG
cracking could increase substantially.130,131 However,
a systematic analysis of the effect of strain rate on
IGSCC in SCW has not yet been conducted. While it
Table 2
Summary of alloys and conditions used in stress corrosion cracking experiments in supercritical water
Alloy
Temp. ( C)
Water chemistry
Loading mode
Results
References
Austenitic
stainless
steel
304, 316L
(sensitized)
310S (fine grain)
316L
290550
8000 ppb DO, 0.06 mS cm1, 25 MPa
slow strain rate test 4 107 s1
IG 304 below 400 C
290, 550
400
400550

slow strain rate test
2.78 106 s1
No IGSCC
IGSCC
304L, 316L
IG at all temperatures
[111]
316 (sensitized)
360, 400
[112]
500, 650

2.78 106 s1
IG, pressure dependent
347H, 316NG,
1.4970, BGA4
316
8000 ppb DO, 25 Mpa

8000 ppb DO, 25 MPa, up to
0.01 mol l1 HCl, up to 3.6 MPa H2
Deaerated (<10 ppb DO),
nondeaerated (8000 ppb DO),
<0.1 mS cm1, 25 MPa
8000 ppb DO, 2560 MPa, 2.413.4
dielectric constant
100150 ppb, <0.1 mS cm1, 25 MPa
[61, 106,
107, 108]
[109]
[110]
IGSCC 316NG and BGA4
[113]
288500
CGR
CGR temperature
dependent
[114]
316L, 316LGBE
500
Nondeaerated (2000 ppb DO),

deaerated (<10 ppb DO), 0.1
0.5 mS cm1 10.324.8 Mpa
<10 ppb DO, <0.1 mS cm1, 25 MPa
[115]
316 (sensitized)
360, 400
316L (SA)
360, 400
S31266
400500
8000 ppb, 2560 MPa, 2.413.4

dielectric constant
8000800 000 ppb, up to 0.01 M H2SO4,
3060 MPa
525 MPa, 10 wt% H2O2, up to 1.6 g l1
NaCl, up to 1 g l1 HCl
316, 347
732
Deaerated, 34.5 MPa
TG crack in 316
[90]
316L, D9 (0,
7 dpa)
316L (0, 7 dpa)
316L (SA and CW,
2744 dpa)
400, 500
<10 ppb DO, <0.1 mS cm1, 25 MPa

2.78 106 s1
2.78 106 s1
slow strain rate test 103 s1,
5 107 s1
Constant load 87% sy, 100% sy
Constant load 103, 83 MPa
for 168 h
IG reduced in GBE
condition
IG, strong dependence on
pressure
IG, strong dependence on
pressure, H2SO4
IG crack under certain
condition
IG at both temperatures
[117]
400, 500
400, 500
<10 ppb DO, <0.1 mS cm1, 25 MPa

<10 ppb DO, hydrogenated,
<0.1 mS cm1, 2427.6 MPa

[118]
[119]
800H
500
400600 ppb DO, <0.2 mS cm1,

25 MPa
800H (0, 7 dpa)
400, 500
<10 ppb DO, <0.1 mS cm1, 25 MPa
slow strain rate test 0.8 107 s1

or 1.5 107 s1 (conflicting
rates given)
IGSCC correlates
w/hardening and
hydrogen
No SCC
[117, 121]
[66]
[66, 68]
[116]
[120]
307
Continued
Alloy class
308
Continued
Alloy class
Alloy
Temp. ( C)
Water chemistry
Loading mode
Results
References
Nickelbased
600
625, C276, MC
290550
400
[106]
[110]
290550
400550

2.78 106 s1
No IGSCC
IGSCC for 625, C276
600, 690, 625

625, 690
IGSCC 625 at 550 C

IG at all temperatures
[107]
[122]
690, 690GBE
500
8000 ppb DO, 0.06 mS cm1, 25 MPa

8000 ppb DO, 25 MPa, up to
0.01 mol l1 HCl, up to 3.6 MPa H2
8000 ppb DO, <0.1 mS cm1, 25 MPa
Deaerated (<10 ppb DO),
<0.1 mS cm1, 25 MPa
<10 ppb DO, <0.1 mS cm1, 25 MPa
[115]
690, 718
N06625, N06030
400
390500
Aerated SCW, 25 Mpa

22.525 MPa, 10 wt% H2O2, up to
1.6 g l1 NaCl
690 (0, 7 dpa)

690 (0, 7 dpa)
12-Cr-1Mo1WVNb
T91, T92
400, 500
400, 500
290, 550
<10 ppb DO, <0.1 mS cm1, 25 Mpa

<10 ppb DO, <0.1 mS cm1, 25 Mpa
8000 ppb DO, <0.1 mS cm1, 25 Mpa

slow strain rate test 103 s1,
5 107 s1
Constant load 100% sy, 140%
sy
IG reduced in GBE
condition
IGSCC in 718
IGSCC in 625
No IGSCC
[117, 121]
[118]
[107]
370600
slow strain rate test 0.8

3 107 s1, fatigue CGR
No SCC
400
<10600 ppb, <0.1171.1 mS cm1,

25 MPa
<10 ppb DO, <0.1 mS cm1
[73, 83,
120]
[124]
400, 500, 600
10, 100, 300 ppb DO, 25 MPa
370, 500
<10 ppb DO, <0.1 mS cm1 inlet,

25 MPa
Corrosion fatigue
400, 500
<10 ppb DO, <0.1 mS cm1 inlet,

25 MPa
8000 ppb DO, <0.1 mS cm1, 25 MPa
100150 ppb, <0.1 mS cm1, 25 MPa
8000 ppb DO, 7.8 MPa
IG in HT-9 only, increase

with irradiation, temp,
DO
Fatigue CGR increased
due to fatigue-oxidation
interaction
IG cracking in all
conditions
TGSCC
No SCC
No SCC
Ferritic
martensitic
T91, T91 CSL

HCM12A, HT-9
(010 dpa)
T91, T91 CSL,
HCM12A, HT-9
(0, 7 dpa)
T91
Ti Alloy
ODS
HT-9, HT-9 CSL

(0, 7 dpa)
Ti-15Mo-5Zr-3Al
PM2000
19Cr, 19Cr-4.5Al
290, 550
500, 650
288
DO, dissolved oxygen; SSRT, slow strain rate test; IG, intergranular; CGR, crack growth rate test.

slow strain rate test 104 to
3 107 s1
IG in HT-9 only
[123]
[116]
[59, 125]
[85]
[126]
[107]
[113]
[64]
Table 2
1.2
Maximum stress (MPa)
600
500
400
IGSCC fraction water density (mg m3)
304 Was et al.(84,111)

304(61,106,108)
316L(84,106,111,122)
316L(108)
316(61,112)
310(109)
347H(113)
1.497(113)
BGA4(113)
300
200
400
450
500 550 600

Temperature (C)
650
700
Figure 38 Maximum stress versus temperature in

constant extension rate tensile tests on austenitic stainless
steel in supercritical water. Solid symbols denote solutionannealed samples in deaerated supercritical water, and
open symbols denote sensitized samples in 8000 ppb
dissolved oxygen.
50
Failure strain (%)
25
0.8
20
Water density
30
20
304(84,111)
304(61,108)
316L(84,111,122)
316L(108)
316(61,112)
347H(113)
1.497(113)
BGA4(113)
10
400
450
500
550
600
650
700
Temperature (C)
Figure 39 Strain to failure versus temperature in constant
extension rate tensile tests on austenitic stainless steel in
supercritical water. Solid symbols denote solution-annealed
samples in deaerated supercritical water, and open symbols
denote sensitized samples in 8000 ppb dissolved oxygen.
has been argued that cracking on the gauge section is

a more accurate measure of SCC susceptibility, both
measures of IG cracking propensity, %IG on the
fracture surface and crack density on the gauge surface, are presented.
Crack
density
0.6
15
10
0.4
IGSCC
fraction
0.2
250
300
350 400 450 500

Temperature (C)
550
0
600
Figure 40 Intergranular stress corrosion cracking

fraction, crack density and water density of 304 stainless
steel strained at 4 107 s1 in supercritical water
containing 8000 ppb oxygen at a pressure of 25 MPa.
Reproduced from Tsuchiya, Y.; Kano, F.; Sato, N.;
Shioiri, A.; Moriya, K.; Kasahara, S. SCC properties of
metals under supercritical-water cooled power reactor
conditions. Corrosion 2004, NACE International, Houston,
TX, 2004; Paper No. 04485.
5.12.3.1
40
0
350
0
200
100
0
350
30
Sensitized 304
Crack density (cracks mm2)
700
309
Austenitic stainless steels that have been tested in

pure SCW include 304, 310, 316, 316L, 347H, D9,
1.4970, BGA4, UNS S31266, and 800H. All of these
alloys have experienced some degree of SCC, most of
which is intergranular. Figures 38 and 39 show the
maximum stress and failure strain, respectively, for
several stainless alloys tested in CERT mode in SCW.
Note that there is a general decrease in the maximum
stress with temperature, but the failure strain does
not show a clear trend. These datasets consist of
essentially two groups, those for CERT tests conducted on sensitized alloys in 8000 ppb dissolved
oxygen and a set consisting of solution-annealed
samples tested in deaerated (<10 ppb O2).
Plots of the extent of IG cracking versus temperature

are shown in Figures 40 and 41. Tsuchiya et al.61
noted that IGSCC susceptibility measured as %IG
on the fracture surface of sensitized 304 stainless steel
in 8000 ppb O2 dropped from 100% at 290 C to 0%
above 400 C (Figure 40). However, they also noted
that over the same temperature regime, there was
an increase in the density of cracks on the gauge
surface. Teysseyre and Was111 noted that in annealed
304 and 316 L stainless steel in deaerated SCW,
310
100
350
80
2500
304
60
2000
40
316L
1500
20
Maximum crack depth (m)
304
Crack length per unit area (m mm2)
3000
400
(a)
450
500
550
Temperature (C)
304
316L
250
200
150
100
50
316L
1000
350
300
0
350
0
600
(b)
400
450
500
550
Temperature (C)
600
Figure 41 (a) Crack length/unit area and crack density versus temperature, and (b) crack depth versus temperature for
304 and 316L stainless steel strained at 3 107 s1 in deaerated supercritical water at 25 MPa. Reproduced from Teysseyre, S.;
Was, G. S. Corrosion 2006, 62(12), 11001116.
10-6
304
316L
625
690
10-7
Q = 105 kJ mol1
Q = 85 kJ mol1
Q = 84 kJ mol1
Q = 87 kJ mol1
10-8
10-9
1.2
1.25
1.3
1.35
1.4
1.45
1.5
1/T (10-3 K-1)
Figure 42 Arrhenius behavior of crack growth rates and

activation energy for cracking for austenitic stainless
steels and nickel-based alloys tested in pure, deaerated
(<10 ppb O2) supercritical water. Rates were determined
from crack depth and test time in constant extension rate
tensile experiments. Reproduced from Teysseyre, S.;
Was, G. S. Corrosion 2006, 62(12), 11001116.
the crack density and crack length per unit area

decreased with temperature, but the crack depth
showed a significant increase with temperature
(Figure 41). The IG amounted to only a few percent. Crack depth measurements permitted determination of the activation energy for crack growth,
which was found to be in the range 85105 kJ mol1
for the stainless steel alloy, as shown in Figure 42.
The cracking mechanism is discussed in more detail
in the section on nickel-based alloys. Examples of
cracks in 304 and 316L stainless steel in 550 C

SCW are shown in Figure 43.
Tests conducted in 500 C SCW containing
100150 ppb oxygen on 316NG, 347H, and 1.4970
stainless steel showed no clear evidence of SCC on
the fracture surface, but cracks were evident on the
side surface of all alloys.113 Both TG and IG cracks
were identified on the 316NG stainless steel sample.
Austenitic alloy BGA4 showed IGSCC on both fracture and side surfaces. Tests in 650 C SCW showed
IGSCC and TGSCC on the fracture surface, but no
cracks were observed on the side surface.
A single study was conducted on the CGR of 316L
stainless steel in SCW. Experiments were conducted
on 20% cold-worked 316L stainless steel in deaerated SCW from 288 to 500 C at a constant K value
of 25 MPa m1/2.114 CGR increased with temperature in the subcritical regime between 288 and
360 C. In the supercritical regime, the rate decreased
with temperature from 400 to 450 C and then to
500 C, as shown in Figure 44. Analysis of the fracture surface using SEM revealed that SCC in both
subcritical and SCW was intergranular. Comparison
of the crack length from SEM and DC potential drop
(DCPD) showed that DCPD measurements of crack
length are within 30% of that measured from the
fracture surface. Crack blunting by rapid oxidation
in the supercritical regime during a CGR test, as
opposed to film rupture by the higher strain rate of
a CERT test, may explain the apparent contradiction
of the temperature dependence of cracking in CGR
versus CERT tests.
311
(b)
(a)
304
316
100 mm
Det
SE T304-550
100 mm
Magn Det
250x SE T316-550
(c)
(d)
690
625
Magn Det WD
250x SE 9.7 T625-550
100 mm
Acc.V Spot Magn

15.0 kV 5.0 2000x
Det WD
BSE 10.0
10 mm
Figure 43 Micrographs of crack morphologies on cross-sections of samples tested in pure, deaerated supercritical
water at 550 C, (a) 304 stainless steel, (b) 316L stainless steel, (c) Alloy 625 and 500 C (d) Alloy 690. Reproduced from
Teysseyre, S.; Was, G. S. Corrosion 2006, 62(12), 11001116.
Very limited tests have been conducted on Alloy

800H. Alloy 800H was tested in CERT mode in
500 C SCW containing 500 ppb dissolved oxygen.120
The sample failed at about 38% strain and exhibited
evidence of brittle-type fracture over a portion of the
fracture surface.
5.12.3.1.2 Microstructure
Some work has been conducted to understand the

role of grain boundary character on cracking behavior.115 Both 316L stainless steel and Alloy 690 were
given thermomechanical treatments to increase the
fraction of special boundaries, and then were tested in
CERT mode in 500 C water. Results showed that the
fraction of cracked grain boundary length in the
specimens with higher fractions of special boundaries
is reduced for 316L stainless steel and Alloy 690 by
factors of 9 and 5 at 15% strain, and 3 and 2 at 25%
strain, respectively. This reduction is due to the
special boundaries which, at 35% strain, have a
probability of cracking that is 918 times lower than

that for a random high angle boundary (RHAB).
Figure 45 shows the probability of crack occurrence
at special boundaries and RHABs following straining
to 15% and 25% in 500 C SCW. Note the very large
difference in probability at both strains, regardless of
the special boundary fraction of the sample.
Fine grain 310 stainless steel, tested at 290 and 550 C
in SCW containing 8000 ppb oxygen, showed no cracking on either the fracture surface or the side surface.109
However, the authors do not report the grain size.
Several studies were conducted on the effect of

chemical additions to SCW during the development
of SCWO processes; chemicals added include
H2SO4, HCl, NaCl, and H2O2. The addition of HCl
to 400 C SCW containing 8000 ppb dissolved oxygen resulted in a decreased strain to failure and
increased IGSCC susceptibility in 316 stainless
312
10-6
0.8
10-7
0.6
0.4
CGR deaerated
CGR in 2 ppm O2 water
-8
10
0.2
10-9
250
300
350
400
450
500
Oxide weight gain rate (mg dm2 day1)

water density (g cm3)
Water density
Oxidation rate
0
550
Temperature (C)
Figure 44 Crack growth rate versus temperature across the subcriticalsupercritical line for a 0.5T CT specimen of
unsensitized type 316L stainless steel in pure water. Redrawn from Peng, Q. J.; Teysseyre, S.; Andresen, P. L.; Was, G. S.
Corrosion 2007, 63, 10331041. Water density is adapted from: W. Wagner, A. Prub, J. Phys. Chem. Ref. Data 31 (2002),
p. 327, and oxide weight gain rate over a period of 500 hr is from: G. S. Was, S. Teysseyre, Z. Jiao, Corrosion 62 (2006),
p. 989.
0.12
15% strain
Cracking probability
0.1
25% strain
Special
RHAB
0.08
0.06
0.04
690GBE
690
316LGBE
316L
690GBE
690
316LGBE
316L
0.02
Figure 45 Probability of crack occurrence at special

boundaries and random high angle boundaries following
straining to 15% and 25% in 500 C supercritical water.
Reproduced from West, E. A.; Was, G. S. J. Nucl. Mater.
2009, 392, 264271.
steel over the range 0.0010.01 mol l1.110 Addition of

0.01 M H2SO4 to SCW resulted in a sharp reduction
in strain to failure in solution-annealed 316L stainless
steel and severe intergranular cracking.66,68 Two
other austenitic stainless steels, superaustenitic
stainless steel UNS S 31266 and 347H, were tested
in SCW with addition of oxidizers. UNS S 31266 was
tested at 400 or 450 C in SCW with additions of
10 wt% H2O2, 1 g l1 HCl, or 10 wt% H2O2 1.6 g l1
NaCl in both CERT mode (5 107 s1) and CLT
(100% of the elastic limit).116 The CERT test in
400 C SCW 10 wt% H2O2 resulted in SCC, but
the CLT test in the same environment at 450 C
showed no evidence of cracking. However, CLT
tests in 10 wt% H2O2 1.6 g l1 NaCl at 450 C
and in 1 g l1 HCl at 400 C resulted in cracks ranging from 5 to 130 mm in length 316 and 347H stainless
steel were exposed to 732 C, 34.5 MPa SCW and
stressed to 90% of the stress required to cause rupture in 1000 h (103 and 83 MPa, respectively).90 After
168 h of exposure, the 316 stainless steel sample had
failed and exhibited several small cracks in addition
to the crack that caused failure.
10
0.35
0.3
0.25
0.2
20
30
40
50
60
2
70
Pressure (MPa)
Figure 46 Failure strain and dielectric constant versus
pressure for 316 stainless steel strained at 2.8 106 s1 in
supercritical water containing 8000 ppb oxygen.
Reproduced from Watanabe, Y.; Abe, H.; Daigo, Y.
Environmentally assisted cracking of sensitized stainless
steel in supercritical water: Effects of physical property of
water. Proceedings of GENES4/ANP2003, Kyoto, Japan,
Sept 1519, 2003; Paper No. 1183.
5.12.3.1.4 Pressure/dielectric constant
Watanabe and coworkers66,68,112 conducted a systematic study of the effect of SCW pressure on the
cracking propensity of sensitized 316 stainless steel
in pure water containing 8000 ppb dissolved oxygen.
Varying the water pressure from 25 to 60 MPa at
400 C, they observed a monotonic decrease in strain
to failure and maximum stress and an increasing
amount of IG fracture with pressure, or dielectric
constant, as shown in Figure 46. By 60 MPa, the
failure was almost totally intergranular. Watanabe
suggested that at high pressure, the higher dielectric
constant has several effects; it favors the formation of
metal ions, tends to increase the solubility of metal
oxides, and increases the electrical conductivity of
the water, resulting in enhanced anodic dissolution
and greater cracking propensity. The reverse is true
under the low-density, gas-like conditions of SCW at
low pressure.
5.12.3.1.5 Irradiation
Irradiation of 304 and 316L stainless steel significantly

increased the IG cracking propensity at both 400 and
500 C. Samples irradiated with 2 MeV protons showed
significant increases in the amount of IG cracking with
8000
120
Crack length
per unit area
6000
80
5000
%IG
4000
60
3000
40 Crack depth
2000
400 C SCW
316L
7 dpa
20
(a)
(b)
7000
100
120
3
4
5
Dose (dpa)
1000
8
8000
Crack length
per unit area
7000
100
6000
%IG
80
5000
4000
60
Crack depth
3000
40
2000
20
0.4
313
316L
1000
7 dpa
12
Dielectric constant of water
Failure strain (%)
0.45
14
Sensitized 316
400 C
Crack depth (m) + %IG on fracture surface
0.5
0
0
380 400 420 440 460 480 500 520
SCW temperature (C)
Figure 47 Crack depth, crack length per unit area and

%IG on the fracture surface (a) versus dose, and (b) versus
temperature for 316L stainless steel strained at 3 107 s1
in deaerated supercritical water at 25 MPa. Reproduced
from Zhou, R.; West, E. A.; Jiao, Z.; Was, G. S.
J. Nucl. Mater. 2009, 395, 1122.
dose, as measured by either crack length per unit area,

crack depth, or %IG on the fracture surface, as shown
in Figure 47.117,118 The crack length per unit area and
the %IG cracking were greater at 400 C than at
500 C, but the behavior of the crack depth was
reversed. The degree of cracking increased with hardness at 400 C (Figure 48(a)), and there appears to be a
correlation with the grain boundary chromium concentration (Figure 48(b)). Austenitic D9 stainless steel
and Alloy 800H also showed increased susceptibility to
IGSCC following irradiation.121 The intergranular
crack length per unit area normalized to strain showed
that irradiation has a very similar effect on D9 and
314
7500
316L, 400 C
316L, 400 C
7000
6500
6000
5500
5000
150
200
(a)
250
Hardness (Hv)
300
350 10
(b)
12
14
16
18
Grain boundary Cr concentration (wt%)
20
Figure 48 Dependence of intergranular cracking on (a) hardness and (b) grain boundary chromium content for unirradiated
and irradiated (27 dpa at 400 C) 316L stainless steel and strained at 3 107 s1 in 400 C deaerated supercritical water
at 25 MPa. Reproduced from Zhou, R.; West, E. A.; Jiao, Z.; Was, G. S. J. Nucl. Mater. 2009, 395, 1122.
Crack length per unit area normalized

to strain to failure (mm mm2)
300
7 dpa
Unirradiated
250
D9
316L
200
150
100
50
690
800H
0
Figure 49 Crack length per unit area measurements on
unirradiated and 7 dpa proton irradiated alloys D9, 316L,
690, and 800H strained in 400 C supercritical water.
Reproduced from West, E. A.; Teysseyre, S.; Jiao, Z.;
Was, G. S. In Proceedings of the 13th International
Nuclear Power Systems Water Reactors, Canadian
Nuclear Society; Allen, T. R., Busby, J., King, P. J., Eds.;
316L stainless steel (Figure 49). Cracking susceptibility in Alloy 800H increased with irradiation, but the
magnitude of the cracking is considerably lower than
that in 316L and D9 stainless steel.
Japanese Prime Candidate Alloy ( JPCA) was

tested in SCW after having undergone neutron irradiation to doses between 26.9 and 43.9 dpa at temperatures ranging from 390 to 520 C in the Fast Flux Test
Facility (FFTF).119,132 This alloy is similar to a Tistabilized 316 stainless steel. Overall, samples were
highly susceptible to IG cracking. Figure 50 shows
the fracture surface of a cold-worked sample irradiated
to 26.9 dpa at 390 C after straining to failure in 400 C
SCW. The sample failed at <5% total strain and
exhibited considerable IG cracking. Figure 51 shows
a stressstrain plot of samples irradiated to 33.2 dpa
at 520 C and tested in either Ar gas or deaerated
SCW at 400 C. The sample tested in SCW exhibits
considerably lower strain to failure and is characterized by significant IGSCC, which is absent in the
sample tested in Ar. As such, the observed IG cracking
is attributed to IGSCC. Results also showed that
whether hardening is due to cold-work or irradiation,
cracking was higher for the cases with higher hardness
(Figure 52). Experiments were also conducted on the
effect of water density and temperature on cracking.
Samples tested in either 385 C SCW at 27.6 MPa or
400 C SCW at 23.4 MPa cracked more at the higher
temperature/lower pressure condition, regardless of
the dose and temperature at which they were irradiated,
as shown in Figure 53. These results indicate that
temperature is a much more important factor than
water density in irradiated samples. Finally, a set of
X50 500 mm
315
X250 100 mm
Figure 50 Fracture surface of alloy Japanese Prime Candidate Alloy in the cold-worked condition and following
irradiation to 26.9 dpa at 390 C in fast flux test facility, and strained at a rate of 3 107 s1 in 400 C deaerated
supercritical water at 25 MPa. Adapted from Teysseyre, S.; Was, G. S. Stress corrosion cracking of neutron-irradiated steel
in supercritical water. In 13th International Conference on Degradation of Materials in Nuclear Power Systems Water
Reactors; Allen, T. R., Busby, J., King, P. J., Eds.; Canadian Nuclear Society: Toronto, 2007; Was, G. S.; Teysseyre, S. Stress
corrosion cracking and corrosion of candidate alloys for the supercritical water reactor; Final Report to U. S. Department
of Energy, Idaho National Laboratory, project #0003852, Sept 30, 2008.
1000
Stress (MPa)
800
SCW
Argon
600
400
200
0
0
4
6
Strain (%)
10
Figure 51 Stressstrain behavior of Japanese Prime

Candidate Alloy irradiated to 33.2 dpa in fast flux test facility
at 520 C, and strained in either argon or deaerated
supercritical water at 400 C and at a strain rate of
3 107 s1 in deaerated supercritical water at 25 MPa. The
sample strained in supercritical water failed in the pinhole by
severe intergranular stress corrosion cracking. Adapted from
Teysseyre, S.; Was, G. S. Stress corrosion cracking of
neutron irradiated steel in supercritical water. In 13th
International Conference on Degradation of Materials in
Nuclear Power Systems Water Reactors; Allen, T. R., Busby,
J., King, P. J., Eds.; Canadian Nuclear Society: Toronto, 2007;
Was, G. S.; Teysseyre, S. Stress corrosion cracking and
corrosion of candidate alloys for the supercritical water
reactor; Final Report to U. S. Department of Energy, Idaho
National Laboratory, project #0003852, Sept 30, 2008.
experiments was conducted to assess the effect of hydrogen addition to the water. It was found that addition of
500 ppb H to 400 C SCW at 23.4 MPa was very effective in suppressing the degree of IGSCC (Figure 54).
In general, austenitic alloys were observed to be

susceptible to IGSCC in SCW, where the extent of
susceptibility varied with both alloy and water chemistry conditions. Higher temperatures resulted in
greater cracking on the gauge section, but a reduction
in the %IG on the fracture surface. Overall, 304
stainless steel exhibits greater susceptibility than
does 316 and additions of small amounts of acid to
the solution increase the susceptibility. Increasing
SCW pressure favors IG cracking in unsensitized
316 stainless steel in pure water 8000 ppb oxygen.
Irradiation greatly increases susceptibility to IGSCC
in SCW at both 400 and 500 C.
5.12.3.2
Nickel-Based Alloys
A total of eight nickel-based alloys have been tested for

SCC susceptibility in SCW (see Table 2). The tests
were performed at temperatures ranging from 390 to
550 C and pressures ranging from 22.5 to 25.5 MPa.
The dissolved oxygen content was maintained either
in the deaerated condition or at 500 or 8000 ppb. The
water chemistry was altered in some tests by the addition of HCl, H2O2, NaCl, or H2SO4. Of the eight alloys
tested, only the MC Alloy110 and the UNS N06030
alloy116 did not show evidence of SCC.
5.12.3.2.1 Alloy
Alloy 718 proved to be extremely susceptible to

SCC.123 A CERT test conducted on a sample of
Alloy 718 in aerated (8000 ppb) SCW at 400 C failed
at a strain of only 9% and a maximum stress of
316
25
16
427 C43.9 dpa specimen
14
SA: 296 Hv
12
CW: 334 Hv
385 C:27.6 MPa

400 C:23.4 MPa
20
15
% IG
%IG
10
8
10
6
4
5
2
0
400 C
deaerated
(a)
385 C
deaerated
400 C
hydrogenated
50
368 Hv
40
%IG
30
20
346 Hv
334 Hv
10
SA:407 C:41.1 dpa MPa
SA:427 C:43.9 dpa
CW:427 C:43.9 dpa
Alloy
Tested environments
400 C deaerated SCW
296 Hv
Figure 53 Effect of water density and temperature on

cracking of Japanese Prime Candidate Alloy in
385 C:27.6 MPa supercritical water and 400 C:23.4 MPa.
Adapted from Teysseyre, S.; Was, G. S. Stress corrosion
cracking of neutron-irradiated steel in supercritical water.
In 13th International Conference on Degradation of Materials
in Nuclear Power Systems Water Reactors; Allen, T. R.,
Busby, J., King, P. J., Eds.; Canadian Nuclear Society:
Toronto, 2007; Was, G. S.; Teysseyre, S. Stress corrosion
cracking and corrosion of candidate alloys for the
supercritical water reactor; Final Report to U. S. Department
of Energy, Idaho National Laboratory, project #0003852,
Sept 30, 2008.
0
SA:407 C:41.1 dpa
SA:427 C:43.9 dpa
(b)
CW:390 C:26.9 dpa

CW:427 C:43.9 dpa
Alloy
Figure 52 Influence of hardening on cracking in Japanese

Prime Candidate Alloy. Cracking increases with hardening
whether hardening is due to (a) cold-work on specimen
irradiated at 427 C to 43.9 dpa and tested in different
environments, or (b) irradiation condition. Adapted from
Teysseyre, S.; Was, G. S. Stress corrosion cracking of
neutron-irradiated steel in supercritical water. In 13th
Nuclear Power Systems Water Reactors; Allen, T. R.,
Sept 30, 2008.
1300 MPa, and the fracture surface was completely

intergranular fracture. The authors attributed this
cracking behavior to the oxidation and swelling of
the primary niobium carbides that cause cracks to
initiate at these carbides.
CERT tests on Alloy 690 have produced mixed

results. Fournier et al.123 tested Alloy 690 in 400 C,
25 MPa SCW under aerated conditions and found
that Alloy 690 failed by completely ductile rupture
and showed a significant amount of necking. Companion tests in air revealed behavior for each alloy
that was similar to that in SCW at 400 C. Was and
coworkers84,111,122 found IGSCC in Alloy 690 at 400,
450, 500, and 550 C, with the extent of cracking
increasing with temperature (see Figure 41).
Alloy 600 was tested at 290, 380, and 550 C in
water containing 8000 ppb dissolved oxygen.108 The
two lower temperature experiments failed by ductile
fracture with no sign of SCC. The sample at 550 C
exhibited a crack density of about 26 cracks mm2.
MC Alloy was tested in pure SCW at 400 C and
8000 ppb and was also tested with the addition of
0.001 mol l1 HCl and 0.01 mol l1 HCl. No cracks
were observed on the specimen and there was no
reduction in the strain to failure when the HCl additions were made.110
317
14
H-SCW
Deaerated-SCW
12
%IG
10
8
6
4
2
10 000
600
625
8000
500
400
6000
625
300
4000
200
2000
690
690
0
350
400
(a)
450
500
550
100
16
Crack length per unit area (mm mm2)
0
600
Temperature (C)
100
CW
SA
427 C43.9 dpa samples condition
Figure 54 Influence of 500 ppb hydrogen addition on
cracking of Japanese Prime Candidate Alloy condition
SA:427 C:43.9 dpa in 400 C supercritical water. Adapted
from Teysseyre, S.; Was, G. S. Stress corrosion cracking of
neutron-irradiated steel in supercritical water. In 13th
Nuclear Power Systems Water Reactors; Allen, T. R.,
Sept 30, 2008.
Figure 55 shows the temperature dependence of IG

cracking in nickel-based Alloy 625 and Alloy 690
compared to that for the stainless steels. Both alloy
systems show a strong dependence on temperature,
with the extent of cracking rising exponentially with
temperature. Figure 43 shows that the maximum
IG crack depth obeys an Arrhenius behavior, with
an activation energy between 84 and 87 kJ mol1.
These values are within the range of activation energies for cracking of nickel-based Alloy 600 in lowpotential primary water in PWRs, for which the
activation energy for CGR in the temperature range
of 310420 C is between 80 and 220 kJ mol1.129 The
low value of the activation energy for crack growth
compared to oxide growth (200 kJ mol1)133 may
indicate either a role of aggressive species in the
water or a short-circuit growth path, for example,
grain boundary oxidation ahead of the growing
crack. Besides a slip-oxidation mechanism, the latter
mode could also occur by selective internal oxidation
(SIO) that has been observed in nickel-based alloys,
Maximum crack depth (mm)
80
60
40
20
0
350
(b)
690
625
400
450
500
550
Temperature (C)
600
Figure 55 (a) Crack length/unit area and crack density

versus T, and (b) crack depth versus T for Alloy 690 and
Alloy 625 strained at 3 107 s1 in deaerated supercritical
water at 25 MPa. Reproduced from Teysseyre, S.;
Was, G. S. Corrosion 2006, 62(12), 11001116.
as described by Scott,134 at the upper end of the

temperature range used in this study. In fact, the
measured CGRs are consistent with the diffusion of
oxygen in nickel by Bricknell and Woodford.135
These results show that both slip-oxidation and SIO
are possible mechanisms for IGSCC in SCW.
Alloy 690 was also tested in both the thermally
treated and solution-annealed conditions.136 Samples
were tested at 385 C and 27.6 MPa and at 400 C and
25.4 MPa. The water density at 385 C was 465 kg m3
versus 175 kg m3 at 400 C. Results of CERT tests
showed that the crack depth was consistently worse,
regardless of sample condition, in the higher temperature, lower-density environment (Figure 56(a)). These
results indicate that temperature is a more important
factor than water density for Alloy 690. It should also be
noted that cracking was mainly observed along TiC
nodules in the 385 C, 26.7 MPa tests. Alloy 600 in the
mill-annealed condition was also tested along with the
318
1400
400 C, 25.4 MPa 175 kg m3
385 C, 27.6 MPa 465 kg m3
690(84,111,122)
690(107,123)
625(107,111,122)
625(116)
625(108,110)
600(107,108)
718(123)
MC alloy(110)
UNS N 10276(110)
800H(120)
1200
Max crack depth observed (m)
10
1000
800
600
400
0
UM-690
(a)
UM-TT690
EPRI-TT690
200
350
Alloy
400
400 C, 25.4 MPa 175 kg m3

385 C, 27.6 MPa 465 kg m3
150
600
60
100
50
50
0
EPRI-600
(b)
550
Figure 57 Maximum stress versus temperature in

constant extension rate tensile tests on nickel-based alloys
in supercritical water.
UM-690 UM-TT690 EPRI-TT690

Alloy
Figure 56 Maximum crack depth observed after failure in

400 C:25.4 MPa and 385 C:27.6 MPa deaerated
supercritical water for (a) Alloy 690, and (b) for all alloys
including mill-annealed Alloy 600. Reproduced from
Materials Reliability Program: Constant Extension Rate
Stress Corrosion Cracking Testing of Alloys 600 and 690 in
Supercritical Water (MRP-233), Technical Report 1016154,
EPRI, Palo Alto, CA, 2007.
Alloy 690 samples136 and was found to be highly susceptible to SCC in SCW, and intergranular cracking was
clearly identified (Figure 56(b)).
The temperature dependence of the maximum
stress and strain to failure for all of the data on
nickel-based alloys is shown in Figures 57 and 58.
Perhaps because of the wide range of conditions,
there is little observable dependence on temperature
for either parameter. However, as shown in the preceding paragraph, samples tested within a single program tend to show a cleaner correlation.
Strain to failure (%)
Max crack depth observed (m)
200
450
500
Temperature (C)
40
30
690(84,111,122)
690(123)
625(107,111,122)
625(108,110)
600(106,107,108)
718(123)
MC alloy(110)
UNS N 10276(110)
800H(120)
20
10
0
350
400
450
500
Temperature (C)
550
600
Figure 58 Strain to failure versus temperature in constant

extension rate tensile tests on nickel-based alloys in
supercritical water.
As part of a study of materials for use in the upgrading of low-quality hydrocarbons using SCW, Fujisawa
et al.110 studied SCC of Alloy C-276, Alloy 625, and
MC Alloy in 400 C SCW containing 8000 ppb dissolved oxygen. No IG cracks were observed in Alloy
C-276 in pure water, but the addition of small
40
20
0
20
15
20
25
30
35
Cr content
40
45
50
Figure 59 Effect of the chromium content of various

nickel-based alloys on the percentage intergranular
stress corrosion cracking in 400 C supercritical water
containing 8000 ppb dissolved oxygen and additions of
HCl. Reproduced from Fujisawa, R.; Nishimura, K.;
Kishida, T.; Sakaihara, M.; Kurata, Y.; Watanabe, Y.
Corrosion 2005; NACE International: Houston, TX, 2005;
Paper no. 05395.
amounts (0.001 mol l1) of HCl resulted in severe IG

cracking. Alloy 625 failed by IGSCC at 0.01 mol l1
HCl, but not at lower concentrations or in deionized
water. Bosch and Delafosse116 also found that Alloy
625 cracked intergranularly at both 390 and 450 C
in constant load tests in water containing 10 wt%
H2O2 1.6 g l1 NaCl. CERT tests in SCW
10 wt% H2O2 revealed IG cracking at both 400 and
500 C, with considerably greater cracking at 500 C.
No cracks were found in the MC Alloy after CERT
tests in 0.01 mol l1 HCl at 400 C and 8000 ppb dissolved oxygen.
Alloy UNS N 06030 was tested in constant load
mode (80% or 100% of yield strength) in SCW
containing either 10 wt% H2O2 or 10 wt% H2O2
1.6 g l1 NaCl at 400450 C.116 No cracking was
observed in the solution containing only hydrogen
peroxide and only localized corrosion, but no cracking, was observed in the latter solution.
Fujisawa showed that IGSCC susceptibility generally follows the inverse of the alloy chromium
content in SCW containing HCl additions, with the
austenitic stainless steel alloys exhibiting the greatest
amount of IGSCC and the high nickel, MC Alloy the
least (Figure 59). However, Teysseyre and Was111
observed that Alloy 625 exhibited the worst IGSCC
resistance among 304 and 316L stainless steel, Alloy
625 and Alloy 690 tested in pure, deaerated SCW.
10 000
690
400 C SCW
25
8000
20
15
4000
10
%IG
2000
5
Crack length
per unit area
0
1
(a)
(b)
6000
Crack depth
4
5
Dose (dpa)
0
8
10 000
120
100
%IGSCC
60
0.001 mol/1 HCl

0.01 mol/1 HCl
30
319
690
7 dpa
8000
Crack
length per
unit area
80
6000
60
%IG
Crack depth
4000
40
20
2000
400 C
8 ppm DO
25 MPa
80
0
0
380 400 420 440 460 480 500 520
SCW temperature (C)
Figure 60 Crack length per unit area, crack depth and

%IG versus (a) dose, and (b) temperature for Alloy 690
irradiated to 7 dpa at 400 C and tested in pure supercritical
water at a strain rate of 3 107 s1. Reproduced from
Zhou, R.; West, E. A.; Jiao, Z.; Was, G. S. J. Nucl. Mater.
2009, 395, 1122.
5.12.3.2.4 Irradiation
Irradiation effects on nickel-based alloys are confined

to Alloy 690 and both 400 and 500 C with 2 MeV
protons to doses of 2, 4, and 7 dpa.117,118 As shown in
Figures 49 and 60, the crack length per unit area,
crack depth, and %IG fracture, all increase with dose
for CERT tests conducted in 400 C SCW. The effect
of irradiation on cracking is greatest at 500 C, where
the crack length per unit area is 40 times greater on
the irradiated side of the sample than on the unirradiated side.
The nickel-based alloys exhibit much the same
dependence of cracking on key experimental parameters
320
10
400 C 500 C Ar 500 C
500 C
600 C
+300 ppb O2
as do the austenitic stainless steels. However, cracking

is generally more severe in some of the alloys such as
Alloy 625. Chromium content appears to be a significant factor in cracking in SCW containing low concentrations of HCl. Also, irradiation has a greater
effect on cracking in Alloy 690 than it does on 316L
stainless steel.
5.12.3.3
FerriticMartensitic Alloys
Six F/M alloys have been tested in SCW to date:

T91, T91a, T92, T92a, HCM12A, and HT-9.
Of these alloys, the only one that showed susceptibility to SCC was HT-9.59,73,83,108,120,125 The crack
densities for HT-9 (218 mm2) were generally
much lower than the crack densities for the austenitic
stainless steels and Ni-based alloys. Tests on F/M
alloys were conducted in pure water with dissolved
oxygen contents ranging from the deaerated condition
(<10 ppb) to 500 ppb and temperatures ranging from
400 to 600 C. The strains to failure of the F/M alloys
were much lower than those of the austenitic alloys,
ranging from 10.9% to 24.4%. One CERT test was
performed on a sample of T91 in argon at 500 C and
the strain to failure was still only 15%. T91a was also
tested as U-bends at 500 and 550 C and showed no
evidence of cracking.
HT-9 shows increasing susceptibility to cracking
with temperature and dissolved oxygen content.
Figure 61 shows that both the crack density and
500 ppb118
<10 ppb73,118
<10 ppb73,118
<10 ppb59,137
300 ppb59,137
10
0
HCM12A
HT-9
T91
T92
Figure 62 Strain to failure versus oxygen content in

ferriticmartensitic alloys tested in constant extension rate
tensile mode in supercritical water at 500 C.
600
HCM12A(59)
HT-9(35,124)
T91(59)
T91(120)
T92(120)
PM2000(113)
500
Figure 61 Effect of temperature and dissolved oxygen

content on crack density and crack depth in HT-9 tested in
constant extension rate tensile mode in nominally deaerated
supercritical water or in 500 C Ar. Reproduced from
Ampornrat, P.; Gupta, G.; Was, G. S. J. Nucl. Mater. 2009,
395, 3036.
300 ppb59,137
10
15
<10 ppb59,137
20
20
20
300 ppb59,137
30
30
25
<10 ppb59,137
40
40
500 C
25 MPa
100 ppb59,137
30
50
Crack density
Maximum crack depth
Maximum crack depth (m)
50
100 ppb73,118
400
300
200
100
0
350
400
450
500 550 600

Temperature (C)
650
700
Figure 63 Maximum stress versus temperature for

ferriticmartensitic alloys. Data points at 500 C are slightly
shifted horizontally so that all symbols could be discerned.
crack depth increase with temperature between 400

and 600 C, and with dissolved oxygen concentrations
between 10 and 300 ppb.125 Cracking is aggravated by
both high temperature and dissolved oxygen in SCW.
Although cracks were not observed on any of the
T91, T91a, T92, T92a, or HCM12A samples, it is
important to note that they did show a substantially
lower strain to failure with increasing dissolved
14
50
HCM12A(59)
HT-9(35,124)
T91(59)
T91(120)
T92(120)
PM2000(113)
12
40
30
20
10
500 C
8
6
4
400
450
500
550
600
650
700
Temperature (C)
Figure 64 Strain to failure versus temperature for ferritic
martensitic alloys. Data points at 500 C are slightly shifted
horizontally so that all symbols could be discerned.
106
Fatigue crack growth rate, da/dN (m per cycle)
400 C
10
350
321
Air
Water
107
300
400
500
Temperature (C)
600
700
Figure 65 Fatigue crack growth rates of T91 in air and

water at DK 24 MPa m1/2 as a function of temperature.
Reproduced from Yi, Y.; Lee, B.; Kim, S.; Jang,
J. Mater. Sci. Eng. A 2006, 429(12), 161168.
oxygen concentration in SCW.73,83,124 Figure 62

shows the effect of oxygen concentration on strain
to failure at 500 C.
The maximum stress and strain to failure are
plotted as a function of temperature in Figures 63
and 64, respectively. Note that the maximum stress
decreases and the strain to failure increases with
Unir
Irr
Unir
Irr
Figure 66 Effect of irradiation on intergranular crack

depth in HT-9 tested in 500 C, deaerated supercritical
water. The temperatures given in the figure are the
irradiation temperatures. Data from Gupta, G.; Was, G. S.
Effect of proton irradiation and grain boundary engineering
on stress corrosion cracking of ferriticmartensitic alloys in
supercritical water. Proceedings of the 12th International
Nuclear Power Systems Water Reactors; The Minerals,
Materials and Metals Society: Warrendale, PA, 2005;
pp 13591367.
temperature. Such a temperature dependence would

not be observed for alloys that exhibit increasing
susceptibility to SCC. Hence, the observed dependence of mechanical properties on temperature is not
related to the SCC propensity.
Yi et al.85 conducted fatigue crack growth tests on 1T
CTsamples of T91 in deaerated water at 370 and 500 C
and in air. Tests were conducted in air at a frequency
of 1 Hz, a R-ratio of 0.1, and a K of 2324 MPa m1/2,
and in water at a frequency of 0.0042 Hz, a R-ratio of
0.16, and a K of 2425 MPa m1/2. The CGR in water
at 500 C was about 1.4 times that in air and the
enhancement in cracking was attributed to rapid oxidation (Figure 65).
Irradiation was also found to enhance the amount
of IG cracking in SCW. HT-9 is known to be susceptible to cracking following irradiation and testing in
air.138 Samples of HT-9 were irradiated with protons
at either 400 or 500 C to a dose of 7 dpa, and tested
in CERT mode in 500 C deaerated SCW. Results
showed that crack density and crack depth increased
because of irradiation and the increase was greatest at
400 C (Figure 66). It should be noted that irradiation hardening at 400 C is quite significant, but
322
30
Crack density
Max. crack depth
25
25
20
20
15
15
10
10
30
0
AR-irr
GBE-irr
AR-unirr
GBE-unirr
Alloy condition
Figure 67 Crack density and maximum crack depth for
HT-9 samples in the as-received (AR) condition and the
grain boundary-engineered condition, and the effect of
irradiation on cracking propensity for each condition.
Irradiation and constant extension rate tensile testing were
both done at 500 C. Reproduced from Gaurav, G.;
Ampornrat, P.; Ren, X.; Sridharan, K.; Allen, T. R.; Was, G. S.
J. Nucl. Mater. 2007, 361(23), 160173.
is only minimal at 500 C.126 Hardening may be

controlling the increased susceptibility to IGSCC
in HT-9.
One additional set of experiments was performed
on grain boundary engineered HT-9, in which the
fraction of 1 grain boundaries was increased by
about 30% compared to the as-received (tempered)
condition by a deformation and heat treatment
process.126 Figure 67 shows that both the crack depth
and crack density in the grain boundary-engineered
samples are less than that in the as-received samples
irradiated at 500 C and tested in CERT mode in pure,
deaerated SCW at 500 C.
5.12.3.4
Other Alloys
Very little data on Ti alloys in SCW exist, though

there is a significant database in subcritical water.
The only experiment conducted in SCW was on
Ti15Mo5Zr3Al in pure SCW at 550 C, 25 MPa,
and 8000 ppb dissolved oxygen. The maximum stress
was 249 MPa, and the strain to failure was 38%,
resulting in a crack density of 26 cracks mm2.107,108
While several experiments have been reported on
ODS alloys in subcritical water,63,64 only two experiments have been conducted to date in SCW. ODS
steel PM2000 was strained in 500 and 650 C SCW
containing 100150 ppb oxygen at an initial rate of
3 108 s1, and then at 3 107 s1 after about

10% strain had been accumulated.113 The alloy
showed no susceptibility to SCC at either temperature. An ODS alloy was also strained in 600 C in
deaerated SCW to 4%, at which point the sample
broke in the threads. There was no evidence of cracking on the gauge surface.
5.12.3.5
Summary of SCC Behavior in SCW
The following trends were observed in the SCC

behavior in SCW.
1. Austenitic stainless steels and nickel-based alloys
exhibit susceptibility to IGSCC in pure SCW over
the temperature range of 400650 C.
2. IGSCC susceptibility, as measured by %IG on the
fracture surface, decreases with temperature, but
as measured by cracking on the gauge section, it
generally increases with temperature.
3. The CGR of cold-worked 316L stainless steel
increases with temperature up to 400 C and
decreases after that because of crack blunting by
rapid oxidation.
4. Small additions of HCl or H2SO4 increase the
susceptibility to IGSCC in the austenitic alloys.
5. Increasing system pressure caused an increase in
the severity of IGSCC in sensitized 316L stainless
steel in pure water with 8000 ppb dissolved oxygen.
6. Nickel-based alloys are very susceptible to IGSCC,
comparable to austenitic stainless steels.
7. There appears to be an effect of alloy chromium
content on SCC cracking propensity in nickelbased alloys in dilute HCl solutions, with higher
Cr alloys showing greater resistance to IGSCC.
8. With the exception of HT-9, F/M alloys are resistant to IGSCC in pure SCW up to 600 C.
9. Irradiation strongly enhances IGSCC in pure
SCW, increasing both the crack density on the
gauge surface and the crack depth, at temperatures
between 400 and 500 C.
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Was, G. S.; Teysseyre, S. Challenges and recent
progress in corrosion and stress corrosion of austenitic
alloys for supercritical water reactor core components.
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5.13
Material Performance in Sodium
T. Furukawa and E. Yoshida

Japan Atomic Energy Agency, O-arai, Ibaraki, Japan
5.13.1
Introduction
327
5.13.2
5.13.3
5.13.3.1
5.13.3.2
5.13.4
5.13.4.1
5.13.4.2
5.13.4.3
5.13.4.4
5.13.4.5
5.13.4.6
5.13.4.7
5.13.5
5.13.5.1
5.13.5.2
5.13.5.3
5.13.6
5.13.6.1
5.13.6.2
5.13.7
5.13.7.1
5.13.7.2
References
Material Selection in the Consideration of Application in Sodium

Corrosion Mechanism of Materials in Sodium
Corrosion Produced by the Dissolution of Alloy Elements to Sodium
Corrosion Produced Through Chemical Reaction with the Impurities in Sodium
Corrosion Behavior and Factors Affecting Steel
Immersion Time
Temperature
Dissolved Oxygen
Sodium Velocity
Alloy Elements
Carburization and Decarburization
Corrosion Estimation of FBR Materials
Effect of Sodium on the Mechanical Strength of Steels
Austenitic Stainless Steel
Ferritic Steels
Others (Ni Base Alloys, ODS)
Damage to Steels with Sodium Compounds
SodiumWater Reaction
Sodium Leak
Tribology
Self-Welding
Frictional Wear
328
328
328
330
331
331
332
332
333
333
333
334
336
336
338
338
338
338
339
339
339
339
340
Abbreviations
EBR-II
FBRs
FFTF
FMS
JAEA
Monju
ODS
PFR
PNC
Experimental Breeder Reactor No. 2 (USA)

Fast breeder reactors
Fast Flux Test Facility (USA)
Ferriticmartensitic stainless steel
Japan Atomic Energy Agency
Japanese Prototype Fast Breeder Reactor
Oxide dispersion-strengthened steel
Prototype Fast Reactor (UK)
Power Reactor and Nuclear Fuel
Development Corporation (present JAEA)
5.13.1 Introduction
Sodium is one of the elements that exhibit the characteristics demanded of coolants for fast breeder
reactors (FBRs). The physical properties of sodium
are shown in Table 1 and see Chapter 2.14, Properties of Liquid Metal Coolants.
Sodium is a solid at room temperature, and the
melting and boiling temperatures are 97.82 and
881.4 C, respectively. Therefore, sodium is in the
liquid phase at FBR operating temperatures without
pressurization. For this reason, it is not necessary to
adopt the proof-pressure design employed in light
water reactors for sodium-cooled FBRs. Moreover,
the thermal conductivity and specific heat of sodium
at 550 C are 0.648 W cm1 C1 and 1.256 J g1 C1,
respectively, and sodium can transfer the heat of the
reactor core to the power generation system efficiently. Furthermore, its insignificant neutronmoderating capability is suitable for the coolant for
the FBR, in which fast neutrons play a major role in the
nuclear reaction.
On the other hand, the weakness of sodium as a
coolant is its reactivity with oxygen and/or water.
327
328
Table 1

Physical properties of sodium
Atomic number
Atomic weight
Melting point ( C/K)
Boiling point ( C/K)
Volume increase on melting (%)
Density (g cm3)
Thermal conductivity (W cm1 K1)
Specific heat (J mol1 K1)
11
22.9898
97.8/371.0
881.5/1154.7
2.71
0.856 at 400 C
0.821 at 550 C
0.727 at 400 C
0.657 at 550 C
29.40 at 400 C
28.88 at 550 C
Table 2
elements1
Element Solubility equation

Cu
Ag
Au
Mg
Zn
When high-temperature sodium is leaked into the

atmosphere, it reacts with the oxygen and moisture
in the atmosphere, and the by-products of this reaction are known to cause structural damage to the
reactor. Moreover, in the event of a steam generator
tube failure, high-temperature steam blows off into
the sodium, and wastage of the adjoining tubes occurs.
5.13.2 Material Selection in the

Consideration of Application in Sodium
In the process of material selection, it is necessary to
take the environment into consideration by estimating
the mechanical properties and thermal characteristics.
Environments specific to the FBR components
include: (a) contact with the coolant (liquid metallic
sodium), (b) high temperature at which the creep
effects must be taken into account, and (c) neutron
irradiation. In this chapter, an outline of the compatibility of materials with sodium is provided.
The oxides formed on the surface of the material
are easily reduced in high-temperature sodium, resulting in direct contact between the material and sodium.
Under this condition, the dissolution of elements
contained in the material, such as iron, chromium,
and nickel, in sodium and the reverse phenomenon
(deposition) occur on the material surface due to the
difference in chemical potential. The behavior is fundamentally controlled by the solubility of the material
elements in sodium and by the diffusion rate of the
materials. The solubility equation of the various elements in sodium is shown in Table 2.
Among the elements in austenitic stainless steel,
the solubility of nickel is greatest. Therefore, the
phase transformation of austenite to ferrite through
nickel dissolution is observed on the surface in longterm immersion in sodium.
The compatibility of various metals with sodium
reported by Borgstedt and Mathews1 is shown in
Solubility equation of metallic and amphoteric
Cd
Al
Ga
In
U
Pu
Sn
Pb
Bi
Cr
Mo
Mn
Fe
Co
Ni
log Swwpm 5.450 3055/T (K)

log Swwpm 7.22 1479/T (K)
Swt% 11 0.52
(T(K) 273.15) 6 104
(T(K) 273.15)2
Swt% 0.1414 2.08 106
(T(K) 273.15) 1.248
103 (T(K) 273.15)2
Swppm 1.4 0.057
(T(K) 273.15)
log Swt% 3.67 1209/T (K)
log Swwpm 1.4 0.057/T (K)
log Swt% 1.349 1010/T (K)
log Swt% 4.48 1552/T (K)
log Swwpm 4.36 6010.7/T (K)
log Swwpm 8.398 10.950/T
(K)
log Swt% 5.113 2299/T (K)
log Swt% 6.1097 2636/T (K)
log Swt% 2.15 2103/T (K)
log Swt% 5.67 4038/T (K)
log Swwpm 9.35 9010/T (K)
log Swwpm 2.738 2200/T (K)
log Swwpm 3.640 2601/T (K)
log Swwpm 4.720 4116/T (K)
log Swwpm 0.010 1493/T (K)
log Swwpm = 2.07 1570/T (K)
Temperature
range (K)
623773
377806
373873
373573
373600
423773
375573
373573
560970
560970
473673
393523
398563
563923
9481198
500720
550811
658973
673973
673973
Table 3. The data can be used to create an index

for the selection of the material used in sodium.
5.13.3 Corrosion Mechanism of

Materials in Sodium
There are two known mechanisms of sodium corrosion. One is corrosion produced by the dissolution of
alloy elements to sodium, and the other is corrosion
produced through chemical reaction with the impurities in sodium. These two corrosion mechanisms are
described in Sections 5.13.3.1 and 5.13.3.2.
5.13.3.1 Corrosion Produced by the
Dissolution of Alloy Elements to Sodium
In this case, corrosion is dependent on the solubility
in sodium of the elemental composition in the material, temperature, and the rate of solution.
The solution rate Rc is given by the following
formula:
Rc K Cs Ci
1
Table 3
329
Compatibility of materials with alkali metals1

Compatible with alkali metal up to ( C)
Material
Mg alloys
Al alloys
Cu alloys
Ag and its alloys
Au and its alloys
Zn coatings
Pb and its alloys
Sn and its alloys
Fe
Low-alloy steels
Ferritic steels
High-Cr steels
Austenitic steels
Ni alloys
Mo alloys
W alloys
Ti alloys
Zr alloys
V alloys
Nb alloys
Ta alloys
Sintered A12O3
Stab. ZrO2/CaO
Stab. ThO2/Y2O3
Glass
UO2
UC
Factors influencing compatibility
Li
Na
Rb and Cs
n.c.
n.c.
300
n.c.
n.c.
n.c.
n.c.
n.c.
500
500
500
500
450
400
1000
1000
700
700
700
700
700
350
350
400
n.c.
n.c
350
400
n.c.
n.c.
n.c.
n.c.
n.c.
700
700
700
700
750
600
1000
1000
700
700
700
700
700
500
350
550
250
750
750
300
400
400
n.c.
n.c.
n.c.
n.c.
n.c.
700
700
700
700
750
600
1000
1000
700
700
700
700
700
500
350
550
250
300
450
400
n.c.
n.c.
n.c.
n.c.
n.c.
700
700
700
700
750
600
1000
1000
700
700
700
700
700
500
350
550
250
Metal solubility, oxygen exchange

Metal solubility
Metal solubility
High metal solubility
Very high metal solubility
Very high metal solubility
Nonmetallic impurities
Flow velocity
Thermomechanical action
Intergranular corrosion
Intergranular corrosion
Chemical reaction
Excess of oxygen
n.c. not compatible.
1.0E + 02
1.0E + 00
Ni
Solubility (ppm)
Mn
1.0E 02
Fe
C
Mo
1.0E 04
Si
1.0E 06
Cr
1.0E 08
1
1.2
1.4
1000/T (K)
1.6
Figure 1 Solubility of alloy elements in sodium.
1.8
where K is the solution rate constant, Cs is the solubility limit in sodium, and Ci is the actual concentration in sodium.
The solution rate constant K is controlled by diffusion. The solubility of the alloy elements of the
steel is shown in Figure 1.15 Included in Figure 1
are the major elements of austenitic stainless steels
(type 304SS and 316SS) and the CrMo steels
(2.25Cr1Mo and Mod. 9Cr1Mo) which are used as
the structural materials of FBRs. The solubility of each
of the elements in sodium at 550 C is less than a few
parts per million. This means that the compatibility of
the steels with sodium is fundamentally excellent.
In the isothermal sodium condition, the corrosion
of the steels stops when the dissolved elements reach
saturation concentration at the temperature of sodium.
However, in the nonisothermal sodium condition,
corrosion resulting from the difference in activity
between sodium and the material surface occurs continually. This corrosion behavior is called thermal
gradient mass transfer. In the cooling system, the elements in the materials in the high-temperature section
330
W (mg cm-2)
Temperature (C)
dissolve as a result of the temperature dependency of

the solubility of the elements in sodium, and the dissolved elements are deposited on the steel surface in
the low-temperature section by the same mechanism.
The results of thermal gradient mass transfer
using a sodium loop made of SUS316, which is equivalent to AISI type 316SS, is shown in Figure 2. The
weight loss caused by the dissolution of the elements
in the steel is measured in the high-temperature
section, and the weight gain caused by the deposit
of the dissolved elements in sodium is observed in the
low-temperature section.
Figure 3 shows the microstructure of the inner
surface of the sodium pipe taken from the flowing
sodium loop operated for 82 000 h. Dissolution of the
elements in the material is observed in the hightemperature section, and precipitation is observed in
the low-temperature section located in the lower
stream.
Generally, selective corrosion occurs at the initial
stage as a result of the dissolution of the elements
600 Sodium flow

550
500
500
400
+1 390
600
520
470
410
0
1
-1
Sodium velocity :3 m s
Oxygen level
:9 ppm
Immersion time
5512 h
7141 h
10644 h
Weight loss
-2
-3
0
10
15
20
Distance from electro magnetic
pump of sodium loop (m)
25
29
Figure 2 Weight change in SUS316 after corrosion test

in flowing sodium. Reproduced from Maruyama, A.;
Nomura, S.; Kawai, M.; Takani, S.; Ohta, Y.; Atsumo,
H. J. Atomic Energy Soc. Jpn. 1984, 26, 59.
in the steel, and then, the behavior moves to general

corrosion with the progress of time. In the hightemperature section, the dissolution of nickel, chromium, manganese, and silicon to sodium occurs
easily, and molybdenum and iron remain in the material. In the low-temperature section, chromium deposits easily with decreasing temperature.
Carbon transfer in the steel affects the mechanical properties of the FBR structural materials.
Decarburization occurring in the high-temperature
section, in particular, has the potential of degrading
creep strength. The effect of sodium on the mechanical strength is described in Section 5.13.5.
5.13.3.2 Corrosion Produced Through
Chemical Reaction with the Impurities
in Sodium
The most important element in the impurities in
sodium is oxygen. Sodium is the reducing agent,
and its affinity to oxygen is very strong.
The temperature dependence of the oxygen
saturated in sodium is shown in Figure 4. The solubility of oxygen in sodium is significantly higher than
in water. However, the control of impurities in
sodium can be achieved by using the cold trap technique6 based on the theory of the deposit of dissolved
impurities in sodium.
The introduction of oxygen into sodium may
occur during nuclear plant construction, refueling,
the supplementing of the reactor cover gas, the opening of the coolant boundary for maintenance operations, etc. These are the paths for contamination
through oxides adhering to the components and the
impurities in the gas.
The relationship between the standard free
energy of the formation of iron oxides and the temperature is shown in Figure 5. The thermodynamically stable oxide in sodium is sodium oxide, Na2O.
Sodium flow
(a)
525 C, 82 000 h (BD-1)
(b)
575 C, 82 000 h (BD-2)
(c)
(d)
625 C, 82 000 h (BD-3)
420 C, 82 000 h (BD-4)
10 m
Figure 3 Corrosion of the inner surface of sodium loops made of type 304SS operated for 82 000 h. Reproduced from
Yoshida, E.; Kato, S.; Wada, Y. Liquid Metal Systems; Plenum press: New York, 1995.
Dissolved oxygen (ppm)
1.0E + 04
oxidize iron thermodynamically (i.e., iron oxide cannot be formed). The iron is oxidized by the formation
of complex NaFe oxides.7
In addition to oxygen, impurities in sodium
include elements in the steel, hydrogen, and nitrogen.
Hydrogen and nitrogen induce changes in the microstructure that lead to the potential degradation of
mechanical properties.
1.0E + 03
1.0E + 02
1.0E + 01
5.13.4 Corrosion Behavior and

Factors Affecting Steel
1.0E + 00
1.0E - 01
1
1.5
2.5
1000/T (K)
Figure 4 Temperature dependence of saturated oxygen
concentration in sodium.
-300
O2
Na 2
2/3
G0f (KJ mol-1 O2)
-400
Fe 2O 3
O
2Fe
The basic mechanism of the steel corrosion in sodium

is described in Section 5.13.3. In this section, the
corrosion behavior and its effects are described. The
major data are obtained for austenitic stainless steels.
The important factors which influence the corrosion of the steels in sodium are: (1) immersion time,
(2) temperature, (3) dissolved oxygen, (4) sodium
velocity, (5) alloy elements, and (6) carburization and
decarburization. The data on each factor are described
in the following sections.
5.13.4.1
-500
1/2
e 3O 4
a 2O
2N
O3
2/3
-600
O4
1/2
Fe
Na 3
O3
e
a 4F
N
2/3
e
a 5F
-700
O2
Fe
Na 2
-800
200
331
400
600
800
Temperature (K)
1000
1200
Figure 5 Relationship between G0f and temperature in

oxides consisting of iron and sodium.
Iron, the main element in the steel, is corroded by the

following reaction:
Fes;l 3Na2 Os;l ! Na4 FeO3 s 2Nas;l
0
0
43:8 KJ mol1 ; Gr298
26:1KJ mol1
Hr298
where [g], [l], and [s] stand for gas, liquid, and solid.
This is an endothermic reaction. However, Gibbs
energy of reaction (Gr0 ) becomes negative at 380 C,
and the reaction progresses spontaneously above
that temperature. In addition, Na2O cannot directly
Immersion Time
As mentioned in Section 5.13.3.1, nickel, chromium,

and manganese dissolve easily in sodium. Therefore,
when austenitic stainless steel is immersed in sodium,
the selective corrosion caused by the dissolution of
these elements progresses in the initial stage. This
process is based on the solid diffusion of the elements
in the steel, and is described by Ficks second law.
Diffusion in sodium is given by the following two
formulas:
dM
dc
D
dt
dx
2
2 p
Mt p Dt C0 Cs
p
3
where M is the diffusion amount, D is the diffusion

coefficient, C0 is the initial concentration, and Cs is
the surface concentration at time (t).
Formula [2] is Ficks first law and its integration is
given as the total diffusion. Formula [3] is the function given as the approximate formula. From these
formulas, it is understood that the corrosion behavior
at the initial stage observes the parabolic law proportional to the root of time. At the initial process of
the corrosion, the parabolic type behavior caused
by the selective corrosion is dominant. The corrosion
behavior is called start-up corrosion.
332
100
400
Weeks et al.9
Steady-state corrosion
Metal loss
Start-up
Temperature (C)
600
500
700
Immersed time, t
Selective loss (Ls) t1/2
Bulk loss (Lb) t
Total loss (Ls + Lb)
Corrosion rate (m year1)
Bagnall and Jocobs12
10
Menken30
Zebroski10
Kolster11
Thorley and Tyzack8

JAEA
Figure 6 Schematic representation of corrosion data for

austenitic stainless steel.
The corrosion behavior of iron, which is the main

element of stainless steel, is general corrosion and the
corrosion progresses as a linear function of time.
Therefore, the corrosion of the dominant factor
changes from start-up corrosion to general corrosion
with the progress of time (Figure 6). The corrosion
behavior that dominates general corrosion is called
steady-state corrosion. The time required for a
change from start-up corrosion to steady-state corrosion is 20005000 h, although it is dependent on
conditions such as sodium volume, temperature,
velocity, and dissolved oxygen.
5.13.4.2
Temperature
Temperature dependence of the corrosion rate in

the sodium of austenitic stainless steels is shown in
Figure 7.
The corrosion rate CR is described by the following Arrhenius function:

E
4
CR / exp
RT
where R is the gas coefficient (8.3145 J mol1 K1), E
is apparent activation energy, and T is temperature.
The apparent activation energy E is a function of
temperature. The values are reported as 100120 kJ
mol1 by numerous researchers (Table 4). The
energy is lower than that of the activation energy of
the diffusion of iron, chromium, and nickel, in
Austenitic stainless steel

Oxygen content: 10 ppm
Na velocity: 3.8 m s1
0.1
0.9
1.1
1.3
1.5
1000/T (K)
Figure 7 Corrosion rate of austenitic stainless steels in
flowing sodium.
stainless steel (250300 kJ mol1), and it agrees

with the activation energy of solubility in sodium
(Figure 1, Fe: 82.5 kJ mol1 and Cr: 104 kJ mol1).
In fact, it is understood that the corrosion of stainless
steel is dominated by the dissolution process of
the major elements (iron, chromium, and nickel)
of the steel. The effect of dissolved oxygen on
sodium, which influences the dissolution reaction,
is described in the following section.
5.13.4.3
Dissolved Oxygen
The effect of dissolved oxygen on the corrosion rate

is described by the following formula because the
corrosion process is dominated by the reaction process of oxides.
CR / O2 n
5
where CR is the corrosion rate, [O2] is the oxygen

concentration, and n is a constant.
The constant n, reported by the researchers, is
listed in Table 5. This result suggests the possibility

Table 4
Comparison of apparent activation energy on
corrosion rate
Sodium
temperature
( C)
Activation
energy
(kJ mol1)
Reference
Thorley
Weeks
Zebroski
Kolster
Bagnall
Maruyama
450725
538705
500700
650700
593723
500650
73.5
108.8
110.5
114.2
167.4
92109
[8]
[9]
[10]
[11]
[12]
[13]
Table 5
Comparison of oxidation coefficient on
corrosion rate
Bibliography
O2 content
(ppm)
Coefficient
(n)
Reference
Thorley
Zebroski
Roy
Kolster
5100
12, 50
530
18
840
2.59
1.5
1, 1.56
1.2
0.91
>1
0.8
[8]
[10]
[14]
[11]
Maruyama
[13]
that the control of dissolved oxygen may significantly

influence the corrosion behavior.
5.13.4.4
Sodium Velocity
It has been observed that the corrosion rate in sodium

increases as sodium velocity increases. However, it is
known that the increase ends when the velocity
reaches a certain limit. It is believed that the limit is
a function of oxygen concentration in sodium and/
or the structure of the sodium loop. According to
Thorley and Tyzack,8 Roy,14 and Kolster,11 the limit
is 3.8, 67, and 3 m s1, respectively. It is believed that
the effect of such a sodium velocity is based on the
thickness of the boundary layer between the material
surface and the flowing sodium. In fact, the thickness
of the boundary layer decreases as sodium velocity
increases, and the diffusion of alloy elements via the
boundary layer increases.
5.13.4.5
Alloy Elements
The effect of the alloy elements on corrosion is

examined because long-term corrosion occurs as a
result of thermal gradient mass transfer. The effect of
the chromium and nickel concentration on the steels
is particularly significant. Figure 8 shows the effect
10
O2 cont.: 1 ppm
Velocity: 1.48 m s1
Immersion time: 29305254 h
Bibliography
333
650 C
1.0
600 C
0.1
20
30
10
Nickel concentration in steel (mass %)
40
Figure 8 Effect of nickel content in stainless steel on the

corrosion rate.
of the nickel content of stainless steel on the corrosion rate. On the other hand, the dependence of the
corrosion rate on elements in the steels is hardly
observed in austenitic stainless steels, such as types
304SS, 316SS, and 321SS, because of the slight difference in chemical composition (Figure 9).
5.13.4.6
Carburization and Decarburization
In monometallic sodium loops, the difference of

the carbon activity, which is the driving force of the
carbon transfer of the material, increases as temperature increases. Therefore, decarburization occurs in
the high-temperature section and carburization
occurs in the low-temperature section. On the other
hand, in bimetallic sodium loops which consist of
austenitic stainless steel and ferritic steel, it is easy
for decarburization to occur in the ferritic steel,
which has a high carbon activity due to the difference
in carbon activity between different materials,
whereas carburization in austenitic stainless steel,
which has low carbon activity, easily occurs at elevated temperature.
Carbon is an important element in maintaining
the superior mechanical strength of steel. Therefore,
the carburization/decarburization behavior of the
steels via sodium is important from the perspective
of mechanical properties.
334
750
650
Temperature (C)
550
450
304SS
316SS
10
Fuel
cladding
tube
(FCT)
321SS
~9 ppm O2
~2.5 ppm O2
~9 ppm O2
~2.5 ppm O2
~9 ppm O2
~2.5 ppm O2
1
20 ppm O2
10 ppm O2
5 ppm O2
Sodium velocity
24 m s-1
(FCT: 24.8 ms-1)
0.1
0.9
2.5 ppm O2
Immersion time
10007200 h
1.1
1 ppm O2
1.3
1000/T (K)
1.5
Figure 9 Comparison of corrosion rates of austenitic

stainless steels.
Carbon concentration in sodium (ppm)
100
7
5
3
2
101
7
5
3
2
Decarburization
Type316
(0.06 wt% C)
FFTF (566 C)
FFTF (474 C)
Type304 L
(0.025 wt% C)
Data band of the carbon
concentration in
EBR-II primary
cooling system
EBR-II (470 C)
102
7
5
3
2
103
400
Carburization
500
600
700
Temperature (C)
Figure 10 shows the boundary between carburization and decarburization in monometallic sodium
loops consisting of austenitic stainless steel (single
alloy).15 At a carbon concentration of 0.2 ppm in
sodium, the temperature boundary is 650 C, with
decarburization occurring over that temperature and
carburization occurring below that temperature.
Although the boundary is influenced by the carbon
concentration in sodium (carbon activity), it is necessary to take decarburization and carburization into
consideration to apply austenitic stainless steel when
the temperature is above 550 C, such as fuel cladding tubes.
On the other hand, in bimetallic sodium loops that
consist of ferritic steel and austenitic stainless steel
(two alloys), decarburization and carburization also
occur in the temperature range of the structural
materials <550 C.
The thickness of decarburization of the component (WD ) can be estimated by the following
formula:
p
WD K t
6
where K is the decarburization coefficient (g cm2
s1/2) and t is time (s).
The temperature dependence of the decarburization of 2.25Cr1Mo steel in bimetallic sodium loops
consisting of type 304SS and 2.25Cr1Mo steel,
which have the same structure as those in FBR
Monju, is shown in Figure 11.
In recent times, the application of high chromium
ferritic steel, which has excellent mechanical strength
at elevated temperatures and superior corrosion
resistance with the coolant, has been used as the
structural material for advanced FBRs.16 The relationship between decarburization and chromium
concentration in the steel is shown in Figure 12.
It is known that the decarburization/carburization
behavior of the ferritic steels is dependent on chromium concentration. The precipitation of chromium
carbide increases as the chromium concentration
increases. In this case, decarburization of the steel
is inhibited because the carbon activity in steel
decreases.
800
Figure 10 Boundary between carburization and

decarburization in monometallic sodium loops consisting of
austenitic stainless steel. Reproduced from Snyder, R. B.
An analysis of carbon transport in the EBR-II and FFTF
primary sodium systems. In Proceedings of the International
Conference on Liquid Metal Technology in Energy
Production, Champion, 1976.
5.13.4.7 Corrosion Estimation of FBR

Materials
The corrosion rate in the sodium of austenitic stainless steel and ferritic steel is very slight (a few
microns per year). Furthermore, since the estimated
corrosion thickness during the operation period is
335
550
Temperature (C)
500
450
400
The depth in microns from the surface is indicated

beside each plot by numerals in brackets.
350
0.25
Carbon concentration near the surface (%)
s
nju
Mo
or
f
ine
dl
de
en
n
sig
de
(15)
(16)
0.15
(10)
(29)
(11)
(16)
0.10
(14)
(11)
(17)
Tube/
pipe
Bar Coupon
2517
5071
0
0
10180
17768
1.1
1.2
1.4
1.3
1000/T (K)
1.5
1.6
Figure 11 Temperature dependency of the

decarburization coefficient of 2.25Cr1Mo steel in
sodium.
small compared with the thickness of the structures

(permanent components) of FBRs, it is not a critical
point in the reactor design.
For the structural materials of Monju, therefore,
the following corrosion formula was applied for all
materials for the design
103
log10 R 0:85 1:5log10 Co 3:9
T 273
7
where R is the corrosion rate (mm year1), Co is the

dissolved oxygen (ppm, 5 Co 25), and T is
the temperature ( C, 400 T 650). This equation
is valid for materials types 304SS, 316SS, 321SS, and
2.25Cr1Mo steel.
After the construction of Monju, the data for corrosion in sodium for the structural materials for
advanced FBRs were obtained by the Japan Atomic
Energy Agency (JAEA),16,17 and it was confirmed
that the corrosion rate of the materials is also
described by the aforementioned formula. The corrosion formula is expected to be applied to advanced
steels as well.
(9)
9Cr1Mo
0.05
Specimen
7Cr1Mo
Time
(h)
10-10
1.0
(17)
(21)
(6)
5Cr1Mo
10
-9
(14)
0.20
2.25Cr1Mo
Decarburization coefficient (G cm-2 s-1/2)
mm
co
Re
10-8
Testing conditions
1000 h, 8 ppm O2
1000 h, 50 ppm O2
3000 h, 9 ppm O2
3Cr1Mo
10-7
700 650 600
2
3
4
5
6
7
8
9
Chromium concentration in steel (mass %)
10
Figure 12 Relationship between decarburization and

chromium concentration in high chromium ferritic steel.
Reproduced from Matsumoto, K.; Ohta, Y.; Kataoka,
T. Nucl. Technol. 1976, 28(3), 452470.
On the other hand, since the thickness of the fuel

cladding materials is thin, the ratio of the corrosion
thickness to the original thickness is larger than that
of the structural materials. Therefore, it is necessary
that corrosion estimation be performed with greater
precision.
The corrosion formula is proposed for each core
material by JAEA.1820
Monju core materials (PNC316 [16Cr14NiB
PTiNb]), type 316SS)
X ti
CRi
8
CNa
8760
i

104
5
CRi 4:92710 exp 1:647
Oxi
9
Ti 273
where CNa is the corrosion thickness (mm), ti is the
operation time (h) at temperature Ti with dissolved
oxygen Oxi, CRi is the corrosion rate (mm year1) at
sodium temperature Ti with dissolved oxygen Oxi,
Oxi: dissolved oxygen (ppm, Oxi 5), and Ti is the
sodium temperature ( C 400 T 700)
For PNC1520 [15Cr20NiBPTiNb]
CNa CR1 CR2 ti Oxi
10
336
log10 CR1 7:6036 6:6021
103
Ti 273

log10 CR2 1:5172 108 exp 2:4275
11

104
Ti 273
12
where CNa is the corrosion thickness (mm), CR1 is the

initial corrosion (mm) at temperature Ti with dissolved oxygen Oxi, CR2 is the steady corrosion rate
(mm h1) at temperature Ti with dissolved oxygen
Oxi, ti is the operation time at temperature Ti with
dissolved oxygen Oxi, Oxi is the dissolved oxygen
(ppm, Oxi 5), and Ti is the sodium temperature
( C, 400 T 650)
For PNC-FMS [11Cr2WMoNbV]
CNa CR1 CR2 ti Oxi
13
103
Ti 273
14
log10 CR1 9:078 8:251

log10 CR2 4:1666 104 exp 1:7580
104
Ti 273
15
where CNa is the corrosion thickness (mm), CR1 is the

initial corrosion (mm) at temperature Ti with dissolved oxygen Oxi, CR2 is the steady corrosion rate
(mm h1) at temperature Ti with dissolved oxygen
Oxi, ti is the operation time at temperature Ti with
dissolved oxygen Oxi, Oxi is the dissolved oxygen
(ppm, Oxi 5), and Ti is the sodium temperature
( C, 400 T 650).
5.13.5 Effect of Sodium on the

Mechanical Strength of Steels
The effect of sodium on the mechanical strength of
steel is determined by three factors: (a) corrosion and
mass transfer, (b) decarburization and carburization,
and (c) nonoxidation (reducing atmosphere) by
sodium. For creep strength whose dominant factors
are time and temperature, the behavior of the carbon
and minor elements in the steels are important factors. For the fuel cladding materials, which are thin
structures, it is necessary to consider the effect of
metal loss by corrosion. On the other hand, fatigue
strength in sodium is enhanced in a nonoxidizing
environment such as vacuum.
Thus, the effect of sodium on mechanical strength
appears as the synthesis of both the corrosion and
mass transfer of the steel elements. In this section, the
important points concerning the effects of sodium on
the mechanical strength of core materials, such as

fuel cladding and wrapper tubes, and structural materials, such as reactor vessels, main components, and
pipes, are described.
To estimate the sodium environmental effect of
the core materials, the following three points must
be taken into consideration: (a) the thin structure
(about 0.5 mm thickness for fuel cladding tubes),
(b) the high temperature (maximum 650 C), and
(c) the exchangeable components. Regarding (a),
since the ratio of the sodium-effect layer (corrosion
layer) to the thickness of the fuel cladding tubes
becomes large, the stress increment affecting the base
metal is larger than that of the structural materials.
Regarding (b), since carbon transfer (decarburization/
carburization) becomes active, the high-temperature
strength of the core materials changes easily. Regarding (c), on the other hand, it can be advantageous to
allow a design that takes into account the degree of
material deterioration.
The structural materials are thick compared with
the core materials, and the operation temperature is
550 C or less. Therefore, the effect of sodium is
lower than it is on the core materials. However,
since the structural materials make up the permanent
structure, the long-term (30 years of more) structural
integrity of the materials has to be estimated
appropriately.
The FBR structure materials are used at high
temperatures under which creep phenomenon will
occur. Therefore, the plant design requires that creep
effects as well as tensile and fatigue strength properties be taken into account. In particular, in the case of
the fuel cladding tubes, internal pressure creep
resulting from the generation of fission product gas
is one of the main failure modes. In the case of the
structural materials, since cyclic stress occurs during
plant start-up/shut-down and creep stress occurs
during operation, creep fatigue, which is determined
by both the creep and fatigue effects, is likely to be
one of the main failure modes.
5.13.5.1
Austenitic Stainless Steel
The creep rupture test results in sodium for the

austenitic stainless steel type 304SS are shown in
Figure 13. The creep strength in sodium is equivalent
to that in air at 650 C or less, and no effect of sodium
on creep strength is observed. The same behavior is
observed in the creep rupture test of material preimmersed in sodium for 20 000 h and the material cut
from the sodium loops operated for 100 000 h.21
337
5.0
Type 304SS
: In sodium
: In air
3.0
2.0
1.0
30
500 C
550 C
0.5
600 C
10
5
101
650 C
102
103
Time to rupture (h)
104
105
Figure 13 Creep strength of type 304SS in sodium.

Reproduced from Yoshida, E.; Aoki, M.; Kato, S.; Wada, Y.
28th Symposium on High Temperature Strength,
The Society of Materials Science: Japan, 1990.
Transgranular
450 C
3.0
2.0
1.0
0.5
550 C
3.0
2.0
1.0
0.5
650 C
Stress (MPa)
500
2102
650 C
200
700 C
20
102
Intergranular
103
104
105
Number of cycle to failure (cycles)
5105
Figure 15 Low-cycle fatigue properties of type 304SS in

sodium. Reproduced from Wada, Y. Genshiryoku-kogyo
1990, 36(3); in Japanese.
100
50
Type of surface crack
Material: SUS304
In air
In sodium
Total strain range (%)
Stress (kg mm-2)
100
In air
In sodium
103
104
Time to rupture (h)
105
Figure 14 Creep strength of PNC316 in sodium.

Reproduced from Yoshida, E.; Wada, Y. Creep rupture
properties of austenitic stainless steel in elevated
temperature sodium. High Temperature Strength
Committee of the Society of Materials Science, Japan,
1992.
Furthermore, no effect on creep strength in the carburization environment of a bimetallic sodium system
was observed. However, a slight degradation of creep
ductility was observed in the carburization environment. In this case, micro cracks caused by carburization were also observed in the ternary creep region.22
On the other hand, the strength reduction caused by
the dissolution of the alloy elements, including carbon, in sodium was observed at temperatures greater
than 650 C (Figure 14).
The results of the low-cycle fatigue test in sodium
are shown in Figure 15. In the temperature range of
550 C or less used for the structural materials of
FBRs, the strength in sodium is greater than in air.
This can be explained by the distribution behavior
of surface cracks. Many surface microcracks were
observed on the surface of the specimen tested
in air due to the fact that oxides formed by
high-temperature oxidation in air cause the appearance of fatigue cracks. On the other hand, hardly any
microcracks were observed on the in-sodium specimens because of the effect of nonoxidation (reducing
atmosphere) by sodium. This is the equivalent of
fatigue behavior in a vacuum, and showed excellent
strength in the low-strain range in particular. However, the superiority of the fatigue strength in sodium
decreases as temperature increases, and the fatigue
strength in sodium at 650 C is equivalent to that
in air. It is thought that the strength of the grain
boundary decreases due to the fact that the selective
dissolution of the material elements to sodium via
the grain boundary increases as the temperature
increases.23
The major failure mode of the structural materials
in the FBR is creep-fatigue loading. In this case,
creep damage becomes the dominant factor, and the
nucleation and growth of the creep cavity exacerbates the failure. Therefore, it is thought that the
effect of sodium on the failure mode is negligible.
Moreover, it has been reported that the creep fatigue
strength of type 304SS, which produced accelerative
carburization in sodium, is comparable to its strength
in air.24 From these results, it is concluded that the
effect of sodium on mechanical strength is negligible
for austenitic stainless steels.
338
5.13.5.2
Ferritic Steels
The corrosion behavior in the sodium of ferritic steel

is fundamentally the same as that of austenitic stainless steel. However, the carbon content in ferritic
steel is high compared with austenitic stainless steel,
and the steel tends to undergo strength reduction by
decarburization.
Figure 16 shows the creep strength of PNC-FMS
steel, which is planned as the core material for the
advanced Japanese FBRs. At 650 C, the strength in
sodium is lower than that in air, and this tendency
becomes more evident when kept for longer periods
of time. Such strength reduction is associated with
the carbon concentration in steel. Therefore, it is
necessary to give the strength reduction coefficient
for the design of the FBRs and to estimate the
strength reduction in sodium conservatively.
5.13.5.3
Others (Ni Base Alloys, ODS)
Nickel base alloys, which have excellent mechanical

strength at high temperature, are used as the liner for
protection from high-cycle fatigue failure caused by
thermal striping near the coolant surface. The corrosion thickness of the nickel base alloy in sodium is
equivalent to that of austenitic stainless steels. However, its tensile and fatigue strength in sodium at
elevated temperatures are lower than in air because
of the nickels dissolution to sodium and the formation of an intermetallic compound by thermal aging
in high temperature.25
Oxide dispersion-strengthened (ODS) ferritic
steel is a promising candidate for the fuel cladding
tubes of advanced FBRs. It was reported that the
ODS steel had excellent creep strength in sodium as

well as in air due to the effect of nano-oxide particles
dispersed in the matrix. On the other hand, it was
reported that the nickel, which is dissolved from the
nickel-containing steels in sodium, penetrated to
ODS steel in flowing sodium at elevated temperatures (Figure 17). To apply the steel simultaneously
with the nickel-containing steels, such as austenitic
stainless steel, it is necessary to carefully estimate the
microstructure change by nickel penetration and its
strength reduction.
5.13.6 Damage to Steels with Sodium

Compounds
5.13.6.1
SodiumWater Reaction
One of the weak points of the present FBRs is the

steam generator, the main component of the power
generation system. When the steam generator tube is
damaged, high-temperature pressurized steam is
blown into sodium, and the following chemical reactions occur:
Nas;l H2 Og ! NaOHs;l 1=2H2 g 16
0
0
Hr298
183:8KJmol1 ; Gr298
150:9KJmol1
2Nas;l H2 Og ! Na2 Os;l H2 g
17
0
0
172:8KJmol1 ; Gr298
147:2KJmol1
Hr298
where [g], [l], and [s] stand for gas, liquid, and solid.
The environment around the failed tube is heated
to high temperature in the aforementioned chemical
Stress (MPa)
600 C
650 C
100
Material: PNC-FMS
In sodium
In air
50
101
102
103
104
Time (h)
Figure 16 Creep strength of PNC-FMS in sodium.
Reproduced from Ito, T.; Yoshida, E.; Kobayashi, T.;
Kimura, S.; Wada, Y. Materials Design Base Standard
Supplement (Tentative) of High Strength Ferritic/Martensitic
Steel (PNC-FMS) Core Components for LMFBR; Research
report of the Japan Atomic Energy Agency, PNC TN9410
93045; 1993.
Ni and Cr concentration (mass %)
500
20.0
16.0
Immersed condition
4.5 m s1, 2604 h
Material: ODS
Temperature: 973 K
12.0
Cr
8.0
4.0
Ni
0.0
0
50
100
150
200
250
Distance from sodium exposed surface (m)
Figure 17 Typical result of Ni diffusion for the ODS steel in

sodium. Reproduced from Yoshida, E.; Kato, S. J. Nucl.
Mater. 2004, 329333, pp 13931397.
reactions. Depending on the condition of failure, the

temperature may exceed 1200 C. Furthermore, the
combination of corrosion by the aforementioned
chemical compounds and erosion by the jet blast
causes damage to the steam generator tubes at a significant rate. This damage behavior is called wastage.
Figure 18 shows an example of wastage test results
from Monju safety analysis. The wastage rate of the
steam generator tubes increases as sodium leak rate
increases.
Furthermore, the progression of wastage may
cause an unstable fracture called a high-temperature
rupture. The phenomenon was observed on the
superheater tubes in the Dounreays Prototype Fast
Reactor (PFR) in the UK.
5.13.6.2
2Nas;l 1=2 O2 g ! Na2 Os;l
Fe1:75 kt
18
0
0
Hr298
414:6KJmol1 ; Gr298
147:2KJmol1
2Nas;l O2 g ! Na2 O2 s;l
19
0
0
Hr298
510:9KJmol1 ; Gr298
447:5KJmol1
Wastage rate (mm s1)
100
10-1
2.25 Cr1Mo steel
10-2
10-3
Although sodium peroxide is a thermodynamically

stable oxide in air (P(O2) = 0.21 atm), sodium oxide
usually exists stably due to the reduction effect of
nonburned sodium. The corrosion reaction occurring
in this case is the same as that caused by chemical
reaction with the oxygen dissolved in sodium. The
corrosion is expressed by the formula shown subsequently. Note that the formula shows the maximum
corrosion in the state where the Na2O that is necessary
for the progress of the corrosion is always supplied.
In air, where an excess of moisture is supplied to
the sodium combustion, the corrosion reaction
known as the molten salt type may occur. The corrosion was caused by the peroxide ion in the molten salt
pool composed of NaOH-containing Na2O and
Na2O2.26
Sodium Leak
When high-temperature sodium is leaked into the

atmosphere, it reacts with oxygen, and sodium oxides
are formed by the following chemical reactions:
Austenitic stainless steel
101
100
Leak rate (g s1)
339
20
k 2:01101 exp17 100=RT

where [Fe] is the number of reaction moles (mol cm2),
t is the time (h), R is the gas constant, and T is the
temperature (K).
5.13.7 Tribology
5.13.7.1
Self-Welding
Parts of the components in FBRs that come into

contact and rub are the pad part of the fuel assembly,
the contact part between the fuel cladding tubes and
the wrapping wire, the axle hole of the mechanical
pump, the control rod actuator, and the steam generator tube support. In sodium, the oxides of the component surface are reduced with sodium. Therefore,
it is easy for self-welding and frictional wear to
occur.27 Although frictional wear is also observed in
air, self-welding is peculiar to sodium. Therefore,
hard-facing material, such as CoCr base alloy
(e.g., Stellite) and NiCr base alloy (e.g., Colmonoy), is used for such parts to protect against the
tribological phenomena.
The self-welding phenomenon is based on the
diffusion of the metallic elements that occurs
between the contact surfaces of the material. Therefore, the dominant factors in self-welding are temperature, stress, and time.
101
Figure 18 Relationship between leak rate and wastage

rate. Reproduced from Tanabe, H.; Himeno, Y.
Genshiryoku-kogyo 1988, 34(1), 6976.
5.13.7.2
Frictional Wear
It is important to maintain sodium at a high level

of purity from the viewpoint of the inhibition of
340
Dynamic friction coefficient
1.0
Material: Chromium-carbide (LC-1H)

Temperature: 600 C
0.8
3.
4.
5.
6.
0.6
7.
0.4
0.2
8.
9.
0
100
220
140
180
Cold trap temperature (C)
260
Figure 19 Relationship between oxygen concentration in

sodium and friction characteristics. Reproduced from
Yoshida, E.; Hirakawa, Y. In-Sodium tribological study on
cobalt-free hard-facing materials for contact and sliding
parts of FBR components. In Fourth International
Conference on Liquid Metal Engineering and Technology,
Avignon, France, 1988, Vol. 2.
material corrosion. On the other hand, since the

oxides formed on the surface are reduced, frictional
wear is promoted. When the oxygen concentration of
sodium increases, complex sodium oxides and material elements form on the surface. The oxides function as a lubricant, and frictional wear is reduced. For
example, the relationship between the oxygen concentration in sodium and friction characteristics is
shown in Figure 19.
On the other hand, it is known that there is an
intimate relation between frictional wear and material hardness. Under the same operating conditions,
frictional wear decreases as material hardness
increases. Therefore, to control frictional wear, generally, surface-hardening materials are used for the
components of nuclear plants. CoCr base alloy,
NiCr base alloy, and chromium carbide are used as
the surface-hardening materials for FBRs.
References
1.
2.
Borgstedt, H. U.; Mathews, C. K. Applied Chemistry of

the Alkali Metals; Plenum Press: New York, 1987;
ISBN 030642326-X.
Stanaway, W. P.; Thompson, R. Solubility of metals, iron
and manganese in sodium. In Proceedings of the 2nd
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
International Conference on Liquid Metal Engineering and

Technology, Harwell, Oxford, 1980; p 1854.
Claar, T. D. Reactor Technol. 1970, 13(2), 124.
Stanaway, W. P.; Tompson, R. Liquid Metal Systems;
Prenum Press: New York, 1982; p 421.
Iizawa, K. Nucl. Eng. 1987, 33(11), 62.
Eichelberger, R. L. The Solubility of Oxygen in Liquid
Sodium: A Recommended Expression; Atomics
International: Canoga Park, CA, 1968; AI-AEC-12685.
Furukawa, T.; Yoshida, E.; Aoto, K.; Nagae, Y. The hightemperature chemical reaction between sodium oxide
and carbon steel. In Proceedings of the Symposium on
High Temperature Corrosion and Material Chemistry, The
Electrochemical Society, 989, San Diego, CA, 1998;
pp 312323.
Thorley, A. W.; Tyzack, C. Liquid Alkali Metals; BNES:
London, 1973.
Weeks, J. R.; Klamut, C. J.; Gurinsky, D. H. Alkali Metal
Coolants; H M Stationery Office: London, 1967; E C 1,
pp 324.
Zebroski, E. L. Liquid Alkali Metals; BNES: London, 1973;
pp 195211.
Kolster, R. H. Corrosion transport and deposition of
stainless steel in liquid sodium. In Proceedings of the
International Conference on Liquid Metal Technology in
Energy Production, Champion, PA, 1976; p 368.
Bagnall, C.; Jocobs, D. C. Relationship for corrosion of
Type 316 stainless steel in liquid sodium, 1975; WARDNA-304523.
Maruyama, A.; Nomura, S.; Kawai, M.; Takani, S.;
Ohta, Y.; Atsumo, H. J. Atomic Energy Soc. Jpn. 1984,
26, 59.
Roy, P. ASME Publ., 74-PWR-19, 1975.
Snyder, R. B. An analysis of carbon transport in the EBR-II
and FFTF primary sodium systems. In Proceedings of the
International Conference on Liquid Metal Technology in
Energy Production, Champion, 1976.
Ito, T.; Kato, S.; Aoki, M.; Yoshida, E.; Kobayashi, T.;
Wada, Y. J. Nucl. Sci. Technol. 1992, 29(4), 367377.
Wada, Y.; Yoshida, E.; Kobayashi, T.; Aoto, K.
Development of new materials for LMFBR components
evaluation on mechanical properties of 316FR steel.
International Conference on Fast Reactors and Related
Fuel Cycles, I, Kyoto, Japan, p 7.2.
The Tentative Materials Strength Standard of Advanced
Austenitic Stainless Steel (PNC1520) for FBRs Core
Components Research report of the Japan Atomic
Energy Agency; PNC TN9410 90051; 1990.
Ito, T.; Yoshida, E.; Kobayashi, T.; Kimura, S.; Wada, Y.
Materials Design Base Standard Supplement (Tentative) of
High Strength Ferritic/Martensitic Steel (PNC-FMS) Core
Components for LMFBR, Decrease in Thickness by
Sodium Corrosion, Strength Reduction Factors by
Decarburization and Fatigue Curves; Research report
of the Japan Atomic Energy Agency, PNC ZN9410
93045; 1993.
Kaito, T.; Mizuta, S.; Uwaba, T.; Ohtsuka, S.; Ukai, S.
The Tentative Materials Strength Standard of ODS Ferritic
Steel Cladding; Research report of the Japan Atomic
Energy Agency, PNC TN9400 2005015; 2005.
Yoshida, E.; Kato, S.; Wada, Y. Liquid Metal Systems;
Plenum press: New York, 1995.
Yoshida, E.; Aoki, M.; Kato, S.; Wada, Y. In 28th
Symposium on High Temperature Strength; The Society
of Materials Science: Japan, 1990.
Wada, Y. Genshiryoku-kogyo; 1990, 36(3); in Japanese.
Asayama, T.; Kagawa, H.; Komine, R.; Wada, Y. J. Mech.
Behav. Mater. VI 1991, 2.

25. Yoshida, E.; Komine, R.; Ueno, F.; Wada, Y. Liquid Metal
Systems; Plenum press: New York, 1995.
26. Aoto, K. In Proceedings of the Symposium on High
Temperature Corrosion and Materials Chemistry, 989,
San Diego, CA, 1998; pp 287298.
27. Yoshida, E.; Hirakawa, Y. In-Sodium tribological study on
cobalt-free hard facing materials for contact and sliding
parts of FBR components. In Fourth International
Conference on Liquid Metal Engineering and Technology,
Avignon, France, 1988, Vol. 2.
28.
29.
30.
341
Materials-oriented Little Thermodynamic Database

for Personal Computers (MALT-2). The Japan
Society of Calorimetry and Thermal Analysis,
1992.
Weeks, J. R. In Proceedings of Symposium on Chemical
Aspects of Corrosion and Mass Transfer in Liquid Sodium,
1971; pp 207222.
Menken, G. In 2nd International Conference on Liquid
Metal Technology in Energy Production, XIII-23,
Richland, WA, 1980.
5.14
Spent Fuel Dissolution and Reprocessing Processes
J.-P. Glatz
5.14.1
5.14.2
5.14.3
5.14.3.1
5.14.3.2
5.14.3.2.1
5.14.3.2.2
5.14.3.2.3
5.14.3.2.4
5.14.3.2.5
5.14.3.2.6
5.14.3.2.7
5.14.3.3
5.14.4
5.14.4.1
5.14.4.1.1
5.14.4.1.2
5.14.4.1.3
5.14.4.1.4
5.14.4.2
5.14.4.2.1
5.14.4.2.2
5.14.4.2.3
5.14.4.2.4
5.14.4.3
5.14.4.3.1
5.14.4.3.2
5.14.4.3.3
5.14.4.3.4
5.14.4.3.5
5.14.4.3.6
5.14.4.3.7
5.14.4.3.8
5.14.4.3.9
5.14.4.4
5.14.5
References
Introduction
Fuel Cycle
Industrial Reprocessing
The Irradiated Fuel
The Process Scheme
Shearing/dissolution/off-gas treatment
Dissolver product liquor conditioning
Hulls and fines handling
Solvent extraction
Product finishing
Reprocessing waste management
High-level waste
Safeguarding and Criticality of the Reprocessing
Advanced Reprocessing
Advanced Aqueous Reprocessing
Uranium extraction
Coextraction of actinides
Direct extraction
Purex adapted for Np recovery
Extended PUREX Process for MA Recovery
Fundamental studies
Extraction mechanisms
Separation of trivalent actinides from lanthanides
Process development
Pyro-reprocessing
IFR pyroprocess
European pyrochemistry projects
Basic data acquisition
Core processes
Electrorefining on solid aluminum cathode in molten chloride media
Exhaustive electrolysis
Liquidliquid reductive extraction in molten fluoride/liquid aluminum
Technical uncertainties of the pyro-reprocessing
Head-end conversion processes
The Direct Use of Pressurized Water Reactor Spent Fuel in CANDU Process
Outlook
Abbreviations
ADS
AEA
AFCI
Accelerator-driven system
Global Consulting Firm based in
the UK
Advanced Fuel Cycle Initiative
AREVA
ASTRID
345
345
346
347
348
348
348
348
349
349
349
349
350
350
352
352
352
353
353
353
353
354
355
355
356
357
358
359
359
359
361
362
363
363
365
365
366
International Group and World

leader in the energy sector
Advanced Sodium Technological
Reactor for Industrial
Demonstration
343
344
ATALANTE
Major Nuclear Cycle R&D facility in

Marcoule (France)
BNFL
British Nuclear Fuel
BPP
Bismuth phosphate process
BTP
Bis-triazine-pyridine
BTBP
Bis-triazine-bis-pyridine
BUTEX
b,b0 -dibutyoxydiethyl ether.
A process-based on a solvation
extraction
CANDU
CANada Deuterium Uranium
Reactor
CEA
Commissariat a` lenergie atomique
et aux energies alternatives
CMPO
n-octylphenyl-N,N-diisobutylcarbamoylmethylphosphine oxide.
COEX
Coextraction of actinides
CRIEPI
Central Research Institute of
Electric Power Industry
DIAMEX
Diamide extraction
DIDPA
Disodecylphosphoric acid
DIREX
Direct extraction
DMDBTDMA Dimethyldibutyltetradecylmalon
amide
DMDCHMA Dimethyldicylohexanomalonamide
DMDOHEMA Dimethylsioctylhexylethoxymalon
amide
DMDPhMA
Dimethyldiphenylmalonamide
DTPA
Diethylentriaminepentacetic acid
DUPIC
Direct use of pressurized water
reactor spent fuel in CANDU
EDX
Energy-dispersive X-ray
spectroscopy analysis
ENEA
Italian National Agency for New
Technologies, Energy, and
Sustainable Economic
Development
EBR-II
Experimental Breeder Reactor-II
EURATOM
European Atomic Energy
Community
FP
Fission products
FZ Julich
Forschungszentrum Julich
GENIV
Generation IV
GIF
Generation IV International Forum
GNEP
Global Nuclear Energy Partnership
HDEHP
Diethylhexylphosphoric acid
HEDTA
Hydroxyethyl ethylenediamine
triacetic acid
HLLW
High-level liquid waste
HLW
High-level waste
ILW
Intermediate-level waste
IFR
Integral fast reactor
INL
ITU
JAEA
JNC
JRC
KAERI
LLW
LWR
MA
MELOX
METAPHIX
MOX
NAS
NMR
NOx
NPT
OMEGA
ORNL
PHENIX
PUREX
PREFRE
P&T
PWR
QSAR
R&D
REDOX
RIAR
SANEX
SEM
SETFICS
SPIN
TBP
THORP
TOPO
TPTZ
TRPO
TRU
TRUEX
UREX

Institute for Transuranium
Elements
Japan Atomic Energy Agency
Japanese Nuclear Cycle
Development Institute
Joint Research Centre
Korea Atomic Energy Research
Institute
Low-level waste
Light water reactor
Minor actinides
Plant design (MOX fuel
manufacturing)
Metallic fuel irradiation ad PHENIX
Mixed oxide
National Academy of Sciences
Nuclear magnetic resonance
Nitrogen oxides
Nuclear Nonproliferation Treaty
Options for Making Extra Gains
from Actinides
French Fast Reactor
Plutonium and uranium
extraction
Fuel Reprocessing Plant (Tarapur,
India)
Partitioning and transmutation
Quantitative structureactivity
relationship
Research and Development
Reductionoxidation reaction
Research Institute of Atomic
Reactors (Dimitrovgrad, Russia)
Selective actinide extraction
progress
Solvent Extraction for Trivalent
f-Elements Intra-group Separation
in CMPO-Complexant System
SeParationIncineration
Tributyl phosphate
Thermal oxide reprocessing plant
Trioctylphosphinoxide
Tripyridyltriazine
Trialkyl phosphine oxide
Transuranium elements
Transuranium extraction process
Uranium extraction process
5.14.1 Introduction
The first large-scale nuclear reactors were designed
for the production of weapon grade plutonium during the Second World War. It is obvious that the
reprocessing technology was focused on the extraction
of plutonium from the irradiated fuel. The bismuth
phosphate process (BPP) was the first process to be
developed and tested in the early 1940s at the Oak
Ridge National Laboratory (ORNL) and scaled up to
the kilogram scale in 1944 at the Hanford site. This
precipitation process had already been used in 1942 by
Glenn Seaborg to separate microgram quantities of
Pu. However, the recovery of uranium is not possible.
In the BPP process, the irradiated fuel is dissolved
in nitric acid and the Pu precipitated with the fission
products (FPs) using sodium phosphate and bismuth
nitrate as Pu3(PO4)4 after adjustment of the valence
with sodium nitrite to Pu(IV). To separate Pu from
the FPs, the precipitate is redissolved in nitric acid,
Pu is oxidized to Pu (VI), and the FPs are reprecipitated. Several cycles are necessary to achieve sufficient decontamination.
The first solvent extraction process used in reprocessing is the reductionoxidation reaction (REDOX)
process, a continuous process where both uranium
and plutonium are recovered at high yields and with
high decontamination factors from FPs. Both uranyl
and plutonyl nitrates are selectively extracted from
dissolved fuel. After development at the Argonne
National Laboratory and testing at the pilot scale at
the ORNL from 1948 to 1949, a REDOX plant was
built in Hanford in 1951.
The b,b0 -dibutyoxydiethyl ether (BUTEX) process
utilizes a dibutyloxydiethyl ether solvent and nitric
acid. This process was developed in the late 1940s at
the Chalk River Laboratory and operated at an industrial scale at the Windscale plant in the UK until 1976.
Again at ORNL in 1949, a successful solvent extraction process for the recovery of pure uranium
and plutonium was developed, initially to separate
239-Pu for military purposes. The plutonium and
Table 1
345
uranium extraction (PUREX) process was invented

by Herbert H. Anderson and Larned B. Asprey at
the Metallurgical Laboratory at the University of
Chicago, as part of the Manhattan Project.1
The so-called PUREX process is still the standard
method of extraction for the reprocessing of commercial nuclear fuels. The first industrial reprocessing
plant for commercial fuels was the UP1 facility at
Marcoule in France. During the 1960s and 1970s,
reprocessing activities were launched in Belgium,
France, Germany, India, Japan, the Russian Federation, the United Kingdom, and the United States.
For various reasons, however, only some of these
plants are still in operation (see Table 1), namely,
at the International Group and World leader in the
energy sector (AREVA) NC La Hague site in France,
the THermal Oxide Reprocessing Plant (THORP)
operated by the British Nuclear Group Sellafield
(BNGSL) in Sellafield in the United Kingdom, the
RT-1 plant in Mayk in Russia, the PREFRE facility in
Tarapur, India, and, since 2010, the Rokkasho plant
operated by JNFL in Japan.
The RT-1 facility in Mayak is the only plant
where fast reactor fuel, from the BN 600 reactor, is
reprocessed on a large scale.
The total amount of used fuel cumulatively generated worldwide by the beginning of 2010 was
approximately 300 000 tons HM. Between now and
2030, some 400 000 tons of used fuel is expected to be
generated worldwide, including 60 000 tons in North
America and 69 000 tons in Europe.
Worldwide, the used fuel generated in 2010 was in
the order of 11 000 tons HM. About one-third of the
fuel inventory is reprocessed at present; the rest is
placed into interim storage facilities, mostly at the
reactor sites.
5.14.2 Fuel Cycle

The various activities associated with the production
of electricity from nuclear reactions are referred to
Major commercial reprocessing plants in operation today
Plant
Country
Site
In operation since
Capacity (tons/year)
UP2
THORP
RT-1
PREFRE
RRP
France
United Kingdom
Russia
India
Japan
La dHague
Sellafield
Mayak
Tarapur
Rokkasho-Mura
1990
1994
1976
1982
2009
800
1000
400
150
800
346
Reprocessing plant
High level
waste
U mining
Uranium
storage
Depleted
uranium
Natural
uranium
Enrichment
Processing
Fissile and
fertile
Repository
Spent
nuclear
fuel
Fuel
fabrication
SNF
storage
Spent fuel
storage
Reactor
Nuclear
reactor
Figure 1 The nuclear fuel cycle.
collectively as the nuclear fuel cycle (see Figure 1).

The nuclear fuel cycle starts with the mining of uranium and ends with the disposal of nuclear waste.
When using reprocessing of used fuel as an option for
nuclear energy, the different stages form a true cycle.
Nuclear energy systems of the future, as they were
defined by the Generation IV International Forum
(GIF), are supposed to provide a sustainable energy
generation for the future (http://www.ne.doe.gov/
genIV/neGenIV1.html). The corresponding fuel
cycles will play a central role in the achievement of
this goal. The major benefits of used fuel recycling are
the conservation of natural uranium resources,
reduced dependence on foreign fossil fuel, and reduction of the nuclear waste radiotoxicity and the heat
load of repositories. Major challenges to the implementation are significant costs, safety, and increasing
proliferation concerns, also affecting the public
acceptance of this technology.
The present reactors use less than 1% of the uranium available in nature. With such a low efficiency,
the uranium resources identified worldwide will be
sufficient for only about 100 years with the currently
installed nuclear power infrastructure. Depending on
the growth rate in the use of nuclear systems in the
future, this time span could be significantly lower. New
energy systems using a technology based on the combination of fast neutron reactors with advanced multirecycling of the fuel would improve the usage of
natural uranium resources by at least a factor of 50.
The new reactor concepts under development will
be able to recycle not only most of the fertile and
fissile uranium and plutonium but also the other
long-lived actinides produced in the nuclear fuel.
The consequence is that on one hand the fuel refabrication will be more complex and difficult, but on
the other, the long-term waste radiotoxicity can be
considerably reduced.
All this should be achieved while maintaining or
even improving the safety and the economic competitiveness, and minimizing the risks of proliferation.
It is obvious that this change toward an enhanced
sustainability is a progressive process, which has
already started. Indeed, the current industrially operated fuel recycling technologies are being constantly
improved and optimized in view of natural resource
utilization and economic competitiveness.
5.14.3 Industrial Reprocessing

The reprocessing of used commercial fuel is done
exclusively by the PUREX extraction process. In a
reprocessing facility, the used fuel is separated into
three fractions: uranium, plutonium, and waste, which
contains FPs and minor actinides (MAs). Reprocessing enables recycling of the uranium and plutonium
into fresh fuel.
Since 2004, commercial reprocessing is used by
the nuclear industry in several countries to separate and reuse plutonium in a mixture with uranium as mixed oxide (MOX) fuel in electricity
producing reactors. The first irradiation of MOX
was done in 1960 in the BR3 reactor in Belgium.
Today, the worlds largest MOX fabrication facility
called MELOX, with a capacity of 1500 HM/year,
is operated by AREVA in Marcoule in the South
of France.
347
In some countries, reprocessed uranium is also

reused after enrichment as nuclear fuel. The uranium
from reprocessing, which typically contains a slightly
higher concentration of U-235 than that occurring in
nature, can be reused as fuel after conversion and
enrichment. However, reprocessed uranium also contains U-236, typically 0.5%, which increases at higher
burn-up. This isotope is a neutron absorber; therefore, only reprocessed uranium from low-burn-up
fuel is reused in light water reactors (LWRs), while
that from high burn-up fuel is best used for blending
or MOX fuel fabrication.
5.14.3.1
The Irradiated Fuel
Generation II reactors were typically designed to

achieve a burn-up of about 40 GWd/MTU. With the
improved fuel technology, these same reactors are
now capable of achieving up to 60 GWd/MTU, and
research and development (R&D) efforts are ongoing
to further increase this burn-up value. The incentive is
the achievement of a better economy of the energy
production process: To produce a given amount of
energy, a smaller number of fresh nuclear fuel elements are required and a lesser amount of used nuclear
fuel elements are generated; furthermore, as a consequence of this, the downtime for refueling is reduced.
At some stage, however, the build-up of FP neutron poisons achieves values that necessitate the reactors being shut down and refueled. Used fuel is a
highly radioactive and very complex material, and
at an average burn-up of 45 GWd tons1, it contains
about 94% U-238, approximately 1% U-235 that has
not fissioned, almost 1% plutonium, and 4.5% FPs
with the following approximate composition:
Rare earths, Y: 24%
Ru, Tc, Rh, Pd: 16%
Kr, Xe: 15%
Zr, Nb: 14%
Mo: 13%
Cs, Rb, I, Te: 11%
Ba, Sr: 7%
Depending on their thermophysical behavior during irradiation, the FPs exhibit a totally different
behavior. A detailed classification of FPs was published by Kleykamp in 1985.2
Dissolved in the matrix: Rb, Sr, Y, Zr, Nb, Te, Cs,
Ba, La, Ce, Pr, Nd, Pm, Sm, Eu
Partly precipitated at grain boundaries (oxides):
Rb, Sr, Zr, Nb, Mo, Se, Te, Cs, Ba
Metallic precipitates: Mo, Tc, Ru, Rh, Pd, Ag, Cd,
In, Sn, Sb, Se, Te
Volatiles: Br, Kr, Rb, I, Xe, Cs, Te
Especially at the beginning of the irradiation process
when the fission event density is the highest, leading
to the highest linear power, a significant relocation of
FPs takes place, depending on their volatility. In fact, in
an oxide fuel, temperature gradients of at least 500 C
between the fuel periphery (500 C) and the fuel
center (>1000 C) lead to significant migration and
diffusion processes. The grain structure of the fuel initially produced by pressing UO2 powder, induces under
irradiation precipitation of some of the FPs at the grain
boundaries; noble elements partially form metallic precipitates. The most volatile elements can migrate outside
of the fuel pellets where they are deposited or potentially
form compounds, with the cladding material as well.
Parts of the volatiles are found in the fuel rod plenum.
The above-mentioned burn-up also has a considerable impact on the content of transuranic elements
which are formed by neutron capture of U-238.
Table 2 shows the composition (major transuranium
(TRU) elements and some FPs) of LWR fuels at
various burn-ups in comparison to MOX fuel.
Especially for Cm, the content is increased by
almost a factor of 10 if the burn-up is increased
from 33 to 60 GWd tons1. A similar increase is
Table 2
Composition (major transuranium elements and some fission products) of LWR fuels at various burnups in
comparison to MOX fuel
Fuel type
LWR
1
Average burn-up (GWd t )

Constituent
1
Pu (g tU )
Np (g tU1)
Am (g tU1)
Cm (g tU1)
Zr (g tU1)
Tc (g tU1)
Ru (g tU1)
MOX
33
45
60
45
9.740
433
325
23
3.580
814
2.165
11.370
611
521
92
4.740
1.085
3.068
12.990
887
765
213
6.280
1.403
4.156
48.850
161
4.480
810
3.440
977
3.924
348
observed for MOX and LWR fuels at the same burnup of 45 GWd tons1.
New generation fast reactors are using MOX fuel
with Pu content before irradiation of about 20%
instead of 5% in LWRs and because they are less
sensitive to increasing amounts of FPs, burn-ups up to
200 GWd tons1 are possible. It is obvious that all this
will have a major impact on the reprocessing process.
5.14.3.2
The Process Scheme
The well-proven hydrometallurgical PUREX process

used by the commercial reprocessing plants involves
the dissolution of the fuel elements in 56 M nitric
acid, the extraction of uranium and plutonium by the
tributyl phosphate (TBP) solvent, the chemical separation of uranium, and a conditioning of the products
(see Figure 2). The raffinate of the extraction process
is a high active waste (HAW) solution, which contains
the major part of the FPs and the MAs.
Uranium and plutonium can be returned to the
fuel cycle the uranium to the conversion plant prior
to re-enrichment and the plutonium to MOX fuel
fabrication.
5.14.3.2.1 Shearing/dissolution/off-gas
treatment
The fuel elements are transferred to the dissolver

equipment, where the shearing equipment cuts the
fuel pins into segments of a few centimeters to ensure
effective fuel dissolution. Dissolver systems with a
critically safe geometry can be operated in a continuous or in a batch mode. For high throughputs in
large-scale reprocessing, continuous rotary dissolvers
are preferred. The sheared fuel falls into the dissolver
basket where it is immersed in hot nitric acid,
contained in the dissolver.
Similar reactions can be written for the direct dissolution of the uranium oxide fuel pellets (not showing
the dissolution of the remaining actinides and FPs):
Spent fuel
HNO3
TBP solvent
Shear
Spent fuel
dissolver
Extraction
Off-gas
Hulls
storage
Vitrified HAW
storage
Figure 2 Simplified PUREX process scheme.
3UO2 8HNO3 3UO2 NO3 2 2NO 4H2 O
1
The basket retains the bulk insolubles contained in

the fuel and the cladding material, also called hulls,
allowing them to be removed from the vessel after the
dissolution process is complete. Finer insoluble solids,
not retained in the basket, are removed with the product liquor and separated subsequently by settling
or centrifugation, according to their size. Insolubles
are washed before being removed. Further, the off-gas
containing mainly nitrogen oxides, iodine, ruthenium,
carbon 14, fuel dust, and aerosols is treated in a dedicated off-gas treatment plant before being either
recycled (NOx) or discharged to the atmosphere.
5.14.3.2.2 Dissolver product liquor
conditioning
Following its removal from the dissolver, the product

liquor containing the dissolved uranium, plutonium,
MAs, and FPs, clarified from any solid material,
together with recovered washings is accurately
measured for adherent radioactive material, before
further conditioning. Therefore, accountancy measurement tanks are fitted with highly efficient mixing
systems, multilevel sampling, high accuracy level
determination and density instrumentation, and very
precise tank weighing systems. After accountancy
determination, the liquor is transferred to conditioning tanks for further adjustments, necessary for the
solvent extraction process.
5.14.3.2.3 Hulls and fines handling
The hulls are checked to be free of residual fuel and

product liquor using gamma spectrometry and neutron measurement techniques (active and passive).
In the unusual case of a high residual fuel content,
the hulls are returned to the dissolver for further
treatment; otherwise, they are either compacted or
encapsulated in a cement matrix. The insoluble residues removed from the product liquor are added to
the calcined high-level waste (HLW) for vitrification.
Uranyl
nitrate
U
evaporator
UO2
conversion
UO2
storage
Pu
evaporator
MOX
conversion
MOX
storage
U, Pu
separation
Pu
nitrate
5.14.3.2.4 Solvent extraction
The central part of the reprocessing is of course the

solvent extraction based on the well-proven PUREX
process (see Figure 2). The solvent is TBP diluted
with odorless kerosene. The extraction happens
through formation of an uranylnitrato complex with
two TBP molecules in the organic phase according to
the following equation:

UO2
2 2NO3 2TBP UO2 NO3 2 2TBP 2
For the primary separation cycle to remove FPs and

to separate uranium and plutonium, a series of
pulsed columns are used. The aqueous, highly active
raffinate containing the FPs from the primary separation cycle is treated by a water steam strip to
remove residual solvent. After storage, the solution
is concentrated and immobilized by vitrification in
view of a final disposal. This vitrification process
shows high flexibility because insoluble residues
(see Section 5.14.3.2.3) and alkaline effluents from
the solvent regeneration can also be incorporated in
the glass matrix. Uranium and plutonium in the
solvent phase are separated by adding uranium IV
which acts as a plutonium reductant. The reduced
plutonium is back extracted into an aqueous phase
which is routed to the plutonium purification and
finishing lines.
Where possible, equipment is designed to operate
without routine maintenance during the life of the
plant. Equipment in contact with radioactivity can
be remotely cleaned and dismantled. In cases where
contaminated equipment must be maintained, it may
be remotely dismantled and rebuilt, or in other cases,
it is routed to special decontamination plant systems
to allow contamination to be removed and also to
allow hands on maintenance. Because of the time
involved in this type of activity, duplicate spares
are generally provided for units requiring routine
removal for decontamination and maintenance.
Radioactively contaminated components are consigned for disposal or waste treatment.
Appropriate materials have to be selected according to the requirements of each item of equipment.
In addition, the integrity of all process equipment in
contact with active materials has to be ensured by
quality control during manufacturing, installation,
inspection, and testing, in order to minimize maintenance requirements and plant downtime.
Stainless steel is the standard material used in the
construction of the majority of the process systems,
with special materials such as titanium or zirconium
utilized for particularly demanding applications.
349
All materials to be used in hot cells are subject to

checks for reliability in a radiation environment.
Radiation-sensitive items are either located outside
the hot cells or locally shielded to minimize radiation
effects. Significant progress has been achieved in the
development of suitable materials. However, even
more reliable materials are needed and R&D efforts
are continuing with a view to enhancing the qualities
of materials used in modern plants.3
5.14.3.2.5 Product finishing
After purification, the plutonium is precipitated by

addition of oxalic acid. The plutonium oxide product,
which is produced by calcination of the oxalate, is
packaged in stainless steel containers. These containers are arranged in a way to provide a criticality safe
geometry for storage. The solvent loaded with uranium from the primary separation cycle passes to
purification and the resulting uranyl nitrate solution
is evaporated and converted to uranium trioxide by
thermal denitration. The uranium trioxide product is
packaged in drums for interim storage in an engineered storage. Both the uranium and the plutonium
products are produced to internationally agreed
specifications and in a form suitable for recycling.
5.14.3.2.6 Reprocessing waste management
A number of categories of radioactive waste are defined, each of them requiring a specific management
approach. HLW is defined as the category of waste
where the heat generated by radioactive decay significantly affects the design of the waste management
route. Solid low-level waste (LLW) is defined as the
solidwaste with radioactivity levels less than the authorized limits for the shallow land disposal. Intermediatelevel wastes (ILW) are those wastes between HLW and
LLW. In addition, very low-level liquid and aerial
effluents are produced, which are discharged into the
environment, provided their monitoring shows compliance with discharge authorization values.
5.14.3.2.7 High-level waste
The major waste fraction from the radioactivity point

of view is the HLW. The general management strategy internationally adopted for this type of waste is
the storage of the liquor for radioactive decay in
storage tanks. The aqueous solution of FPs and
MAs is concentrated up to about a factor of 15 before
it is vitrified at 1150 C using a borosilicate glass
matrix (see Chapter 5.18, Waste Glass). In France,
a cold crucible vitrification process is currently
350
proposed as a replacement for the conventional system, aiming at a simplified single-step process. Commercial vitrification plants in Europe produce about
1000 tons per year of such vitrified waste (2500 canisters) and some have been operating for more than
20 years.
The glass properties must be guaranteed to ensure
the satisfactory long-term performance of the waste
package. The alteration behavior of the glass is
therefore assessed against the performance criteria
required for interim storage or disposal purposes.
5.14.3.3 Safeguarding and Criticality of
the Reprocessing
The goal to foster the peaceful uses of nuclear energy
based on the Treaty on the Non-Proliferation of
Nuclear Weapons (NPT) is achieved through the
implementation of a highly efficient safeguarding
process at reprocessing plants. The particular interest
in bulk-handling facilities like reprocessing plants
where large quantities of plutonium are handled is
obvious. Nuclear material flows (in or out) are monitored at key measurement points, such as storage
areas (tanks, containers, used fuel ponds), the headend fuel treatment, shearing and dissolution area, and
product storage area (plutonium, uranium).
The National Academy of Sciences (NAS) has
declared that the large and growing stocks of plutonium from weapons dismantlement in the United
States and the former Soviet Union are a clear and
present danger to peace and security. Moreover,
experts consider that plutonium of any isotopic blend
is a proliferation threat; this means of course that
plutonium produced in the civilian fuel cycle is itself
a proliferation threat. Assuring that separated plutonium, from dismantled warheads as well as from civilian power programs, is under effective control has
(again) become a high priority worldwide. If plutonium
is considered as an energy resource, it is mandatory to
safeguard it against diversion, putting it into active use
in the civilian power program. The ultimate choice
cannot be separated from the long-term strategy for
use of peaceful nuclear power.
However, continued use of a once-through fuel cycle
will also lead to an ever-increasing quantity of excess
plutonium, requiring safeguarding as well. Alternatively, recycling the worlds stocks of plutonium in fast
reactors will cap the world supply of plutonium and
hold it in working inventories for generating power.
Transition from the current-generation LWRs to a
future fast-reactor-based nuclear energy supply under
international safeguards would limit world plutonium

inventories to the amount necessary and useful for
power generation, with no further excess production.
A concept like the integral fast reactor (IFR) in the
United States foresees complete recycle of plutonium, and indeed, of all transuranics, with essentially
no transuranics sent to waste, so the need for perpetual safeguards of IFR waste is eliminated. The pyrorecycle process is more proliferation resistant than
the current PUREX process because at every step of
the IFR recycle process the materials meet the usedfuel standard. The scale of IFR recycle equipment is
compatible with colocation of power reactors and
their recycle facility, eliminating off-site transportation and storage of plutonium-bearing materials.
Self-protecting radiation levels are unavoidable at
all steps of the IFR cycle, and the resulting limitation
of access contributes to making covert diversion of
material from an IFR very difficult to accomplish and
easy to detect.
Another key issue for any reprocessing activity is
the criticality. As already mentioned several times in
the process description section above, the criticality
control in the PUREX process is mandatory throughout the process scheme and in this respect plutonium
is a key element, especially in view of increasing
burn-up, the usage of MOX fuel, and in the long
term the implementation of fast reactor systems.
The factors that mainly affect criticality safety are
the fissile nuclides (235U, 238Pu, and to a lesser
extent 233U);
the fraction of fertile nuclide diluting fissile
nuclides (238U and 240Pu);
the mass and concentration of fissile nuclides;
the geometries and volumes of fissile materials in
the facility; and
the neutron moderators, reflectors, and absorbers.
5.14.4 Advanced Reprocessing

A sustainable energy generation for the future with
the major objectives of effective fuel utilization and
waste minimization through recycling of all actinides
can only be achieved with substantial modification of
the corresponding fuel cycles. The waste minimization goal is in fact based on a waste management
strategy, its main motivation being the reduction in
the long-term radiotoxicity. In this partitioning and
transmutation (P&T) scenario studied for many decades already, long-lived radionuclides are recovered
(partitioning) and converted into shorter-lived or

stable isotopes by irradiation (transmutation). The
transmutation efficiency should be especially high
in dedicated reactors such as accelerator-driven systems (ADS), where a subcritical reactor is connected
to a cyclotron or linear accelerator. Numerous
research activities carried out in P&T have shown
that efficient P&T scenarios can shorten the time
needed for isolation of nuclear waste from >100 000
years down to about 500 years. From the viewpoint of
radiotoxicity reduction of the actual waste, P&T must
first concern the actinides, particularly plutonium
and the MAs (mainly Am, Cm), which make up
more than 99% of the radiotoxicity already after a
few hundred years of storage.4
Advanced reactor systems of the IVth generation,
especially those using a fast neutron spectrum, offer
excellent transmutation features. Therefore, an inherent P&T scheme can be used to reduce the long-term
waste radiotoxicity. On the partitioning side, one
can rely on the considerable scientific and technical
progress made through domestic and international
projects such as SeParationIncineration (SPIN)
(France),5 Options for Making Extra Gains from Actinides (OMEGA) ( Japan),6 Global Nuclear Energy
Partnership (GNEP)/Advanced Fuel Cycle Initiative
(AFCI) (USA) (http://www.gnep.gov/), as well as
bilateral cooperations and European Atomic Energy
Community (EURATOM) Framework Programs711
over the last couple of decades.
The most long-lived radionuclides contained in
used nuclear LWR fuel are listed in Table 3.
Two types of processes can be applied to the
separation of long-lived radionuclides: hydrochemical (wet) and pyrochemical (dry) processes. Both
have advantages and disadvantages and should be
Table 3
351
applied in a complementary way. If a so-called

double-strata concept, for example, as proposed in
the above-mentioned OMEGA project is adopted,
the well-established industrial reprocessing of commercial LWR fuel with recycling of U and Pu based
on PUREX extraction should be logically combined
in the first stratum with an advanced aqueous partitioning scheme, also based on liquidliquid extraction
to separate the long-lived radionuclides. In the second
stratum, new generation reactor systems should preferably be combined with pyro-reprocessing, because
most of the fuels under investigation for advanced
reactor systems are more soluble in molten salts;
shorter fuel cycles are possible because of a higher
radiation resistance, and a higher proliferation resistance is due to reduced product purity.
Therefore, the decision on the partitioning process
to be applied should depend on the boundary conditions, such as the type of fuel material to be treated,
but aqueous- and pyropartitioning are not to be seen
as competitive options to achieve the partitioning of
long-lived MAs and FPs from used nuclear fuel.
In any case, an efficient and selective recovery of
the key elements from the spent nuclear waste is
absolutely essential for a successful and sustainable
fuel cycle concept. This necessitates the selective
separation of Am and Cm from lanthanide FPs, certainly the most difficult and challenging task in
advanced reprocessing of used nuclear fuel because
of the very similar chemical behavior of the trivalent
elements. There are three major reasons to separate
actinides from lanthanides:
Neutron poisoning: lanthanides (esp. Sm, Gd, Eu)
have very high neutron capture cross sections,
for example, >250 000 barn for Gd-157.
Long-lived radionuclides in used nuclear fuel
Category
Element
Isotope
Period (years)
Mass (g t1)
Isotope content (%)
Minor actinides
Np
Am
237
241
243
243
244
245
79
93
99
107
126
129
135
2 140 000
432
7380
28.5
18.1
8530
65 000
1 500 000
210 000
6 500 000
100 000
15 700 000
2 300 000
430
220
100
0.3
24
1
4.7
710
810
200
20
170
360
100
67
31
1
94
5
9
20
100
16
40
81
10
Cm
Fission products
Se
Zr
Tc
Pd
Sn
I
Cs
352
Material burden: in used LWR fuels, the lanthanide content is up to 50 times that of Am/Cm.
Segregation during fuel fabrication: upon fabrication, lanthanides tend to form separate phases,
which grow under thermal treatment; Am/Cm
would also concentrate in these phases.
Further, the lanthanide actinide separation can be
derived from aqueous or pyrochemical partitioning
processes of MAs.
5.14.4.1
Advanced Aqueous Reprocessing
The actual PUREX process is the industrial hydrochemical reprocessing technique to separate pure U and
Pu fractions from used fuel. For the advanced fuel
cycles mentioned above, world-wide efforts are made
to use modified versions of the present PUREX process
with the goal to cope with sustainability goals and to
improve the economy and the proliferation resistance.
5.14.4.1.1 Uranium extraction
The US Department of Energy proposes the uranium

extraction (UREX) process in the frame of their
advanced fuel cycle development programs, where
only uranium is recovered and recycled. The central
feature of this concept is the increased proliferation
resistance by leaving the plutonium with other transuranics for a grouped recycling in fast reactors. Several variations of the UREX process have been
developed, with different options on how the plutonium is combined with various MAs, lanthanide, and
nonlanthanide FPs. A major challenge is the fuel
fabrication mainly because of the americium volatility and the fact that curium is a neutron emitter.
Remote fuel fabrication facilities would be required,
leading to high fuel fabrication costs and significant
technological development.
Spent fuel
Shear
Off-gas
5.14.4.1.2 Coextraction of actinides
AREVA and Commissariat a` lenergie atomique et

aux energies alternatives (CEA) have developed the
COEX (coextraction of actinides) process on the
basis of extensive French experience with PUREX
(see Figure 3).
The COEX process is based on coextraction and
coprecipitation of uranium and plutonium (and usually neptunium), as well as a pure uranium stream,
but without separation of a pure plutonium fraction.
This process allows the production of a high-quality
MOX for both light water and fast reactors. An industrial deployment for LWR-MOX is foreseen for the
near term. The sodium fast reactor prototype
Advanced Sodium Technological Reactor for Industrial Demonstration (ASTRID) planned for deployment in the early 1920s could also be based on the
COEX process.
In the longer term, the goal is to have a technology
validated for industrial deployment of generation IV
(GENIV) fast reactors around 2050; at this stage, the
present La Hague plant will also be due for replacement around 2050.
The long-term goal is to make a large capacity of
spent fuel reprocessing (in the range 20003000 tons
year1) available with a potential to further reduce
the reprocessing costs and to address the potentially
increasing spent fuel reprocessing needs. Another
objective is to enhance the flexibility in material
management with a design adapted to the treatment
of a wide spectrum of fuel types, that is, legacy fuel
stored for decades, newly discharged fuel for reprocessing, and fuels with high fissile isotopes content
(MOX fuel, very high burn-up fuels).
The goal is also to have the spent fuel reprocessing
and fresh fuel refabrication on same site (limited fuel
transports and storage needs). Also the implementation of MA reprocessing would be facilitated.
HNO3
TBP solvent
Spent fuel
dissolution
Extraction
Hulls
storage
Vitrified HAW
storage
Figure 3 COEX: a simplified PUREX process scheme.
Depleted U
Coconversion
Fuel pellet
manufacturing
5.14.4.2 Extended PUREX Process for MA

Recovery
5.14.4.1.3 Direct extraction
Another alternative reprocessing technology being

developed by Mitsubishi and Japanese R&D establishments is Super-DIREX (supercritical fluid direct
extraction). This technology is designed to cope with
uranium and MOX fuels from light water and fast
reactors. The fuel is dissolved in a mixture of nitric
acid, TBP, and supercritical CO2, resulting in complexation and extraction of uranium, plutonium, and
MAs with TBP.
For the separation of MAs, the PUREX process has to

be modified/extended using also hydrochemical
extraction techniques.13 Extensive R&D is carried
out worldwide to synthesize special extractants and
to develop the corresponding process schemes
required for a selective separation of MAs (mainly
Am and Cm) from high-level liquid waste (HLLW).
The process development requires a good basic
understanding on the extraction mechanisms.
5.14.4.1.4 Purex adapted for Np recovery
In the standard PUREX process, Np is partially

extracted by TBP; this part follows the U stream, is
separated in the second U purification cycle, and then
added to the HLW and vitrified. In the fuel solutions
feeded to the first decontamination cycle, Np is present as a mixture of Np (IV), Np (V), and Np (VI), but
only Np(IV) is extracted. Therefore, in the PUREX
process adapted for Np recovery,12 Np is completely
oxidized to the oxidation state VI and then coextracted with U and Pu in the first decontamination
cycle where it again follows the U stream. Finally it is,
as in the standard process, recovered through a
reducing scrub in the second U cycle. After separation, the Np nitrate, contaminated by bg emitters,
may be purified by solvent extraction with TBP
and finally transformed to oxide by calcination of
the oxalate.
5.14.4.2.1 Fundamental studies
As aqueous partitioning is based on liquidliquid

extraction from an acidic solution into an organic
phase, it is crucial to understand extraction selectivity, thermodynamics, mechanisms, and kinetics. In
aqueous MA partitioning schemes, two main routes
are possible (see Figure 4). The optimal strategy
would be of course a process, where MAs are directly
extracted from the PUREX raffinate, HLLW. However, till date, no extractant capable of selective and
efficient separation of the MAs at high acidities
(>2 M HNO3) in a highly radioactive solution containing all FPs, among them lanthanide elements in
a mass excess of 20 times compared to MAs, has
been found. Partitioning of MAs involving coextraction of lanthanide (Ln) elements and a subsequent
LWR fuel
Dissolved fuel
PUREX
U, Pu, (Np)
HLLW
FP
Selective extraction
MA extraction
(org. complexant)
Coextraction of
MA, Ln
MA /Ln
Selective stripping
MA stripping
(aq. complexant)
Ln
Selective
Ln
extraction
High acid
MA extraction
MA
Am/Cm sep.
Am
353
Cm
Transmutation
Figure 4 Strategies for the separation of the minor actinides from HLLW.
Developed
Future ?
FP (Ln)
354
separation of the two element groups is therefore the

only viable option at present.
5.14.4.2.2 Extraction mechanisms
One of the major concerns to be addressed with

respect to the extraction of lanthanides (III) and
actinides (III) from aqueous nitrate solutions requires
the knowledge of the nature of the extracted species.
A dual mechanism of extraction would be based on
the formation of solvates having the general formula
M(NO3)3Ln according to the following equation:
M3 HNO3 nL MNO3 3 Ln 3H
with M(III) Ln(III) or An(III) and L organic
extractant.
In European research programs, the reference
organic extractant is based on the diamide molecule
with the general formula (R(R0 )NCO)2CHR00 (where
R, R0 , and R00 are alkyl or oxyalkyl groups, e.g., N,N0 dimethyl-N,N0 -dibutyltetradecyl-1,3-malonamide
(DMDBTDMA); see Figure 5).
For concentrated aqueous nitric acid solutions, as
encountered when extracting U(VI) or actinide (IV)
from nitric acid media by monoamide extractants
ion-pairs, of formula [LH]n, [M(NO3)3n]n3n.
Several experiments, involving UV-visible and
13
C NMR (nuclear magnetic resonance) spectroscopies and solvent extraction, have been conducted to
answer this question. From the data obtained so-far,
one can conclude that even if a dual extraction mechanism exists, the second mechanism does not seem
to be an ion-pair mechanism involving a protonated
diamide. It can therefore be concluded that the
occurrence of an ion-pair mechanism is unlikely.
A comparison of diamides with different R0 groups
(butyl, phenyl, and chlorophenyl) as regards their
ability to extract An(III) or Ln(III) from aqueous
nitrate media shows that a less basic malonamide
has better extraction properties for the M(III) nitrate.
If in the central R00 position the alkyl group is replaced
by a dioctylhexylethoxy group (see Figure 6), the
diamide dimethyl-dioctyl-hexylethoxy malonamide
(DMDOHEMA) exhibits better affinities for M(III)
nitrates.
Arrhenius activation energies close to 40 kJ mol1

for all M(III) studied indicate that the extraction is
chemically limited at the aqueousorganic interphase. For a diffusion limited kinetic regime, this
energy is generally found close to be 20 kJ mol1.
The extraction kinetics of M(III) nitrates by
DMDBTDMA were found to be much slower than
for the extraction of U(VI) or Pu(IV) nitrates by TBP
(extractant of the PUREX process).
Crystal structures were determined by X-ray
absorption spectroscopy and using synchrotron light
for a large number of lanthanide and actinide
diamide complexes. Molecular modeling studies
have been conducted to compare calculated structures and X-ray determined crystal structures and to
propose structural explanations for experimental differences observed during extraction of M(III) metallic nitrates by several malonamides.
Using the Quanta/CHARM code, the lowest
conformation calculated for dimethyldiphenylmalonamide (DMDPhMA), dimethyldicylohexanomalonamide (DMDCHMA), and BDMDPhMA structures
were found to be similar to the experimentally determined crystal structures. The differences between
the structures of DMDPhMA and BDMDPhMA,
and of DMDCHMA were also confirmed by calculations. The differences in M(III) extraction efficiency
between cyclohexano (DMDCHMA) and phenylsubstituted (DMDPhMA and BDMDPhMA) malonamides can be correlated with the difference of
the preferred conformations of the malonamide
extractants.
Using the Gaussian 94 program, protonation of
cyclohexano (DMDCHMA) and phenyl-substituted
(DMDPhMA) malonamides was studied. Results are
equivalent for both malonamides and show that monoprotonated malonamide contains an intramolecular
hydrogen bond, while the di-protonated malonamide
does not.
A quantitative structureactivity relationships
(QSAR) study related to the extraction of Nd(III)
O
C8H17
O
C4H9
N
CH3
N
CH3
C4H9
C14H29 CH3
Figure 5 N,N0 -dimethyl-N,N0 -dibutyltetradecyl-1,

3-malonamide (DMDBTDMA).
O
C8H17
C2H4 CH3
O
C6H13
Figure 6 N,N0 -dimethyl-N,N0 -dioctylhexylethoxymalonamide (DMDOHEMA).
nitrate by a set of 17 malonamides supported the

above mentioned improved M(III) nitrate extracting
properties in the presence of an oxygen ether atom in
the R00 substituent.
5.14.4.2.3 Separation of trivalent actinides
from lanthanides
To explain the great affinity of actinides for nitrogenbearing molecules, numerous fundamental studies
were carried out using a wide range of experimental
methods, including spectroscopy. For Ln(III) and An
(III) ions, the formula, stability, and structure of the
complexes were determined both in aqueous solution
and in various solvent media. It has been demonstrated that bonds between the nitrogen atoms of
these ligands and Ln(III) and An(III) ions include
some definite covalence. The covalence observed in
bonds with the electron-donor nitrogen atoms of
ligands seems higher for An(III) ions than for Ln
(III) ions, and could be an indication of the greater
affinity of these ligands for An(III); however, the
difference is too small to really explain the sometimes
very high differences in the distribution factor.
Theoretical studies in the fields of quantum
chemistry and molecular dynamics have provided
greater insight into certain crucial aspects of reactions between these metal ions and nitrogen-bearing
ligands. In particular, the synergetic extraction
mechanism of Ln(III) ions using a mixture of a
nitrogen-bearing ligand and a carboxylic acid has
been identified by computer calculations. The calculated synergetic complex seems consistent with the
experimental results.
5.14.4.2.4 Process development
Three alternative approaches are proposed. The first

is based on coextraction of trivalent MAs and lanthanides (Lns) and separation of MA and Ln fractions in
a second step.13 For the first part, the following are
the most important processes:
The TALKSPEAK process (the Unites States)14
and disodecylphosphoric acid (DIDPA) process
( Japan)15 use acidic organophosphorus extractants.
The TRansUranium Extraction (TRUEX) process
(the Unites States)16 and Solvent Extraction for
Trivalent f-elements Intra-group Separation in
CMPO-complexant System (SETFICS) ( Japan)17
are based on the use of CMPO (n-octyl-phenyldiisobutyl-carbomoylmethyl-phosphine-oxide).
The Trialkyl phosphine oxide (TRPO) process
(China) uses a trialkyl phosphine oxide. The hot
355
demonstration of this process using genuine

HLLW has been done at the Institute for Transuranium Elements (ITU) (Karlsruhe).18
The DIAMEX (diamide extraction) process using
malonamides as extractant19 has been developed at
CEA (France) and is also the reference process
under investigation in the European partitioning
projects.
For an efficient recycling scheme, losses of the relevant elements should be as low as possible (0.2% or
less), and a compromise between extraction and back
extraction has to be made.
The MA/Ln separation can be achieved by the socalled selective actinide extraction process (SANEX).
The major options are as follows:
The BTP (bis-triazine-pyridine) developed at
FZK-INE Germany20 or BTBP (bis-triazinebis-pyridine), which is capable of achieving the
selective extraction of MAs at high nitric acid
concentration (2 M).
The TPTZ (tripyridyltriazine) developed at CEA,
France to be used at much lower nitric acid
concentrations.21
Variants of the dithiophosphinic acids (ClPh)
2PSSH mixed with trioctylphosphinoxide (TOPO)
at Forschungszentrum Julich (FZ Julich),
Germany.22
Promising results have been obtained on simulated as
well as on genuine solutions at lab scale. Among
many extractants tested worldwide, the combination
of DIAMEX and BTP (see Figure 7)23 is shown to be
the best combination for an efficient recovery of MAs
from HLLW or transmutation targets.
Diamides do not require feed adjustment, can
easily be recycled to the process, and do not leave
any residue upon incineration. With regard to the
separation of MAs from Ln, BTP has been shown to
be the most efficient extractant, giving at the same
time the highest separation factor with no feed acidity adjustment required. Separation factors between
MAs and lanthanides up to 80 are reached in a
single-stage extraction. These values are considerably improved in a continuous multistage process,
N
N
N
N
Figure 7 2,6-Bis-(5,6-di-isopropyl-1,2,4-triazine-3-yl)pyridine (iPr-BTP).
356
and an Am/Cm product containing less than 1% of

Ln is obtained. Unfortunately, an industrial application of the BTP molecule requires further investigation because it is highly sensitive to hydrolysis and
radiolysis.
The second alternative under investigation aims at
a direct selective extraction of MAs from the PUREX
raffinate in a single operation leaving all the lanthanides in the HLLW.
A third option is the COEX and lanthanides with
DMDOHEMA, as in the extraction step of the DIAMEX process, followed by selective stripping of the
trivalent actinides from the loaded diamide solvent
using a mixture of hydroxyethyl ethylenediamine triacetic acid (HEDTA) (actinide-selective polyaminocarboxylate complexing agent) and citric acid.24
The scientific feasibility of this process has been
demonstrated by the CEA in the Major Nuclear Cycle
R&D (ATALANTE) facility in Marcoule, France. An
MA recovery of 99.9% with less than 0.3 wt% Ln in
the MA fraction was achieved with a flow sheet, where
the DIAMEX solvent was supplemented by an acidic
extractant, diethylhexylphosphoric acid (HDEHP), to
ensure effective extraction at pH > 2.
In Japan the Japan Atomic Energy Agency (JAEA)
has studied an advanced aqueous process combined
with a U crystallization process. The main features
compared with the conventional PUREX are as
follows:
The purification steps of U and Pu in the conventional PUREX are eliminated, resulting in coextraction of U/Pu/Np, and the simplification of the
system. A compact-sized centrifugal type equipment is used to reduce the size of the reprocessing
facility.
Crystallization method is used to separate excess
U before extraction of U/Pu/Np.
A combination of the SETFICS process, developed by Japanese Nuclear Cycle Development
Institute ( JNC), and the TRUEX process is
applied for the recovery of Am and Cm.

A recovery ratio of U/TRU has been estimated
to be 99.7%, and the decontamination factor of the
reprocessed product is higher than 102.
Another process developed by JAEA is known as
the Four-Group Separation Process; it includes
the following features:
Extraction of all TRU elements including Np (V)
with DIDPA at 0.5 M nitric acid.
Separation of Tc and platinum group metals by
precipitation through denitration.
Separation of Sr and Cs by adsorption with inorganic ion exchangers.
Selective back extraction of Am and Cm by
0.05 M dietylentriaminepentacetic acid (DTPA).
In Table 4, the separation efficiency and estimated
recovery values obtained in the various processes
mentioned above are compared to target values for
the recovery of TRU elements and some key FPs in
advanced reprocessing.
The separation efficiency and the estimated
recovery of TRU elements are quite high and almost
fulfill the target recovery. The recoveries of Tc and
platinum group metals are around 9095% which is
lower than the target recovery. This lower recovery is
less important because of a lower potential radiotoxicity contribution of HLW.
5.14.4.3
Pyro-reprocessing
Pyrochemical processes rely on refining techniques

at high temperature (500900 C) depending on the
molten salt eutectic used. Typically chloride systems
operate at lower temperature compared to fluoride
systems. In nuclear technology, the processes are
mainly based on electrorefining or on extraction
from the molten salt phase into liquid metal.
For more than 50 years, pyrometallurgy has been
studied as an alternative strategy in the reprocessing
Table 4
Target recovery, experimentally obtained separation efficiency, and estimated recovery of elements in the fourgroup partitioning process
Elements
Target recovery (%)
Separation efficiency (%)
Estimated recovery (%)
Np
Pu
Am
Cm
Tc
Sr, Cs
99.5
99.9
99.99
99.9
99
99
>99.95
>99.99
>99.99
>99.99
98
>99.9
99.85
99.85
99.97
99.97
95
>99.9
of used fuel. Until now, only two processes have

been developed up to the pilot scale, both in chloride media; the first one developed by Research
Institute of Atomic Reactors (RIAR) in Dimitrovgrad (Russia) is for oxide fuels25 and the second one
is using metallic fuel and is being developed in the
United States as part of the so-called IFR. The
RIAR process can be operated in an air atmosphere,
whereas the metallic process require a more or less
pure Ar atmosphere, However, only the metallic fuel
process allows also the treatment of TRU elements
and is therefore discussed in more detail in the
following paragraph.
5.14.4.3.1 IFR pyroprocess
The electrometallurgical process was applied for the

first time as a part of the IFR system in the pyrochemical separation processes for the recovery of
uranium and, to some extent, of plutonium. These
processes have been investigated for decades26,27 and
remain the core process in the present Experimental
Breeder Reactor-II (EBR-II) Spent Fuel Treatment
Program. Many of the pyroprocessing systems presently proposed for development are spin-offs of this
process, shown in Figure 8.
The fuel is recycled using an electrochemical process based on molten chloride salts and liquid metals.
The molten salt medium for electrorefining is a solution of a certain amount of UCl3 dissolved in a LiCl
KCl eutectic. At an operating temperature of about
500 C, chopped used fuel is loaded into the electrorefiner using specially designed stainless steel baskets. The fuel is electrochemically dissolved using an
appropriate potential between the basket used as
anodes and a stainless steel electrode in the salt
phase being used as cathode. Once the fuel starts to
dissolve, uranium and a small part of the TRU elements are collected on the cathodes. Once the fuel is
dissolved and most of the uranium is deposited on the
solid steel, this cathode is replaced by a liquid cadmium cathode, and the remaining TRUs can be
codeposited with the remaining uranium. A liquid
cadmium cathode is a ceramic crucible containing
molten cadmium that can be lowered into the salt
bath. The cadmium in the crucible is put at cathodic
potential.27 Because of the chemical activities of the
TRU elements in cadmium, they can be more easily
deposited with uranium in liquid cadmium cathodes
than on solid cathodes. The cathode products from
electrorefining operations are further processed to
Refabrication
for recycle
Casting furnace
Electrorefiner
Cathode processor
Oxide
reduction
Metal
Uranium,
transuranics,
salt
Oxide
Spent
fuel
Metal
Salt
Zeolite + FPs
Cladding
+
noble metal
+
FPs
Legend
Product line
Cleanup and waste
Furnace
Salt
Zeolite
+
FPs
Metal casting
furnace
Zeolite columns
Highlevel
waste
Metal waste form
Figure 8 Metal and oxide fuel pyroprocess flow sheet.
357
Glass
powder
Ceramic waste
form
358
distill adhering salt and cadmium and to consolidate

the recovered actinides. Those are remotely fabricated into new fuel for recycling.
The alkali, alkaline earth, rare earth, and halide
FPs remain primarily dissolved in the salt phase.
These elements can be separated from the salt
phase (e.g., by extraction or precipitation processes)
and are eventually conditioned in a ceramic HLW
before being disposed. More than 90% of the noble
metal FPs and fuel alloy material are retained in the
chopped fuel cladding segments in the anode baskets.
This residue can be stabilized into a metal HLW to
prepare it also for disposal.
Adaptations of this technology exist for the treatment of both oxide and nitride fuels. The flow sheet for
the treatment of nitride fuels is similar to that of the
metal fuel. The nitride fuels are also fed directly into
the electrorefiner; the actinides are dissolved from the
fuel cladding and collected all together electrochemically in liquid cadmium or bismuth cathodes.
A specificity of this process is the evolution of nitrogen
gas. If the formation of 14C from 14N is to be avoided
during the fuel irradiation, the initial nitride fuel should
be enriched in 15N. Depending on an economic assessment, it should be decided where and when nitrogen
should be recycled. This process and the fuel refabrication are of course not very easy. After distillation of the
cadmium, the recovered nitrides are separated and then
fabricated into new fuels using a vibro-packing step.
This process is being developed in Japan.28
5.14.4.3.2 European pyrochemistry projects
On the basis of these past studies, pyrometallurgy

based on the US process has been considered not
only as the reference route for the molten salt reactor
fuel treatment, but also as an alternative technology
that could be applied to some types of fuels envisaged
for Gen IV systems or ADSs, that is, in case they turn
out to be incompatible with current hydrometallurgical processes.
The European pyro-reprocessing projects have
the following main objectives:
to obtain basic data to allow conceptual design and
assessment of reprocessing processes suitable for
many different types of fuel and targets;
to assess the feasibility of separating uranium, plutonium, and MAs from FPs using pyrometallurgy
in a molten chloride or fluoride systems;
to identify and characterize solid matrices for
the conditioning of the wastes issuing from the
pyroprocesses;
to carry out system studies for comparing selected

reprocessing of used fuels of advanced nuclear
reactors including the ADS;
to revive and consolidate European expertise in
pyroprocessing.
As an underpinning support for the pyroprocess
developments, basic properties of An and some FPs
in molten salts (chlorides and fluorides) and in liquid
metal solvents have been studied.
A very important work was done in the thermodynamic data acquisition in molten chloride media,
with a comprehensive study of actinides, lanthanides,
and some other important FPs. In comparison to
molten chloride salts, studies in molten fluoride are
much less developed. Even though a lot of experiments were carried out on various salts, it seems in
this case to be more difficult to get relevant thermodynamic data, mainly because of the lack of a reliable
reference electrode. Especially for Cm, the data
available are very scarce.
Two efficient processes for the separation of An
from Ln have been selected as promising core processes: (i) electrorefining process on a solid reactive
cathode in molten chloride and (ii) liquidliquid
reductive extraction in liquid metalmolten fluoride.
As a result of the data collected for a variety of liquid
metals, aluminum was the clear choice for both the
cathode material for the electrochemical process in
molten chlorides and the extractant for the reductive
extraction process in molten fluorides. Several reference flow sheets have been assessed.
These results were used to optimize the two reference core processes. Moreover, several new experimental installations for process tests have been
designed and constructed. In the United Kingdom,
Nexia Solutions has built a new facility in an alphaactive glove-box and in Italy Italian National Agency
for New Technologies, Energy and Sustainable Economic Development (ENEA) has commissioned the
Pyrel II facility for process scale-up and modeling. It
has become clear that the construction of a largescale electrolyzer for studies in molten salts is a
complex and laborious task requiring a lot of additional efforts to be successful.
Another key issue is similar to the aqueous technology, specifically the waste issue. A successful recycling should have similar targets for dry and aqueous
reprocessing regarding the loss of fissile materials and
the long-lived radionuclides to be recovered.
A realistic value is below 0.1% for all actinides.
Furthermore, the pyroprocess should also produce
the lowest achievable amounts of waste, and the waste

produced must be converted into a convenient form
for storage or disposal. Here, real progress has been
made in the decontamination of used chloride salts
resulting from electrorefining, and the complementary techniques of zeolite ion-exchange filtration and
phosphate precipitation have been selected for their
potential to clean up used salt efficiently. A number
of specific matrix materials for salt confinement have
been identified (sodalite, pollucite); however, a lot of
work is still to be done in this field.
The system studies which were performed in the
course of the European Research Programs included
(i) double-strata concept (ADS), (ii) IFR, and (iii)
molten salt reactor. In a first step, the general principles for the assessment of pyrochemical separation
processes were defined and a common methodology
for technical and economic comparisons and the
selected flowsheets was determined. During the second step, the work was focused on detailed flowsheet
studies and mass balance calculations. The major
interest of these studies is the validation of the process approach, a very useful tool to identify key
issues and eventually reorient R&D programs. Nevertheless, as the flowsheets address different scenarios
and fuels, it is very difficult to make a direct intercomparison in terms of advantages and drawbacks.
5.14.4.3.3 Basic data acquisition
As mentioned in the previous paragraph, a large

variety of basic properties of An and some FPs in
molten salts (chlorides and fluorides) and in liquid
metal solvents have been studied.2931
Concentrated efforts were made in basic data
acquisition for molten chloride media, mainly at
ITU, with a comprehensive study of actinides
(U, Pu, Np, Am, Cm), lanthanides, and some other
important FPs. Thermochemical properties are
derived from the electrochemical measurements and
from basic thermodynamic data, for instance, in the
case of Np of NpCl3 and NpCl4 in the crystal
state.32,33 It could be demonstrated, that the NpCl3
has a strong nonideal behavior in molten LiClKCl
eutectic. For these experiments, a double glove box
has been constructed, where the outer glove box is
operated under nitrogen and the inner box under a
purified argon atmosphere at overpressure conditions. This allows keeping a very pure Ar atmosphere
and thereby excellent conditions for a precise determination of the required data. Auxiliary equipment is
devoted to chlorination, material processing, and
electrochemistry in room temperature ionic liquids,
359
a potential alternative to the high-temperature molten salt systems.34

5.14.4.3.4 Core processes
Initially, three potential chemical routes were identified as candidates for core process development
activities. The first one was based on selective precipitation; it was also investigated by RIAR in Russia
as a possible option in the selective separation of the
TRU elements. However, the success of this process
is not very encouraging; the decontamination factors
that can be obtained are always very low. The second
route is the electrochemical one, which includes
electrolysis or electrorefining techniques, in either
chloride or fluoride molten salts. The third one is
based on the liquidliquid reductive extraction
between a molten salt and a liquid metal phase.
Therefore, only the processes based on electrorefining on solid aluminum cathodes in molten chloride
and the one based on liquidliquid reductive extraction in molten fluoride/liquid aluminum were extensively studied in the European programs. In parallel,
some studies were carried out on electrolysis in molten fluoride or liquidliquid reductive extraction in
molten chloride but with a much lower priority.
5.14.4.3.5 Electrorefining on solid aluminum
cathode in molten chloride media
To comply with the sustainability goals defined for

innovative reactor systems, a major objective is the
development of a grouped actinide recycling process
based on molten salt electrorefining. Special emphasis is given to a selective electrodeposition of actinides with an efficient separation from lanthanide
FPs. In contrast to the IFR concept, where U is
deposited on a solid stainless steel cathode and
TRU actinides on a liquid Cd cathode,35 the electrorefining processes rely on codeposition of all actinides on a solid Al cathode material.
In fact, the choice of the cathode material onto
which the actinides are deposited in the electrolysis is
essential in this context.36 In contrast to stainless steel
or tungsten, aluminum is a reactive electrode material, that is, it forms stable alloys with the actinides,
thereby avoiding the redissolution of trivalent actinides. Also the redox potentials on solid cathodes
show a much larger difference in the reduction
potential between actinides and lanthanides. Figure 9
shows the reduction potentials for U3, Pu3, Am3,
La3, and Nd3 determined by transient electrochemical techniques (mainly cyclic voltammetry and chronopotentiometry) on different cathode materials. On Bi
360
and Cd, the selectivity of the MA recovery seems to be

limited because of the small difference in reduction
potentials between actinides and lanthanides.
Solid Al has therefore been selected essentially
because of two reasons:
experiments in which the cathodic potential was

maintained at a suitable level for separation of An
from Ln. With an increase in the charge passed, that
is, with the buildup of a surface layer of AnAl alloy,
the applied current is gradually reduced in order to
stay above the cathodic potential limit.
On the basis of a large set of data obtained for the
electrodeposition on aluminum cathodes, the process
scheme is being proposed as shown in Figure 10.
The electrorefining process as presented here is
operated in a batch mode. After multiple use of the
eutectic salt bath, an exhaustive An electrolysis is
required to avoid losses >0.1% to the waste, before
the cleaning of the salt bath takes place. It is evident
that the electrodeposited AnAl alloy in the exhaustive electrolysis contains more Ln than in the runs
where metallic fuel is deposited and must eventually
be recycled. For the cathode processing, three options
are possible, chlorination, back extraction, and electrorefining. Among these, chlorination is the most
promising. This step is needed to recycle the actinides to the fuel fabrication.
Laboratory experiments have shown that 3.72 g of
actinides were deposited in 4.17 g Al, corresponding
to 44.6 wt% An in Al or 68 wt% of the maximal
loading, considering that AnAl4 alloys are formed.37
A successful demonstration of the Am/Nd separation
was carried out using a mixture of 255 mg Am, 281 mg
Pu, and 140 mg Nd. Am and Pu were codeposited in
two steps on two Al cathodes of 0.8 g each. The cathodes used were made of Al foam to increase the
reaction surface area. The Nd content in the deposit
of only about 0.5% proves the feasibility of a selective
actinide separation by electrolysis onto Al electrodes.
The results were confirmed in a multiple run
experiment inducing an accumulation of lanthanides
1. Stable actinide deposits (alloys) are formed and

are consequently very adherent to the cathode; at
the same time, redissolution of the trivalent An by
comproportionation with the trivalent actinides
in the salt to form divalent Ans can be avoided
(cf. equation: Am(III) Am(0) 3 Am(II).
2. The difference in the reduction potentials compared to lanthanides is sufficiently high to avoid
their codeposition.
In these electrolytic processes, the rate of the alloy
formation depends on the diffusion of the involved
elements in and through the solid alloy phase.
Therefore, the maximum amount of actinides that
can be collected on a single Al electrode has been
investigated in constant current electrorefining
Potential (V vs. Ag/AgCl)
-1
-1.2
-1.4
Pu
Am
La
U
Pu
Am
Pu
Am
La
Nd
La
-1.6
Pu
-1.8
Am
-2
Nd
La
-2.2
Liquid Bi
Liquid Cd Solid W
Solid Al
Figure 9 Reduction potentials of some actinides and

lanthanides on different cathodic materials.
Used salt
with high
content of
FP
Salt +
remaining Ans
+ Lns
Metallic
AnLn
fuel
Electrorefining
on AI cathode
Exhaustive
electrolysis
Cathode
processing
AnAl alloys
An
AI
Three identified
ways
Chlorination
Back-extraction
Electrorefining
Figure 10 Process scheme for the electrorefining of metallic fuels.
Salt
cleaning
Salt +
waste
and/or
storage
in the salt. The fuels used for these experiments had

already been developed in the frame of the IFR
concept (see previous paragraph) in the mid-1980s
in the United States. These fuels contain about 15%
of Zr in the metallic alloy to stabilize the fuel during
reactor irradiation. The same type of fuel, used for
transmutation studies initiated by Central Research
Institute of Electric Power Industry (CRIEPI), Japan,
in collaboration with ITU, was irradiated in the
metallic fuel irradiation ad PHENIX (METAPHIX)
experiment in the PHENIX reactor in France.38
This fuel containing 2% of Am and lanthanides
(U61Pu22Zr10Am2Ln5) was fabricated at ITU and
the remnants of the fuel fabrication campaign were
used for separation studies.
In the pyro-reprocessing, the metallic alloy is
anodically dissolved in a LiClKCl eutectic39 and
the actinides are collected together onto Al cathodes as alloys, leaving lanthanides in the salt phase.
It is very likely that a large-scale pyroprocessing by
molten salt electrorefining will be operated as a
batch process similar to the industrial Al fabrication
process. In view of a large-scale development of the
process, an experiment with 25 successive runs was
carried out to demonstrate the feasibility of a
grouped actinide recovery from larger amounts of
fuel without changing the salt bath.36 A total
amount of more than 5 g of U61Pu22Zr10Am2Ln5
fuel was treated in this experiment and various
process parameters were studied. Figure 11 shows
361
the cyclovoltamogram of the alloy on Al and

W electrodes.
The goal of this 25-run test was to find optimal
conditions for the recovery of Am. The recovery rate
of actinides was difficult to evaluate because new
fuel was added in each run. Nevertheless, a stable
recovery rate [mAn/(mln mLn)], nearly 99.9%, was
achieved throughout the whole experiment. Uranium, the main constituent of the fuel with a less
electronegative electrodeposition potential is preferentially deposited in the earlier runs. At the same
time, the relative Am content in the actinide deposit
and the separation from lanthanides (mAm/mLn)
increase despite an increasing content of lanthanides
not electrodeposited in the salt. This means that the
target of 99.9% recovery can be reached for this
process.
The results of this 25-run electrorefining experiment for which genuine fuel materials were used and
for which the salt bath was not changed are very
promising in view of a large-scale development of
pyro-reprocessing in advanced nuclear fuel cycles.
5.14.4.3.6 Exhaustive electrolysis
When a salt bath is being used for the electrorefining

of large amounts of fuel, the FPs are accumulated in
the salt bath and their concentration becomes too
high and thereby prevent a selective deposition of
actinides on the cathode. An exhaustive electrolysis is
proposed for the first purification step, a complete
150
W electrode
Al electrode
Al => Al3+
100
U3+ => U
Current (mA)
50
Cl => Cl2
Np3+ => Np
Pu3+ => Pu
0
U3+ => UAl4
50
100
Pu3+ => PuAl4

Ln3+ => Ln
Li+ => Li
150
3.00 2.50
Cut-off potential (1.25 V)
2.00 1.50
1.00 0.50
0.00
0.50
1.00
1.50
Potential (V vs. Ag/AgCl)

Figure 11 Cyclic voltammogram of U61Pu22Zr10Am2Ln5 on W and Al wires. Reference electrode: Ag/AgCl 1 wt%,
v 100 mV s1, T 450 C. Salt composition in wt%: U 0.29, Np 0.12, Pu 0.28, Am 0.06, Zr < 0.07, and Ln 1.0.
362
i
-
+
Cl2
e-
Cl2 (g)
producing anode
e-
FPn+
Selective
reduction
AnAl alloy
Ann+
AnAl alloy
AI
Cl-
Molten LiCl-KCI (450 C)

Figure 12 Principle of the exhaustive electrolysis
process.
grouped recovery of the remaining actinides without

further fuel dissolution on a solid aluminum cathode
(see Figure 10). The anode basket is therefore
replaced by a chlorine electrode. Partial oxidation
of the chloride salt to chlorine gas allows the actinide
reduction on the cathode side. A scheme of the process is shown in Figure 12.
In order to prove feasibility of the method, two
galvanostatic electrolyses were carried out using
a mixture of UCl3 and NdCl3.40 The potentials
of both electrodes were constantly followed and a
decrease of the uranium concentration from 1.7 to
0.1 wt% with no codeposition of neodymium was
observed. Although the maximum applicable current
densities were relatively low, the results are promising and showing high current efficiency and
selectivity of the proposed method.
5.14.4.3.7 Liquidliquid reductive extraction
in molten fluoride/liquid aluminum
The alternative process to electrorefining in molten

chloride salts is the liquid metal/molten salt process.
This option was extensively studied by CEA in several
European Research Programs.4143 An experimental
device and a process scheme have been developed to
study the distribution of actinides and lanthanides
between molten fluoride salt and liquid metal media.
The results obtained with plutonium, americium,
cerium, and samarium in the (LiFAlF3)/(AlCu)
medium revealed the excellent potential of the system
for separating actinides from lanthanides.
With a salt composition corresponding to the basic
eutectic (LiFAlF3, 8515 mol%), up to 99% of Pu
and Am could be recovered in a single stage, with

cerium and samarium separation factors exceeding
1000. The effect of the AlF3 concentration in the salt
has been investigated. The distribution coefficients
logically go down as the initial AlF3 concentration
increases. A thermodynamic model to describe the
extraction as a function of the fluoroacidity has been
developed on the basis of the experimental results for
cerium and samarium. The model clearly reveals a
difference in solvation between divalent and trivalent
lanthanides in fluoride media.
The results obtained for each element were confirmed by demonstration experiments under more
realistic conditions, at a lab scale. Two runs were
carried out at 830 C using LiFAlF3 (8515 mol%)
as a salt phase: one with an AlCu alloy (7822 mol%)
as metallic phase, the other with pure Al, to check
the influence of Cu on the extraction, both in terms
of separation performance and in terms of process
implementation (phase separation). The metal phase
was treated with salt with the following composition
(wt%): PuF3 (11), AmF3 (0.2), CeF3 (2.5), SmF3 (0.5),
EuF3 (0.5), and LaF3 (0.5). The results show that the
distribution ratios of Pu and Am are in the same
order of magnitude, similar to the ones previously
measured at low concentration without lanthanides.
The results obtained with AlCu and Al are very
similar. The distribution coefficients of the lanthanides
are low and thus the separation from actinides is very
efficient. In a test with Al without Cu, the distribution
coefficient of Cm (trace concentration in Am starting
material) has been measured for the first time; it is
very close to the values obtained for the other actinides (U, Np, Pu, Am). The tests without Cu addition
to the metallic phase show that a satisfactory phase
separation can be achieved; therefore, Cu addition is
not mandatory for the process implementation. In
Table 5, the main test results are summarized.
The results show that the distribution ratios of Pu
and Am have similar high values independent from
the presence of Cu in the metallic phase and that in
all cases high separation efficiency from lanthanides
can be achieved.
The actinide back extraction from the Al is of
course an important step in view of fuel refabrication.
In a bibliographic study three possible routes were
identified44:
Electrorefining: Main drawback is the complexity
of the process which requires three steps.
Volatilization of the Al matrix by a chlorinating
reagent: It is a simple and efficient method.
363
Table 5
Mass distribution coefficients and separation factors of actinides and lanthanides with and without Cu in the
metallic phase
AlCu (7822 mol%)
Al
Metal
Distribution actor
Separation factor Am/metal
Metal
Distribution factor
Separation factor Am/metal
Pu
Am
Ce
Sm
Eu
La
197 30
144 20
0.142 0.01
0.062 0.006
<0.013
<0.06
0.73 0.21
1
1014 213
2323 488
>11 000
>2400
Pu
Am
Cm
Ce
Sm
Eu
La
273 126
213 30
185 31
0.162 0.02
0.044 0.004
<0.03
0.03
0.78 0.47
1
1.15 0.35
1315 289
4954 1139
>7100
7100
Nevertheless, high volumes of chlorination gas

have to be managed and an additional step is
necessary to convert the AlCl3 to Al metal.
Oxidizing liquidliquid extraction in molten
chloride.
An experimental study is necessary to select the most
efficient option.
5.14.4.3.8 Technical uncertainties of the
pyro-reprocessing
In the Spent Fuel Treatment Program at Idaho

National Laboratory (INL), many parts of the pyroprocess fuel cycle could be demonstrated up to the
100 kg scale. Nevertheless, there are key aspects that
have yet to be demonstrated, particularly the recovery
of transuranics. Large-scale equipment designed and
constructed was never tested beyond the laboratory
scale, because of the termination of the IFR program.
The remote fabrication of IFR fuel was not part of
the Spent Fuel Treatment Program, but this technology was used to fabricate cold fuel for EBR-II and a
demonstration of another pyroprocess (melt refining)
for recycling EBR-II in the 1960s employed remote
fabrication for 34 500 fuel elements.23
Another key challenge for a pyroprocessing system is the selection of appropriate construction
materials for the high-temperature processes. Material improvements are needed in order to reduce the
formation of dross streams and to increase the material recovery and throughput.
The quantity of waste generated requiring geological disposal from pyroprocessing seems to be quite
similar to that in present modern commercial aqueous processes. Advancements are being pursued to
further reduce the disposal volumes using specially
adapted zeolite ion-exchange technology, which has
at present not yet been demonstrated beyond the
laboratory scale.
Most of the radioactive work performed to date

has been on the pyroprocessing cycle for metal fuel.
Laboratory work has been performed on the headend operations for oxide reduction and on the nitride
fuel cycle. Demonstrations of these technologies with
actual used fuel have started at a laboratory scale.
Additionally for nitride fuels, a demonstration of
the above-mentioned recycling of nitrogen (15N) is
essential for the economic considerations.
5.14.4.3.9 Head-end conversion processes
Today, all commercial reactors are operated with

oxide fuels, and advanced reactor systems selected
in the GENIV roadmap also rely on oxides as one of
the major fuel options. As mentioned above, the
pyrometallurgical process based on oxides developed
in RIAR, Dimitrovgrad (Russia) does not allow the
recycling of MAs. Pyro-reprocessing where all actinides are recycled is based on metallic materials;
therefore, a head-end reduction step for oxide fuels
is needed to convert oxides into metals. This conversion can be performed chemically, for example, by
reaction with lithium dissolved in LiCl at 650 C.
The recovered metal can directly be subjected to
electrorefining and the Li2O is converted back to
lithium metal by electrowinning. A more elegant
method is the so-called direct electroreduction.43 In
this case, the heat generating FPs are removed and
the fissile materials are recovered as an alloy, which
can be again directly reprocessed by electrorefining.
Numerous experiments are carried out today to
study this conversion process. The lithium reduction
process using lithium metal as a reductant is carried
out in molten lithium chloride. The reduction of
UO245 and simulated used LWR fuel46 was studied
mainly by CRIEPI in Japan in collaboration with AEA
Technology in the United Kingdom. The optimized
thermodynamic conditions for the reduction of TRU
364
elements47 and the behavior of major FP elements46

were determined. Li is converted into Li2O and constantly removed during the process from the molten
salt bath to prevent the reoxidation of the reduced fuel
material. Li is recovered by electrochemical decomposition of the Li2O and recycled to the process.
A simulated used oxide fuel in a sintered pellet
form, containing the actinides U, Pu, Am, Np, and
Cm, and the FPs Ce, Nd, Sm, Ba, Zr, Mo, and Pd,
was reduced with Li metal in a molten LiCl bath
at 923 K. The pellet remained in its original shape;
it became porous, and a shiny metallic color was
observed throughout the pellet. The Pu/U ratio did
not change during the reduction process. The reduction yield of U and Pu determined by measuring the
H2 formed on reaction of the reduction product with
HBr and using a gas burette was more than 90%.
A small fraction of Pu has formed an alloy with Pd.
The RE elements are found in the gap of the porous
UPu alloy. As expected from the oxygen potential of
Ce, Nd, Sm, and Li, they remained in an oxide form.
Small fractions of the actinides and lanthanides are
leached from the pellet into the molten LiCl bath or
found as precipitates on the crucible bottom. A large
part of Am is found in the RE oxide phase rather than
in the reduced UPu alloy. This represents of course
a major problem for a grouped actinide recovery. In
addition, the handling of highly reactive Li and problems in developing the corresponding equipment,
especially for the lithium recovery, are major drawbacks of this process.
The electrochemical reduction process is clearly
the more reliable technique to convert oxides into
metal. The difficult handling of Li metal and recycling
through reconversion from Li2O can be avoided. The
oxide ion produced at the cathode is simultaneously
consumed at the anode and thus the concentration of
oxide ions in the bath can be maintained at a low level.
A more complete reduction of the actinide elements
can be achieved and the subsequent electrorefining to
separate actinides as described in the previous paragraph can be carried out in the same device.47
An electrochemical process is being developed,
mainly in the United States at INL in Idaho and
also in Japan at CRIEPI in Tokyo, in collaboration
with the EC, DGJRC/ITU in Karlsruhe, Germany.
Both unirradiated and irradiated fuel materials were
treated with slightly different concepts.
The oxide fuel is loaded into a permeable stainless steel basket as crushed powder.48 The basket
immersed into a molten LiCl1 wt% Li2O electrolyte
at 650 C is used as the cathode and a platinum wire is
used as anode. The reduced fuel is retained in the

basket. The oxygen ions liberated at the cathode diffuse
to the Pt anode, where they are oxidized to oxygen gas.
The corresponding reactions are as follows:
Cathode: MxOy 2ye xM yO2
Anode: yO2 y=2O2 g 2ye
where M metal fuel constituent.
The Li2O present in the salt is reduced to Li
together with U and reduces chemically the fuel
oxide. Consequently, the INL process is a combined
chemicalelectrochemical process.
The molten salt can be either LiCl or CaCl2. In
CaCl2, the higher temperature of 1123 K in comparison to 923 K for LiCl induces a faster diffusion of
oxygen ions to the anode. At the same time, an
increased initial reaction rate leads to the formation
of a thin dense metal layer at the fuel surface hampering the diffusion of oxygen ions into the salt.
For the CRIEPI/ITU process, the anode is made
of carbon, and the fuel is not crushed but loaded as
fuel element segments in a cathode basket that is
made of Ta.49 The corresponding cathodic and
anodic reactions are as follows:
Cathode: MxOy 2ye xM yO2
Anode: yO2 y=2C CO2 g 2ye or
yO2 yC COg 2ye
The INL process scheme was successfully demonstrated using irradiated used LWR oxide fuel in a hot
cell. More than 98% of the U was reduced. Cesium,
Ba, and Sr were dissolved in the salt phase, as
expected. The rare earth and noble metal FPs
remained with U and transuranics Pu and Np were
reduced together with U; however, about 20% of the
Am remained as oxide.
The CRIEPI/ITU process was tested on various
MOX (Pu content 545%) fuels which were reduced.
It could be shown that U and Pu are efficiently coreduced, but because of the problems mentioned
above, the complete reduction requires very long
reaction times. The reduction of irradiated FR fuel
particles at ITU was considerably faster and a complete reduction of all fuel constituents including FPs
and MAS was achieved. Figure 13 shows the reduced
fuel particles in the cathode basket.
The analyses of the salt bath used for these experiments, the examination of the reduced product by scanning electron microscope (SEM)/energy-dispersive
Figure 13 Schematic layout of an electroreduction

process developed by CRIEPI/ITU.
X-ray spectroscopy analysis (EDX), and the analysis of

the reduced fuel after dissolution allow for establishing
a mass balance of the electroreduction process. The
results show that the fuel is completely reduced; that is,
all actinides are in the reduced product, the light FPs
Rb, Mo, Cs, Ba, Se are dissolved in the salt, and the
lanthanide FPs are divided between the reduced fuel
and an oxide precipitate found at the bottom of the
salt crucible.
A first experiment has shown that the reduced fuel
can be treated similar to the metallic fuels described
above and using the same equipment and the same
type of salt bath as the one used for the electrorefining tests.
5.14.4.4 The Direct Use of Pressurized
Water Reactor Spent Fuel in CANDU
Process
Another approach to used nuclear fuel recycling which
could be employed by some countries is the Direct Use
of Pressurized Water Reactor Spent Fuel in CANDU
(DUPIC) process,49 which enables direct recycling
of used pressurized water reactor (PWR) fuel in
CANada Deuterium Uranium (CANDU) reactors.
CANDU reactors use natural uranium fuel without enrichment and could therefore be fuelled with
uranium and plutonium from used LWR fuel. In the
DUPIC process, the used fuel assemblies from LWRs
are dismantled and refabricated into fuel assemblies
for CANDU reactors. This process could involve
simple cutting of used LWR fuel rods to be adapted
as CANDU fuel elements (about 50 cm), resealing,
and reengineering them into cylindrical bundles
suitable for CANDU geometry.
The more likely alternative is a dry reprocessing
treatment, where the volatile FPs are removed from
the used LWR fuel. No materials are separated during the refabrication process. After removal of the
365
cladding, the used LWR fuel is converted into powder by a thermalmechanical process and fresh natural uranium is added before CANDU pellets are
sintered and pressed.
However, as noted above, used nuclear fuel is
highly active and generates heat. The high radioactivity of the materials to be handled in the DUPIC
process requires heavy shielding and remote operation. The restricted diversion of fissile materials and
hence increased proliferation resistance go together to
make a much more complex manufacturing process.
Canada, where the CANDU reactor line has
been developed, and South Korea, which hosts four
CANDU units as well as many PWRs, have initiated
a bilateral joint research program to develop the
DUPIC process, and the Korean Atomic Energy
Research Institute (KAERI) has been implementing
a comprehensive development program since 1992 to
demonstrate the DUPIC fuel cycle concept.
Challenges that remain include the development of
a technology to produce fuel pellets of the correct
density, the development of remote fabrication equipment, and the handling of the used PWR fuel. However, KAERI successfully manufactured small DUPIC
fuel elements for irradiation tests inside the HANARO
research reactor in April 2000 and fabricated full-size
DUPIC elements in February 2001. Research is also
underway on the reactor physics of DUPIC fuel and
the impacts on safety systems. A trial period of the
technology has started in 2010 with irradiation of used
LWR fuel in the Qinshan reactor in China.
5.14.5 Outlook
Industrial reprocessing as it is in operation today
mainly in France, United Kingdom, and Japan will
certainly for several decades continue operation; new
capacities will be installed or extended in China,
Russia, and India in the near future and France and
Japan consider installation of new or additional capacities in a few decades from now. If the sustainability
goal strongly promoted in the GENIV initiative and
also in INPRO coordinated by IAEA or the European
SNE-TP platform is to be inherent to new generation reactor systems, the waste minimization will
require recycling of long-lived waste constituents
including MA. As a consequence, extended and modified reprocessing technologies will have to be implemented on a large scale. As a first step, the actual
PUREX process will be adapted to these needs. If
advanced fuel materials such as composites, metals,
366
nitrides, or carbides are selected for the new reactor

systems, adapted reprocessing technologies based on
pyroprocesses might be well suited to reprocess these
fuels. Significant efforts are being made in South
Korea, India, Japan, and United States to develop
these processes to an industrial scale. A possible strategy for the second half of this century could be based
on a double-strata concept with an advanced aqueous
reprocessing of LWR fuel in the first stratum combined with a fast reactorpyroprocess combination in
the second stratum to reach the sustainability goal.
20.
21.
22.
23.
24.
25.
26.
27.
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5.15
Degradation Issues in Aqueous Reprocessing Systems
B. J. Mincher
Idaho National Laboratory, Idaho Falls, ID, USA
Published by Elsevier Ltd.
5.15.1
Introduction
368
5.15.2
5.15.2.1
5.15.3
5.15.3.1
5.15.3.2
5.15.3.3
5.15.4
5.15.4.1
5.15.4.2
5.15.5
5.15.5.1
5.15.5.2
5.15.6
5.15.6.1
5.15.6.2
5.15.6.3
5.15.7
References
Chemistry of Irradiated Aqueous and Organic Solutions

Produced Transient Reactive Species
PUREX Process
Tributylphosphate Degradation
Alkane Diluent Degradation
Radiolysis Versus Hydrolysis
Fission Product Extraction Processes
HCCDPEG Process Radiolysis
FPEX Process Radiolysis
Minor Actinide and Lanthanide Extraction Processes
TRUEX Solvent Degradation
Diamide-Based Processes
Processes for the Separation of Minor Actinides from Lanthanides
TALSPEAK Process
Bis(triazinyl)pyridine-Based Processes
Dithiophosphinic Acid-Based Processes
Conclusions
369
369
371
371
373
374
375
375
376
378
378
380
382
382
383
384
385
386
Abbreviations
ALINA
BATP
BOBCalixC6
BTP
(ClPh)2PSSH
CMPO
Cs-7SB
DCH18C6
DHOA
DIAMEX
DMDOHEMA
DtBuCH18C6
DTPA
FPEX
FS-13
ActinideIII-Lanthanide
INtergroup separation from
Acidic medium
Annulated bis(triazinyl)pyridine
Calix[4]arene-bis-(t-octylbenzo)crown-6
Bis(triazinyl)pyridine
Bischlorophenyldithiophosphinic
acid
Octylphenyldiisobutylcarbamoylmethyl phosphine oxide
1-(2,2,3,3,-tetrafuoropropoxy)3-(4-sec-butylphenoxy)-2-propanol
Dicyclohexano 18-crown-6
Dihexyloctanamide
Diamide extraction
Dimethyl dioctyl
hexylethoxymalonamide
Di-t-butylcyclohexano-18-crown-6
Diethylenetriamine pentaacetic
acid
Fission product extraction
Phenyltrifluoromethylsulfone
H2MBP
H2MEHP
HCCDPEG
HDBP
LET
MDOHEMA
NMR
NPH
Ph2PSSH
PUREX
R2POOH
R2PSOH
R2PSSH
SANEX
TALSPEAK
TAP
TBP
Monobutylphosphoric acid
Monoethylhexyl phosphoric acid
Cobalt dicarbollidepolyethylene
glycol
Dibutylphosphoric acid
Linear energy transfer
Methyldioctyl 2-hexyloxyethyl
malonamide
spectroscopy
Normal paraffinic hydrocarbon
Bisphenyldithiophosphinic acid
Plutonium and uranium refining by
extraction
Phosphinic acid
Monothiophosphinic acid
Dithiophosphinic acid
Selective actinide extraction
Trivalent actinide lanthanide
separation by phosphorousreagent extraction from aqueous
komplexes
Triamylphosphate
Tributyl phosphate
367
368
TCE
TODGA
TOPO
TRUEX
UREX
Trichloroethylene
Tetraoctyldiglycolamide
Trioctylphosphine oxide
Transuranium extraction
Uranium extraction
5.15.1 Introduction
The first use of nuclear energy to produce electricity
occurred in 1951 at the Experimental Breeder Reactor 1 in Idaho, USA.1 For several decades thereafter,
nuclear energy promised an inexpensive and inexhaustible supply of electricity. However, concerns
about reactor safety, nuclear weapons proliferation,
and nuclear waste disposal resulted in nuclear power
becoming politically, if not technically, untenable.
During that period, many countries abandoned
electricity generation by nuclear reactors. Today,
in the early twenty-first century, renewed interest
in nuclear power is being expressed around the
globe. New power plants are under construction in
China, Russia, and India, and orders for new constructions are anticipated in the United States. This
rebirth of interest in nuclear technology has been
brought about by concerns about the contribution of
fossil fuel burning to climate change and the unreliable sources of those fossil fuels.
Currently, about 437 reactors generate 17% of
the worlds electricity. To create a nuclear power
industry that can supply an increased portion of
world energy demand, it is likely that the reprocessing of spent fuel will be necessary. Spent fuel contains unfissioned 235U and other fissionable actinides
generated from uranium by neutron capture reactions during reactor operations. It has been estimated
that the fuel available for recycling could extend
natural uranium supplies by 30%.2 However, in the
United States, a once-through fuel cycle has been
adopted wherein used fuel is buried, rather than
recycled. Japan, France, and the United Kingdom,
however, continue to reprocess spent nuclear fuel
using the PUREX (plutonium uranium refining by
extraction) solvent-extraction process.
Future nuclear fuel recycling operations for the
oxide fuels used in the current generation of reactors
will have goals in addition to the recovery of uranium
and/or plutonium for fuel. For nuclear power to be
environmentally sustainable, recycling must also minimize the amount of long-lived radioactive waste
produced and create proliferation-resistant process
streams. Therefore, a global collaboration is currently
investigating modified solvent-extraction processes to

meet these goals. Based on decades of success with the
conventional PUREX process,3 new extractions will
recover neptunium and plutonium in a proliferationresistant form, selected fission products of high environmental consequence, and the minor actinides for
incorporation in fast reactor fuels. Such a process will
both recover energy-containing elements for energy
production and minimize the amount of hazardous,
long-lived, radioactive waste that must be disposed in
a geological repository.
Aqueous reprocessing begins with the chopping
and dissolution of the used fuel in nitric acid. In the
currently used PUREX process, uranium, neptunium, and/or plutonium are recovered by the
extraction of the acidic phase with 30% tributyl
phosphate (TBP) in an alkane diluent. Uranium is
always hexavalent and extracted, while neptunium
and plutonium can be extracted or rejected depending on their oxidation state adjustments prior to the
contact.
Proposed fuel cycles will contain additional
extraction steps designed to recover additional elements of interest. Although these new extractions are
still undergoing research and development, some
have been successfully tested on a pilot scale. In the
United States, a series of extractions collectively
known as UREX (uranium extraction) has been
developed with five main steps. In the first, uranium
is extracted using TBP from an acidic nuclear fuel
dissolution containing a reducing agent to prevent
neptunium and plutonium extraction. The raffinate
is next extracted with a combination of crown ethers
selective for strontium and cesium,4 the main heatgenerating fission products. After treatment to remove
the reducing agent, neptunium and plutonium are
then removed together with another TBP contact.
The raffinate still contains the minor trivalent actinides, long-lived a-emitters that are undesirable to
bury from an environmental perspective but are valued as fuel for fast reactors. In the United States, they
are proposed to be extracted using octylphenyldiisobutylcarbamoylmethyl phosphine oxide (CMPO) in
the TRUEX (transuranium extraction) process.5
A complicating factor is that the fission-product
lanthanides are also trivalent and thus have chemistry
similar to that of the minor actinides. These lanthanides
are very radioactive although relatively short-lived, and
some are also neutron poisons. They must be removed
from the minor actinide product prior to the fabrication
of new fuel. The extraction proposed for this final step is
the TALSPEAK (trivalent actinide lanthanide separation by phosphorous-reagent extraction from aqueous
komplexes) process in the United States.6 The aforementioned sequence may change as improvements are
discovered by researchers working in the collaborative
countries. Competitive technologies are also under
investigation. In European and Japanese work, for example, alkylamides and diamides are being investigated
as replacement compounds for the phosphorouscontaining TBP and CMPO. The absence of phosphorous in the amides may be an important advantage
in that molecules containing only C, H, O, and
N atoms are incinerable, simplifying the disposal of
spent solvents. Other benefits may include easier actinide back-extraction and solvent regeneration, and
the production of relatively benign radiolysis products. Mainly in French work, a process known as
DIAMEX (diamide extraction) would rely on the
diamide dimethyl dioctyl hexylethoxymalonamide
(DMDOHEMA) for trivalent actinide and lanthanide
extraction.7 Tributylphosphate would be replaced by
dihexyloctanamide (DHOA) in Indian work,8 or tetraoctyldiglycolamide (TODGA) in Japanese9 and
European10 proposals. A process analogous to TALSPEAK employing a combination of malonamides
and bistriazinebipyridines is called DIAMEX/
SANEX (diamide extraction/selective actinide
extraction) and is being studied for the separation of
the minor actinides from lanthanides. Dithiophosphinc acids are also under investigation as softdonor ligands for this difficult separation.11
Regardless of which complexing agents are
adopted, they will need to be effective in a harsh
environment. Dissolved nuclear fuel is very acidic
and highly radioactive. This subjects complicated
organic molecules that are designed to selectively
complex specific metal ions to a severe hydrolysis
and radiolysis environment. The adverse effects of
these reactions could include a loss in solventextraction efficiency due to ligand degradation and
concentration decrease, a decrease in separation factors between desired and undesired metals due to
the creation of degradation products that are new
complexing agents, and changes in viscosity or phase
disengagement time due to the generation of high
molecular weight decomposition products.12 For a
process to be successful, the ligands and their diluents
must be relatively stable in such an environment.
Short contact times, such as those achievable with
centrifugal contactors, are of benefit in minimizing
the effects of hydrolysis and radiolysis on organic
solvent-extraction formulations. This chapter reviews
the radiation and acid hydrolysis stability of the main
ligands and diluents currently being studied for
application in the fuel cycle of the future.
369
5.15.2 Chemistry of Irradiated

Aqueous and Organic Solutions
5.15.2.1 Produced Transient
Reactive Species
Most of the radiolytic damage done to ligands in an
irradiated solvent-extraction solution occurs due to
indirect radiolysis. Indirect radiolysis is caused by the
reactions of the ligands with reactive transient species
created by direct radiolysis of the diluent. Since ligands
are normally present in millimolar concentrations,
their diluent absorbs most of the radiation energy. In
nuclear aqueous solvent extraction, these diluents are
usually alkanes in the organic phase and aqueous nitric
acid in the aqueous phase. Direct radiolysis ionizes and
excites diluent molecules to produce short-lived but
highly reactive ionic and free-radical species. These
produced reactive species may undergo recombination
to create molecular species, or they may diffuse away
from their point of origin to react with ligands. For
water irradiated by low linear energy transfer (LET)
particles, the species in eqn [1] are produced with their
yields (G-values in mmol J1) shown in brackets13:
H2 O
!0:28 OH 0:27e
aq
0:06H 0:07H2 O2
0:27H3 O 0:05H2
1
The most reactive species produced are the oxidizing

hydroxyl radical (OH) and hydrogen peroxide
(H2O2), and the reducing aqueous electron (e
aq ) and
hydrogen atom (H).
Massive, highly charged particles such as a-particles
(He2) generated mainly by actinide decay have short
ranges and high LET (156 eV nm1 for 5 MeV He2)14
and therefore deposit energy in areas of high localized
concentrations of reactive species. These may undergo
recombination, and thus higher yields of molecular
species and lower yields of radicals are found.
Oxidizing and reducing species have identical initial yields but in aerated nitric acid, the environment
is predominantly oxidizing due to fast scavenger
reactions. The aqueous electrons and hydrogen
atoms are scavenged according to

e
aq H ! H
k 2:3 1010 M1 s113
2

e
aq O2 ! O2
k 1:9 109 M1 s113
3

2
e
k 9:7 109 M1 s115
aq NO3 ! NO3
H O2 !HO2 k 2:1 101016
4
5
370

17
HO2 $ H O
2 pka 4:8
6
HNO3
This leaves H2O2 and the strongly oxidizing OH

radical as the most reactive species in solution. The

OH radical reacts with organic solutes by hydrogen
abstraction, addition to unsaturated carbon bonds or
with organic and inorganic solutes by electron transfer reactions. Rate constants for OH radical reactions have been tabulated.13,18
Additional reactive species are created by nitric
acid radiolysis. A thorough review of the radiation
chemistry of nitric acid is given by Katsumura.19
Among the most important species, the oxidizing

NO3 radical is produced indirectly by the reaction
of the OH radical with undissociated nitric acid and
directly by radiolysis of the nitrate anion dissociation
product of nitric acid20:
NO
3
OH HNO3 !NO3 H2 O
k 5:3 107 M1 s1
NO
3

! e
aq NO3
7
8
The reactions of the NO3 radical are similar to those

of the OH radical, including hydrogen atom abstraction and addition and electron transfer reactions,
although with decreased electrophilic character and
lower reaction rates.21,22 Rate constants for its reaction with numerous species have been compiled.23
In acidic solution, the NO2
radical product of
3
eqn [4] protonates24:

$ HNO
NO2
3
3 $ H2 NO3
pK a1 4:8; pK a2 7:5
9
The product H2 NO3 decays to produce the NO2

radical25:
H2 NO3 !NO2 H2 O
k 7 105 s1
10
This species is less reactive than the NO3 radical,

but has been shown to add to unsaturated carbon
bonds, or to carbon-centered radicals to produce
nitrated derivatives of the original compound.2628
Perhaps more importantly, the addition product of
these two nitrogen-centered radicals decays to produce nitronium ion, a powerful nitrating species:
NO2 NO3 ! N2 O5
k 1:7 109 M1 s120
29
N2 O5 ! NO
2 NO3
11
12
Another important product of nitric acid radiolysis is

nitrous acid. It is produced by direct and indirect
effects:
30
!O HNO2
NO
2 H $ HNO2
31
!O NO2
pK a 3:232
NO2 NO2 ! N2 O4
kf 4:5 108 M1 s133
kr 6:0 103 s133
N2 O4 H2 O ! HNO2 HNO3
k 18M1 s125
13
14
15
16f
16r
17
Nitrous acid is also an important nitrating agent that

catalyzes nitration reactions via production of the
nitrosonium ion:
HNO2 H ! NO H2 O34
18
Nitrosonium ion may then react with the organic

compound by addition, shown for an aromatic species
in eqns [19][21],35 or by electron transfer as shown
in eqns [22] and [23]34:
NO ArH ! ArHNO
19
ArHNO ! ArNO H
20
ArNO HNO3 ! ArNO2 HNO2
21
ArH NO ! ArH NO
22
ArH NO2 ! ArNO2 H
23
Nitrous acid also affects actinide oxidation states, especially for neptunium, in irradiated aqueous nitric acid
solution. The valence state of neptunium is set by the
concentration of nitrous acid according to eqn [24]36:

NpO
2 3=2H 1=2NO3
$ NpO2
2 1=2HNO2 H2 O
24
The maximum concentration of radiolytically produced

nitrous acid is limited by radiolytically produced H2O2,
as shown37,38:
H2 O2 HNO2 ! H NO
3 H2 O
25
It should be noted that irradiation is not required

to produce nitrous acid in nitric acid solution. The
nitric acid oxidation of solution constituents is also
accompanied by the production of nitrous acid, an
example of which was shown in eqn [21]. Equations
[18][21] show that nitrous acid nitration is catalytic,
and once produced, only small concentrations are necessary to cause the nitration of organic compounds.
Irradiation enhances the production of nitrous acid in
nitric acid, enhancing yields of nitrated products.
Radiolysis also occurs in the organic phase. Normal
and branched-chain alkanes are the typical organic
diluents for the ligands used in nuclear solvent extraction. The radiolysis of alkanes is represented by39:
CH3 CH2 n CH3

! e
sol CH3 CH2 n CH3
CH3 CH2 n CH2 CH3 H H2
26
Specific yields for the products depend on the specific

alkane irradiated. Branch-chain alkanes have higher
product yields, in the range of 0.20.6 mmol J1
for molecular hydrogen and 0.0050.1 mmol J1 for
methane. Bishop and Firestone40 reported a yield of
H atom of 0.07 mmol J1 for C6C10 hydrocarbons.
The carbon-centered radical products may also be
produced indirectly by hydrogen abstraction reactions with OH or NO3 radicals. Regardless of their
origin, these carbon-centered radicals react with solutes
by hydrogen atom abstraction or they may undergo
radicalradical addition to create higher molecular
weight products:
CH3 CH2 n CH2 CH3 CH2 n CH2
! CH3 CH2 2n2 CH3
27
As these higher molecular weight products accumulate,

they change the physical characteristics of the solvent,
including the phase disengagement time, density, and
viscosity. These physical changes may in turn affect
process performance. Alkane radicals may also undergo
disproportionation, to produce unsaturated products41:
CH3 CH2 n CH2 CH3 CH2 n CH2
! CH3 CH2 n CH3
CH3 CH2 n1 CH CH2
28
Unsaturated products are susceptible to addition reactions by OH radical or N-centered radical species.
Among the most important of carbon-centered
radical reactions is oxygen addition to produce peroxyl radicals42:
R O2 ! ROO
29
Peroxyl radicals will undergo addition reactions to

form tetroxides which then decompose to produce
aldehydes, ketones, and alcohols from the original
compound.43 They are therefore important intermediates in the oxidative mineralization of organic
compounds by radiolysis.
371
5.15.3 PUREX Process

5.15.3.1
Tributylphosphate Degradation
The PUREX process for the extraction of the major

actinides, especially uranium, consists of 30% TBP in
an alkane diluent. It has been in use worldwide for
decades for the recovery of fissionable materials from
used nuclear fuel.3 The metal-loaded solvent is stripped
with a mildly acidic aqueous phase for recovery of the
actinide metal ions, and the solvent is recycled. However, its recycle potential is limited by the radiolytic
degradation of TBP and its diluents. It has long been
recognized that the major products of TBP radiolysis
are hydrogen, methane, and dibutylphosphoric acid
(HDBP), with monobutylphosphoric acid (H2MBP)
and phosphoric acid produced in lesser amounts. The
radiation chemistry of TBP was recently reviewed and
the following discussion is abbreviated from that
source.44
The accumulation of radiolytic degradation products in the PUREX solvent results in decreased
extraction performance with regard to separation
factors and physical parameters.4547 The acidic radiolysis products of TBP degradation are complexing
agents that interfere with uranium and plutonium
stripping and fission-product separation factors.4850
Interfacial crud formation and poor phase separation
have been attributed to the formation of precipitable
complexes of zirconium with H2MBP and phosphoric acid.47,5155 The adverse effects of the buildup of
these acidic phosphate products in the organic phase
are mitigated during process extractions by solvent
washing with aqueous Na2CO3.56,57 However, with
continued recycling, washing becomes less effective
and the washed solvent shows increased retention of
undesirable Pu, Zr, and Ru and increased solution
viscosity.58 This has been attributed to the accumulation of radiolysis products of higher molecular weight,
resulting from radical addition reactions. These species have high organic phase solubility.47,59 The result
is a permanently degraded and radioactively contaminated solvent that is expensive to dispose.
Several mechanisms have been proposed to
explain the production of HDBP in irradiated TBP
solutions. Zaitsev and Khaikin60 reported that dissociative electron capture resulted in the production of
the butyl radical and HDBP in irradiated neat TBP:

e
sol C4 H9 O3 PO ! C4 H9 C4 H9 O2 OPO
30
Jin et al.61 attributed the formation of HDBP under

these conditions to a combination of dissociative
372
electron capture and decay of excited TBP molecules, while Haase et al.62 reported that electron
attachment could also result in free hydrogen atoms
and a TBP carbon-centered radical. However, the
electron-initiated reactions are unlikely to be of consequence in solvent extraction due to the scavenging
of electrons by nitrate and hydronium ions in the
acidic phase (eqns [2][4]). Additionally, the direct
excitation of TBP becomes less important when TBP
is dissolved in a diluent.
Burr63 proposed that HDBP was formed by the
decay of the TBP carbon-centered radical:
C4 H9 O2 C4 H8 OPO
!
C4 H
8
C4 H9 O2 OPO
C4 H9 O2 PO O C4 H8 H2 O
! C4 H9 O2 PO O C3 H7 CHO
2H
36
68
Wilkinson and Williams proposed yet another

mechanism for HDBP formation based upon direct
TBP radiolysis:
C4 H9 O3 PO

! e
sol C4 H9 O3 PO
C4 H9 O3 PO ! C4 H9 O2 POHOH
CH2 CHCH CH3
31
This TBP radical could be produced by hydrogen

atom abstraction63 by reaction with either the radiolytically produced H atom or OH radical:
OHH TBP ! C4 H9 O2 C4 H8 OPO
H2 OH2
kOH 5:0 109 M1 s164
kH 1:8 108 M1 s164
32a
32b
Besides the direct decay to HDBP shown earlier, the

TBP radical could also undergo hydrolysis to again
produce HDBP65:
C4 H9 O2 C4 H8 OPO H2 O
! C4 H8 OH C4 H9 O2 POO H
33
Khaikin66 suggested that HDBP was also the stable
product of dissolved oxygen addition to the TBP
radical, which gives the TBP peroxyl radical:
C4 H9 O2 C4 H8 OPO O2
! C4 H9 O2 PO O C4 H8 OO
34
Superoxide elimination followed by hydrolysis produces HDBP and butyraldehyde, also a measured
product.67
C4 H9 O2 PO O C4 H8 OO
! O
2 C4 H9 O2 PO O C4 H8
35
37
38
C4 H9 O2 POHOH
! C4 H9 O2 POOH H
39
Intramolecular hydrogen bonding between the phosporyl oxygen and a butoxy hydrogen atom of the
radical cation formed in eqn [37] forms a ring structure, which decays as shown in eqns [38] and [39].
However, based on a relative rates analysis, Mincher
et al.64 calculated that the literature G-values of 0.05
0.5 mmol J1 for TBP decomposition could be
explained solely by radical reactions, without a need
to invoke direct radiolysis. However, even with a
contribution due to direct radiolysis, the reactions
described earlier would all lead to the production of
HDBP, and occur competitively. Continued irradiation produces H2MBP and phosphoric acid from
HDBP via analogous reactions.
It should be noted that although the G-value is
commonly used to report the degradation rates of
ligands in solvent formulations, it is not an ideal
figure of merit for this purpose. Unlike the radical
yields for a neat solution presented in eqn [1],
the degradation yield of a solute irradiated in a solvent is highly dependent on the experimental conditions used. These include the presence or absence of an
aqueous phase, the dissolved oxygen content of the
solution, and even the ligand concentration in the irradiated solvent. Thus, they should be interpreted with
caution when comparing various studies. Further, not
all studies report results in terms of G-values. With
these considerations in mind, G-values for some of
the ligands discussed in this chapter are presented in
Table 1.
Among the less abundant but still important TBP
radiolysis products are the acid phosphates of higher
molecular weight. These species with varying alkane
chain lengths suggest that radical addition reactions
373
Table 1
Radiolytic degradation yields (G-value; mmol J1) for selected ligands discussed in the text. It should be noted
that the magnitude of the G-value depends on experimental conditions and ligand concentration
Ligand
Solution
References
TBP
Crown ether
CMPO
DMDOHEMA
TODGA
Alkane solution in contact with aqueous HNO3

Alkane solution in contact with aqueous HNO3
TRUEX dodecane in contact with aqueous HNO3
0.65 M in alkane in contact with aqueous HNO3
Neat
0.050.5
0.1
0.01
0.40.5
0.85
44, 64
69
70
7, 71, 72
73, 74
occur between TBP, HDBP, and alkane solvent radicals, including the production of TBP dimers.52,75
These compounds of higher molecular weight are
among those species that are not adequately removed
from irradiated solvent by aqueous carbonate
washing.
Additional products of TBP radiolysis in the presence of nitric acid are nitrated phosphates, which also
impede stripping efficiency. He et al.76 proposed that

NO3 reacts with TBP by hydrogen atom abstraction,
producing the TBP radical:
NO3 TBP ! C4 H9 O2 C4 H8 OPO HNO3

k 4:3 106 M1 s164
40
The TBP radical was then postulated to undergo reaction with additional NO3 to produce nitrated TBP77:
NO3 C4 H9 O2 C4 H8 OPO
! C4 H9 O2 OC4 H8 NO3 PO
41
The NO2 radical might be expected to add in the

same way:
NO2 C4 H9 O2 C4 H8 OPO
! C4 H9 O2 OC4 H8 NO2 PO
42
Methylated, hydroxylated, and nitrated phosphates,

resulting from the radical addition reactions of methyl
radical, hydroxyl radical, and the nitro-radicals shown
earlier, have been identified in postirradiation TBP
solutions by numerous investigators.7780
5.15.3.2
Alkane Diluent Degradation
The alkane diluent, usually kerosene, dodecane, or a

mixture of normal paraffinic hydrocarbons (NPHs),
also undergoes radiolytic degradation to generate
metal complexing agents that do not wash out in
solvent treatment with alkaline solutions.45 The
decomposition of diluents in TBP solvent extraction
was reviewed by Tahraoui and Morris.81 Alkanes

undergo radiolytic nitration of their carbon-centered
radicals, in analogy with the aforementioned eqns
[41] and [42]. Stieglitz and Becker47 and Tripathi
et al.58 identified both nitro-, and nitrosoalkanes
(RNO2 and RONO2) in alkanes irradiated in the
presence of nitric acid. These nitroparaffins and
their hydroxamic acid reaction products have been
implicated in fission-product complexation in the
PUREX process. Nitroparaffins are thought to be
converted to the complexing enol form by contact
with the alkaline scrub intended to remove the acidic
products of TBP decomposition56:
RCH2 N OO $ RCH NOO
43
45,54
are metal complexing and

Hydroxamic acids
reducing agents formed from nitroparaffins by the
Victor Meyer reaction:
RCH2 NO2 ! RCONHOH
44
Although hydroxamic acids rapidly hydrolyze in acidic

media, small but steady-state organic phase concentrations have been identified in irradiated solvent.8284
Additional diluent radiolysis products identified in
irradiated TBPdodecanenitric acid include alkane
oligomers, aliphatic ketones, and acids.85 Thus, stripping difficulties and poor separation factors result from
a combination of higher molecular weight acidic phosphates from TBP radiolysis and from compounds produced by diluent nitration.
As has been previously noted, nitration may also
occur in the absence of irradiation when solvents
are exposed to nitric acid. For example, when
Blake et al.56 boiled Amsco 125-82 (a commercially
available branch-chain aliphatic hydrocarbon solvent
in the C12C14 range) in contact with nitric acid under
reflux, infrared analysis of the treated solvent showed
absorption bands attributable to nitroparaffins and
alkane oxidation products. Intense absorbance in the
UV spectrum at 200 nm was also attributed to nitroparaffins, and was also obtained upon g-irradiation of
the solvent. An absorbed dose of 450 kGy produced

the same effect as an 11 h reflux in the presence of
2 M nitric acid. Less severe effects were noted for
purified normal alkane diluents such as dodecane.
According to Moore,86 the exclusion of nitrous
acid from hot nitric acid solutions by the use of
scavengers such as urea or sulfamic acid prevented
degradation of alkane diluents. The products of reaction with nitrous acid were nitrite esters, nitroso
compounds, and oxidation products, and the degree
of reaction was found to be dependent on the nitric
acid concentration. This resulted in enhanced fissionproduct retention by the solvent and increases in
phase disengagement times, similar to the effects
produced by the radiolytic nitration of the solvent.
These reactions may be more important than those of

NO3 and NO2 radicals in irradiated acid.87
Finally, it should be noted that the use of more
stable TBP diluents results in higher yields of HDBP
due to increased TBP degradation. This has been
attributed to the diluent ionization potential.81 Direct
diluent radiolysis produces the diluent radical cation,
as was shown in eqn [26]. A common radical cation
stabilization route would be that of charge transfer by
reaction with a solute such as TBP:
CH3 CH2 CH3 TBP
! CH3 CH2 n CH3 TBP
45
Thus, a diluent with a higher ionization potential

than the ligand is not necessarily desirable. For this
reason, it has often been noted that the use of aromatic diluents, with their low ionization potentials,
leads to more radiation-stable solvent-extraction systems. Examples of this will be discussed later.
5.15.3.3
Radiolysis Versus Hydrolysis
The nitration reactions in irradiated and unirradiated

nitric acid produce similar products. It is also often
reported that the products of radiolysis and hydrolysis are the same, although sometimes with differing yields. For example, Brodda and Heinen88
reported hydrolytically produced HDBP in 30%
TBP/n-paraffin solutions that had been preequilibrated with nitric acid at 23 C. They found a linear
relationship between the amount of HDBP produced
and the acid concentration in the organic phase,
although hydrolysis did not continue after the phases
were separated. The product H2MBP was not
detected, since it would have partitioned to the aqueous phase and that phase was not analyzed.
Hydrolysis presumably occurs according to the following reaction, in the presence of acidity:
C4 H9 O3 PO H2 O
46
! C4 H9 OH C4 H9 O2 POOH
As with radiolysis, continued dealkylation would

result in the products H2MBP and H3PO4.
Stieglitz und Becker47 measured the production of
HDBP, H2MBP, and phosphoric acid from hydrolyzed 0.001 M TBP in various concentrations of
aqueous nitric acid. Hydrolysis was represented
according to eqn [47]:
k1
k2
k3
TBP ! HDBP ! H2 MBP ! H3 PO4
47
They noted a linear dependence of the rate constants

k1k3 on the concentration of nitric acid, as shown in
Figure 1. The half-life for the loss in TBP concentration in 3 M HNO3 at a temperature of 50 C was
2310 h, and at 90 C, it was 30 h. Using mixed-phase
experiments of 30% TBP in alkane diluent in contact
with 3 M HNO3, it was found that hydrolysis rates
were lower by a factor of 4060. For mixed-phase
experiments in the presence of uranium or zirconium, it was found that the hydrolysis rate increased
and the dependence on nitric acid concentration was
no longer evident. The authors attributed this to
preferred hydrolysis of the metalTBP complex.
0.015
k1
First-order rate constant, k (h-1)
374
0.01
0.005
k2
k3
0
-1
1
2
3
4
Nitric acid concentration (M)
Figure 1 The first-order rate constants (h1) for the

hydrolytic production of dibutylphosphoric acid (HDBP)
from aqueous tributyl phosphate (k1), monobutylphosphoric
acid (H2MBP) from HDBP (k2), and phosphoric acid from
H2MBP (k3) as a function of nitric acid concentration at
75 C. Modified from data of Stieglitz, L.; Becker, R.
Kerntechnik 1985, 46, 7680.
The related extractant triamylphosphate (TAP)

was investigated for changes in Pu retention ability
by Venkatesan et al.89 following both hydrolysis and
radiolysis. Chemical degradation was studied by stirring the 1.1 M TAP/NPH solution with 4 M HNO3
at room temperature or at 75 C for periods up to
200 h. Increased Pu retention following hydrolysis
was mitigated by sodium carbonate washing, and
thus, it was attributed to the mono- and dibasic
acids of TAP, in analogy with the hydrolysis and
radiolysis of TBP.
5.15.4 Fission Product Extraction

Processes
In some proposals, the major heat-generating but
short-lived fission products will be extracted for separate disposal following UREX. Separate disposal of
these short-lived activities would permit more efficient utilization of the long-term geological repository. Two solvent-extraction processes have been
considered for the separation of the main heatemitting radionuclides 137Cs and 90Sr from fuel
dissolution. They are the cobalt dicarbollide
polyethylene glycol (HCCDPEG) and fission
product extraction (FPEX) processes, discussed
subsequently.
5.15.4.1
HCCDPEG Process Radiolysis
The HCCDPEG process consists of cobalt dicarbollide (HCCD) for cesium extraction and PEG for
strontium extraction, dissolved in a phenyltrifluoromethylsulfone diluent called FS-13 (C6H5SO2CF3).90
The structure of the sulfone is shown in Figure 2.
The dependence of the cesium and strontium extraction distribution ratios for g-irradiated 0.12 M HCCD
and 0.027 M PEG-400 in FS-13, in the presence of
1.5 M HNO3, is shown in Figure 3.91
There was no deleterious effect observed for
cesium extraction efficiency even at an absorbed dose
CF3
O
Figure 2 The structure of the sulfone diluent

phenyltrifluoromethylsulfone (FS-13) used in the cobalt
dicarbollidepolyethylene glycol fission product extraction
process. The direct ionization of this compound initiates
reactions that interfere with strontium extraction.
375
of 432 kGy. In contrast, strontium extraction distribution ratios decreased with absorbed dose in an exponential fashion, suggesting that PEG is susceptible to
radiolytic damage. The apparent decrease in PEG
concentration was proposed to be initiated by reaction
with the OH radical product of water radiolysis, and
the NO3 radical product of nitric acid radiolysis. The
hydrogen atom abstraction reactions of these species
and their associated rate constants with ethylene glycol are shown in eqns [48] and [49]92,93:
HOCH2 CH2 OH OH ! H2 O CHOHCH2 OH
k 2:4 109 L mol1 s1
48
HOCH2 CH2 OH NO3 ! HNO3 CHOHCH2 OH

k 1:6 106 L mol1 s1
49
In either case, a carbon-centered PEG radical will be

produced, which initiates oxidative decomposition of
PEG by oxygen addition to produce the corresponding
peroxyl radical (eqn [29]). However, as can be seen
from Figure 3, the strontium extraction distribution
ratios decreased exponentially, albeit at a lower rate,
even when irradiated in the absence of an aqueous
phase. This was attributed to reaction with the products of direct sulfone diluent radiolysis. The ionization of sulfone by irradiation is shown in eqn [50]:
C6 H5 SO2 CF3 ! C6 H5 S O2 CF3 e
50
The decay of the produced radical cation results in the

generation of the carbon trifluoride radical:
C6 H5 S O2 CF3 ! C6 H5 S O2 CF3
51
The addition product of the CF3 radical, hexafluorethane, is a measured product of sulfone irradiation.
Hydrolysis of the sulfone radical cation product of eqn
[50] with trace water in the solvent produces benzenesulfonic acid, also a measured product.
C6 H5 S O2 H2 O ! C6 H5 SO2 OH H
52
However, if the sulfur-centered cation product shown

in eqn [51] undergoes an analogous reaction with
PEG, benzenesulfonic acid also results, and the functionality of PEG as a strontium extractant would be
decreased:
C6 H5 S O2 CHOHCH2 CHOH
! C6 H5 SO2 OH CHOHCH2 CH
53
It can be seen from Figure 3 that HCCDPEG solvent irradiated to high absorbed doses, and in the
376
700
Strontium distribution ratio
600
500
Neat organic
400
300
200
Aqueous phase present
100
0
-100
100
200
300
Absorbed dose (kGy)
400
500
Figure 3 The decrease in strontium distribution ratios versus absorbed g-dose for cobalt dicarbollidepolyethylene
glycol solvent formulation irradiated in the presence and the absence of the acidic aqueous phase.
presence of nitric acid, still provided adequate performance from which to implement a process. However,
the HCCDPEG process is unusual in that it relies on
a heavy-phase organic solvent.90 This limits its compatibility with the other advanced reprocessing extractions, and it has been supplanted in current process
designs by the FPEX process.
5.15.4.2
FPEX Process Radiolysis
The FPEX process was developed using the calixarene

crown ether calix[4]arene-bis(t-octylbenzo)-crown-6
(BOBCalixC6) and the conventional crown ether:
di-t-butylcyclohexano-18-crown-6 (DtBuCH18C6) in
combination to facilitate the simultaneous extraction of cesium and strontium from acidic dissolved
nuclear fuel.4 This formulation also contains
1-(2,2,3,3,-tetrafluoropropoxy)-3-(4-sec-butylphenoxy)2-propanol (Cs7SB) as a solvent modifier to help
solubilize the BOBCalixC6 and the calixarene and
crown ether metal complexes in an alkane diluent.
The structures of the ligands and Cs7SB are shown
in Figure 4.
Steady-state 60Co g-ray irradiation experiments
using 0.007 M BOBCalixC6, 0.075 M DtBuCH18C6,
and 0.75 M Cs7SB, in Isopar L have been reported.94
When irradiated in contact with 1.5 M HNO3, the

organic phase changed from colorless to yellow, turning to yellow-orange with increasing absorbed dose.
In an unpublished work by the same authors, the same
color changes were noted in unirradiated samples after
long exposures to the nitric acid phase. Investigation
by gas chromatography with electron capture detection (ECD) revealed products that appeared only in
the presence of the acidic aqueous phase. This combination of color change and new peaks with high ECD
response was attributed to nitration reactions. Since
the decrease in metal distribution ratios after irradiation was the same for both strontium and cesium, the
effect of irradiation was proposed to be on the Cs7SB
modifier, the only solvent constituent in common to
both metal complexes. However, cesium and strontium
extraction was only modestly affected to an absorbed
dose of 200 kGy. A plot of distribution ratio versus
absorbed dose revealed only a slight negative slope
for both extracted metals, as shown in Figure 5.
Thus, the FPEX process also appears to be robust
enough to support a process.
The radiation chemistry of the calixarenes and
crown ethers was recently reviewed.95 The crown
ethers exhibit high radiation stability, with low degradation G-values of about 0.1 mmol J1 in organic
377
OCH2CF2CF2H
O
OH
O
O
O
O
O
O
O
O
Figure 4 The structures of 1-(2,2,3,3,-tetrafluoropropoxy)-3-(4-sec-butylphenoxy)-2-propanol (Cs7SB) (top); calix[4]arenebis-(tert-octylbenzo-crown-6) (BOBCalixC6) for Cs extraction (left); and 4,40 ,(50 )-di-(t-butyldicyclohexano)-18-crown-6
(DtBuCH18C6) for Sr extraction (right), used in the FPEX fission product extraction process.
12
11
Strontium
Distribution ratio
10
9
8
7
6
Cesium
5
4
-50
50
100
150
Absorbed dose (kGy)
200
250
Figure 5 The analogous decrease in strontium and

cesium distribution ratios versus absorbed g-dose for the
fission product extraction solvent formulation irradiated in
the presence of the acidic aqueous phase. Error bars shown
are 10%.
solution irradiated in contact with aqueous nitric

acid.69 This value is about half that for TBP degradation under the same conditions.44 Noncyclic polyether
products result. For dicyclohexano-18-crown-6
(DCH18C6) irradiated in 1 M aqueous nitric acid to
a very high absorbed dose of 3290 kGy, seven noncyclic products containing 3, 5, or 6 oxygen atoms were
reported.69,96 They represent a range in product ether
fragments from as small as ethane and up to fully half
the macrocycle and suggest simultaneous splitting of
two CO bonds. When these water-soluble products
were synthesized and millimolar amounts of each was
added to a surrogate spent-fuel raffinate solution, it

was found that the extraction of uranium and strontium by DCH18C6 was not affected.97 However, plutonium extraction was suppressed by about 20% and
this metal was precipitated by the most abundant
radiolysis product (G 0.04 mmol J1). The same products were produced by hydrolysis and radiolysis,
although the abundance of the lower molecular weight
products was favored in hydrolysis.98 For neat crown
ether irradiation, recyclization to produce lighter
molecular weight ethers has often been reported.95
However, recyclization in solution is not expected
due to the abundance of reactive species in irradiated
diluents available to react with crown ether radicals.
The initiation of crown ether degradation to noncyclic
ethers is thought to be due to hydrogen abstraction
reactions99 to produce carbon-centered radicals. This
initiates additional reactions resulting in CO bond
rupture.
When Horwitz et al.100 irradiated DtBuCH18C6
in octanol, they reported that DSr was apparently
stable until about 200 kGy, after which it dropped
until it was one-third the original value at 300 kGy.
Stripping distribution ratios climbed gradually with
the absorbed dose, but were still 0.1 at 300 kGy.
This decrease in performance was at least partially
attributable to diluent radiolysis; however, solvent
performance was acceptable, given that the absorbed
doses employed were in excess of those expected in a
process application. Decreases in DCs and DSr of
2035% and an increase in DZr of more than 30%
were reported by Shuler et al.101 for irradiated solutions of DCH18C6-derivative crown ethers. The
macrocycles were dissolved in a TBPkerosene
378
O2N
O
O
O
O
O
O
O
O
O
O
Figure 6 The structure of a nitrated calix[4]arene, showing

the presence of the nitro group which interferes with
cesium complexation.
solution and irradiated in contact with the acidic

aqueous phase over the dose range 20100 kGy. The
increase in DZr was probably due to TBP radiolysis
products.
The nitration of calixarene phenyl rings resulted
in decreased cesium extraction efficiency as reported
for the irradiation of these macrocycles in the presence of nitric acid.102,103 Higher levels of nitration, as
determined by mass spectrometry, resulted in lower
DCs, suggesting that nitro substitution occurred on
the calixarene phenyl rings to sterically hinder
cesium binding. This is shown in Figure 6.
However, as noted earlier, no significant reduction
in cesium extraction was found for the FPEX irradiations.94 This may be because BOBCalixC6 has alkylated phenyl groups activated toward nitration that
are remote from the phenyl rings adjacent to the
crown moiety, which is responsible for cesium complexation (Figure 4). These remote phenyl rings may
scavenge nitrogen-centered radicals or nitrosonium
ions that might otherwise react at the cesium binding
site. Thus, the structure of BOBCalixC6 appears to
provide a radiation stability superior to that of many
other calix[4]arene-crown-6 ethers. While the result
was fortuitous, it represents an example of the possibility of designing ligand molecules with high radiation resistance for use in nuclear solvent extraction.
5.15.5 Minor Actinide and

Lanthanide Extraction Processes
Following the extraction of major actinides and
heat-emitting fission products in the steps described
earlier, the aqueous raffinate contains the minor actinides americium and curium, as well as the lanthanides. The solution will also contain plutonium and
neptunium depending on whether their valence states
were previously adjusted to remove them in the initial
separation. The minor actinides, with Z 95, are

predominantly trivalent in acidic aqueous solution
and therefore have separations chemistry very similar
to that of the lanthanides. Because they are long-lived
a-emitters and are fissionable, it is desirable to partition them for inclusion in fast reactor fuels, rather
than bury them as long-lived, high-level waste. This
would allow of their use in energy production and
their transmutation to short-lived fission products.
However, the lanthanides are neutron poisons, and
being relatively short-lived, they are intended for
geological disposal. Thus, the separation of the trivalent 4f and 5f elements is necessary, yet this is a
challenging separation even at the analytical scale.
The separation is proposed to be performed in
two steps. In the first, the actinides and lanthanides
are extracted together using a conventional oxygendonor ligand. These are then stripped to an aqueous
phase of proper acidity and the f-element separation
is affected using soft-donor ligands. The radiation
chemistry of these actinidelanthanide extraction
processes is discussed subsequently.
5.15.5.1
TRUEX Solvent Degradation
The ligand for the group separation extraction in US

proposals is octyl(phenyl)-N,N-diisobutylcarbamoylmethyl phosphine oxide (CMPO), developed at the
Argonne National Lab by Horwitz et al.5 The structure of this compound is shown in Figure 7.
The TRUEX solvent is composed of 0.10.2 M
CMPO, 12 M TBP, and a NPH diluent. The role
of CMPO is to increase the extraction efficiency of
the trivalent actinides and lanthanides over that
of TBP alone, due to its more basic phosphoryl
group.104
The g-irradiation of CMPO has been studied with
respect to its effects on the solvent-extraction efficiency of americium. Irradiation has adverse affects
on both forward extraction and stripping. For example, the effect of radiolysis on extraction by 0.2 M
CMPO/1.4 M TBP in NPH was studied by Simozadeh et al.105 The DAm decreased from 30 to 10
at an absorbed dose of 848 kGy, for samples irradiated
in contact with nitric acid concentrations between
1.6 and 6.0 M. Similar results were obtained by
Logunov et al.106 for 0.2 M CMPO dissolved in
m-nitrobenzotrifluoride. The DAm was decreased
from 6 to about 3 after an absorbed dose of 1650 kGy,
when in contact with 1 M HNO3. The irradiated
solvent was reported to develop a dark reddishblack color, some of which was extracted by sodium
O
C4H9
H17C8
C4H9
OH
CMPO (0.12)
HN
H17C8
C4H9
379
C4H9
Octylphenylphosphinyl acetic acid (0.17)
O
+
CO2
CH3
O
H17C8
P
Octylphenylphosphine oxide
OH
H17C8
Octylphenylphosphinic acid (0.22)
Figure 7 The radiolytic decomposition of octylphenyldiisobutylcarbamoylmethyl phosphine oxide (CMPO) used in the
transuranium extraction (TRUEX) process. The initial reaction is CN bond cleavage to produce an acid and an amine.
Decarboxylation of the acid produces a phosphine oxide which maintains the forward extraction of americium. Oxidation of the
phosphine oxide to an organic soluble phosphinic acid interferes with stripping. The G-values (mmol J1) given in brackets are for
0.2 M CMPO/1.2 M TBPdodecane TRUEX formulation in contact with 5 M HNO3, as measured in Nash et al.70
carbonate washing, implying the creation of acidic,

nitrated products.
Americium stripping was also affected, for samples irradiated in contact with the nitric acid concentrations of 2.5 or 6 M, the DAm using 0.01 M HNO3
actually exceeded those of the forward extractions
at the highest absorbed dose of about 600 kGy. For
samples irradiationed in contact with 0.25 M nitric
acid, the strip values were 1.107 The acid-induced
thermal hydrolysis of CMPO solutions using the
same nitric acid concentrations at elevated temperatures affected DAm similarly. The inability to strip
after radiation exposure was attributed to the buildup
of the acidic degradation products of CMPO and/or
TBP radiolysis.107
Similarly, Chiarizia and Horwitz107 reported
decreasing DAm for forward extractions and increasing DAm for stripping extractions for the irradiation of
CMPO solutions in contact with 5 M HNO3. The
changes in extraction efficiency were linear with an
absorbed dose for 0.25 M CMPO in decalin. Americium distribution ratios from 2 M HNO3 decreased
from 80 to 26 at an absorbed dose of 195 kGy,
while stripping distribution ratios increased to 3000
over the same absorbed dose range. Carbonate washing decreased CMPOdecalin stripping distribution
ratios, although not restoring them to their initial

values. This suggested the production of an organophilic acidic degradation product.
The addition of TBP to CMPO solutions in the
TRUEX formulation decreased stripping distribution ratios, perhaps due to TBP hydrogen bonding
to CMPO degradation products.107 However, TBP
would also scavenge radicals that might otherwise
have reacted with CMPO. While the kinetic constants for the reactions of CMPO with the main
radicals produced in irradiated aqueous nitric acid
are unknown, TBP reacts at high rates with OH and

NO3.64 Thus, the presence of TBP as a TRUEX
constituent not only improves CMPO solubility and
third phase and metal loading characteristics,108 but
also contributes to the radiation stability of CMPO.
The radiolytic decomposition of CMPO was
found to be first order versus absorbed dose, with
GCMPO 0.012 mmol J1 for TRUEXdodecane,
0.045 mmol J1 for TRUEXtrichloroethylene (TCE),
0.055 mmol J1 for CMPOTCE, and 1.64 mmol J1
for CMPOCCl4.70 This dramatically illustrates the
role of diluents in the radiolytic degradation of
ligands. The chlorinated solvents resulted in lower
radiation stability due to the production of chlorine
radicals and HCl upon irradiation. These results also
380
show the ability of TBP to protect CMPO from

degradation.
The formation G-values for the main radiolysis
products of CMPO when irradiated in contact with
5 M HNO3 were measured by Nash et al.70 and are
given in Figure 7. It can be seen that those for product
appearance are actually higher than those for CMPO
degradation. This inability to close the mass balance
probably represents the difficulty of quantifying these
product concentrations, or of making accurate
absorbed dose measurements. These compounds, and
other related species, were also identified by Mathur
et al.109 using GC and GCMS techniques.
The products responsible for degraded stripping
performance probably include organophilic acids;
octylphenylphosphinic acid, octylphenylphosphorylacetic acid, and octylphenylphosphinylacetic acid
from CMPO degradation, and HDBP from TBP
degradation. The hydrolysis and radiolysis products
of CMPO were found to be identical; however, they
were produced in different yields.110
A mechanism was proposed by Chiarizia and
Horwitz107 wherein CMPO degradation was initiated
by CN bond scission, resulting in the creation of a
carboxylic acid and an amide. As shown in Figure 7,
decarboxylation of the carboxylic acid results in
methyloctylphenylphosphine oxide, a neutral compound that would complex americium to maintain
high DAm values even as CMPO is degraded. Oxidation
of this phosphine oxide would produce octylphenylphosphinic acid. The addition of these compounds to
unirradiated CMPOCCl4 solutions was used to qualitatively reproduce the changes in americium extraction efficiency observed in irradiated solutions.107
5.15.5.2
Diamide-Based Processes
In most of the European and Japanese work, tetraalkyldiamides have been proposed as replacement compounds for CMPO.111 The radiation chemistry of
these compounds was recently reviewed, and the
following discussion is adapted from that review.112
The potential advantages and uses of amides as actinide extractants have been reviewed by Gasparini
and Grossi.113 They concluded that the products of
tetraalkyldiamide radiolysis were water soluble and
thus easily washed from the solvent. These authors
also reported that the major hydrolysis products of
alkylamides were due to CN bond rupture to generate carboxylic acids and secondary amines, in analogy with the mechanism shown for CMPO in
Figure 7.
The pentaalkylpropane diamides (malonamides)

have the general structure (RR0 NCO)2CHR00 .
Cuillerdier et al.114 compared the hydrolysis and
radiolysis of diamide derivatives and concluded that
stability as a function of R00 increased in the order
H < C2H5 < C2H4OC6H13 < C2H4OC2H4OC6H13.
Long oxyalky chains appear to protect extraction
efficiency. The radiolysis products were not identified,
although hydrolysis yielded octanol for the diamide
with R00 C2H4OC8H17, suggesting cleavage at the
ether linkage. It appears that the inclusion of a sacrificial ether linkage in the molecule may result in the
generation of relatively harmless radiolysis and hydrolysis products while maintaining DIAMEX capability.
This provides an example of intelligent ligand design,
with respect to degradation effects. This ether cleavage
is reminiscent of CO bond cleavage in crown ether
radiolysis, or CN cleavage in amides, and may
also be initiated by hydrogen abstraction reactions
for irradiated solution. Other monoamides and
diamide products were also reported. For the diamide
with R00 C2H4OC2H4OC6H13, actinide extraction
performance was reported to remain satisfactory after
700 kGy absorbed dose.114 The DIAMEX solventextraction process for the recovery of the minor
actinides was developed using the malonamide
DMDOHEMA shown in Figure 8.
The hydrolysis and g-radiolysis of this compound
have been thoroughly investigated by Berthon et al.7,71
The radiolysis of DMDOHEMA and two other malonamides in dodecane or TPH solutions in contact
with nitric acid was examined using a suite of analytical techniques, including gas chromatography,
potentiometry, and mass spectrometry. Higher acid
concentrations led to greater rates of malonamide
decomposition, with a GDMDOHEMA of 0.37 mmol J1
for 3 M HNO3. For 0.65 M DMDOHEMA in
C6H13
O
CH3
CH3
N
C8H17
H17C8
O
Figure 8 The structure of the malonamide: dimethyl

dioctyl hexylethoxymalonamide (DMDOHEMA) used in the
DIAMEX actinide extraction process. The radiolytic
decomposition of this compound is analogous to that for
CMPO in Figure 7.
dodecane also containing a dialkylphosphoric acid

ligand, a GDMDOHEMA of 0.55 mmol J1 was obtained
for irradiation in the presence of either a pH 3 or
a 0.5 M nitric acid aqueous phase.71 Bisel et al.72
reported GDMDOHEMA of 0.49 mmol J1 for a 0.5 M
alkane diluent solution also containing diethylhexylphosphoric acid (HDEHP), preequilibrated with
3 M HNO3 prior to irradiation. These G-values are
somewhat higher than those usually reported for
TBP.44
Organic acids were major radiolysis and hydrolysis products of diamides, and alcohols were created
by a rupture of the ether linkages in the R00 group.
The hydrolysis products of DMDOHEMA included
seven species detectable by capillary zone electrophoresis with UV detection, including C4 through C7
carboxylic acids, three unidentified species, and an
acidamide.115 The loss of one amide function by CN
bond rupture produced an amine and an acidic
amide as products, when irradiated in the presence
of the acidic aqueous phase. Products detected
by Berthon et al.71 for DMDOHEMA radiolysis
included the monoamide methyloctylhexyloxybutanamide, the acid amide methoxyoctylcarbamoyl
4-hexyloxybutanoic acid, the malonamides dimethyloctyl 2-hexyloxyethyl malonamide (DMOHEMA)
and methyldioctyl 2-hexyloxyethyl malonamide
(MDOHEMA), and the amine methyloctylamine.
Thermal decomposition of the acidic amide
resulted in the monoamide. The monoamide was a
significant product in hydrolyzed solutions, but is rapidly degraded in irradiated solution. The mechanisms
are similar to those proposed for the aforementioned
CMPO radiolysis.
In a diamide molecule which has suffered both the
rupture of the CN and CO bonds, an amide lactone was produced by an intermolecular reaction
between the acid and alcohol functional groups.
For DMDOHEMA, with its eight carbon R0 group,
all these species are soluble in the organic phase.
A dose of 690 kGy to 1 M DMDOHEMA in dodecane in contact with 4 M nitric acid resulted in a
final malonamide concentration of 0.59 M.116 The
decrease in malonamide concentration was accompanied by decreases in DAm, DEu, and DNd. When solutions containing varying amounts of the major
degradation products were prepared, all products
were found to interfere with Am and Nd extraction,
the amine being the most harmful. An acidic solvent
wash quantitatively removed the amine degradation
product, while an alkaline wash removed about 80%
of the acidic amide. The combination of an acid wash,
381
followed by water scrubbing and then an alkaline

wash restored the solvents extraction capabilities to
that expected for the decreased malonamide concentration.71,72 In testing using a DMDOHEMA
HEDHPTPH solvent irradiated and hydrolyzed in
a continuous flow system that included alkaline solvent washing, Bisel et al.72 reported that most diamide
degradation products were removed from the organic
phase, with only the monoamide, the acidic amide, and
MDOHEMA accumulating. The products due to an
exposure equivalent to 12 years of process operation
(800 kGy) did not affect metal distribution ratios,
phase disengagement, surface tension, refractive
index, or solvent density. Acceptable increases in
viscosity were also measured.
A related compound, the diglycolamide extractant
N,N,N 0,N 0 -tetraoctyl-3-oxapentane-1,5-diamide
(TODGA), shown in Figure 9, has also been
examined as an actinide extractant.
Exponential decreases in TODGA concentration
with absorbed dose have been measured, with
a GTODGA for the neat compound of 0.85 mmol J1.
This is about twice the yield of decomposition as for
TBP.44 Sugo et al.73,74 measured even higher rates of
TODGA decomposition in dodecane and octane
than for neat TODGA, with increasing rates with
higher diluent content. The addition of benzene to
dodecane solutions9,73 or the use of aromatic diluents9 decreased TODGA decomposition due to their
low ionization potentials, as has been found for other
ligands.117 Glycolamide derivatives containing aromatic functional groups also exhibited higher radiation stability, possibly due to intramolecular energy
transfer to the benzyl ring, providing another example of attempts to design radiation-stable ligands.73
The products of TODGA radiolysis included
dioctylamine, dioctylacetamide, dioctylglycolamide,
and dioctylformamide.9,74 The presence of nitric acid
did not enhance radiolytic degradation yields but did
favor cleavage of the CN bond to form the amine
and acidic products over CO bond cleavage to form
acetamide and glycolamide, in analogy with the
results for DMDOHEMA reported earlier.
C8H17
C8H17
N
N
O
H17C8
O
C8H17
O
Figure 9 The structure of diglycolamide extractant N,N,

N0 ,N0 -tetraoctyl-3-oxapentane-1,5-diamide (TODGA).
382
Modolo et al.10 investigated the postirradiation

solvent-extraction performance of 0.2 M TODGA
in alkane diluent. The DAm gradually decreased
with the absorbed dose for TODGA and TODGA
TBP mixtures irradiated in the presence and absence
of nitric acid. The DEu remained unchanged over the
absorbed dose range 01000 kGy. No degradation
products were detected by NMR. In an unpublished
work, Modolo reported nine products of irradiated
0.1 M TODGA in TPH in the absence of the aqueous
phase, as determined by HPLCmass spectrometry.
These included products created by the rupture of
CN bonds to eliminate one or more octyl groups
from the amide nitrogen and CN bond rupture to
generate secondary amines. Carboxylic acids were not
detected, however, the glycolamide and acetamide
products of CO bond cleavage were, in agreement
with Sugo et al.9 for irradiation in the absence of the
acidic aqueous phase.
In general, the foregoing discussions demonstrate
that the diamides are about twice as susceptible to
degradation by radiolysis and hydrolysis as is CMPO.
However, diamide degradation appears to have less
severe affects on solvent extraction performance.
The inclusion of the sacrificial ether linkage in the
malonamides mitigates the production of harmful
acidic degradation products by favoring the production of innocuous water-soluble alcohols. Solvent
washing steps appear to be necessary for both processes, however.
5.15.6 Processes for the Separation

of Minor Actinides from Lanthanides
5.15.6.1
TALSPEAK Process
To effect a separation between the trivalent actinides

and lanthanides, soft donors such as nitrogen- or
sulfur-containing complexants must be exploited to
selectively complex the minor actinides. The process
which has received most study in the United States is
TALSPEAK, based upon the competition between
HDEHP in the organic phase and lactate-buffered
diethylenetriamine pentaacetic acid (DTPA) in the
aqueous phase.6,118 The preferential complexation of
the actinides by DTPA holds them in the aqueous
phase while the lanthanides are extracted.
Tachimori and Nakamura119 investigated the
effects of HDEHP irradiation on solvent extraction
as a component of the TALSPEAK formulation.
When neat HDEHP was irradiated with g-rays,
and then used to prepare a 0.5 M solution in NPH
diluent, both DAm and DNd for extractions from

0.05 M DTPA1 M NaNO3 solutions at pH 3 gradually increased in a fashion analogous to the case of
the maximum absorbed dose of 2000 kGy. This was
attributed to an increase in the concentration of
monoethylhexylphosphoric acid (H2MEHP), which
also acts as a complexing agent. The separation factor
was, however, unchanged.
These authors also irradiated the aqueous phase
as either 0.05 M DTPA in 1 M NaNO3, or
0.05 M DTPA in 1 M lactic acid.119 When these pH 3,
irradiated aqueous solutions were then spiked with
the lanthanide and actinide metals, they were next
extracted with unirradiated and appropriately preequilibrated 0.5 M HDEHP solution. For the nitrate
solution, there was a rapid increase in D for both
metals, probably due to a decrease in concentration
of the DTPA. The increase was more severe for DAm,
resulting in a decrease in aAm/Nd. In contrast, the
lactate solution showed a comparatively modest
increase in D for both metals, but with a constant
separation factor. The loss in DTPA concentration
was also less for irradiated lactate solution, suggesting
that lactate, in addition to serving the role of a pH
buffer, was acting as a radical scavenger to protect
DTPA. When the organic and aqueous phases were
mixed during irradiation, simulating an actual process, lactate not only mitigated the adverse effects on
the extraction but also minimized the radiolytic yield
of H2MEHP and inorganic phosphates from HDEHP
decomposition.
Martin et al.120 measured the rate constant for
the reaction of the OH radical with lactate ion and
lactic acid over a range of temperatures. They found
room temperature values of 7.8 108 (pH 6) and
5.2 108 M1 s1(pH 1), respectively. When compared with the literature value for the DTPA reaction of 5.2 109 M1 s1,121 it was determined via a
relative rates analysis that lactic acid was incapable of
completely protecting DTPA from OH radical reactions. Only 33% of OH reactions occur with the
DTPA under these conditions. Increased protection
for DTPA could be had by increasing the lactic acid
concentration (2 M lactic acid would reduce DTPA
reactions to 20%), or by substituting an organic acid
with a faster OH radical reaction rate constant.
Numerous acids have been used in TALSPEAKlike formulations,122 with a-hydroxybutyric and
butyric acids having high OH radical reaction rate
constants. These, and the associated aEu/Am for those
systems, are given in Table 2. Since the OH radical
reaction is likely to be one of H atom abstraction,120
it can be predicted that organic acids with large,

branched alkane groups will provide greater protection to DTPA. Unfortunately, none of the alternatives
investigated to date provides both a good actinide
lanthanide separation factor and a high rate constant.
5.15.6.2 Bis(triazinyl)pyridine-Based
Processes
Among compounds that have shown promise for
minor actinidelanthanide separations are the tridentate bis(triazinyl)pyridines (BTPs). Their exceptional
americium solvent-extraction efficiency and high
separation factors for americium from europium
aAm/Eu have prompted a great deal of investigation
of these molecules for the purposes of minor actinide
recovery from nuclear fuel dissolution. The general
structure of the BTPs is shown in Figure 10. The key
functional groups are the tridentate arrangement of
soft-donor nitrogen atoms and the large alkyl
Table 2
The OH radical reaction rate constants
1 1
(M s ) and Eu/Am separation factors for organic acids
that have been used in TALSPEAK formulations
Acid
aEu/Am
kOH
Formic
Acetic
Propionic
Butyric
Glycolic
Lactic
Citric
Malonic
a-Hydroxyisobutyric
GlycineHNO3
19
24
29
10
84
91
105
57
62
16
1.3 108
1.7 107
6.2 108
2.2 109
6.0 108
5.2 108
5.0 107
2.0 107
1.0 109
1.7 107
Rate constants are those of Buxton et al.,12 at pH 12, except for

lactic acid which is from Martin et al.120 The aEu/Am are those of
Nilsson and Nash.118
R2
383
substituents on the triazinyl rings that minimize the

solubility of the protonated form of the extractant in
the aqueous phase.123
Unfortunately, the BTPs have limited hydrolytic and radiolytic stability. When octanol solutions
of the BTP 2,6-bis(5,6-n-propyl-1,2,4-3-yl)pyridine
(nPr-BTP), were investigated for hydrolytic stability,
it was found that DAm decreased by 80% only after
2 days of exposure to 1 M HNO3.124 Even greater
losses in extraction efficiency were encountered
in the presence of nitrous acid. A concentration
of 0.01 M nitrous acid in 1 M nitric acid caused a
decrease in DAm of 50% in only 2 h. Hydrolysis
appeared to be initiated by attack on the a-CH2
group of the n-propyl chain of the triazinyl ring,
and substitution with branched alkane chains greatly
decreased its rate. Hydrolysis and radiolysis products
of nPr-BTP included BTP derivatives that were
hydroxy, keto, or nitro substituted at the a-CH2 position of one or more propyl chains, and dealkylation
products.125 The isopropyl derivative (iPr-BTP) is
more resistant to hydrolysis than nPr-BTP.126
In radiolysis experiments, 1.8 103 M 2,6-di
(5,6-diethyl-1,2,4-triazin-3-yl)pyridine (tE-BTP) was
irradiated by Nilsson et al.127 in 1-hexanol solution in
the absence of an aqueous phase. Americium distribution ratios decreased with increasing absorbed
dose, falling below unity at <5 kGy for extraction
from 0.01 M HClO4. The authors proposed a mechanism for BTP degradation initiated by direct radiolysis of the alcoholic diluent:
RCH2 OH
! e
sol RCH2 OH
54
Dissociative electron capture would then dealkylate

the BTP, increasing its water solubility and decreasing distribution ratios for americium.
Nilsson et al.127 found that the addition of nitrobenzene to hexanol solutions of tE-BTP inhibited the
decrease in DAm and thus presumably the decrease in
BTP concentration with absorbed dose. This was
attributed to nitrobenzene scavenging of solvated
electrons as shown in eqn [55]128:

C6 H5 NO2 e
aq ! C6 H5 NO2
R1
R1
N
N
R1
N
N
R1
Figure 10 General structure of the bis(triazinyl)pyridines

(BTPs), soft-donor ligands used in the separation of the
minor actinides from the lanthanides.
k 3:8 1010 M1 s1
55
While these reactions adequately explain the situation in a pure organic phase, in the presence of an
aqueous phase, the reactions of the OH radical with
BTP must also be considered. This species, which
probably reacts by H atom abstraction, also reacts
quickly with nitrobenzene (3.9 109 M1 s1),12 and
384
thus, nitrobenzene should provide the same protection under those circumstances.
Kolarik129 and Ekberg et al.123 have reviewed the
history of the development of these and other heterocyclic nitrogen donor ligands with regard to attempts
to improve radiolytic and hydrolytic stability. The
alkyl groups attached to the triazinyl rings were
replaced with cyclohexyl rings, and the new molecules were designated BATPs, or annulated BTPs.130
These rings were also substituted with alkyl groups
to eliminate a-benzylic hydrogen atoms, thus mitigating H atom abstraction reactions from initiating
BTP decomposition at that vulnerable position. The
resulting compound, shown in Figure 11, is 2,6-bis
(5,5,8,8-tetramethyl-5,6,7,8-tetrahydrobenzo[1,2,4]
triazine-3-yl)pyridine, or BATP-1, or CyMe4-BTP.
This molecule provided both good hydrolytic
stability and a very high aAm/Eu 5600 for extractions from 0.5 M HNO3, using malonamide-modified
n-octanol diluent. The malonamide DMDOHEMA
was added to the solvent formulation to improve
actinide extraction kinetics, which can be slow with
BATPs alone. Unfortunately, an absorbed dose of
100 kGy resulted in 80% decomposition of BATP-1
in n-octanol.130 Similarly, Hill et al.126 reported that
DAm was reduced by 50% for 0.01 M solution of
BATP-1 in malonamide-modified n-octanol in contact with 1 M HNO3, after an absorbed g dose of
100 kGy. Once again, the radical-scavenger nitrobenzene reduced the decomposition of CyMe4-BTP,
with only 15% loss at the same absorbed dose.
The very high distribution ratios for americium
using the BATPs are actually a disadvantage due
to difficulties in stripping. Therefore, a second pyridine ring was introduced into these compounds
to moderate this high extraction efficiency.131 The
resulting derivative of CyMe4-BTP is 6,60 -bis
(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-benzo[1,2,4]
triazin-3-yl)[2,20 ]bipyridine, or CyMe4-BTBP, shown
in Figure 12.
A solvent formulation containing 0.01 M CyMe4BTBP/0.25 M DMDOHEMA in n-octanol was

found to provide a DAm 10 and aAm/Eu 120, for
extractions from 1 M HNO3. These parameters were
unchanged after a 2-month contact of the solvent
with 1 M HNO3, indicating adequate hydrolytic stability. Radiolytic stability studies of CyMe4-BTBP as
a ligand for use in the SANEX process were performed by Magnusson et al.132 The solvent formulation
was 0.015 M CyMe4-BTBP/0.25 M DMDOHEMA
in n-octanol, in contact with an equal volume of
americium-spiked 1 M HNO3, using either a- or
g-sources. These authors reported that g-irradiation
effects were more severe, resulting in a loss in about
35% of extraction efficiency within 100 kGy, in agreement with Hill et al.126 and 70% within 1200 kGy.
The loss in extraction efficiency was 40% greater
due to g-irradiation.
5.15.6.3 Dithiophosphinic Acid-Based
Processes
Comparatively little work has been done on the radiation stability of the dithiophosphinic acids, which
are also proposed for minor actinide separations.
These compounds tend toward oxidation upon storage, even in the absence of hydrolysis and radiolysis.
The products of the oxidation are the corresponding
phosphinic acids, resulting from the replacement of
S with O atoms.133
Modolo and Odoj134 studied bis(2,4,4-trimethylpentyl)dithiophosphinic acid (R2PSSH or Cyanex
301) radiolysis by irradiating both neat, purified
R2PSSH and 0.5 M R2PSSH in n-dodecane. Using
NMR, they found that for pure, neat R2PSSH, 80%
was decomposed at 1000 kGy, with the production
of 6% R2PSOH and 5% R2POOH. Numerous
N
N
N
N
N
N
N
N
Figure 11 The structure of 2,6-bis(5,5,8,8-tetramethyl5,6,7,8-tetrahydrobenzo[1,2,4]triazine-3-yl)pyridine

(BATP-1 or CyMe4-BTP) used in the separation of the
minor actinides from the lanthanides.
Figure 12 The structure of 6,60 -bis(5,5,8,8-tetramethyl5,6,7,8-tetrahydro-benzo[1,2,4]triazin-3-yl)[2,20 ]bipyridine,

or CyMe4-BTBP used in the separation of the minor
actinides from the lanthanides.
unidentified products were also detected. For

0.5 M R2PSSH in n-dodecane, irradiation over the
range 0700 kGy produced a steady increase in DEu,
due to the production of monothiophosphinic and
phosphinic acids. The pH of the aqueous phase was
controlled in these experiments, thus the effects on
distribution ratios cannot be accounted for by changing acidity. Following an absorbed dose of 700 kGy,
the DEu was nearly as high as DAm. The aAm/Eu
dropped from 1000 to 10 at pH 3.3.
Substitution of dithiophosphinic acid alkane
chains with aromatic groups apparently increases
radiation stability, but also necessitates the use of
aromatic diluents and neutral organophosphorus
compound synergists.135 The aromatic derivatives
bisphenyldithiophosphinic acid (Ph2PSSH) and bischlorophenyldithiophosphinic acid ((ClPh)2PSSH)
were investigated for radiation stability as 0.5 M solutions in toluene with and without a 0.25 M TBP
phase modifier by Modolo and Odoj.135 No aqueous
phase was present during these irradiations. Over the
range 100700 kGy, the DAm decreased slightly, while
DEu increased greatly resulting in a decreased separation factor. This interesting result was attributed to
the radiolysis products of TBP. When TBP was
added to irradiated, TBP-free dithiophosphinic acid
solutions, the decrease in aEu/Am was not as dramatic.
The difference in the effect of irradiation for the
extraction of the two metals suggests that the actinides and lanthanides form different complexes in
this mixed solvent system. Slope analysis was used
to confirm this finding.
In continued work, Modolo and Seekamp11 investigated the performance of (ClPh)2PSSH (Figure 13)
for both radiolytic and hydrolytic stability. This
Cl
S
P
SH
Cl
Figure 13 The structure of bis(chlorophenyl)
dithiophosphinic acid, used in the separation of the minor
actinides from the lanthanides.
385
compound has now been proposed for use in the

ALINA (ActinideIII-Lanthanide INtergroup separation from Acidic medium) solvent system. Hydrolysis
with 2 M HNO3 oxidized (ClPh)2PSSH to produce
(ClPh)2PO(SCH3),
and
(ClPh)2PS(OCH3),
(ClPh)2PO(OCH3), after 1-day exposure. These are
the same products created during radiolysis, except
that the abundances of the individual products differed. Hydrolytic degradation did not occur with
exposure to HCl, and was insignificant with exposure to H2SO4. Further, the addition of nitrous
acid scavengers such as hydrazine and urea mitigated
the hydrolysis of (ClPh)2PSSH exposed to 2 M HNO3.
When (ClPh)2PSSH was irradiated as a 0.5 M
solution in toluene, about 40% of the starting material was destroyed after the high absorbed dose of
2000 kGy, with only slightly more decomposed
when irradiated in the presence of 0.5 M HNO3.
This probably illustrates the radical scavenging protective function of the aromatic diluent. When
0.5 M (ClPh)2PSSH was irradiated as a component
of the ALINA solvent, also containing a 0.15 M trioctylphosphine oxide (TOPO) phase modifier in toluene, in the presence of 0.5 M HNO3, the distribution
ratios for the lanthanides remained nearly constant
while DAm decreased due to loss of the dithiophosphinic acid. This resulted in a rapidly decreasing
separation factor. However, the absorbed doses studied were as high and the aAm/Eu was still >10 at an
absorbed dose of 600 kGy.
5.15.7 Conclusions
The conditions under which the organic molecules
used in nuclear solvent extraction will be employed
are demanding. They will be subjected to both acid
hydrolysis and to reaction with the transient reactive
species produced by direct diluent radiolysis. However, in the presence of the aqueous phase, the reducing transient species are scavenged by acidity and
dissolved oxygen to produce secondary, less reactive
species, and the system can thus be thought of as
predominantly oxidizing with respect to organic compounds. The OH and NO3 radicals are especially
important transient species, with fast reaction kinetics.
Both are capable of electron transfer and hydrogen
atom abstraction reactions, and addition to unsaturated compounds or carbon-centered radicals.
Hydrogen atom abstraction or electron transfer
reactions may result in dealkylation by creating
carbon-centered radicals, initiating the reactions
386
that cause the rupture of CC bonds. Dealkylation

may produce new complexing agents such as HDBP
in the example of TBP radiolysis, which may be more
water soluble as in the example of BTP radiolysis.
CN and CO bonds are more susceptible, and
therefore the rupture of these bonds results in the
generation of amides from diamides and phosphinic
acids, and lighter phosphine oxides from CMPO.
This susceptibility has been used to design diamides
containing both linkages that allow the compound to
undergo radiolysis in a predictable way to produce
nondeleterious products.
Nitration of diluents and ligands must be expected
even in the absence of irradiation in the presence of
nitric acid. Nitration of aromatic functional groups
and alkane diluents occur due to reaction with the
nitrosonium ion when nitrous acid occurs in nitric
acid. Nitrous acid is the product of nitric acid oxidation reactions, and is also produced by radiolysis.
Nitration reactions also occur due to the addition of
nitrogen-centered radicals such as NO3 and NO2
with carbon-centered radicals, although direct radical addition reactions are probably not common in
the condensed acidic phase. Nitration of the diluent
results in the production of undesirable nitroparaffinic complexing agents, while the nitration of ligands
such as calixarenes may reduce extraction efficiency.
The use of very stable diluents, however, may actually increase radiolytic decomposition of the ligands.
The addition of scavengers, especially aromatic compounds and/or functional groups, may be used to
reduce ligand and diluent decomposition.
The radiolytic and hydrolytic degradation of solvent formulations is unavoidable in nuclear solvent
extraction. However, an understanding of the reaction mechanisms involved can allow of intelligent
ligand design or scavenger choices that improve the
efficiency and lifetime of solvent formulations. The
elucidation of these mechanisms requires the ability
to perform both steady-state and pulse-radiolysis
experiments.
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Geist, A.; Hill, C.; Modolo, G.; Foreman, M. R. S. t. J.
Magnusson, D.; Christiansen, B.; Malmbeck, R.; Glatz, J. P.
Radiochim. Acta 2009, 97, 497502.
Higgins, W. A.; Vogel, P. W.; Craig, E. G. J. Am. Chem.
Soc. 1955, 77, 18641866.
Modolo, G.; Odoj, R. J. Radioanalyt. Nucl. Chem. 1998,
228, 8388.
Modolo, G.; Odoj, R. Solv. Extract. Ion Exchange 1999,
17, 3353.
5.16
Spent Fuel as Waste Material
P. Carbol, D. H. Wegen, and T. Wiss

P. Fors
Vattenfall Power Consultant AB, Goteborg, Sweden
5.16.1
5.16.1.1
5.16.2
5.16.2.1
5.16.2.1.1
5.16.2.1.2
5.16.2.1.3
5.16.3
5.16.3.1
5.16.3.2
5.16.3.2.1
5.16.3.2.2
5.16.3.2.3
5.16.3.2.4
5.16.4
5.16.4.1
5.16.4.2
5.16.4.2.1
5.16.4.2.2
5.16.4.3
5.16.4.3.1
5.16.4.3.2
5.16.4.3.3
5.16.4.3.4
5.16.4.3.5
5.16.4.3.6
5.16.4.3.7
5.16.5
References
Introduction
Waste Handling Strategies
Fuel Evolution During Storage
Concentration of Radionuclides/Elements in Fuel
UO2 fuel
MOX fuel
Comparison of UO2 and MOX
Mechanical Stability of Spent Nuclear Fuel After Irradiation
Evaluation of the Temperature and Thermal Conductivity
Structural Stability of the Fuel
Radiation damage
Helium built-up
Oxidation of the fuel
Fuel cladding interaction/mechanical properties
Chemical Stability of Spent Nuclear Fuel After Irradiation
Distribution and Chemistry of the Fission Products
Storage Before Final Disposal
Wet storage of fuel in cooling ponds
Dry storage of fuel
Repository Storage
Groundwater composition
Corrosion of copper
Iron canister corrosion
Radiolysis
Corrosion of spent fuel under reducing conditions
Corrosion of fuel under oxidizing conditions
Instant release
Summary
Abbreviations
ANDRA
CANDU
CASTOR
dpa
EBS
FGR
FIAP
Agence Nationale Pour la Gestion des

Dechets Radioactifs (The French
National Radioactive Waste
Management Agency)
Canadian deuterium uranium reactor
Cask for storage and transport of
radioactive material
Dislocations per atom
Engineered barrier system
Fission gas release
Fraction of inventory in aqueous phase
GW
GWd/tHM
HBS
HLW
IRF
KBS-3
LWR
MBq
MOX
390
390
392
393
393
395
397
399
399
400
400
401
402
402
402
402
404
405
405
405
405
408
408
408
409
414
415
417
417
groundwater
Giga Watt day per tonne heavy metal
High burn-up structure
High-level waste
Instant release fraction
Karnavfallets Behandling och
Slutforvaring-3 (nuclear waste
treatment and disposal, report
number 3)
Light water reactor
Mega Becquerel
Mixed oxide fuel ((U,Pu)O2)
389
390
NAGRA
PWR
SHE
SKB
SNF
STP
tHM
XRD
Zircaloy
Nationale Genossenschaft fur die

Lagerung Radioaktiver Abfalle (Swiss
National Cooperative for the Disposal
of Radioactive Waste)
Standard hydrogen electrode (a
reference)
Svensk Karnbranslehantering AB
(Swedish Nuclear Fuel and Waste
Management Co.)
Spent nuclear fuel
Standard temperature and pressure
(273.15 K, 100 kPa)
tones of heavy metal
X-ray diffraction
Zirconium alloy, used as fuel pellet
cladding
5.16.1 Introduction
The moment a nuclear fuel assembly is taken out of
a commercial reactor, it becomes spent nuclear fuel
(SNF). At this point, two main options exist for
the future handling of the fuel. The decision on the
preferred option varies among the countries and
is based on whether the state considers the SNF as
waste or a resource.
The once-through cycle encompasses final storage
of the SNF in, for example, a deep underground
repository. The emplacement takes place after around
40 years of storage in cooling ponds or after 1 year of
water cooling at the nuclear power plant followed
by decades of dry storage in, for example, Castor
containers. In the closed fuel cycle, the fuel is reprocessed, that is, the uranium and plutonium (95 wt%)
is separated from the rest, leaving fission products
such as Tc, Mo, I, Cs, and lanthanides and heavy
actinides such as Np, Am, and Cm as waste.1 The
U and Pu are reused in new fuel assemblies, whereas
the waste is vitrified in glass and intermediately
stored at the power plant while waiting for a final
storage solution.
At the moment, most spent fuel is kept in storage at
nuclear power plants, at centralized storage sites, and
at reprocessing facilities. This fuel has been successfully and safely stored in wet and dry conditions for
several decades. As of the end of 2004, a total of 276 000
tonnes of heavy metal (tHM), that is, U and Pu, had
been discharged from nuclear power reactors in the
world, of which 90 000 tHM had been reprocessed2
(see Chapter 5.14, Spent Fuel Dissolution and

Reprocessing Processes).
The progress in finalizing spent fuel repositories
has been slow, forcing countries to enlarge their
intermediate storage capacity for spent fuel. Without
decisions on more permanent solutions, there could
be the prospect of continued storage for times of up to
and beyond one hundred years. Looking to the future,
the projection of the total amount of spent fuel to be
discharged from reactors would reach 445 000 tHM
in 2020.2 Consequently, the management of SNF will
be a key issue for strategic, economic, and safety
reasons for the future of nuclear power, and is an
issue that many states yet have to decide upon.3
This chapter focuses on SNF as waste material
and aims to highlight the changes of the most important fuel properties during storage. Many types of
SNF exist; however, as the vast majority of the SNF
kept in storage today is UO2 and MOX (mixed U and
Pu oxide) fuels, these fuel types are given most focus.
The main emphasis in this chapter, when it comes to
the type of repository, is laid on a deep granitic repository since this type is closest to a stepwise implementation (Sweden handled in their application to build
the repository, to the regulatory body, in 2011).
5.16.1.1
Waste Handling Strategies
The nuclear power-producing countries have undertaken different strategies for the final storage of their
SNF. Most countries have developed concepts in
which the fuel is emplaced in subsurface repositories
below the groundwater table. The selected geological formation varies among these countries, but the
main options are crystalline bedrock, clay, or salt.
These repository types are all expected to become
free of oxidants once they are closed. The United
States, on the other hand, have developed a dry
storage concept above the groundwater table. In this
concept, the fuel containers will be surrounded by
air. Table 1 summarizes the key features of some
different concepts. Depending on the type of repository, different engineered barrier systems (EBS)
have been developed. The following paragraphs
aim to give some details on the EBS in each repository concept.
The strategy in Belgium is to dispose the spent fuel
in a deep geological repository excavated in the Boom
clay formation. The main feature of EBS is the, socalled, supercontainer. In the supercontainer, containment is achieved by placing the canisters of spent fuel
assemblies in a carbon steel overpack and surrounding
Table 1
Characteristics of selected disposal systems for spent fuel repositories (main information from Bennett and Gens4)
Country
Waste
support/inner
container
Overpack
Buffer
material
Buffer pore
water pH
Host rock
Groundwater
Peak temperature
at outer surface of
overpack
Peak g-dose
rate at outer
surface of
overpack
Belgium
3 cm carbon steel
Boom clay
Reducing NaHCO3
waters, pH 8.5
Repository site search
from 2009
95 C
25 Gy h1
5 cm copper
Portland
cement
Bentonite
12.513.5
Canadaa
Cast iron and

sand
Cast iron
Finland
Cast iron
5 cm copper
Bentonite
78
7090 C
0.33 Gy h1
France
Cast iron
5.5 cm carbon
steel
None
Callo-Oxfordian
clay
90 C
<10 Gy h1
Sweden
Cast iron
5 cm copper
Bentonite
78
Fractured
crystalline
basement
Switzerland
Carbon steel
15 cm carbon
steel
Bentonite
78
Opalinus clay
United Kingdom
United Statesc,d
Cast iron
stainless steel,
316
5 cm copper
Nickelchromium
alloy, Alloy-22
Bentonite
Titanium drip
shields
78
5.512.0
depend on
evaporation
Not determined
Tuff, Yucca
Mountain
(reconsidering)
Brackish NaCl to
saline NaCaCl
waters. Eh 300 mV,
pH 7.58
Reducing CaNaCO3
waters, near-neutral
pH
Dilute NaHCO3
waters, brackish
NaCaCl waters
and saline CaNaCl
waters; reducing Eh
Reducing, nearneutral, NaCl
waters
Assumed reducing
Oxidizing
90 C
140160 Cb
0.035 Gy h1
Assumed <100 C
100200 C
Suggested repository concept.5

See Johnson and King.6
c
The Yucca Mountain Project came to an official halt in March 2010.
d
See refs. EPW,7 Carter and Pigford,8 Mon and Hua,9 Long and Ewing,10 and Rosenberg et al.11
In order to reduce the number of radionuclides, only the radionuclides that were present with substantial activity after 1 year, have a deviation of more than 40%, and have a half-life longer than
1 year, are listed. Positive values indicate that radionuclides are produced in larger proportion in MOX than in UO2 fuel.
b
Canadian shield
granite,
Ordovician
sedimentary
rock basins
Fractured
crystalline
basement
391
392
the overpack with a Portland cement concrete buffer

and an outer stainless steel envelope.
Both Finland and Sweden are moving toward geological disposal of SNF using the, so-called, KBS-3
(Karnavfallets Behandling och Slutforvaring-3 (nuclear
waste treatment and disposal, report number 3)) concept. In this concept, the spent fuel will be disposed
of at a depth of about 500 m in crystalline bedrock.
The main barrier to radionuclide release is a cylindrical copper-lined cast-iron canister.4 The canister
is surrounded by a bentonite clay buffer, which is
designed to provide mechanical protection and to
limit the access of groundwater, living microbes, and
corrosive substances to their surfaces (see Chapter
5.17, Waste Containers). Reducing conditions are
expected to prevail inside the canister due to the
anoxic corrosion, both before and after water intrusion, of the cast-iron inserts.
A number of concepts have been developed, by
Nuclear Waste Management Organization, in Canada.
The present is based on the storage of the SNF in a
deep rock formation and shows great similarities with
the KBS-3 concept. The EBS is a copper-lined castiron container surrounded by a bentonite clay buffer.
However, the decision taken at a governmental level
is that, although a technically safe disposal could be
achieved, the level of public acceptance is insufficient
to allow the proponents to progress to a site selection
stage (2008).
The French National Radioactive Waste Management Agency, ANDRA (Agence Nationale Pour la
Gestion des Dechets Radioactifs), is investigating
reversible and irreversible radioactive waste storage/
geological disposal in deep granite and clay formations. The French concepts for spent fuel disposal
foresees carbon steel as the first choice material for
the overpack because under the relevant geochemical
conditions, it is less prone to localized corrosion than
materials that are passivated (e.g., stainless steels,
nickel-based alloys).4 The overpack will be surrounded
by a bentonite clay buffer. The standpoint in France,
in 2010, was that all French SNF will be reprocessed.
In Switzerland, concept studies (by NAGRA,
Nationale Genossenschaft fur die Lagerung Radioaktiver Abfalle (Swiss National Cooperative for the Disposal of Radioactive Waste)) have been performed for
both crystalline12 and clay options.13,14 An Opalinus
clay formation in northern Switzerland has been chosen as the first priority option. The reference design
concept for spent fuel canisters involves a cast carbon
steel body, with a machined central square channel
fitted with cross-plates to permit emplacement of
different types of fuel assemblies. Carbon steel was

selected as a canister material because there is long
industrial experience with its fabrication, it has high
strength, and it has a relatively low and predictable
corrosion rate in anoxic environments. When emplaced
in the repository, the SNF containers would be surrounded by a bentonite clay backfill.4
In United Kingdom, the responsibility for
radioactive waste disposal is with the Nuclear Decommissioning Authority. Until now, 2011, the working
model is the UK reference high-level waste, HLW/
SNF geological repository concept an adapted KBS3 concept in terms of canister length, diameter, and
structure of the insert to handle HLW and spent fuel
from the UKs advanced gas cooled reactors and
pressurized water reactor (PWR).
The United States has started to construct a
repository in the Yucca Mountain. This repository
is built within a mountain ridge of volcanic tuff in
the Nevada Desert. The rock in the ridge is unsaturated, that is, not all fractures and pores are filled
with water. As a result, air can move freely through
interconnected, dry fractures. This keeps the conditions in the repository oxidized. The spent fuel containers consist of an inner Type 316 stainless steel
vessel and an outer highly corrosion-resistant cylindrical barrier composed of an nickel based-alloy
(Alloy 22). Titanium drip shields have been constructed to keep the containers dry from dripping
water. An option discussed is to pack the waste containers narrow to increase the surrounding rock temperature above 100 C to vaporize any water in the
vicinity of the repository and make it migrate outwards.8,9 The Yucca Mountain project was, due to a
political decision, halted in March 2010. However,
the termination of the project has been questioned by
a large number of congress members and a legal action
regarding the withdrawal of its repository license
application is to be resolved by the U.S. Court of
Appeals and the Nuclear Regulatory Commission.
5.16.2 Fuel Evolution During Storage

This section discusses the physical changes of
SNF in terms of radioactive decay and temperature.
The timeframe of these changes stretches beyond
10 000 years into the far future. The long-term
behavior of the SNF will be dependent on its irradiation history. However, this chapter discusses the
changes as they evolve for a general fuel, that is, a
fuel without a history of extreme power excursions,
393
106 years. 239Pu is created by neutron capture reactions

in 238U followed by two b-decays. The 239Pu itself is
susceptible to further neutron capture that leads to the
formation of 240Pu. Due to the ingrowth of 239Pu and
240
Pu during irradiation, plutonium is the element
with the second highest concentration in the SNF.
The concentration of elements such as Pb, Bi, Th,
Pa, and Np increases with time since they are longlived, or stable, daughters in the decay chains of more
short-lived heavier actinides. The helium concentration also increases with time as He is formed through
all a-decays.
Americium is, on this timescale, an intermediate element whose concentration during the initial 100 years increases due to ingrowth from the
b-decaying 241Pu and after this period decreases
slowly due to decay of 243Am (t1/2 7380 to 245Cm
(t1/2 8502 years) but also due to the presence of smaller amounts of 243Am (t1/2 7380 years) in the spent
fuel. The absence of (with cutoff at 1 mg/tHM)
Po, At, Rn, Fr, and Ac is a consequence of the short
half-life of the isotopes of these elements.
Figure 2 shows the concentration of fission products in the same UO2 fuel as exemplified above, but
on a shorter timescale.
ramping (described in Chapter 2.19, Fuel Performance of Light Water Reactors (Uranium Oxide
and MOX)), or extreme burn-up etc.
5.16.2.1 Concentration of
Radionuclides/Elements in Fuel
In performance assessments of nuclear repositories, the
boundary conditions are governed by the radiotoxicological impact of individually released radionuclides
rather than by the amount of released elements. It
is therefore important to understand the amounts,
radioactivity, and spatial distribution of the radionuclides in order to make long-term predictions of the
SNF behavior in a deep underground repository.
5.16.2.1.1 UO2 fuel
After irradiation, the UO2-fuel still contains around

95 wt% UO2. The remaining 5 wt% are mainly composed of heavier actinides (Np, Pu, Am, and Cm) and
fission products. In Figure 1, the concentration of the
selected elements in a typical spent UO2 fuel is shown
for five different times after the end of irradiation.
Due to the long half-life of 238U (4.699 109 years),
the uranium concentration remains constant even after
1 000 000
100 000
Concentration (g per tHM)
10 000
1000
100
10
1
0.1
0.01
0.001
He
Tl
Pb Bi
Po
At
Discharge
Rn
Fr Ra Ac Th
Elements
1
100
10 000
Pa
Np Pu Am Cm
1 000 000
Figure 1 Elemental composition of actinides and decay daughters in a UO2 fuel with an initial enrichment of 4 wt%
235
U irradiated for five cycles in a PWR to a burn-up of 40 GWd/tHM as a function of time (years) after discharge from reactor.
394
10 000
Discharge
1000
10
1000
Concentration (g per tHM)
100
10
0.1
Xe
Cs
Ba
La
Ce
Pr
Nd
Pm
Sm
Eu
Gd
Tb
Dy
Ho
Er
0.001
H
He
Li
Be
C
Ge
As
Se
Br
Kr
Rb
Sr
Y
Zr
Nb
Mo
Tc
Ru
Rh
Pd
Ag
Cd
In
Sn
Sb
Te
0.01
Elements
Figure 2 Elemental composition of fission products in a UO2 fuel with a burn-up of 40 GWd/tHM at different cooling
times (discharge from reactor, 10, and 1000 years).
The two humps of the two fission fragments

created after the initial 235U and later 239Pu fissions,
in the element intervals RbRh and XeNd, are
easily recognizable. The majority of the fission products decay by b-emission. The majority of fission
products have, in comparison to actinides, relatively
short half-lives (<10 years) that lead to smaller
change in their concentration on the timescale 10
1000 years. Nevertheless, some long-lived fission
products (t1/2 > 104 years) can be seen, for example,
79
Se (3.27 105 years), 93Zr (1.53 106 years), 94Nb
(2.03 104 years), 99Tc (2.11 105 years), 107Pd
(6.5 106 years), 126Sn (2.3 105 years), 129I (1.57 107
years), and 135Cs (2.3 106 years).
The drop in hydrogen concentration is related to the
decay of 3H (tritium, t1/2 12.346 years). The decrease of
strontium is due to the significant amount of short-lived
90
Sr (t1/2 28.503 years). Niobium has only one stable
isotope, 93Nb, and this is shielded by the long-lived
radionuclide 93Zr (t1/2 1.53 106 years). A shielded
radionuclide is a radionuclide that is, on the isobar,
preceded by a long-lived mother. As a result, the concentration of Nb, which initially is dominated by its
short-lived isotope 95Nb (t1/2 35.2 days), decreases four
orders of magnitude during the initial 10 years. As 93Zr
decays, the concentration of 93Nb increases, which
leads to a total increase of the niobium concentration.
The decrease in the cesium concentration and increase
of barium are due to 137Cs (t1/2 30.104 years) decay into

Ba, which within 153 s decays to stable 137Ba. The
stepwise decrease in promethium concentration is a
result of the single, relatively long-lived, Pm radionuclide 147Pm (t1/2 2.62 years).
Based on Figures 1 and 2, it can be concluded that
(i) after an initial period of 1000 years, only minor
changes in the elemental concentrations occur in the
spent UO2 fuel, and (ii) the changes occur at a concentration range, which is a fraction of the total mass of
U. Accordingly, the chemical composition of the fuel
will only change within a narrow concentration range
on repository timescales. Despite that, the radioactivity emitted from the fuel changes orders of magnitudes
over the repository timescale. Figure 3 shows the total
number of a- and b-decays in the same fuel.
a-particles can only be emitted by quantum tunneling out of the nucleus. Since the probabilities for
tunneling are extremely small and decrease with the
energy of the a-particles, low-energy a-emitters are
generally much more long-lived than b(g)-emitters.15
For the SNF, this results in a gradual change in the
radiation field.
Fresh SNF emits a very intense b(g)-field due
to the decay of short-lived radionuclides, such as
85
Kr, 89Sr, 90Sr90Y, 91Y, 95Zr95Nb, 106Ru106Rh,
125
Sb, 134Cs, 137Cs137mBa, 144Ce144Pr, 147Pm, and
154,155
Eu. However, already after 300500 years in the
137m
395
1.0E + 19
1.0E + 18
tot
Radioactivity (Bq per tHM)
1.0E + 17
1.0E + 16
tot
1.0E + 15
1.0E + 14
1.0E + 13
1.0E + 12
charge
1.0E + 11
1.0E + 10
0.001
0.01
0.1
10
100
1000
10 000
100 000 1 000 000
Time (years)
Figure 3 Radioactivity, divided in total number of a- and b-emissions, in UO2 fuel with a burn-up of 40 GWd/tHM as a
function of cooling time. The lower line indicates the a-activity in the UO2 fuel before irradiation in the pressurized
water reactor.
repository, most of the b(g)-emitters have decayed

and a-radiation will dominate the energy deposition
to the surrounding material. The tail of the total
b-activity at cooling times longer than 1000 years is
due to the long-lived fission products: 79Se, 93Zr,
94
Nb, 99Tc, 107Pd, 126Sn, 129I, 135Cs, and b-decay in
the decay chains of 233,236,238U. The initial a-activity
mainly originates from the decay of 242,244Cm, 238Pu,
and 241Am, whereas the late decrease is caused by the
decay of long-lived a-emitters such as 239,240Pu and
243
Am (see Figure 4).
During the first years after irradiation, the decay
of curium completely dominates the a-field. The
sharp ingrowth of 241Am during the first 100 years
originates in decay of 241Pu (t1/2 15.16 years) which is
a daughter of the long-lived 245Cm (t1/2 8.5 103
years). In the time period between 2000 and
200 000 years, the a-field is exclusively dominated
by the decay of 239Pu and 240Pu.
The activity of the most intensive b-decaying radionuclides is given in Figures 5 and 6. The left part of the
graph shows the radionuclides that mainly contribute
to the b-activity at discharge from the reactor such as
(in declining order) 140La140Ba, 141Ce, 103Ru,
95
Zr95Nb, 143Pr, 103mRh, 144Pr144Ce, 91Y, 89Sr, and
106
Ru106Rh. Many of these radionuclides have short
half-lives and decay within the time period 15 years.
The b-activity from decay of 137Cs137mBa, 90Sr90Y,
147
Pm, 134Cs, 106Ru106Rh, 85Kr, 144Ce144Pr, 154Eu, and
125
Sb dominates the fuel-cooling period, 540 years,
in a wet or dry cask storage. During the period

40400 years, mainly the radionuclides 137Cs137mBa,
90
Sr90Y, 85Kr, 151Sm, and 154Eu contribute to
the b-field. At longer time periods, >400 years, the
main b-activity comes from the long-lived radionuclides 99Tc, 135Cs, 107Pd, 126Sb, 129I, and 79Se.
Observing the intermediate- and the long-lived
radionuclides in Figures 5 and 6 explains the shape
of the total b-decay curve in Figure 3.
5.16.2.1.2 MOX fuel
MOX fuel is a blend of around 93 wt% natural,

reprocessed, or depleted UO2 and PuO2, and is an
alternative to low-enriched UO2 for use in light water
reactors. It can be fabricated through different processes yielding slightly different fuel types and properties. The fabrication process and fuel properties,
such as the microstructure and fission gas release
(FGR), are given by Fisher et al.16 and also discussed
in Chapter 2.15, Uranium Oxide and MOX
Production and Chapter 2.20, Fission Product
Chemistry in Oxide Fuels.
Depending on the production technique, MOX fuel
often obtains a duplex structure with the plutonium
concentrated in Pu-rich agglomerates. This is, for
example, the case for the optimized comilling process
(OCOM) where Pu agglomerates up to 200 mm in size
are dispersed in a matrix of natural UO2.17
The Pu content in the agglomerates often ranges
up to 30 wt%. During irradiation to a normal burn-up,
396
1.0E + 16
233U
234U
1.0E + 15
236U
a-activity (Bq per tHM)
238U
237Np
1.0E + 14
238Pu
239Pu
240Pu
1.0E + 13
241Pu
242Pu
241Am
1.0E + 12
243Am
242Cm
243Cm
1.0E + 11
244Cm
U start
1.0E + 10
0.001
0.01
0.1
10
100
1000
10 000
100 000 1 000 000
Time (year)
Figure 4 The decay of actinides in UO2 fuel with a burn-up of 40 GWd/tHM as a function of cooling time. The dashed
line, U start, indicates the a-activity in the UO2 before irradiation.
1.0E + 17
79Se
85Kr
87Rb
1.0E + 16
89Sr
90Sr
b-activity (Bq per tHM)
90Y
91Y
1.0E + 15
95Zr
95Nb
99Tc
1.0E + 14
103Ru
106Ru
103mRh
1.0E + 13
106Rh
107Pd
110Ag
1.0E + 12
110mAg
126Sn
125Sb
1.0E + 11
0.001
126Sb
0.01
0.1
10
100
Time (years)
1000
10 000
100 000 1 000 000
126mSb
Figure 5 The decay of lighter fission products (mass number 79126, the heavier mass numbers are shown in Figure 6)
in UO2 fuel with a burn-up of 40 GWd/tHM as a function of cooling time. In order to reduce the number of radionuclides
from 613 to 45, only these radionuclides that were present at the end on the irradiation in a concentration
>1 1016 Bq/tHM and still existed after 1 year are shown.
around 75% of the fissions occur in the Pu-rich

agglomerates (calculation based on data from Walker
et al.18). This creates an uneven fission product distribution in the fuel. The high local burn-up in the
agglomerates, up to 270 GWd/tHM,18 results in a

microstructure of fine grains and large pores with
a diameter of several microns,19 which is similar to
the high burn-up structure (HBS) formed at the
397
1.0E + 17
125mTe
127Te
127mTe
129Te
1.0E + 16
129mTe
129I
b-activity (Bq per tHM)
134Cs
1.0E + 15
135Cs
137Cs
137mBa
140Ba
1.0E + 14
140La
141Ce
144Ce
143Pr
1.0E + 13
144Pr
147Pm
148Pm
1.0E + 12
148mPm
151Sm
154Eu
1.0E + 11
0.001
155Eu
0.01
0.1
10
100
Time (years)
1000
10 000
100 000 1 000 000
Figure 6 The decay of heavier fission products (mass number 125155, complementary to Figure 5) in UO2 fuel with a
burn-up of 40 GWd/tHM as a function of cooling time. In order to reduce the number of radionuclides from 613 to 43, only
these radionuclides that were present at the end on the irradiation in a concentration >1 1016 Bq/tHM and still existed
after 1 year are shown.
periphery (rim) of UO2 pellets with local burn-up

above 6080 GWd/tHM.17 The plutonium concentration in the MOX fuel is typically reduced by 25%
during irradiation, as an example a 5.00 wt% Pu
OCOM MOX fuel has been measured to contain
3.68 wt% Pu after irradiation.17
This heterogeneity is maintained during the
irradiation and gives a spent fuel with different characteristics such as local intensive radiating agglomerates in a relatively low-radiating UO2 matrix, a
subgrain disintegration (<1 mm), and different chemical composition (less uranium, larger fraction of
fission products, plutonium, and higher actinides)
compared with the UO2 matrix.
5.16.2.1.3 Comparison of UO2 and MOX
A simulation of MOX-fuel irradiation in a PWR

using the same irradiation parameters as for the
UO2 fuel in Section 5.16.2.1.1 shows that burned
MOX fuel contains significantly more long-lived
radionuclides such as 107Pd, 126Sn126Sb, and 135Cs
(see Table 2). On the other hand, significantly less
long-lived 87Rb is formed in MOX than in UO2 fuel.
This is a consequence of the slightly shifted fission
yield curve toward higher mass for fission of 239Pu in

comparison to 235U.
On shorter timescales, <1000 years, the dose contribution due to decay of 106Ru106Rh, 125Sb, 151Sm,
and 154,155Eu is more prominent in MOX fuel than in
UO2 fuel, whereas 85Kr and 90Sr90Y are found
in greater quantities in the UO2. Based on Table 2,
it can be concluded that recycled MOX fuel gives a
moderately different composition of both long- and
short-lived radionuclides, and that the difference
reflects the mass shift in fission yield of the two fissile
radionuclides.
An increased a-activity after irradiation of MOX
fuel in comparison to UO2 is clearly observable
if Figure 7 is compared with Figure 4. The main
reason is the build-up of larger amounts of heavier
actinides (mainly Am and Cm) due to the initial
presence of Pu in the MOX fuel.
In general, the same a-emitting radioisotopes
are created but at an elevated concentration in the
MOX fuel. The consequence of the larger actinide content is a more intensive a-radiation field,
which leads to a higher fuel temperature and for
repository conditions, a more intense a-radiolysis
398
(see Section 5.16.4.3.4) upon contact with groundwater. A comparison between the two kinds of fuels, fresh
and after irradiation at different cooling times, up to
100 000 years, shows that the total a-activity in the
Table 2
Comparison of amount radioactivity produced
in a MOX fuel compared to a UO2 fuel under the same
irradiation conditions (PWR, 5.0 wt% recycled Pu, 40 GWd/
tHM, and five annual cycles) after 1 year of cooling time
Radionuclides
(MOXUO2)/UO2 (%)
85
41
46
50
70
128
82
88
58
112
60
130
Kr
Rb
90
Sr90Y
106
Ru106Rh
107
Pd
125
Sb
126
Sn126Sb
135
Cs
151
Sm
154
Eu
155
Eu
87
In order to reduce the number of radionuclides, only these

radionuclides that were present with substantial activity after
1 year disclose a deviation of more than 40% and have a half-life
longer than 1 year. Positive values show radionuclides produced in
larger proportion in MOX than in UO2 fuel.
MOX is nearly 7000 times larger than the a-activity in

the UO2 before being loaded into the reactor
(Table 3). On the other hand, once the fuels are
discharged from the reactor, the difference is only a
factor of 6 having decreased by a factor of 1000.
The difference in power output between the
two fuel types remains almost constant with time.
Ingrowth of long-lived radionuclides such as 233U,
236
U, and 237Np in the irradiated MOX fuel restrains
the power output to decrease to levels comparable to
those in unirradiated UO2, even on geological timescales. The higher power output leads to higher temperatures in the repository and as a consequence
higher reaction kinetics of all repository-relevant
geochemical reactions of minerals. Reactions that
under low temperatures are kinetically hindered
might become dominating under hot repository conditions as temperatures in the range of 70100 C are
expected to prevail in most repositories over substantial timescales (Table 1).
It can be concluded that the fission product composition after irradiation of MOX and UO2 fuels is
similar. The plutonium content in the MOX will be
nearly 30% lower after irradiation than initially introduced in the reactor. However, the spent MOX fuel
1.0E + 17
1.0E + 16
233U
1.0E + 15
234U
236U
-activity (Bq per tHM)
1.0E + 14
238U
237Np
238Pu
1.0E + 13
239Pu
240Pu
1.0E + 12
241Pu
242Pu
1.0E + 11
241Am
243Am
1.0E + 10
242Cm
243Cm
1.0E + 09
244Cm
MOX start
1.0E + 08
1.0E + 07
0.001
0.01
0.1
10
100
1000
10 000
100 000 1 000 000
Time (years)
Figure 7 The decay of actinides in MOX fuel with a burn-up of 40 GWd/tHM (PWR, five irradiation cycles) as a
function of cooling time. The dashed line indicates the a-activity in unirradiated MOX fuel.
399
Table 3
Comparison of total a-activity in fresh UO2 and MOX fuel and after irradiation (PWR, five irradiation cycles) to a
burn-up of 40 GWd/tHM and after different cooling times
Time
a-activity in UO2 (Bq/tHM)
a-activity in MOX (Bq/tHM)
MOX/UO2
Charge into reactor

Discharge from reactor
Cooling time of 1000 years
Cooling time of 10 000 years
Cooling time of 100 000 years
8.6 1010
2.7 1015
7.0 1013
1.7 1013
4.0 1012
5.8 1014
1.7 1016
3.1 1014
6.6 1013
1.4 1012
6823
6.3
4.5
3.8
2.9
will contain considerably larger amounts of heavier

actinides than a corresponding spent UO2 fuel. This
will result in a hotter fuel, which needs longer time in
the final repository to decay to background level.
It should be noticed that when radionuclides
decay other elements are created. As most of the
fission products decay by b(g)-decay, they form an
element with one proton number higher. For example, 137Cs decays to 137mBa which within 153 s decays
to 137Ba, a stable nuclide. With this transformation of
one element into another, the chemical composition
changes which affects the chemical stability of the
fuel. In the example given above, cesium is more
soluble in a granitic groundwater than barium,
which can form insoluble BaCO3. This situation is
more accentuated when long-lived daughters are
part of a decay chain, for example, the chain: 244Cm
(t1/2 18.1 years)240Pu (t1/2 6.537 103 years)236U (t1/2
2.34 107 years)232Th (t1/2 1.41 1010 years). This
issue is further discussed in Section 5.16.4.
5.16.3 Mechanical Stability of Spent

Nuclear Fuel After Irradiation
This section discusses the changes of inherent
properties affecting the mechanical stability of the
SNF. Examples of such properties are He gas buildup, dislocations, grain disintegration, hardness, heat
capacity, swelling, and microstructural changes of the
spent fuel matrix. The changes are discussed with
focus on the SNF alone, that is, without interaction with the surrounding environment. Additional
information can be found in Chapter 1.03, RadiationInduced Effects on Microstructure; Chapter 1.05,
Radiation-Induced Effects on Material Properties of
Ceramics (Mechanical and Dimensional); Chapter
1.06, The Effects of Helium in Irradiated Structural
Alloys; Chapter 2.17, Thermal Properties of Irradiated UO2 and MOX; Chapter 2.18, Radiation
Effects in UO2; and Chapter 2.20, Fission Product
Chemistry in Oxide Fuels.
5.16.3.1 Evaluation of the Temperature and

Thermal Conductivity
The temperature in a granitic spent fuel repository will be considerably above the temperature
in undisturbed bedrock (15 C at 500 m depth).20
The increased bedrock temperature is a consequence
of radioactive decay of radionuclides in the fuel
(Figure 8) and heat transfer through container walls.
In the figure, it can be observed that both fuel types
release about the same amount of thermal power
right after removal from the reactor since they contain roughly the same amount of b-activity and as the
b-activity dominates over a-activity by three orders
of magnitude (Figure 3), despite the fact that an
average a-decay emits more or less one order of magnitude more energy per decay than b-decay.
With time, MOX fuel gives of three to four times
more thermal power due to its higher content of
actinides, hence a-decaying elements (Table 3).
The spatial distribution of the canisters in a granitic
repository is laid out so that the temperature in the
outer bentonite layer, surrounding a container, is
lower than 90 C (Table 1).
The thermal conductivity of oxide fuels deteriorates very rapidly at the beginning of irradiation,
mostly due to formation of radiation damage, and
then with increased burn-up by the formation of
a solid solution of UO2 with the oxides of Zr, Sr,
the rare earths, and other fission products in lower
concentrations. This effect is counterbalanced, but
not quenched, by the production of metallic fission
products inclusions precipitated within the UO2 and
grain boundaries.21
At discharge of a LWR fuel with a burn-up of
40 GWd/tHM and a temperature of 500 K, the thermal conductivity has decreased by 50%, from
5.8 W m1 K1 as in fresh fuel to 3.0 W m1 K1.22
The lower the temperature of the fuel, the higher the
degradation of the thermal conductivity. However,
the total thermal power decreases with time, and in
wet storage conditions, the fuel temperature will not
400
1.0E + 07
MOX
MOX before irradiation
1.0E + 06
UO2 fuel
UO2 before irradiation
Thermal power, Ac + FP (W per tHM)
1.0E + 05
1.0E + 04
1.0E + 03
1.0E + 02
1.0E + 01
1.0E + 00
1.0E - 01
1.0E - 02
0.001
0.01
0.1
10
100
1000
10 000
100 000 1 000 000
Time (years)
Figure 8 The thermal power production in irradiated UO2 and MOX fuel with a similar burn-up of 40 GWd/tHM (PWR,
five irradiation cycles) as a function of cooling time. The points indicate the thermal power in unirradiated MOX and UO2.
exceed 200 C (which would also be the limit in dry

conditions after a few decades23).
5.16.3.2
Structural Stability of the Fuel
The stability of the fuel in the repository, as long it

is not exposed to water, is mainly governed by its
microstructural and chemical evolution due to radiation damage, helium build-up, and oxygen potential variation. In the event of exposure of SNF to
groundwater in a final nuclear fuel repository,
the possible preferential dissolution of grain boundaries rather than matrix a process driven by the
penetration rate of water could cause a rapid
increase of the fuel wet surface area, and therefore
increase the fraction of inventory becoming available for fast release. While this has a direct impact
on the mobilization of radionuclides, the water penetration, additionally, weakens the cohesion between
UO2 grains which leads to degradation of the overall mechanical stability of the fuel pellet. Furthermore, an increase of the wetted surface area
increases the amount of oxidants produced through
a-radiolysis.24
5.16.3.2.1 Radiation damage
Defects created by displacement cascades are extensively recombined in UO2 and PuO2; hence, no
matrix amorphization could be detected in those
materials.25,26 Nevertheless, lattice parameter increase
caused by a-radiation damage that displaces atoms in
the lattice, and leading to microscopic swelling was
measured. In polycrystalline UO2, the lattice parameter reaches saturation (0.4%, which corresponds to
1% volume increase) for a dose of 1 dpa (displacements per atom) because of recombination of defects
created by the displacement cascades.27
One of the more spectacular evolutions during
the irradiation in reactor of the light water reactor,
LWR oxide fuels is the eventual formation of the
high burn-up structure, HBS. In the periphery region
of the pellet, plutonium builds up more than in the
central region because of the neutron resonant capture cross-section of 238U; as a consequence, more
plutonium burns up in the rim region. Finally, the
local burn-up at the rim is a few times higher than at
the center of the pellet. Therefore, the rim structure
is associated with this higher burn-up. This restructuring is characterized by the existence of highly
dense small subgrains whose size is 200 nm and the

accumulation of small pores with an average size of
around 1 mm.28 This restructuring could influence
the fuel performance including, for example, fission
gas release (FGR), fuel temperature, hardness, and
swelling during irradiation, and moreover, would be
the first exposed layer in case of water contacting.
The specificity of the HBS region has therefore to be
taken into account in any failure scenario. For more
detailed information on the HBS region, see Chapter
1.03, Radiation-Induced Effects on Microstructure and Chapter 1.05, Radiation-Induced Effects
on Material Properties of Ceramics (Mechanical
and Dimensional).
5.16.3.2.2 Helium built-up
Helium is continuously produced in the spent fuel

due to a-decay of actinides. An example of the accumulated amount of He produced in a UO2 and MOX
fuel rod during storage is shown in Figure 9. The
initial content of 35 wt% Pu in MOX fuel gives a
higher He accumulation in the fuel rod.
In storage condition, it is of prime importance to
assess whether the fuel can retain the radiogenic
helium in order to predict its long-term mechanical
stability (see also Chapter 1.06, The Effects of
Helium in Irradiated Structural Alloys). Indeed,
accumulation of gas which ultimately creates helium
bubble and of a-damage defects, evidenced by lattice
parameter increase, might cause swelling of the fuel

and therefore its early failure. Interactions between
the radiogenic helium formation and the defects
induced by a-particles and recoil nucleus need
to be understood to predict the evolution of the
system.
The helium behavior becomes even more relevant
for the MOX fuel because of the higher production of
this rare gas due to the higher actinide content.
Two major parameters have to be considered as
regarding the helium behavior: its solubility and diffusion coefficient. These two parameters need to be
evaluated from a thermodynamical point of view and
extrapolated to their apparent values (considering
the fuel as a nonperfect crystal, that is, containing
defects, hence trapping sites for the gas).
In an early work, Rufeh et al.29 have determined a He solubility in UO2 of 6.7 104 cm3
(STP) gUO2 1 atm1. The solubility in a UO2 monocrystal is approximately one order of magnitude lower
(2.4 105 cm3 (STP) gUO2 1 atm1).30 Recent work
have been carried out to determine the solubility in
conditions of high pressure confirming that the
Henry law applies for the helium solubility in UO2.
The reported value for the solubility is 5.1 104
104 105 cm3 gUO2 1 for samples infused at a
pressure of 1 kbar and a temperature of 1570 K.31
Work is ongoing to assess the solubility in nonstoichiometric UO2.
12 000
UO2
MOX
Helium production (cm3 STP/rod)
10 000
8000
6000
4000
2000
0
1
10
100
401
1000
Time (years)
10 000
100 000
1 000 000
Figure 9 Accumulated volume of helium produced through a-decay of actinides in UO2 and MOX, inside a PWR
fuel rod, with a burn-up of 40 GWd/tHM (PWR, five irradiation cycles) as a function of cooling time.
402
The higher dissolution of He in polycrystalline

UO2 in comparison to single crystal is attributed to
the larger amount of defects, particularly vacancies,
able to accumulate He. Through thermal and nonthermal diffusion, He accumulates in gas bubbles
inside the matrix and at grain boundaries. A part of
the He is released to the free volume of the fuel
rod with the consequence of increased internal rod
pressure and thereby risk for cladding creep failure.
The accumulation of He bubbles, especially at grain
boundaries, can eventually result in loss of cohesion
of the grains.32
5.16.3.2.3 Oxidation of the fuel
The chemical composition change due to decay has

to be accounted for, for its possible implication on
the oxygen potential change of the fuel. The oxygen
content in a UO2 fuel after discharge from reactor is,
in general, more or less stoichiometric, the O/U ratio
is very close to 2. This ratio has a major impact on the
radionuclide mobility in the fuel as any deviation
from stoichiometry increases the diffusion coefficient
of cation vacancies (O/U > 2) or anion vacancies
(O/U < 2) in the matrix. Additionally, the thermal
conductivity decreases when the stoichiometry
changes from 2.00.
Once the fuel is removed from the reactor, it exhibits
intensive b-decay during the initial 300 years (Figure 3)
dominated by the b-decay of 137Cs ! 137mBa,
90
Sr ! 90Zr, and 241Pu ! 241Am. The b-decay results
in formation of elements of different valence state
than the parent element and could eventually change
the oxidation state of the spent fuel by modifying the
overall oxygen ratio.
Nevertheless, measurements of high burn-up UO2
fuel33 showed that the oxygen potential in the fuel
appears to be controlled by molybdenum (Mo/
MoO2), an abundant fission product in spent fuel
(see Figure 2). Even though the composition of the
spent fuel and the temperature change during the
initial 300 years of storage, the oxygen potential
seems to be stabilized at approximately 450 kJ
mol1, independently of burn-up, and is controlled
by the oxidation of Mo.34
5.16.3.2.4 Fuel cladding interaction/
mechanical properties
Once the fuel is out-of-pile and the temperature has

decreased below 800 K, the fuel-cladding (Zircaloy)
interaction of fission products (Cs, Te, and I) is
minimal.21 Due to the a-damage, the mechanical
properties of the fuel might evolve depending on
the temperature and recovery of the defect or their

evolution toward extended defects. The associated
swelling due to the damage and gas production
could also cause an increase in the stresses in the
spent fuel.
The evolution of the hardness of UO2 due to
a-damage has been studied by monitoring the
Vickers hardness evolution as function of the damage
of UO2 samples doped with intensive a-emitters
(238Pu). Two types of UO2 samples have been used,
doped either with 8.8 wt% 238Pu ((U0.9Pu0.1)O2) or
with 0.088 wt% 238Pu (U0.999Pu0.001)O2).
Figure 10 shows the results of hardness measurements as a function of time for the two a-doped
materials. Each data point represents the average
of five indentations. The values measured for
(U0.9Pu0.1)O2 increased quite rapidly, and after 2
months appeared to have reached a saturation value,
corresponding to an increase of 20% in hardness. Even after 2 years of storage the values for
(U0.999Pu0.001)O2 show a clear augmenting trend,
with an overall increase of 13%, or 1.6 104 kg
mm2 d1 in hardness.
A comparison with the initial rate of increase of
the hardness for (U0.9Pu0.1)O2, which can be roughly
estimated as 1.2 102 kg mm2 d1, is consistent
with the 100-fold difference in activity between the
two a-doped materials.35 The a-damage evidently
diminishes the yield strength (elastic limit), which
in case of strong swelling could also contribute to
early failure of the fuel. Additional information is
given in Chapter 3.16, Ceramic FuelCladding
Interaction.
5.16.4 Chemical Stability of Spent

Nuclear Fuel After Irradiation
Knowledge of the relative amount, distribution, and
nature of each element created in the fuel during
reactor operation is important for the understanding
of the long-term behavior of the fuel. The distribution and chemical form are of special interest when
studying the corrosion behavior of the fuel.
5.16.4.1 Distribution and Chemistry of
the Fission Products
Figure 11 shows a schematic of an irradiated fuel
pellet. The different regions marked in the figure
indicate locations with potential fission product
accumulation.
950
403
(U0.9,238Pu0.1)O2
(U0.999,238Pu0.001)O2
Hardness (kg mm-2)
900
850
800
750
Measurement time ~ 3000 d
700
10-4
10-3
10-2
10-1
100
Displacements per atom (dpa)

Figure 10 The evolution of the hardness is directly related to the a-damage rather than to the composition in the case of
the a-doped material. Courtesy of Thierry Wiss.
Gap
Crack
3. oxide precipitates: Rb, Cs, Sr, Ba, Zr, Nb, Mo,

and Te;
4. dissolved as oxides in the UO2 matrix: Sr, Ra, Zr,
Nb, Y, Te, Cs, Ba, La, Ce, Pr, Nd, Pm, Sm, Eu, and
the actinides.
Grain
Grain
boundary
Cladding
Pellet gap
Figure 11 Schematic illustration of an irradiated fuel

pellet with cladding. The fuel pellet cracks during irradiation
due to temperature gradients. Volatile fission products
accumulate in the cracks and in the gap between the fuel
and the cladding. Metallic and oxide precipitates are formed
at the grain boundaries and in the grains of the fuel.
Courtesy of Patrik Fors.
Kleykamp36 divided the fission products and actinides into four classes depending on their chemical
state in the fuel and the list was complemented with
more elements by Ferry et al.34
1. volatile and gaseous fission products: He, Kr, Xe,
Br, Rb, Cs, Te, and I;
2. metallic precipitates: Mo, Tc, Ru, Rh, Pd, Ag, Cd,
In, Sn, Sb, and Te;
The abundance of the major fission products for two

45 GWd/tHM fuels, one UO2 and one MOX, is listed
in Table 4. The elements are divided into the four
groups given by Kleykamp.36
The first group will be found distributed between:
(i) fission-induced solution within the oxide lattice,
(ii) closed intragranular and intergranular bubbles
within the fuel,37 and (iii) in the open porosity of
the fuel and the gap between the fuel and cladding.21
This group of elements is expected to dissolve quickly
in case of fuel contact with groundwater. The approximate rare gas distribution in a UO2 fuel rod is shown
in Table 5.
The second group forms metallic precipitates
in the fuel, usually referred to as e-phase particles.
In these particles, alloys are formed whose composition is dominated by molybdenum and ruthenium.38
The e-particles are generally accumulated at the
grain boundaries. The e-particles are, in performance
assessments, assumed to become dissolved in groundwater. However, as pointed out by Shoesmith39 this
assumption is conservative as most of the grain
404
235
Table 4
U and 239Pu fission product creation rates in
45 GWd/tHM burn-up PWR UO2 and MOX19
Table 5
Distribution of the rare gases (Kr, Xe) in UO2
fuel rod with a burn-up of 60 GWd/tHM34
Typea
Element
PWR UO2
(wt%)
PWR MOX
(wt%)
Gas fraction in free volume
Rare gases and

volatiles
Xe
Kr
I
12.7
1.1
0.6
13.3
0.6
0.8
Ru
Pd
Rh
Tc
Ag
Cd
Sn
6.9
3.6
1.2
2.3
0.3
0.2
0.2
8.9
7.3
2.2
2.4
0.6
0.5
0.2
Mo
Te
9.6
1.4
9.0
1.6
Cs
Ba
Rb
11.0
4.4
1.0
11.4
4.2
0.5
Zr
10.4
7.4
Y
Ce
Nd
La
Pr
Sr
Pm
Sm
Eu
Gd
1.4
7.7
11.1
3.5
3.2
2.6
0.4
2.0
0.5
0.2
0.7
6.9
9.8
3.4
3.0
1.3
0.5
2.4
0.7
0.3
Metallic
precipitates
Oxide precipitates
In solution in the
oxide
The initial 235U enrichment in the UO2 was 4.25 wt%, the Pu
content in the MOX was 7.8 wt%.19
a
The grouping of elements is made according to Kleykamp36 and
not as originally given by Bailly et al.19
boundaries are not immediately accessible to water,

and the dissolution, therefore, to a significant degree
could be controlled by the corrosion/dissolution of
the fuel matrix. A part of the elements in group 3 are
separated from the fuel matrix into cubic perovskitestructured precipitates, sometimes referred to as gray
phases.21,40 This precipitate is a solid solution with
the general composition ABO3 with Ba, Sr, and Cs
in the A sites and Zr, Mo, U, Pu, and rare earths in the
B sites.21,41 The gray phase is found to be distributed
in the entire fuel, but accumulates in the grain
boundaries of the colder parts of the fuel.21,42
The relative partition of molybdenum between
metallic and oxide precipitates depends on the oxygen
to metal ratio, and the chemical potential of oxygen,
in the fuel.40,43 As the oxygen potential increases with
the fuel burn-up, the amount of oxidized molybdenum
Intergranular gas fraction
0.03
0.0190.042 in central part
(r < 0.5r0)
0.0140.048 intermediated
part (0.5r0 < r < 0.975r0)
0.0450.062 in the rim pores
(0.975r0 < r)
Total intergranular gas

fraction
0.080.15
Fraction in the grains
0.800.90
increases and, as a result, the molybdenum fraction in

the metallic precipitates decreases.40 Table 6 shows
an example of a metallic precipitate composition in a
UO2 fuel.44
The elements in group 4 form solid solution with
the UO2 matrix, and can only be released by dissolution of the UO2 grains themselves.
Some elements such as Cs, Sr, Ba, Ra, Zr, Nb, and
Mo can exist in more than one phase. The UO2
matrix encompasses the major part of the elements
in solid solution, but it also contains almost all gaseous and volatile fission products contained in gas
bubbles.37 The metallic precipitates exist in the UO2
matrix, as inclusions, as well as at the grain boundaries.34 The oxide precipitates are present either as
individual inclusions or, to a minor degree, as soluble
oxides in the UO2 matrix.
It is estimated that about 30% of the fission products form solid solutions with the matrix.45 However, due to the limited migration of the nonsoluble
elements (groups 13), about 95% of all fission products are present in the oxide lattice46 and can be
released only by dissolution of the latter. Consequently, the dissolution of UO2 will be the major
factor in determining the release rate of radionuclides from the repository, in case of a canister failure.
5.16.4.2
Storage Before Final Disposal
The chemical behavior of the fuel in the repository

depends to some degree on the intermediate storage
conditions during the time the fuel is cooled and
stored in the final repository. Nowadays, two main
intermediate storage strategies are employed, wet
and dry storage.
The release rate of fission products from the spent
fuel in the repository depends to some degree on the
previous handling of the fuel. Of primary importance is
Table 6
405
The relative composition of elements in e-particles together with the theoretical fission yields44
Measurement (fraction)
Fission yield (fraction)
Mo
Ru
Tc
Pd
Rh
Te
0.327
0.429
0.405
0.260
0.070
0.101
0.117
0.109
0.042
0.059
0.038
0.043
Data from a UO2 fuel with a burn-up of 23 GWd/tHM (irradiated at a linear power effect of 20 kW m1).
to avoid oxidation of the fuel before it is encapsulated.

This requires that the spent fuel is kept in an airtight
container in the Zircaloy cladding during the complete
intermediate cooling period (see also Chapter 5.17,
Waste Containers).
5.16.4.2.1 Wet storage of fuel in cooling ponds
The experience of more than 40 years of wet storage

of several million light water reactor rods shows that
SNF with zirconium alloy cladding has had excellent
durability.47 Investigations made on CANDU fuel
rods as well as on PWR Zircaloy-cladded rods showed
no detectable changes in the cladding characteristics
after 2030 years of wet storage.
These investigations were supported with destructive and nondestructive examinations of fuel rods,
visual evidence, and coupon studies all showing resistance to aqueous corrosion.47 Additionally, there have
been no reports of FGRs, indicative of cladding failure in wet storage. Given the fact that the Zircaloy
corrosion rates in wet storage are very low, indicative
techniques were applied and yielded a suggested
corrosion rate of <0.007 mm year1.47
5.16.4.2.2 Dry storage of fuel
SNF with zirconium alloy cladding has been placed

into dry storage in approximately a dozen countries.47
The resistance of Zircaloy cladding to corrosion
in water and in water vapor, the absence of a
hydrated zirconium oxide, and the low oxidation
rate of Zircaloy cladding in air mean that there are
few chemical problems in drying Zircaloy clad fuel,
or indeed in storing incompletely dried unfailed fuel.
For power reactor fuel, the decay heat promotes
drying when the fuel is removed from water. Due
to the high decay heat of the SNF, the cladding
temperatures in dry storage needed to be limited by
design. Acceptable cladding temperature limits tend
to be based on mechanical properties such as creep,
but cladding strength can be degraded by internal
fission product attack, especially at burn-ups above
45 GWd/tHM.
The technical basis for satisfactory dry storage of
fuel clad with zirconium alloys includes hot cell tests
on single rods, whole assembly tests, demonstrations

using casks loaded with irradiated fuel assemblies,
and theoretical analysis. The principal method of
monitoring cladding behavior has been to periodically sample cover gases for evidence of 85Kr since its
presence offers an indication that cladding has been
breached. The technique is used in the assembly and
in cask storage tests and demonstrations. The fact that
only a few rod failures have been detected provides
evidence that cladding integrity is satisfactory in dry
storage.
The CASTOR V/21 dry storage demonstration
referred to above involved visual, nondestructive,
and destructive examination of PWR Zircaloy clad
fuel rods after 14 years in dry storage. There was no
indication of degradation of the cladding or fuel and
little or no FGR from fuel pellets during the period
of dry storage. The cladding retained significant
creep ductility after dry storage.47
5.16.4.3
Repository Storage
Most concepts for SNF repositories are designed

to obtain oxygen-free (more commonly expressed as
reducing) conditions within a few years after closure. The oxygen-free conditions will be achieved
since any oxidants remaining in the repository at
the time of its closure will be consumed by microbiological processes and reducing minerals.48,49
This section focuses on the mechanisms governing the spent fuel behavior under oxygen-free conditions and takes the Swedish KBS-3 concept as an
example (see Figure 12). The KBS-3 concept has
been chosen to illustrate the chemistry of the repository since it is well examined and close to implementation. Generally, the same reactions will be applicable
in other repository types with oxygen-free conditions;
however, differences in groundwater composition will
be seen if the repository is placed in a clay or salt
formation.
5.16.4.3.1 Groundwater composition
The water that will be in contact with the container

will govern the corrosion processes of the
406
Groundwater in bedrock is
oxygen-free
Oxygen-free H2O reacts with canister

iron to produce hydrogen
3Fe + 4H2O Fe3O4 + 4H2
a-radiation splits the groundwater in

a process known as radiolysis
Iron canisters containing the spent fuel are
emplaced in the repository boreholes
H2O H2O2, H2, and O2
Figure 12 Granitic repository for spent nuclear fuel.50 Geologic repositories contain spent nuclear fuel enclosed in massive
copper/iron or steel/cast-iron containers 5001000 m deep in the bedrock. The containers prevent water from interacting with
the spent fuel for at least 1000 years. By the time spent fuel may become exposed to groundwater, b(g)-emitting nuclides in
the fuel will have decayed to a negligible level.51 Therefore, only long-lived a-emitters will be responsible for the formation of
oxidants at the fuelwater interface through radiolysis (for simplicity, the radiolytic reaction presented in the figure is
unbalanced; a complete set of reactions can be found in Pastina and LaVerne52). Anoxic corrosion of iron will form large
amounts of hydrogen, a reductant.51 The graphics to the left is used with permission from SKB, illustrator: Jan Rojmar.
container itself, during the initial time period, as well

as the cladding and spent fuel at the time the canister
fails. The composition of the natural groundwater
moving through the repository will change as it
passes the different barriers since the barriers contain
foreign material, in respect to mass and composition, in comparison to the bedrock. An example of
different groundwater compositions in respect to
repository type is given in Table 7. It should be
remembered that the natural groundwater composition will change over the long period of an active
repository, especially due to the processes occurring
during glaciations and deglaciations.57
The groundwater compositions shown in Table 7
are selected as representative groundwater at repository depth. This means that there exists a variation
in groundwater composition, at each repository site,
that depends on the fracture orientations and fracture
pathways. The chemical composition of old (>5000
years, small exchange/mixing with surface waters)
groundwater, shown by its 18O and 3H content,
depends on the composition of the fracture filling
minerals it has exchanged ions with. Geochemical
modeling of groundwater composition changes as a
function of fracture filling minerals composition
increases our understanding of groundwater behavior
and can be extrapolated to changes in future
groundwater compositions due to water mixing as a

result of changed groundwater flow paths, for example, during glaciations and deglaciations.54
Groundwater compositions from two suggested
repository sites located in Sweden, Forsmark (selected
as first choice) and Aspo which are 400 km apart can
be compared in Table 7. Although the difference in
composition of cations such as Na, K, Ca, and Mg are
varying by factor of 6, these differences mirror different fracture filling mineral compositions.
Since the solubility of the different ionic complexes
will determine when saturation is reached, the rate
of spent fuel dissolution will depend on the composition and concentration of ions in the groundwater and
their respective ability to form ionic complexes. Alkali
metal cations, in millimolar range, together with high
concentration (in micrometer range) of dissolved
U(VI) can form precipitates such as sodium diuranate,
Na2O (UO3)26H2O.
Alkaline earth metals (Ca, Mg, and Sr) together
with Si and U(VI) form U(VI) silicates such as uranophane, Ca(UO2)2(SiO3OH)25H2O. Uranophane
and soddyite ((UO2)2(SiO4)(H2O)2) are uranium
(VI)-containing silicate minerals which have a
relatively low solubility and in presence of silicates
can keep the U(VI) concentration below 106 M.58
Coffinite, USiO4(cr), a uranium(IV) silicate mineral
407
Table 7
Representative groundwater compositions in crystalline bedrock (Forsmark, borehole KFM02A, 509516 m
depth), Aspo crystalline bedrock groundwater (borehole KAS02, 530-m depth), Aspo crystalline bedrock groundwater after
contact with bentonite (MX-80), Opalinus clay pore water, and salt (Gorleben inclusion brine)
Components
Granitic
groundwater
at Forsmark,
Sweden53
(mol l1)
Granitic groundwater
at Aspo, Sweden54
(mol kg1)
Granitic groundwater
from Aspo
equilibrated with
bentonite55 (mol l1)
Opalinus clay
pore water,
Switzerland13
(mol l1)
Brines at Gorleben,
Germany56 (mol per
kg H2O)
[Na]tot
[K]tot
[Ca2]tot
[Mg2]tot
[Sr2]tot
[Fe]tot
[Mn]tot
[Si]tot
[F]tot
[Cl]tot
[Br]tot
[HCO
3]
[SO2
4 ]
[S2]
[S]tot
T( C)
log pCO2
pH
Eh against
SHE (V)
8.9 102
8.8 104
2.3 102
9.3 103
9.1 102
2.1 104
9.6 103
1.7 103
4.0 104
4.4 106
5.3 106
1.5 104
7.9 105
1.8 101
5.0 104
1.6 104
5.8 103
6.4 101
3.1 103
1.0 102
4.9 103
2.5 104
1.7 101
5.7 103
1.1 102
7.5 103
3.0 104
4.3 105
2.4 105
1.8 104
1.7 104
1.6 101
2.4 104
2.7 103b
2.4 102
1.4 1011
15
20
3.5
8.4
Oxidizing
0.060
0.016
0.051
5.70
0.0014
0.0206
0.0003
n.g.
0.0163
11.35
n.g.
n.g.
0.0011
n.g.
0.0011
n.g.
n.g.
7.0
n.g.
3.3 105
1.8 104
1.5 101
3.0 104
1.8 103
6.8 103
7.0
0.143
8.1
0.258
3.2 104
6.4 101
2.5 103a
1.6 102
25
2.2
7.24
0.167
n.g.: Not given in the reference.

a
[C]tot.
b
[CO3]tot.
is mainly found in association with UO2(cr) and

SiO2(cr). Its solubility, at high silica concentrations,
is considered to be even lower than for UO2(cr).59
Iron and manganese are normally present in their
reduced form and control the redox potential, Eh,
in the groundwater. Of the anions, Cl and Br form
relatively weak complexes with the cations and U(VI)
in comparison to hydroxide (OH) and carbonate

(CO2
3 ). On the other hand, at higher Cl and Br
concentrations (>1 mM), they take part in radiolysis
reaction scheme through OH scavenging, resulting
in decreased production of H and thereby creating
a more oxidizing condition.60 Calcite (CaCO3) and
carbonate-containing minerals in the bedrock control
the pH of the groundwater.
The change of the water composition when contacted with bentonite (MX-80) is also shown in
Table 7. The main change occurs due to the dissolution of impurities of calcite present in bentonite,
thereby increasing the carbonate concentration and
decreasing pH.61 Presence of minor amounts of
CaSO4 in the bentonite gives an almost tenfold
increase of the sulfate concentration.
Due to its marine origin, the pore water of the

Opalinus clay is relatively saline and sodium chloride
dominated, while the pH is close to neutral (Table 7).
Redox conditions are reducing as evidenced by the
large amounts of unoxidized pyrite and siderite.13
A comparison of the granitic groundwater from Aspo
and the pore water from the Opalinus clay shows
significant differences mainly in Na, K, Fe, Mn, and
carbonate. While Na is twice as high in Opalinus clay
pore water compared to Aspo GW, K is almost 30
higher because of the high cation exchange capacity
of the layered clay. Comparing the redox potential in
Aspo groundwater with Opalinus clay pore water
shows a higher redox potential despite the higher concentration of total Fe and Mn in Opalinus clay pore
water, exemplifying the importance of determining the
oxidation state of dissolved Fe, Mn, and S. For the case
where the SNF repository is situated in Opalinus Clay,
as planned in Switzerland (Table 1), the canisters will
be exposed to bentonite pore water that is expected to
have a composition similar to that of the Opalinus clay
pore water, with minor differences in composition due
to ion-exchange processes with the bentonite clay.6
408
Granitic or argillaceous host rocks contain formation water in fractures or in pores of the rock
matrix. In contrast to these groundwater bearing
rock formations, salt rock formations are free of
fresh flowing water and relatively impermeable. The
Gorleben salt dome in Germany has been studied
as a potential site for the disposal of SNF. Brine
reservoirs found in the Gorleben complex having so
far occurred in the explored parts of the salt dome
had a limited volume and do not have any contact
with the groundwater. Reservoir tests resulted in
brine occurrences in the order of magnitude of maximum some thousand cubic meters.6264 The composition of Gorleben inclusion brine, which was
characterized and used for corrosion experiments
with SNF,56 is given in Table 7.
Considering the reducing conditions, it can be
concluded that the groundwater compositions in
Tables 1 and 7 show groundwaters at repository
depth with a redox potential, Eh, below zero (SHE).
5.16.4.3.2 Corrosion of copper
The slow corrosion of the copper lining, surrounding

the iron insert in the repository, plays a crucial role
giving the intensively radioactive fission products
time to decay (see Figure 3). Corrosion experiments
on copper coupons in contact with bentonite have
been performed under reducing conditions in the
Aspo hard rock laboratory. The result showed an
average corrosion rate of <0.53 mm year1.65 No
pit corrosion could be recognized. The corrosion
product identified was cuprite, Cu2O, and paratacamite, Cu2(OH)3Cl. The low corrosion rate was verified by real-time corrosion experiments performed
at the same location, using copper electrodes inserted
into bentonite. The results of these experiments
showed corrosion rates in the range of 0.12.4 mm
year1. It was concluded that general copper corrosion is not a problem either from a structural integrity point of view or from any risk of impairing the
properties of the bentonite.65
Assuming an average copper corrosion rate of
3 mm year1 and a 50-mm-thick copper wall, a copper
lining penetration will occur after 17 000 years.
At this time, mainly long-lived, a-emitting actinides
will dominate the radiation field (see Figure 3).
A more detailed discussion on this subject can be
found in Chapter 5.17, Waste Containers.
5.16.4.3.3 Iron canister corrosion
The oxygen trapped in the repository after its closure

will have had been consumed by bacteria and
reducing minerals, a process already finished within

a few years of closure48,49 and leading to an anoxic
deep groundwater. If the copper lining is penetrated
due to corrosion, after >10 000 years, and water
comes into contact with the cast-iron canister, anaerobic corrosion of the iron will start:
Fe 2H2 O ! FeOH2 H2 g
3Fe 4H2 O ! Fe3 O4 4H2 g
These processes will produce large amounts of Fe2

and H2 since the reverse reactions occur first at H2
pressures in the order of 100 MPa.66 Experiments have
shown that the reactions are not limited by dissolved
ferrous ions.67 The anoxic corrosion rate of the iron
in the canister is very low, starting in the order of
1030 mm year1, but decreases to 0.1 mm year1, as
soon as an oxide film is formed on the iron surface.67
The amount of hydrogen present in the damaged
canister will initially be determined by the rate of
hydrogen production and the transport of dissolved
H2 away from the production site. Since the transport
of dissolved gas is limited through the capillaries in
the bentonite clay buffer, H2 will accumulate in the
canister. After a few years, the pressure of H2
becomes higher than the hydrostatic pressure at the
depth of the repository (i.e., 5 MPa at 500-m depth)
and a gas phase will start to form. The pressure inside
the gas phase will continue to increase until it is
higher than the hydrostatic pressure plus the swell
pressure of the clay (in a repository at 500-m depth,
this is expected to be around 1015 MPa). Once the
swell pressure is exceeded, a breakthrough of gas will
occur that brings the pressure in the gas phase back to
the hydrostatic pressure of the repository. The bentonite will recover totally after this breakthrough, and
the pressure increase will start again.68
5.16.4.3.4 Radiolysis
Although the redox conditions in deep granitic

waters are reducing (200 to 350 mV(SHE) at pH
78),65 oxidizing conditions might be created near
the fuel surface as a result of the fuels radioactive
decay (maximal range of a 5 MeV a-particle in pure
water is 37 mm). The energy released when the radioactive particles interact with the groundwater leads
to splitting, or radiolysis, of the water molecules (see
Figure 13).
Generally, equimolar amounts of oxidizing and
reducing species are created. However, due to the
much higher reactivity of the oxidizing species, an
oxidative environment is expected to result from the
409
Ionizing radiation (, , )
H2O
H2O+
H2O
H2O
H 2O
H+
H2O
OH
OH
H
OH
H2
H2O2
+ e + H+
HO2
H2O
HO2
O2
Figure 13 Simplified radiolysis scheme. Radiation interacts with the electron structure in the water molecule and deposits
enough energy to ionize one of the atoms. This results in the release of an electron. The positively charged water thereby
created decomposes into a hydrogen ion and a hydroxide radical; the free electron continues to interact with water
molecules until its kinetic energy is low enough for the electron to be absorbed by one of the water molecules. The resulting
negatively charged water decomposes into a hydroxide ion and a hydrogen radical. Hence, the sum reaction is that a water
molecule is split into one hydrogen radical and one hydroxide radical. The reactive radicals, the water, and the ions react
further with each other in multiple steps according to a scheme of nearly 80 reactions.52,69 Some of the most important are
shown. The overall result of the radiolysis is the formation of new molecular species: H2O2, H2, and O2 (produced through
the decomposition of H2O2 on UO2 surface with a yield of 0.267). Courtesy of Patrik Fors.
radiolysis.51 The radiolytic yield of the interaction

process varies with the different types of emission.
b(g)-radiation leads to sparse ionizations and, therefore, low probability for reaction between different
radicals and a radical-rich yield. a-radiation, on the
other hand, due to the a-particles larger size, leads to
a dense track of ionizations, in which combination
reactions between radicals are likely. a-radiolysis,
therefore, mainly results in the formation of the
molecular species H2O2 and H2.70 A more detailed
description of the radiolysis process is given in
Chapter 5.02, Water Chemistry Control in LWRs.
The radiolysis processes can be simulated computer
programs, such as CHEMSIMUL71 or MACKSIMACHEMIST72, which calculates the yield of radiolytic
species as a function of time. The necessary rate
constants can be obtained from the literature, as
for example from Kelm et al.60
5.16.4.3.5 Corrosion of spent fuel under
reducing conditions
As mentioned above, the inventory of different elements in spent fuel is divided between the gap, cracks,
grain boundaries, and the fuel grains. The elements in

the gap, cracks, and the grain boundaries will be the
first to come into contact with water if the canister is
breached. Some of them will be quickly dissolved in
the water and are referred to as the instant release
fraction (IRF), see separate discussion in Section
5.16.4.3.7.
Even though the IRF will be quickly released, the
main problem from activity spreading point of view is
dissolution of the UO2 matrix, since it contains more
than 95% of the radionuclides (see Section 5.16.4.1).
Two different types of UO2 matrix dissolution can take
place; (i) chemical dissolution governed by the solubility of UO2 in the groundwater; (ii) oxidative corrosion of the uranium leading to dissolution of uranium
in its much more soluble hexavalent oxidation state.
5.16.4.3.5.1
UO2 dissolution
The chemical dissolution of UO2 will be governed by

its solubility in groundwater. The solubility in turn
will be dependent on factors such as pH, temperature, ionic strength, complexing ions, but also on the
crystallinity of UO2.
410
In crystalline UO2(cr), the uranium and oxygen

atoms build up a fluorite lattice. This perfect structure is hard to dissolve as many bonds have to be
broken to bring an atom into solution. However,
surface U(IV) atoms are strongly hydrated in contact
with water.73 As the coordination of water molecules
takes place already on the UO2 surface before detachment, it helps break the bonds in the fluorite lattice.
Once the U(IV) is dissolved, mononuclear hydroxo
complexes will be formed, due to the strong hydrolysis of U(IV).74 In pure water with pH above 5, the
hydroxo complexes consist of a U(IV) atom with four
coordinated OH ions in tetrahedral positions.75 The
dissolution can be described by the reaction:
UO2 cr 2H2 Ol ! UOH4 aq
When the U(OH)4(aq) precipitates from a supersaturated solution, a solid is created by condensation
reactions between the OH-groups. However, this
process is not perfect and results in an amorphous
solid (Figure 14). Due to the imperfect structure,
the amorphous UO2 is easier to dissolve and equilibrates at higher solution concentrations than the
crystalline.76
A theoretical solubility of crystalline and amorphous UO2 can be calculated as a function of pH
from thermodynamic hydrolysis and formation constants.77 The resulting plot, for the temperature of
25 C, is shown in Figure 15. As shown in the figure,
a solution with pH between 7 and 9 (i.e., in the range
relevant for groundwater in a repository) in contact
with UO2(am) will equilibrate at a dissolved uranium
concentration of 108.5 M. The lower curve shows the
theoretical solubility of crystalline UO2 in water at
25 C. Owing to the low UO2 solubility, the dissolution
rate of the spent fuel matrix will be limited by the
diffusive or advective transport of uranium away from
the fuel. As those transports are slow, the practical fuel
dissolution under reducing conditions becomes
negligible.39
(a)
(b)
However, the reducing condition is easily disrupted

by the presence of oxidants near the fuel surface since
uranium, under oxidizing conditions, can be oxidized
to U(VI) and the solubility of hexavalent uranium, for
example, as UO2
2 , is many orders of magnitude higher
than that of U(IV) from UO2.75
The redox potential, Eh, of the groundwater determines whether the uranium will become oxidized or
not. If the Eh is more positive than the equilibrium
potential for fuel dissolution, that is, the potential for
the UO2/UO2
2 couple, the potential difference will
govern the corrosion rate of the fuel. The highest Eh
at which UO2 still should be resistive to oxidation
could be thermodynamically calculated to 50 mV
(SHE) at pH 8.5 (based on data from Grenthe et al.,80
Paquette et al.,81 and Lemire and Tremaine82 according to calculations by Shoesmith39).
Experiments have, for example, shown the presence of an a-activity threshold in UO2 pellet below
which the oxidants created by a-radiolysis are too few
to corrode the fuel surface.83 Today, this a-activity
threshold is suggested to be as high as 18 MBq/g
(UO2), which corresponds to 10 000-year-old fuel
(with a burn-up of 47 GWd/tHM).84
5.16.4.3.5.2 Radiolysis-driven dissolution of fuel
under reducing conditions
As mentioned above, a-radiolysis affects the redox

conditions at the fuel surface. The otherwise reducing
environment in the groundwater (300 mV (SHE))
inevitably becomes partly oxidizing near the fuel surface. On the other hand, the corrosion of cast-iron
canister gives rise to high concentration of Fe2 (in
the range of 1 105 to 1 106 M85 and H2 concentration of 130 mM, corresponding 150 bar H2 pressure) in the groundwater in contact with the fuel.
In order to test the influence of Fe and/or H2 on
fuel corrosion, young fuels such as irradiated UO2
and MOX fuels cooled for 530 years have been
corroded in presence and absence of Fe/H2.
(c)
Figure 14 Amorphous UO2. (a) Two U(OH)4 approach each other, which (b) leads to a condensation reaction between the
OH-groups. (c) The hydrous, or amorphous, solid-phase generated after multiple condensation reactions constitutes an
irregular network. Courtesy of Patrik Fors.
411
2
UO2 100C; Parks and Pohl74
UO2; Ollila et al.79

2
UO2; Rai et al.78

233UO
log [U(IV)]
2;
Carbol et al.50
6
UO2(am)
8
10
12
UO2(cr)
14
16
0
10
12
14
pH
Figure 15 Concentration of U(IV) in pure water in contact with UO2 as a function of pH. The input data for the
calculations of the UO2(am) and UO2(cr) were taken from Neck and Kim.77 The total U concentrations measured in
different experiments performed under anoxic/reducing conditions, and found in the literature, are inserted (detailed
information on the experimental conditions can be found in Carbol et al.,50 Parks and Pohl,74 Rai et al.,78 and Ollila et al.79).
European Atomic Energy Community, 2011.
A summary of these experiments is given in Table 8.

It can be deduced that corrosion of irradiated fuels
independently of UO2 or MOX fuel give three to four
orders of magnitude lower final uranium concentration when metallic Fe/H2 is present in the leachant in
comparison with the cases when H2 is absent, for
example, under oxidizing condition in air.
A number of possible explanations exist in the
literature for the observed low U concentration
measured during corrosion of fuels, such as:
reaction of Fe2 and radiolytic oxidants;
a reaction between H2 and radiolytic oxidants;
catalytic dissociation of H2 on e-particles (Ru, Rh,
and Pd);
catalytic dissociation of H2 on UO2.
The different processes are discussed in the following
sections.
5.16.4.3.5.3 Fuel corrosion in presence of iron
Dissolved Fe2 ions have been shown to be able to

react with H2O2 according to the so-called Fenton
reaction95,96:
Fe2 H2 O2 ! Fe3 OH OH
Fe2 OH ! Fe3 OH
4
5
These reactions lead to the reduction of H2O2 in

the aqueous phase and precipitation of oxidized
Fe3. Simulations have shown that the Fenton reaction
may reduce the rate of fuel dissolution with as much as
a factor of 50.97 But, even though the Fe2 leads to a
decreased H2O2 concentration at the fuel surface, the
Fenton reaction will not prevent the fuel surface from
corroding. Loida et al.98 showed this experimentally by
corroding fuel in presence of magnetite (Fe3O4, a
mixed Fe2 and Fe3 oxides). In the experiment,
very little effect of dissolved Fe2 was seen and the
atmosphere in the autoclave became oxidizing.
On the other hand, a reduction of oxidants and
U(VI) has been observed if the magnetite is replaced
by metallic iron.69,79,89,99 In a fuel corrosion experiment in presence of metallic iron, Loida et al.89
measured a partial pressure of 2.7 bar H2 after
4 years (due to the reactions with iron given
above). Additionally, an analysis of iron samples
from this experiment showed formation of reduced
iron corrosion products (green rust and magnetite).
Moreover, it was found that negligible amounts
of U(IV) had precipitated on the iron. Since it is
well known that U(VI) is quickly reduced and
precipitates on Fe(s),100103 the observations by
Loida et al.89 clearly show that no larger amounts
412
Table 8
Steady-state uranium concentrations in leachate together with experimental parameters for reported corrosion
experiments on irradiated UO2 fuel and spent MOX fuel
Burn-up
(GWd/tHM)
H2
(MPa)
Temperature
( C)
pH
Corrosion
time (d)
Concentration
U (M)
Solution
UO2 fuel with H2

Spahiu et al.86
43
5.0
70
8.5
312
1 1010
Spahiu et al.86
43
5.0
25
8.5
50
5 109
Albinsson
et al.87
Spahiu et al.88
41
1.0
25
8.1
21
5 109
10 mM NaCl/
2mM NaHCO3
10 mM NaCl/2 mM
NaHCO3
Mod. Allard Fe strip
43
0.5
70
8.5
376
2 1010
Loida et al.89
Loida et al.89
50
50
0.32
0.28
25
25
7.8
9.5
1095
1619
1 108
1 108
Fors et al.90
67
4.1
23
8.1
502
2 1010
MOX fuel with H2

Carbol et al.91
47.5
5.3
23
8.1
2100
7 1010
10 mM NaCl/
2mM NaHCO3
UO2 fuel in air

Forsyth et al.92
Jegou et al.93
42
60
0
0
25
25
8.2
6.3
1083
15
1 105
1 108
Synthetic groundwater
Pure water
MOX fuel in air

Jegou et al.94
49
25
6.2
14
3 107
Pure water
of oxidized uranium can have reached the iron at

any stage of the experiment.
Since Fe2 alone is not able to keep the uranium
reduced, the results observed by Loida et al.89 must be
related to the ingrowth of H2. A similar system was
studied by Albinsson et al.87 in which a clearly more
efficient reduction of oxidized species was obtained
by simultaneous presence of H2 and Fe2 in comparison with H2 alone.
A synergistic effect of H2 and Fe2 could be
expected in the bulk solution since the dissolved H2
will react quickly with the OH radicals104,105 created
by the Fe2 in the Fenton reaction (reactions [4] and
[5]). As the radical reaction:
H2 OH ! H H2 O
converts an oxidizing radical (E0 1.8 V in basic solution) into a reducing (E0 2.3 V),70 the combined
effect of Fe2 and H2 will be much stronger than
the effect of Fe2 alone (compare reactions with Fe2
[4] and [5]).
Interestingly, Albinsson et al.87 did not report any
red Fe3 precipitates in their test. This indicates that
probably a back reduction of the oxidized Fe3 by the
hydrogen in solution took place.
10 mM NaCl/
2mM NaHCO3
5.6 mol NaCl (kg H2O) 1
5.6 mol NaCl (kg H2O) 1
Fe powder
10 mM NaCl/
2mM NaHCO3
Although Albinsson et al.87 only saw a minor effect in

presence of pure hydrogen, Loida et al.89 did see an
equally efficient reduction of uranium in presence of
3.2 bar H2 as they did in the system with presence
of both Fe2 and H2. The reductive effect of pure
hydrogen is clearly contradictory in these two experiments. Dissolved H2 has, thermodynamically, the capacity to reduce both radiolytic oxidants and dissolved
U(VI). However, it is kinetically hindered at low temperatures and should be inert.46 Nevertheless, there
exists today, except from the results reported by
Loida et al.,89 substantial experimental evidence that
hydrogen becomes activated on spent fuel surfaces.
5.16.4.3.5.4
Fuel corrosion in presence of H2
Early pulse radiolysis studies showed that an electron

beam from a linear accelerator induces an OH scavenging reaction with H2 in homogeneous solutions
according to radical reaction [6].104,106,107 The radical
yield from the accelerated electrons is comparable
with the one obtained from b- and g-radiation emitted from spent fuel. The production of oxidants by
the radical-rich, low-linear energy transfer b- and
g-radiation emitted by spent fuel will be considerably
lower in hydrogen containing solutions because of
this relatively fast reaction. However, modeling has

shown that this reaction will not protect the fuel
surface from oxidation.108,109
More recent experiments on 4He ions accelerated
to 5 MeV (comparable with a-radiation emitted from
fuel) in a tandem Van de Graaff accelerator show
that dissolved H2 has almost no influence on the production of radiolytic oxidants.52 Since the a-radiolysis
will be dominating in the repository after 300500
years of storage (Figure 3), any OH scavenging
effect induced in the bulk solution by b(g)-radiation
will be negligible. Consequently, a-radiolysis has
been predicted to give oxidizing conditions in the
near surroundings of the fuel surface inside a failed
canister in a future repository, even in presence of H2.
Even though oxidation is expected, many experiments have clearly shown that dissolved hydrogen does
block oxidative corrosion of UO2 on (i) spent fuel
surfaces,86,8991,110,111 (ii) a-doped UO2,50,84,111 and
(iii) solid UO2 and g-radiation112 or a-radiation.113 It
is clear from the accelerator studies mentioned above
that bulk reaction between H2 and radiolytic radicals
cannot explain these results. Since H2, as mentioned
above, is kinetically hindered at room temperature
(thermal activation excluded), and experiments on dissolved UO2
2 in contact with H2 (without any UO2
surface) showed no reaction between the species,114 the
hydrogen must become activated on UO2 and fuel
surfaces.
Ample results exist to support a catalytic reaction
between H2 adsorbed on e-particles on the fuel
surface and oxidants reacting with the surrounding
uranium: (i) electrochemical studies report a clear
suppression of the fuel corrosion potential in presence of dissolved H2,112,115 (ii) corrosion studies
show a clear influence of noble metal doping and
e-particles,44,116119 and (iii) modeling of e-particles,
galvanically coupled to the UO2 matrix, has been
shown to explain the absence of corrosion.97,115,120
Despite the notable amount of results supporting
an e-particle-mediated reduction of oxidants by H2,
it is clear that other surfaces can support this reaction. Already in the late 1950s, Bunji and Zogovic121
reported reduction of UO2
in presence of H2
2
and UO2 surfaces only. Later, experiments without
e-particles present, but with iron in the system, have
shown to become reduced due to the Fe2 and H2
created in the system,79 and electrochemical experiments on pure UO2 surfaces have indicated a surface
reaction between oxidants and dissolved H2 in presence of g-radiation.122 Additionally, the experiment
with dissolved UO2
in presence of H2 mentioned
2
413
above showed immediate signs of H2 activation after

introduction of pure UO2 surfaces.114 A comprehensive summary of corrosion experiments in presence of
H2 is given by Cui et al.123
5.16.4.3.5.5
Influence of fuel heterogeneity
Elemental heterogeneity in fuels could be found in

irradiated MOX (see Section 5.16.2.1.2). Such heterogeneity will also exist in HBS of UO2 fuels. These
structures are formed at the periphery (rim) of irradiated UO2 pellets with an average burn-up exceeding
45 GWd/tHM and are a result of the high local burn-up
at the periphery (about twice the average burn-up).37
Since these heterogeneous structures give rise to high
a-dose rates, and therefore high local concentrations
of radiolytic oxidants, the question is whether these
surfaces will be protected by the hydrogen.
Irradiated MOX fuels have previously been
shown to have a higher dissolution rate under aerated
conditions than corresponding UO2 fuels.124,125 This
indicates that the intense a-field from the Pu
agglomerates accelerates the dissolution and that
the agglomerates themselves are relatively readily
dissolved. Nevertheless, the experimental evidence
presented by Carbol et al.91 shows that heterogeneous
MOX fuel surfaces become completely protected by
dissolved hydrogen, in the same way as irradiated
UO2 surfaces. Furthermore, Carbol and coworkers
saw an indication of lower dissolution of the Pu-rich
agglomerates, in comparison to surrounding UO2
matrix dissolution, which implies that the Pu-rich
agglomerates are harder to dissolve than the matrix.
Similar indications were found by de Pablo
et al.,126,127 in a comparison of the dissolution behavior of UO2 fuel periphery (containing rim) and core.
Also in this case, the rim seemed to be stabilized
against corrosion.
A possible explanation for the lower dissolution of
the rim and Pu agglomerates, in comparison to the
surrounding matrix, might be found in the stabilization of the UO2 matrix caused by solid solution of
fission products (mainly lanthanides, Ln) and actinides (Pu, Am, and Cm).128,129
Both MOX and UO2 fuels become restructured
(disintegrated from grain size of 510 mm to 0.2
0.3 mm), in Pu agglomerates or at the pellet rim, once
the local burn-up exceeds 45 GWd/tHM. Due to this
restructuring, a part of the fission products are
expected to be found at the grain surfaces instead of
the interior of the grains. As a result, corrosion of HBS
fuel is assumed to release significantly more fission
products than nonrestructured fuel. Additionally, the
414
increased amount of fission products at the fuelwater

interface might affect the surfaces ability to interact
with dissolved hydrogen.
A corrosion experiment of HBS containing UO2
fragments, presented by Fors et al.,90 showed a significant release of cesium (3.5 wt% of total Cs), as
expected. However, once the cesium available at the
fuel surface had been dissolved, the cesium release
stopped. In the experiment, it was found that the
activation of dissolved hydrogen takes place also on
restructured grain surfaces. The uranium concentration of 1.5 1010 M obtained after long-term stable
redox conditions was lower than previously found
in a similar system with a lower burn-up UO2 fuel,
5 109 M.86 Consequently, all three studies on heterogeneous fuel structures show that these do not
increase the corrosion rate in comparison to normal
(40 GWd/tHM) UO2 fuels.
the 1-mM dissolved H2 concentration in the Carbol

experiment is probably close to the actual threshold.
It should be mentioned that studies have been
performed on UO2H2OH2 systems without
e-particles,50 clearly indicating that UO2 does not
corrode despite presence of a-radiolysis (the UO2
was doped with 10 wt% 233U). These results indicate that another H2 activation mechanism, so far
unknown, must take place in these systems. The
threshold pressure of dissolved H2, necessary for
keeping the uranium reduced in the experiment performed by Carbol et al.,91 was found to be in the range
of 105 M (corresponding to 0.01 bar partial pressure
of H2). Interestingly, this value is also well correlated
with the model predicted by Jonsson et al.97 (if the
10 wt% 233U-doped UO2 is assumed to be a 3000year old fuel), despite the lack of e-particles.
5.16.4.3.5.6 Threshold pressure of H2
5.16.4.3.6 Corrosion of fuel under

oxidizing conditions
Another issue concerns the threshold H2 concentration at which H2 starts to inhibit corrosion of fuel.
Carbol et al.91 in their paper on corrosion of MOX
have made an attempt to determine the lowest
amount of dissolved H2 necessary for keeping the
uranium reduced. The results indicate that a stable
uranium concentration level of 7 1010 M could be
kept at the lowest tested amount of 1 mM dissolved
H2. The amount of 1 mM dissolved H2 corresponds
to a gas pressure of 1 bar. This amount of hydrogen
has also been shown to reduce uranium dissolution
rates in flow-through experiments of SNF by four
orders of magnitude (as compared to oxidizing conditions).110 Based on these results, SNF is expected to
be protected by dissolved hydrogen already at concentrations around 1 mM.
Jonsson et al.97 concluded, based on experimental
evidence and modeling, that e-particle-catalyzed
solid-phase reduction by H2 will efficiently block
any oxidative dissolution of fuel 100 years or older
already at a partial pressure of 0.1 bar H2. They did
not extrapolate their discussion to younger fuels. However, as a nearly linear relation is seen between the
logarithm of the fuel age and the logarithm of the
dissolution rate in their results, it is possible to get
an approximate value of the theoretically required
hydrogen pressure for the nearly 20-year-old MOX
fuel studied by Carbol et al.91 If this extrapolation
is made, around 0.5 bar H2 is found as the required
pressure. Considering the difference in fuel and
burn-up, MOX, 44 GWd/tHM, in comparison to
UO2, 38 GWd/tHM, in the paper of Jonsson et al.,97
Corrosion of SNF in oxidizing conditions is motivated,

for example, to assess the impact of possible accident
scenarios during the cooling of the fuel in storage pools.
Three sets of experiments were set up to study corrosion of spent UO2 fuel fragments (60 GWd/tHM) after
having them washed free from the inventory in gap and
grain boundaries.93 The first was carried out in presence of an external g-radiation field of 650 Gy h1,
representing a fuel bundle, the second in presence of
1.2 104 M H2O2 in the start solution, as oxidative
a-radiolysis product, and the third with only fuel fragments and water. The leachant was pure water (except
when H2O2 was added) at 25 C, with pH 6.3. The
highly oxidizing conditions motivated a relatively
short experimental time of 14 days.
The results showed that the hydrogen peroxide
concentration was almost equally high (1 104 M)
for the external irradiated fuel and in the experiment
with added H2O2, while it was 1 107 M in the
aerated solution containing only fuel fragments.
The U concentration, at the end of the experiment,
reached for the externally irradiated fuel 1 106 M,
for the one with addition of H2O2 1 107 M, and for
the aerated 1 108 M, which shows that under continuous g-irradiation, the U concentration continues
to increase until the solubility of studtite (UO2(O2)
4H2O) is reached (5 106 M).
Presence of studtite on the fuel surface, as needlelike and rodlet crystals, was confirmed by XRD both on
the fuel surfaces in the experiment with g-irradiated
fuel and on the surfaces of the H2O2-exposed fragments. No studtite was observed on the fuel surface
in the experiment with only fuel fragments and water.

A mass balance showed that 7090% of the dissolved
uranium has precipitated on the fuel surfaces.
Postexperimental leaching of the fuel surfaces with
aerated carbonated water resulted in dissolution of
UO2x but no studtite, while change of the leachant to
Ar/4 vol% H2 purged carbonated water gave a disintegration of studtite, as could be expected due to the
simultaneous presence of the reactive peroxide and H2.
Spent fuel corrosion in simulated groundwater
under oxidizing conditions was also studied by Ekeroth
et al.130 The authors observed an almost linear
increase in corrosion, measured as fraction of inventory in aqueous phase (FIAP), of fuels with increased
burn-up, up to 4045 GWd/tHM, whereas spent
fuels with a higher burn-up than 50 GWd/tHM
showed a decrease in corrosion. The authors offered
a possible explanation in that the UO2 matrix may
become chemically stabilized against oxidation by
the increased fraction of lanthanides present in the
fuel, either as fission products or as added dopant
(Gd). Similar results were obtained by Kline et al.131
when they compared the corrosion of UO2 with
Gd-doped UO2, under oxidizing conditions. It can
be concluded that doping of the UO2 matrix with
lanthanides seems to stabilize the matrix against oxidation and dissolution.
5.16.4.3.7 Instant release
When the container breaches, groundwater can come

in contact with the waste. For repository safety
assessments, the fission gas release, FGR has been
used as an indicator for rapid release of segregated
radionuclides such as 14C (t1/2 5.73 103 years),
36
Cl (t1/2 3.01 105 years), 79Se (t1/2 3.27 106 years),
99
Tc (t1/2 2.11 105 years), 107Pd (t1/2 6.5 106 years),
126
Sn (t1/2 2.3 105 years), 129I (t1/2 1.57 107 years),
and 135Cs (t1/2 2.3 106 years).132 The principle is
that the above-mentioned elements can form volatile
compounds, in-pile, at a temperature range of 300
1200 C, which behaves similarly as the fission gases.
An initial release of radionuclides is expected to
occur from all easily accessible sites. At first, the fuel
assembly structural materials and the fuel cladding
(e.g., steel, Zircaloy, etc.) will be affected. Here
long-lived activation products of structural materials
and impurities like 14C, 36Cl, 59Ni, and 63Ni are
considered, which are homogeneously distributed
in the material or trapped in, for example, a porous
oxide layer.
In case of damaged fuel cladding, water can
penetrate into the pin, and a radionuclide release
415
can occur initially from the gap filling material and

the outer periphery of the fuel pellets. This is followed by a release from the gap region and the fuel
grain boundaries. At these sites, volatiles (129I, 137Cs,
135
Cs, 79Se, and 126Sn) and fission gases have accumulated during irradiation and fission gases are
also present.
It is expected that release from the gap region and
the grain boundaries will be faster than the release
from the fuel matrix where the fission products are
incorporated in solid solution or trapped in bubbles
and other structural defects. The fraction of radionuclides released by these rapid initial processes
is generally defined as instant release fraction, IRF.
Up-to-now, there is no consensus on the exact definition of IRF.
Table 9 gives an overview of different components of the spent fuel assembly system, key radionuclides associated with them, and characteristics
affecting the release mode of these radionuclides,
indicating also those possibly belonging to the IRF.
Experimental determination of IRF of SNF is very
difficult. As a result, experimental IRF data based on
leaching of spent fuel are limited. Some measured
IRF values of volatile fission products like 129I, 135Cs,
and the activation product 36Cl show a good correlation with the FGR. Therefore, FGR is often used
to estimate the IRF of those nuclides.134 Cesium, for
instance, has a low solubility in UO2 and a high
amount is therefore removed from the UO2 fuel
matrix during reactor operation. Similar release of
cesium and xenon from fuel grains was found above
1200 C indicating that both Cs and Xe follow the
same release paths in the fuel135 and accumulate at
colder outer parts of the pellet.
Due to the transport processes determining the
relocation of volatile fission products, the IRF depends
on the irradiation history of the fuel. Fuels that are
irradiated with high linear power like commercial
CANDU fuel present high pellet centerline temperatures and show a strong correlation between FGR and
linear power. Commercial PWR fuels are irradiated at
lower and more constant linear power, but up to much
higher burn-up. In this case, the effect of burn-up on
FGR is stronger than that of linear power.27 Table 10
summarizes calculated IRF estimates of PWR UO2
fuel for burn-ups between 41 and 75 GWd/tU.136
Despite the experimental difficulties, a small number of experiments have been performed to determine
the gap and grain boundary fraction of 129I and 135Cs.
Recently, Roudil et al.137 have determined the IRF of
Cs from UO2 fuels with different burn-ups, in the range
416
Table 9
Expected distributions of radionuclides in fuel assemblies and possible modeling approaches133
Components
Key radionuclides
Characteristics and possible modeling

approach
Fuel assembly structural materials

14
C (organic?)
Zirconia (corroded Zircaloy)
Oxide film typically about 4080 mm thick is

formed in reactor (about 10% of cladding
thickness). The oxide has a low solubility; the
outer part is porous and may incorporate
nuclides present in Zircaloy as the film grows
Limited data on oxidized Zircaloy indicating
preferential release; consider 14C as part of IRF.
No data on steels cladding
14
Very low general corrosion rate

Release of all nuclides plus remaining
14
C congruent with the slow corrosion rate
Fission gases, volatiles (129I, 137Cs,

135
Cs, 36Cl, 79Se, 126Sn(?)).
Also 14C (nonvolatile but partially
segregated)
Reliable data available for some nuclides.

Assessment through fission gas release
measurements and correlation with leaching
experiments
Part of IRF
Rim porosity

135
Cs, 36Cl, 79Se, 126Sn(?))
Rim width is a function of burn-up; good data

available. Large proportion of nuclides in rim
region segregated into pores and secondary
phases during in-pile restructuring. No
experimental data indicating release
Could be part of the IRF in a very conservative
assumption
Rim grains
Actinides, fission products
Release through dissolution when water arrives.

FP may also diffuse to rim pores by
a-self-irradiation enhanced diffusion (a-SIED)
FP inventory may thus be part of IRF or matrix
release
Grain boundaries

135
Cs, 36Cl, 79Se, 126Sn(?)).
Segregated metals (99Tc, 107Pd)
Limited data
As for the rim pores, it could be considered part
of IRF in a very conservative assumption
Grains
Most of the actinides, fission products,

and activation products inventory
Belongs to matrix release
Zircaloy, Inconel, and steel
Uranium oxide
Gap
C (organic?), 36Cl, 59Ni, 63Ni
of 2260 GWd/tHM, and one MOX fuel (47 GWd/

tHM). The linear powers of the investigated fuels
were low, about 20 kW m1, and the FGR were 0.14,
0.23, 0.41, and 2.8% for the UO2 fuel burn-ups of
22, 37, 47, and 60 GWd/tHM, respectively.
The gap inventories were determined by static
leaching experiments using 20-mm-long clad segments
and 1 mM HCO
3 leachant. The tests were performed
in air atmosphere and lasted for 62 days. Determination of the Cs concentration in the leachates after 3,
10, 24, and 62 days made it possible to calculate the
FIAP value of Cs.
The results showed that, for the UO2 fuels,
the FIAP stabilized after day 10. However, due
Table 10
IRF estimates (% of total inventory) for various
radionuclides for PWR UO2 fuel
Radionuclide
Fission gases (Kr, Xe)

C
36
Cl
90
Sr
99
Tc, 107Pd
129
I
135
Cs, 137Cs
14
Burn-up (GWd/tHM)
41
48
60
75
1 (2)
10
5
1 (2)
0.1 (1)
1 (3)
1 (2)
2 (4)
10
10
1 (3)
0.1 (3)
2 (4)
2 (4)
4 (8)
10
16
1 (5)
0.1 (5)
4 (8)
4 (8)
8 (16)
10
26
1 (9)
0.1 (9)
8 (16)
8 (16)
Best estimate values, with conservative estimate values in

brackets.136
to the difficulty in determining the breakpoint between

the inventory in gap and the grain boundaries, the
conservative values for the 62 days of leaching were
reported. The experimentally determined inventory
of cesium in the gap increased from 0.3% to 2.2%
with increasing UO2 fuel burn-up up from 22 to
47 GWd/tHM. At the highest burn-up (60 GWd/
tHM), the Cs release was only 1%. This could possibly be explained by a closed fuel-cladding gap at
this burn-up. A higher Cs release, about 3%, was
observed for the 47 GWd/tHM MOX fuel. However,
the actual release might be even higher as the leachate concentration in this experiment had not fully
reached a stable FIAP plateau after 62 days.
In another experiment,137 a pseudodynamic
leach test was carried out on UO2 fuel powder
with a burn-up of 60 GWd/tHM. The powder had
been prepared from fuel fragments sampled from
the center of a 35-mm-long clad segment previously
leached in 1 mM HCO
3 leachant to eliminate the
gap inventory. The powder samples contained particles with a size fraction of 2050 mm. The number
of grains in each particle was estimated at about 40.
Thirty sequential leach cycles were carried out,
initially of short duration (12 h) to avoid any precipitation resulting from leaching of the oxidized
UO2x layer, then longer (2448 h) to determine
the grain boundary inventory.
The FIAPCs/FIAPU ratio decreased toward 1
after the sixth leaching cycle which showed that
further Cs releases originate from the UO2 matrix.
After subtracting the uranium release fraction, the
Cs inventory at the grain boundaries was determined
to be 0.38 wt% for UO2 fuel with a burn-up of
60 GWd/tHM.
The measurement performed by Roudil et al.137
show that, for a 60 GWd/tHM UO2 fuel, the labile Cs
inventory (gap grain boundaries) is about 1.4%, of
which 1% is located in the gap and 0.4% in the grain
boundaries.
More detailed descriptions of IRF can be found
elsewhere.27,34,83,133,138
5.16.5 Summary
It can be concluded that the segregation of the elements in the spent fuel will mainly depend on the
in-pile linear power (>25 kW m1) and thereafter on
the fuel burn-up. The higher linear power the fuel
has experienced, the larger fraction of the in-UO2
matrix nonsoluble elements (volatile and gaseous
417
fission products: He, Kr, Xe, Br, Rb, Cs, Te, I) will
have diffused to the grain boundary and the gap
(including cracks).
The length and the time period at which the
increased linear power has been applied will influence the fraction of elements moved to grain boundaries and gap. The longer and yet later in the fuel
cycle the linear power has been applied, the larger
fraction of the elements will exist in the grain boundaries and the gap. This segregation of elements in the
fuel will govern the release rate of these elements in
the deep underground nuclear fuel repository.
The burn-up affects the same process by increasing the amount of fission products in the UO2 matrix
which might lead to the fact that they reach their
solubility in UO2 and consequently move to the grain
boundary and the gap.
Even though reducing conditions prevail in deep
underground repositories (Eh around 0.3 V(SHE)),
a spent fuel younger than 10 000 years will create partly
oxidative conditions near the fuel surface upon contact
with groundwater due to a-radiolysis of the water.
Since the chemical environment is, in general,
oxygen-free, a number of reactions will come into
action that can consume the radiolytically produced
oxidants, mainly OH, H2O2, and O2. Examples of such
oxidants scavenging reactions are oxidation of canister
iron, Zircaloy cladding and rock minerals, and oxidation of the fuel matrix. The competition between the
reducing and oxidizing species at the fuel surface will
determine the oxidation state of the UO2 and thereby
its dissolution rate.
It is univocally important that hydrogen is present
in the repository since its catalytic dissociation reaction on the e-particles leads to the formation of
hydrogen radicals. This radical is strongly reducing
(2.6 V) and will reduce radiolytically oxidized
UO2x to UO2 and thereby hinder the dissolution
of the UO2 matrix and consequently the release of
fission products, present in the matrix, to the groundwater. A number of experiments with a-doped UO2
show that the e-particles are not alone responsible
for the corrosion-inhibiting effect seen on fuel in presence of H2, and the interactions in the UO2H2OH2
system clearly show that, despite presence of
a-radiolysis, the UO2 oxidation is stopped.
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5.17
Waste Containers
F. King
Integrity Corrosion Consulting Ltd, Nanaimo, BC, Canada
5.17.1
Introduction
422
5.17.2
5.17.2.1
5.17.2.1.1
5.17.2.1.2
5.17.2.1.3
5.17.2.1.4
5.17.2.1.5
5.17.2.1.6
5.17.2.1.7
5.17.2.1.8
5.17.2.1.9
5.17.2.1.10
5.17.2.1.11
5.17.2.2
5.17.3
5.17.3.1
5.17.3.2
5.17.3.3
5.17.4
5.17.4.1
5.17.4.2
5.17.4.3
5.17.4.4
5.17.4.5
5.17.5
5.17.6
References
Repository Environments
Environmental Factors
Temperature
Chloride concentration
Groundwater and pore-water chemistry
pH
Sulfur species
Redox conditions
Radiolysis and irradiation
Degree of saturation
Mass-transport conditions
Microbial activity
External loads and residual stress
Evolution of the Environment
Material Selection
Target Lifetime
Active Versus Passive Materials
Environmental Considerations
Corrosion Behavior of Candidate Canister Materials
Carbon Steel
Stainless Steels
Copper
Titanium Alloys
Nickel Alloys
Canister Lifetime Predictions
Conclusions
423
423
423
423
424
424
425
425
426
426
426
426
426
426
427
428
428
428
429
429
433
437
441
443
446
447
448
Abbreviations
AISI
C-steel
EVA
HFIC
HIC
HLW
IGA
ILW
LILW
MIC
PREN
SCC
SCE
SF
American Iron and Steel Institute

Carbon steel
Extreme-value analysis
High-field ion-conduction (mechanism)
Hydrogen induced cracking
High-level waste
Intergranular attack
Low- and intermediate-level waste
Microbiologically influenced corrosion
Pitting resistance equivalent number
Standard calomel electrode
Spent fuel
SHE
SKB
TBD
UNS
Standard hydrogen electrode

Svensk Karnbranslehantering AB
To be determined
Unified Numbering System
Symbols
D
EB
ECORR
EFB
EOC
Ercrev
ERP
Diffusivity or diffusion coefficient

Pitting or breakdown potential
Corrosion potential
Flat band potential
Open-circuit potential
Crevice repassivation potential
Repassivation potential
421
422
HC
d
DE
Waste Containers
Critical absorbed hydrogen concentration

Diffusion layer thickness
Potential difference
5.17.1 Introduction
Methods for the permanent disposal of nuclear waste
are being investigated internationally.19 Without
exception, these methods involve a series of natural
and engineered barriers in an underground geological
repository, with one of the engineered barriers being a
metallic canister (Figure 1). The canister is unique

among these various barriers since it is the only one
that is absolute, the others being permeable to a
greater or lesser degree. Canisters are required for
both high-activity wastes, typically spent fuel (SF) or
high-level waste (HLW) from reprocessing operations
immobilized in some sort of insoluble matrix, and
certain low and intermediate-level wastes (LILWs).
Different types of geological setting are being
considered in different countries, but here the
emphasis is on the long-term performance of the
canister material. The canisters may ultimately fail
as a result of either mechanical overload or
4
3
5
7
Legend
1. Surface facilities
2. Main shaft complex
3. Placement rooms
4. Backfill
5. Container and buffer

6. Container
7. Used nuclear fuel
Figure 1 Illustration of a typical multibarrier system for the disposal of nuclear waste comprising various natural and
engineered barriers. Reproduced with permission from Nuclear Waste Management Organization, Toronto, ON, Canada.
Waste Containers
penetration by corrosion. Mechanical overload

should be avoidable through proper engineering
design, although the time-dependent effects of
creep, even at near-ambient temperature, can be
more difficult to predict. Nevertheless, the most
likely cause of canister failure, and that addressed
here, is corrosion.
Selection of an appropriate canister material
depends on a number of factors, including
target canister lifetime,
nature of the repository environment and how it
changes over time,
effect of the canister material on other barriers,
robustness of lifetime predictions,
ease of canister fabrication, sealing, and inspection,
resource availability, and
cost.
Various classes of alloy have been considered for canisters for SF/HLW and LILW.717 For SF/HLW, for
which absolute containment is a prerequisite and for
which longer canister lifetimes are often desirable,
the main classes of materials that have been considered
are oxygen-free copper,5,6,10,11 carbon or mild steel
(C-steel),2,3,13,14 titanium alloys,1,2,7,8,12 and certain
nickel-based alloys.1,79 For LILW, for which absolute
containment is not always required (indeed, some
LILW canister designs incorporate a vent to allow
gases produced by degradation of the waste form to
escape), the main classes of materials considered are
C-steel and various grades of stainless steel.8,1517
An important aspect of the selection of nuclear
waste canister materials is the ability to make justifiable long-term predictions of the corrosion behavior.
Various methods have been developed for predicting
either the rate of, or the susceptibility of a given
material to, different types of corrosion, including
general corrosion, localized corrosion in the form of
pitting or crevice corrosion, stress corrosion cracking
(SCC), microbiologically influenced corrosion
(MIC), and the effects of absorbed hydrogen.
This chapter discusses the major aspects of
the corrosion of canister materials for the disposal
of nuclear wastes, namely material selection, the
corrosion behavior under repository conditions, and
lifetime prediction. The nature of the disposal environments is also briefly described in order to provide
necessary background for the corrosion discussion.
Specifically excluded from the current discussion
are corrosion issues associated with interim storage,
the long-term behavior of nonmetallic canister materials such as ceramics, and any discussion of canister
423
design, fabrication, and sealing except inasmuch as it

might impact the corrosion behavior.
5.17.2 Repository Environments

5.17.2.1
Environmental Factors
Table 1 provides a brief summary of selected national

nuclear waste programs. Detailed descriptions of the
environmental conditions in different repositories in
different host rocks can be found elsewhere. The most
important of these conditions have been discussed.
High-activity wastes emit heat, resulting in elevated

canister surface temperatures. A maximum canister
surface temperature of 100 C is specified in many
repository designs in order to minimize adverse
effects on other barriers and to minimize the effects
of the initial thermal transient on the near-field
environment.2,3,5,6 In contrast, the Yucca Mountain
Repository in the United States was designed to
operate at an elevated temperature (maximum canister surface temperature of 200250 C) for a period
of several hundred years, partly to preclude the possibility of aqueous corrosion processes until the initial activity of the waste had decayed significantly.1
Low- and intermediate-level wastes (ILWs) do not
produce significant decay heat and containers for
these wastes will be subject to ambient repository
temperatures, except for a period of elevated temperature due to the curing of cementitious backfilling
materials, if used.17
5.17.2.1.2 Chloride concentration
The Cl concentration depends largely on the nature

of the host-rock environment and can vary from a few
tens to many thousands of milligrams per liter. Sedimentary clay host rocks in Belgium, for example,
exhibit Cl concentrations in aquifers close to the
proposed Boom Clay host formation of 18 mg L1.22
In contrast, salt formations contain brine inclusions
with Cl concentrations of up to 200 g L1.8 In some
host-rock formations, such as fractured granitic formations in Finland, Sweden, and Canada, the salinity
of the groundwater increases with increasing depth
(Figure 2).5,6,21 Higher salinity groundwaters tend to
be older groundwaters that have concentrated due to
prolonged waterrock interactions and/or waters that
were originally formed from ancient seawaters. In
either case, the fact that there is a distinct gradation
of salinities indicates that the deeper waters have had
little interaction with the shallower fresher waters,
424
Table 1
Waste Containers
Main characteristics of various national nuclear waste disposal programs
Waste type Host rock
Repository
locationa
Backfillb
UK
ILW
Generic
Saturated
Cementitious Ambient
UK
Germany
Spain
HLW (SF)
HLW/SF
SF
Saturated
Saturated
Saturated
TBD
100?
Crushed salt 200
Bentonite
100
Belgium
France
HLW (SF)
HLW/SF
Generic
Salt
Granite,
clay
Boom clay
Clay
Saturated
Saturated
Saturated
Cementitious <100
None HLW <100
Bentonite-SF
Bentonite
130
Saturated
Saturated
Saturated
Saturated
Bentonite
Bentonite
Bentonite
Bentonite
Switzerland HLW/SF
Sweden
Finland
Japan
Canada
SF
SF
HLW
SF
USA
SF/HLW
Opalinus
clay
Granite
Granite
Generic
Granite
Shale/
limestone
Tuff
Unsaturated None
Maximum canister Groundwater Notes References

temperature ( C) [Cl] (mg L1)
To be
determined
(TBD)
TBD
300 000
6550
17
2
3
4
18
8
8
27
2000
4,8,19
20
3450
<100
<100
100
100
6900
16 000
TBD
34 300
200 000
5
6
5
6
2
14,21
200220
a
Refers to whether the proposed repository location is below the water table in the saturated zone or above the water table in the
unsaturated, or vadose, zone.
b
Refers to the material in contact with the canister. The same or other materials may be used as backfill elsewhere in the repository.
1 No specific location has been identified to host an ILW repository in the United Kingdom. 2 No specific location has been identified to
host a HLW (and SF if it is deemed to be a waste) repository in the United Kingdom. Three generic types of host rock have been defined
(a lower-strength sedimentary rock, a higher-strength rock, and an evaporite) and indicative groundwater compositions defined. 3 After
a period of some R&D activity, progress on the German program has slowed. 4 Spain has considered both clay and granite host-rock
formations. The groundwater [Cl] given is that for granite host rock. 5 The Japanese program has considered various generic host rock
types and associated groundwaters and awaits a volunteer host community. 6 Canada has investigated both granitic and sedimentary
host rocks. The Cl concentrations given are the maximum for each type of host rock. 7 At the time of writing, the US Department of
Energy has applied to withdraw the License Application for the Yucca Mountain Repository. The [Cl] concentration refers to that of J-13
well water, but the seepage water dripping on to the hot drip shields and waste packages will be evaporated to dryness, potentially
resulting in highly concentrated electrolytes.
an obvious advantage for deep geological disposal of

nuclear wastes.
5.17.2.1.3 Groundwater and pore-water
chemistry
Chemical species other than Cl can also influence

the corrosion behavior of the canister. Sulfur species
are discussed in more detail below. Carbonates can
induce passivity of active materials, such as copper
or C-steel, and can inhibit the localized corrosion of
passive materials, such as stainless steel and Ni-based
alloys.7 Cations can also influence the corrosion
behavior; for example, the hydrolysis of Mg2 leads
to acidification of brine inclusions, and species such
as Ca2 and Mg2 can become incorporated into
corrosion product layers.7,8
It is important to recognize that the composition
of the aqueous phase contacting the canister may
differ from that of the groundwater.6 In many disposal
systems, the canister is to be surrounded by a bentonite
clay buffer material.2,3,5,6 Bentonite is an ion-exchanger
and will modify the cationic composition of the

groundwater depending on the nature of the counterion (typically either Na or Ca2).3,6 Naturally
occurring bentonite clays also contain impurity minerals, such as gypsum, anhydrite, calcite, pyrite, and
halite, the dissolution of which will further modify
the composition of the solution contacting the canister.
5.17.2.1.4 pH
Natural groundwaters tend to have neutral or slightly

alkaline pH values. The presence of calcite in the
bentonite will buffer the pore water at pH 8.3,6
In some disposal systems, a cementitious material is
used to control the interfacial pH in the near field,
either to promote passivation of the canister material
as in the case of the Belgian Supercontainer or to
control the solubility of radionuclides.4,8,17,19,22 The
pH of a cementitious backfill will evolve as the pore
fluids are flushed by incoming groundwater, from an
initial value of pH 13 due to the presence of alkali
metal hydroxide phases, to a period of pH 12
Waste Containers
KR 1
KR 3
Sea
Dilute
NaClHCO3
brackish
Oxid. of
org. matter
Silicate + Calc.
dissolution
Brack. NaClSO4
425
KR 23
KR 4
SO4 red. +
DOC oxid.
Calcite +
pyrite ppt.
100 m
HZ19
Carb. reduction
Brack. NaCl
Methanogenesis
SO4 red. +
CH4. oxid.
Calcite +
pyrite ppt.
300 m
Saline NaCaCl
HZ20
400 m
Carb. reduction
Saline CaNaCl
Methanogenesis
HZ21
900 m
Figure 2 Hydrogeochemical site model of the baseline groundwater conditions and main waterrock and microbial
processes at Olkiluoto. KR1, KR3, KR4, and KR23 denote different boreholes and HZ19, HZ20, and HZ21 denote major
reaction zones between compositionally different ground waters. Reproduced from Pastina, B.; Hella, P. Expected Evolution
of a Spent Fuel Repository at Olkiluoto; Posiva Oy: Olkiluoto, Finland, 2006; POSIVA 2006-05.
controlled by Ca(OH)2 phases, and eventually to the

background pH of the groundwater.23
5.17.2.1.5 Sulfur species
Pyrite and other sulfide minerals are found in many

potential host-rock formations, as well as being present as an impurity in some of the clay materials that
may be used to backfill and seal the repository.3,5,6,22
Oxidation of these minerals by atmospheric O2 during the operational and early postclosure phases will
not only consume O2 but will also produce acid and a
range of oxidized sulfur species, including thiosulfate
8,24
Sulfide and thiosulfate are particularly
(S2O2
3 ).
aggressive toward a number of candidate canister
materials.7,8,10,11
In addition to sulfur-containing minerals in the
host rock and backfill materials, the groundwater itself
can be a source of sulfide. Most groundwaters contain
sulfate which can be reduced by sulfate-reducing
bacteria to form sulfide.25 A number of deep groundwaters also contain natural background levels of
sulfide ions.6,8
5.17.2.1.6 Redox conditions
There are two distinct types of redox behavior, determined by the location of the repository with respect
to the water table. Because deep groundwaters are
anoxic, for the majority of repository designs that
are located below the water table, the redox conditions will become anaerobic after a brief period of
aerobic conditions during which initially trapped
atmospheric O2 is consumed.3,6,7,13,21,26 The transition from aerobic to anoxic conditions will have a
significant impact on the corrosion behavior of the
canisters. (Here, the term anoxic is used to denote
the absence of O2, whereas the term anaerobic is
used in a relative sense to describe a system that is
less oxidizing.)
426
Waste Containers
For repositories located above the water table, the

Yucca Mountain repository being the most obvious
example, the system is essentially continuously aerated.1 This has a significant impact on material
selection.27
5.17.2.1.7 Radiolysis and irradiation
High-activity wastes (SF and HLW) produce a significant g-radiation field that can penetrate the wall
of the canister and produce both oxidizing and reducing species by the radiolysis of the surrounding pore
or groundwater. However, canister designs generally
comprise a sufficiently large wall thickness so that the
external radiation absorbed dose rate is minimal
(1 Gy h1).28
Radiolysis effects are generally insignificant for
the corrosion of LILW canisters.
5.17.2.1.8 Degree of saturation
Repositories located above the water table are, by

definition, permanently unsaturated. This has the
advantage that the rate of transport of dissolved
radionuclides is low, but does mean that the rate of
transport of atmospheric O2 to the canister surface is
rapid, resulting in permanently aerobic conditions
and the need for highly corrosion-resistant materials.1,27 In addition, groundwater can evaporate on the
canister surface resulting in highly concentrated
aqueous phases.1 Even for repositories located
below the water table, there will be a period of
unsaturated conditions until the excavated workings
have resaturated and/or until the thermal pulse from
heat-generating wastes has subsided.29
5.17.2.1.9 Mass-transport conditions
Besides being important for the transport of radionuclides following canister failure, the rate of transport of oxidants to and of reactants away from the
canister surface also affects the corrosion behavior.30
In bentonite-backfilled systems, mass transport will
be by diffusion only. The steady-state mass-transfer
coefficient (D/d, where D is the diffusivity and d is
the diffusion layer thickness) in compacted bentonite
is five to seven orders of magnitude lower than in
bulk solution, with obvious implications for film formation and the supply of oxidants.31 Conversely, in
nonbackfilled repository designs, the rate of mass
transport can be rapid.
5.17.2.1.10 Microbial activity
In general, nuclear waste repositories are inhospitable environments for microbes.25 The combined
effects of high temperature, radiation fields, saline
groundwaters and pore fluids, mechanical forces from

swelling smectite clays, redox conditions, the lack of
organic nutrients and terminal electron acceptors, and
low water activity contribute to this lack of microbial
activity. Although microbes can be identified that can
survive extremes of each of these conditions, the combined effects of a number of environmental stressors
will limit both the activity and diversity of the microbial population in the repository.
5.17.2.1.11 External loads and residual stress
Nuclear waste canisters will be subject to a number

of sources of stress.5,6,13,26 Residual stress from
HLW/SF canister fabrication and sealing is difficult
to relieve by heat treatment because of thermal limits
for the waste forms, although various nonthermal
stress-relief methods are available.1 For bentonitebackfilled repository designs, external forces due to
buffer swelling and hydrostatic pressures will exert
loads of 510 MPa, depending on bentonite density
and the depth of the repository.5,6,13 An additional
2030 MPa hydrostatic load may occur during periods of glaciation. Lithostatic loads will result from the
creep of the rock in the case on nonself-supporting
host formations, such as salt.8 Canisters may also be
exposed to shear loading due to seismic activity or, in
nonbackfilled repository designs, rock impact from
degradation of the excavated tunnels and rooms.1
5.17.2.2
Evolution of the Environment
Regardless of the repository design, the environmental conditions to which the canisters are exposed will
evolve over time.5,6,13,21 For heat-generating wastes in
repositories located beneath the water table, this evolution can be generally described as a shift from an
initially warm and aerobic phase to a period of longterm cool, anoxic conditions (Figure 3).9,21 Even for
permanently aerobic repositories in the unsaturated
zone, environmental conditions will become more
benign as the heat from the canisters dissipates
throughout the host rock.1 Other aspects of the repository environment will also change over time, such as
the degree of saturation or the composition of the
backfill pore fluids (Figure 4).29
This evolution in the repository environment has
profound implications for the corrosion behavior of
the canisters.7 Just as the environmental conditions
will evolve, so too will the corrosion mechanisms to
which the canisters are subjected. In general terms,
relatively rapid forms of localized corrosion or SCC
are most likely during the initial warm, aerobic phase.
Waste Containers
Vault redox
conditions
Oxidizing
Container temperature (C)
100
Warm, oxidizing
period
427
Cool, nonoxidizing
period
Temperature
80
60
40
20
[Oxygen]
Nonoxidizing
10
102
103
Time since emplacement (year)
104
Figure 3 Schematic illustration of the evolution of the repository environment from an initial warm, oxidizing phase to an
eventual cool, nonoxidizing period.
Dry-out
phase
Redistribution of initial
moisture content
Poor thermal conduction
No swelling of sealing
materials
Dissolution and reprecipitation
of minerals
No deliquescence
No corrosion
No gas generation
No O2 consumption
No microbial activity
Transition
phase
Saturated
phase
Gradual saturation of bentonite

Improving thermal conduction
Development of swelling
pressure
Dissolution of minerals
Deliquescence of precipitated
salts
Corrosion due to formation of
thin surface water film
Gas generation possible for
nonnoble canister materials
once O2 depleted
O2 consumption
Complete saturation of bentonite

Good thermal conduction
Swelling pressure fully developed
Gradual equilibration of pore water
with groundwater
Corrosion in fully saturated
bentonite
Gas generation possible for
nonnoble canister materials once O2
depleted and for Cu/steel
container once outer shell
breached
O2 completely consumed
Onset of anoxic conditions
Time
Figure 4 Summary of some of the processes accompanying the evolution of the environment in a bentonite-backfilled
repository during and after the thermal transient.
As the environmental conditions become more

benign, so too will the forms of corrosion, with relatively slow general corrosion replacing the rapid
localized attack. This is an important consideration
since if it is possible to design a canister that will
remain intact for the duration of the relatively short
early transient period, then there is a possibility of
achieving long-term containment.
Although most forms of corrosion become more
benign as the environment evolves, it can be argued
that various forms of MIC and hydrogen-related

degradation become more likely.25,32
5.17.3 Material Selection

A number of factors come into the decision about
which material(s) should be considered for the fabrication of nuclear waste canisters, some of which are
discussed briefly below. Table 2 summarizes the
428
Waste Containers
Table 2
Reference and alternative candidate canister materials in various national nuclear waste programs
Waste type
Reference canister material(s)
Alternative canister material(s)

considered
References
UK
UK
Germany
ILW
HLW (SF)
HLW/SF
HLW/SF
Belgium
France
Switzerland
Sweden
HLW (SF)
HLW/SF
HLW/SF
SF
BS4360 C-steel
C-steel, copper, Ti alloys, NiCrFe alloys
Inconel 625, Incoloy 825, Cu10Ni,
Cu30Ni, cast steel, cast iron
AISI 316L, Hastelloy C-22, oxygen-free
copper
AISI 316L hMo
Undefined passive alloy
Copper
Ti alloy
17
18
8
Spain
AISI 304L/316L
TStE 355 C-steel, Hastelloy C-4,

Ti 99.8-Pd, pure copper
TStE 355 C-steel
Finland
SF
6,11
Japan
Canada
USA
HLW
SF
SF/HLW
Ti alloys, copper
Ti alloys
C-steel, various NiCrMo alloys
2
9,14,3538
1,7,27,3946
C-steel
C-steel
C-steel
Copper, cast iron structural
support
Copper, cast iron structural
support
C-steel
Copper, C-steel
Alloy 22, Ti-7 drip shield
reference and alternative canister materials in a number of national nuclear waste programs.
5.17.3.1
Target Lifetime
A primary consideration when selecting a canister

material is the desired period of containment.9
A number of materials can be expected to provide
containment for a period of 300 years, the length of
time generally associated with the period of maximum radiological hazard (since it corresponds to ten
half-lives of 137Cs). However, if indefinite containment is required (generally taken to be a period of
105106 years) to ensure the safety of the entire disposal system, then only materials that may become
thermodynamically stable (e.g., copper) or which
provide excellent corrosion resistance (e.g., certain
Ti and NiCrFe alloys) are suitable candidates.
5.17.3.2
Active Versus Passive Materials
Materials can be generally classified as being either

passive or active depending on whether they form a
highly protective passive film or whether they dissolve actively under repository conditions.7 Examples of active materials are pure copper and C-steel
in chloride-dominated environments at near-neutral
pH. The range of passive materials that have been
considered as canister materials include stainless
steels, a-titanium alloys, certain NiCrFe alloys,
and, in the presence of a cementitious backfill,
C-steel. Active materials will tend to corrode uniformly and are less subject to localized forms of
corrosion. Passive materials, on the other hand,
8
4,8,19
20
13
5,10,26,33,34
exhibit slow or negligible rates of general corrosion

but can be subject to rapid forms of localized attack
under certain conditions.
An associated consideration is the robustness of
any prediction of the future corrosion performance of
the canister. In this regard, there has been a preference to select active materials since there is more
confidence in making long-term predictions of materials that undergo general corrosion. Although significant advances have been made in recent years in our
mechanistic understanding of, and the development
of predictive models for, localized corrosion and of
environmental-assisted cracking, there is still a reluctance to accept that we can make justifiable longterm predictions for materials that are susceptible to
localized attack or cracking.
5.17.3.3
Environmental Considerations
The environmental conditions to which the canisters

will be exposed clearly influence the choice of material. Stainless steels are clearly unsuitable in nearneutral pH chloride-rich environments because
of the risk of localized corrosion and SCC.47,48 The
thermodynamic immunity enjoyed by copper in
anoxic environments is compromised by sulfide ions,
in the presence of which copper will corrode with
the evolution of hydrogen.10,11,49 In permanently
aerobic environments, highly corrosion-resistant materials are required, such as NiCrFe and crevicecorrosion-resistant Ti alloys.1,27,42,50
However, it is always necessary to consider the
nature of the interfacial environmental conditions
Waste Containers
when selecting a canister material. For example,

copper may be perfectly suitable for use in sulfidecontaining groundwaters if the rate of supply of sulfide to the canister surface is limited by the presence
of highly compacted bentonite.5,6,26 Similarly, stainless steels may be used in chloride environments
without threat from localized corrosion or SCC
provided the pH is alkaline and/or the environment
is anoxic.15,16,51 It is possible, therefore, to modify the
near-field environment to improve the canister corrosion performance through appropriate repository
design and engineering.
5.17.4 Corrosion Behavior of

Candidate Canister Materials
In a given environment, a given canister material will
be subject to one or more corrosion mechanisms. The
corrosion mechanisms investigated in the various
national programs are summarized in Table 3 and
discussed in more detail below for each (class of )
canister material.
5.17.4.1
Carbon Steel
Carbon steels are alloys of iron and carbon with a

C content of <2 wt% and typically contain Mn
(<1.65 wt%), Si (<0.60 wt%), Cu (<0.60 wt%),
and small amounts of other alloying elements, such as
Cr, Ni, Mo, W, V, and Zr.68 The alloys proposed as
candidate canister materials fall into the subset of
alloys referred to as low-carbon (0.050.15 wt% C) or
mild (0.160.29 wt% C) steels. In some cases, cast
steels or cast iron (an ironcarbon alloy containing
Table 3
UK
Germany
Spain
Belgium
France
Switzerland
Sweden
Finland
Japan
Canada
USA
a
429
>2 wt% C and 13 wt% Si) have been proposed either

as canister materials or, in the latter case, as structural
inserts inside a primary corrosion barrier.8,26
Carbon steels have been proposed for use in a
number of countries (Table 2). Although specific
grades have been defined in some programs, the
majority of countries are still at a relatively early
stage of investigation, and refinement of the chemical,
microstructural, and physical properties of the alloy
is still required.
Although it was at one time considered as a
corrosion barrier for the permanently aerobic Yucca
Mountain repository,39 C-steel is best suited as a canister material in repositories located in the saturated
zone which will become anoxic. Not only can the rate
of corrosion of C-steel be excessive in the presence of
O2 (tens to hundreds of micrometers per year depending upon salinity and the rate of mass transport),
but localized corrosion and certain forms of SCC are
also more likely under aerobic rather than anaerobic
conditions.14 Although there will always be a period
of aerobic conditions even in repositories located
beneath the water table, the extent of the oxidizing
phase will be limited and the resultant corrosion
minimal. Once the initially trapped O2 has been consumed, the rate of general corrosion will be lower and
the probability (and potential severity) of localized
corrosion and SCC much diminished. However,
anaerobic corrosion will produce hydrogen and the
consequences of gas production for both the material
itself and the performance of the other engineered and
natural barriers need to be considered.
Figure 5 shows the potential-pH (Pourbaix) diagram for the FeH2O system at 25 C.69 Iron, and by
Corrosion processes for reference canister materials in various national nuclear waste programs
Reference canister
material(s)
Corrosion processes considereda
References
AISI 304L/316L
TStE 355 C-steel
TStE 355 C-steel
C-steel
C-steel
C-steel
Copper
Copper
C-steel
Copper
C-steel
Alloy 22
Ti-7 drip shield
Atmospheric corrosion, pitting, SCC, general corrosion

General corrosion, pitting, SCC, intergranular attack (IGA)
General corrosion, localized corrosion, SCC, IGA
General corrosion
Oxidation, general corrosion
General corrosion, localized corrosion, SCC, HIC
General corrosion, localized corrosion, SCC, MIC
General corrosion, localized corrosion, SCC, HIC
General corrosion, localized corrosion, SCC, HIC, MIC
General corrosion, crevice corrosion, SCC, MIC
General corrosion, HIC, SCC
1517,5154
8
8
4,8,19,55
20,56
3,13,32,57,58
5,10,26,59
6,11
2,6062
25,29,3537,6365
14,25,66
1,7,25,27,4045,67
1,12,17
Corrosion processes considered to be most important are given in italic.
430
Waste Containers
2
2.2
10
11
12
13
14
15
1.8
1.8
1.6
1.6
20
1.4
1.2
1.4
0 2 4 6
Fe3+
FeO42
10
1.2
1
0.8
1
FeOH2+
4
0.4
E(V)
0.8
0.6
11
0.6
Fe(OH)+2
28
0.4
Fe2O3
0.2
0
Fe2+
0.2
0.2
0.4
16
2.2
0.2
26
23
0.6
0
2
4
6
0.4
17
0.6
Fe3O4
13
0.8
27 6
0.8
HFeO2
1
24 6
1.2
1
1
Fe
1.2
1.4
1.4
1.6
1.6
1.8
2
10
11
12
13
14
15
1.8
16
pH
Figure 5 Potential-pH (Pourbaix) diagram of the ironwater system at 25 C considering Fe2O3 and Fe3O4 as the stable Fe
(III)- and Fe(II)-containing solid phases. Lines a and b represent the equilibria between water and hydrogen and water and
oxygen, respectively, for unit fugacity of the gaseous species. The 0, 2, 4, and 6 indicate the equilibrium conditions
between the various solid and dissolved phases for activities of 0, 102, 104, and 106, respectively. Reproduced from
Pourbaix, M. Atlas of Electrochemical Equilibria in Aqueous Solutions, 2nd ed.; NACE International: Houston, TX, 1974.
inference C-steel, corrodes at all pH and redox conditions associated with the various repository environments. Furthermore, solid corrosion products are
predicted to be stable over a wide range of conditions,
with Fe(III) corrosion products stable under the relatively oxidizing conditions associated with the presence of O2 (represented by Fe2O3 in Figure 5) and
Fe(II)-containing corrosion products (here represented
by Fe3O4) stable under anaerobic conditions. Magnetite, in particular, is thermodynamically stable over a
wide range of pH in anaerobic environments, extending from the near-neutral pH conditions associated
with bulk groundwater or bentonite pore water to the
alkaline range representative of cement pore waters.
The thermodynamic tendency for C-steel to corrode under anaerobic conditions has significant
implications since it involves the formation of
H2.2,13,32,57,70 The most likely reaction scheme for
the formation of Fe3O4 involves the initial formation
of ferrous hydroxide followed by the transformation
of Fe(OH)2 via the Schikkor reaction
Fe 2H2 O ! FeOH2 H2
I
3FeOH2 ! Fe3 O4 2H2 O H2
II
A large fraction of the hydrogen that forms from

reactions [I] and [II] will be evolved as gaseous H2.
The generation of gaseous H2 in a repository that is,
Waste Containers
431
Corrosion rate (mm year1)
30
20
10
Time (years)
Figure 6 Time dependence of the anaerobic corrosion rate of carbon steel in compacted bentonite saturated with synthetic
seawater or groundwater. Reproduced from Taniguchi, N.; Kawasaki, M.; Kawakami, S.; Kubota, M. Corrosion behaviour of
carbon steel in contact with bentonite under anaerobic condition. In Prediction of Long Term Corrosion in Nuclear Waste
Systems, Proceedings of the 2nd International Workshop, Nice, France, Sept 2004; pp 2434, European Federation of
Corrosion and Andra.
by design, meant to be sealed can be problematic.3 In

nonbackfilled repositories, typically those for the
disposal of LILW, the concern is that the large
volumes of metallic and organic wastes (and metallic
container materials) may result in the formation of
excessive gas pressures and either the enhanced
release of gaseous radionuclides or structural damage
to the host rock.71 The high organic content of LILW
results in significant microbial activity and the conversion of H2 and CO2 to methane by methanogens.
In bentonite-backfilled HLW/SF repositories, even
small amounts of anaerobic corrosion can result in
the formation of a H2-gas phase because the permeability of the compacted bentonite is so low. Hydrogen is likely to be transported through the bentonite
by two-phase flow involving both dissolved and gaseous H2. A similar transport mechanism is likely to
occur in low-permeability host rocks, such as the
sedimentary Opalinus Clay.
The rate of general corrosion determines not only
the canister lifetime (and, hence, the required wall
thickness for a given target lifetime), but also the rate
of H2 generation (under anaerobic conditions). As
noted above, the rate of aerobic corrosion of C-steel
in saline environments can be of the order of tens to
hundreds of micrometers per year.14 If the amount of
available O2 is limited, as in a repository located
beneath the water table, the rate of aerobic corrosion
is not particularly important since the total amount of
corrosion is determined by the initial oxygen inventory
and is typically limited to a few hundred micrometers.
Of greater interest is the rate of anaerobic corrosion, since it is this rate that primarily determines the
lifetime of the canister (in the absence of localized
corrosion or environmentally assisted cracking).
Figure 6 shows the measured time dependence
of the anaerobic corrosion rate of C-steel in compacted bentonite saturated with either synthetic seawater or simulated groundwater.72 The corrosion rate
decreases with increasing exposure time due to the
formation of a protective corrosion product layer.
The long-term corrosion rate is of the order of a
few micrometers per year, although steady state has
not been achieved even after 4-year exposure. In bulk
groundwater solution at near-neutral pH, the corrosion rate reaches an apparent steady state after
a period of 46 months exposure and is of the
order of 0.11.0 mm year1.5,7,70 In simulated cement
pore-water solutions, the anaerobic corrosion rate
of C-steel is even lower, being of the order of
0.010.1 mm year1, due to the stability of a passive
Fe3O4 film.8,16
The nature of the corrosion products on C-steel
vary depending upon the redox conditions and the
composition of the aqueous phase (Figure 7).
Regardless of the environmental conditions, the initial phase formed is precipitated ferrous hydroxide,
Fe(OH)2. Under aerobic conditions various forms of
ferrioxyhydroxide (a-FeOOH, goethite; g-FeOOH,
lepidocrocite; and, more rarely, b-FeOOH, akaganeite) develop, although in the presence of Cl, sulfate, and carbonate ions, various forms of Green Rust
432
Waste Containers
Fe
103
+HCO3
Fe(OH)2
+O2
GR1, GR2
-, (-), -FeOOH
FeCO3,
(Fe,Ca)CO3
Anaerobic
(Schikkor reaction)
+Fe(II)
47 kinds of soils
118 years
1350 data
102
101
Fe3O4
Long-term slow oxidation
-, -Fe2O3
Pitting factor
Data in various soils

(Romanoff, 1989)
-Fe2O3
Figure 7 Summary of the formation and transformation of

corrosion products on carbon steel in aerobic, anaerobic,
and carbonate-containing environments. GR1 and GR2
represent Green Rust 1 and Green Rust 2, respectively.
are the more-likely corrosion products. Under anaerobic conditions, the Fe(OH)2 is transformed to Fe3O4
via the Schikkor reaction [II]. Magnetite can also form
from the transformation of ferrioxyhydroxide in the
presence of Fe(II), a process that will occur during
the transition from aerobic to anaerobic conditions
during the evolution of the repository environment.
In the presence of compacted bentonite, the pore
water of which will contain bicarbonate ions due to
the dissolution of calcite, or in CO2-saturated systems
(as may occur in a LILW repository), the primary
anaerobic corrosion product will be FeCO3 (with
possible incorporation of other cations such as Ca2).
The surface of C-steel canisters will be subject to a
certain degree of localized attack.2,13,32 In nearneutral pH environments, such as in compacted bentonite or bulk groundwater environments, the surface
is protected by a layer of precipitated corrosion products, but the surface film is not sufficiently protective as to be deemed passive in the classical sense as is
the case for stainless steel or titanium alloys. Instead,
the precipitated corrosion product layers tend to be
spatially heterogeneous or patchy, resulting in localized dissolution and the formation of low aspect ratio
pits, that is, local asperities with a width that greatly
exceeds the depth of corrosion. Any localized penetration tends to degenerate into uneven surface
roughening as corrosion progresses. This evolution
toward more uniform corrosion with increasing
depth (or exposure time) can be seen in Figure 8 in
which the pitting factor (the depth of the maximum
penetration divided by the average depth of corrosion) is plotted against the average depth.2 This form
100 5
10
104
103 102 101 100

101
Average corrosion depth (mm)
102
Data in various soils

(surface area, 182364 cm2)
Results in carbonate/chloride
solution (surface area, 182 cm2)
Results in carbonate/chloride
solution (surface area, 364 cm2)
Figure 8 Depth dependence of the pitting factor for
carbon steel exposed to soil and simulated repository
environments. Reproduced from JNC. Repository Design
and Engineering Technology, Supporting Report 2; Japan
Nuclear Cycle Development Institute, 2000.
of surface roughening is a consequence of different

degrees of protection of the surface as a result of the
spatially inhomogeneous corrosion product and may
continue even under anaerobic conditions.
Localized corrosion in the classical sense, that is,
spatially separated but electrochemically coupled
anodic and cathodic reactions, can only occur during
the aerobic phase in the presence of O2 or, possibly, in
the presence of Fe(III). Permanent separation of
anodic and cathodic reactions is only likely to occur
if the surface film is both passive and also semiconducting so that it can support the cathodic reaction.
These conditions are most likely to be met under
more-alkaline conditions when the surface is protected by a passive Fe3O4 film. However, the pH of
fresh cement pore waters is too alkaline and permanent film breakdown is unlikely even in highly saline
waters.16 Although detailed analyses have not been
performed, it is likely that the initially trapped O2
will be consumed before the pore-water pH
decreases due to the flushing of the alkaline cement
minerals. Such an analysis requires knowledge of the
critical [Cl]:[OH] ratio above which film breakdown is possible.
Carbon steels are known to be susceptible to SCC
in a range of environments, although the possibility of
Waste Containers
SCC in repository environments seems remote.14

Many of the environments in which C-steel has been
shown to be susceptible to SCC, such as phosphate and
nitrate solutions, high-temperature water (>250 C),
and environments containing COCO2CH4, are
irrelevant for nuclear waste repositories. Still others,
such as carbonate/bicarbonate and caustic environments, are unlikely to cause cracking either because
of the absence of cyclic loading which appears to be
necessary in the former case or, in the latter case,
because the caustic concentration in cement pore
waters is less than those in which cracking has been
observed. However, prudence dictates that a thorough assessment of the possibility of SCC should be
carried out in these latter cases. Certainly, engineering solutions, such as selecting an SCC-resistant
grade (if such exists) or minimizing tensile residual
stress through a suitable nonthermal stress-relief process, should also be sought.
Hydrogen will be absorbed by the canister during
anaerobic corrosion.2,58,66 Hydrogen can cause a
number of failure mechanisms in steels but these
generally occur either in aggressive environments
(e.g., sour systems containing high concentrations
of H2S and CO2) or in high-strength materials.
The most likely forms of hydrogen degradation for
C-steel in repository environments are blister formation and hydrogen-induced cracking (HIC). However,
even these forms of degradation seem unlikely
because58,66:
repository environments are relatively benign,
resulting in low diffusible H concentrations in the
steel,
the materials proposed for use as nuclear waste
canisters are generally low strength, with maximum yield strengths of the order of 500600 MPa,
the maximum applied stress (3040 MPa) is relatively low,
the surface residual stress can be mitigated by a
suitable nonthermal stress-relief treatment,
surface defects that may act to concentrate stress,
and hence H, can be machined following the final
closure weld, and
the canister material and the design of the final
closure weld can be selected to minimize H effects.
One location on the canister for which it is not possible to mitigate the residual stress or notches or
crack-like defects is the inner surface of the final
closure weld.58 Over time, the H2 partial pressure in
the canister will achieve the same level as that on the
outside of the canister (perhaps 68 MPa). It is
433
possible, therefore, that cracking could initiate from

the inside of the canister. This possibility needs to be
taken into consideration when designing the final
closure weld and when selecting the canister material.
Carbon steels offer a number of advantages and
disadvantages as canister materials for the disposal of
nuclear waste. The advantages include18:
good corrosion characteristics, corroding actively
in compacted bentonite or under passive conditions in a cementitious backfill with minimal
impacts of localized corrosion, SCC, or H-related
degradation;
sufficient structural strength that simple singleshell canister designs are possible;
extensive experience in fabricating and sealing
large C-steel structures, with a corresponding
large number of suppliers;
canister lifetimes of thousands to tens of thousands
of years are achievable, with robust predictive
models supported by archaeological artifacts;
suitable for use in a number of repository designs.
The major disadvantage of the use of C-steel is that
the products of anaerobic corrosion, H2 and Fe(II),
can adversely affect the properties and performance
of other barriers. The effects of H2 have been discussed above. Ferrous species can cause alteration of
bentonite to a nonswelling, and hence nonsealing,
illitic clay structure.73
5.17.4.2
Stainless Steels
Stainless steels are FeCr alloys containing a minimum of 1113 wt% Cr to impart stainless properties.47 A wide range of alloying additions are possible
resulting in an equally wide range of properties. Stainless steels are generally classified according to their
method of manufacture (wrought, cast, or precipitation
hardened), their microstructure (hence, ferritic, austenitic, martensitic, and duplex ferriticaustenitic alloys),
and, within these categories, according to their overall
corrosion resistance (hence austenitic and superaustenitic or duplex and super-duplex alloys). Figure 9
shows the relationship between the different classes of
stainless steel.47
Stainless steels have not been widely considered as
a canister material for HLW/SF because of the poor
performance of many austenitic alloys in warm chloride environments. Chloride is ubiquitous in deep
groundwaters and, even if it is present in only small
concentrations (a few mg g1), evaporative concentration on the warm canister surface can lead to localized
434
Waste Containers
Superferritic
stainless steels
NiCrFe
alloys
Add Cr, Mo
Add Ni for corrosion

resistance in high
temperature environments
430
No Ni,
ferritic
347
Add Nb + Ta
to reduce
sensitization
Add Cr and Ni for

strength and
oxidation
resistance
316L
317L
Superaustenitic
stainless
steels
304
Fe19Cr10Ni
Add Mo for
pitting resistance
304L
Add S or Se for
machinability
Duplex
stainless
steels
309, 310, 314, 330
Add Ti
to reduce
sensitization
321
303, 303 Se
Lower C
to reduce
sensitization
Increase Cr, lower Ni

for higher strength
Precipitation
hardening
stainless
steels
Add Cu, Ti, Al,

lower Ni for
precipitation
hardening
Add Mn and N, lower Ni

for higher strength
201, 202
316
Add more Mo for
pitting resistance
Add Ni, Mo, N

for corrosion
resistance
317
No Ni addition
lower Cr,
martensitic
403, 410, 420
Figure 9 Compositional relationship between different classes of stainless steels. Reproduced from Sedriks, A. J.
Corrosion of Stainless Steels, 2nd ed.; Wiley: New York, NY, 1996.
corrosion (crevice corrosion and/or pitting) and

SCC.47,48 Type 316L austenitic stainless steel was
considered for the Boom Clay repository in Belgium
(Table 2) with a pore-water Cl concentration of
27 mg g1 (Table 1), but was rejected because of localized corrosion caused by thiosulfate ions (S2O2
3 )
formed from the oxidation of pyrite.8,24 Where stainless steel has found acceptance is for the disposal of
nonheat-producing LILW in cement-backfilled
environments (Table 2).17 Overall, however, it is
probably accurate to say that insufficient consideration has been given to the entire range of stainless
steels, particularly the more corrosion-resistant and
duplex alloys, primarily because of the perceived (and
real) problems with the common austenitic alloys.
Stainless steels are stainless because they are protected by a Cr(III)-containing passive film (Figure 10).
The passive film is stable over a wide range of pH
representative of those in natural waters or cement
pore water and over a range of reducing and oxidizing
potentials. However, the film is unstable in acidic
solutions (as may form in pits or crevices), dissolving
as Cr3, and at more-oxidizing potentials, dissolving as

Cr(VI). The range of passivity is reduced in the presence of Cl, other halides, and S2O2
3 and by increased
temperature.24,47,48 The susceptibility to localized corrosion and SCC is diminished by sulfate, carbonate,
and nitrate ions.
Because of the passive nature of stainless
steels, the rates of general corrosion are typically
low.8,1517,51 Rates tend to be higher in aerobic environments than in the absence of O2 and increase with
decreasing pH, increasing [Cl], and increasing
temperature. Even under aerobic conditions in
near-neutral pH environments, however, the rate of
general corrosion is of the order of 1 mm year1 or
less. In simulated cement pore water, the corrosion
rate can be up to a factor of 100 times lower.18
Localized corrosion of stainless steels takes the
form of either crevice corrosion of physically
occluded regions or the pitting of exposed surfaces.48
Crevice or pit initiation is accompanied by film
breakdown and the transpassive dissolution of the
film as Cr(VI). Passivity breakdown can be studied
Waste Containers
2
1.8 log C = 0
1.6
H2CrO4
1.4
2
2.2
10 11 12 13 14 15 16
2
4 0
6
Cr2O27
16
1.6
11
HCrO4
1.8
1.4
CrO42
1.2
1
53
52
0.8
0.6
Cr3+
E (V)
0.8
18 17
0.4
0.6
19
0.4
54
0 2 4 6
27
0.2
0.2
26
34
0.2
0.2
Cr (OH)3
0.4
28
12
0.6
2.2
2
2
4
6
1.2
0.8
435
Cr2+
0
2
4
6
38
47
0.6
0.8
39
15
1.2
CrO23
30
1.4
CrO3
42
1.2
1.4
Cr
1.6
1.8
2 1
0.4
7 8
pH
1.6
1.8
10 11 12 13 14 15 16
Figure 10 Potential-pH (Pourbaix) diagram of the chromiumwater system at 25 C considering Cr(OH)3 as the stable
Cr(III)-containing solid phase. Lines a and b represent the equilibria between water and hydrogen and water and oxygen,
respectively, for unit fugacity of the gaseous species. The 0, 2, 4, and 6 indicate the equilibrium conditions between the
various solid and dissolved phases for activities of 0, 102, 104, and 106, respectively. Reproduced from Pourbaix, M.
Atlas of Electrochemical Equilibria in Aqueous Solutions, 2nd ed.; NACE International: Houston, TX, 1974.
electrochemically by polarizing the sample to

increasingly positive (more-oxidizing) potentials.
Figure 11 shows a series of cyclic voltammograms
in which the potential of the electrode is scanned first
in the positive direction and then in the reverse
direction toward the starting value.1 Passivity breakdown is characterized by a rapid increase in current
(a measure of the rate of dissolution), with the potential at which it occurs referred to as the pitting or
breakdown potential (EB).48 Upon reversing the
potential scan, the measured current is higher
because the film is no longer protecting the surface.
The potential at which the current is the same on the
forward and reverse scans is referred to as the repassivation potential (ERP) and represents the potential
at which a pit or crevice no longer propagates. Breakdown and repassivation potentials can be defined for
both crevice corrosion and pitting by using either
occluded or planar samples, respectively.
The resistance to localized corrosion can be

increased by increasing the Cr, Mo, and N contents.47
The resistance of a particular alloy can be estimated
based on the pitting resistance equivalent number
(PREN) which is given by Sedriks47
PREN %Cr 3:3%Mo 16%N
III
A critical temperature exists above which an alloy is

susceptible to crevice corrosion or pitting for a given
environment. Figure 12 shows a so-called corrosion
map showing the dependence of the critical temperature on Cl concentration for a range of alloys,
including: the austenitic Type 316L (UNS S31603,
with a typical PREN of 27), duplex grade 2205
(S31803, PREN 34), and two higher austenitic alloys
904L (N08904, PREN 36) and 254 SMO (S31254,
PREN 44).74 Theoretically, a given alloy is immune
to localized corrosion if the combination of temperature and Cl concentration lies to the left of the
436
Waste Containers
1500
316L stainless steel
Greater than 1500 mV

without breakdown
Titanium grade 7
Alloy 22
Ercrev
500
E Alloy 22
Ecorr
00264DC_LA_0780c.ai
Potential (mV vs. Ag/AgCl)
1000
Ecorr
500
Ecorr
1010
108
106
Current density
104
102
(A cm2)
Figure 11 Potentiodynamic scans for Type 316L stainless steel, titanium grade-7, and Alloy 22 in concentrated
chloride solution. Reproduced from DOE. Yucca Mountain Reposiotry license application; US Department of Energy,
DOE/RW-0573; 2008.
the critical temperature decreases with increasing

Cl concentration as would be expected and that
the critical pitting temperature is higher than the critical crevice temperature. Furthermore, the localizedcorrosion susceptibility is seen to follow the trend
predicted by the PREN.
An alternative method for assessing susceptibility
to localized corrosion is to compare the value of the
corrosion potential (ECORR) with EB or ERP.48 The
condition for film breakdown under naturally corroding conditions is that
80
Temperature (C)
70
60
50
40
30
20
100
10 000
1000
Chloride concentration (g g1)
316L (S31603) crevice
316L (S31603) pitting
2205 (S31803) crevice
2205 (S31803) pitting
1 00 000
904L (N08904) crevice

904L (N08904) pitting
254 SMO (S31254) crevice
254 SMO (S31254) pitting
Figure 12 Critical temperature for the crevice corrosion

and pitting of various grades of stainless steel as a function
of chloride concentration. Reproduced from ASM. ASM
Handbook, Volume 13B, Corrosion: Materials; American
Society for Metals International: Metals Park, OH, 2005.
respective line, but immunity is also a function of

the nature and duration of the test used to determine the critical temperature. The figure shows that
ECORR > EB
1
To maintain conservatism, the criterion for localized

corrosion is often based on the repassivation potential
ECORR > ERP
2
Clearly, as the repository becomes more anaerobic,

the probability of localized corrosion diminishes as
ECORR shifts to more-negative values.
The susceptibility of stainless steels to localized
corrosion is also a function of the [Cl]:[OH]
ratio.51 The film breakdown potential is observed to
increase significantly above pH 1011.47 Pitting of
Type 304L stainless steel was only observed at a
Waste Containers
300
SCC
Temperature (C)
250
SAF 2507
No cracking
200
SAF 2205
SAF 2304
150
100
AISI 304/304L
50
AISI 316/316L
No SCC
0.0001 0.001
0.01
0.1
10
Chloride concentration (%)

Figure 13 Corrosion map for the susceptibility of
stainless steels to stress corrosion cracking in aerated
chloride environments as a function of temperature.
Reproduced from Sedriks, A. J. Corrosion of Stainless
Steels, 2nd ed.; Wiley: New York, NY, 1996.
temperature of 60 C in simulated cement pore water

for Cl concentrations >50 000 mg g1, which represents a [Cl]:[OH] ratio of 29 at pH 13.8 The
Mo-containing Type 316L alloy was even more resistant. Localized corrosion of stainless steel in contact
with cement backfill is only likely, therefore, once the
pore-water pH has decreased due to flushing of the
alkaline phases from the cement, but then only if
there is sufficient O2 present that the criterion represented by eqns [1] or [2] is met.
The susceptibility of stainless steels to SCC is
closely related to their localized-corrosion resistance
because pits and crevices act as locations for crack
initiation.47,48 Figure 13 shows an SCC susceptibility
map for various austenitic and duplex stainless
steels.47 The austenitic 304 and 316 alloys are clearly
not suitable for use as HLW/SF canisters because
of the elevated temperatures (on the assumption
that the possibility of canister failure by SCC is
unacceptable). The ferriticaustenitic duplex alloys
2304, 2205, and 2507 are significantly more resistant
to SCC (and to localized corrosion, Figure 12),
although they have not been widely considered for
this application.
Stainless steels possess a number of positive attributes as candidate canister materials, but also exhibit
a number of potential weaknesses.18 The strengths of
stainless steels include:
437
low rates of general corrosion, especially under

anaerobic or alkaline conditions, permitting the
use of thin-walled canisters;
a wide range of alloying options and corresponding
mechanical and chemical (corrosion) properties;
extensive experience in fabricating, sealing, and
inspecting stainless steels vessels with a correspondingly large number of possible suppliers; and
minimal impact on other barriers in the repository.
However, these attributes are countered by the perceived susceptibility of stainless steels to localized
corrosion and SCC in repository environments. Certainly, the common austenitic grades are unsuitable
as canister materials for HLW/SF, although they
might be acceptable when used in conjunction with
a cementitious backfill. Furthermore, study of the use
of duplex alloys seems warranted.
5.17.4.3
Copper
Copper was the first material to be proposed for use

as a SF canister material34 and its suitability is
demonstrated by the fact that it continues to be
the reference material in Sweden, Finland, and
(for crystalline rock) in Canada (Table 2).5,6,10,11,38
Copper has also been investigated in the Spanish and
Japanese programs and even for the salt repository
program in Germany.2,8 The main characteristic of
copper that makes it suitable as a canister material for
the disposal of HLW/SF is that, in the absence
of sulfide, it is thermodynamically stable in deep
groundwaters or bentonite pore water (Figure 14).
As a consequence, once the initially trapped O2 and
any Cu(II) species that are produced by the oxidation
of Cu(I) by O2, have been consumed then corrosion
will theoretically cease.10,11
Although there are a large number of copper
alloys, the main focus of research activities has been
oxygen-free copper. In Sweden, Svensk Karnbranslehantering AB (SKB) have developed specific requirements and propose an alloy referred to as oxygen-free
copper with added phosphorus (OFP copper), where
the P is added to improve the creep rupture strain of
the material.5,26 Because of the high ductility of copper, canisters must include an internal structural
support to withstand the external load, which is typically either cast iron or C-steel.5,6
Apart from its thermodynamic stability in O2-free
water, the other major attribute of copper as a candidate canister material for HLW/SF is the fact that it
will tend to corrode uniformly in the repository environment with little tendency for localized corrosion
438
Waste Containers
1.2
2 4
0 (b)
6
4
Cu2O3 Hydr.
CuCl+
0.8
CuCl2 3Cu (OH)2

6
0
0.4
HCuO2- CuO22
CuCl
E (VSHE)
CuO
CuCl2-
2
4
Cu2O
6
0.4
Cu
0.8
1.2
(a)
10
12
14
pH
Figure 14 Potential-pH diagram for the CuH2OCl system at 25 C with 1 mol dm3 Cl. The shaded box represents the
range of corrosion potentials observed in laboratory experiments in O2-containing solutions.
or SCC.10,11 Copper dissolves actively in Cl environments to form soluble complexes, such as CuCl
2
and CuCl2
3 . The Pourbaix diagram in Figure 14
shows that the solubility of these complexes exceeds
102 mol dm3 in acidic 1 mol dm3 Cl solution
with the formation of solid CuCl at higher concentrations. At near-neutral pH, Cu2O is the thermodynamically stable solid phase and will precipitate at
increasingly lower dissolved copper concentrations
as the pH increases. However, these reactions do not
occur spontaneously in the absence of O2.
Oxygen will be present during the initial period
in the evolution of the repository environment.10,11
Figure 15 shows the various electrochemical, chemical, precipitation/dissolution, adsorption/desorption, redox, and mass-transport processes involved
in the corrosion of copper in compacted bentonite
in the presence of O2 (and sulfide, see below). In
sulfide-free environments, the anodic dissolution of
copper as CuCl
2 is coupled to the cathodic reduction
of O2 on the canister surface. The relative rates of
these reactions establish the value of ECORR, the
range of measured values of which in aerobic and
anaerobic solution are shown by the shaded box in
Figure 14.31 Three of these measurements are shown
in Figure 16, where the atmosphere above the solution has been gradually changed to make the environment less aerobic.10,11 These changes in the
partial pressure of O2 in the experiments (up to
point D on curves (a), (b), and (c)) simulate the

evolution of the repository environment as the initial
aerobic phase transitions to the long-term anoxic
period. Even in deaerated solution (point D), the
value of ECORR lies above the H2O/H2 equilibrium line in Figure 14, indicating that H2O is not
reduced with the evolution of H2. (Note the difference in potential scales in Figures 14 and 16. The
most-negative steady-state potential in Figure 16
of 0.4 VSCE is equivalent to a potential of 0.16 VSHE
on the scale used in Figure 14. The pH of the tests
in Figure 16 was pH 7.) The other processes shown in
Figure 15 have been discussed in detail elsewhere.10,11
Some researchers have questioned the conventional wisdom that copper is thermodynamically stable in O2-free water.7577 On the basis of a series of
experiments, it has been claimed that not only does
copper corrode in O2-free water, but that the rate of
corrosion exceeds that observed in the presence of
O2. Evidence is presented for both evolved H2 gas
and large amounts of H apparently absorbed into the
copper. It is proposed that a previously unrecognized
copper hydroxide species is sufficiently stable that
the potential of the copper surface is at or below that
required for the reduction of H2O,76 although the
only potentials reported by the authors do not support this position. Furthermore, ab initio modeling
studies which have been performed in support of
the claimed mechanism involved a hydroxide radical
Waste Containers
CuCl23Cu(OH)2
k3
kAb
kBf
CuClADS
kS2
CuCl2
kBb
Cu(HS)ADS
k2
kS3
JCu(II)
k6
k1
kS1
Cu
k3
k 4
k 3
Cu2+
Fe(II)
kD
kAf
k4
k 3
CuCl23Cu(OH)2
Cu2+
Cu2+
Cu
Cu(II)ADS
Fe(II)
k1
k6
Fe(III)
JCuCl
k 2
Fe(III)
CuCl2
FeS2
(R0e-Pt + R1)
Cu2O
Cu2S
HS + Fe(II)
k7
Fe(II)
FeS
k7
HS
kE
HS
SRB
JHs
H2 + S2
Fe(III) + SO42
OH
439
kC
O2
SO2
4
Aerobic
microbes
k9
FeS2
+O2
k5
k10
O2(aq)
JO2
k8
O2(g)
Figure 15 Reaction mechanism for the corrosion of copper in compacted bentonite in the presence of O2 or sulfide and
saline groundwater.
0.2
A
B
(b)
C
0.4
A
B
ECORR (VSCE )
0.6
2 h for
curve (a)
only
0.8
1.0
(c)
(a)
0
50
100
150
200
Time (h)
250
300
350
400
Figure 16 Time dependence of the corrosion potential (ECORR) of copper electrodes in 1 mol dm3 NaCl solution at 25 C in
the presence of dissolved oxygen or sulfide. Curve (a) is for a bare copper electrode and curves (b) and (c) are for a copper
electrode covered by a 1-mm-thick layer of compacted Na-bentonite. At points A, B, and C, the original air purge was
changed for gas mixtures of 2 vol% O2/N2, 0.2% O2/N2, and pure N2, respectively. At points D and E, Na2S was added to the
solution to produce a dissolved HS concentration of 10 and 100 mg dm3, respectively.
species, rather than a hydroxide anion.77 The evidence presented to date is far from compelling, but
the question of whether water does corrode in pure
water is being actively studied.
Figure 16 shows the effect of sulfide on the corrosion behavior of copper. At points D and E,
various concentrations of HS were added to the
solution to simulate the effect of sulfide in the
440
Waste Containers
groundwater. In bulk solution (curve (a)), the value of

ECORR fell precipitously to approximately 0.9 VSCE,
while a similar effect was observed for the claycovered electrode (curve (c)) after a delay period
during which the HS diffused through the clay to
the copper surface. Such a potential lies below the
H2O/H2 equilibrium line (Figure 14) and indicates
that copper is corroding with the evolution of H2.49
This reaction mechanism is shown schematically in
Figure 15. This observation has important implications for copper canisters since it demonstrates that
copper will continue to corrode following the consumption of the initially trapped O2 if sulfide is
present and can reach the canister surface.5,6,26 In
an overall sense, curves (a) and (c) in Figure 16
simulate the expected evolution of the corrosion
behavior of copper canisters in the repository as the
initial aerobic environment gives way to one that is
sulfide dominated.
Copper may be susceptible to some degree of
localized corrosion in the repository environment,
although the treatment of localized effects has
changed over the years as we have learnt more about
the corrosion behavior of copper in disposal environments.10,11 The earliest analyses of the corrosion
behavior of copper canisters were theoretically, rather
than experimentally, based.33,34 Because of the wellknown phenomenon of the pitting of copper potable
water pipes, it was deemed appropriate to make an
allowance for pitting. In the absence of specific experimental studies in repository environments, literature
data from a long-term underground corrosion study
were used to estimate a pitting factor, the ratio of the
maximum to the average penetration. Some of the
data from this study showed a pitting factor as high
as 25.34 In subsequent analyses using additional
sources of data, a pitting factor of between 3 and 5
was proposed.33 In other approaches, extreme-value
statistics was applied to the same dataset to predict the
depth of the deepest pit on a canister over a period of
106 years, resulting in a maximum pit depth of
6 mm.36 Both approaches, however, incongruously
predict pit depths of many mm for a material that is
known to be dissolving actively.
It is now recognized that copper is not susceptible
to localized corrosion under repository conditions
but instead corrodes unevenly resulting in a roughened surface.10,11 The evidence for this comes from
experiments in which copper samples have been corroded in contact with compacted bentonite saturated
with an O2-containing Cl solution. At the end of
these tests, the average depth of corrosion was of the
order of 40 mm, with local penetrations of an additional 1015 mm. There was no evidence for the permanent spatial separation of anodic and cathodic
reactions, as would be required for classical
localized-corrosion mechanisms.
Oxygen-free copper is known to be susceptible to
SCC in a limited number of environments that
include ammonia, nitrite, acetate, and, possibly,
sulfide.10,11,59,62,63 Although the canister will be
largely under compressive loading (due to the hydrostatic load and bentonite swelling pressure), it is
difficult to argue convincingly that there will not be
some part of the canister that is not under tensile load
at some stage. Therefore, most studies to date have
focused on whether the appropriate environment can
form. In the case of ammonia, nitrite, and acetate, it is
apparent that cracking only occurs for specific combinations of potential and pH and that the presence of
an oxidant (O2 or, more likely, Cu(II)) is required.63
Since such oxidizing conditions will only be present
in the repository for a relatively short period of time
and since the concentration of these SCC agents in
the repository is so small, it is argued that cracking
due to the presence of ammonia, acetate, or nitrite is
highly unlikely.59 The experimental evidence for
the SCC of copper in sulfide solutions suggests a
threshold [HS] of 0.001 mol dm3.62 Such a high
concentration is unlikely in the repository (due to
precipitation with Fe(II) as FeS) making cracking
equally unlikely, especially since the interfacial sulfide concentration will be minimal because of transport control through the compacted bentonite.59
The possibility of SCC is closely tied to the issue of
MIC because the most likely source of ammonia,
acetate, and nitrite in the repository is microbial
activity.64 All of the candidate canister materials considered here, with the possible exception of Ti-based
alloys, are susceptible to MIC of one form or
another.78 From the viewpoint of the impacts on the
canister, the approach for the different materials is
similar; to demonstrate that microbial activity will
either not occur in the repository or will be extremely
limited. Therefore, the discussion here for copper
canisters is applicable to the other classes of canister
material.
In general, the repository environment is inhospitable for microbes.25 The combined effects of high
temperature, radiation fields, saline groundwaters
and pore fluids, alkaline cementitious pore water,
mechanical forces from swelling smectite clays,
redox conditions, the lack of organic nutrients and
terminal electron acceptors, and low water activity
Waste Containers
will suppress microbial activity. Although microbes

can be identified that can survive extremes of each of
these conditions, the combined effects of a number of
environmental stressors will limit both the activity
and diversity of the microbial population in the
repository. For bentonite-backfilled repositories,
there is much evidence to indicate that the combined
effects of high salinity and high clay density suppress
microbial activity due to the low water activity.79
Although some microbial activity has been reported
in compacted bentonite, it has only been reported in
the presence of added nutrients.80 For cementbackfilled repositories, the alkaline pore fluids will
suppress the activity of the vast majority of microbes,
and taken in conjunction with other environmental
stressors, they will also minimize any impact of
microbes.81 In contrast, microbial activity is expected
to be dominant in LILW repository designs with no
or limited use of cementitious materials.71
Oxygen-free copper would appear to be a suitable
canister material for the disposal of HLW/SF, a conclusion that has been reinforced by the results of extensive studies performed since the idea was first proposed
in the late 1970s. The primary advantages of the use of
copper are its thermodynamic immunity in the absence
of O2 (and sulfide) and the tendency toward general, as
opposed to localized, corrosion in the chloride-rich
environments encountered in most deep groundwaters.
If the conventional thermodynamic wisdom is proven
correct, copper canister lifetimes in excess of 105 years
are entirely possible, and supported by numerous natural and archaeological artifacts.82
5.17.4.4
Titanium Alloys
Titanium alloys have been considered as candidate

canister materials for the disposal of HLW or SF
in a number of countries (Table 2). Early work
focused on the properties of commercially pure
grades, such as Ti-1 and Ti-2, and the dilute Ni,
Mo alloy Ti-12.2,7,12 The key to the use of Ti alloys,
however, is to prevent crevice corrosion and most
recent efforts have been directed toward the potential
use of the Pd-containing alloys Ti-7 (0.080.17 wt%
Pd) or Ti-16 (0.040.08 wt% Pd).7,12 In the US Yucca
Mountain Project, Ti alloys were proposed for use as
a drip shield to be placed over the waste packages
to protect them from seepage drips and rockfall.1
To provide structural strength, crevice-corrosionresistant Ti-24 (0.040.08 wt% Pd) or the
Ru-containing Ti-29 were proposed, both alloys
being based on the basic 6Al4V Ti-5 composition.
441
The passive film on Ti exhibits one of the broadest

ranges of thermodynamic stability of any oxide for
any common structural material (Figure 17). Titanium dioxide is stable at all potentials corresponding
to the stability of water and only becomes soluble in
acidic or highly alkaline solution. The absence of
multiple oxidation states in the oxide makes the
oxide electrically insulating and may contribute to
the apparent immunity to MIC.25 Titanium(III)
forms under cathodic polarization.
As would be expected for such a passive film, the
rate of general corrosion of Ti alloys in repositorytype environments is very low.12 The average corrosion rate of Ti-7 in a range of aerated solutions with
salinities up to several moles per cubic decimeter is
20 nm year1 and is independent of temperature over
the range 6090 C.12 Even lower rates (of the order
of 1 nm year1) have been reported in bentonite
environments.83,84
Localized corrosion of Ti alloys is important not
only because it could lead to more rapid wall penetration but also because it can lead to rapid absorption of
hydrogen.2,7 The pitting potential of Ti alloys in
natural environments is >3 V at temperatures
100 C and pitting does not therefore occur under
freely corroding conditions.7,12 Some Ti alloys, however, are susceptible to crevice corrosion in Cl environments resulting in acidification of the crevice
region and sustained creviced propagation supported
by a combination of O2 reduction on exposed surfaces
outside of the occluded region and the reduction of
H inside the crevice. For Ti-2 and, especially, Ti-12
the internal reduction of H can account for the
majority of the crevice propagation.7,9,12 However,
continued external O2 reduction is required to sustain
the acidified crevice, and without it the crevice would
stifle due to the loss of the critical crevice chemistry.
In that regard, even Ti alloys that are susceptible to
crevice corrosion may not fail in a sealed repository in
which the amount of available O2 is limited.
The more prudent approach to crevice corrosion,
however, is to select a crevice-corrosion-resistant
grade.1,7,12 Additions of Pd suppress crevice corrosion
by promoting passivity by catalyzing H reduction,
thus reducing the local acidity and increasing ECORR.
Figure 11 demonstrates the resistance of Ti-7 to crevice corrosion and the extensive range of passivity of this
particular alloy that extends over more than 1500 mV.1
Another benefit of using a crevice-corrosionresistant Ti alloy is that the amount of absorbed
H is greatly diminished. Titanium forms hydrides and
exhibits slow crack growth or fast fracture above a
442
Waste Containers
2
2.2
TiO22+
2
?
1.8
10
11
12
13
14
15
16
2.2
TiO32H2O
22 ?
1.8
1.6
0
1.4
?
2
? HTiO4
TiO42
1.6
1.4
6
?
1.2
1.2
15
1
0.8
TiO2+
1
0.8
0.6
0.6
?
0.4
0.4
5
0.2
E (V)
TiO2H2O
20
0.2
Ti3+
0.4
0.6
2 4 6
0.8
0.8
11
?
18
Ti2+
21
Ti(OH)3
1.2
1.4
1.8
0.4
3
0
1.4
17
TiO
1.6
1.8
Ti
2.2
2.4
2
1
1.2
13
0
2
4
6
0.2
HTiO3
14
0.6
1.6
0.2
16
2.2
1
7
pH
10
11
12
13
14
15
2.4
16
Figure 17 Potential-pH (Pourbaix) diagram of the titaniumwater system at 25 C considering TiO22H2O as the stable
Ti(IV) containing solid phase. Lines a and b represent the equilibria between water and hydrogen and water and oxygen,
respectively, for unit fugacity of the gaseous species. The 0, 2, 4, and 6 indicate the equilibrium conditions between the
various solid and dissolved phases for activities of 0, 102, 104, and 106, respectively. Reproduced from Pourbaix,
M. Atlas of Electrochemical Equilibria in Aqueous Solutions, 2nd ed.; NACE International: Houston, TX, 1974.
critical absorbed hydrogen concentration7,12 or a critical hydride layer thickness.85 The most common routes
for the absorption of H are cathodic polarization or
galvanic coupling to a more-active material (neither of
which are of concern for nuclear waste canisters) or via
an acidified crevice or pit. Increased acidity not only
promotes H generation but also destabilizes the normally passive TiO2 film.
In the absence of crevice corrosion, however, hydrogen must be absorbed through the passive oxide which
greatly reduces the fraction of H absorbed
(Figure 18).12 The rate of H absorption is a function
of temperature, potential, and the presence of intermetallic particles. Increasing temperature and
decreasing potential promote the rate of H discharge and the fraction of H absorbed by the oxide
Waste Containers
Crevice
corrosion
Development of acidity/
oxide dissolution
443
Film breakdown/recrystallization/
rapid thickening
70 C
Active corrosion under

occluded conditions
Increasing
temperature
Ti3+ dissolution in acidic solution

Rutile
formation
TiIV TiIII (oxide)
TiH2 (1.0 V ) TiOOH
H2 evolution
H absorption
In metal
Hydrogen-induced
cracking
(0.65 V) (0.54 V)
Threshold for
H absorption
In oxide
EOc
H2O
absorption
TiO2
Pitting
(89 V)
Amorphous/crystalline Anatase formation

(TiIIII, OIIv )
Film growth (HFIC)
ND decreases
Film breakdown/
recrystallization/
rapid thickening
EFB (acidic solution)
Figure 18 Schematic illustration of the properties of the passive film on titanium as a function of potential. Reproduced from
Shoesmith, D. W. Corrosion 2006, 62, 703722.
and subsequently by the Ti substrate. Increasing temperature increases the diffusivity of H in a-Ti, with a
temperature of 80 C considered a threshold for the
onset of H problems in practical applications.86
Although intermetallic phases, such as Ti2Ni in
Ti-12 or Pd particles in Ti-7 and Ti-16, can suppress crevice corrosion, they may also promote
H absorption, both by catalyzing the reduction of H
and by acting as preferential sites for H absorption.
There is wide variation in the reported H absorption
efficiency on passive Ti, with values as high as 2%.12
The solubility of H in a-Ti is of the order of
20150 wppm.12 The critical absorbed H concentration (HC) for HIC is alloy-dependent, varying from
500800 wppm for Ti-2, 400600 wppm for Ti-12,
and 10002000 wppm for Ti-16.
Although Ti alloys have not been widely adopted
as candidate canister materials, they offer a number
of advantages for the disposal of HLW/SF.18 Chief
among these advantages are the prospect of very
long canister lifetimes for crevice-corrosion-resistant
grades, the minimal impact on other barriers,
and design flexibility for use in backfilled or nonbackfilled repositories. However, on the assumption
that Ti canisters would be constructed with relatively
thin walls, an internal structural support would
be required. Perhaps the greatest hurdle to the adoption of Ti as a canister material, however, is
the perceived difficulty of predicting and, more
importantly, justifying long-term predictions of passivity and H absorption.

5.17.4.5
Nickel Alloys
Of the various classes of Ni-based alloys, those

considered as candidate canister materials fall
into the NiCrMo or NiFeCrMo families.
Within the NiCrMo family of alloys, Inconel
625 was considered for the salt repository program
in Germany, along with the more-corrosionresistant Hastelloy C-4 (Table 2).8 Hastelloy C-22
(Alloy 22) has been considered in the Spanish program8 and was the reference canister material in the
US Yucca Mountain Project.1 The NiFeCrMo
alloy Incoloy 825 was also considered in Germany
(Table 2).8
As for stainless steels, NiCrMo and NiFe
CrMo alloys rely on the formation of a passive
Cr(III) film for their general corrosion resistance.
Alloying additions of Mo and W (Alloy 22) or Co
(Hastelloy C-4) improve the resistance to localized
corrosion.86 Addition of Si to Inconel 625 and Incoloy
825 improves corrosion resistance under oxidizing
conditions. One of the main advantages of Ni alloys
is the high solubility of many alloying elements,
resulting in both a wide range of material properties
and the general absence of adverse effects due to
secondary phases.
444
Waste Containers
1.00
0.50
0.25
Low uncertainty
Medium uncertainty
High uncertainty
Measured data
0.00
0
20
10
15
General corrosion rate (nm year1)
25
00264DC_LA_0468.ai
Cumulative probability
0.75
30
Figure 19 Cumulative distribution function of the rate of general corrosion of Alloy 22 in saline simulated evaporated
waters at 60 C. Reproduced from DOE. Yucca Mountain Repository license application; US Department of Energy,
DOE/RW-0573; 2008.
Because of their superior passivity, Ni alloys

exhibit low rates of general corrosion in a wide
range of environments. Figure 19 shows a cumulative
distribution function of corrosion rates of Alloy 22
exposed to various aerated synthetic saline solutions
at a temperature of 60 C for a period of 5 years.1 The
mean corrosion rate is 510 nm year1, implying that
a 6.35-mm-thick (0.25 in.) canister would have a lifetime of 106 years. What has not been adequately
addressed in making these sorts of predictions is
how the corrosion rate will vary over the very long
term as the oxide thickens and the underlying substrate becomes depleted in Cr, Mo, W, and other
alloying elements. Corrosion rates are higher in
aggressive acidic Q brine solutions representative
of those that may be present in salt formations, with
rates of up to 0.9 mm year1 at 200 C.8
As for stainless steels, Ni alloys are susceptible to
localized corrosion.1,27,42 Although pitting of exposed
surfaces does occur, most attention has been focused
on the possibility of crevice corrosion as it is difficult
to guarantee that occluded regions will not be present
somewhere on the canister surface and because crevice
corrosion initiates under less-aggressive conditions
than pitting. Figure 11 illustrates the relative susceptibility to crevice corrosion of Alloy 22, Type 316L
stainless steel, and the Pd-containing Ti-7. Although

not as resistant as Ti-7, there is a significant difference
between the corrosion potential and either the breakdown or repassivation potential for Alloy 22. (Note:
the value of ECORR is not strictly given by the point of
zero net current during a potentiodynamic scan, as
indicated in Figure 11. Nevertheless, the difference
of 900 mV between ECORR and Ercrev is an indication of the significant resistance of Alloy 22 to crevice
corrosion.)
The crevice corrosion behavior of Alloy 22 was
extensively investigated as part of the Yucca Mountain Project.1 The focus of these studies was the
initiation of localized attack, with less attention paid
to crevice propagation. The susceptibility to crevice
corrosion was assessed based on the critical potential
criterion in eqn [2].1 A series of measurements were
made of ERP which were then fitted to a polynomial
expression involving T, [Cl], and [NO
3 ]. The crevice repassivation potential shifts to more-negative
values with increasing T and [Cl], but nitrate ions
inhibit localized corrosion. A similar series of longterm ECORR measurements were made and similarly
fitted to a polynomial involving the same variables.
Increasing temperature and nitrate concentration
ennoble ECORR whereas increasing [Cl] shifts
Waste Containers
445
Repassivation potential (mVSCE)
1200
1000
Alloy
825
800
Alloy
625
No crevice Crevice
corrosion corrosion
Autoclave
Glass cell
600
400
Alloy 22
200
0
316L
-200
-400
10-4
10-3
10-2
10-1
100
101
Chloride concentration (mol dm3)
102
Figure 20 Chloride concentration dependence of the crevice repassivation potential for various Ni-based alloys.
Reproduced from Brossia, S.; Browning, L.; Dunn, D. S.; Moghissi, O. C.; Pensado, O.; Yang, L. Effect of environment on the
corrosion of waste package and drip shield materials; Report No: CNWRA 2001-03; Center for Nuclear Waste Regulatory
Analysis, 2001.
1000
Cracking
No cracking
100
Time to failure (h)
ECORR in the active direction.1 The net effect of these

dependencies is that the driving force for localizedcorrosion initiation, that is, the difference DE
between ECORR and ERP, increases with increasing
T and [Cl], but decreases with increasing [NO
3 ].
Figure 20 shows the dependence of ERP on Cl
concentration for the crevice corrosion of various Nibase alloys and Type 316L stainless steel at 95 C.40
The resistance to crevice corrosion increases in the
order 316L (least resistant) < Incoloy 825 < Inconel
625 < Alloy 22 (most resistant) (on the assumption
that the respective values of ECORR are not significantly different).
Possibly because of the continuously aerated environment in the Yucca Mountain repository, it was generally assumed that once initiated a crevice would
propagate rapidly to failure. However, there is convincing evidence that this is not the case and that the
material naturally stifles, without any assistance from
the depletion of O2 that would occur in a saturated
repository.44 Stifling is clearly a result of the loss of the
critical chemistry necessary to sustain crevice propagation, but quite why this should occur is not fully understood. It may well be due to the inherent resistance of
the material (e.g., catalysis of H reduction on Mo- or
W-enriched surface layers in the crevice or the stability
of Mo- and/or W-containing films in the low-pH crevice solution), or it could be due to mass-transport or iR
restrictions. Regardless, there is reason to believe that
the extent of crevice propagation would be limited.
An advantage of Ni alloys over stainless steels is
that they are relatively immune to SCC in warm
10
Minimum time
to cracking
1
0
60
20
40
Nickel content (wt%)
80
Figure 21 Effect of Ni content on the SCC susceptibility of

stainless steels and nickel alloys in boiling MgCl2 solution.
Reproduced from Sedriks, A. J. Corrosion of Stainless
Steels, 2nd ed.; Wiley: New York, NY, 1996.
chloride environments.47 Figure 21 shows the

dependence of the time-to-failure of tensile samples
on the Ni content of the alloy for a range of stainless
steels and various Ni alloys in boiling MgCl2 solution
446
Waste Containers
at 154 C. The NiCrMo alloys with a minimum Ni

content of 50 wt% are clearly more resistant to SCC
than the 300-series stainless steels with Ni contents in
the range 815 wt%. This is borne out by corrosion
testing in which it has proven impossible to crack
Alloy 22 at ECORR in simulated Yucca Mountain
environments.1 Only anodic polarization or the addition of Pb(II) were found to induce SCC.
The passivity of Ni alloys is known to be lost
because of the accumulation of S at the Ni/oxide
interface.87 The source of S is typically the alloy itself
with S accumulating at the interface as a consequence
of the slow dissolution of the alloy. This is one mechanism by which the alloy could periodically lose
passivity and the oxide spall off. However, following
oxidation and dissolution of the accumulated S,
it would seem likely that the alloy would simply
repassivate.
Nickel alloys are suitable canister materials for
a wide range of environments (both permanently
oxidizing and eventually anoxic) and have minimal
impact on other barriers in the overall system. There
is good experience with the design and fabrication of
Ni-alloy vessels in various industries. The corrosion
Table 4
resistance of Ni alloys is excellent, given appropriate alloy selection. However, Ni alloys suffer
from the same negative perception as Ti alloys
regarding the ability to predict the long-term corrosion behavior of a material that depends on a thin
passive layer. This perception is unfortunate since
passive alloys could provide very long-term containment of nuclear wastes.
5.17.5 Canister Lifetime Predictions

Ultimately, it is necessary to make some form of
lifetime prediction for the canister. Table 4 summarizes the general approaches that have been taken
toward predicting different forms of corrosion for the
different classes of candidate canister materials.
The most common method for predicting the
extent of general corrosion is simply to extrapolate
empirically measured corrosion rates, typically
determined using mass-loss measurements. Where
appropriate, as in the general corrosion of Alloy 22
waste packages in the Yucca Mountain repository,
the temperature (and, hence, time) dependence of
Methods used for the long-term prediction of the corrosion behavior of canister materials
General corrosion
Localized corrosion
Environmentally assisted
cracking
MIC
C-steel
Mass-balance,
electrochemical
modeling, and
empirical rates for
aerobic corrosion
Empirical rates for
anaerobic corrosion
Pitting factor
Maximum penetration
based on extremevalue analysis (EVA)
Reasoned argument for no SCC

No effects of H because of low
H concentration and use of
low-strength steel
Stainless
steel
Empirical corrosion
rates
Suppression of SCC by use of

cement backfill
Copper
Mass-balance or
detailed reactivetransport modeling
for aerobic phase
Mass-transport limited
corrosion due to
sulfide
Empirical corrosion
rates
Suppression of localized
corrosion by use of
cement backfill
Pitting factor or EVA
maximum pit depth
Allowance for surface
roughening
Mass balance
based on either
organic C or
sulfate
limitation
Reasoned argument
based on lack of
microbial activity
Reasoned argument for no SCC
Reasoned argument
based on lack of
microbial activity
Limited propagation
argument for Ti-2, Ti-12
or use of resistant Ti-7,
Ti-16, Ti-29 alloys
Threshold potential
(ERP) for initiation,
followed by rapid
propagation
HIC based on either critical

absorbed H concentration or
critical hydride layer thickness
Slip dissolution model
Enhancement factor
for general
corrosion
Ti alloys
Ni alloys
Empirical corrosion
rates
Waste Containers
the corrosion rate may also be taken into account.1 To

account for the time-dependent decrease in corrosion rate due to the formation of a protective or
passive film, empirical rates are generally determined
from relatively long-term tests (up to 510 year duration).1,70,72 For repositories in which there is a limited
inventory of O2, the empirical extrapolation of
measured rates is typically used for the anaerobic
period, with a mass-balance approach based on
the available O2 used for the aerobic period.5,6,13,32
In the case of copper canisters in compacted bentonite, a reactive-transport model, coupled with a
mixed-potential model to predict ECORR, has been
developed.37 The results of this detailed model are
consistent with those based on mass-balance and/or
mass-transport calculations.
There have been many different methods used to
predict the localized-corrosion behavior of canister
materials. For materials that are generally active,
that is, C-steel and copper, the most common
approach has been to use empirical data to either
derive a pitting factor or a time-dependent maximum pit depth.2,13,3234,36 For passive materials, the
approaches taken include:
demonstrating that localized corrosion will not
initiate in the repository environment, in the case
of stainless steels with a cementitious backfill;51
arguing that the extent of propagation will be limited, for example, for Ti-2 and Ti-12 in a bentonitebackfilled repository with limited O29; and
determining whether crevice corrosion will initiate based on a threshold potential criterion and
assuming rapid propagation for those canisters for
which initiation does occur, the approach adopted
for the localized corrosion of Alloy 22 waste
packages.1,27,42
Typically, proponents of the use of a given material
have developed reasoned arguments that the material is not susceptible to SCC.2,13,14,59,63 This is
generally the preferred approach as crack growth
rates are fast compared with repository timescales.
If a material is deemed to be susceptible to SCC,
then this would be sufficient reason to exclude this
material from further consideration. However, even
though the material seems to be immune to SCC
under repository conditions, a slip dissolution was
developed for Alloy 22 waste packages in the Yucca
Mountain Project.1
Hydrogen-related degradation mechanisms are
issues only for C-steel and Ti alloys. In the case
of C-steel, it is argued that the grades of material
447
under consideration (i.e., low-strength steels) are

not overly susceptible and that repository environments will not produce a sufficiently large absorbed
H concentration.2,66 Titanium alloys, on the other
hand, will inevitably form hydrides once sufficient
H has been absorbed. In this case, therefore, the issues
are how fast H is absorbed and the failure criterion
that is to be used for determining failure.7,12 For
crevice-corrosion-resistant Ti alloys, H absorption
can only occur under passive conditions, which is a
slow and not entirely understood process. The two
failure criteria that have been developed are based on
either a critical absorbed H concentration7,12 or a
threshold hydride layer thickness.85
Various attempts have been made to predict the
extent of MIC. Mass-balance arguments based on
the availability of organic C88 or sulfate2 have been
made, and an enhancement factor based on the rate of
general corrosion has been proposed.1,27 Alternatively,
it is possible to argue that the extent of microbial
activity in the repository will be restricted by the
adverse effects of various environmental stressors.25
A reactive-transport model to predict the rate of
microbial activity has been developed based on such
an approach.64
5.17.6 Conclusions
The five classes of alloys that have been proposed as
canister materials for the disposal of nuclear waste
are: C-steels, stainless steels, copper and copper
alloys, Ti alloys, and Ni alloys. Each of these materials has advantages and disadvantages for this application and the selection of the appropriate material
should be based on consideration of the target canister lifetimes, the nature of the disposal environment
and how it evolves over time, and the ability to make
robust and justifiable lifetime predictions.
The corrosion behavior of candidate canister
materials has been the subject of extensive research
over the past 30 years and a number of trends have
emerged during that time:
For repositories that are located below the water
table and for which the amount of oxidant is limited, the preferred approach appears to be based
on the use of either oxygen-free copper (structurally supported by a steel or iron insert) or C-steel,
both in combination with a bentonite backfill.
Copper is the preferred material for crystalline
host rocks for which less credit can be taken for
the geosphere as a barrier, whereas C-steel is
448
Waste Containers
preferred in sedimentary host rocks which themselves provide significant containment.

There are exceptions to this general rule, the most
obvious being the C-steel/cement overpack in the
Belgium program and the nonbackfilled disposal
boreholes being considered for the disposal of
HLW in France.
Passive materials are primarily considered for
highly aggressive environments, such as those in
salt formations or during the early thermal transients in unsaturated repository designs.
The apparent emphasis of active over passive canister materials is partly a consequence of the perceived difficulty in making long-term predictions
of passive behavior and of localized corrosion. This
perception is considered to be unfortunate, since
we have learnt much about predicting the longterm behavior of passive materials over the past
30 years and the use of thin-walled canisters made
from passive alloys offers a number of advantages.
At the time of writing, there is no active program
for repositories located in the unsaturated zone,
the Yucca Mountain Program apparently being on
the brink of cancellation. Although prediction of
the nature of the environment in unsaturated repositories is challenging, location of a nuclear waste
repository above the water table does offer certain
advantages and the issues related to predicting
long-term performance of the canisters are not
considered to be insurmountable.
References
1.
2.
3.
4.
5.
6.
7.
8.
DOE. Yucca Mountain Reposiotry license application; US

Department of Energy, DOE/RW-0573; 2008.
JNC. Repository Design and Engineering Technology,
Supporting Report 2; Japan Nuclear Cycle Development
Institute, 2000.
Nagra. Project Opalinus Clay, Safety Report; Nagra
Technical Report NTB 02-05; National Cooperative for the
Disposal of Radioactive Waste, 2002.
ONDRAF-NIRAS. A review of corrosion and material
selection issues pertinent to underground disposal of
highly active nuclear waste in Belgium; ONDRAF Report
Ref: NIROND 2004-02; 2004.
SKB. Long-term safety for KBS-3 repositories at
Forsmark and Laxemar A first evaluation; Main
Report of the SR-Can project; Technical Report TR-06-09;
Swedish Nuclear Fuel and Waste Management Co.,
2006.
Pastina, B.; Hella, P. Expected Evolution of a Spent Fuel
Repository at Olkiluoto; Posiva Oy: Olkiluoto, Finland,
2006; POSIVA 2006-05.
Shoesmith, D. W. Corrosion 2006, 62, 703722.
Kursten, B.; Smailos, E.; Azkarate, I.; Werme, L.; Smart, N. R.;
Santarini, G. COBECOMA, State-of-the-Art Document on
the Corrosion Behaviour of Container Materials; Contract No.

FIKW-CT-20014-20138, Final Report;European
Commission, 2004.
9. Johnson, L. H.; Tait, J. C.; Shoesmith, D. W.;
Crosthwaite, J. L.; Gray, M. N. The disposal of Canadas
nuclear fuel waste: Engineered barriers alternatives;
AECL-10718, COG-93-8; Atomic Energy of Canada
Limited, 1994.
10. King, F.; Ahonen, L.; Taxen, C.; Vuorinen, U.; Werme, L.
Copper corrosion under expected conditions in a deep
geologic repository; Report No: SKB TR 01-23; Swedish
Nuclear Fuel and Waste Management Company, 2001.
11. King, F.; Ahonen, L.; Taxen, C.; Vuorinen, U.; Werme, L.
Copper corrosion under expected conditions in a deep
geologic repository; Posiva Oy Report POSIVA 2002-01;
2002.
12. Hua, F.; Mon, K.; Pasupathi, P.; Gordon, G.; Shoesmith, D.
Corrosion 2005, 61, 9871003.
13. Johnson, L. H.; King, F. Canister options for the disposal
of spent fuel; Technical Report 02-11; Nagra, 2003.
14. King, F. Overview of a carbon steel container corrosion
model for a deep geological repository in sedimentary
rock; Report No: NWMO TR-2007-01; Nuclear Waste
Management Organization, 2007.
15. Smart, N. R.; Wood, P. Corrosion resistance of stainless
steel radioactive waste packages; Report N/110; UK Nirex
Limited, Nirex, 2004.
16. Smart, N. R.; Blackwood, D. J.; Marsh, G. P.; et al. The
anaerobic corrosion of carbon and stainless steels in
simulated repository environments: A summary review of
nirex research; AEAT/ERRA-0313; 2004.
17. Smart, N. R.; Naish, C. C.; Pritchard, A. M. Corrosion
principles for the assessment of stainless steel radioactive
waste containers; Report No: SA/EIG/14921/C010; Serco
Assurance Report to Nirex, 2006.
18. King, F.; Padovani, C. Corrosion Eng. Sci. Technol. 2011,
in press.
19. Bel, J. J. P.; Wickham, S. M.; Gens, R. M. F. In Scientific
Basis for Nuclear Waste Management XXIX, Materials
Research Society Symposium Proceedings;
Van Iseghem, P., Ed.; Materials Research Society:
Warrendale, PA, 2006; Vol. 932, pp 2332.
20. Feron, D.; Crusset, D.; Gras, J. M. Corrosion 2009, 65,
213223.
21. McMurry, J.; Dixon, D. A.; Garroni, J. D.; et al. Evolution of
a Canadian deep geologic repository: Base scenario;
Report No: 06819-REP-01200-10092-R00; Ontario Power
Generation Nuclear Waste Management Division, 2003.
22. SAFIR 2. Safety Assessment and Feasibility Interim
Report 2; ONDRAF/NIRAS; 2001.
23. Berner, U. R. Waste Manag. 1992, 12, 201219.
24. Kursten, B.; Druyts, F. In Corrosion/2000; NACE
International: Houston, TX, 2000; paper no. 00201.
25. King, F. Corrosion 2009, 65, 233251.
26. SKB. Fuel and canister process report for the safety
assessment of SR-Can; Report No: SKB TR 06-22; Swedish
Nuclear Fuel and Waste Management Company, 2006.
27. Farmer, J.; McCright, D.; Gdowski, G.; et al. In
Proceedings of Transportation, Storage, and Disposal
of Radioactive Materials 2000; American Society
of Mechanical Engineers: New York, NY, 2000;
PVP-Vol. 408, pp 5369.
28. Shoesmith, D. W.; King, F. The effects of gamma radiation
on the corrosion of candidate materials for the fabrication
of nuclear waste packages; Report No: AECL-11999;
Atomic Energy of Canada Limited, 1999.
29. King, F. Review and gap analysis of the corrosion of
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Generation, Nuclear Waste Management Division,
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King, F.; Kolar, M.; Shoesmith, D. W. In Corrosion/96;
NACE International: Houston, TX, 1996; paper no. 380.
King, F.; Litke, C. D.; Quinn, M. J.; LeNeveu, D. M.
Corrosion Sci. 1995, 37, 833851.
Johnson, L. H.; King, F. J. Nucl. Mater. 2008, 379, 915.
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No: KBS-3; Swedish Nuclear Fuel Supply Company, 1983;
Vol. IIV.
Swedish Corrosion Institute. Copper as canister material
for unreprocessed nuclear waste Evaluation with respect
to corrosion; Report No: KBS-TR-90; Swedish Nuclear
Fuel Supply Company, 1978.
King, F.; Kolar, M. The copper container corrosion model
used in AECLs second case study; Report No:
06819-REP-01200-10041-R00; Ontario Power
Generation, Nuclear Waste Management Division:
Toronto, ON, 2000.
King, F.; LeNeveu, D. In Proceedings of Conference on
Nuclear Waste Packaging, FOCUS 91; American Nuclear
King, F.; Kolar, M.; Maak, P. J. Nucl. Mater. 2008, 379,
133141.
Maak, P. The selection of a corrosion-barrier primary
material for used-fuel disposal containers; Report No:
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505514.
Brossia, S.; Browning, L.; Dunn, D. S.; Moghissi, O. C.;
Pensado, O.; Yang, L. Effect of environment on the
corrosion of waste package and drip shield materials;
Report No: CNWRA 2001-03; Center for Nuclear Waste
Regulatory Analysis, 2001.
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for waste package materials; Prepared for US DOE;
ANL-DSD-MD-000001; Oct 2004.
Cragnolino, G.; Dunn, D. S.; Brossia, C. S.; Jain, V.;
Chan, K. S. Assessment of performance issues related
to alternate engineered barrier system materials and
design options; Report No: CNWRA 1999-003; Center for
Nuclear Waste Regulatory Analysis, 1999.
Dunn, D. S.; Cragnolino, G. A.; Sridhar, N. In Corrosion/96;
NACE International: Houston, TX, 1996; paper no. 97.
Mon, K. G.; Gordon, G. M.; Rebak, R. B. In Proceedings of
the12th International Conference on Environmental
Degradation of Materials in Nuclear Power System Water
Reactors; Allen, T. R., King, P. J., Nelson, L., Eds.;
The Minerals, Metals & Materials Society: Warrendale, PA,
2005; pp 14311438.
Rebak, R. B.; Koon, N. E.; Dillman, J. R.; Crook, P.;
Summers, T. S. E. In Corrosion/2000; NACE International:
Houston, TX, 2000; paper no. 00181.
Sridhar, N.; Cragnolino, G. A. Corrosion 1993, 49,
967976.
Sedriks, A. J. Corrosion of Stainless Steels, 2nd ed.; Wiley:
New York, NY, 1996.
Szklarska-Smialowska, Z. Pitting and Crevice Corrosion;
NACE International: Houston, TX, 2005.
Smith, J.; Qin, Z.; King, F.; Werme, L.; Shoesmith, D. W.
Corrosion 2007, 63, 135144.
King, F.; Kolar, M.; Kessler, J. H.; Apted, M. J. Nucl. Mater.
2008, 379, 5967.
Smart, N. R. Review of effect of chloride in cementitious
environments on corrosion of stainless steels; Serco
Assurance Report for UK Nirex Limited; SA/SIS/14921/
R001; 2002.
52.
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waste containers during storage; Report No:
AEA-TPD-262, issue C; AEA Technology, 2000.
Smart, N. R. Atmospheric pitting corrosion of
stainless steel radioactive waste containers; Serco
Assurance Report to Nirex; Report No: SA/EIG/14921/
C0050; 2005.
Blackwood, D. J.; Gould, L. J.; Naish, C. C.; et al. The
localised corrosion of carbon steel and stainless steel in
simulated repository environments; AEAT/ERRA 0318;
Dec 2002.
Kursten, B.; Druyts, F. J. Nucl. Mater. 2008, 379, 9196.
Andra. Materials Baseline; Andra Report C.RP.
AMAT.01.060; 2001, Vol. 4.
King, F. Corrosion of carbon steel under anaerobic
conditions in a repository for SF and HLW in Opalinus
Clay; Nagra Technical Report 08-12; Nagra: Wettingen,
Switzerland, 2008.
Turnbull, A. A review of the possible effects of hydrogen
on lifetime of carbon steel nuclear waste containers;
National Cooperative for the Disposal of Radioactive
Waste; Nagra Technical Report NTB 09-04; 2009.
King, F.; Newman, R. C. Stress corrosion cracking of
copper canisters; Swedish Nuclear Fuel and Waste
Management Company Report; SKB TR-2010-04; 2010.
Asano, H.; Wakamatsu, H.; Akashi, M. In Proceedings of
High Level Radioactive Waste Management Conference,
Las Vegas, NV, Apr 1216, 1992; American Nuclear
Society/American Society of Civil Engineers: La Grange
Park, IL/New York, NY, 1992; pp 16581669.
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Pittsburgh, PA, 1990; Vol. 176, pp 525532.
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154161.
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stress corrosion cracking of used fuel disposal
containers using the CCM-SCC.0 model; Report No:
King, F.; Kolar, M. Consequences of microbial activity
for corrosion of copper used fuel containers
Analyses using the CCM-MIC.0.1 code; Report No:
King, F.; Stroes-Gascoyne, S. In Microbial Degradation
Processes in Radioactive Waste Repository and in Nuclear
Fuel Storage Areas; Wolfram, J. H., Ed.; Kluwer:
Dordrecht, Netherlands, 1997; pp 149162.
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Waste Management Organization, 2009.
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King, F. In Scientific Basis for Nuclear Waste Management
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Browning, L., Eds.; Materials Research Society:
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Corrosion; American Society for Metals International:
Metals Park, OH, 1987.
Pourbaix, M. Atlas of Electrochemical Equilibria in Aqueous
Solutions; 2nd ed.; NACE International: Houston, TX,
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Smart, N. R.; Blackwood, D. J.; Werme, L. O. The anaerobic
corrosion of carbon steel and cast iron in artificial
groundwaters; SKB Technical Report TR-01-22; 2001.
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71. Suckling, P.; Calder, N.; Humphreys, P.; King, F.;

Leung, H. In Proceedings of the 12th International
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289320.
5.18
Waste Glass
E. Vernaz and S. Gin

Commissariat a` lEnergie Atomique et aux Energies Alternatives, Bagnols sur Ce`ze, France
C. Veyer
Veyer-Consultant, St Waast la Vallee, France
5.18.1
Introduction
452
5.18.2
5.18.2.1
5.18.2.2
5.18.2.3
5.18.2.4
5.18.2.5
5.18.2.6
5.18.3
5.18.3.1
5.18.3.1.1
5.18.3.1.2
5.18.3.1.3
5.18.3.2
5.18.3.2.1
5.18.3.2.2
5.18.3.2.3
5.18.3.2.4
5.18.3.3
5.18.3.3.1
5.18.3.3.2
5.18.3.3.3
5.18.3.3.4
5.18.4
5.18.4.1
5.18.4.2
5.18.4.2.1
5.18.4.2.2
5.18.4.2.3
5.18.4.3
5.18.4.3.1
5.18.4.3.2
5.18.4.3.3
5.18.4.3.4
5.18.4.3.5
5.18.4.3.6
5.18.4.3.7
5.18.4.3.8
5.18.4.3.9
5.18.4.4
5.18.5
5.18.5.1
5.18.5.1.1
5.18.5.1.2
Glass and Vitreous State

Phenomenological Approach of Glass
Glass Transition Temperature
Glass Structure at Atomic Scale
Polymerization and Depolymerization of the Glass Network
Structure of R7T7-Type Containment Glass
Crystallization Mechanisms
Waste Glass Definition and Characterization
The Waste Streams to Vitrify
Nature and composition of HLW solutions
Other kinds of nuclear waste
Hazardous waste
Glass Formulation
Establishment of glass formation diagrams
Optimization of glass formulation
Validation of the reference formulation
Sensitivity to chemical composition
Glass Characteristics of Interest
Microstructural homogeneity
Physical properties
Thermal stability and crystallization potential
Chemical durability
Long-Term Behavior of Nuclear Waste Glasses
Glass Crystallization and Long-Term Thermal Stability
Glass Resistance to Self-Irradiation
Investigations of glasses doped with a short half-life actinide
Atomistic modeling of glass self-irradiation
External irradiation of glasses
Nuclear Glass Alteration by Water
Basic mechanisms of glass alteration
Initial rate of glass dissolution
Alteration rate in saturated conditions and final rate of glass dissolution
Essential role of the passivating reactive interphase
Influence of glass composition
Influence of groundwater and environmental materials
Influence of glass fracturing
Modeling glass long-term behavior
Natural an archaeological analogues
Conclusions on Glass Long-Term Behavior
Vitrification Processes
Existing Processes for Radioactive Waste Vitrification
The French two-step continuous vitrification process
Liquid-fed ceramic melters
453
453
454
454
456
456
456
457
457
457
458
458
459
459
461
461
461
462
462
463
464
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465
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467
468
469
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470
470
470
470
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471
471
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475
477
451
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Waste Glass
5.18.5.2
5.18.5.2.1
5.18.5.2.2
5.18.6
References
Emerging Processes for Radioactive Waste Vitrification

Cold-crucible induction melters
Incinerationvitrification processes
Conclusions and Outlook on Waste Glasses
Abbreviations
AVM
Atelier de Vitrification de Marcoule

(the first industrial vitrification plant in
France)
BO
Bridging oxygen
CEA
Commissariat a` lEnergie Atomique et
aux energies alternative (The French
Atomic and Alternative Energy
Commission)
EXAFS
Extended X-ray absorption fine
structure
FP
Fission product
GCR
Gas-cooled reactor
GRAAL
Glass reactivity with allowance for the
(model)
alteration layer
HLW
High-level waste
ICP-AES
Inductively coupled plasma atomic
emission spectroscopy
ICP-MS
Inductively coupled plasma mass
spectroscopy
LWR
Light water reactor
MAs
Minor actinides
MOX (fuel) Mixed oxide (fuel)
NBO
Nonbridging oxygen
NMR
PUREX
SEM
SIMS
STEM
TEM
UP1
479
479
480
481
482
Plutonium and uranium refining by

extraction
Secondary ion mass spectrometry
Scanning transmission electron
microscope
Transmission electron microscope
The first French reprocessing plant
located in Marcoule
5.18.1 Introduction
Fission products (FPs) and minor actinides (MAs)
produced during fuel irradiation in a nuclear reactor
represent only about 5% of the weight of used nuclear
fuel, but about 98% of its radioactivity. When the fuel
is reprocessed, these FPs and MAs end up in concentrated solutions (called high-level waste (HLW) solutions) that are stored in tanks fitted with stirring
systems and cooling facilities to evacuate the heat
resulting from radioactive decay. Figure 1 presents
an example of such a storage tank, made of stainless
steel, in a commercial reprocessing plant.
Figure 1 Example of a high-level waste storage tank for concentrated fission product solutions.
Waste Glass
Such a storage principle can be safe for several

decades. However, it requires active monitoring and
maintenance, and cannot reasonably be extended for
the durations required for complete decay of the activity (thousands of years). As early as the mid-1950s, the
major western countries started designing plans for
their nuclear waste, and work on FP immobilization
was initiated at Oak Ridge (USA), Harwell (UK),
Chalk River (Canada), and Saclay (France).
Several materials were considered at first, with a
rapid convergence on glass or glass-ceramics compositions. For instance, the first attempts at the
Commissariat a` lEnergie Atomique et aux energies
alternative (CEA) in 1957 targeted crystals of
mica-phlogopite (M2Mg6(AlSi3)2O20F4, M being
an alkali or an alkaline earth metal), but this was
soon abandoned because of the impossibility of
incorporating all the elements of the concentrated
solution within one specific mineral. During these
first tests, a glassy component was frequently
observed at the bottom of the crucible, with often
better durability than that of the targeted mineral.
As, at the same time, some favorable results had
been obtained at Chalk River, where a confining
glass had been obtained by melting natural aluminosilicates impregnated with FP solutions at
1350 C, glass was selected for further investigations in France.1
A new application for glass was born: glass for the
containment of radioactivity.
At least, the idea was born, but a long path
remained to be covered from the idea to industrial
deployment, to optimize glass compositions adapted
for each type of FP solution, and to develop processes
operable in highly radioactive environments.
Similar exploratory work was performed in the
other countries, which ended up 20 years later in
the quasi-unanimous selection of borosilicate glass
as the preferable matrix.2
5.18.2 Glass and Vitreous State

Glass is one of the oldest materials known to man.
During prehistoric times, man used natural glasses (volcanic) to make knives or arrowheads. The first glass
actually melted by man could date back to 4500 BC.
Although, in common language, the term glass
often refers to a fragile and transparent material, the
scientific approach regarding vitreous state is both
much wider (for instance, nuclear glasses are not
transparent) and more difficult to define. This
453
chapter aims at providing the basis to understand

vitreous state, by considering the aspects of the formation of a glassy structure, the major glass properties (viscosity, durability, and thermal stability), and
the fine atomic scale structure of glass.3
5.18.2.1 Phenomenological Approach
of Glass
Why are most of natural rocks crystalline, while only
a small number of them display amorphous structures
(absence of diffraction peaks as evidenced by XRD)?
Most mineral compounds, when in the molten state,
form liquids with a low viscosity (some centipoises).
(The Poise (P) is a viscosity unit commonly used in the
glass industry; 1 P 0.1 Pa s1, 1 cP 103 Pa s1.)
Upon cooling, these liquids easily crystallize when
they reach their melting temperature. Some of these
liquids, however, are very viscous in the range of their
melting temperature (typically 105107 P). Such
liquids, if they are kept below their liquidus temperature (in this case, they are supercooled liquids), will tend
to crystallize very slowly. If the cooling rate is faster
than the crystallization rate, crystallization will not
occur. During cooling, the viscosity of the supercooled
liquid increases progressively until the material rigidifies: the liquid vitrifies or transitions from supercooled
liquids to the vitreous state. A phenomenological definition of glass could then be glass is a rigidified
supercooled liquid.
This definition is nevertheless too restrictive,
because a glass can be obtained by other routes,
(solgel for instance). Several alternative approaches
can be proposed:
Structural approach: absence of order in the distribution of elementary structural units at scales
larger than 1030 A,
Thermodynamic approach: glass is in a metastable
state. It is nevertheless not unstable because the
energy gap that must be overcome to bring it to its
more stable crystallized state is generally significant due to the high viscosity,
Physical approach: glass is a nonporous, impermeable, isotropic, noncleavable, elastic solid with a
fragile rupture behavior (absence of plastic deformation before failure),
Kinetic approach: glass is a material which transitions
continuously and reversibly from liquid to solid
state with temperature (Figure 2).
Figure 2 provides an example of a typical evolution
of viscosity between 250 and 1500 C. One can
454
Waste Glass
h = 10x P
A
Solid glass (elastic)
B
x = 15
Tg
Blowing
(hollow glass)
x = 10
C
Working
range
x=5
Transformation domain
(plastic glass)
Devitrification zone
D
E
Devitrification
domain
250
500
Liquid glass (viscous)
750
1000
1250
1500 C
Figure 2 Typical evolution of glass viscosity with temperature.
uid
Volume
d
liq
ole
co
er
Su
id
iqu
B
E
Glas
Crysta
Temperature
Tg
Tf
Figure 3 Evolution of the specific volume V of a glass or a

crystal during cooling.
distinguish an elastic solid domain below 500 C,

a plastic domain between 500 and 1000 C, where
the glass can be worked (blown, made to fibers,
moulded, etc.), and a liquid domain above 1000 C.
5.18.2.2
Glass Transition Temperature
Figure 3 compares the evolutions of the specific

volumes (inverse of densities) for a glass and a crystal
with temperature. During cooling of a liquid, a sharp
step is observed in the evolution of density when the
material crystallizes at melting temperature. If the
material does not crystallize, the specific volume
continues to decrease smoothly below this melting
temperature until a change of slope is observed at a
temperature Tg. This temperature is called the glass

transition temperature. At this temperature, the material
transitions from a supercooled liquid to a solid whose
expansion coefficient (the slope of the curve) is
roughly one-third of that of the liquid.
Similar glass transition patterns are observed for
other thermodynamic parameters such as specific
heat. The glass transition temperature corresponds
to a glass viscosity of 1013 P.
One can then propose another definition: glass is
an amorphous solid that displays the glass transition
behavior.
5.18.2.3
Glass Structure at Atomic Scale
Numerous compounds can be stabilized in the

vitreous structure: oxide (silicates, borates, phosphates, etc.), chalcogenide (sulfides, selenides,
tellurides, etc.), ionic compounds (BeF2, ZrF4BaF2,
AlF3, ZnCl2, etc.), specific metallic alloys subjected to
overhardening (Pd4Si, FeB, ZrCo, CaMg, etc.), and
also organic compounds such as glycerine, polyethylene, or glucose. For instance, the shiny caramel of a
tiered cake is obtained by cooling molten sugar fast
enough to obtain a vitreous state; candy floss is an
organic glass fiber whose Tg is around 55 C!4
The most common glass compositions are silicabased oxide glasses. Even if pure silica can vitrify by
itself (application to optic fibers), all-days glasses
are enriched with other oxide-based components.
They include, for instance, window glass (alumina
sodiumcalciumsilicate), Pyrex (a high silica
455
Waste Glass
borosilicate), crystal-glass (silicate glass with a high

content of lead oxide), optical glass (such as flint
glass with high barium oxide), nuclear glass (alumina
borosilicate), and so on.
The constitutive oxides of an oxide glass can be
categorized into three families:
Glass network forming oxides (network formers): these
oxides are able to form glass by themselves; SiO2,
B2O3, GeO2, and P2O5 are the most common.
In silica glass, the basic structural units are silica
tetrahedra [SiO4] sharing corners. Their linking
creates a continuous network with some degree of
disorder (groupings in cycles of five or six tetrahedra for instance), while, in a crystalline form such as
quartz, the tetrahedra are perfectly ordered.
Network modifiers: these oxides cannot give a glass
by themselves. When they are coupled with network formers they are inserted into the vitreous
structure and modify the properties of the material. Typically, these oxides are alkali or alkaline
earth oxides (Na2O, Li2O, Cs2O, CaO, BaO, etc.).
As an example, the introduction of sodium oxide in
a silicate network induces the breakdown of
strongly covalent SiO bonds and their replacement by SiO. . .Na bonds with a more ionic
character.
O
|
O
|
O
|
Na+
O Si O Si O + Na2O O Si O
|
|
|
O
O
O
Na+
O Si O
|
O
The oxygen atoms bonding two silicon atoms are said

to be bridging oxygen (BO) atoms. The introduction
of two sodium atoms in the structure creates two
nonbridging oxygen (NBO) atoms. The same
mechanisms may be observed with CaO, but here
only one Ca2 is needed to compensate the negative
charge of the two NBO atoms.
The presence of NBO atoms weakens the vitreous
structure and allows decreasing melting temperature
(the glass becomes less refractory) and viscosity (the
glass can be poured more easily). This explains why
alkali oxides are often used as fluxes. NBO atoms also
loosen the network, and then help incorporating
more elements in the structure. A counterpart is a
decrease in chemical durability.
Finally, it should be recalled that the amount of
modifiers must remain limited if one wants to obtain
a glass from a molten liquid. If the number of NBO
atoms is too high, the liquid becomes very fluid and
tends to crystallize easily upon cooling.
Intermediate oxides: these oxides cannot give a glass

by themselves. However, when mixed with network modifiers, they behave like network formers
within the vitreous structure. These oxides are
typically Al2O3, Fe2O3, ZnO, ZrO2, PbO, TiO2,
and so on.
Alumina is specifically important for the glass
industry, as it improves chemical durability (for
container glass, particularly). In order to behave
like a network former and to form a tetrahedron
similar to that of silica, the [AlO4/2] ion needs a
positive charge to maintain local electroneutrality.
This will be achieved by fixing an alkali ion (or one
alkaline earth ion for two [AlO4/2]).This results
in the following structure:
O
Na+
|
O Si O
|
Na+
O
O
|
O Si O + Al2O3 2 O
|
O
O
|
O
|
|
O
|
O
Na
Si O Al O
Introducing alumina into an alkali silicate glass

thus hardens the glass, as NBO atoms are eliminated according to the stoichiometry (1Na for
1Al or 1Ca2 for two Al). This will allow keeping
a structure slightly looser than that of a pure silica
glass (as the AlO bonds are slightly weaker than
the SiO bonds), while leaving only a small number of NBO atoms. The introduction of calcium
and some alumina into the formulation allowed the
transition from the poorly durable alkali glass used
for medieval stained glass to the window glass
used at present.
The specific role of boron: the behavior of boron oxide
in the presence of alkalis differs from the general
pattern described for silica. Adding alkalis to pure
B2O3 or to a mixture of SiO2 and B2O3 leads at first
to the formation of BO atoms, as a result of the
formation of BO4 tetrahedra from the BO3 triangles
initially present in the B2O3 glass (in this case, the
alkali cation is used to compensate the charge of the
[BO4/2] structural unit). (The elementary structural units of glass are often written [SiO4], [BO4],
[AlO4] to indicate the tetrahedral environment of
Si, B, or Al; however, for more detailed structural
descriptions, the more rigorous notation [SiO4/2],
[BO4/2], [AlO4/2], is preferred. In addition to
indicating that the base atom is surrounded by four
oxygen atoms, this notation stresses the fact that the
oxygen atoms are shared between two tetrahedra and
that, for B and Al, a negative charge exists, which
will need compensation by a neighboring cation.)
456
Waste Glass
It is only for higher alkali contents that NBO atoms

are formed, in the environment of boron or silicon
atoms. Consequently, the addition of alkalis to a
borate or borosilicate glass initially induces an
increase in viscosity. It is only for higher additions
that viscosity starts to decrease. This deviation in
the behavior of boron when compared to silica is
often termed boron anomaly.
Boron, in right amount, plays a key role in nuclear
borosilicates for several reasons: (1) it helps
decrease the glass melting temperature without
drop of the durability as [BO4] units decrease the
number of NBO by fixing an alkali ion; (2) it helps
digest a number of chemical elements that would
be only sparingly soluble in pure silica; (3) it prevents glass crystallization; (4) it contributes to the
long-term good glass behavior by allowing the formation of a very fine gel structure (without boron)
and by decreasing the final pH.
5.18.2.4 Polymerization and
Depolymerization of the Glass Network
On the basis of the above classification, it is observed
that the progressive addition of network modifiers to
silica (SiO2) leads to network depolymerization by
the formation of NBO atoms. At a certain limit, the
liquid is strongly depolymerized, its viscosity
becomes very low, and it is not possible to obtain a
glass by quenching any more. On the contrary, adding
boron or intermediate oxides favors network polymerization by fixing alkalis or alkaline earths as
charge compensators.
The very good performances of nuclear borosilicate (moderate melting temperature coupled with
good durability) come from an adequate balance
between boron and intermediate elements (Al, Fe,
Zr, etc.) on one side and the alkali elements on the
other side, allowing a high polymerization rate as
most of the alkalis are found as charge compensators
rather than forming NBOs.
5.18.2.5 Structure of R7T7-Type
Containment Glass
The atomic structure of nuclear waste glasses has
been studied using spectroscopic techniques such as
nuclear magnetic resonance (NMR) or extended
X-ray absorption fine structure (EXAFS), at first on
simplified glass compositions (SiO2B2O3Na2O
Al2O3), and then on compositions with increasing
complexity.
These studies show that all the intermediate

cations in the R7T7 glass composition are in positions of network formers. Their substitution on Si4
sites induces charge deficits which are compensated
by a network modifier cation in order to ensure
charge neutrality. The sum of negative charges cre2

ated by the (AlO
4/2), (ZrO6/2), (FeO4/2), and (BO4/2)
groups in R7T7 amounts to 5.19 mol per 100 mol of
elements (computed from elemental mol%). On the
other hand, the sum of positive charges created by
alkalis and alkaline earths is 9.44 mol%. This results
in the following situation:
All the intermediate cations behave as network
formers,
A somewhat limited number of network modifiers
remain available to create NBOs.
These considerations show that the network of this
glass composition is homogeneous and very well
copolymerized, owing to the good incorporation of
intermediate cations in the network. The network is
most probably composed of numerous mixed SiO
M bonds (with M Al, B, Zr, Zn, and even some rare
earths). This strong polymerization, as well as all the
structural data, is confirmed by molecular dynamics
modeling.
5.18.2.6
Crystallization Mechanisms
Crystallization in a supercooled liquid or a glass

occurs via a nucleation-growth mechanism which
starts by the formation of small ordered germs. The
germination can be enhanced by the presence of
rough interfaces in the melt.
Figure 4 gives an example of nucleation and
growth curves for a glass.
A
r
b
i
t
r
a
r
y
u
n
i
t
s
(n), (g)
(n) is the
nucleation rate in
number of seeds
per time unit
Tg 600 C
700 C
(g) is the seeds

growth rate in
microns per time
unit
800 C
Temperature
Figure 4 Nucleation and growth of a crystalline phase

within a glass.
Waste Glass
Several crystalline phases can be formed during

cooling of a supercooled liquid, according to its composition. The chemical composition of the formed
crystals can be very different from those of the liquid
or of the glass. For a given phase, graph (n) plots
the number of supercritical germs per unit volume
and time as a function of temperature. Graph (g) plots
the growth rate for this phase as a function of
temperature.
If those two curves do not overlap, the given
crystal cannot form spontaneously during cooling.
In this case, when the glass is in the growth zone,
there are no germs liable to grow, and when it is in the
nucleation zone, the temperature is too low to allow
the formed nuclei to grow. Crystallization will then
be possible only after a two-stage heat treatment, one
stage for nucleation and the second for growth. This
is a favorable situation for the production of glassceramics with homogeneous and well controlled
crystallization.5,6 On the other hand, if the two curves
overlap, a risk of uncontrolled crystallization appears
in the overlap region, where germs can be formed and
can grow. The relative position of the nucleation and
growth curves in the temperature field will then be an
important parameter determining the sensitivity of
the glass to crystallization; it must be studied for each
of the phases liable to be formed in a given glass
composition.
5.18.3 Waste Glass Definition and

Characterization
Vitrification is not a simple encapsulation process
(as immobilization in bitumen for instance) but consists of making a new material in which the waste
components are contained at the atomic scale within
the matrix and can only be released by destruction of
the network bonds.
One major requirement is that the selected matrix
should be able to incorporate all of the waste stream
components in its structure. By using the flexibility
brought about by the disordered and relatively loose
structure of a glass, it is possible to design glass
compositions able to integrate a very wide range of
elements within their structure, and which are tolerant to compositional variations in the waste stream.
This approach constitutes waste vitrification, where
waste components are usually mixed with suitable
additives and molten to give a glass wasteform.
A recent development of vitrification has been the
design of glass-ceramics that combine the flexibility
457
of glass formulation to digest most of the waste components with the possibility of targeting well defined
crystalline phase(s) for specific waste components
that may not be soluble in large amounts in glass, as
molybdenum for instance. Vitrification usually
involves a small number of processing steps, with a
robust design, compatible with operation in a highly
radioactive or hazardous environment.
5.18.3.1
The Waste Streams to Vitrify
A large variety of nuclear waste compositions have

been considered for vitrification since the first
attempts in the late 1950s, including not only highlevel, but also intermediate or low-level effluents.
More recently, this approach has been extended
to other types of inorganic hazardous waste for
which other types of immobilization were not considered suitable.
5.18.3.1.1 Nature and composition of HLW
solutions
FPs and MAs produced in the reactor by fission or

neutron capture display a wide range of atomic numbers. One can find for instance alkalis (rubidium and
cesium), alkaline earths (strontium and barium), a
wide range of transition elements (zirconium, molybdenum, etc.), noble metals (ruthenium, rhodium,
and palladium), chalcogenides (Se and Te), nonmetals (As, Sb, etc.), lanthanides, and actinides. The
amount and composition spectrum of the FPs and
MAs varies with fuel initial composition, enrichment,
and burnup.
The separation process used for light water reactor (LWR) oxide fuel at the commercial reprocessing
plants of La Hague (France), Rokkasho Mura ( Japan),
or Sellafield (UK) is a hydrometallurgical process
based on plutonium and uranium refining by extraction (PUREX), where, after nitric dissolution of the
fuel and a series of solvent extraction steps used
for U and Pu recycling, most FPs and MAs from
the fuel end up in a concentrated nitric solution
(HLW solution), which constitutes the major target
feed for vitrification. In addition to the isotopes
extracted from the fuel, the HLW stream holds some
chemicals added during reprocessing. The current
PUREX-based process for LWR oxide fuel has been
designed to minimize these additions, by using essentially chemicals that will not add to the waste load.
However it is not possible to avoid the addition of
some selected chemicals, mainly sodium, during
458
Waste Glass
ancillary operations such as solvent purification or

equipment cleaning operations. Some impurities
resulting from a slight corrosion of the piping (namely
Fe, Cr, and Ni) or solvent degradation (phosphate)
also end up in the HLW solution.
In addition to commercial LWR fuel, other fuels
have been reprocessed worldwide in the past, and
other processes have been used or are considered for
separating uranium and/or plutonium from the fuel.
Fuel alloy metals (Al and Mo) or dissolved cladding
material (Al, Mg, and stainless steel) may follow the
HLW stream. The chemicals used to perform the
dissolutions or separations can also be very diverse
(mercury, fluorine, ferrous sulfamate, bismuth phosphate, etc.). In several instances, the HLW solution
(which is, initially, acidic) has been neutralized by
adding massive amounts of caustic to prevent corrosion of the tanks, thereby precipitating most of the
FPs and MAs as hydroxides. This is for instance the
case in the United States, at Hanford or Savannah
River; The HLW solutions are thus quite complex
and not unique, with a large number of constituents.
Typically, in France, concentrated HLW solutions
are nitric solutions (12 N) with high bg activities
(several tens of TBq per liter) including suspended
solids such as colloids (zirconium phosphate and
cesium phosphomolybdate) and some metallic fines
(insoluble residue, cladding fines generated during
the fuel shearing operation). Table 1 gives examples
of solutions derived from reprocessing various types
of fuel from past or present reactors in France.
5.18.3.1.2 Other kinds of nuclear waste
In addition to HLW, vitrification is increasingly considered for waste of lower radioactivity content,
although other, less costly, immobilization methods,
such as grouting, are more common. Despite the
cost, vitrification has the advantage of providing
durable matrices, with significant volume reduction.
For liquid effluents, a vitrification plant is for
instance being designed and built at the Hanford
site, USA, as part of the Waste Treatment Plant
(WTP) to immobilize the low activity fraction of the
waste from 177 underground tanks. This low activity
fraction consists mainly of concentrated sodium
nitrate and sodium hydroxide solutions, with some
aluminum, chrome, sulfur, and some minor metals.
In Russia, at the Radon facility near Moscow, borated
low activity power plant effluents are also vitrified.
Vitrification is also applied to low activity solid
combustible waste, in conjunction with incineration:
the combustible fraction is incinerated and the
Table 1
France
Example of HLW compositions to vitrify in
Reactor type
PWR
Gas-cooled, graphite
moderated, natural
uranium reactor
Fuel type
UO2
SiCrAl
UMoMoSnAl
Burnup
(MWd t1)
HLW solution
(l tU1)
Oxide contents
(g l1)
Free acidity (N)
Oxide
composition
(g l1)
Fe
Al
Cr
Ni
Na
Mg
Zn
Mo
Sn
P
F
PF oxides
(g l1)
Actinide oxides
33 000
40006000
15003500
660
100120
75100
90100
240
0.95
1.0
0.8
13
02
2.3
1.9
20
01
1.26
52.23
714
1938
01.5
01.3
711
37
12
28
45.1
3.14
2.76
0.65
0.31
14
1.6
163.2
0.67
41.16
11.46
3.83
3.65
3.62
inorganic fraction, under the form of ashes, is vitrified. This is for instance the case at Ulchin, S. Korea,
where a facility based on French technology has been
recently commissioned to simultaneously incinerate
and vitrify dry active waste and resins from nuclear
power plants. At the Zwilag waste management facility, in Switzerland, a plasma-torch powered facility
has been built to incinerate, melt, and vitrify low
activity waste conditioned in drums.
In the end, vitrification has also sometimes been
considered for actinide-bearing waste or residues.
In the United States, for instance, a significant program has been launched in the 1990s in the frame
of the START-II program, to study the possibility of
vitrifying plutonium-rich residues from the weapon
industry that could not be easily made into mixed
oxide (MOX) fuel.
5.18.3.1.3 Hazardous waste
Vitrification, alone or combined with incineration,

provides a convenient method for immobilizing or
rendering hazardous waste innocuous. For instance,
Waste Glass
in the United States, vitrification has been considered

as Best Demonstrated Available Technology (BDAT)
by the US-EPA (US Environmental Protection
Agency) for waste containing toxic metals such as
arsenic. In situ vitrification of soils has been applied
in some contaminated sites in the United States.
Owing to the potential for immobilizing inorganic, nonvolatile, toxic metals into a stable and
durable matrix, vitrification is used in several facilities worldwide, including France and Japan, to
immobilize the slag and ashes from municipal waste
incineration or waste-to-energy conversion facilities.
The product is completely inert and can be disposed
of in a conventional disposal facility. Efforts are under
way in several institutions to improve the product for
reuse, mostly in the building industry (as road base or
tiles for instance). Another significant application of
vitrification is the destruction of asbestos: once vitrified, asbestos becomes a compact, harmless substance.
Such a facility for asbestos vitrification has been
operating in southwestern France since 2003.
5.18.3.2
Glass Formulation
Glass formulation is aimed at defining a compositional domain within which the matrix will display a
number of required characteristics related to technological feasibility, durability, containment properties,
and all the properties required for the intended use or
destination of the product. For HLW glass, for instance,
the product will have to ensure long-term safety in the
proposed geological disposal environment.
Glass formulation then consists in reaching
the best compromise between a large number of
constraints: glass formation domain (solubility of the

various waste components, waste loading, and homogeneous glass), technological feasibility (melting
temperature limits, viscosity allowing to pour the
product, minimum volatilization, and minimum
corrosion of the melter), as well as stability and containment properties (thermal stability, resistance
to self-irradiation, chemical durability, mechanical
properties, etc.) (Figure 5).
For radioactive waste immobilization, borosilicate
systems represent the best compromise between the
various constraints, and they have been selected as
the reference matrix compositions for HLW in most
countries (France, USA, UK, Japan, Germany,
Belgium, etc.). Other matrices for HLW include
phosphate glasses in Russia.
Glass formulation involves several successive (and
often iterative) steps illustrated below by the methodology used at the French CEA for HLW borosilicate glass formulation: in this instance, it was
necessary to design a matrix with very good containment and long-term properties, to immobilize a highly
radioactive, heat-generating, waste stream, whose composition was expected to be very stable throughout the
years. In other countries, or for other waste streams,
the practical organization of formulation studies may
differ, but these steps are always necessary to ensure
consistent and reliable waste form properties.
5.18.3.2.1 Establishment of glass formation
diagrams
The glass-forming domain is determined by establishing quaternary phase diagrams with the expected
four major components of the glass, to identify the
Ability to accommodate the waste

Solubility (Cr, Ru, Rh, Pd, Ce, Pu, SO4, Cl)
Phase separation (Mo, SO4, Cl, P)
Devitrification (Mo, P, F, Mg, ...)
Maximize the waste loading
Process/technology
Ease of processing
Melting temperature
Viscosity, reactivity, residence time,
electrical condition, thermal condition
Additives needed
Figure 5 Waste glass formulation is a compromise.
459
Glass performance
Properties for storage/disposal
Thermal stability
Chemical durability
Resistance to self-irradiation
Mechanical properties
460
Waste Glass
glass-forming regions. For waste solutions dominated

by FP oxides, the four major components can be
summarized as silica SiO2, boron oxide B2O3, sodium
oxide Na2O, and FP oxides (considered collectively,
with a chemical spectrum corresponding to the
expected spectrum for the solution). This leads to
SON-type glass formulations such as those selected
for the LWR FP solutions at La Hague. When the
waste solution is dominated by aluminum, the quaternary diagram considers SiO2, Al2O3, B2O3, and
Na2O. This leads to SAN-type glass formulations,
such as those selected for the gas-cooled reactor
(GCR) FP solutions processed at the Atelier de
Vitrification de Marcoule (AVM) facility at Marcoule
(Figure 6).
The glass-forming domain is established by melting a large number of glass compositions in small
laboratory crucibles and performing visual or
microscopic observations. As can be seen in Figure 7,

boron helps to dissolve the entire FP spectrum into
the glass, prevent crystallization, and lower viscosity.
The chosen boron content is however limited to the
minimum needed to have a sufficient domain of
homogeneous glass while keeping the best durability
(for instance 18 wt% B2O3 is sufficient in the quaternary systems shown on Figure 7).
Once this glass-forming region has been determined, additional constraints are used to further
limit this domain, for instance, limitation of the melting temperature, which will result in limits on the
refractory elements such as silica or alumina, limitation of waste loading by thermal considerations (for
HLW), and limitation of network modifiers to keep
an acceptable chemical durability. Each of these constraints establishes one side of the diamond in which
the glass composition will be chosen.
B2O3
B2O3
24% B2O3
24% B2O3
10% B2O3
10% B2O3
SiO2
Na2O
SiO2
Na2O
Ox PF
Al2O3
Figure 6 Basic quaternary glasses for gas-cooled reactor on left (SAN-type glasses) and light water reactor on right
(SON-type glasses).
SiO2
SiO2
730
Ox.
PF +
110
40
315
75
80
310
230
Ox.
115
Na2O
10
PF +
Act.
Act.
24% B2O3
18% B2O3
Nonglassy state
Heterogeneous glasses
Homogeneous glasses
Viscosity (P [= dPa.s] )
Figure 7 Effect of boron oxide content on the vitrification domain in quaternary glasses. Domains of glass formation
into the quaternary diagram SiO2Na2OOxPFB2O3 for two different B2O3 contents.
Waste Glass
5.18.3.2.2 Optimization of glass formulation
Optimization consists in adding or substituting various additives (such as Li2O, CaO, ZnO, ZrO2, etc.)
to improve the matrix properties. Among all properties of interest, the waste load (considering the final
glass homogeneity), the viscosity of the molten glass,
and the chemical durability have to be specially
mentioned. Depending on the choice for industrial
process, other properties may be targeted in addition.
As an example, small amounts of lithium may be
substituted for sodium to decrease melt viscosity,
without affecting the chemical durability. Aluminum
and calcium oxide may be substituted for a small
amount of silica to improve durability.
It has to be pointed out that those optimizations
result from sharp compromises and high-level expertises in mixing the appropriate oxides in a synergic
way (for instance too high aluminum content would
enhance short term durability but would decrease
long term durability; it would also increase the risk
of crystallization of undesirable phases; controlled
etc.).
At the end of this phase, a reference composition is
proposed for a given effluent composition and a given
melting technology. Dozens of compositions are published in the literature, for a very wide range of waste
compositions, in many countries. Table 2 gives the
composition of the French reference glass for the
HLW solutions derived form processing 33 GWdt1
LWR fuel at La Hague: the so-called R7T7 composition, named after the vitrification facilities R7 and
T7 at La Hague plant.
5.18.3.2.3 Validation of the reference
formulation
Once a reference composition has been defined at

lab-scale for a specific simulated waste stream, it
needs to be validated for actual industrial application.
(During the development stage of reference matrix,
as the main consideration is on the basis of chemical
incorporation, radioisotopes issued from FPs and
MAs are replaced by their inactive representatives.)
To this effect, several additional programs are
performed:
complete characterization of the reference composition and determination of all its important
properties,
validation of technological feasibility in industrial
conditions by performing long-duration demonstrations on an inactive industrial-scale pilot
facility, and confirmation of the maintenance of
461
Table 2
Chemical composition range of the French
R7T7 glass
Chemical composition range of R7T7 glasses produced in
the AREVA La Hague plant workshops
Oxides
SiO2
B2O3
Al2O3
Na2O
CaO
Fe2O3
NiO
Cr2O3
P2O5
Li2O
ZnO
Oxides
(FP Zr actinides)
fines suspension
Actinide oxides
SiO2 B2O3 Al2O3
Specified
interval for
the industry
(wt%)
Min
Max
42.4
12.4
3.6
8.1
3.5
51.7
16.5
6.6
11.0
4.8
<4.5
<0.5
<0.6
<1.0
2.4
2.8
18.5
1.6
2.2
7.5
>60
Average
composition of
industrial
glasses (wt%)
45.6
14.1
4.7
9.9
4.0
1.1
0.1
0.1
0.2
2.0
2.5
17.0
0.6
64.4
the characteristics defined at lab-scale on the

product made during scale one demonstrations,
and
validation of the representativeness of the inactive
glasses made in the laboratory by making a glass of
the same composition with actual radioactive waste
in a hot laboratory and determining its characteristics. The fabrication of active samples is also
necessary to study the effect of self-irradiation
and the specific behavior of some radioactive
elements.
5.18.3.2.4 Sensitivity to chemical composition
In industrial situations, one must expect day-to-day

variations in the composition of the solution to
be vitrified, and also process upsets or variability
which may affect the product. It is then necessary
to determine what is the flexibility of the formulation towards these variations, in order to provide
a wide enough operational domain, while keeping
acceptable glass properties. For this, a sensitivity
study is launched, to study systematically the
effect of selected composition variations on glass
properties, and establish acceptable limits for these
components.
462
Waste Glass
For instance, in order to be pourable, the glass

must display a viscosity lower than about 100 P at
the melting temperature. This will limit the possible
increase in refractory elements such as SiO2 or Al2O3
or the decrease in fluxing components such as
Na2O or Li2O. On the other hand, in order to keep
an acceptable chemical durability, the increase in
alkali oxides will be limited.
In such a multidimensional space, with more than
ten constituents of interest in a formulation, sensitivity studies can become very cumbersome and involve
a large number of crucible melts and the associated
characterization measurements. In order to minimize the number of experiments while obtaining a
reliably acceptable composition domain, statistical
tools, propertycomposition models, and experiment
design are implemented. These allow identifying
acceptability limits and modeling matrix properties
within these limits.
For illustration, Table 2 displays the range of
acceptable composition for the R7T7 glass produced
at La Hague. One can see that the acceptable variations may be small for some components, and much
larger for other components.
5.18.3.3
(Figure 8). The black color, analogous to the color of

some volcanic glasses, is the result of the wide diversity of chemical elements included in the glass and,
more particularly, transition metals and rare earths,
which absorb light over a wide range of wavelengths.
By visual observation, some small bubbles and
some cracking associated with stress relaxation during
cooling can be observed on industrial-size blocks. Conservative durability modeling accounts for the impact
of this physical heterogeneity (see Section 5.18.4.3.7).
Under the microscope (optical or scanning electron microscope, SEM), a small volume of chemical
heterogeneities can be observed, essentially noble
metal inclusions (Pd, Rh, or PdTe alloy), ruthenium
oxide, nickel, zinc, and iron chromites (Figure 9).
This type of inclusion represents a small volume
of the matrix, and has been shown to have no effect
on the long-term behavior of R7T7 glass. For other
waste glass compositions, it is necessary to make
sure that the precipitated phases do not alter the
matrix properties, such as chemical durability. For
instance, for Fe- and Cr-rich glasses, spinels have
been observed, which do not alter glass chemical
durability. On the other hand, for Al-rich glasses,
it is necessary to avoid the formation of nepheline
Glass Characteristics of Interest
Glass characterization is the determination of all the

physical and chemical properties of the product.
Generally, and as observed in many laboratories, the
products made with simulated waste by substituting
the inactive counterparts for the radioactive components of the waste display properties that are very
representative of those of the actual radioactive product. Glass characterization is thus generally performed on a simulated, nonradioactive glass for
convenience, and validated in the end on radioactive
glasses (see Section 5.18.3.2).
Figure 8 Obsidian glass and nuclear waste glass (cannot

be distinguished with the naked eye).
20 m
5.18.3.3.1 Microstructural homogeneity
As it is generally more difficult to characterize and

demonstrate a favorable long-term behavior for a
chemically heterogeneous material, the objective is
usually to produce a homogenous glass, or a glass that
contains, after cooling of industrial-size blocks, only a
small amount of harmless precipitates or insoluble
phases. Nevertheless, the notion of homogeneity is
relative and depends on the resolution of the measuring instrument used.
Upon visual observation, HLW glasses such as the
R7T7 composition are homogenous, black, and shiny
Palladiumtellure
Ruthnium
oxide
Chromites
Figure 9 Scanning electron microscope observation on a

zone of platinoIde concentration into the glass.
Waste Glass
(aluminosilicate) crystals on cooling, as these tend

to be detrimental to resistance to aqueous leaching.
In the end, the presence of precipitates or insoluble
alloys in the molten glass may promote settling in the
melter and have detrimental effects on the process
(pouring difficulties and electrical short-circuiting
in some types of melters). For the La Hague process,
stirring allows processing melts with significant
amounts of insoluble noble metals.
Another form of heterogeneity is phase separation, whereby the glass separates (during melting or
during cooling) into two or more different liquid or
glassy phases. This type of phenomenon has to be
carefully controlled to avoid the formation of a phase
that is weaker than the other, inducing some loss of
general durability.
Nevertheless, in some specific instances, it may be
acceptable to formulate microcrystalline or phaseseparated glasses, if it can be demonstrated that this
does not alter chemical durability. Such an approach
has been retained in France to formulate glasses to
immobilize molybdenum-rich solutions resulting
from the processing of UMo fuel.
Lower resolutions of observations (such as the one
reachable by transmission electron microscope,
TEM, as well as structural techniques) are not relevant to link the heterogeneities at that scale to a
significant effect on durability, but are of great use
for understanding.
5.18.3.3.2 Physical properties
The physical properties of nuclear waste glasses are

usually quite comparable to those of classical industrial glasses,7 as illustrated on Table 3. Most of them
have to range in between a minimum and a maximum
value to suit industrial processes.
The density of waste glasses is slightly higher than
those for the industrial glasses, owing to the presence of heavy metals. The viscosity at 1100 C is
much lower. This is because nuclear glasses are
Table 3
463
formulated to be poured at 1100 C while the melting temperature of industrial glasses is significantly
higher. It should also be noticed that the presence of
noble metals or other heterogeneity in the nuclear
glass can significantly modify its rheological behavior. Glass transition temperature occurs in similar
ranges, although it is slightly lower for nuclear
waste glass. The thermal expansion coefficient of nuclear
waste glasses is similar to that of window glass,
and significantly higher than that of Pyrex: Pyrex
is formulated specifically to resist thermal shocks.
Thermal conductivity is similar for all three types
of glass. It should be noted that this low value is
significant in nuclear waste glasses which hold
heat-generating FPs: temperature at the centre of
the glass block will need to be controlled. Youngs
modulus, which characterizes rigidity, is slightly
higher for nuclear waste glass, while fracture toughness is similar.
Electrical resistivity, not included in the table is
another significant parameter if the glass is heated
by direct electromagnetic induction or within electrodes (in the case of Joule Melter technology, this
property can be neglected). Electrical resistivity
decreases when temperature increases and when
the alkali content of the glass increases. Electrical
resistivity depends mainly on ionic diffusion in the
material. It decreases from around 1.5 104 at
500 C to a few O cm at 1200 C. Other parameters
not included are the thermal conductivity and the
redox behavior. Thermal conductivity impacts
directly the energetic efficiency in the melter. If
too high, the thermal losses out of the melter
make the process energetically (and economically)
inefficient; if too low, the energy transmitted to the
glass is nonhomogenous. Regarding redox behavior,
the presence of multivalent elements (Ce oxide for
instance) in the glass composition may induce
foaming at high temperature due to their reduction.
The monitoring of oxygen partial pressure in the
Comparison of physical properties of selected nuclear and industrial glass compositions
3
Density (kg m )
Viscosity at 1100 C (P)
Tg ( C)
Expansion coefficient (106 K1)
Thermal conductivity (W m1 K1)
Youngs modulus (1010 Pa)
Fracture toughness KIc (106 Pa m1/2)
Typical HLW glass compositions
Pyrex glass
Window glass
2.502.75
50150
510
8.39.9
1.0
8.48.6
0.750.95
2.28
80 000
565
3.2
1.09
6.1
0.85
2.46
4000
527547
9.3
1.05
7.3
0.700.80
464
Waste Glass
molten glass, and if necessary the use of redox

buffer (FeII/FeIII) as well as physical means can
overcome this inconvenience.
5.18.3.3.3 Thermal stability and
crystallization potential
Devitrification is the process by which the glass loses

part or all of its glassy nature through crystallization.
It depends on the composition of the glass and its
thermal history.
For instance, increasing the levels of FPs, noble
metals, molybdenum, phosphorus, chrome, nickel,
iron, or magnesium can favor crystallization in a
nuclear waste glass. Furthermore, the time needed
to reach the glass transition temperature (Tg) from
melting temperature is also important (this depends
mainly on glass thermal conductivity and specific
heat, canister geometry, and process parameters such
as pouring rate). However, it is considered that once
Tg is reached in cooling conditions, the devitrification
process is kinetically frozen (cf. Section 5.18.4.1).
Devitrification studies are on the basis of subjecting glass samples to short-duration heat treatments
(around 15 h) at stabilized temperatures and observing the heat-treated samples under the microscope to
detect, observe, and quantify the crystals formed.
Several indicators are determined:
starting crystallization temperature: the temperature
below which crystalline phases can be observed in
the bulk of the sample after about 10 h of isothermal heat treatment,
crystallization temperature range: range in which these
crystals are observed,
maximal crystal growth rate (generally expressed
in mm mn1),
crystallization potential: characterizes the ability of a
composition to devitrify. It is the maximum percentage of crystals that can form after a heat treatment. This can vary from 0% (pure borate glass) to
100% (lithium disilicate glass). It is about 4% for
R7T7 glass.
XRD and X-ray microprobe are used to identify the
crystalline phases formed within a glass while image
analysis and quantitative XRD are used to evaluate
the percentage of phases formed.
The amount of crystals that form in an actual large
size industrial glass block is different from the maximal values found at lab-scale: indeed, the thermal
profile in the glass canister involves a continuous
decrease of temperature, and is different in the various parts of the canister (close to the canister wall,
cooling is faster than in the centre of the glass block).

Several approaches can be used to bracket an estimation of the amount of crystals in the industrial
glass block. In France, for instance, the maximum
possible amount of crystallization is determined on
laboratory samples, by subjecting them to a heat
treatment designed to promote crystallization (5 h
at 610 C nucleation temperature and 100 h at
780 C maximum growth temperature this cannot
happen in a real glass block) and it is postulated that
the amount of crystals in the glass block cannot be
higher than the fraction determined in this way
(which is in fact quite small for the R7T7 glass).
In the United States, where the glass blocks are
quite large, crystallization studies are performed by
establishing systematic TTT (timetemperature
transformation) diagrams and by considering the
cooling profile at the centre of the canister (CCC,
canister centerline cooling curve), which is the slowest cooling part of the canister.
Whatever be the approach, the important aspect is
the fact that crystallization must not be detrimental
to glass durability. It is thus necessary to avoid
depleting the glass matrix of elements that are favorable to durability, such as silica or alumina.
5.18.3.3.4 Chemical durability
Water is the major cause of glass alteration and radionuclide (or hazardous metal) dispersion during the
life of the product, and more particularly during
geologic disposal. The resistance of glass to aqueous
alteration is generally called chemical durability. It is
the essential property required for a containment
matrix. It is also essential for classical industrial glass
compositions (container glass, window glass, etc.) and
as such is also considered during their formulation.
The process by which glass constituents are
washed into water is called leaching, and it is the
combination of a variety of mechanisms described
in Section 5.18.4.
Chemical durability is assessed by various leach
tests during which glass samples are contacted with
aqueous solutions, under a large range of experimental conditions. The leaching behavior of glasses varies
according to glass composition, test conditions, and
time. There is no unique evaluation of chemical
durability, and the performance of different glass
compositions can only be compared under the conditions of a given test. In order to fully evaluate the
behavior and performance of a given glass, it is advisable to understand the various mechanisms that are
involved during its interaction with water and the
Waste Glass
environment, and to design testing to obtain the

parameters that allow modeling this performance.
Several types of leach tests can be listed:
Static tests, during which glass samples, either monolithic or crushed to powders, are exposed to a solution and left standing there for the duration of the
test. During these tests, the components dissolved
from the glass progressively accumulate into the
solution and are left to interact between one another
and with the sample. Two of these tests have been
normalized in the United States: the so-called
MCC-1 test on monolithic samples (also known as
ASTM-C1220) and the PCT test on crushed glass
samples (also known as ASTM-C1285). Both these
tests are available with several variants (temperature,
volume of solution, type of solution, etc.).
Flow-through tests, during which the sample is
exposed to a continuous flow of fresh leachant to
prevent the accumulation of reaction products into
the solution, thereby testing the initial alteration.
Among those tests, one can list the Soxhlet test
(also known as ISO 16797:2004), by which a monolithic sample is exposed to a continuous flow of
condensed water at 100 C recirculated in a distillation apparatus, or the flow-through test (also
known as ASTM C1662-07) by which the sample
is inserted in a column or a container and subjected
to a continuous flow of fresh solution.
Integral tests or service conditions tests or tests
including environmental materials are tests
designed to account for the overall service environment expected during the life of the product.
Glass alteration may be measured in three different ways:
Elemental analysis (ICP-MS, ICP-AES, etc.) of the
leachate (solution after contacting the sample), in
order to obtain information on the leaching kinetics for each element, as a function of time.
Weighing of the sample, to determine the overall
weight loss.
Analysis of the alteration rind on the sample (SEM,
secondary ion mass spectrometry, SIMS, scanning
transmission electron microscope, STEM, etc.) in
order to study the thickness of the altered layer and
to understand the fate of the various elements
released from the glass and retained in the alteration layer.
The quantitative expression describing the rate of
release of an element in water is the leach rate,
usually expressed in g m2 d1, and normalized with
465
respect to the mass fraction of the given element in

the glass.
LRi mi =xi St
where mi is the weight (or activity) of element i
released into solution, xi is the mass fraction (or
specific activity) of this element in the glass, S is the
area of the glass surface exposed to the leachant, and
t is time.
During a static test the normalized mass loss is
often used as an indicator:
NLi mi =xi S;
expressed in g m2
The evolution of NL(i ) f (t) describes the overall

kinetics of the process for the given experimental
conditions. This curve is the basis for all the glass
behavior studies.
If an element (i) is a good alteration tracer, that is,
congruently released with glass dissolution and not
trapped back into the alteration products, then the
equivalent thickness of altered glass Eth can be calculated by dividing the normalized mass loss by the
glass density r:
Eth i NLi=r
Boron is most often a good tracer of glass alteration.
Sodium, lithium, and molybdenum are good tracers
in dilute media, but they may be integrated in alteration products in more concentrated media.
More information on glass alteration mechanisms
is provided in Section 5.18.4.
Exhaustive leaching characterizations are performed on inactive but chemically representative
samples; some tests are performed on fully active
material to check the impact of radioactive environment on leaching behavior.
5.18.4 Long-Term Behavior of

Nuclear Waste Glasses
The main phenomena that could alter glass containment properties over the long term are heat (for
HLW only), radiation damage, and alteration by
water. Their occurrence is not expected at the same
time scale (Figure 10). For instance, the risk of crystallization is principally limited to the thermal phase,
that is, in interim storage over the few decades during
which the maximum glass temperature will decay
from about 400 to <100 C.
For thousands of years, the glass matrix is
expected to remain dry and the major potential
466
Waste Glass
glass alteration mechanism is self-radiation damage.

Can it change the glass containment properties when,
after a few thousands of years, canister and over-pack
breach, and glass alteration by water start? Many
studies on glass self-radiation damage address this
question.
Eventually, in the very long term, the rate of radio
nuclides released into the near field will be controlled by the rate of glass alteration by water. Worldwide, for over 30 years, large research efforts have
been conducted to understand all the mechanisms of
glass alteration by water and to develop comprehensive models, and to adapt them for the evaluation of
repository performance. (A repository is the final
destination of HLW glass, a disposal site selected
and engineered to definitively isolate the radioactivity contained within the waste from the biosphere
and man.)
5.18.4.1 Glass Crystallization and
Long-Term Thermal Stability
Thermal stability constitutes one of the prime criteria for glass selection. It underlies the preservation
of a homogeneous glass over time. Theoretically,
glass could naturally evolve to a crystalline state
that is thermodynamically more stable. But such
thermally induced transformation gets dramatically
slow (or even stops), when the glass is maintained at
temperatures lower than the glass transition temperature (Tg). Predicting thermal stability at low temperature and in the long term therefore requires
experiments performed in supercooled liquids, as
well as modeling.
For nuclear glasses, the main work in this field was
performed by Orlhac,8 which helped confirm the
thermal stability of R7T7 glass in the very long term.
Devitrification experiments conducted on this
glass9 made it possible to identify three major
100
crystalline phases (CaMoO4, CeO2, and ZnCr2O4)

and two minor phases (albite NaAlSi3O8 and silicophosphate) between 630 and 1200 C. Yet, their
crystallization remains limited (a maximum 4.24 wt%),
as these phases consist of minor glass constituents. Even
after a heat treatment designed for a maximum crystallization (100 h at 780 C), no change can be observed in
the main properties of the nuclear glass (chemical
durability and mechanical properties).
Plotting the nucleation and growth curves of these
phases highlighted several essential points:
Nucleation sharply emerges during the first few
hours of the treatment, and then stops beyond this
period of time. Nucleation is heterogeneous,
inducing crystallization on the preexisting active
sites. Moreover, nucleation curves are strongly
amplified and shift to lower temperatures in the
presence of insoluble noble metal particles;
Seed crystal growth is very low, and, after a few
dozen hours, displays a saturation phenomenon;
Strong nucleation coupled with slow growth globally leads to a material which can hardly be devitrified (Figure 11).
The stability of high-level R7T7-type nuclear glass
at low temperature and in the long term was then
investigated by modeling. The mathematical model
selected is on the basis of the KJMA theory (KJMA,
for Kolgomorov, Johnson, Mehl, and Avrami), and
describes the transformation kinetics as a function
of time and temperature.10
Atomic diffusion is the main factor which limits
crystallization, as demonstrated by measuring the
diffusion activation energy. Viscosity is therefore the
key parameter which determines the nucleationgrowth kinetics in glass: it is this very parameter
which conditions diffusive atomic transport in the
silicate-based liquid. Consistently, nucleation-growth
kinetic processes can be determined by means of
1000
10 000
Time (years)
Figure 10 The sequence of alteration of a vitrified waste package.
Waste Glass
467
Maximum
theoretical
crystallized
fraction (wt%)
0.6%
ZnCr2O4 zincochromite
1%
2.44%
CeO2 cerianite
CaMoO4 powellite
Total 4.24%
NaAISi3O8 albite
Silicophosphate
600
700
800
900
1000
1100
1200
Temperature (C)
Figure 11 Temperature range for the nucleation and growth of the main crystalline phases likely to be formed after a
devitrifying thermal treatment of a borosilicate nuclear glass, which confines high-level effluents arising from Uranium Oxide
(UOX) fuel treatment. From CEA DEN Monographs Nuclear Waste Conditioning. Etienne Vernaz, Editions du Moniteur:
Paris, 2009; ISBN 978-2-281-11380-8.
independent viscosity measurements in a broad

range of temperatures.
The model validation was achieved under isothermal conditions on a simplified barium disilicate glass,
known for its homogeneous, fast crystallization.
Applying this model to the R7T7 glass shows that
periods of several millions of years are required for
the three main phases to be completely crystallized at
any temperature below 600 C. Clearly, if during the
slow cooling of large industrial block there is no,
or minute, crystallization in the temperature range
900600 C, then there will be neither any other
crystallization, nor crystal growth in the long term,
for kinetics reasons. These results confirm the thermal stability of actual HLW confining glasses.
5.18.4.2 Glass Resistance to
Self-Irradiation
The main sources of irradiation in nuclear glasses are
a-decays from actinides, b-decays from FPs, and g
transitions accompanying a- and b-decays.11
Alpha disintegrations are characterized by the production of a heavy recoil nucleus and the emission of a
light a-particle, yielding a helium atom at the end of
the path. Recoil nuclei (RN), shedding large amounts
of energy over a short distance result in atom displacement cascades, thus breaking a large number
of chemical bonds. Alpha decays are thus the main
cause of atomic displacement. On the other hand,
b disintegrations produced by FPs and g transitions
lead mainly to electronic interactions (electron excitation and ionization) with the glass network atoms
but not to atomic displacements.
The effects of self-irradiation have been studied
by investigation of glasses doped with short half-life
actinides, by atomistic modeling, and by external
irradiations.
5.18.4.2.1 Investigations of glasses doped
with a short half-life actinide
This investigation method is the most representative

of nuclear glasses aging: isotropic irradiation is produced in the whole of the glass volume preserving
the electrical neutrality (unlike external irradiations),
a particle and the recoil nucleus are produced allowing electronic interactions and atomic displacements,
and eventually helium builds up in the glass, exactly
as it will in the real case.
The effects of a disintegrations were mainly
investigated through studying 244Cm-doped-glass
glasses that can integrate within a few years doses
468
Waste Glass
equivalent to those to be delivered to the nuclear

glass during thousands of years under disposal
conditions.12
Figure 12 shows the DHA Atalante laboratory.
It is an example of a shielded line at Marcoule
(France) devoted to HLW studies, where actinidedoped glass samples are fabricated to carry out
accelerated studies of the effects of self-irradiation.
The inset in the figure shows a 238Pu-doped glass
block manufactured in the Vulcain laboratory in 1975.
Results produced all over the world, in France,13
UK,14 US,15 or Japan16 are quite consistent. Because
of the effect of a-decay, the glass density decreases
slightly (Figure 13) and its mechanical properties

appreciably improve, especially fracture toughness
that characterizes glass resistance to cracking. The
variations in these properties reach a saturation level
and stabilize beyond 21018 a g1.
Up to a dose of 1019 a g1, no helium accumulation (He bubble) is observed. No significant change
in glass durability is observed either. Furthermore,
there is no dose rate effect, as variations can be
reproduced among the various glasses under study
that exhibit quite different integration rates, spreading over four orders of magnitude.
5.18.4.2.2 Atomistic modeling of glass
self-irradiation
The second approach to understand radiation

damages focuses on atomistic modeling. In particular,
molecular dynamics can provide insight into the
ballistic effects induced by the deceleration of RN
emitted at the end of a decay. Numerous studies
conducted on simplified glasses representative of
the basic matrix nuclear glass (SiO2, B2O3, Al2O3,
Na2O, and ZrO2) demonstrated the remarkable
capacity of this type of glass to restore its structure
following the passage of a recoil nucleus.
The following conclusions could be drawn from
the whole of the calculations performed in relation to
individual cascades in glasses:
Figure 12 The Atalante laboratory for high-level waste

DHA.
a-decay dose ( g1)

1018
2.1018
3.1018
4.1018
5.1018
Density variation (%)
0.1
0
244Cm-doped
glass (0.04%)
244Cm-doped
glass (0.4%)
0.1
244Cm-doped
glass (1.2%)
244Cm-doped
glass (3.25%)
Fitting by an exponential law
0.2
0.3
0.4
0.5
0.6
0.7
Figure 13 Evolution of the density of curium-doped glasses with the a-decay dose. From CEA DEN Monographs Nuclear
Waste Conditioning. Etienne Vernaz, Editions du Moniteur: Paris, 2009; ISBN 978-2-281-11380-8.
Waste Glass
Figure 14 Evolution of displacement cascade from the

initial glass to the reconstruction of the glass structure after
the ballistic phase. From CEA DEN Monographs Nuclear
Waste Conditioning. Etienne Vernaz, Editions du Moniteur:
Paris, 2009; ISBN 978-2-281-11380-8.
displacement cascades take place in two separate

steps (Figure 14):
The ballistic stage during which collisions
between atoms take place as a whole. This phase
coincides with the strong heating of the matrix
and a depolymerization of the structure by interatomic bond breaking. In parallel, a decrease in
atom density can be observed within the cascades;
The relaxation stage during which glass structure reconstruction takes place. The glass
structure then experiences significant reconstruction to a state close to its initial state, but
still with a slight structural depolymerization
and a slight swelling on the whole.
In Figure 14, four stages of the evolution of displacement cascade can be seen. In the top left corner, the
initial glass containing the uranium atom (light blue
atom) to be accelerated with 800 eV energy (t 0 ps).
In the top right corner, the start of the ballistic phase
induced by the uranium projectile (t 0.013 ps).
In the bottom left corner, the final step of the ballistic
phase when the maximum number of broken bonds
can be observed (t 0.038 ps). In the bottom right
corner, reconstruction of the glass structure after
the ballistic phase (t 0.25 ps).
A model of cumulative local quenching was built
from these data in order to help explain the origin of
469
the small evolution observed under irradiation, as

well as the origin of their stabilization under high
doses.17
As displacement cascades accumulate, the glass
structure is fully destabilized by nuclear interactions.
Then the material can be quickly reconstructed without any external energy and its structure is close to
that of glass frozen at high temperature, which results
in the observed evolutions.
When the whole of the glass volume has been
damaged once by the displacement cascades, any
new a disintegration produced will again temporarily destabilize the structure, but the latter will
be rebuilt in the same way as after the first damage.
So the glass no longer undergoes significant change,
which could explain why its properties are stabilized beyond a given dose. It is worthwhile mentioning that the saturation dose experimentally
observed in relation to macroscopic property evolutions (as seen on Figure 13) coincides with that
required for full glass damaging by displacement
cascades, which corroborates with the proposed
model.
As a conclusion, the insignificant evolution of
nuclear glasses under a self-irradiation with respect
to crystallized minerals could be explained by the self
repairing properties of the glass structure.
5.18.4.2.3 External irradiation of glasses
This complementary type of investigation is based

upon the use of nonradioactive glasses in which irradiation stress is simulated by external irradiation
techniques (neutrons, heavy ions, electrons, and g).
The major disadvantages of this experimentation
type consist of the upsetting effects of injected high
dose rates in low irradiated volumes. Today, accurate
knowledge of these offsets allows relevant effects to
be sorted out from experimental artifacts and the
results obtained are quite comparable to those
obtained with other investigation methods.
This type of study was undertaken as early as the
1980s to evaluate the effects of b disintegrations.
Glasses with chemical compositions representative
of the industrially produced nuclear glasses were
thus irradiated by electrons during 1 year up to
doses equivalent to those received in about
1000 years of disposal, that is, 70% of the total bg
dose received in 1 My. These irradiations have not
entailed detectable modifications of the macroscopic
properties (density and mechanical properties).
In addition, glass still displays a homogeneous
microstructure after irradiation.
470
Waste Glass
5.18.4.3
Nuclear Glass Alteration by Water
The mechanisms which control nuclear glass leaching kinetics have been investigated worldwide for
more than three decades. This large accumulated
knowledge allows building computational models
likely to be used for performance assessment of a
geological repository. These models have to be applicable to all the vitrified waste packages industrially
produced, taking into account many different environmental conditions.
With an activation energy of about 75 kJ mol1, r0

ranges over seven orders of magnitude between the
temperatures of 4 and 300 C. This is why natural
glasses exhibit very low alteration at room temperature even after millions of years but high alteration
under hydrothermal condition (hyaloclastites). This
value explains also the inherent difficulty of measuring r0 at room temperature, (alteration of about 1 nm
per day hindered by interdiffusion) while a Soxhlet
measurement operating at 100 C will allow a prompt
measurement, representative of the sample in its mass.
5.18.4.3.1 Basic mechanisms of glass

alteration
5.18.4.3.3 Alteration rate in saturated

conditions and final rate of glass dissolution
In contact with water, the main alteration mechanisms of borosilicate glass are the following18,19:
In a closed system or under conditions in which the

water renewal rate is very slow, such as in the case of a
geological repository, apparent silica saturation is
observed in the leachate and a strong rate drop is
systematically evidenced for borosilicate glass.
(Leachate refers to the leaching solution after contact
with the glass sample.) This rate drop has been related
both to affinity effects (a decrease in the hydrolysis rate
coupled with an increase in the concentrations in solution), and to the formation of an alteration gel standing
as a diffusive barrier between glass and solution.20
Once these saturation conditions are established, a
steady rate of glass alteration is generally observed.
This residual rate seems to be related to the phenomenon of gel dissolution and to the rate of secondary
phase precipitation. For most nuclear borosilicate glass
composition this final rate is very slow (about 5 nm
year1 at 50 C for R7T7-type glass).
The origin of such a small residual rate of glass
alteration observed in saturation conditions seems to
be related to the persistence of a weak dissolution
rate of the gel probably itself resulting from the slow
precipitation of secondary phase (mainly phyllosilicates if pH does not exceed 10).15
In some specific cases alteration resumption can
be observed, once a residual rate regime has been
established. This so-called renewed alteration is
observed only for very alkaline conditions (equilibrium pH higher than 10) and specific glass composition (with high Al/Si ratio). This can be related to a
high precipitation rate of some specific secondary
phases (zeolites).21
Exchange and hydrolysis reactions involving the

mobile glass constituents (alkalis, boron, etc.) rapidly occur during the initial stages.
Slower hydrolysis, especially of silicon, drives the
initial glass dissolution rate.
The in situ condensation of many hydrolyzed species (Si, Zr, Al, Ca, RE, etc.) results in the creation
of an amorphous gel layer at the glass/solution
interface regardless of the alteration conditions.
This layer is more or less reorganized by hydrolysis and condensation mechanisms according to the
environmental conditions.
This amorphous layer can soon constitute a barrier
against the transport of water toward the glass and
of solvated glass ions into solution. The existence
of this transport-inhibiting effect rapidly causes
this layer to control glass alteration when water
renewal becomes very low.
Some glass constituents released from the glass
during process can precipitate as crystallized secondary phases. The precipitation of these crystallized phases within or on top of this amorphous
layer or in solution, can sustain glass alteration by
consuming the elements that form the protective
barrier.
5.18.4.3.2 Initial rate of glass dissolution
The initial dissolution rate r0 is the hydrolysis rate

obtained in pure water when no diffusion barrier
slows down the kinetics of alteration. It is an intrinsic
property of the material that characterizes its chemical durability in water. This rate depends mainly on
the glass composition, the temperature, and the pH.
It is the maximum rate of glass alteration for a given
temperature and pH.
5.18.4.3.4 Essential role of the passivating

reactive interphase
Historically, this apparent saturation state described

above was expressed in equations as if equilibrium
with the fresh glass could be achieved. Today it is
Waste Glass
considered that a saturation state can only be

achieved with respect to a hydrated layer. As saturation is approached in solution, the rate of condensation of many gel forming elements (Si, Al, Zr, Ca, etc.)
increases, allowing the formation of a thin amorphous
layer. Frugier et al.19 proposed the term passivating
reactive interphase (PRI) to take into account the
fact that not all of the gel layer becomes passivating
but only a thin inner layer in which a high condensation rate has led to closed porosity.22
Diffusion coefficients in the PRI are consistent
with diffusion in solids with values of the order of
magnitude of 1020 m2 s1. Furthermore, Monte
Carlo modeling of the gel layer formation by hydrolysis and condensation mechanisms allows describing
the conditions for which porosity closure is reached,
in good agreement with experimental data.23
It will be noticed that phosphate glass that can in
some cases24 display quite low initial alteration rates is
not expected to form any PRI, and therefore, no large
rate drop can be expected in saturation condition.
5.18.4.3.5 Influence of glass composition
Within a given domain, glass dissolution kinetics

strongly depends on its composition.25 Some nonlinear effects have been evidenced on the basis of semiempirical statistical methods26 or, in a few cases, fully
explained using experimental approaches and Monte
Carlo numerical model. A given element usually
modifies specifically each kinetic regime. As an example, Ca has no effect on the forward rate but strongly
favors the rate drop as it is incorporated into the PRI
in contrast to Mg that is incorporated in secondary
clay minerals acting as a silicon sink and promoting
higher dissolution rate. From an operational point of
view, rates of actual glass or rates corresponding to the
best or the worst glass within a given domain are
calculated from an empirical equation built from a
limited number of tested glasses. Considering the
R7T7 domain, forward rate ranges from 1.6 to 4.1 g
m2 d1 at 100 C and residual rate from 2.7105 to
3.2104 g m2 d1 at 90 C in initially pure water.
5.18.4.3.6 Influence of groundwater and
environmental materials
In a geological repository, water chemistry initially in

equilibrium with the host rock will be disturbed by
engineered materials (stainless steel canister, overpack, liner, concrete, etc.) and also by the heat produced by the glass canister itself. As a consequence, it
is expected that glass dissolves in an open medium
in which temperature, water flow, and composition
471
evolve with time and space, at least during the first

ten thousand years (this time depends on the host
rock and the disposal design). Chemical elements
brought by water, like Ca, Mg, organic matter, etc.,
may influence glass dissolution mechanisms, for
example, by promoting the PRI condensation,27
increasing the hydrolysis rate of the silicate network,28 or the allowing the precipitation of secondary
crystalline phases.29
In a fractured rock environment, such as a granitic
disposal site, the water renewal rate will be the main
environmental parameter. In a clay environment,
with no flow rate (or too low compared to diffusion),
the predominant effects of environmental materials
will be silica sorption onto likely oxide and hydroxide
minerals, and low precipitation of silicate minerals
that act as silica sinks.30 In any environment, these
phenomena can also be expected with iron corrosion
products. This kind of reaction will maintain a high
glass dissolution rate until the close environment of
the glass is saturated. Beyond this transient regime
that can be investigated by reactive-transport codes,
the final rate regime will control long-term glass
dissolution. Predicting such final rate is a challenge
that requires specific integrated mock-ups, in situ
tests, simulation by reactive-transport codes, and validation by natural or archaeological analogues.
Finally, in salt rock, lower rates than in pure water
are expected, especially if the water is weakly
renewed. Numerous studies have investigated effects
of ionic strength and chemical composition of the
brine.3134 Because most of these studies are quite
ancient, and also because the prediction of the
water availability near the glass and the migration
of soluble species in salt is more complicated than in
other host rocks, their conclusions, namely in terms
of performance assessment should be revisited as
mechanistic knowledge has been improved.
5.18.4.3.7 Influence of glass fracturing
As glass is fractured after cooling, the reactive surface

is greater than the geometrical one. Neither the surface of an actual glass block nor the evolution of the
reactive surface in geological disposal condition has
been precisely determined or estimated. Several
experimental techniques have been employed to
investigate glass blocks cracking networks and determine their impact on glass lifetime.35 Considering an
inactive R7T7 glass block, the largest cracks are
estimated to increase the geometric surface by a
factor around 5 and smallest ones by a factor around
40. Up to now, all countries have calculated glass
472
Waste Glass
package lifetimes considering a constant cracking

factor. Mechanistic modeling under development
will help address this issue in the near future. However, most studies on natural or archaeological analogues have shown that inner cracks have generally
a minor contribution to the overall glass alteration
(cf. Section 5.18.4.3.9).
5.18.4.3.8 Modeling glass long-term behavior
Predicting long-term behavior of glass requires a

multiscale approach as space and time scales related
to key phenomena are too large to be simulated by a
single mechanistic model. As a consequence, discrete
modeling approaches have been developed from
ab initio calculation at atomistic level36 up to performance assessment model at macroscopic level (also
called operational models).37 In between, Monte
Carlo model allows bridging the gap between atomistic level and measured dissolution kinetics.38,39 One
key point is the glass dissolution rate law.
Many mechanistic models based on rate equations
have been proposed.4042 The most advanced one is
probably the glass reactivity with allowance for the
alteration layer, GRAAL, model proposed by Frugier
et al.19 In this model, the glass-related parameters are
the solubility limit of the PRI, the water, and solvated
ions interdiffusion coefficient in this interphase, the
PRI dissolution rate. The other model parameters are
relative to secondary phases likely to precipitate,
depending on the chemical elements supplied by
the glass or by the surrounding medium: phase solubility limits and precipitation kinetics. For R7T7
glass, a very good agreement is observed between

simulation and experimental data for a very large
set of experimental conditions.43
The operational model that is proposed to assess
the R7T7 glass long-term behavior in the proposed
setting for the French geological repository, is the socalled r0!rf model.44 In this model, the rate of glass
alteration is supposed to keep its initial r0 value until
all conditions are obtained to get the final rate (i.e.,
full saturation of the media, with all silica sorption
sites saturated). Then the final rate rf is applied.
For R7T7 glass, the model parameters (alteration
rates r0 and rr, and glass surface area accessible
toward water) were determined as a function of temperature, pH, and glass composition throughout the
whole R7T7 composition range. Uncertainties on
the parameters values were also determined. The
model can be used to calculate the glass block lifetime depending on the timetemperature profile,
the pH of the medium, the date of water ingress in
contact with the glass, and the quantity of accessible
silicon sorption sites on the metal canister alteration
products.
A typical calculated glass lifetime plot is given on
Figure 15. Two assumptions concerning the quantity
of unsaturated sorption sites during the initial rate
phase are proposed and water ingress in contact with
the glass after 4000 years45 is assumed. Should the
environment be saturated, the total package lifetime
of a R7T7 glass will exceed 300 000 years, even in a
pessimistic scenario where a large amount of iron
corrosion product acts as a silica sink.
60
100.0%
50
10.0%
Numerical uncertainties (1s)
40
30
1.0%
20
Temperature (C)
Total fraction of altered glass (%)
Mass of corrosion products = 2730 kg

Mass of corrosion products = 100 kg
Two environmental conditions
10
0.1%
1000
10 000
100 000
Time (years)
1000 000
0
10 000 000
Figure 15 Operational modeling; example of calculation of R7T7 glass lifetime in two different environmental conditions.
Waste Glass
5.18.4.3.9 Natural an archaeological

analogues
Validating predictive models is one of the major

difficulties of investigating the long-term behavior of
containment materials because the relevant time
scales largely exceed what is accessible to laboratory
experimentation. Whenever possible, therefore, natural or archaeological analogues are examined for this
purpose. They enable to check that no long-term
mechanism is forgotten. They give us some very
long-term integrated experiments, against which predictive models can be qualitatively validated.
For instance, archaeological glass blocks from
a shipwreck discovered near the French Mediterranean
island of Les Embiez have been examined because
of their morphological analogy with nuclear glasses
and their known, stable environment. Like nuclear
glasses, these blocks were fractured after production;
they were then leached for 1800 years in seawater.46
In that specific case, a quantitative agreement has
been achieved between geochemical simulation and
measurements on the archaeological artifact showing
that bridging the gap between short-term laboratory
data and long-term natural system is possible via a
rigorous methodology47 (Figure 16).
The same methodology could be applied to much
older basaltic glasses for which the environment can
be characterized. These glasses not only exhibit the
same alteration mechanisms and kinetics as nuclear
glasses in laboratory experiments, but their alteration
473
products also reveal strong similarities, especially

between the palagonite on basaltic glasses and the
gel on nuclear containment glasses, which can constitute a diffusion barrier. These studies can contribute to a finer definition of the chemical model of
nuclear glasses and to the long-term validation of
the gel protective properties.48
5.18.4.4 Conclusions on Glass Long-Term
Behavior
For more than 30 years, a very significant research
effort on nuclear glass alteration mechanisms has
been carried out worldwide, and a large database
has been produced. Academic researches on longterm crystallization, radiation damage, and alteration
by water, enable nowadays a good mechanistic understanding of the key phenomena that can alter nuclear
waste glass properties in the long term.
A sound methodology was established to use the
best of academic knowledge of alteration mechanisms for performance assessment of glass package in
complex environments. This methodology includes
the following:
Assessing the evolution of the boundary conditions
including normal and incidental scenario of
evolution.
Understanding elementary alteration processes at
a mechanistic level.
100
Embiez glass
80
Total
% of altered glass
Sext. (r0)
Sint. (D)
60
Total (measured)
Sext. (measured)
40
Sint. (measured)
20
0
102
103
104
105
Time (years)
Figure 16 Predicted percentage of alteration for Embiez glass (curves) and measured alteration of both kinds of
surfaces (stars). Geochemical modeling has been achieved using the Hytec code including the glass reactivity with
allowance for the alteration layer model for glass dissolution, water diffusion within smallest cracks, advection within the
largest ones, and specific boundary conditions related to 56-m deep seawater.
474
Waste Glass
Assessing the couplings between the different

mechanisms which simultaneously occur within a
given scenario. Such couplings may indeed modify
significantly the global evolution.
Finally, the models describing the different processes
have to be integrated in a global predictive model
which often requires to be simplified by selecting the
most significant processes and parameters. Operational models also include a conservative approach
to overcome the lack of knowledge and wrap the
general trend.
The use of this kind of operational model demonstrates that waste glass lifetime can be over millions of
years if the glass composition is optimized and disposal conditions are appropriate.
Furthermore, through this long-term research on
waste glass a new science of long-term behavior has
been developed. This science and methodology is
now applied to numerous other matrixes (cement,
bitumen, spent fuel, etc.).
5.18.5 Vitrification Processes

As nuclear energy is very concentrated, the overall
volume of nuclear waste is small. This is especially
true for HLW that will be concentrated into a small
volume of glass. (For example, the amount of HLW
glass produced each year in France, related to the
reprocessing of the spent fuel of about 50 reactors, is
in the range of 100 m3.) Consequently, the scale of
radioactive waste vitrification facilities is usually
much smaller than that found in traditional glassmaking. In addition, and especially when processing
HLW, the very high levels of radiation preclude
direct contact with the equipment. Any waste resulting from exchange of failed equipment, for instance,
becomes radioactive waste and must be managed as
such. Consequently, HLW vitrification facilities must
be designed to be remotely operated, and to minimize
maintenance as well as secondary waste generation.
Off-gas treatment systems must be very efficient to
remove any volatilized or entrained radionuclide. As
most of waste streams are nitrate-rich, NOx fumes
are produced and must be abated. The whole vitrification process must be contained efficiently in order to
prevent release of radionuclides to the environment.
Another significant difference between traditional
glassmaking and waste vitrification is that, most often,
the waste is in a liquid form while, in glassmaking, the
batch materials are dry solids. For waste vitrification
it is then necessary to evaporate the liquid and calcine the salts prior to reacting them with the glassformers. This operation requires large amounts of
additional energy provided directly in the melter or
in a specific pretreatment step.
In the end, the glass product must be disposed of,
usually in metallic canisters. For that purpose, most
of the time, the glass product must be poured into
these canisters. This requires, first, that glass viscosity
be around 100 P or lower at the time of pouring and,
second, that the vitrification equipment be designed
with a pouring function.
According to the nature of the waste to be vitrified, and the context, a number of processes have
been studied, among which several have been
deployed industrially.
The first attempts were extrapolations of the crucible work performed in the laboratories. The process
was performed batch wise in a single crucible, where
all the operations of evaporation, calcination, vitrification, and evacuation of the product were performed successively. The melting crucible could be
the canister itself (the process was then a lost-crucible process) or a melter from which the glass product
was poured into the canister. The first French industrial facility, PIVER (Figure 17), for instance, was of
this type. The metallic melter was heated from the
outside by a stack of inductors.
The facility was used to process actual high-level
radioactive waste into 100 kg glass blocks. Similar
facilities, operated with lost crucibles or not, were
designed or built in various other countries (UK,
Italy, etc.). Very soon, however, it was concluded
that batch processes did not allow throughputs compatible with commercial operation. The PIVER
throughput, for instance, was around 5 kg h1 of glass.
Most countries, then, decided to abandon batch
processes and design continuous vitrification processes, with two major options for feeding the waste:
One-step processes, where liquid waste is fed
directly to the melter and all the steps of evaporation, calcinations, and vitrification are performed
in it. This is the case for instance of the Defense
Waste Processing Facility at Savannah River, USA.
Two-step processes where liquid waste is first fed
to a calciner before entering the melter. This is the
case for instance in France, at the AVM facility at
Marcoule or at the R7 and T7 facilities at La
Hague.
In the following sections we will describe the major
existing facilities and the emerging new processes
Waste Glass
HLW solutions
475
Glass frit
Inductors
Feeding
evaporation
Calcination
Melting
refining
Pouring
Figure 17 The PIVER process in France (19691980).
being designed to further improve the capabilities

and efficiency of these processes.
5.18.5.1 Existing Processes for
Radioactive Waste Vitrification
FP solution
Recycling
Additive
Calciner
Gas
5.18.5.1.1 The French two-step continuous

vitrification process
Following the PIVER experience, the French CEA

started to develop a two-step process, in order to separate the functions of evaporation-calcination and vitrification, as illustrated in Figure 18. This allows
keeping a melter of relatively small size, as most of
the energy is provided at the level of the calciner.
Another major decision was to select a vitrification
method by which power is supplied to the glass from
the outside, without direct contact of the glass with the
power source. A metallic melter heated by induction
provided by an external stack of inductors was selected,
following the good results obtained with PIVER. This
disposition allows protecting the power source from
contamination. On the other hand, the size of the
melter is limited by the ability to transmit heat to the
core of the molten bath.
The first industrial facility for vitrifying HLW in
France was the AVM which was the first industrial
vitrification facility in the world, commissioned in
1978. This facility has vitrified the HLW solutions
from the UP1 reprocessing plant and is now used to
vitrify the effluents resulting from the decommissioning and decontamination of the same UP1 plant.
This mission is nearing completion, and the AVM
facility is now facing decommissioning after more
than 30 years of successful operation. The experience
Glass
frit
Scrubber
Melter
Canister
Figure 18 The French two-step continuous vitrification

process.
gained from the operation of AVM has been later

incorporated into the design of the larger facilities
R7 and T7 at La Hague, with three vitrification lines
each, which started operation in 1989 and 1992
respectively. The same technology has been selected
for the WVP (Waste Vitrification Plant) at Sellafield
in the United Kingdom.
In the French continuous process used at
La Hague, the concentrated HLW solutions are
received and stored in cooled and stirred tanks. After
sampling and analysis, they are fed at a metered rate to
476
Waste Glass
the calciner. In the calciner, they are heated progressively up to about 400 C to evaporate the liquid and
transform them into a finely divided powder called
the calcine. The calcine falls into the melter, together
with glass-formers which are fed under the form of a
prefabricated glass called frit. The mixture is heated
at the surface of the molten glass bath and undergoes
the final vitrification reactions (from temperatures of
about 700 C) and finally become digested into the
homogeneous molten glass at about 1100 C. The
molten glass is then poured batchwise into metallic
canisters which are then weld-sealed and evacuated.
The calciner is a tilted rotating tube inserted
into a furnace heated by resistors. In the calciner,
the solution is evaporated and most of the nitrate
salts (with the exception of alkalis) are converted to
oxides by decomposition of the nitrates. A calcination
additive, which decomposes under the action of temperature and reacts with the nitrates, is added to ease
the fragmentation of the calcined mass and to limit
the volatility of some radionuclides.
The calcined mass then falls into the melter
together with the glass frit. The melter is a metallic
crucible made of nickel-base alloy heated by induction. In order to promote heat transfer and enhance
melt homogeneity, the melter is equipped with stirring and gas sparging devices.
The melter fills progressively during continuous
feeding. When the higher operating level is reached
in the melter, a batch of 200 kg of the molten glass is
poured into a stainless steel canister through a pouring nozzle situated below the melter. Pouring is activated by heating the nozzle with a specific inductor.
The melter then continues to process the next batch.
Each glass canister holds two batches of 200 kg of
glass. After filling and cooling, the glass canisters are
closed tightly by welding a cover on top of their
mouth. The sealed canisters are decontaminated by
shot-blasting and checked for absence of residual
contamination. They are then transferred to a storage
facility (Figure 19) where they are stacked in pits
cooled by a forced flow of air to evacuate the residual
heat produced by radioactive decay of the FPs. At the
time of production, the heating power of each individual canister can be higher than 2 kW. After several
years of cooling in a forced ventilation storage facility, the residual power decreases sufficiently to allow
transferring the canisters to a facility cooled by natural convection.
The off-gas from the calciner and the melter is
composed of water vapor, nitrogen compounds, and
entrained material. It is extracted at the top of the
Figure 19 The French La Hague high-level waste glass

storage facility. # AREVA.
calciner and goes through a dust-scrubber, to remove

most of the large particulate material and aerosols for
recycling to the calciner, a condenser, washing columns, and filters to decontaminate the gas prior to
release to the stack in compliance with radioactive
and chemical release standards. The liquid effluent
from off-gas treatment is collected and treated in
specific effluent treatment facilities to concentrate
the activity and recycle most of it to vitrification.
This technology is now used in the French industrial facilities of R7 and T7 at La Hague and has
proven its efficiency and operability. By the end of
2009 more than 18 300 glass canisters have been
produced (of which about 3400 have been produced
at the AVM facility and about 14 900 at La Hague).
This amounts to 7240t of glass and more than
2.5108 TBq of activity safely immobilized. The
small size and modular design of the technology
make it easily operable and maintainable. The following are the major limitations of this process:
The life expectancy of the metallic crucible which
is in direct contact with hot (1100 C) and corrosive molten glass. Through continuous developments, it is now possible to replace the metallic
melters about once a year in the current La Hague
facility. On the other hand, this operation is made
easy by the small size and design of the facility;
melter exchange is performed within a week, and
the resulting waste can be size-reduced and processed together with the other metallic waste of the
reprocessing facilities.
Capacity : As the glass is heated from the outside,
the size of the melter, and thus the capacity, is
limited. In the current facilities, the capacity of a
metallic melter is about 25 kg h1 of glass, and
several lines are needed if a higher throughput
Waste Glass
is required. On the other hand, this small size is

also an advantage for maintenance and waste generation, as seen above.
Limitation in melt temperature: In order to preserve
the integrity of the metallic crucible, operation
temperature is limited to about 11001150 C.
This, in turn, is a limit for throughput (as throughput theoretically varies like T4). Moreover, this
temperature limit also reduces the range of glass
compositions that can be processed in such a facility to those which have melting temperature below
or around 1150 C.
5.18.5.1.2 Liquid-fed ceramic melters
Not all the liquid waste is amenable to separate

calcination: when the waste holds large amounts of
alkalis, the corresponding nitrate salts tend to form
molten phases in the calciner and prevent adequate
calcination, generating numerous sticking and caking
problems. In such situations, direct liquid feeding of
the melter has been implemented. This is the case in
the United States (Defense Waste Processing Facility,
DWPF; West-Valley Demonstration Plant, WVDP;
Hanford WTP), where the acidic high-level liquid
waste has been neutralized by caustic prior to storage.
Direct liquid feeding can also be selected with the
intent of keeping only one processing step such as in
Belgium (PAMELA), Germany (VEK), Russia, or
Japan (Tokai Vitrification Plant (TVF) and K-Plant
in Rokkasho Mura).
In these situations, the liquid waste and glass frit
(or separate glass-formers) are fed continuously to
the top of the melter, and evaporation, calcination,
and vitrification reactions are performed in the coldcap, a colder layer that sits on top of the molten bath
and progressively dissolves into the melt. In such a
configuration, it is necessary to supply all the heat to
perform those transformations through the surface
of the glass bath and the cold-cap. The power
requirements are such that, in order to obtain an
adequate throughput, the surface area of the melt
must be extended (throughput theoretically varies
proportionally to the melt surface area). Even if
boosting can be provided by implementing radiative
heaters in the melter plenum above the cold-cap, this
results in much larger melters, which cannot be
heated from the outside any more. A technology
directly inspired from traditional glassmaking melters has been selected. The melters are lined with
layers of refractory bricks in order to protect the
cooled metallic walls, and heating is performed by
directly applying current to the conductive melt
477
through metallic electrodes, usually made of Inconel

690 and sometimes cooled by an internal circulation
of air. The current heats the melt by Joule effect.
The melt, in its turn, transfers the heat to the
cold-cap. As, owing to the larger surface area, these
melters hold large volumes of glass, pouring is usually performed by overflow, air-lift, or vacuum siphon
and can be continuous. Batch bottom pouring is
nevertheless implemented for some specific applications described below.
Several facilities have been operated or are still in
operation worldwide.
The first industrial facility to have been operated
with a ceramic melter has been the PAMELA facility
in Belgium, commissioned in 1985, which has processed 490 MT (metric tonne) of glass in about
6 years. The melter had a flat bottom and pouring was
performed essentially by overflow. Two melters were
used, with a melter life of around 3 years. The melter
was 2.6 2 2 m in size, weighed about 20 MT
and held about 300 l (750 kg) of glass. This facility
experienced difficulties owing to the settling of glassinsoluble noble metals from the waste at the bottom.
This conductive settled layer tended to disturb current
distribution in the bulk of the melt and led to loss of
capacity and, ultimately melter failure.
In order to prevent such occurrences when dealing
with noble-metal-rich feeds, the bottom of the cavity
can be designed with a dead zone below the level of
the electrodes, to collect the sludge in a manner that
should prevent any interactions with power distribution to the melt. This solution was implemented at
WVDP in the United States for the vitrification of a
backlog of HLW solutions from a pilot commercial
reprocessing plant. This melter started operation in
1996 and produced 275 canisters of glass before being
stopped and emptied in 2002. The melter, with a
design throughput of about 45 kg h1 of glass, was
of large dimensions (33.23.3 m), with a glass
hold-up of about 860 l (1150 kg) and a melt surface
area of 2.2 m2. The melter was equipped with two
pouring chambers and a bottom electrode to promote
evacuation of the noble metals. Despite these dispositions, at the end of its life, the melter showed signs of
declining capacity and power distribution upsets,
probably attributable to the slow accumulation of
conductive noble metals at the bottom.
Another solution to deal with this issue is to provide sloped walls above a bottom pouring device,
to promote the evacuation of the settled noble
metals. This solution has been implemented in the
Tokai Vitrification Facility (TVF) (Figure 20) and
478
Waste Glass
HLLW
feed line
Glass
feed line
Off-gas line
Start-up
heater
Main
electrode
Auxiliary
electrode
Discharge
nozzle
Figure 20 The Tokai Vitrification Facility ceramic melter
(Japan). Reproduced from Aoshima, A.; Kozaka, T.; Tanaka,
K. Glass melter replacement and melter technology
development in the Tokai vitrification facility. In Proceedings
of ICONE12 International Conference on Nuclear
Engineering, 2004; with permission from ASME.
K-plant in Japan, (but did not completely suppress

the issue) and in VEK in Germany, which has been
recently commissioned. TVF has been commissioned
in 1995 and the first melter processed 130 canisters
before its replacement in 2002. Melter #2, with an
improved bottom configuration, is now implemented
and operating. The melter section is 0.80.83 m, with
a glass hold-up of 350 l, and a design throughput of
9 kg h1. The sloped walls at the bottom make an
angle of 45 with respect to the vertical direction.
Pouring is activated by heating the pouring nozzle
with an inductor. Pouring is stopped by blowing cold
air to freeze the glass inside the nozzle. The electrodes are cooled with air.
In Rokkasho (Japan), a much larger plant, with a
design throughput of 80 kg h1 and a similar conception, is in the process of active start-up.
VEK in Germany has been designed to process a
backlog of HLW produced by a pilot reprocessing
plant. The melter has a conical bottom, with slopes of
around 60 with respect to the vertical direction. The
melter is designed to process 10 l h1 of feed, or
produce 7 kg h1 of glass. It is a cylindrical melter
with an outside diameter of 1.5 m and a height of
1.7 m, with a glass hold-up of 150 l (375 kg), a melt

surface area of 0.44 m2, and an overall weight of 8 MT.
The electrodes are cooled with air.
Very large capacity ceramic melters have also
been commissioned or are in the process of commissioning for Defence High Level Waste in the United
States. These wastes are not as radioactive as the
waste from commercial reprocessing, and they do
not contain significant amounts of noble metals. For
these applications, throughput is the major concern,
as the volumes of waste to be vitrified are quite
impressive.
The first vitrification facility commissioned in the
United States was the DWPF, at Savannah River, in
the United States. The liquid-fed ceramic melter has
been designed to process a thick slurry retrieved from
the Savannah River Site (SRS) tank farms at a design
rate of up to 100 kg h1 of glass (or 200 l h1 of feed).
The frit is introduced as a powder and mixed with the
feed suspension. This facility has been commissioned
in 1996 and has produced more than 5300 MT of
glass. The melter holds a melt volume of 2500 l
(6.5 MT), with a melt surface area of 2.6 m2. Pouring
is continuous except at the time of canister changeout, and performed via a siphon. The overall weight
of the melter (including the glass and cooling water)
is around 80 MT. Melter #1 was decommissioned in
October 2002 and Melter #2 started operation
5 months later, in March 2003 (Figure 21).
After completing its useful life, Melter #1,
together with its supporting rack, was inserted into
a box, evacuated on a trailer, and entombed for longterm storage in a specific underground cavity on site.
For Hanford WTP, two vitrification facilities are
being built. For HLW, the facility will host two
ceramic melters with surface areas of 3.75 m2 for a
design throughput of 125 kg h1 per melter. For low
activity waste, it is intended to implement two elongated melters with melt surface areas or 10 m2, for a
throughput of 625 kg h1 per melter. For these melters, capacity is critical. In order to improve capacity,
and enhance heat transfer from the melt to the coldcap, extensive air sparging is being implemented.
Liquid-fed ceramic melters are also used in Russia
to process HLW into a phosphate-based matrix.
The selection of the phosphate-based matrix allowed
reducing melting temperature to below 1000 C,
but this matrix is still very corrosive and detrimental
to the melter lifetime.
The interest in liquid feeding is because one single
piece of equipment is needed to perform all the
necessary reactions. Ceramic melters are also quite
Waste Glass
Feed tubes
479
Lifting bail
T.V. camera/borescope
assembly
Off-gas
film cooler
Riser heater
Dome heaters
Vapor thermowell/
conductivity probe
Pour spout
heater
Melt thermowell
Electrodes
Drain valve
Figure 21 The Defense Waste Processing Facility melter (USA). Reproduced from Norton, M. R.; Shah, H. B.; Stone, M. E.;
Johnson, L. E.; ODriscoll, R. Overview defense waste processing facility operating experience. In WM02 Conference,
Tucson, AZ, Feb 2428, 2002; Westinghouse Savannah River Company: Aiken, SC, 2002; Copyright WM Symposia, Inc.,
2002, reprinted by permission.
stable in operation. The major limitations of these

melters are the following:
They are large pieces of equipment which, once
used, become a large quantity of waste. Melter
exchange can require several months.
With some exceptions, once started, they must be
maintained hot until their decommissioning,
in order to avoid deterioration of the ceramics.
Their tolerance to glass-insoluble elements, such as
noble metals, or crystal forming elements, is limited.
As the molten glass is in direct contact with the
refractories and electrodes, operating temperature is
limited, usually around 1150 C, sometimes a little

higher, in order to preserve the integrity of the refractories and electrode material. This is a limiting factor
for capacity and for the type of glass that can be processed, as for the hot metallic melters described above.
5.18.5.2 Emerging Processes for
Radioactive Waste Vitrification
5.18.5.2.1 Cold-crucible induction melters
As seen above, the two major current processes for

radioactive waste vitrification, although they have
proven their sturdiness and adaptation to very
480
Waste Glass
demanding environments, have reached their limits, in

terms of throughput, tolerance to some elements in the
glass, or glass composition. Other solutions have then
been sought in the last two decades, with the emergence of the cold-crucible induction melter (CCIM)
technology both in Russia and France.
For this technology, the crucible itself is composed
of a water-cooled metallic structure. The heating
mode is direct induction in the molten bath, a technique that allows transmitting power directly at the
heart of the glass, using a water-cooled inductor
(Figure 22).
In order to allow the penetration of the magnetic
field provided by the inductor past the metallic crucible (to avoid the Faraday cage effect), the crucible is
made of several sectors separated by a thin layer of
isolating material. The power (typically around
600 kW) is directly induced in the glass by the
high-frequency magnetic field (typically 300 kHz in
France). As cold glass is not conductive, melting is
started by introducing a conductive material (for
instance graphite) on the cold glass in order to generate the first molten zone. This molten zone then
progressively extends to fill the whole volume of the
melter. A thin layer of molten material freezes at the
zone of contact with the cold metallic wall. This
frozen layer, several mm thick, forms a cold crucible
which prevents further contact between the molten
mass and the metallic wall.
This technology offers a number of advantages
over the previous processes:
As the molten glass does not contact the melter
wall, temperature is not limited any more, offering
a whole new range of possibilities for glass or even
ceramics formulations.
The cold layer also protects the equipment from
corrosion, and thus allows processing effluents that
Cold
cap
CCIM
Cold glass
layer
Inductor
Molten glass
Figure 22 The cold-crucible induction melter (CCIM).

were deemed too corrosive for the previous techniques (such as effluents containing sulfur, chlorine, molten salts, etc.).
The molten glass is not polluted by any material
from the crucible.
Significant increase in capacity associated with the
possibility of raising the operating temperature.
As the crucible is protected from both heat and
corrosion, its lifetime is extended.
The cold crucible layer can be easily removed at
the end of operation, thus allowing easier decontamination of the crucible.
The use of CCIMs in industrial facilities has started.

The cold-crucible technology is used in Russia to
vitrify low activity effluents from nuclear power
plants. In S. Korea, an incinerationvitrification facility based on the French CCIM technology has been
recently commissioned to process dry active waste
and resins from nuclear power plants.
And in France, for high-level radioactive waste, a
first CCIM has been retrofitted in one of the lines of
the R7 facility to process corrosive decontamination
effluents.49 Hot start-up is in progress. It is the first
cold-crucible melter (CCM) implemented in a high
activity cell. The retrofitting has been performed
fully remotely. This deployment is the apex of more
than 20 years of R&D work and will shift the status of
this technology to that of a fully mature technology.
5.18.5.2.2 Incinerationvitrification processes
Alternative processes of incinerationvitrification

coupling CCM and plasma torches are developed
with the aim of drastically reducing intermediatelevel waste (ILW) volume while confining it in a
more durable glassy matrix. The proposed technology relies on the great skill developed by the CEAs
vitrification teams on the CCM and also on the
Waste Glass
oxygen plasma transferred mode plasma torches that

have been tested for more than 10 years in Marcoule.
The Systeme Hybride dIncineration Vitrification
Avance (SHIVA) process (Figure 23) has been developed to study the feasibility of these technologies for
the future.50 It allows performing in the same vessel
the incineration of the burnable wastes, the vitrification of their mineral charge, and the combustion of
off-gases.
Significant advantages can be obtained by supplying the waste directly into oxygen arc plasma located
above a glass bath heated by direct induction in a cold
crucible. The temperature is very high and so is the
efficiency of the combustion in the excited free oxygen rich atmosphere that also promotes a thorough
oxidation of the glass. The treatments of different
kind of wastes have been investigated. Burnable
wastes such as ionic exchange resins, bituminous
wastes, sulfate slurries, and graphitic sludge have
been successfully incinerated with a good incorporation of their mineral charge in the glass.51 In addition,
mineral wastes such as sludge issued from nuclear
treatment have also been treated. The current studies
concern the incinerationvitrification of chlorinated
organic wastes. In this case, the main difficulty is to
manage the volatile metallic chlorides in the process.
Some studies are also in progress on the treatment of
mixed wastes containing organics and metals.
Waste
+
Glass precursor
Oxygen
Oxygen
Cathode
Anode
Burned gases
exhaust
Metallic
cooled
walls
Plasma
Molten glass
Inductor
HF current
Figure 23 The Systeme Hybride dIncineration
Vitrification Avance process principle.
481
5.18.6 Conclusions and Outlook on

Waste Glasses
Today vitrification is the world reference solution to
the containment of HLW. Since the first trials of
vitrification of FPs solutions in Saclay (France) in
the 1950s, until the recent development of a new
generation of CCM in the 2010s, vitrification is a
success story that allowed having waste glasses that
meet all industrial requirements while providing an
excellent long-term behavior. Thus, in all countries
where reprocessing of nuclear fuel is practised, vitrification plays a vital role in our ability to safely
manage the HLW from nuclear energy.
Given the importance of this matrix for HLW
management, a huge number of research activities
devoted to nuclear glasses have been supported over
the last 30 years either by the nuclear industry or
by governmental organizations. These studies have
focused on both optimizing complex glass properties
(solubility of components, structure, durability, etc.)
understanding the containment properties and the
long-term behavior, and on the continuous improvement of vitrification processes operating in
hostile environments. Through these studies, general
knowledge of complex glasses has considerably progressed, particularly in the area of understanding the
mechanisms of glass alteration by water. To date,
there are probably many more publications on the
alteration of the R7T7 glass than on the alteration of
window glass.
Significant progress was achieved on radiation
damage of glass too. If 30 years ago fear existed that
the glasses could disintegrate under the effect of selfirradiation, today it is known that glass is a self
repairing material whose macroscopic properties are
not affected by long-term autoirradiation. Great
progress has also been made in atomistic modeling
of complex glasses that allows checking that our
models are on the basis of an atomistic understanding
of basic phenomena.
This success of vitrification is expected to further
increase in the next 30 years, for at least two reasons.
First, in a context of global nuclear renaissance with
the need to conserve resources, more and more
countries will choose nuclear fuel recycling and vitrification will prevail for waste treatment. On the other
hand, with the increasing desire to protect the environment, a large number of matrices used today to
confine intermediate nuclear waste and even hazardous waste, will be probably replaced by glass, as
incinerationvitrification allows both a drastic waste
482
Waste Glass
volume reduction and a final containment with

improved performance.
With the proliferation of waste types treated, we
should expect a proliferation of glass compositions
too. One should have to be very careful about the
quality of glass products to never degrade the image
of this excellent containment matrix. In fact, the glass
is a wonderful material that can pass almost continuously from a soluble borax glass to almost eternal
obsidian. Care should be taken that the great glass
flexibility is not used at the expense of its quality. The
development of good containment glass requires
mastering glassy materials and process aspects, all
together with the science of their long-term behavior.
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Proceedings).
5.19
Ceramic Waste Forms
E. R. Vance
Institute of Materials Engineering, Australian Nuclear and Technology Organisation, Menai, NSW, Australia
Crown Copyright 2012 Published by Elsevier Ltd. All rights reserved.
5.19.1
Introduction
485
5.19.2
5.19.3
5.19.4
5.19.5
5.19.6
5.19.7
5.19.8
5.19.9
5.19.10
5.19.10.1
5.19.10.2
5.19.10.3
5.19.11
5.19.12
References
Desirable Performance Characteristics of High-Level Nuclear Waste Forms

Design of Waste Form Ceramics
Historical Evolution of Candidate Ceramic Waste Forms for HLW
Titanate Ceramics
GlassCeramics
Aqueous Dissolution
Radiation Damage
Thermodynamic Stability of Multication Oxides
Processing of Ceramics and GlassCeramics
Hot Uniaxial Pressing
Hot Isostatic Pressing
Melting
Cements and Geopolymers
Conclusions
488
488
490
492
494
495
495
496
496
497
497
498
499
500
501
Abbreviations
An
ANSTO
Actinide
Australian Nuclear Science and
Technology Organisation
AWE
Atomic Weapons Establishment
BET
BrunauerEmmettTeller
DWPF
Defense Waste Processing Facility
EA
Environmental Assessment
FP
Fission product
FUETAP Formed under extreme temperatures
and pressures
HIP
Hot isostatic press
HLW
High-level waste
HUP
Hot Uniaxial Press
ICPP
Idaho Chemical Processing Plant
ILW
LLNL
Lawrence Livermore National Laboratory
LLW
Low-level waste
MCC
Materials Characterization Center
MOX
Mixed oxide
MPP
Magnesium potassium phosphate
NIMBY Not in my Backyard
NZP
Sodium zirconium phosphate
OPC
ordinary Portland cement
PCT
Product consistency test
PNNL
Pacific Northwest National Laboratory
RE
Rare earth
SI
SRL
Synroc
USDOE
International System of Units

Savannah River National Laboratory
Synthetic rock
United States Department of Energy
5.19.1 Introduction
Worldwide inventories of high-level waste (HLW)
from nuclear power and weapons production, other
than spent fuel, constitute hundreds of thousands and
perhaps millions of tonnes.1 Figures 1 and 2 show the
abundances and the time dependences of the radioactivity of HLW from nuclear fuel reprocessing,
respectively. Disposal of HLW other than spent fuel
itself basically involves adding specific material to the
waste and processing it to transform it to a dense
refractory solid the waste form that can withstand
prolonged immersion in groundwater. In a large
majority of cases, the solid would be an oxide, but
metallic components may also be present, depending
on the waste and the processing conditions. The solid,
which would be a glass, ceramic, glassceramic, or
cementitious material, depending on the nature of
the waste to be dealt with, would then be transferred
in a metal disposal canister to a geological repository
(Figure 3), in which the radioactive and toxic
485
486
Ceramic Waste Forms
10
14 Mev
103
1
Fission product
total activity
Fission yield (%)
102
0.1
10
Actinides
total activity
1
0.01
101
Thermal
0.001
0.0001
70
102
103
90
110
130
Mass number
150
Figure 1 Relative atomic abundances of fission products

elements in a commercial power plant nuclear fuel.
components would be immobilized for long periods,

up to millions of years if necessary, depending on the
half-lives of the dangerous species. Glass is currently
seen as a baseline option for HLW.
In this article, the focus of the immobilization is on
the waste form, but of course the repository would also
be expected to play a significant role in preventing the
transport of radionuclides and toxic ions to the biosphere. Because it seems unlikely that spent fuel in
the form of irradiated UO2, a ceramic, will be chemically processed, but rather simply allowed to cool as
the short-lived fission products decay, and then containerized for eventual repository disposal, we will not
discuss spent fuel in this article, but it will be the subject
of Chapter 5.16, Spent Fuel as Waste Material.
Tables 1 and 2 show approximate compositions of
Purex-type reprocessing and tank wastes in the
United States. Since the activity of the waste falls
with increasing time, it is technically advantageous
to store the waste as long as possible, although this
should not be seen as an excuse to delay immobilization unduly. Moreover, the method of storage is critical and needs frequent attention. For instance, a
strong initial driver of HLW cleanup in the United
States in the early 1990s was that at the Hanford
reservation in the state of Washington, the stainless
steel tanks containing the old military wastes from
nuclear weapons production were leaking into the
104
105
106
10
102 103 104 105 106 107

Time (year)
Figure 2 Time dependence of radioactivity of reprocessing

waste from commercial power plant nuclear fuel.
Earths surface
Rock
Backfill, plus
cement
13 km
Canisterized HLW
Figure 3 Schematic diagram of a deep geological
repository.
surrounding environment. Also, the tanks in which

the water had largely evaporated over the years of
storage, because of radiogenic heating, gave periodic
gas evolution in the form of large hydrogen bubbles,
Ceramic Waste Forms
which had safety implications via potential radionuclide removal from the tank into the atmosphere and
ground area adjacent to the tanks, as well as ignition
and explosion.
Historically, there has been explicit and implicit
competition between ceramics and borosilicate glasses
for immobilization of HLW (e.g., the Atlanta shootout) for Savannah River Laboratory (SRL) waste in
19812,3 and the US Department of Energy (USDOE)
decision on impure US/Russian surplus Pu in 1998.4,5
However, as there are now so many types of HLW
or intermediate-level wastes (ILWs) having a large variety of chemical compositions remaining to be immobilized around the world, it is becoming clear that glass,
glassceramics, ceramics, and on occasion, cementitious
materials have their place for different HLWs and ILWs.
In this article, the focus is on ceramics and glass
ceramics targeted mainly to immobilize HLW.
Table 1
Approximate compositions (wt%) and halflivesa of main fission product (FP) and actinide oxides in
Purex fuel reprocessing HLW that has been stored for
>10 years
FP oxideb
wt%
Half-life (year)
Cs2O
SrO
BaO
RE2O3
ZrO2
MoO3
TcO2
AnO2
RuO2
PdO
Rh2O3
6
3
4
15
15
15
6
6
10
6
2
30
30
100a
210 000
>10 000
Water excluded; RE: rare earth; An: actinide.

a
Group half-lives are very approximate as they range from short to
long times for different components. Absence of half-life value
stable elements.
b
Contains additional stainless steel corrosion products.
487
The specific activity of reprocessing HLW is in the

order of tens of terabecquerels per liter, while the US
tank wastes from Pu production for atomic weapons
production have specific activities that are perhaps
1000 times lower. Indeed, in other countries, some of
these latter wastes would be considered as ILW. We note
that hot isostatic pressing (HIPing) in waste form production has been validated recently at INL, ID, USA
(Idaho National Laboratory) by US regulators, and a de
facto validation of crystalline waste forms may be taken
from the 1998 decision,4 albeit overturned in 2001 in the
sense of not proceeding with the immobilization option,
to use ceramics for surplus Pu disposition in the United
States.
Ceramic materials for the incorporation and the
immobilization of nuclear waste range from refractory, dense, fine-grained ceramic, or glassceramic
candidates for HLW to cementitious product options
for low-level waste (LLW). Here, we discuss the
design of mainly ceramics and glassceramics for
HLW, but we also discuss cementitious materials for
ILW. How such materials meet the regulatory criteria
for properties such as retention of radionuclides
and toxic ions when the materials are exposed to
water, fire resistance, and mechanical strength, together
with other properties such as waste loading, and simplicity or otherwise of processing methods, will be
outlined. The influence of self-damage due to decay
of the radioactive species is also an important feature
and is briefly mentioned, noting that detailed discussions of this phenomenon appear in Chapter 5.22,
Minerals and Natural Analogues.
The final destination of HLW is generally agreed
to be a deep (0.53 km) geological repository
(Figure 3), so the principal object of fabricating a
waste form for HLW is, using the simplest and cheapest possible processing methods, to incorporate the
waste in a solid that is minimally porous and has high
leaching resistance when exposed to water, adequate
strength, and a high fraction (>20 wt%) of waste per
Table 2
Approximate oxide compositions and half-lives of An, FP, and process chemical oxides in US tank wastes and
surplus Pu-bearing waste (ignoring minor cations and assuming anions such as nitrates, nitrites, hydroxides, and carbonates
are removed upon calcination)
US tank waste (wt%)
Half-life (year)
Surplus Pu-bearing waste (wt%)
Half-life (year)
Na2O (40)
K2O (5)
Al2O3 (50)
Fe2O3 (4)
FP (<1)
AnO2 (<1)
various
>10 000
PuO2 (20)
UO2 (20)
Fe2O3 (20)
Al2O3 (20)
CaF2 (20)
24 000
4 109
An: actinide.
488
Ceramic Waste Forms
unit volume. A limiting feature for HLW is the radiogenic heat output (see, e.g., Sizgek6) as it is desirable
to keep the repository temperature to 100 C or less
to minimize the reactivity of the waste form with
groundwater.
After presenting some desirable characteristics of
waste forms and features impacting on the design
of multiphase ceramics for wastes containing many
radionuclides and process chemicals, we outline
the historical development of ceramic waste form
research. Alternative means of preparing appropriate
candidate waste form ceramics is put forward. Then,
we conclude that the best way to treat a given nuclear
waste depends on the nature of the waste itself and
that there is no single optimum method of treating all
nuclear wastes. We further note that disagreement
among waste form proponents as to the best way to
dispose of a given waste does not suggest that the
nuclear waste problem is not basically solved. Given
this, it would follow that nuclear power is sustainable
from that point of view.
In the design of an appropriate ceramic, it is
advantageous if the component phases are similar to
those of naturally occurring multication oxide minerals such as oxyapatite (Ca2La8(SiO4)6O2) or zirconolite (CaZrTi2O7) that are known to survive in hot,
wet conditions for millions of years. This feature and
the relative thermodynamic stability of crystalline
material versus amorphous glass were the principal
stimuli in the 1970s for the candidacy of ceramic
waste forms for HLW.
5.19.2 Desirable Performance

Characteristics of High-Level Nuclear
Waste Forms
Again, it is imperative that waste forms have very
high chemical durabilities in terms of resistance to
leaching by groundwater. The durability of the waste
form can be subjected to laboratory study and then
optimized. In this context, normalized leach rates
of <1 g m2 day1 at temperatures below 100 C
are considered as baseline. One gram per square
meter per day (1.16 105 g m2 s1) corresponds
to around 0.20.5 mm day1 in terms of thickness.
(While g m2 day1 is not an SI unit, it is almost
universally used within the nuclear waste community.) The normalized leach rate is defined as the
gross release rate of the ion in question divided by
the concentration of the ion, and the aim of using
normalization was to defy the dilute and disperse
strategy in which sufficient dilution could reduce

gross leach rates to apparently acceptable values.
The latter approach is objectionable because it
creates very large volumes of (weakly) radioactive
waste, which take up space and inflate cleanup costs.
The effect of self-irradiation needs to be taken into
account in these determinations. The higher the proportion of waste that can be incorporated per unit
volume of the waste form, the less repository space
will be needed and so the costs will be minimized.
The waste form needs to be easily and reliably processed in a remote environment, and minimization of
secondary wastes such as radioactive off-gases (needing recycle) during the production of the waste form
is important.
Given the need for aqueous durability, it is obvious
that open porosity would be a very bad feature because
entry of water into the interior of the waste form solid
greatly increases the potential for leaching. This is a
key factor in fabrication of waste forms and is discussed
later in regard to cementitious materials.
5.19.3 Design of Waste Form

Ceramics
When waste ions, assumed to be present as oxides or
as compounds that form oxides upon melting in air,
are incorporated in borosilicate glass, they are normally incorporated as network formers or network
modifiers, and the waste oxides can simply be added
to the precursor glass chemicals, which are usually in
the form of glass frit produced by pouring the molten
glass into water. However, the situation is somewhat
different when waste oxides are added to targeted
ceramic precursors with the object of forming nearly
water-insoluble multication mineral oxide phases,
insofar as the waste ions in the mineral phases enter
by a substitution mechanism, not by simple addition.
The partitioning of the waste ions will depend on
the cation site in which they substitute so that
unequal partitioning of the waste ions will result in
the formation of extra phase(s) if the waste ions are
just added to the mineral phase precursor. Therefore,
substitution of waste ions in a multication mineral
phase requires prior adjustment of the overall stoichiometry and detailed knowledge of the preferred sites
of the waste ions in the mineral phase. Moreover, if the
valences of the guest and host ions are different, charge
compensation is necessary to preserve electroneutrality of the phase. If the valence of the guest ion is less
than that of the host ion, charge compensation can be
Ceramic Waste Forms
maintained by oxygen vacancies or by the addition of

cations with higher valences than that of the host.
So, for example, if it is desired to substitute two
monovalent alkali ions into two divalent host ion
sites, we can maintain phase electroneutrality by
2M2 2O2 $ 2M O2 hO
I
O is a vacant oxygen site. However, we can also

introduce a trivalent charge compensating cation for
a monovalent ion substituted in divalent host sites via
2M2 $ M M3
II
Similar considerations arise when it is desired to

incorporate higher valence guest ions on to host
sites, except that the charge compensators will be
cation vacancies or substitutional cations with
valences less than those of the host ions.
Ceramics containing several phases are necessary
when a full range of fission products, minor actinides,
and process chemicals require immobilization, and
the same principles of chemical accounting apply to
multiphase ceramics made up of mutually compatible
mineral phases.
A first guess as to the way that the waste ions
will incorporate themselves in the mineral phases
will derive from a similarity of the approximately
known7 ionic sizes between the host sites and the
waste ions. The ionic sizes depend also on the valence
of the ions so that the valences of the waste (and
the host) ions need to be known. Also, the more
similar the valences of the guest and host ions,
generally the larger the solid solubility of the guest
ions in the host phase. The valence depends on the
crystal chemistry of the host site as well as on
the prevailing oxygen fugacity (note that some elements such as the Pd group will likely form metals
under some processing conditions, even oxidizing
environments).
A good example of crystal-chemical valence
stabilization is the fact that monazite, CePO4, in
which Ce exists as Ce3, can be fabricated by firing
in air at 1200 C, whereas CeO2 (Ce4) can also be
similarly formed in air, and analogous results are
obtained for PuPO(48) and PuO2. Table 3 is a partial
library of candidate ceramic phases for radionuclide
immobilization.
Experimental studies to define the valences of
variable-valence ions fortunately do not require
the use of radioactive ions if stable ions of the
corresponding elements exist and can be made from
X-ray near-edge absorption spectroscopy, electronic
optical spectroscopy, electron paramagnetic resonance,
Table 3
489
Partial library of ceramic host phases
Phase
Radionuclide
Pollucite, CsAlSi2O6
Hollandite,
(Cs,Sr,Ba,Rb)1.14 (Al,Ti3,Fe)2.28TiO16
Feldspar, CaAl2Si2O8
Apatite, Ca10([P,Si]O4)6(OH,F,Cl)2
NZP (Na,Ca0.5)(Zr,Ti)2(PO4)3
Monazite, REPO4
Garnet, Ca1.5GdTh0.5FeFe3SiO12
Zircon, ZrSiO4
Xenotime, YPO4
Zirconolite, CaZrTi2O7
Perovskite, CaTiO3
Fluorite, (RE,An)O2
Pyrochlore, RE2Ti2O7
Titanite, CaTiSiO5
Rutile, TiO2
Sodalite, Na4Al3Si3O12I
Cs
Cs, Rb, Sr, Ba
Sr, Ba
RE, An, Sr, Ba
Many
RE, An
RE, An
RE, An
RE, An
RE, An
Sr, RE, Tc, An
RE, An
RE, Zr, An
RE, An, Sr
Tc
I
RE: rare earth; An: actinide; NZP: sodium zirconium phosphate.
electronic energy-loss spectroscopy, and Mossbauer

experiments, to name but a few. Scanning/transmission electron microscopy can be employed to derive
the stoichiometry of the various phases. For actinides
and Tc, the actual radioactive isotopes have to be
employed, although popular inactive simulated substitutes are Ru for Tc and Ce for the trivalent and
tetravalent actinides. Facilities for examination of significantly radioactive samples are restricted to a few
national laboratories in various countries.
Having established the relevant ionic valences
and the desired set of candidate mineral analog
phases in the multiphase ceramics, the next requirement is to establish that the different phases are
compatible (can coexist at elevated temperatures).
Although attempts have been made to construct single phases to immobilize single or a range of waste
ions, this strategy is difficult (see Section 5.19.4).
Also, for a given waste form for a given HLW chemical composition, it is important that the waste form
properties are flexible and not unduly compromised
because of mismatches of waste/additives ratios, and
variations of waste form chemistry, noting that HLWs
are very frequently inhomogeneous mixtures of solutions and sludges, calcines, etc. Flexibility derives
from the use of multiple phases and chemical buffering via the presence of a phase(s) that does not
include radionuclides then variations of chemical
composition just result in a change of the proportions of the phases present, not the identities of the
phases themselves.
490
Ceramic Waste Forms
5.19.4 Historical Evolution of

Candidate Ceramic Waste Forms
for HLW
Although borosilicate glass worldwide had been the
main candidate waste form for Purex-type HLW (see
Chapter 5.18, Waste Glass) up to the mid-1970s,
Pennsylvania State University workers noted9 that
glasses were fundamentally unstable from a thermodynamic point of view, and they devised ceramic
waste forms for HLW derived from nuclear fuel
reprocessing, based on the known natural longevity
of crystalline silicate, phosphate, and molybdate
minerals. These so-called supercalcine ceramics10
were sintered in air at 1100 C and had very high
loadings of fission products, typically 70 wt% of
fission product oxides, and the chemistry of the different phases was driven by the fission products as
majority components. Typical phases were pollucite
(CsAlSi2O6), powellite (CaMoO4), and rare earth
apatites (Ca2RE8(PO4)6O2) and phosphates (e.g.,
monazite, REPO4) (RE is trivalent rare earth). All of
these had mineral analogs that were known to be very
durable in the hot, wet conditions likely to characterize a deep geological repository for the waste.
Following work at Sandia Laboratories in the
United States on phase assemblages occurring on
heating sol-gel titania particles on which simulated
HLW fission products and actinides were sorbed,11
Ringwood and his coworkers in Australia in the
late 1970s devised multiphase titanate-based ceramics in which nearly all the fission products and
actinides in HLW from nuclear fuel reprocessing
were incorporated substitutionally in the various
mineral analog phases.1214 Typical waste loadings
were 20 wt% of HLW oxides and the production
technology was slurry mixing of the waste and precursor oxides, calcination of the waste/precursor
mixture in a reducing atmosphere, followed by hot
uniaxial pressing (HUP) at 1100 C to make a dense
ceramic. These ceramics are discussed in a little more
detail in following sections. Primarily, these ceramics
were focused on Purex-type HLW, but some work
was done to immobilize SRL tank wastes from
weapon production. At about the same time, and
perhaps in part driven by the appearance of the
synroc-type ceramics, there was a worldwide surge
of interest in the immobilization of HLW.
However, in the United States, a key decision was
made during 19811982 to use borosilicate glass
to immobilize HLW at SRL,2,3 and there was a substantial decrease in US funding for HLW waste form
research from then on. Nevertheless, a variety of

alternative waste form development work continued
around the world, and the book by Ewing and Lutze15
gives an excellent survey of research up to nearly
the end of the 1980s. Candidate materials included
glasses, ceramics, glassceramics, cermets, coated
materials, and cements. However, in the course of
time, it has been widely (but not universally) agreed
that the only real remaining candidate types of material for HLW immobilization are glasses, ceramics,
and glassceramics. These can be produced by Joule
or cold-crucible melters, sintering or hot pressing,
and particularly HIPing. However, cementitious materials may yet be useful for less active HLW such as US
defense wastes from weapons production.
Waste form development for HLW is still continuing in some shape or form in different nuclear
countries, although Japan chose borosilicate glass in
the mid-1990s and therefore ceased work on alternatives except in some niche areas, such as immobilization of 129I. France instituted the law of 1991,
which placed a moratorium on waste disposal until
2006, giving them 15 years of research to make a
decision on the best choices of waste forms for their
particular HLWs. In the 1990s, much work was done
in France on apatites as candidate ceramics, and
collaborations with the ANSTO group on titanate
ceramics were initiated. A Th double phosphate
Th4(PO4)4P2O7 ceramic for immobilization of tetravalent actinides has also been under development in
France for several years. The material is claimed to
have good aqueous chemical durability even when
amorphized by swift heavy ions.16 Although numerous scientific papers on candidate ceramic waste
forms still emanate from France, it is as yet not totally
clear whether France will ultimately continue only
with vitrification for their HLW or whether ceramics
may play some role.
Work has continued in Australia on titanate ceramics (see Section 5.19.5) although since around
2000, the work has evolved from a narrow focus on
titanate ceramics to the use of HIPing technology to
fabricate candidate glassceramic and ceramic waste
forms to immobilize a wide range of HLW/ILWs that
are generally perceived to be not very suitable for
vitrification. Such waste forms have been directed at
Pu-bearing wastes, Magnox sludges (UK), K-basin
sludges (Hanford, WA, USA), Tc-rich waste,17 I-rich
waste,18 Cs/Sr/Ba/Rb partitioned wastes,19 pyroprocessing wastes,20 and U-rich 99Mo production wastes.21
Collaborative work has also been done with UK workers on titanate ceramics, and UK workers have also
Ceramic Waste Forms
worked on other ceramic formulations. The AWE plc

(Aldermaston, UK) has had an ongoing 10-year program to immobilize ILW derived from pyrochemical
processing of Pu metal: they are using chlorapatiteand spodiosite (Ca2(PO4)Cl)-based ceramics.22 At
ANSTO, work is being carried out under the Europart
effort on pyroprocessing to try to immobilize waste
pyroprocessing chloride salt in apatite-based ceramics.20 Russian workers are investigating murataite
and garnet-based ceramics, together with perovskites.23,24 Also in Russia, investigations of the crystal
chemistry of sodium zirconium phosphate (NZP)structured and other phosphates having a wide range
of ionic substitutions have been carried out by Orlovas
group for many years.25 The effects on the NZP
structure of a-damage from 238Pu and 239Pu substitutions have been observed.26 Other phosphates,
notably monazites, have also been studied in regard
to a-damage effects from 238Pu doping.27
It is appropriate at this stage to reiterate the
diverse nature of HLW, depending in part on whether
it derives from commercial Purex-type reprocessing
or military Pu production.
Generally speaking, the Purex wastes are highly
active and are basically solutions of fission products
and minor actinides in 3 mol l1 nitric acid solutions.
The Pu production tank wastes, however, consist
mainly of process chemicals, a relatively small amount
of fission products in an alkaline solution derived from
the need to neutralize nitric acid that would in time
attack the stainless steel tanks. Thus, these wastes consist of a concentrated solution of Na salts plus
hydroxide-rich sludges and are very inhomogeneous
(and largely uncharacterized) even in single tanks.
Hence, there is a possible need to actually separate
individual wastes into solution and sludge fractions,
and a definite need to design waste forms that can
cope with diversity and compositional uncertainty.
More importantly, longer-term (periods of years)
tests need to be carried out to gain a mechanistic
chemical understanding of the leaching behavior
as distinct from the raw numbers in the prescribed
leach tests (see Section 5.19.7). An important facet
of leaching and long-term aqueous durability is the
existence or otherwise of natural analogs of the phases
making up HLW waste forms, because if the natural
mineral can be found to exist in a wet environment,
knowledge of the local geology can give information on
the time of exposure to water, and measurements of
trace quantities of natural radionuclides in the mineral
(such as U, Th, K, Rb) and their daughter products
can allow the age of the mineral to be determined.
491
In favorable circumstances, it can be determined that

mineral analog phases can last up to millions of years
in wet environments, just what is needed for the manmade phases for the sequestration of HLW. Thus, again,
there is a powerful argument to use waste forms based
on natural analog minerals that have demonstrated
their survival over geological time frames.
The well-known Oklo phenomenon in the African
country of Gabon is worthy of mention in this context.
Roughly 2000 Ma, enough U had aggregated in a
geological formation there to form an intermittently
self-sustaining nuclear reactor in the presence of water
to moderate the neutron flux. At that time, the natural
235
U content of U was around 6%, as distinct from
0.71% today. The principal evidence for nuclear
activity is a low abundance of 235U in the residual
U-bearing material. It is reassuring that the movement
of the fission products having half-lives long enough to
be still active has been shown to be only a few meters
at most away from the residual ore body. A recent
description of the disposition of fission products at
Oklo has been given by Hidaka.28
Single-phase ceramics have been widely advocated for both single radioactive elements formed
by partitioning of reprocessing wastes or even for
the entire complement of waste elements. NZP structures have been widely studied and/or advocated for
the full range of fission products and actinides.2931
Monazite, apatite, and zircon have been studied to
immobilize actinides, while pollucite10 and CaAlSi5O1232,33 have been investigated for Cs immobilization. However single phase waste forms lack
chemical flexibility. An exact match of waste and
precursor stoichiometries in single-phase multication
hosts, such as those mentioned earlier, is industrially
unrealistic when dealing with radioactive waste materials. What is needed is an extra minor durable phase
whose abundance may vary as the waste/precursor
ratio varies while still maintaining the same qualitative
phase assemblage-as in the synroc-type ceramics.
As mentioned previously, the sintered supercalcines10 consisted of apatite and monazite phosphates,
powellites, feldspar, pollucite, etc. But there are difficulties of diluting it with materials such as alumina,
silicate, or phosphate to deal with radiogenic heat
production, apart from the very inelegant approach
of using cold fission products as diluents.34 Also,
volatility losses during sintering would be severe,
although these could be minimized by heating in
neutral or reducing atmospheres, and using HIPing.
The Rockwell Science Center (CA, USA) realized
this latter factor as early as 1981, and they put
492
Ceramic Waste Forms
forward HIPing as the preferred consolidation

method for their ceramics35 directed at the tank
waste-type HLWs at the Savannah River Laboratory.
The ceramics based on alumina tailoring contained
magnetoplumbite [Ca(Al,Fe)12O19], UO2, spinel [Mg
(Al,Fe)2O4], nepheline (NaAlSiO4), and corundum,
with the former phase being seen as a near-universal
solvent for fission products other than gaseous species.
A titanate-based ceramic was broadly similar to the
synroc-D ceramic (the following section) and contained
zirconolite, nepheline, spinel, magnetoplumbite, perovskite, murataite (a complex fluorite-based phase), and
glass. The waste loadings were around 60 wt%, and
HIPing was carried out at 1040 C/60 MPa. There
were no problems in these materials with radiogenic
heat because the waste was quite dilute in fission
products.
5.19.5 Titanate Ceramics

Ringwood et al.,1214 devised ceramics containing
phases based on durable natural titanate minerals.
These ceramics were called synroc (synthetic
rock). To deal with Purex-type waste, these theoretically dense materials are made by first mixing inactive precursors of Al, Ba, Ca, Ti, and Zr oxides with
liquid (simulated) HLW, drying, and calcining in a
H2/N2 atmosphere for 1 h at 750 C. The calcine was
then mixed with 2 wt% of powdered Ti metal
for redox control and then subjected to uniaxial
graphite die hot-pressing or HIPing at 1100 C.
The precursor composition and the titanate phases
in the early synroc-C titanate ceramic designed for
reprocessed commercial power reactor wastes are
given in Table 4. Since 1984, rather than using oxides, a slurry mixture of Ba and Ca hydroxides and
transesterified Al, Ti, and Zr alkoxides has been used as

the precursor. This provides better solid-state reactivity
than the corresponding powdered metal oxides and
hydroxides. The principal advantage of this synroc-C
ceramic was that the waste ions were dilutely
incorporated in durable titanate mineral phases that
were considerably more insoluble in water than the
silicates and phosphates, and the like used in supercalcine. The waste loading could be varied between
zero and 35 wt% using the same inert additive
chemistry without substantially changing the basic
zirconolite perovskite hollandite rutile phase
assemblage, although of course the percentages of
the different phases varied somewhat.36 This flexibility is seen as a large advantage. There were minor
alumina-rich phases in the more dilute formulations.
The grain size is on the order of 1 mm (Figure 4)
to optimize mechanical properties and prevent subsequent radiation-induced microcracking (see Section
5.19.8). For comparison, the grain size of a synroc-C
sample prepared by sintering at 1300 C is somewhat
larger (Figure 5). The alloy phases derive from ions
that form metals under the reducing conditions prevailing during hot pressing. These ions are Mo, Tc, Pd,
Rh, and Pd, plus any corrosion products from stainless
steel. The leach rates at 90 C in water from synroc-C
of the most soluble elements, alkalis and alkaline earths,
are typically <0.1 g m2 day1 for the first few days,
and they decrease asymptotically to values of 105 g
m2 day1 after 2000 days (Ringwood et al.14 and see
Figure 6). Leach rates of other elements are much
Table 4
Composition and mineralogy of synroc-C
(20 wt% reprocessing waste loading)
Phase
wt%
Radionuclides in lattice
Hollandite,
BaAl2Ti5O14
Zirconolite,
CaZrTi2O7
Perovskite, CaTiO3
Ti oxides, mostly
TiO2
Alloy phases
30
Cs, Rb
30
RE, Zr, An
20
15
Sr, RE, An
None
RE: rare earth; An: actinides.
Tc, Pd, Ru, Rh, Mo, Ag, Cd,

Se, Te
6864
1.5 kV
X1000
10 m WD37
Figure 4 Backscattered electron micrograph of

Synroc-C. Large feature at bottom right is a partly oxidized
lump of Ti metal that was added for redox control. Bright
spots are metallic alloys and the remaining micron-sized
features are the ceramic phases, rutile, hollandite,
perovskite, and zirconolite.
Ceramic Waste Forms
493
Table 5
Seven-day MCC-1 leach results for different
elements in synroc-C
Element
Leach rate
(g m2 day1)
Element
Leach rate
(g m2 day1)
Mo
Cs
Tc
Ru
Sr
Ca
0.4
0.1
0.05
0.03
0.02
0.02
Al
Zr
Ti
RE
An
<0.4
8 104
2 104
104 103
2 105 5 104
RE: rare earth; An: actinides.
9636
1.5 kV
X3000
10 m
WD 8
Figure 5 Synroc-C prepared by pressureless sintering

at 1300 C. The black phase is rutile (R). The dark-gray
phase is perovskite (P), the white spots are the metallic
alloys, and the matrix is a mixture of Ba-hollandite and
zirconolite of similar contrast.
Differential leach rate (g m2 day1)
1.0E+00
1.0E01
1.0E02
Cs
1.0E03
Ba
Sr
Mass
1.0E04
0
10
20
30
40 50 60
Time (days)
70
80
90
Figure 6 Leaching of synroc-C in seven-day Materials

Characterization Center-1 test.
lower (see Table 5). Leach rates of 105 g m2 day1

correspond to a corrosion rate of 1 nm day1.
In parallel, a HIPed synroc-D formulation having
comparable performance to synroc-C was put forward in conjunction with the Lawrence Livermore
National Laboratory (LLNL) in the United States13,37
to deal with the SRL defense waste, and this synroc
derivative was based on zirconolite, perovskite, spinel,
and nepheline.
In the 1980s, the inactive Synroc production process was scaled-up via the Synroc Demonstration
Plant at ANSTO (then the Australian Atomic Energy

Commission) to produce 50 kg monoliths containing 20 wt% of simulated Purex HLW (synroc-C),
with leaching and microstructural properties as
good as those of gram-sized laboratory samples.
In the early 1990s, the synroc ceramics were tailored toward the study of zirconolite-rich materials
for immobilization of actinide-rich wastes such as Pu
or partitioned transuranic elements. The initial work
during 19911994 was directed at the latter application in conjunction with the Japanese Atomic Energy
Research Institute. There was a strong focus on radiation damage via the incorporation38 of the a-emitter
244
Cm (18 year half-life), as had been done with
synroc-C and a Na-doped variant thereof.39 Perovskite was also studied for comparison.
The work on surplus Pu immobilization, with
LLNL as the lead laboratory for the USDOE,
moved from zirconolite- to pyrochlore-rich ceramics
during 19941997. This was because of solid solution
limits in the first instance when the target of the work
changed from immobilization of 10 wt% Pu (impure)
alone to the additional inclusion of 20 wt% U.
The estimated time for amorphization of these ceramics to be complete is on the order of 1000 years and
the resultant volume expansion would be around
6%.40 This expansion in polycrystalline samples
doped with 238Pu, which became X-ray amorphous
after around 2 years storage at ambient temperatures,
did not produce microcracking, and no significant
radiation-enhanced aqueous dissolution rates were
observed with the crystalline ! amorphous transition.
In addition, these ceramics incorporated an atom each
of neutron-absorbing Gd and Hf for each atom of Pu
to deal with potential criticality in the sample. Nearfield aggregation of Pu due to leaching was shown to
be not a problem from the criticality aspect either,
because the measured leach rates of Pu were spanned
by those of the neutron absorbers5: hence, any leached
494
Ceramic Waste Forms
1 m
10 wt% HLW, cooled 20 C min1
Figure 7 Pellets of Pu-bearing hockey pucks prepared
by sintering.
Pu would be accompanied by neutron absorbers,

which in turn would inhibit criticality problems.
The final baseline (no impurities) version4 of the
pyrochlore-rich ceramics chosen by the US DOE in
1998 contained 95 wt% of a pyrochlore-structured
Ca0.89Gd0.23Hf0.23U0.44Pu0.22Ti2O7 phase plus 5 wt%
of rutile-structured Ti0.9Hf0.1O2. The form of the
ceramic was to be 76-mm diameter pellets weighing
500 g (Figure 7). Five hundred and sixty such pellets
were to be enclosed in a US standard canister of
Savannah River DWPF glass to provide a radioactive
barrier (gamma field) to prevent diversion. This product was the first crystalline material to be validated in
the United States. However, in early 2002, it was
decided to remove the disposal option for US/Russian
surplus Pu and to proceed only with a MOX fuel
option for utilization. This latter option however has
not been realized.
While it has been realized that substituting Zr for
Ti in these ceramics would severely limit the amount
of radiation damage sustained by the pyrochlore
lattice,41,42 it has to be stressed that this would both
increase the fabrication temperature by roughly
300 C and severely restrict the entry of impurities
in the target impure Pu into the pyrochlore structure.43 Other synroc derivatives have been devised
for immobilization of Tc44,45 and Cs/Sr/Rb/Ba19
formed when reprocessed waste is subjected to partitioning into chemically similar groups.
5.19.6 GlassCeramics
Glassceramics in principle combine the advantages
of glasses and ceramics. They can be made by melting, cooling, and reheating at 1000 C to induce
Figure 8 Phase separation shown by scanning electron

microscopy in sphene glassceramic body after furnace
cooling from melt. The continuous phase is Si-rich and the
discontinuous phase is a (Ca, Ti, Si)-rich phase that forms
sphene on reheating. Etched for 30 s in 1% HF solution.
crystallization, or processed at subsolidus temperatures and slowly cooled to ambient temperatures.

Careful design can produce crystalline mineral analog phases chosen for their immobilization qualities
together with a durable glass that can provide further
tolerance for variations in the waste/precursor ratios
and variations of the waste feedstock.
Sphene glassceramics were developed for
6 years in Canada for HLW arising from a reprocessing option, until it was eventually decided in 1984 to
follow the United States and concentrate on spent
fuel immobilization. The Canadian glassceramics
consisted of sphene, CaTiSiO5, in a durable aluminosilicate matrix. The overall composition of the wastefree precursor in mol% was: Na2O (6.6); Al2O3 (5.1);
CaO (16.5); TiO2 (14.8); SiO2 (57.0) and considerable
variations in this composition were allowable without
compromise of the essential properties. The material
was produced by melting at 1350 C, cooling to ambient
conditions, then reheating for 1 h or so at 9501050 C
to allow the sphene to crystallize within the durable
glass phase.46,47 Considerable phase separation occurred during the postcooling step (Figure 8). Loadings of
Purex-type HLW were feasible, although additional
perovskite and other phases were observed at waste
loadings of >10 wt% fission product oxides.
Workers at the Hahn-Meitner Institute in Germany
studied the properties of borosilicate glasses containing
Purex-type HLW and the glasses were devitrified.
Different formulations yielded celsian (BaAl2Si2O8),
fresnoite (Ba2TiSi2O8), diopside (CaMgSi2O6), or
perovskite as major crystalline phases.48,49 The best versions were the materials yielding celsian and these were
also studied in the United States. In the United States,
Ceramic Waste Forms
different groups studied the glassceramics derived

from melting mixtures of natural basalt powder and
HLW calcines.50,51 Hanford (WA, US) tank wastes are
rich in alkali nitrates and transition metal hydroxides,
and a range of glassceramics was designed for
these.52,53
The 4400 m3 of calcines stored at the INL are rich
in alumina, zirconia, and CaF2. While only about
30 wt% of these calcines can be incorporated in
glass,54 glassceramics studied in the late 1980s and
early 1990s and produced by HIPing to immobilize
the calcines had waste loadings of around 70 wt%.55
These utilized SiO2-rich frit additives. Subsequently,
ANSTO workers in unpublished reports have recently
developed separate glassceramics for immobilization
of the alumina-rich and the zirconia-rich ICPP (Idaho
Chemical Processing Plant) calcines.
Actinides in various HLWs have been preferentially
partitioned toward synroc phases, principally zirconolite, in boroaluminosilicate glass matrices (unpublished
work at ANSTO, Loiseau et al., 56 Mahmoudysepehr
and Marghussian57). These glassceramics have waste
loadings of 3080 wt% and leach rates are often 10100
times lower than those for standard US EA glass, the
baseline glass to pass the product consistency test
(PCT) leach test (see next section). These glass
ceramics were prepared by melting, apart from the
ANSTO work in which the HIP method described in
Section 5.19.10.2 was used.
5.19.7 Aqueous Dissolution

Reactivity with water of solids in the first instance
depends on the state of aggregation of the solid and
clearly the dissolution rate of a solid body will be less
than that of a fine powder. The dissolution rate itself
can be quantified by measuring the concentration of
dissolved species in the water in relation to the original inventory in the solid before the onset of leaching.
Dissolution rates can then be expressed as elemental
loss by mass per unit surface area (expressed as geometrical or BrunauerEmmettTeller (BET) values)
per unit time (see Section 5.19.5). These rates, however, can depend critically on (surface area/liquid
volume), pH, temperature, presence of salts in the
water, etc. Dissolution rates can be further complicated by the presence of colloids and adherence of
primarily dissolved species to vessel walls. However,
separation of the solids from the liquid, followed by
acidification of the liquid, can dissolve species
attached to the leach container walls as well as colloids.
495
Colloids themselves can be detected by light scattering

measurements. Ultimately, the dissolution rate of a
solid in water is controlled by thermodynamics and
various software programs are available to describe the
dissolution process, although they are usually limited
by lack of basic data for some of the ions in the solid.
Many laboratories now use apparatus in which the
liquid of interest flows over the solid at a given
rate, and the rate is not too high to prevent a measurable concentration of dissolved species to accumulate
and not too low as to allow the buildup of high
concentrations of dissolved materials and consequent
complications by solution saturation. In most repositories, the limiting temperature would be designed
as 100 C, so measurements on candidate waste
forms are experimentally relatively simple.
Key regulatory leaching tests are the Materials
Characterization Center (MCC)-158 and PCT-B59
protocols (see Chapter 5.18, Waste Glass), which
employ polished flat samples and powders, respectively, that are exposed to hot water.
The required time of immobilization for real
HLW is variously targeted as 104106 years, and it is
worthy of inquiry as to how real-time measurements
can be accelerated. This is very difficult as attempts
to accelerate leaching by using higher temperatures
or more aggressive solutions are easily compromised
because the thermodynamics of the solidliquid
interaction can be grossly affected by such means.
In practice, short-term (a few days) leach rates of
1 g m2 day1, normalized to take account of the
fractional elemental extraction, rather than the absolute quantities, are considered as satisfactory and
these rates correspond to 0.1 mm year1, further
noting that the leach rates of solids tend to decrease
with increasing leaching time even at high degrees of
dilution. This is generally attributed to the presence
of active surface sites on the cut or polished
prepared surface of a candidate solid.
5.19.8 Radiation Damage

The radionuclides to be immobilized in an HLW
waste form include a, b, and g emitters. The most
serious damage to the waste form derives from
a-decay, in which the a-particle displaces around
100 atoms in the solid during its 20 mm traverse
and more importantly, the heavy a-recoil atom
which displaces 1500 atoms over its 20 nm trajectory. b- and g-processes produce ionization damage
but very few atomic displacements. These effects
496
Ceramic Waste Forms
have been amply demonstrated in natural minerals

that contain small amounts of U and Th and have
ages of many millions of years, and they have been
essentially reproduced in experiments on synthetic
materials doped with a few percent of short-lived
actinides (238Pu or 244Cm, which have half lives of
87 and 18 year, respectively). Thus, only radiation
damage processes in waste forms hosting significant
amounts of actinides, especially Pu and other transuranics, need serious consideration.60
The variety of radiation effects include a crystalline ! amorphous transformation after hundreds or
thousands of years, with an associated lattice expansion and an associated decrease of several percent
in density (e.g., 16% in zircon, ZrSiO4), the production of lattice defects in solids that do not undergo
amorphism, formation of gas bubbles, potential for
enhanced leaching, and radiolytic effects in which
radiolysis of the water leads to the production of species such as H2O2 that may responsible for enhanced
leaching. Careful work at Pacific Northwest National
Laboratory (PNNL) by Strachan et al.40 has shown that
there is no significant leachability increase in pyrochlore- and zirconolite-based ceramics (see Section
5.19.5) as radiation damage progressively builds up.
Although it has also long been argued that these
kinds of radiation effects on glasses are relatively trivial, it needs to be remembered that the baseline leachabilities of glasses tend to be some orders of magnitude
higher than those of crystalline waste forms.
Another effect is transmutation damage, due to the
ionic size and valence changes that may accompany
a- or b-emission. Particular examples are Cs ! Ba2
and Sr2 ! Y3 ! Zr4 , where the ionic size
decreases are 20 and 30%, respectively, for the full
decay schemes. These effects have not been studied in
much detail because of the intense radioactivity associated with waste forms containing several percentages
of the parent isotopes, but sympathetic valence
changes in the matrix ions, for example,
Cs Ti4 ! Ba2 Ti3
and/or the production of hole centers can help to
mitigate the charge changes in these decay series.61
Although for ions with half-lives of several years the
radioactivity is extremely intense (terabecquerels per
gram) and so severely limits available experimental
data for these effects, transmutation effects are amenable to study using current atomistic modeling codes
and predictions may soon be made by these techniques.
In polycrystalline ceramics, there are two significant potential effects that can lead to microcracking.62
Microcracking can lead to greatly increased leach rates
because of the increase in surface area available for
water to contact. First, if the actinide-bearing phase is
anisotropic, stresses are set up because of unequal lattice dilatations from radiation damage, and secondly,
different actinide concentrations in the different phases
lead to unequal lattice dilatations between the different
phases. However, these effects can be minimized by
minimizing the grain size, and this will be discussed in
the processing section later.
5.19.9 Thermodynamic Stability of

Multication Oxides
The intrinsic thermodynamic stability of crystalline
waste forms over glasses has long been discussed. For
multication oxides, one question is whether the multication oxide has a lower free energy than the component oxides. If not, the multication oxide is
unstable with respect to the component oxides.
Another question is whether a multication oxide is
stable with respect to a simpler multication oxide.
The fundamental experimental method is to measure the heat of dissolution of the oxides in question in
molten salts such as Pb borates or molybdates at
temperatures of around 700 C, and studies of many
candidate ceramic waste form phases have been made
by Navrotskys group in the United States.63 For
pyrochlore-type phases, it has been found that several
are unstable with respect to forming perovskite phases,
but stable with respect to decomposition into simple
oxides, whereas both Zr- and Hf-zirconolites are stable
with respect to both decomposition modes.64
5.19.10 Processing of Ceramics and

GlassCeramics
The principal options for the production of refractory ceramic or glassceramic materials are sintering,
uniaxial hot pressing, HIPing, and melting. As mentioned earlier, it is clearly advantageous if these materials are fully dense or at least devoid of open
porosity to prevent ingress of water into the interior
of the material.
All wastes are calcined to remove organics,
nitrates, water, carbonates, hydroxides, etc. If relatively small amounts of material are to be dealt with
Ceramic Waste Forms
(say a few tens of tons only), it might be advantageous

to mix the waste with precursors before calcination.
Though sintering is the baseline method in industry
for making (inactive) ceramics, making dense ceramics
via sintering is not a trivial task. Metal oxide phases,
preferably with multiple cation sites to allow substitution of a variety of fission products, actinides, and
process chemicals form the main constituents of
ceramic waste forms, and it is necessary to achieve
good mixing at an early stage of processing. Best mixing
would utilize water-soluble liquid precursors such as
metal nitrates to achieve atomic-scale mixing for highquality homogeneous ceramics, but this is easily seen to
probably constitute overkill because the footprint of
such a plant would be much larger, there are more
process steps and nitric acidbased gases evolved
which need to be dealt with as a separate (low-level)
waste materials. Moreover, if Pu-bearing or enriched
U-bearing materials are being immobilized, the use of
water presents a criticality risk.
So, it is not surprising that the synroc derivative
(see above) for surplus US/Russian impure Pu utilized dry feeds that were attrition milled to achieve
mixing and reactivity with the dry precursors. MOX
fuel is also made by dry powder milling and sintering.
These dry operations are most useful if radioactive
volatile losses upon sintering are very small, as in the
two cases just mentioned, but if volatile losses are
potentially significant, HIPing of waste form ceramics has advantages (see Section 5.19.10.2).
5.19.10.2
497
Hot Isostatic Pressing
In HIPing of ceramics or glassceramics, the reactive

calcined waste form (waste additives) material is
first packed by vibratory means inside a relatively
thin-walled metal can. This is then evacuated and
heated to 300600 C for several hours to remove
adsorbed gases, sealed, and then consolidated to full
density by compressing it with several tens or even
hundreds of MPa of argon gas during the heating cycle.
The use of a suitable metal container, which may be
stainless or mild steel, nickel, or other metals, can help to
achieve the desired redox conditions, minimize any
potentially deleterious reaction between the waste
form and the container, and of course prevents offgas
escape. So the entire process produces offgas only in
the calcination stage where temperatures are much
lower than those in the final consolidation (roughly
the same as those used for vitrification, that is, 1000
1400 C). Figure 9 shows the steps involved in HIPing.
Figure 10 shows stainless steel HIP cans before and
after consolidation, and Figure 11 shows a diametrically
cut section.
The process inherently has a batch approach but
cans containing more than 100 kg are feasible, with
a processing time of 10 h. Work to shorten this time
Radioactive
wastes
5.19.10.1 Hot Uniaxial Pressing

Hot Uniaxial Pressing (HUP) is a batch process.
An inductively heated graphite die can be used and
this imposes reducing conditions on the sample, even
if the sample is contained in a collapsible metal
container or can within the bore of the graphite die.
Only 20 MPa of pressure can be exerted with
graphite, but very high temperatures (>2000 C)
are possible. However, for waste forms, it is usual to
keep the temperature to a maximum of around
1400 C to minimize volatile losses. The use of alumina dies allows the use of more pressure and oxidizing conditions, but it is more difficult to extricate the
sample, especially when it is radioactive. Of course, in
principle, the hot-pressed sample may be left in the
graphite or alumina die, which then would constitute
an expensive transport container insert. However,
HIPing has basically superseded HUP as a processing
option for oxide-based ceramics.
Additives
Mixer/drier
Calcination
(if required)
Off gas
treatment
Fill and seal

HIP canister
Preheat
HIP
Canister disposal
Figure 9 Flowsheet for hot isostatic pressing.
498
Ceramic Waste Forms
Figure 10 Stainless steel cans before and after hot

isostatic pressing.
submarines and has been validated at INL as a credible (and advantageous) method of consolidating radioactive ceramic waste forms. Moreover, the method
is widely used in industry for preparing inactive
ceramics.
A large advantage is also the relatively small footprint of HIP equipment, arising in the first instance
because of the absence of off-gas in the hotconsolidation step. Moreover, the main part of the
HIP equipment can be located outside the hot cell so
that the HIP does not experience significant radioactive contamination and therefore require disposal at
the end of the waste treatment campaign. Also, the HIP
process can be used for encapsulation in metal for
some wastes. Such examples that have been demonstrated inactively are Sn encapsulation of 129I sorbed
on zeolites18 and unpublished ANSTO work on Cu
encapsulation of spent fuel pellets and zircalloy liners.
For radioactive ceramic waste forms, a prime
advantage is to achieve theoretical density with minimum temperature and therefore minimum grain size,
thereby adding to the overall strength and reducing
the potential of microcracking via radiation damage
when the waste form contains a substantial amount of
a-emitting waste actinides. In addition, it has been
shown for several types of ceramic waste forms that
HIP can/ceramic interactions are not deleterious.6567
5.19.10.3
Figure 11 Diametrically cut can that was hot isostatically

pressed.
using hot calcined powders instead of allowing them

to cool to ambient temperatures is under way, and
throughputs of tonnes per day are targeted. Figure 10
shows that the consolidated can has a basic cylindrical shape, that is part of the can design allowing it
to occupy a minimum of space in a cylindrical US
transport container. While the relationship of the
shapes of the can before and after HIPing is quite
complex, the basic variable is the ratio of the densities
of the final ceramic and the calcined powder. The
dumbbell shape of the can gives quite a deal of
flexibility, but it is advantageous to maximize the
density of the calcined powder to avoid undue rippling and substantial deviations from cylindrical
geometry of the HIPed can.
The HIP process, invented by the Battelle
company in the United States in the 1950s, has been
used since the 1960s in preparing nuclear fuel for
Melting
Joule melters employ large refractory ceramic baths

(several square meters in area and 1 m or so deep)
containing ceramic electrodes to directly heat mixtures of glass frit and nuclear waste to a molten state.
The melt is then poured into steel transport canisters
in which it cools slowly to yield a borosilicate glass.
Such melters are only viable in the longer term if
temperatures do not exceed 1150 C.
For higher temperatures, cold crucible melters are
necessary. Cold crucible melting utilizes inductive
coupling between a water-cooled high-frequency coil
and conductive waste form.68 This coupling is inclined
to be low when heating is commenced, so metal or
graphite often needs to be added to the ceramic charge.
This oxidizes and the metal oxide combines with the
charge when high temperatures are reached, while the
graphite is lost as CO2 under these conditions.
While some ceramics such as synroc-C can readily
be melted at temperatures below 1500 C,69,70 there
are serious questions of fission product volatility (captured and recycled), especially if reducing conditions
are not maintained. Moreover, on cooling from the melt
Ceramic Waste Forms
at rather low cooling rates governed by the large size of

canisters into which the melts would be poured (pouring would not be easy if melts were not produced in an
air atmosphere), crystallization of the waste form would
allow the formation of quite large grains (Figure 12).
This factor would adversely affect the mechanical
strength and the response to a-radiation if the wastes
contained significant actinide inventories.
attendant fission product volatility can be avoided.

The composition of ordinary Portland cement (OPC)
is given approximately in Table 6. The curing of
cement after mixing it with water and aggregate is
complex and takes place over months and years; the
phases in the dry cement clinker gradually transform
to hydrated phases, with a CaOSiO2H2O (CSH)
tobermorite phase of variable composition as the main
contributor to the eventual strength of the material.
OPC can be diluted with flyash from coal-fired
power plants or ground blast-furnace slags (approximate compositions in Table 7). In addition to utilizing waste materials, the well-known alkali-aggregate
deleterious reaction can be minimized. The behavior
of such cements in immobilizing LLWs and ILWs has
been extensively reviewed.7274
Work on cements processed under steam pressure
conditions at 100400 C (FUETAP) at the end of
the 1970s and early 1980s75 indicated that good compressive strengths and thermal conductivities were
achievable, and the derived leach rate was in the
zone of 1 g m2 day1 or better for most species,
especially if Cs had been sorbed on to zeolite and
then incorporated in the cement, apparently showing
that cements were intrinsically leach resistant, nearly
on a par with borosilicate glasses. However, cements
in which the Cs is not presorbed on to zeolites fail the
standard leach tests described earlier by factors in the
range of 10100 for ions that do not form insoluble
hydroxides such as Cs (especially in MCC-1 tests in
which the sample geometrical surface area to leach
liquid volume is low) and they are not these days
seen as serious candidates for HLW immobilization.
Also, the presence of water even in a bound state is
problematical for radiolytic hydrogen buildup. However, cementitious material is currently seen generally as still having strong potential for LLW and ILW
immobilization.
5.19.11 Cements and Geopolymers

Cement is at first sight a particularly attractive means
of HLW consolidation since high temperatures and
15277
23 m
Figure 12 Microstructure of synroc formulation
designed71 for (Al,U)-rich high-level waste and processed
by cold crucible melting. Dark areas: spinel, MgAl2O4;
Light gray: pyrochlore-structured (Ca,U) titanate phase;
darker gray areas: hollandite and rutile.
Table 6
499
Approximate cement and geopolymer compositions (excluding hydrous material and carbonate)
Composition (wt%)
CaO
SiO2
Al2O3
Fe2O3
Na2O
MgO
SO3
OPC
Geopolymer
60
5
20
50
5
25
5
5
2
15
Table 7
Flyash
Slag
Approximate blast-furnace slag and flyash compositions

CaO
MgO
Al2O3
SiO2
Fe2O3
Na2O
K2O
5
40
1
10
25
10
50
40
10
500
Ceramic Waste Forms
Geopolymers are a class of cementitious materials

that can be described as alkali-activated cements.7679
They are made by reacting at ambient temperatures
aluminosilicates such as metakaolin, fly ash, or
ground blast-furnace slags with alkaline solutions,
usually strong NaOH solutions. The baseline stoichiometries (Table 6) for the materials participating
in the reaction are typically Na/Al 1 and Si/Al
2 on a molar basis, maximizing the strength80 and a
minimum amount of water (H2O/Na 7 on a molar
basis) is used to assure approximately a maximum
amount of reaction. The properties are relatively
insensitive to variations in the molar ratios at the
level of 10 or 20%. The aluminosilicates partly dissolve in the solutions and polymerize and solidify.
Curing is carried out at 4090 C. Extensive studies
by solid-state nuclear magnetic resonance have been
carried out over the years together with porosity
studies, so it is now accepted81 that geopolymers
consist of nanoporous aluminosilicate networks,
with water in the pores, although micro- and macroporosity is also present. Further evidence for nanoporosity has been gleaned from transmission electron
microscopy and mercury porosimetry82 and positron
annihilation lifetime measurements.83
Samples that pass the PCT aqueous dissolution
test84 (but which have high MCC-1 leach rates of
alkalis) can be fabricated by this technique. Systematic studies of the aqueous leaching behavior of
geopolymers have not yet been carried out, but
measurements of time dependence (190 days) and
surface area/volume ratios suggest that at ordinary
temperatures (90 C) the principal leaching mechanism derives from exchange of the pore water with
the leaching solution, rather than attack of the aluminosilicate framework. As expected from the strength
measurements,80 metakaolinite-based geopolymers
having Na/Al 1 and Si/Al 2 molar ratios have
maximum aqueous durability.85,86 Further measurements in progress at ANSTO are looking at the
effects of temperature over the range of 2090 C,
pH in the range of 212, and the effect of bicarbonate
and chloride ions in the leaching solution. Geopolymers have better fire and acid resistance than standard OPC. Moreover, geopolymers are serious
candidates for ILW, especially as they can be dewatered by heating to 300400 C without significant
effects on their mechanical and chemical properties87
as long as the thermal ramp rate is kept fairly low to
minimize structural disruption from the egress of the
water. This is to be contrasted with OPC in which the
CSH strength-building phase is decomposed at
temperatures above 200 C, thereby severely impacting the mechanical properties. Geopolymers have been
used in Slovenia and Kazhakstan to immobilize large
amounts of ILWs.88
Magnesium potassium phosphate (MPP) ceramics
based on MgKPO46H2O have been developed at
the Argonne National Laboratory since the early
1990s.89,90 Inactive versions of these materials have
also been used in fertilizers for agricultural purposes.91
These materials can in some sense be regarded as
cementitious or low-temperature ceramics. The distinction is perhaps academic as phosphate cements are
well known. MPPs are prepared by mixing calcined
MgO with strong solutions of KH2PO4 and allowing
the following reaction to take place:
MgO KH2 PO4 5H2 O ! MgKPO4 6H2 O
While it has recently been suggested that MPPs
are appropriate for HLW immobilization,92 the leach
rates in that work were based on BET surface areas.
Perhaps more importantly, the hydrous nature of
MPPs gives rise to a radiolytic H2 hazard, and unpublished experimental work at ANSTO has shown that
MPPs become very weak structurally when heated
above 400 C for the purposes of dewatering and/
or attempted conversion to anhydrous ceramics.
5.19.12 Conclusions
In spite of more than 40 years of work, the disposition
of high-level nuclear fuel wastes around the world in
future is still subject to many uncertainties, especially
with Yucca Mountain as an HLW repository in the
United States being currently abandoned. Apart from
political and NIMBY arguments, much of the scientific debate surrounds the question of how to validate
physical models that lead to the calculated maximum
radiation dose to persons living close to the repository, and more particularly how to convince a lay
audience that the very complex calculations, including the uncertainties, are meaningful.
However, the waste form is a key containment
barrier because it can be subjected to rigorous experimental study, and optimization of its behavior can be
studied directly at least over a few years. In this
respect, more analog studies of natural minerals are
needed, where although the water/thermal history of
the analog mineral itself may be hard to derive, the
history may well be derivable from the surrounding
minerals in the rock formation. It seems clear that
Ceramic Waste Forms

Table 8
Radioactive HLW particularly amenable to
ceramification over vitrification
Waste
Difficulty for vitrification
Contaminated metalsa
High-Al and high-Zr wastes
(ICPP, for example)
Tc and Cs
Actinides
Incompatible with glass

Low solubility in silicate
glass
Volatile losses
Low solid solubility of lower
actinide valence states
Can be encapsulated in ceramics using HIPing.
5.
6.
7.
8.
9.
waste form development for the large spectrum of

chemically distinct HLWs already in existence for
many years, plus those yet to be generated by ongoing
and future nuclear power programs, will continue.
The twin foci of this continuance are simply (a)
increased waste loading, especially in cases where
radiogenic heating is not serious, to ease the amount
of space required to contain the waste forms in repositories and (b) cost savings via development of technologies that maximize waste form throughputs and
minimize plant footprints and radioactive offgas
emissions. It is certain that HIPing will play an
important role in achieving these improvements, particularly for wastes which are problematic for vitrification (Table 8) and for which there will be a strong
preference for ceramics and glassceramics. Cements
and particularly geopolymers remain as potentially
viable for ILW. (See also Chapter 5.22, Minerals
and Natural Analogues; Chapter 5.18, Waste
Glass and Chapter 1.05, Radiation-Induced
Effects on Material Properties of Ceramics
(Mechanical and Dimensional)).
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
Acknowledgements
20.
The author wishes to acknowledge numerous colleagues at ANSTO and around the world for many
discussions and contributions over many years.
21.
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189192.
5.20
Metallic Waste Forms
W. L. Ebert
Argonne National Laboratory, Argonne, IL, USA
Published by Elsevier Ltd.
5.20.1
Introduction
506
5.20.2
5.20.2.1
5.20.2.2
5.20.2.3
5.20.2.4
5.20.3
5.20.4
5.20.4.1
5.20.4.2
5.20.5
5.20.5.1
5.20.5.2
5.20.5.3
5.20.6
5.20.6.1
5.20.6.2
5.20.6.3
5.20.7
5.20.7.1
5.20.7.2
5.20.7.3
5.20.8
5.20.8.1
5.20.8.2
5.20.8.3
5.20.8.4
5.20.8.5
5.20.8.6
5.20.8.7
5.20.9
References
Waste Streams
Electrometallurgical Wastes
Aqueous Processing Wastes for UREX + Flowsheets
Hulls and Hardware
Processing Additives
Alloy Compositions
Processing Methods
Alloy Production
Waste Conditioning
Testing Objectives
Matrix Degradation and Radionuclide Release
Waste Form Consistency Through Process Control
Waste Form Acceptance and Regulatory Requirements
Modeling
Matrix Corrosion and Radionuclide Release Mechanisms
Performance in Disposal System
Processing Control
Test Methods
Electrochemical Test Methods
Corrosion Test Methods
Service Condition Test Methods
Tests with INL MWF
Formulation and Phase Compositions
Radionuclide Distribution
Electrochemical Tests
Corrosion Tests
Corrosion Models
Repository Model
Metallic Waste Form Product Consistency
Summary
509
509
510
512
512
513
514
514
515
515
515
516
517
517
518
520
520
521
522
523
524
525
525
526
528
529
531
533
534
535
536
Abbreviations
DOE
EBR-II
EBS
FCR&D
FPEX
GTCC
HLW
MWF
US Department of Energy
Experimental breeder reactor
Engineered barrier system
Fuel Cycle Research and
Development
Fission product extraction
Greater-than-Class C
High-level radioactive waste
Metallic waste form
NIST
US National Institute of Science and

Technology
NL(i )
Normalized mass loss (based on
element i)
RCRA
Resource conservation and
recovery act
SEM
TALSPEAK Trivalent actinidelanthanide
separations by phosphorous reagent
extraction from aqueous complexes
505
506
TEM
TRUEX
UDS
UREX
VHT

Transuranic element extraction
Undissolved solids
Uranium extraction
Vapor hydration test
5.20.1 Introduction
This chapter provides an overview of current strategies
and approaches for formulating, processing, testing,
and developing performance models for the metallic
waste forms that are being designed to immobilize
high-level radioactive wastes. Some aspects have been
completed and demonstrated, while others are planned
approaches based on previous experience that have
not yet been fully implemented. Issues that must
be addressed when designing a waste form are conveniently grouped as performance, processing, and waste
acceptance issues, although these are interrelated.
Waste acceptance issues include regulatory requirements that the waste form and disposal system as a
whole must meet, identification of waste form properties that can be measured to demonstrate that the waste
form is acceptable, and specifications for performing
those measurements. Performance issues include
determining the capacity of the waste form to restrict
the release of radionuclides to rates at which the engineered repository can meet regulatory requirements
(this is the basis for waste form acceptability), and,
importantly, the ability to predict the release rates
over very long durations under the anticipated range
of environmental conditions with a mathematical
model. Processing issues include the ability to produce
waste forms from the anticipated range of waste stream
compositions and additives that have consistent, predictable, and acceptable chemical, radiological, and
physical properties by maintaining a consistent phase
assemblage and distribution of radionuclides. Although
the primary role of a waste form is to retard the release
of the radionuclides it contains to the surrounding
environment, this should occur in a predictable manner that can be related to both long-term performance
and waste form production controls. The link between
production and performance will provide confidence
to regulators that the performance of any waste form
produced within the anticipated range of waste stream
compositions is adequately represented in the performance assessments used to license the disposal facility.
The radionuclide release rates and the degradation rate of the host waste form matrix are used as
source term models in performance assessment calculations to predict the capacity of the disposal system to meet regulatory limits, such as groundwater
dose limits or contamination levels at or beyond the
system boundary. Assessments must address very long
time periods and both anticipated environmental conditions and possible extreme conditions, including
highly unlikely scenarios. The unprecedented challenge of predicting material performance for waste
management over a geologic time scale has led to
highly conservative bounds being used in risk and
safety assessments. For example, the assessment calculations for the proposed Yucca Mountain repository
include igneous intrusion (a magma plume from volcanic activity) and eruption scenarios. The inclusion of
catastrophic events that have extremely low probabilities of occurring in performance assessments may be
necessary for identifying conditions under which a
repository may fail to meet regulatory requirements.
Although those conditions will likely be far outside the
anticipated range of service conditions, the possible
impacts on the performance of the waste form should
be considered when developing testing programs. In
the case of metallic waste forms, this may call for an
understanding of the impacts of long-term heating on
the phase composition and retention of radionuclides
of the host phases. The term phase composition is
used to denote the assemblage of component phases in
the waste form, including solid solution and intermetallic phases, the chemical composition of each phase,
and the distribution of radionuclides.
The matrix material used to immobilize radioactive waste must be compatible with both the waste
stream and the disposal environment. Although the
specific disposal site may not be identified at the time
waste forms are being designed, general site characteristics may be known, for example, if the site will
be located in clay, salt, tuff, granite, or other medium,
if it will be in a reducing or oxidizing environment, in
a hydrologically saturated or unsaturated horizon,
etc. If not even the generic disposal conditions are
known, then testing programs must consider waste
form compatibility in all potential environments.
In most cases, the general compatibility of a waste
stream and potential host matrix can be anticipated
from known materials characteristics, but it must be
evaluated experimentally to determine details of the
phase composition and microstructure. The radionuclide(s) may be incorporated into the host matrix or
sequestered in separate phases that are encapsulated
by the matrix. For example, radionuclide-bearing
oxide phases may be encapsulated within a metal
matrix. In that case, compatibility may simply mean

that the waste form can be processed to encapsulate
the radionuclide-bearing phases within the matrix.
Some waste forms may simply serve as a diffusion
barrier to the ingress of water or the diffusive release
of the radionuclides, but degradation of metallic
waste forms will likely be required prior to radionuclide release. Note that degradation is used to refer
to alteration that results in the release of radionuclides, whereas corrosion is used to refer to alteration that does not necessarily result in release.
Regardless of the mode, the radionuclide release
rate from each waste package must be predictable
over the service life of the disposal system as a source
term in performance assessment calculations. This
usually means that waste form products must have
consistent composition, degradation behaviors, radionuclide inventories, and size (exposed surface area).
Consistent does not mean identical in the present
context. Rather, it means within the range deemed to
ensure acceptable performance. The anticipated range
of waste stream compositions, which may vary due
to variations in the fuels being treated and efficiencies
of separations processes, and the capacity to blend
waste streams and adjust additives, will affect the composition range of the waste forms. The impact of the
anticipated range of waste form compositions on radionuclide release must be determined and taken into
account in the source term model and preliminary
performance assessment calculations. The impact on
the performance of the disposal system can then be
used to establish the acceptable composition range.
This may require reformulation of the waste form,
such as lowering the waste loading or changing the
additives, to accommodate the range of waste stream
compositions.
Some radioactive waste streams are better immobilized in a metallic matrix than in glass or other
matrices because the waste materials are metallic,
because the radionuclides in the waste can be more
efficiently retained during waste form processing if
they are in the metallic state, or because the radionuclides are more effectively retained in the waste
form if they are in the metallic state. Technetium is
an important example of a radionuclide that is best
processed and immobilized as a metal. The predominant species in most aqueous waste streams is the
pertechnetate ion TcO
4 , but Tc(VII) is neither readily processed due to volatility of species such as
CsTcO4 nor strongly incorporated into the structure
of a glass or other matrix. The most stable form in an
oxidizing disposal environment, TcO2, is sparingly
507
soluble in water, but sublimes at 900 C and Tc(IV)

disproportionates to metallic Tc and gaseous Tc2O7
at about 1100 C.1 In contrast, metallic Tc can be
processed at high temperatures under reducing conditions and alloyed in a metallic waste form without
the loss of volatile species. Waste streams with high
concentrations of Tc and other transition metals can
also be immobilized in a metallic waste form at
higher waste loadings than in a glass or other waste
form matrix. Specific waste streams that are expected
to be amenable to metallic waste forms are discussed
in Section 5.20.2.
In a metallic waste form, most radionuclides are
dissolved or alloyed in a host metal with other waste
constituents. Formulations of alloy waste forms must
identify host metals and mixtures that can be processed at practicable temperatures and form durable
phases to incorporate all radioactive components.
Many metallic components in waste streams have
very high-melting points and must be reactively dissolved into molten metals before they can be alloyed.
Available binary and ternary phase diagrams provide
insights into likely melting temperatures and phase
compositions for processing complex mixtures of
wastes and added metals. For example, significant
amounts of Zircaloy scraps from cladding hulls in a
waste stream can be dissolved into molten copper
or iron below 1600 C, even though Zircaloy itself
(Zircaloy-2 and Zircaloy-4) melts at about 1850 C.
Other metals present in spent nuclear fuel and
expected to be present in metallic waste steams either
as pure metals or in alloys include Mo (2623 C), Ru
(2334 C), Tc (2204 C), Rh (1963 C), and Pd
(1555 C). The five-metal alloy formed from these
components during irradiation of oxide fuels is
expected to have a melting point near 2000 C (see
Kaye et al.2). These high-melting wastes can be processed into a metal waste form at temperatures lower
than their melting points by utilizing eutectic mixtures.
The binary phase diagrams give insights into the solubilities of waste components in iron and identify intermetallic phases likely to form in the two-component
systems. Elemental substitutions can also be predicted
based on metallurgical data. For example, each component in the five-metal alloy is expected to be dissolved
by molten iron at a temperature well below 1600 C,
and so is the five-metal alloy. The ability to produce a
waste form is an obvious initial requirement in waste
form design. Formulation of metal alloy waste forms
is discussed in Section 5.20.3.
Contaminants will be present in the waste stream
(e.g., oxides and sulfates) and absorbed by the molten
508
metal from the crucible and furnace atmosphere

(trace O2, CO, etc.) during processing. Slags (and
dross) typically form on the surfaces of molten metals
from impurities that are not incorporated into the
alloys. Silica, calcium, and other oxidizable materials
are commonly added to molten metals in industrial
processes to help sequester impurities in slag layers
that can be removed from the surface of the molten
metal and discarded. The addition of silica usually
results in the formation of a glassy phase in the slag
that encapsulates other phases of metal oxide, carbide,
sulfate, etc., and may itself be quite durable. Whereas
slags are removed and discarded as waste from metal
and alloy products, they can serve to immobilize contaminants excluded from the alloy phases of a metal
waste form. The use of slag phases as a component of
metallic waste forms is being studied.3 Processing
methods are discussed in Section 5.20.4.
The durability of a metallic waste form will
depend on the durabilities of the component phases
and their interactions with other phases in the waste
form and with engineering materials, primarily
through galvanic couples. The phases that are present
and potential couples will affect the capacity of the
waste form to retain radionuclides, and long-term
performance models must take both into account.
Clearly, a constant phase assemblage and a constant
distribution of radionuclides between those phases
will simplify performance models. Although a mechanistic understanding of waste form corrosion and
radionuclide release adds confidence to predictions
of long-term waste form performance, a fully mechanistic model for waste form degradation may be
impractical due to budget limitations or unachievable
due to an incomplete understanding. Many aspects
can be adequately captured with empirical models,
such as pH and temperatures effects, but confidence
in empirical models based solely on experimental
observations is usually limited to the duration of the
longest experiments. A mechanistic understanding of
processes that establish the time-dependent aspects
of corrosion should be the top priority of a testing
program. This could include understanding how passivating layers form, mechanisms for their breakdown,
and the kinetics of their healing. The term passivating
is used in the very general sense of slowing the corrosion, regardless of the controlling factor. Key testing
objectives are summarized in Section 5.20.4, including
performance modeling, process control, and waste
acceptance. Modeling is discussed in Section 5.20.5
and testing to develop a mechanistic degradation
model is discussed in Section 5.20.6.
Consistency is another important requirement for

metallic waste forms related to the need to predict
waste form performance (particularly radionuclide
release) over a very long disposal system service
life. The performance of a metallic waste form in a
given disposal system will, in general, depend on the
phase assemblage that comprises the waste form and
the radionuclide inventory. The preferred approach
for producing consistent waste forms is control of the
feed (waste streams and additives) and the processing
conditions. Controlling the feed controls the gross composition of the waste form, and controlling the composition and processing condition controls assemblage
of phases that form, and presumably, maintains a
consistent distribution of radionuclides among the
component phases. A key objective of waste form
design and testing is to determine the relationships between (1) the process conditions and the
phase composition and (2) the phase composition
and waste form performance. These relationships
link the radionuclide release rates calculated using
the waste form degradation model with the controlled
production of the waste form. These two sets of
relationships should take precedence in waste form
development and their importance should not be
underestimated. Whereas both high waste loadings
and high chemical durabilities are key objectives of
waste form design, the acceptance by regulators for
disposal will likely require evidence that the waste
forms will perform to the level modeled in performance assessment calculations. Because it is not practical to subject samples of each waste form product
to the suit of tests needed to characterize and model
performance in the disposal system, the performance of each waste form product that is made can
instead be related to the performance measured for
the representative material based on the phase composition and microstructure. That relationship must
be established through the waste form composition
and processing conditions as a part of waste form
development. Therefore, it is important to determine
and experimentally demonstrate the ranges of waste
form compositions and processing conditions that are
represented by the model. That range of compositions
is the basis for waste form acceptance. For borosilicate
waste glasses, the relationship between performance
and process control is demonstrated using the Product Consistency Test (ASTM standard test method
C 1285), which is a partial dissolution test conducted
under specified test conditions.4 An extensive database
was generated to show the relationship between glass
composition and test response,5 and the test response
can be related to the modeled glass degradation and

radionuclide release behavior.6 An analogous test
method and database must be developed to establish
the link between production control and performance
for metallic waste forms.
A metallic waste form was designed and developed to immobilize metallic wastes generated during
the electrometallurgical treatment of spent sodiumbonded nuclear fuel from the Experimental Breeder
Reactor-II (EBR-II).79 That waste stream consists of
Type 316 stainless steel anode baskets, steel cladding
hulls, and residual metals from the fuel that were not
oxidized during the electrorefining procedure (primarily Zr). The primary radionuclide in the metallic waste
from the fuel is 99Tc, but the waste stream also includes
a small amount of entrained salt that contains actinides
(primarily U and Pu). The work done to formulate
this waste form, measure the corrosion behavior and
radionuclide release, develop a performance model,
and develop an approach for tracking waste form consistency provides a valuable example of the general
approach for developing a metallic waste form and
generating the database to support acceptance for
disposal. To distinguish the specific metallic waste
form alloy developed for electrometallurgically treated
EBR-II fuel from other metallic waste forms, it will be
referred to herein as the EBR-II metallic waste form
(MWF). The work done to develop, test, and model
the EBR-II MWF is summarized in Section 5.20.8.
All testing, modeling, and production activities
related to waste form development and qualification
will likely be governed by Quality Assurance requirements. Most of the work done to formulate compositions, determine degradation mechanisms, develop
models, and evaluate processing effects can probably
be performed at less stringently controlled research
and development levels. Other aspects, such as parameterizing the degradation models and establishing
processing and consistency test limits, must likely
meet higher Quality Assurance standards. These typically involve the use of documented and approved
testing and analytical methods, certified and calibrated
standards and equipment, fully documented and technically reviewed data and analyses, etc. Additional
requirements apply to processing equipment and the
actual waste form products.
5.20.2 Waste Streams

Waste streams amenable to a metallic waste form
either include a significant amount of metal waste
509
components or include radionuclides that are best

immobilized in the metallic state. Waste streams that
are currently being immobilized in a metal waste
form10 or being evaluated for immobilization in a
metallic waste form3,11 are discussed in the following
sections.
5.20.2.1
Electrometallurgical Wastes
An electrometallurgical process has been developed

under the auspices of the US DOE Office of Nuclear Energy to treat the spent sodium-bonded fuel
inventory from the Argonne Experimental Breeder
Rector-II (EBR-II) at the Idaho National Laboratory.9,12 The inventory includes 1.1 MT of what are
referred to as driver fuel rods, which contain the
majority of the fission products, and 22 MT of blanket fuel rods.10 The driver rods contain an enriched
U10Zr fuel alloy (63% 235U) and the blanket rods
contain depleted U. Both fuel types are fixed in the
rods with metallic sodium, which provides a thermal
bond between the fuel and cladding. Treatment is
necessary to separate waste radionuclides from the
metallic sodium prior to their disposal. The electrometallurgical process recovers the uranium from the
fuel and generates two waste streams: sodium and most
fission products dissolve in the waste salt, whereas
steel cladding hulls and metals not oxidized under the
refining conditions remain as metallic waste. A ceramic
waste form has been developed to immobilize the salt
wastes and a metallic waste form has been developed to
immobilize the metallic wastes. The electrometallurgical process may be used to treat other DOE-owned
spent sodium-bonded fuel in the future, for example,
34 MT of sodium-bonded blanket fuel from the Fermi
1 reactor,10 but that decision remains to be made.
Electrometallurgical treatment of other spent fuels
that would generate metallic waste streams is being
considered. Scoping work was conducted to evaluate
the use of electrorefining on oxide fuels that have
been reduced as an alternative to aqueous reprocessing of oxide fuels, but that option is not currently
being pursued. The more likely use of electrorefining will be treatment of the used metallic fuels being
developed as part of a closed fuel cycle within the
DOE Fuel Cycle Research and Development program (FCR&D). New metallic waste forms will
be needed for these wastes due to the planned used
of Zircaloy cladding for the new fuels. The alloy
developed for the steel-clad sodium-bonded EBR-II
fuel is not appropriate for Zircaloy-clad fuel. However, it should be noted that Zircaloy cladding could
510
be recycled in the future and the waste stream

compositions might not be dominated by Zircaloy
cladding hulls.
About 90% of the EBR-II inventory is steel-clad
fuel and the rest is Zircaloy-clad fuel. The blanket
fuel cladding is Type 304L stainless steels and the
driver fuel claddings include Type 316, Type D9, and
Type HT9 stainless steel. The waste form made with
steel cladding was the primary focus during waste
form development research, and only few scoping
studies were carried out to evaluate potential waste
form compositions for waste streams dominated by
Zircaloy cladding.8,1317 The composition and the
microstructure of the waste form are affected primarily by the relative amounts of stainless steel fuel
cladding and Zr from the driver or blanket fuel in
the mixture used to make the alloy. The cladding
supplies Fe, Cr, Ni, Mo, Mn, Co, Cu, V, and Si to
the metal waste stream, plus trace amounts of Sn, C,
and S. The chemical composition of the waste stream
is dominated by Fe and Zr. The low-melting eutectic
composition Fe15Zr was selected as the target composition of the waste form to allow processing at
about 1600 C. This requires adding Zr to the mixture. The predominant phases that are formed are
those predicted by the FeZr binary phase diagram,
namely, similar amounts of an iron solid solution and
an Fe2Zr intermetallic phase. Radionuclides and
other components in the steel (e.g., Ni and Cr) are
distributed between these phases and minor amounts
of other phases (e.g., Fe23Zr6). This is discussed in
detail in Section 5.20.8.1.
The primary radionuclide is 99Tc, but the waste
contains a small amount of carry-over salt with actinides that are retained as contaminants in the waste
form. A small amount of depleted uranium is added to
some waste mixtures to down-blend the 235U content
in the waste form to below 20 mass%. Most waste
forms are expected to contain about 1 mass% U, but
some could contain as much as 11 mass% U.
Table 1
Nuclide
14
C
Co
93m
Nb
94
Nb
59
Ni
63
Ni
60
The radionuclides expected to be immobilized

that provide the highest activities are listed in
Table 1, expressed as the activity in a disposal canister containing two waste form ingots (see Appendix
A in Ebert.)18 The 18 radionuclides listed in Table 1
provide 99.6% of the total 3 1012 Bq expected in a
canister. For comparison, the total radionuclide activity in an average canister of high-level radioactive
waste (HLW) glass is estimated to be more than
2.8 1015 Bq.
5.20.2.2 Aqueous Processing Wastes for
UREX + Flowsheets
The US Department of Energy is evaluating methods
to reprocess commercial spent fuel from light water
reactors through the FCR&D program. The technologies developed to partition fuel elements and recycle actinides are intended to expand the nuclear
power capacity to meet the global future energy
needs while minimizing the amount of high-level
radioactive waste requiring geologic disposal. The
near-term goal is to develop the technologies needed
for a proliferation-resistant nuclear fuel cycle. To this
end, various operational flowsheets are being developed and tested to recover uranium and actinide
elements from spent oxide fuel for recycle and separate long-lived fission products from other fuel wastes
for separate immobilization and disposal. An important potential benefit of the processing operation is
minimizing the heat load of wastes destined for geologic disposal. The partitioning of short-lived heatgenerating radionuclides, such as 137Cs and 90Sr, from
short-lived (e.g., lanthanides) and long-lived radionuclides that do not generate significant heat loads,
such as the 129I, 99Tc, and 79Se, provides the opportunity to tailor waste forms to the properties of particular waste streams and dispose these waste forms
according to risk.3,11 Although current US regulations classify all waste streams from reprocessed fuel
Estimated radionuclide activities in EBR-II metallic waste form

Bq/canister
10
2.63 10
1.01 1011
3.24 1010
1.68 1010
6.59 1010
1.93 1012
Nuclide
234m
Pa
Pu
125
Sb
126
Sb
126m
Sb
126
Sn
239
Bq/canister
8
5.99 10
2.04 109
3.30 109
2.42 109
1.73 1010
6.22 109
Nuclide
Bq/canister
99
7.84 1011
8.07 108
5.99 108
4.74 109
1.55 108
5.99 108
Tc
Te
234
Th
234
U
235
U
238
U
125m
Data from Ebert, W. L. Testing to Evaluate the Suitability of Waste Forms Developed for Electrometallurgically Treated Spent SodiumBonded Nuclear Fuel for Disposal in the Yucca Mountain Repository, Argonne National Laboratory Report ANL-05/43; Argonne National
Laboratory: Argonne, IL, 2005.
as high-level radioactive waste, safety analyses might

indicate some waste streams/waste forms as benign
and the risks low enough that they could be regulated
as Class C or Greater-Than-Class C (GTCC)waste
rather than high-level waste.
The FCR&D program is currently studying the
application of aqueous separation technologies to
spent oxide fuels. Prior to dissolution, the cut fuel is
heated in a voloxidation step intended to remove
gaseous and volatile fuel components, including 3H,
14
C, and 129I. These are volatilized at increasing temperatures and are captured (separately) from the offgas
for immobilization and disposal. Dissolution of these
fuels (typically in hot HNO3 with HF) is incomplete,
with residues including five-metal particles and Zr
from the fuel and minute scraps of Zircaloy cladding
generated when the cladding was cut. (Additional gas
release occurs during dissolution.) The undissolved
solids (UDS) are removed from the dissolved fuel
solution by filtration. The UDS waste stream is suitable for immobilization in a metallic waste form. The
dissolved fuel solution is subjected to a uranium
extraction (UREX) operation that separates the
U and Tc in the solvent phase and the other fuel
components in the raffinate. The Tc (as pertechnetate
ion) is removed from the UTc solution using an
anion exchange change column. The U is recovered
for recycle. The pertechnetate is later eluted from the
column and can be recovered as either TcO2 or tetra
n-butyl pertechnetate using one of the two methods
that are being developed. The TcO2 can be reduced to
Tc metal by heating in a reducing atmosphere (e.g.,
CO or Ar/H2 gas) and the tetra n-butyl pertechnetate
can be reduced to Tc metal by steam reformation in a
separate operation. The recovered metallic Tc is suitable for immobilization in a metallic waste form. The
UREX raffinate can be treated to separate Rb, Sr, Cs,
and Ba from the rest of the dissolved fuel with the
fission product extraction (FPEX) operation. The
137
Cs and the 90Sr are the major heat-generating constituents of the fuel waste. Both have half-lives of about
30 years, decaying to stable 137Ba and 90Zr, respectively. The Cs/Sr/Ba/Rb stream will likely be immobilized in a glass waste form. The transuranic elements
and lanthanides are next separated from the fuel solution by a transuranic element extraction (TRUEX)
operation. The TRUEX raffinate contains dissolved
transition metals from the fuel, but is dominated by
ferrous sulfamate added to improve the efficiency of
the TRUEX separation for Np and Pu. The sulfur
must be removed from the TRUEX raffinate before
it can be immobilized in either a glass or a metallic
511
waste form. The dissolved transition metal fission products can be recovered by increasing the pH to coprecipitate them with iron as hydroxides and then
reduced for incorporation into a metallic waste form
at higher waste loadings. Finally, the lanthanides are
separated from the actinides using TALSPEAK (trivalent actinidelanthanide separations by phosphorous
reagent extraction from aqueous complexes). The actinides are recycled (as fuel) and the lanthanides immobilized in a glass waste form with the Cs/Sr/Ba/Rb
stream. For a typical light water reactor fuel, this
scheme would result in about 37% of the waste immobilized in a metallic waste form, about 46% immobilized in glass, and about 17% immobilized as
captured offgas in another waste form.
The compositions of the waste streams will depend
on the dissolution conditions, separation efficiencies,
fuel burn-up (weakly), and fuel aging prior to reprocessing. The compositions of waste stream suitable
for immobilization in metallic waste forms 51 GWd/
MTHM (gigawatt days per metric ton metal) fuel
stored 20 years before reprocessing are given in
Table 2.19
Table 2
Estimated metallic waste stream compositions
for 20-year-old 51 GWd/MTHM fuel
S
Fe
Se
Rb
Zr
Mo
Tc
Ru
Rh
Pd
Ag
Cd
Sn
Sb
Te
Total
UDS
(kg/
MTHM)
Recovered TRUEX
Recombined
Tc
with
(kg/MTHM) ferrous
sulfamate
(kg/MTHM)
kg/
Mass
MTHM %

0.00463
0.114
1.86
4.75
0.0275
1.64
0.0238
0.0684
0.0517
0.0513

0.166
9.876

0.875

0.875
13.5
23.5
0.0394

3.78
0.357

1.85
0.373
1.67
0.0631
0.146
0.141
0.0279
0.589
32.536

23.5
0.0857
0.114
5.64
5.11
1.15
3.49
0.611
2.35
0.115
0.197
0.141
0.0279
0.755
43.288

54.29
0.20
0.26
13.03
11.80
2.66
8.06
1.41
5.44
0.27
0.46
0.33
0.06
1.74
Data from Ebert, W. L. Immobilizing GNEP Wastes in

Pyrochemical Process Waste Forms, US Department of Energy
Report GNEP-WAST-PMO-MI-DV-2008-000150; Idaho National
Laboratory: Idaho Falls, ID, 2008.
512
Current waste form research under the FCR&D

program is focused on two options for these waste
streams: combining the UDS, recovered Tc, and pretreated TRUEX raffinate wastes in a single alloyed
waste form or combining the UDS and recovered Tc
in a metallic waste form and immobilizing the TRUEX
raffinate wastes separately or in glass. The composition
of the three combined streams is dominated by Fe from
the TRUEX raffinate, which accounts for 54% of the
total mass. The next most abundant elements are Zr,
Mo, and Ru. Those elements dominate the combined
UDS and recovered Tc streams. The amount of ferrous
sulfamate assumed in Table 2 is conservatively high,
but Fe is expected to still dominate the waste stream
composition after the amount of ferrous sulfamate is
optimized. Research is in progress to replace ferrous
sulfamate with an alternative reductant. However, iron
could be added to the TRUEX raffinate to recover the
dissolved metals by coprecipitation. The gross composition of the recombined waste streams is similar to the
composition of the EBR-II SS15Zr metallic waste
form considering that Mo, Ru, and other components
will dissolve in iron to produce a solid solution similar
to the steel phase in the SS15Zr alloy.
5.20.2.3
Hulls and Hardware
The metallic wastes from the electrometallurgical

treatment of EBR-II spent sodium-bonded fuel are
dominated by the cladding hulls, and the metallic
fuel wastes (primarily Zr) are only a small component
of the waste stream.
In the aqueous reprocessing flow sheets for oxide
fuels, the fuel can be mechanically separated from the
cladding hulls after voloxidation (if that operation is
used) or after fuel dissolution. The hulls can be acid
washed to remove adhering TRU contamination and
disposed of separately; the hulls will likely retain
enough residual contamination and activation products
in the bulk metal to require disposal as GTCC waste.
Some of the Zircaloy hulls could be used as a source of
Zr added to alloy other waste streams. The remaining
hulls could be alloyed separately, combined with the
separations waste streams, or compacted with the
assembly hardware for separate disposal. Preliminary
studies17 indicate that Zircaloy hulls can be alloyed
with waste components if significant amounts of
metal additives are added to lower the processing temperature to practicable levels. However, the amount of
added metal needed to lower the processing temperature is by itself adequate to alloy the wastes (i.e., without the hulls). Because there will be about 10 times
more cladding hulls than metallic fuel wastes, compacting the hulls as a separate waste form will probably be
more economical than alloying them with the wastes.
Neutron activation products generated by components in the various hardware materials used in fuel
assemblies will include 14C, 55Fe, 59Ni, 60Co, 63Ni,
93
Zr, 94Nb, and 99Tc. The activity contribution of
each can be calculated from the elemental concentration in the metal, the neutron flux, the abundance
and thermal neutron capture cross-section of the
reacting isotope, and the specific activity of the product radionuclide. The last three are constants and
their product provides a measure of the efficiency
of each neutron activation reaction; that product is
referred to herein as the efficiency factor and provides insight into the likely contribution of that radionuclide to the overall radioactivity.
Activation of 98Mo leads to the production of 99Tc
with an efficiency factor 2 109 Bq barns g1. Small
amounts of Mo (23 mass%) are present in Type 316
and other stainless steels, Inconel-718, and in trace
amounts in the Zircaloys. Activation of nitrogen, carbon, and oxygen in the fuel and hardware produces
14
C with efficiency 1.27 1012, 1.70 108, and
1.48 108 Bq barns g1, respectively. Activation
of 92Zr in Zircaloy (only) produces 93Zr, which has
a very long half-life, but the efficiency factor for 73Zr
is only 5.55 108 Bq barns g1. Activation of Ni and
Nb produces 59Ni, 63Ni, and 94Nb with efficiency
factors 8.99 1011, 9.16 1013, and 7.96 1011 Bq
barns g1, respectively. All hardware materials contain Ni, but 94Nb will only be produced in assemblies
with Inconel components. Generation of 63Ni will
dominate the initial radioactivity, but it will decay
faster than 59Ni and 94Nb. Both 55Fe and 60Co are
short lived and neither will be a significant long-term
dose contributor. The efficiency factors are
1.09 1015 and 8.14 1015 Bq barns g1, respectively.
5.20.2.4
Processing Additives
Metals can be added to the waste streams to tailor the

phases comprising the waste form or serve a role in the
processing operation. The steel anode baskets used in
the electrorefiner are a source of Fe, Cr, and Ni to the
waste form. Zirconium is added to provide a neareutectic composition to facilitate processing and generate a consistent phase composition. Some of the
metal components used in waste separations and containment can be selected based on how they would
impact the waste form. One method for recovering
99
Tc that is being investigated within the FCR&D
program is reductive deposition on steel wool. The

steel wool and the canister in which it is housed could
provide the Fe and other components used to make the
waste form. Many components of steels are added to
improve the durability. Some of the waste components
could serve the same role in the steel-like phases
formed in Fe-based alloy waste form. The waste components might also increase the durability of intermetallic phases that form.
The approach taken when formulating metallic
waste form compositions is to minimize the amounts
of additives (and thereby minimizing the mass and
volume of waste) while optimizing the processing
conditions, waste form durability, and consistency of
the phase composition and distribution of radionuclides. The addition of metal to the waste streams
allows for better control of the waste form phase
composition. Variances in the amounts or compositions of the waste streams from different processed
fuels can be compensated for by adjusting the amounts
of additives to result in a consistent waste form. The
need for a consistent phase composition (because that
results in consistent performance) will likely take precedence over the desire to minimize the amount of
waste forms produced.
5.20.3 Alloy Compositions

Metallic waste forms are formulated to incorporate
high concentrations of radionuclides into durable
phases at low processing temperatures. The very
high-melting temperatures of many metallic waste
components require reaction with a lower-melting
metal to be dissolved. An example of this is the
Fe15Zr composition used for the EBR-II MWF
(see Section 5.20.8.1). The melting temperature of
Zr is 1855 C, but reaction with molten Fe allows Zr
to be dissolved at temperatures as low as 1337 C at
the 84.9Fe15.1Zr wt% eutectic and at 928 C at the
16.2Fe83.8Zr wt% eutectic. Eutectics permit waste
processing at practical temperatures. Compositions
slightly off the eutectic can be used to promote a
particular phase assemblage. In the case of the
EBR-II MWF, the fact that the actinide elements
report to the intermetallic phase demands that an
adequate amount of that phase be present in the
alloy to avoid forming another phase, which would
probably change the waste form performance. Using
an alloy composition that is slightly Zr-rich relative
to the eutectic will generate a sufficient amount of
the intermetallic phase to sequester all the actinides.
513
On the other hand, a sufficient amount of a solid

solution phase may be needed to encapsulate the
intermetallic phases in a physically robust monolith.
Binary and ternary phase diagrams are useful for
estimating the solubilities of waste components in a
host metal, the intermetallic phases that may form,
and the required processing temperature. In complex
waste mixtures, competition between solutes (e.g., for
interstitial sites in intermetallic phases) will usually
lower the solubilities and could affect the phase
assemblage and waste form performance. This is
most readily determined experimentally.
Multiphase alloy waste forms having a simple
phase composition are preferred over more complex
compositions due to the importance of waste form
product consistency. The need to take into account
only a few phases will benefit performance calculations, waste form analyses, and waste form qualification. Host matrices that can accommodate a wide
range of waste elements within a few phases balance
the desire to minimize the amount of waste form
produced with the benefits of a simple phase composition that provides enough flexibility to accommodate the anticipated range of waste stream
compositions. The austenite and the ferrite solid
solution phases form in the SS15Zr alloy developed
for EBR-II wastes provide compositional flexibility
for the formation of intermetallic phases having a
narrower range of stoichiometries by accommodating
the excesses.
In a multiphase alloy waste form, the corrosion
potential of one phase will necessarily be lower than
those of the other phases, and that phase will corrode
preferentially and mitigate corrosion of the other
phases. The dissolving phase serves as the anode in
the oxidationreduction reactions of the other phases,
which act as cathodes. Such a phase is often engineered into systems to serve as a sacrificial anode to
protect other metals. The waste form should be
designed so that the phases containing radionuclides
are not the least durable phases. Although a sacrificial
phase could be added as a surface coating similar to
zinc-coated iron, it could instead be distributed
throughout the bulk of the waste form. This would
have the advantage of not being scratched off the waste
form by abrasion, but the disadvantage that corrosion
of that phase would leave a porous waste form with a
high specific surface area. Pits and crevices usually
provide microcells that promote corrosion and should
be avoided. Steel is galvanized by dipping into a bath
of molten zinc at about 455 C. Although steel melts
at about 1510 C, an oxide-free steel surface will react
514
with molten zinc to form various FeZn intermetallic

phases (referred to collectively as the alloy layer)
between the steel and the pure zinc outer surface
within minutes in a batch process. It may not be
necessary to coat the entire surface, since steel corrosion commonly occurs at point defects at the surface
and where microcells develop.20
5.20.4 Processing Methods

Requirements for processing facilities will depend on
the processing temperature and atmospheric conditions needed to melt the wastes and added metals
into an assemblage of durable phases in a physically
robust waste form. Small prototype alloys have been
made using laboratory-scale furnaces under vacuum
and under flowing inert gases. Reducing gases such as
Ar/H2 and CO could also be used to control the
furnace atmosphere. It may be necessary to contain
the furnace in a radioactive hot cell.
5.20.4.1
Alloy Production
Alloys can be produced in resistance or induction

furnaces using single-batch or continuous casting
methods. Batch melts provide a convenient means
of controlling the composition through the relative
amounts of wastes and additives placed in the crucible and may be better suited for the required process
controls. Continuous casting commonly provides
energy and total cost savings, but can result in products having microstructures significantly different
than those made with a batch method and a different
assemblage of phases. Continuous casting usually
generates coarser and more elongated phases,
although the microstructure can be modified by
annealing. The need to contain the furnace, such as
in a hot cell, may dictate which process is used.
The EBR-II MWF to be made at INL will be
processed using an induction furnace and cast from
batch melts as ingots in a crucible. The planned
method is summarized here as an example of designing a batch processing method for a specific waste
stream. The EBR-II metallic waste stream will be
composed of 0.025-m (1-in.) sections of chopped
cladding hulls with adherent metallic fuel wastes,
primarily Zr, and a small amount of entrained salt.
These are removed from the steel anode basket and
loaded into a crucible with appropriate amounts of
added Zr metal and depleted U. A 2-piece crucible
assembly is used to facilitate loading the hulls and
accommodating the 60% volume reduction that

occurs upon melting. The crucible assembly includes
a crucible funnel that drains into a casting crucible.
Both are made of graphite coated with an yttria
refractory. The crucible funnel is also lined with
steel to protect the refractory-coated graphite funnel
during loading. The wastes are loaded into the funnel, which channels the metal into the receiving
crucible as it melts. The steel liner melts during
processing and drains into the casting crucible with
the waste and becomes incorporated into the waste
form. Typical processing conditions ramp to a maximum processing temperature of 1600 C over about
2.5 h and hold the mixture at that temperature for
about 2 h. A vacuum of about 133 Pa (1 torr) is applied
while the temperature increases to about 1300 C to
distill the entrained salt. The distilled salt is condensed and recovered outside the furnace; it can be
recycled back to the electrorefiner or added to the
salt waste stream. The furnace is then backfilled with
argon gas to atmospheric pressure (or slightly higher)
before the furnace temperature is further increased.
Melting begins when the temperature exceeds
about 1350 C, but processing at 1600 C provides
a 250 C overtemperature that helps dissolve waste
metals into the molten iron and form an intimate
mixture of iron solid solutions and intermetallic
phases as the mixture is allowed to cool. Laboratory
tests have shown the importance of locating the
lower-melting Fe waste on top to flow over the
higher-melting Zr waste. Cooling rates for prototype
waste forms have been about 10 C min1, but fullsized waste forms may cool more slowly. Low cooling rates facilitate solid-state diffusion impacting
the formation of the thermodynamically preferred
phases, but phase changes predicted to occur at
below about 1000 C are not expected to be complete because of slow diffusion. Subsequent heat
treatments of prototype waste forms have shown that
modifications to the phase composition do occur, such
as increasing amounts of intermetallics.21 Ferritic and,
to a lesser extent, austenitic steels are susceptible to
accelerated intergranular corrosion, primarily due to
depletion of Cr near the interface, and this may be
exacerbated by heat treatments. The concentrations of
some waste components may have a similar effect on
the severity of intergranular corrosion in metallic
waste forms.
The aggressive environment created by molten
metal dictates the use of durable materials. Yttrialined graphite crucibles have been used to successfully cast alloys during the development and
demonstration phases of electrometallurgical treatment. These are sufficiently durable in the furnace
environment, but fragile. Developing better crucible
materials is an on-going effort. Waste forms can be
cast directly in these crucibles, but it may not be
practical to pour or drain the molten metal into
separate molds. A steel rod can be inserted into
radioactive cast alloys to simplify both removal
of the waste form from the furnace and loading it
into a disposal canister.
5.20.4.2
Waste Conditioning
Some waste streams contain nonmetallic components

that cannot be immobilized in an alloy. Small
amounts of these contaminants are expected to be
sequestered within slag phases that form on or near
the surface of the waste form, but large amounts will
probably need to be removed prior to alloying. As
described earlier, contaminant chloride salts are
removed from EBR-II metals by distillation within
the furnace. Other waste streams to be alloyed will
likely contain contaminants from the fuel, from
separations operations, from storage containers and
transfer lines, etc. It may be possible to remove some
contaminants within the processing furnace, as is
done with entrained EBR-II salt, whereas other contaminants will need to be removed beforehand. It
may not be possible or worthwhile to remove low
levels of contaminants from the feed. The presence of
some nonmetallic materials may even be desirable to
help immobilize other contaminants, and waste forms
could be formulated to utilize phases to sequester
contaminants. Small amounts of slag were formed in
surface layers 110-mm thick on all SS15Zr materials made for testing during the development of the
EBR-II MWF. These were commonly enriched in C,
O, and, in some cases, N. For example, examination of
the slag that formed during the production of a
SS15Zr material in a graphite casting mold with
scanning electron microscopy (SEM) revealed the
presence of ZrC and ZrO2 inclusions within the
alloy. The alloy associated with the slag was also
enriched in Zr relative to the underlying intermetallic phases. Slags were not detected on Zr8SS materials. This may be due to the higher solubilities of C,
N, and O in Zr(b) than in Fe(g), which are the metal
phases that form initially when the Zr8SS and
SS15Zr materials are produced. These convert to
Zr(a) and Fe(a) as the alloy cools. Contaminants are
less soluble in these phases, but cannot diffuse out
during the phase transition.
515
Slags were formed intentionally on some test

materials by oxidizing the steel (in air) before melting. These were used in tests to measure the durability of the slag, which was found to be similar to
the durability of the alloy. Whereas slags can simply
be removed from industrial metal products, they
must remain a part of the waste form, and their role
in immobilizing radionuclides must be taken into
account in performance models. The presence of a
slag layer will not necessarily be deleterious to the
waste form and could be used to an advantage.
Although metallic radioactive waste forms are likely
to be produced with induction or resistance melters,
blast furnace slags provide insight useful for tailoring
slag phases in waste form alloys. Blast furnace slag
consists of nonmetallic contaminants from the ore
and from additives (e.g., coke and limestone) that
are not incorporated in molten metals but combine
to form slag. The slag is less dense and floats on the
surface of the molten iron where it can be physically
separated from the metal product. Materials are
often added to the mixture to facilitate the formation and removal of slag. Slag is readily skimmed
from the surface of the molten metal or the metal
can be drained from beneath the slag, but slag can
adhere strongly to the cooled metal and be very
difficult to remove. It may be possible to control
the composition of the slag phase to influence both
its physical nature and its capacity to retain radionuclides. The role and benefits of a slag layer remain
to be studied and evaluated.
5.20.5 Testing Objectives

The laboratory tests conducted with radioactive
waste forms can be grouped according to three primary objectives to be addressed by testing: (1) waste
form performance, (2) waste form consistency, and
(3) regulatory acceptance for disposal. These objectives are not independent, since both performance
and consistency must be deemed adequate for disposal, etc., but listing information needs in each
group can help guide the planning and interpretation
of laboratory and field tests conducted.
5.20.5.1 Matrix Degradation and
Radionuclide Release
The key measure of waste form performance is the
rate at which radionuclides are released under the
anticipated range of environmental conditions. Tests
516
are conducted to determine the modes and rates of

waste form degradation and radionuclide release, to
develop a mechanistic model that takes into account
the effects of key variables in the disposal environment, to quantify the effects of environmental variables on the waste form degradation and radionuclide
release kinetics, and to parameterize the model.
Several test methods are needed to highlight particular processes. The initial tests are conducted to determine and understand the processes that control the
release of radionuclides from the host phase and the
degradation of the host phase. The test methods and
testing conditions are selected based on conceptual
models for degradation and release. For metallic phases,
oxidation of the metal is usually the first step followed
by dissolution of the metal oxide. The oxidation of some
radionuclides, such as Tc, may result in the formation
of a species with diffusion-controlled release, such as
TcO
4 . Therefore, the intent of the initial tests should
be to determine whether there is an effect of the electrochemical potential (Eh) or an imposed potential on
the generation and release of soluble species. A separate
set of tests is needed to determine the effects of environmental variables on the degradation and release
rates. These could include temperature, solution pH,
solution or atmospheric Eh, dissolved halide concentrations, groundwater composition, radiolysis products,
etc. The sensitivity of the rates to these variables should
be measured under conditions spanning the anticipated
values of the disposal system to ensure that the model
bounds the modeled environment. How the dissolution
step is coupled with the oxidation step, if this is indeed
the mechanism, should also be determined.
Although a fully mechanistic model is desired, it is
usually not possible to fully describe the waste form
degradation and radionuclide release based on atomistic and theoretical understanding. Instead, empirical models are usually required to describe some
aspects of the observed corrosion and degradation
behavior. For example, although the effect of Cl
on steel corrosion is well known, quantifying the
effect of the Cl concentration on the measured
release of Tc will probably require an empirical
model supported by a series of laboratory tests. To
the extent possible, the tests used to measure the
dependence should be based on an understanding of
the effect so as to highlight its impact on the test
response. Some degree of coupling in the measured
parameter values is unavoidable, such as temperature
and pH. Separating the effects of temperature and
pH neglects the possible dependence of the activation energy on the pH.
After the model has been developed, it should be

validated using tests other than those used to develop
and parameterize the model. Validation is intended to
show that the model adequately represents the process determined to control waste form degradation
and radionuclide release under relevant conditions.
Separate confirmation tests may be needed to demonstrate that the mechanism that is being modeled is
appropriate for the integrated disposal system.
The computational requirements for atomistic
and detailed mechanistic models usually exceed the
capabilities of repository assessment calculations.
Simplified (abstracted) models that represent the
effects of environmental conditions and the degradation and release rates are used instead. Confidence in
the predictions using simplified models is based on
the underlying mechanistic models and, usually, conservative aspects built into the simplified model.
Performance assessment calculations are usually
based on reactive transport models in which radionuclide release due to waste form degradation is treated
as a source term that is coupled with expressions for
groundwater flow, diffusion, sorption, and other relevant transport processes (vapor transport, diffusion
through thin films of water, etc.) in equations expressing conservation of mass and conservation of energy.
These are used to calculate contaminant transport
over time under a range of conditions to determine
dose to individuals under various scenarios such that
the impact of the radionuclide release on the calculated dose depends on many other factors. Depending
on the approach taken for risk assessment, a specific
performance requirement might not be assigned for
radionuclide release or waste form degradation rates.
Specific performance requirements were not assigned
to waste forms for the Yucca Mountain total system
performance assessment, but are specified for lowactivity waste glasses in the performance assessments
for the Hanford disposal system, which includes glass
and grouted waste forms.
5.20.5.2 Waste Form Consistency Through
Process Control
Consistent waste form behavior is of primary importance for waste form acceptance. Performance assessment calculations will relate regulatory dose limits to
radionuclide release rates, which will be related to
waste form composition (and phase composition) by
the source term model(s). Confidence in the performance assessment relies on confidence in the waste
form composition, which must be controlled during
production. Important aspects of a metallic waste

form composition might include the domain sizes of
the component phases, the degree of mixing, the
fraction of slag phases, etc. Process controls might
include the amounts and chemical compositions of
the feed materials, both the wastes and additives, and
particular processing conditions, including the mixing and loading of the feed materials, the heating
schedule (temperature, time at temperature, cooling
rate, heat treatment, etc.), furnace atmosphere, and
crucible material. The operating range of each processing variable that results in consistent waste products must be determined based on its direct impact
on the component phases that form and the distributions of radionuclides (and the indirect impact on
performance). The relationships that must be established by testing and modeling are summarized
in eqn [1].
Production control $ Phase composition
control $ Matrix degradation rate
control $ Radionuclide release
control $ Acceptable performance
1
Ultimately, the processing limits must be related to

the performance of the disposal system, usually
through the release rates of radionuclides contributing to the regulated dose. In the performance assessment calculations, transport through natural and
engineered barriers can decrease the dose contributions of some radionuclides at the point of interest so
that the radionuclide that is released the fastest or to
the greatest extent may not have the greatest impact.
For example, a low solubility limit and strong adsorption to mineral phases retard the transport of plutonium isotopes and their impact on total dose at a
regulated point. The relative impact of Tc may be
greater regardless of the relative amounts of Pu and
Tc released from the waste form due to the high
solubility and negligible transport retardation of the
pertechnetate ion in an oxidizing environment.
5.20.5.3 Waste Form Acceptance and
Regulatory Requirements
In the United States, regulatory requirements include
compliance with Nuclear Waste Policy Act, as
amended, and dose limits specified by the US Environmental Protection Agency for disposal systems.
Disposed waste is also subject to hazardous waste
regulations, including the Resource Conservation
517
and Recovery Act (RCRA). Additional safeguard and

security requirements may be added in the future.
Although waste form acceptance ultimately occurs
through a US Nuclear Regulatory Commission
license for a facility to receive and dispose waste,
separate acceptance criteria may be established
between various DOE agencies responsible for producing, characterizing, packaging, licensing, and disposing the waste forms. In general, the acceptance
criteria are intended to provide assurance that the
chemical, physical, and radiological performances of
the waste form are such that the disposal system will
meet regulatory requirements over its service life as
predicted by performance assessment calculations.
These are obviously closely related to the degradation
behavior of the waste form (and radionuclide release),
the radionuclide inventory, and the disposal environment. For example, the DOE Office of Civilian Radioactive Waste Management has provided the Waste
Acceptance System-Requirements Document22 to
address the acceptance of commercial spent nuclear
fuel, DOE-owned spent nuclear fuel, naval spent
nuclear fuel, and high-level radioactive waste for disposal in the planned Yucca Mountain repository.
Requirements are described in that document for
the waste form materials, such as phase composition,
radionuclide content, product consistency, and chemical durability; for the canistered waste forms, such as
criticality and thermal outputs; and for the canisters
themselves, such as material, dimensions, maximum
weight, labeling, handling fixtures, required levels of
surface decontamination, etc. Although most of these
requirements are not regulatory requirements, they
provide insight into additional issues that should be
considered when designing a testing program.
5.20.6 Modeling
Modeling activities should be integrated with testing
activities at the earliest stages of developing test
plans. The initial model will probably be a conceptual model based on the identity of the waste stream
and matrix material, the expected material alteration
modes based on literature surveys, anticipated environmental conditions for the disposal system, and
insights from the behaviors of available analog materials. Testing and modeling should evolve iteratively
as test results are collected and the model is modified.
When the model progresses to the point of predicting degradation behavior, validation tests should
be conducted for direct comparisons with model
518
predictions. Other tests are needed to confirm that

the modeled process is operational under disposal
conditions. Eventually, the validated and confirmed
model is adapted for use in performance assessment
calculations.
An important aspect of the performance model is
correlation of the phase composition to performance.
For homogeneous glass waste forms, the chemical
composition can be directly related to performance
through the glass dissolution rate. For multiphase
alloyed waste forms, performance will probably
depend on the assemblage of alloyed phases that
form and the distribution of radionuclides. The
more complicated corrosion mechanism of alloys is
an added challenge to modeling and to demonstrating
process control of waste form performance.
5.20.6.1 Matrix Corrosion and
Radionuclide Release Mechanisms
A mathematical model is required to represent the
release of radionuclides from the waste form to become
available for transport through the disposal system as a
function of time. Release may occur by diffusion of
radionuclides out of the waste form or by degradation
of the waste form matrix and phase(s) that contain the
radionuclide. A mechanistic model that takes into
account the key processes in waste form degradation
and radionuclide release will provide maximum confidence to long-term predictions and performance assessments. Rate equations have been developed for
various release models, including constant dissolution
rate models, concentration-dependent models, reaction affinity models, and diffusion-controlled release
models. Empirical rate expressions have been developed based on detailed measurements.
An approach for developing a source term model
for waste forms is provided in ASTM Standard C 1174
Prediction of the Long-Term Behavior of Materials,
Including Waste Forms, used in Engineered Barrier
Systems (EBS) for Geological Disposal of High-Level
Radioactive Waste.4 This standard provides a philosophy and logic that can be followed to develop a performance model by integrating testing and modeling
activities. It stresses the importance of a clear definition of the problem, characterizing the disposal environment, maintaining interfaces between testing and
modeling to evolve the model based on test results and
design tests based on model predictions, using analog
materials and systems, and both validating the fidelity
of the model to the mechanism and confirming the
appropriateness of the model for the disposal system.
A variety of test methods is needed to understand

the degradation mechanism of a waste form material
and how environmental and engineering factors will
affect the releases of important radionuclides, and to
develop and parameterize a performance model. Many
of the information needs related to waste form processing and waste form acceptance require an understanding of the corrosion mechanism. It is usually
wise to address aspects of the mechanistic, environmental, and engineering system early in a testing
program to gain confidence that all the important
factors are being taken into account in the model. As
the mechanistic understanding develops, other aspects
of waste form behavior that must be investigated usually become apparent. The general information needs
for developing a performance model are summarized
as follows.
Identify the radionuclide release mechanism: The objective is to determine whether each radionuclide is
released stoichiometrically as the matrix degrades
or whether separate models are required. In most
cases, these tests will serve to confirm the release
mode based on an understanding of the matrix material and how the radionuclide is incorporated. For the
various waste forms being developed for reprocessing
wastes, the release of radionuclides may be controlled
by diffusion (leaching), congruent dissolution of the
matrix, or degradation of the matrix to expose the
sequestering phase that contains the radionuclide,
which could then dissolve, be leached of radionuclides, be released as a colloid, etc. Release may
require prior oxidation of the sequestering phase
and/or the radionuclide itself, as is expected for Tc
in a metallic waste form.
Characterize the matrix degradation mechanism: It is
expected that the release of radionuclides will be
affected physically or chemically by the degradation
of the waste form matrix. Degradation of the matrix
may be required before a radionuclide can be released; it may simply need to be physically or chemically altered rather than dissolved. For some of the
multiphase waste forms considered for reprocessing
wastes, dissolution of an encapsulating phase may be
required before water can react with the phase bearing the radionuclide. Radionuclide release will be
affected by both the radionuclide-bearing phase
and the host matrix. These could degrade by different mechanisms, for example, in the case of an oxide
phase encapsulated in a metal matrix.
Characterize the effects of environmental variables: The
release rates of radionuclides and the degradation
rates of matrix materials will probably be affected
directly by environmental variables such as temperature and the groundwater chemistry (pH, Eh, dissolved
component concentrations, etc.) and indirectly by
sorption onto colloids, minerals, and engineering
materials in the disposal system. The groundwater
chemistry may change significantly due to interactions
with engineering materials and waste form degradation. Tests generally need to be conducted under
conditions exceeding the expected range of values
for environmental variables to initially determine and
model the dependency and then to verify that the
mechanism remains operative over the anticipated
range of disposal conditions. A variable that affects
the degradation of a waste form but is not tracked in
performance assessment calculations can be captured
using another variable that is tracked or through the
uncertainty ranges of coefficients in the rate equation.
Develop a degradation model that accounts for environmental variables: If possible, the dependence of the
degradation rate or radionuclide release on each
environmental variable that affects the rate should
be modeled mathematically according to the mechanism. It may be beneficial (or necessary) to combine
the effects of two or more variables in a bounding
semiempirical model rather than modeling each
explicitly. This may be necessary if factors cannot
be distinguished in tests or practically differentiated
by modeling. Residuals from fitting the test data using
separate dependencies will include the effects of
cross terms, and the interdependence will be taken
into account through both the regressed values and
the uncertainties.
Consider waste package interactions: The effects of
the waste package materials on the groundwater
chemistry, transport of released radionuclides, etc.
must be considered in performance assessment calculations. Although these are taken into account separately from waste form degradation in performance
assessments, the interactions that affect the groundwater prior to contacting the waste form should be
considered when defining the range of environmental
variables to be represented in tests. Standardized test
methods routinely call for control tests and/or blank
tests in which interactions of test solutions, dissolved
components, and test specimens with vessels and
supports are measured and taken into account in
analyses of the test data. Interactions between metallic waste forms, waste packages, and engineering
materials need to be evaluated, such as Galvanic
coupling, and taken into account in models. Alloyed
waste forms should not serve as sacrificial anodes for
other metallic components in the disposal system.
519
Measure model coefficients: The same test methods

used to characterize the effects of environmental
variables often provide data that can be used to
determine the values of model coefficients. To measure model coefficient values, the effects of variables
other than the one being quantified must be held
constant or reliably taken into account when evaluating the results. Typically, this involves conducting a
series of tests in which the values of all variables are
held constant, except the variable of interest. Such
tests can be conducted at constant temperature, in
pH-buffered solutions, with spiked leachant solutions, in controlled atmospheres, etc. It is important
that the measured coefficients are appropriate over
the anticipated range of conditions in the disposal
system, and it is possible that different coefficient
values could be required for specific ranges if the
degradation mechanism changes.
Model validation: The intent of model validation is
to demonstrate that the mathematical model adequately represents the particular process of interest,
be it oxidation, diffusion, radionuclide release, or
matrix degradation. A model is considered validated
if it predicts responses consistent with the results of
separate tests that were not used for model development or parameterization with an acceptable range.
The validation test should focus on the specific process being modeled and the measured response
should be sensitive to that process. For example, if
diffusion-controlled release from a solid is being
modeled, the validation test should be conducted
under conditions that avoid saturation in the contacting fluid. The effects of other processes are considered in model confirmation tests.
Model confirmation: The intent of model confirmation is to demonstrate that the process represented in
the degradation model controls the waste form
behavior under the range of conditions and other
interactions expected in the disposal system. Confirmation tests generally couple the modeled process
with other system processes that could affect waste
form behavior. Model confirmation cannot be completed until the disposal system is identified and
characterized. However, aspects of potential disposal
systems likely to affect waste form behavior should be
taken into account when developing the model,
including the groundwater chemistry and flow characteristics, interactions with engineering materials
and the host geology, radiation fields, etc. In most
cases, the laboratory tests used to determine waste
form corrosion behavior must subject the test specimen to more aggressive conditions than those
520
expected in a disposal system to generate a measurable response. For example, the dissolution of a waste
form due to contact by groundwater may have been
modeled using the results of static immersion tests,
whereas the disposal system is hydrologically unsaturated. A possible model confirmation test would be
to expose the waste form to intermittent contact by
dripping water to see how well the model represents
degradation under these conditions. Other test methods that could be used include vapor hydration tests
to simulate contact by vapor and unsaturated flow
tests to simulate intermittent contact with flowing
water. The responses of model confirmation tests
will usually be too complicated for use in determining mechanisms for specific processes. This is
because they will be affected by several processes
acting simultaneously. They provide data that are
responses to several interacting processes that must
be taken into account in the model either directly
through model variables or the ranges of model
coefficient values. Nevertheless, such tests can provide confidence in the testing process that the correct process is being modeled early for a particular
environment.
5.20.6.2
Performance in Disposal System
As with the waste form degradation and radionuclide

release model, performance assessment models based
on a mechanistic understanding of processes affecting
the spread of radionuclides through engineered and
natural barriers would provide the highest confidence.
This is usually not possible because of the complex
pathways and interactions affecting transport. Instead,
transport models use effective distribution coefficients
to model complex interactions with various minerals
in the soil, including reversible and irreversible sorption to fixed and mobile substrates, effective flow rates
for advection through fractures and along grain
boundaries, diffusion and dispersion, etc. Small variations in temperature and water content spatially and
temporally are neglected, but large variations can be
modeled by separating the regions of interest into
several cells that can be assigned different characteristic values.23
The solute transport models that have been developed for environmental impact analyses generally
include equations to account for water infiltration
rates through the system, source term release rates
for important nuclides, and solute transport rates
through the geologic media. Based on the conservation of mass for a transported radionuclide, the
dependence of the change in concentration C with

time on these factors is written as
@C
@C
@2C X
Qn r
n D 2
@t
@x
@x
n
2
Reactive transport models usually only consider

transport in the direction of flow (x in this example),
except for dispersive effects.23,24 The first term on the
right-hand side represents advective transport, where
n is the groundwater velocity, and the second term
represents dispersive transport. The dispersion coefficient, D, is sometimes written as the sum of
an effective diffusion coefficient for the geologic
medium and
Pthe coefficient of mechanical dispersion.
The term n Qn represents the sum of the effects
from each of the n processes that affect the solution
concentration C, which may include waste form degradation, leading to radionuclide release (the source
term), sorption, colloidal and secondary phase formation, and several other processes depending on the
species of interest and the disposal system. The value
of C is usually constrained in models by a speciesspecific solubility limit. The fourth term in eqn [2], r,
takes into account the in-growth and decay of the
radionuclide of interest.
Most transport calculations for contamination
assessments include transport through hydrologically
unsaturated (vadose) zones. A dimensionless volumetric moisture content y can be included to represent the fraction of the total pore volume available in
the medium that is occupied by water, and C can be
replaced in eqn [2] by the product Cy. This simply
scales the solution volume by the moisture content.
The radionuclide release model provides the
source term Q used in the transport model. Depending on the form of the rate equation for radionuclide
release from a metallic waste form, its integration
into a reactive transport expression may require additional terms to represent electrochemical processes.
5.20.6.3
Processing Control
The ability to maintain acceptable waste form performance (the retention of radionuclides) using
processing controls must be demonstrated by establishing a correlation between the assemblage and
compositions of alloy phases in the waste form and
waste form performance measured in laboratory tests.
The correlation should have a mechanistic basis,
and, ideally, the dependence of the performance
on the phase composition should be quantified and
parameterized in the degradation model. This may

not be possible because waste form performance cannot be measured with a single test method. Instead,
a test method having a response that is correlated
with the performance of the anticipated range of
waste form compositions can be used to represent
the relative performance. In the case of high-level
waste glasses, the Product Consistency Test (ASTM
method C 1285)4 is used to correlate performance
with composition; the response in that test is used by
DOE to identify acceptable waste glasses.22 The use
of an analogous approach for metallic waste forms
will require the identification of a test method and
development of a correlation model that can be
related to the performance model. These will then
allow processing limits to be established for producing acceptable waste forms, such as waste loadings,
additives, and processing temperature.
5.20.7 Test Methods

A variety of test methods is required to understand
the corrosion behavior of metallic waste forms, measure the kinetics of various processes, and accelerate
corrosion to simulate aspects of long-term degradation. The degradation rates of well-designed waste
forms should be difficult to measure under anticipated service conditions if they effectively retain
radionuclides. Test conditions that differ significantly from the service conditions are often required
to produce a measurable test response or measure the
effect of a variable. Relating the corrosion occurring
under extreme test conditions to service conditions
usually requires an understanding of the corrosion
mechanism, even though an understanding of the
mechanism is often the objective of the tests. Testing
and modeling to determine the corrosion mechanism
should be coordinated and iterative activities. The
selection of initial test methods should be based
on a conceptual model and hypothesized mechanism, both of which should be developed from literature reviews and considerations of possible analog
materials. In the case of metal waste forms, experience with steel corrosion provides a logical starting
point. The initial tests should be conducted to evaluate the hypothesis and conceptual model, and both
the conceptual model and the suite of tests should
evolve as new data are collected.
The degradation of a metal waste form and subsequent release of radionuclides is hypothesized to
involve oxidation reactions to convert the metal
521
components to oxides and hydrolysis reactions to

dissolve the oxides. Diffusion of oxygen through the
evolving oxide layer is another important process
required to continue the corrosion. It is likely that
the oxidation, dissolution, and diffusion processes
may each control the radionuclide release rate at
some point and under some reaction conditions.
Components might be released as quickly as the
metal surface is oxidized early in the reaction but
slow as an oxide layer develops and slowly dissolves.
The oxide layer will likely serve as a diffusion barrier
to oxygen, such that diffusion rate controls the
continued corrosion rate. Passivation of the surface
(of each component phase) may occur to prevent
further corrosion, or the layer could become thick
enough that the mismatch between the metal surface
and the crystalline oxide layer causes the layer to
spall off the metal surface and corrosion resumes. To
characterize this hypothetical corrosion mechanism,
separate test methods would be needed to highlight
the oxidation reactions, the dissolution reactions,
and the long-term stability of a passivating layer.
The majority of test methods and techniques developed by industry for metal corrosion address shortterm behavior (surface oxidation, pitting, passivation,
etc.) related to the service objectives, whereas the
release of radionuclides to the solution over very
long corrosion times is of primary interest for alloys
used as waste forms. The oxidation of metal components will have no effect on waste form performance
until transportable radionuclides are released to solution, either by dissolution or colloid formation. Many
of the tests used to study the degradation of glass,
minerals, and ceramics address the effects of the solution chemistry on the dissolution reaction. These materials dissolve by an affinity-controlled mechanism that
is sensitive to the accumulation of components in the
solution. The effect of the solution chemistry on the
degradation of metals is not expected to be as significant because the most abundant components (e.g., Fe
and Zr) are sparingly soluble in most solutions and will
have a very limited dissolved concentration range.
Nevertheless, similar test methods are needed to
study dissolution of the oxide layers resulting in radionuclide release and diffusion (e.g., of oxygen) through
the layers. Passivity is usually investigated by studying
the nature of the films that form and the kinetics of the
electrochemical processes. Corrosion tests in which
specimens are immersed in solution or contacted by
steam can be used to measure the release of components to solution and generate oxide layers for detailed
examination. Electrochemical tests can be used to
522
measure the kinetics of processes taking place on clean

surfaces. Several useful electrochemical and corrosion
test methods are discussed in the following sections.
5.20.7.1
Electrochemical Test Methods
Metal corrosion by oxidation reactions is conveniently and efficiently measured with traditional
electrochemical techniques.25,26 These include construction of potentiostatic curves (anodic and cathodic charge curves), studying potential shift curves
and double-layer capacity, electrochemical impedance spectroscopy, etc. Measurements can be conducted at a range of temperatures and in various
solutions to determine and quantify the effects of
many environmental parameters on the oxidation
rate, such as pH and the presence of various solute
species, and combined effects such as the Cl concentration and critical pitting temperature for various
alloy formulations. Electrochemical techniques used
to determine corrosion rates utilize the corrosion current to calculate the corrosion current density, corrosion intensity, and corrosion penetration rate. The
current that is passed upon application of an external
potential can be related to the mass of material reacted
using Faradays law and then expressed as a rate using
the reaction time and specimen area. This gives the
reaction rate in terms of the current density. The
polarization resistance can be determined from a plot
of the applied potential against the current and can be
related to the current density by the anodic and
cathodic Tafel constants for the material. The corrosion rate of the material can be calculated from the
current density and the density and atomic weight of
the metal (or the equivalent weight of an alloy). This
gives the rate for uniform corrosion (oxidation) of a
bare metal or alloy surface. If the corrosion is localized
rather than uniform, the penetration rates at particular
sites can be orders of magnitude higher than the
average value. Some of the reacted specimens should
be examined to look for areas of localized corrosion
(pitting). Because the data analysis techniques require
extrapolating measured curves, the accuracy of the
experimental measurements is crucial to the calculated rates and their sensitivity to the compositions
of the alloy and the solution. Standardized procedures
should be followed whenever possible.
The ASTM procedure Standard Test Method for
Conducting Potentiodynamic Polarization Resistance
Measurements (G 59) provides a standardized method
for measuring corrosion potentials and potentiodynamic polarization resistance for determining the
general corrosion rates of metals.27 A small potential

scan near the corrosion potential of the metal is
applied to a sample and the resulting currents are
measured. Tests conditions can be varied to study
the effects of temperature, pH, dissolved O2, solution
composition (e.g., oxidizers), etc. Potentiodynamic
measurements (in general) provide a convenient comparison of the oxidation behaviors of various metals
and alloys, and a rapid and economical approach for
studying the oxidation step of the corrosion mechanism. Interpretation of the measurements requires
assumptions regarding Tafel slopes and equivalent
weights of alloys.
A galvanic cell is formed when two (or more)
metals or alloys having different polarization resistances are coupled and in contact with an electrolyte
solution, including the separate phases in a multiphase alloy. In such a system, the least stable material
will act as the anode material and corrode in preference to the other materials, which will act as cathodes. Galvanic couples can also form between waste
form phases and engineering materials such as waste
canisters. Obviously, radionuclide-containing alloy
phases should not serve as the anode of a galvanic
couple; rather, such phases should be protected by
phases without hazardous components. Galvanic
couples with sacrificial anode materials are used
extensively to protect other metals, such as steels
galvanized with zinc and iron anodes in residential
water heaters. It may be possible to add such a phase
as part of the waste form to protect radionuclidebearing phases, but it is crucial that radionuclidebearing phases do not act on the anode.
The ASTM procedure Standard Guide for Conducting and Evaluating Galvanic Corrosion Tests in
Electrolytes (G 71) addresses conducting and evaluating galvanic corrosion tests.27 The standard
addresses selection of materials and preparation of
test specimens, selection of test conditions (electrolyte, materials coupling, atmosphere, duration, etc.),
and the evaluation of test results. Galvanic corrosion
measurements provide insights into likely materials
interactions, including interactions between different
phases within an alloy and between an alloyed waste
form and the waste canister material. Microscopic
examination of the specimen before and after analysis
can provide confirmatory evidence of the relative
durabilities of the components phases, although test
results are sensitive to specimen preparation and
electrical contact.
Several other standardized test methods, practices, and guides are available for conducting and
evaluating electrochemical measurements, and consensus standards should be followed when available
and appropriate. Besides providing the benefits of
experience, standardized methods often provide reference test results for comparisons and quantify testing bias. For example, the ASTM standards G 1, G 3,
G 5, G 15, G 50, G 60, and G 102 provide helpful
insights into preparing specimens, conducting electrochemical tests and measurements, and interpreting test results.27
5.20.7.2
Corrosion Test Methods
Corrosion tests are used to study the release of waste

form components into solution during waste form
degradation. Many corrosion test methods have
been developed to study the dissolution of oxide
materials, such as glasses, that do not require a preceding oxidation step. These methods can be applied
to a metal waste form, but the results may be complicated by the coupled oxidation reactions and depend
on whether the metal test specimen is grounded or
insulated.
The ASTM procedure Standard Practice for Laboratory Immersion Corrosion Testing of Metals
(G 31) provides a standardized method for directly
measuring mass loss in laboratory immersion tests
to determine the general corrosion rates of metals.27
Conditions that may be controlled include test duration, temperature, pH, oxygen concentration, solution
flow, solution composition, and solution concentration.
This procedure addresses factors important to sample
preparation, test conditions, methods of cleaning specimens, and cautions regarding the interpretation of test
results that are relevant to any test method.
The relative contributions of generalized corrosion
cannot be distinguished from localized or intergranular corrosion based on the mass loss alone. Although
the mass can increase due to the formation of oxide
surface layers or decrease as the layers dissolve, the
corrosion products are removed from reacted specimens prior to weighing in the ASTM G 31 procedure.
Simply tracking the mass change in test specimens will
not be sufficient to understand the corrosion mechanism, but other analyses can be conducted to gain
insight into the corrosion behavior, such as microscopic examinations of reacted specimens to detect
pitting and identify corrosion products.
The ASTM Test Method for Static Leaching of
Monolithic Waste Forms for Disposal of Radioactive
Waste (C 1220) provides a standardized method for
measuring the mass of a monolithic test specimen
523
that has dissolved into solution under static conditions.4 The test results are sensitive to the corrosion
behavior of the waste form with little feedback from
dissolved components occurring in short-term tests.
The geometric surface area of the specimen can be
measured to allow accurate calculation of the specific
release rate of soluble components. The test is easy to
run, can be conducted under a wide range of conditions, provides sufficient solution volumes for analysis, and is economical. Only small volumes of waste
solution are generated. Short-term tests can be used to
measure the effects of temperature, pH, and components in the leachant on the release rates. Responses
may become affected by the chemical affinity of the
solution in long-term tests. Aspects of ASTM G 31
regarding specimen preparation and cleaning should
be followed when conducting ASTM C 1220 tests with
metallic specimens.
Two important variations of ASTM C 1220
involve interrupting the test intermittently to recover
solution for analysis: the partial replacement test and
the solution exchange test. In the partial replacement
test, a small portion of the solution is removed for
analysis and replaced with fresh leachant solution.
This allows the extent of reaction to be tracked in
an otherwise static test, but dilutes the remaining
solution slightly. The impact of diluting the solution
is usually negligible in tests with metallic specimens
because dissolved components do not affect the continued corrosion to a significant degree. The entire
volume of solution is replaced with fresh leachant in a
solution exchange test. Solution exchange can have
a significant effect on metal corrosion due to opening
the vessel to refresh the air and oxygen content.
Replacing the entire solution volume will also
replace all the dissolved oxygen (assuming that the
added solution is air saturated), whereas partial
placement will only replace a small fraction of the
dissolved oxygen. This will be important for oxidation reactions forming oxide layers. In addition, solution exchange will re-establish the initial pH, but
partial replacement will allow the pH to drift as the
specimen corrodes.
ASTM Standard Test Method for Diffusive
Releases from Solidified Waste and a Computer Program to Model Diffusive, Fractional Leaching from
Cylindrical Waste Forms (C 1308) provides a standardized method for solution replacement tests that
should be consulted prior to running a modified
ASTM C 1220 test.4 The test conditions specified
in the standard are better suited to rapid release from
grouted waste forms than slow release expected from
524
metallic waste forms, although long-term tests at

elevated temperatures could lead to measurable test
responses.
The vapor hydration test (VHT) is a static test in
which a monolithic specimen is suspended in a
sealed vessel with a small amount of water.28 When
heated (typically in the range 125200 C), the
vapor phase becomes saturated and a thin film of
water condenses on the specimen. The specimen
temperature rises more slowly than that of the test
vessel and provides the coolest surface when the test
is initiated. As the specimen corrodes, the condensed
solution usually becomes hygroscopic, so the thin
film of water remains on the test specimen even
after thermal equilibrium. In the standard VHT, the
amount of water added to the vessel is carefully
controlled so that a condensed layer forms on the
specimen but no liquid water remains in the vessel to
establish a reflux cycle. Alteration of the reacted sample can be analyzed and thickness of the altered surface layer measured on a cross-sectioned specimen.
This method has been used to promote the formation
of oxide layers on metallic specimens for microscopic
investigations.
Neither the actual acceleration factor nor the
chemistry and the volume of the solution contacting
the specimen during reaction are known in VHTs.
The test response is sensitive to the volume of water
that condenses on the specimen, which cannot be
controlled accurately or measured during the test.
The extent of corrosion can be estimated based on
the amounts of alteration phases that formed. However, the VHT is not well suited for quantifying
corrosion rates, because the precision of the test
(i.e., the amounts of alteration phases formed) is usually poor. The consistency of the corrosion mechanisms at the relatively high temperatures at which most
VHTs are performed and at temperatures relevant to
disposal environments must be established to extrapolate VHT results to service conditions.
In a modification of the VHT, enough water is
added to promote refluxing during the test to flush
components released from the specimen to the bottom of the vessel. The test is interrupted intermittently to recover and analyze the solution and track
the release of waste form constituents. This modification is similar to a Soxhlet test,29 except that water
vapor condenses on the sample itself rather than in a
separate condenser and maintains an adhering layer
of water on the sample rather than filling a sample
boat. The modified VHT method has been used to
measure the release of U from metallic specimens

(see Section V.C.3 in Ebert).18
5.20.7.3
Service Condition Test Methods
The electrochemical and corrosion tests discussed

earlier are usually conducted to understand the corrosion mechanism and to develop and parameterize a
degradation model. The test conditions that are used
are typically very different than the environment that
will exist in a disposal system (referred to as the
service conditions). Most laboratory tests are conducted by contacting a small metal surface area with a
large volume of water to highlight alteration processes or at elevated temperatures to promote corrosion and facilitate measurements. The service
conditions of most disposal sites will be restricted to
small volumes of water and thin films contacting
small waste form surface areas. Metallic waste forms
will likely not be thermally hot due to the low activities expected in amenable waste streams (e.g., those
given in Table 2).
The effects of limited groundwater volumes on
waste form degradation have been studied in laboratory tests in which groundwater is periodically
dripped onto crushed material or a monolithic specimen and in tests where a mixture of water and air is
passed through crushed material. The unsaturated
test was developed to simulate small volumes of
groundwater dripping through a breached waste container onto spent fuel or HLW glass.30 The water
collects on and reacts with the specimen, and occasionally drips off the specimen into the bottom of the
test vessel. The accumulated solution is collected and
analyzed periodically to track the release of radionuclides. The pressurized unsaturated flow test was
developed to simulate disposal in a hydrologically
unsaturated environment.31,32 A mixture of water
and air is pumped through a column of crushed
materials that may include soil, rock, waste form,
and backfill materials to simulate a disposal system.
Water interacts with these materials as it flows
through the column, and the effluent chemistry is
tracked during the test. Changes in the solids due to
dissolution and precipitation of secondary phases can
be measured at the end of the test.
Column tests are commonly used to simulate
groundwater interactions with soils and minerals to
measure dissolution rates, distribution coefficients of
contaminants, transport parameters, etc.33,34 Column
tests can be conducted in the laboratory to control
test conditions, such as temperature, water content,

and flow rates, and to simplify sample collections.
Column tests are also conducted in the field using
lysimeters.3538 Lysimeters are simply columns
placed in the ground and filled with soil (sand, rock,
etc.) of interest. Containers and probes can be placed
at the bottom and various intermediate locations to
analyze and collect groundwater that passes through
the column. The top of the lysimeter can be left open
to allow meteoric water (rain and snow) to enter and
flow through the lysimeter or intermittently covered to regulate the amount of water entering the
lysimeter. Waste form corrosion can be coupled with
transport by emplacing one or more waste form specimens within the soil. The waste form specimens and
adjacent soil can be recovered for analysis after testing.
Finally, materials can be simply buried in the soil
and allowed to corrode naturally with no attempt to
control, collect, or analyze the groundwater. Examples of this are underground corrosion studies conducted by US National Institute of Standards and
Technology (NIST), formerly the National Bureau
of Standards, such as the corrosion of stainless steels
buried in various soils in the early 1970s.20 These
studies were focused on the corrosion effects on the
specimens, such as etching, blistering, cracking, and
pitting, which are important for steels used as canisters (see Sullivan39), but less so for steels used to
immobilize radionuclides that are components of
the alloy or solid solution.
5.20.8 Tests with INL MWF

Electrometallurgical treatment is being used to condition used sodium-bonded fuel from the EBR-II
reactor for disposal as high-level radioactive
waste.9,12,40 Waste forms have been developed for
the salt and metallic wastes resulting from the electrorefining process. The development of the waste
form for metallic wastes is summarized in the following sections as an example of formulating and testing
an alloy to address performance and processing
issues, and development of a degradation model.
A few key results are provided here; a more extensive
summary of the test results and full bibliography are
provided in Appendix B of Ebert.18 Detailed analyses
of the alloy structure and phase composition provide
a crucial link between the consistency of the metallic
waste form maintained by process controls and the
performance of the waste form in the disposal site as
525
modeled in assessment calculations and utilized for

waste acceptance. Of course, the waste form performance reflects the combined behavior and interactions between all the component phases, which are
not modeled individually for the MWF.
5.20.8.1 Formulation and Phase
Compositions
Two alloy compositions were identified as potential
waste forms to immobilize waste streams that were
dominated by stainless steel or Zircaloy cladding
hulls. These target compositions were selected to
maintain consistency in the phase compositions for
the fairly narrow range of waste stream compositions
and simplify the waste form qualification process.
The binary FeZr phase diagram41 was used as a
guide for waste forms made by alloying stainless
steel and Zircaloy claddings with the metallic
wastes.17 An eutectic exists at about 84.9 mass% Fe
and 15.1 mass% Zr with a melting temperature of
1337 C, whereat Zr6Fe23 and g-Fe are predicted to
form. A maximum processing temperature of 1600 C
was desired to allow use resistance or inductively
heated furnaces.
Alloys having various proportions of steel and Zr
were made for analysis, and the microstructures,
likely distribution of radionuclides, and durabilities
of these materials were studied. Steel-dominated compositions from SS5Zr to SS42Zr and zirconiumdominated compositions from Zr50SS to Zr8SS
were studied. The analog of the Fe15Zr alloy was
selected as target composition for waste streams dominated by steel cladding hulls based on phase composition, chemical and physical durability, and processing
considerations. The analog of the Zr8Fe alloy was
identified as a possible target composition for waste
streams dominated by Zircaloy cladding hulls. Both
mixtures result in alloys having similar amounts
of metallic and intermetallic phases but with one
important difference: the metallic waste components
in the fuel (Zr, Mo, Ru, Rh, Pd, Tc, etc.) and other
metals in the cladding (e.g., Cr and Ni) form solid
solutions in iron but are essentially insoluble in zirconium. Whereas the Fe-dominated alloys include
an iron solid solution phase that serves to encapsulate the intermetallic phases in a physically durable
monolithic waste form, the Zr-dominated alloys comprise loosely aggregated intermetallic phases without
a binding metal phase. Because the initial focus was
on steel-clad fuels, only the SS15Zr mixed alloy
526
was developed as a waste form for EBR-II wastes.

However, these initial results suggest that a Zrdominated mixed alloy that is not well consolidated
will not be useful as a waste form.
5.20.8.2
Steel
Radionuclide Distribution
The likely distributions of many elements in the

component phases of the mixed alloy can be inferred
from well-established binary phase diagrams, but the
distribution of the radionuclides from the fuel in
these phases must be measured because they are
less studied and more important to performance
than other waste components. Several SS15Zr
materials were made to study the dispositions of Tc
and other radionuclides in the component alloy
phases. The behavior of these radionuclides during
corrosion was also measured for some of these materials. The results of tests and analyses with the materials made during development of EBR-II MWF
alloys (both with and without added radionuclides)
provide valuable insight into potential waste forms
for the other waste streams that could be generated in
the aqueous and pyrochemical processes.
Samples of SS15Zr were prepared with various
amounts of added U, Np, Pd, Ru, and Tc. The
capacity of the MWF to incorporate U is of interest,
whether U is present as a contaminant or is added
intentionally to down-blend 235U to below 20 mass
%42 to meet criticality limits. The backscattered
electron SEM image of a SS15Zr11U mixed
alloy in Figure 1 shows U to be concentrated nonuniformly in the intermetallic phase.43 The darkest
phase is the iron solid solution, the gray phase is the
intermetallic phase without U, and the white phase
is the intermetallic with U. Note the intimate mixing
of the iron and intermetallic phases on a 100-mm
scale. The polytypes detected in MWF materials
during analyses are noted later, although the effects
on performance are not known. Intermetallic phases
with the general formula AB2 are commonly referred to as Laves phases; the A and B sites are
usually occupied by several different elements in the
Laves phases formed in the MWF. For example, the
Fe sites in ZrFe2 are occupied by various amounts
of Fe, Cr, and Ni in the MWF materials that have
been studied by McDeavitt and coworkers.17 Some
of the intermetallic phases can exist in cubic, hexagonal, and dihexagonal structures depending on the
packing arrangement of identical (or very similar)
layers. These related phases are referred to as
polytypes.
U-rich
intermetallic
U-poor
intermetallic
200 m
Figure 1 Backscattered electron scanning electron

microscopy image of SS15Zr11U showing iron solution
phase (black), U-poor intermetallic phase (gray), and U-rich
intermetallic phase (white). Modified from Figure 4 of
Keiser, D. D. Jr.; Abraham, D. P.; Sinkler, W.; Richardson,
J. W. Jr.; McDeavitt, S. M. J. Nucl. Mater. 2000, 279,
234244, used with permission. License number
2287090615691.
The compositions of the (mostly) ferrite and intermetallic phases of three MWF materials are summarized in Table 3.43 The value reported for each
element has an absolute uncertainty of 2 at.%. Actinides were only detected in the ZrFe2-type intermetallic phase of SS15Zr. The U-rich and U-poor
designations indicate analyses of the brighter and
the darker regions of the intermetallic phases, respectively. (The U-rich areas are brighter due to the
higher electron density of U.) Differences in the
relative concentrations of Zr and U in the U-rich
and U-poor zones and the fairly similar Fe concentrations indicate that U substitutes at Zr sites rather
than Fe sites in the intermetallic phase. Comparison
of the SS15Zr5U alloy with the SS15Zr alloy
(see Table 4 in Keiser et al.18) showed relative
increases of 5, 5, and 15 vol.% in the amounts of
ferrite, ZrFe2 (cubic), and Zr6Fe23, and decreases of
4 and 20 vol.% in the amounts of austenite and ZrFe2
(dihexagonal). Although Zr6Fe23 could not be distinguished from ZrFe2 in the SEM analyses of most Ucontaining MWF materials, neutron diffraction
revealed its presence in trace amounts and indicated
that the lattice was contracted about 2%.43 Analysis
of Zr6Fe23 that could be distinguished in the
SS15Zr11U0.1Pd0.6Ru0.3Tc material indicated that phase accommodates less U than the ZrFe2
phase. This is consistent with the preferred accommodation of U in cubic structures.
Table 3
527
Phase compositions in SS15Zr MWF materials
Additions to SS15Zr
Composition (at.%)a
Phase
5U
2U1Nb1Pd1Rh1Ru1Tc
11U0.1Pd0.6Ru0.3Tc
Ferrite
U-rich Laves
U-poor Laves
Ferrite
U-rich Laves
U-poor Laves
Ferrite
U-rich Laves
U-poor Laves
Zr6Fe23
Fe
Cr
Ni
Zr
67.5
44.9
49.1
67.6
43.2
46.5
65.9
49.3
53.3
58.1
23.2
3.3
6
22.3
3.3
4.1
26.8
3.1
6.5
11
5
25.7
18
3.5
22.5
17.9
3.1
18
12.1
9.5
Negligible
7.6
20.6
Negligible
10.9
19.1
Negligible
8
21.9
17.2
Negligible
17.2
1.5
Negligible
12.2
3
Negligible
19.3
2.7
1.7
a
Absolute uncertainty of each value estimated to be 2 at.%.
Data from Keiser, D. D. Jr.; Abraham, D. P.; Sinkler, W.; Richardson, J. W. Jr.; McDeavitt, S. M. J. Nucl. Mater. 2000, 279, 234244, used
with permission. License number 2287090615691.
Table 4
Phase compositions for actinide-bearing SS15Zr alloys
Alloy
SS15Zr2U2Pu
SS15Zr6Pu
SS15Zr10Pu
SS15Zr2Np
SS15Zr6Pu2Np
Phase
Ferrite
U-rich Laves
U-poor Laves
Ferrite
U-rich Laves
U-poor Laves
Ferrite
U-rich Laves
U-poor Laves
Ferrite
U-rich Laves
U-poor Laves
Ferrite
U-rich Laves
U-poor Laves
Composition (at.%)a
Fe
Cr
Ni
Zr
Pu
Np
74
49
57
71
38
55
70
35
55
71
42
58
70
46
60
21
3
7
24
3
8
25
2
7
23
3
7
24
3
8
3
22
13
4
34
14
3
34
14
5
34
21
5
30
17
1
21
22
1
8
22
1
7
22
0.4
6
13
0.5
6
13
0.2
9
0.5

0.2
5
0.5
0.2
17
1
0.5
20
2

0.4
10
1

0.5
15
0.5
0.1
5
0.5
a
Data from Keiser, D. D. Jr.; Abraham, D. P.; Sinkler, W.; Richardson, J. W. Jr.; McDeavitt, S. M. J. Nucl. Mater. 2000, 279, 234244, used
with permission. License number 2287090615691.
Table 4 shows the compositions of phases in

SS15Zr materials made with added U, Np, and
Pu.43 Like U, both Np and Pu are contained almost
entirely (and in the same vicinity) within the intermetallic. Selected area electron diffraction and EDS
in an analytical transmission electron microscopy
study indicated that the U was accommodated primarily in the cubic structure and segregated to the
edges of the intermetallic adjacent to ferrite domains.
The higher magnification transmission electron
microscopy image in Figure 2 of a SS15Zr5U
material shows the actinides to be segregated at

grain boundaries of the intermetallic phase.44 The
distribution of U and other radionuclides within the
intermetallic phase is not uniform on a millimeter
scale.45
The measured concentrations of contaminants in
the phases formed in the SS15Zr2Tc materials
are summarized in Table 5.46 Similar amounts of
cubic and dihexagonal ZrFe2 were detected in neutron diffraction analysis (19 vol.% dihexagonal and
22 vol.% cubic), but these were not distinguishable in
528
SEM analysis. Compared with SS15Zr, the

SS15Zr2Tc material had more cubic ZrFe2, less
dihexagonal ZrFe2, and more Zr6Fe23. Slightly lower
lattice parameter values were measured for both
ZrFe2 structures in the SS15Zr2Tc material than
in SS15Zr, which suggests that Tc was substituted at
the Zr sites in that lattice. Small increases were seen
in both the ferrite (0.104%) and the austenite
(0.056%) lattices. Small amounts of Cr, Mn, Ni, and
Si were detected in all phases, and Mo was detected
in all but perhaps the Zr6Fe23 intermetallic phase.
The assessed (theoretical) TcFe binary phase
diagram47 indicates that Tc is soluble in Fe(d) and
Fe(g) (up to about 30%), but is essentially insoluble
Intermetallic grains
Steel
in Fe(a), which is the thermodynamically preferred

phase below about 912 C. Discrete Tc-bearing
phases were not detected in any of the samples that
were examined. However, similar amounts of Tc were
detected in the ferrite, austenite, and ZrFe2-type and
Zr6Fe23-type intermetallic phases formed in a
SS15Zr2Tc material.43 The Tc was probably dissolved in the Fe(d) formed initially at high temperatures and not excluded when it transformed to Fe(g)
and then partially to Fe(a) as the material cooled.
That is, the Fe(a) is probably supersaturated with Tc.
Although austenite could be converted to ferrite by
aggressive heat treatment, austenite was usually seen
to remain as a metastable phase in as-cast MWFs
made with austenitic steel.43 The authors suggested
that the solubility of technetium in the austenite and
ferrite may be due to the presence of chromium and
nickel in these iron solid solution phases. The alloy
that was studied only contained about 1.7 wt% Tc.
The capacity of the iron solid solution in the MWF
for Tc is not known, but the assessed FeTc phase
diagram suggests that up to 66 wt% Tc can be
accommodated in an FeTc1 + x intermetallic phase.
Actinide-enriched
5.20.8.3
10 m
Figure 2 Scanning electron microscopy backscattered
electron images of SS15Zr5U alloy. The dark gray areas
are steel and the lighter areas are intermetallic phases.
Several small white areas seen between some of the
intermetallic grains (located by the arrows) are enriched in
actinides. Modified from Figure 2b of Janney, D. E. J. Nucl.
Mater. 2003, 323, 8192, used with permission. License
number 2287090487208.
Table 5
Host phase
Ferrite
Austenite
ZrFe2b
Zr6Fe23
a
Electrochemical Tests
The initial corrosion rates (of bare metal surfaces)

were calculated from linear polarization resistance
measurements of several alloy compositions in various solutions. The results of tests in simulated tuff
groundwater solutions and groundwaters spiked with
NaCl at 20 C are summarized in Table 6 (data from
Snyder et al.48). The simulated tuff groundwater solution SJ-13 had a pH of 9 and contains 109 kg m3
3
3
HCO
Si, 18 kg m3
3 , 51 kg m , Na, 34 kg m
2
3

SO4 , and 4.3 kg m
Cl , and the concentrated
3
SJ-13 contained 12 700 kg m3 HCO
3 , 5300 kg m
3
3
2
Na, 30 kg m Si, 22 kg m SO4 , and 727 kg m3
Cl and had a pH of 8.2. In general, the MWF alloys
Elemental compositions of phases formed in SS15Zr2Tc alloy

Elemental concentration (at.%)a
Cr
Fe
Mn
Mo
Ni
Si
Tc
Zr
23.5
17.8
5.7
8.4
66.2
66.4
45.4
51.7
1.6
1.9
1.6
1.0
1.2
0.7
0.7
Negligible
5.3
11.3
23.9
19.1
0.4
0.6
1.4
1.3
1.6
1.3
1.0
0.9
Negligible
Negligible
20.2
17.6

Includes cubic and dihexagonal polytypes.
Data from Keiser, D. D. Jr.; Abraham, D. P.; Richardson, J. W. Jr. J. Nucl. Mater. 2000, 277, 333338, used with permission. License
number 2287090753236.
b
529
Table 6
Corrosion rates measured in a simulated tuff groundwater solution SJ-13, SJ-13 spiked with NaCl, and
concentrated SJ-13 at 20 C, in micrometer per year
Material
SJ-13
SJ-13 1000 kg m3

Cl
SJ-13 10 000 kg m3

Cl
Concentrated
SJ-13
SS5Zr2Nb1Ru1Pd
SS15Zr1Nb1Ru1Pd1Rh
SS20Zr2Nb1Ru1Pd
Type 316 stainless steel
Alloy C22
AISI 1018
0.11 0.05
0.20 0.02
0.19 0.03
0.42 0.15
0.17 0.09
16.9 6.60
0.70 0.56
0.52 0.17
0.99 0.59
1.70 0.65
0.56 0.04
105 24
0.75 0.86
1.53 1.89
2.12 1.62
2.31 1.41
0.81 0.56
176 14
1.25 1.00
2.18 2.02
1.80 0.91
2.18 1.40
0.88 0.38
2.20 0.19
Data from Snyder, C. T.; Barnes, L. A.; Fink, J. K. Metal Waste Form Corrosion Release Data from Immersion Tests, Argonne National
Laboratory Report ANL-04/15; Argonne National Laboratory: Argonne, IL, 2004.
are more durable than Type 316 stainless steel and

became more reactive as the dissolved Cl concentration was increased in both the spiked SJ-13 and the
concentrated SJ-13 solutions. However, the corrosion
rates increased by less than a factor of 12. The results
in Table 6 are based on at least three linear polarization measurements, and the standard deviations indicate large uncertainties for some values. The effect of
pH on the corrosion rates was likewise small, less than
a factor of 20 for rates measured at pH 2, 4, 7, and
10.17,49 These test responses reflect the oxidation rate;
the effects of the solution chemistry on the dissolution
step may be different.
A galvanic cell is formed when alloys having different corrosion potentials are coupled by direct contact
or through an electrolyte solution. Possible galvanic
couplings between the phases in the EBR-11 MWF
and Alloy C22 were studied. Alloy C22 was expected to
be the most stable metal in the waste package for the
proposed Yucca Mountain disposal system and to act as
the cathode in all galvanic couples. Tests were conducted to measure the coupling of Alloy C22 with
SS15Zr and SS15Zr1Nb1Pd1Rh1Ru
waste form compositions.49 The SJ-13 solution (pH 9)
and the SJ-13 solution adjusted to pH 2 were used as
electrolytes. Both materials were found to be electrochemically noble when coupled with Alloy C22. Companion tests coupling AISI 1018 steel with Alloy C22
showed the steel to be electrochemically active and
preferentially oxidized. The galvanic potentials were
about 200 and 62 mV for the SS15Zr and
SS15Zr1Nb1Pd1Rh1Ru specimens and
600 mV for AISI 1018 steel. Similar results were
obtained in the pH 2 solution, except that all potentials
were shifted to higher values and the currents were
slightly higher. The currents measured in tests with
each MWF specimen were very small (but nonzero)
and positive, indicating that both alloys are noble
relative to Alloy C22. Enhanced corrosion of the

EBR-II MWF is not expected due to galvanic coupling
with Alloy C22 or any other material (e.g., carbon steel)
that is part of the waste package.
5.20.8.4
Corrosion Tests
Various test methods have been used to study the

degradation behavior of alloys and the release of
radionuclides. Initial tests indicated that degradation
of the alloy occurs through a two-step mechanism of
oxidative dissolution in which the metal atoms at the
surface are first oxidized to form an oxide layer, and
then the oxide layer dissolves. The oxidation step was
studied with electrochemical tests and the combined
oxidative dissolution processes were studied with
static immersion tests, solution-exchange tests, and
vapor hydration tests.
The release of waste components as the steel and
intermetallic phases corrode has been measured in
immersion tests under a range of conditions. The
metal waste form was subjected to test methods commonly applied to glass waste forms for direct comparison. Composition differences prevented direct
comparisons of particular elements, but the releases
of all components from the EBR-II MWF were well
below the releases of elements from glasses.50 Other
tests were conducted with saw and drill shavings of
EBR-II MWF material for comparison with tests
conducted with crushed glass to assess the possible
use of ASTM C 1285 to track metallic waste form
consistency.51 Particles reacted under those conditions for 2 years were examined with transmission
electron microscopy (TEM) and found to generate
oxide layers similar to those formed on alloys reacted
at 200 C for shorter durations.52 This suggests that
temperature can be used to accelerate corrosion
progress.
0.5
U
Tc
0.4
NL(i) (g m2)
In most tests with EBR-II MWF materials, the

solutions in which the test specimens were immersed
were either partially or completely replaced periodically to detect and minimize any effects that released
components accumulating in the solution might have
on the release rate. For example, the concentration
of dissolved Zr may affect the dissolution of the
intermetallic phase. Dissolution of EBR-II MWF
materials was not stoichiometric, and U was found
to be released to the greatest extent under most test
conditions. The fractional release of U from SS15Zrbased materials was typically about 10 times greater
than the fractional release of Tc (i.e., when normalized
to the amounts of U and Tc in the materials). The
results of tests conducted with EBR-II MWF materials
containing different amounts of U and Tc are shown
in Figure 3.53 The normalized mass loss, NL(i ), is
calculated as the mass of an element i that is released
into solution divided by the mass fraction of element i
in the corroding solid and by the surface area of the
solid. This allows the releases of different elements in
the same and different tests to be compared directly.
The release rates of both U and Tc are high initially
(i.e., during the first 50 days) but decrease and then
become nearly constant over time. The initial
decrease in the release rate is interpreted to correspond to the formation of oxide layers over the steel
and intermetallic phases, which limit the continued
corrosion (oxidation) of those metal phases. The negligible release at longer sampling times is probably
due to the very slow dissolution of the oxide layers.
To characterize the oxide layers, relatively thick
layers were generated on the surfaces of exposed steel
and intermetallic phases by reacting a SS15Zr
material in steam at 200 C for 91 days.54,55 Oxide
material at the solution interface appears less compacted and has a higher oxygen content than oxide at
the metal interface. The difference is probably due to
dissolution of oxide at the outer surface, while corrosion of the metal generates oxide at the oxide layer/
metal interface. Oxygen must diffuse through the
oxide layer to oxidize the metals and grow the inner
layer, while the outer region of the oxide layer dissolves slowly into solution. As seen in the photomicrographs in Figure 4, both oxide layers adhere to
the underlying metallic phase.56 Solids analyses indicate that both Tc and U are retained in the oxide
layers.56 This implies that Tc is oxidized to insoluble
TcO2 that is immobilized within the oxide layer and
that further oxidation is required to release the
soluble species TcO
4 . Immersion tests with various
Tc-doped EBR-II MWF materials indicate that Tc is
0.3
0.2
0.1
50
(a)
100 150 200 250 300 350 400

Time (days)
0.4
U
Tc
0.3
NL(i) (g m2)
530
0.2
0.1
0
0
(b)
200
400
600
800
Time (days)
1000
1200
Figure 3 Releases of U and Tc measured in a long-term

solution exchange tests with (a) SS15Zr4NM2U1Tc
and (b) SS15Zr11U0.6Ru0.3Tc. Data from Johnson,
S. G.; Noy, M.; DiSanto, T.; Keiser, D. D. Jr. In Proceedings
of the DOE Spent Nuclear Fuel and Fissile Materials
Management Meeting, Charleston, SC, Sept 1720, 2002;
American Nuclear Society: La Grange Park, IL, 2002; Waste
Form Testing session.
released initially (presumably as TcO

4 ) when the
surface is still active, but that the release decreases
with time as the oxide layers form on the underlying
steel and intermetallic phases. This is probably due to
the slow dissolution of the oxide layers and their roles
as diffusion barriers to oxygen infiltration. Additional
evidence is needed to demonstrate that the passivating effect of the oxide layers will be maintained over
geological time scales.
A series of immersion tests was conducted to characterize the effects of temperature, pH, and Cl concentration on the release of U from a SS15Zr10U
alloy.57 A modification of the ASTM C 1220 method
was used wherein monolithic test specimens were
immersed in a pH buffer solution spiked with 0,
1000, or 10 000 kg m3 NaCl at a specimen surface
531
Oxide
layers
Steel
Oxide
layers
100 nm
(a)
(b)
Intermetallic
100 nm
Figure 4 Transmission electron microscopy photomicrographs of oxide layers formed over (a) steel phase and
(b) intermetallic phase of MWF reacted at 200 C for 91 days. Modified from Dietz, N. L. Transmission Electron Microscopy
Analysis of Corroded EBR-II Metallic Waste Forms; Argonne National Laboratory Report ANL-05/09; Argonne National
area-to-solution volume ratio of 10 m1 at 50, 70, and

90 C. The entire solution was removed for analysis
and replaced with fresh buffer solution after 14, 28,
and 70 days. Although the test conditions are not
representative of disposal conditions, the tests provide
a convenient means to measure the effects of temperature, pH, and Cl concentration on the release of
U as the oxide layer forms. These dependencies can
be incorporated into a more realistic model that
more accurately represents the disposal environment.
Figure 5(a) and 5(b) shows the results of tests conducted at 50 C in pH 4 and pH 8 solutions spiked
with 0, 1000, and 10 000 kg m3 NaCl, where the
normalized mass losses based on the cumulative mass
of U released to solution are plotted against the reaction time.57 Note that each test under a particular
set of pH/Cl/temperature conditions was conducted
with a single specimen to eliminate the variance in
U concentration at the surface. These results show
significant effects of pH, Cl concentration, and time
on the amount of U released. The release slows with
time such that release during the initial 14 days
accounts for about half the cumulative release over
70 days. The release of U is of primary interest because
U is the most rapidly released radionuclide and is used
to provide a conservative bound for the release rates
of all radionuclides in performance assessments. The
average release rates based on the cumulative values
over 70 days are plotted against the final pH in
Figure 5(c) for all tests at 50 C, where NR(U) NL
(U)/70 days.57 The variance in the results of replicate
tests may reflect the nonuniform distribution of U in
the alloy and between test specimens. The release of
U is faster than most other elements in most tests.
Figure 5(c) shows that the release rates do not have
a simple pH dependence.
5.20.8.5
Corrosion Models
The corrosion, degradation, and release of radionuclides from the EBR-II MWF is hypothesized to
occur through an oxidationdissolution mechanism
in which metallic components exposed at the surface
are first oxidized and form an oxide layer and then
the outer layer dissolves. Formation of oxide layers
on the exposed surfaces of the steel and intermetallic
phases slows the release of all components to solution. The release rates of all radionuclides were modeled to equal that of the most efficiently released
constituent in each particular test regardless of
whether the component was released from the steel
or intermetallic phase. In this regard, the waste form
was modeled to be a homogeneous single phase that
dissolved stoichiometrically.
An empirical model for EBR-II MWF degradation
was developed based on the results of electrochemical
and dissolution tests with several materials.48,58,59 That
model incorporated the dependencies of the release
rate on temperature, pH, and Cl concentration that
were measured in test environments ranging from
pH 2 to 12, 25 to 90 C, and about 0 to 10 000 kg m3
Cl. The model is based on the general concept that
the initially bare alloy surface becomes covered with
an oxide layer that slows the releases of radionuclides
and matrix components to solution. The layer is
modeled to protect the EBR-II MWF surface from
continued corrosion, but credit is only taken for the
length of time this was observed in the tests that were
used to measure the dependencies. At the end of that
period, the passivating effect of the layer is modeled
to vanish and then redevelop at the same rate during
the next period. That is, the layer is modeled to
periodically spall from the underlying metal and
532
pH 4
10
0.1
20
40
60
Test duration (days)
(a)
pH 8
NL(U) (g m2)
NL(U) (g m2)
100
0.1
0.01
0.001
0
80
20
40
60
Test duration (days)
(b)
80
NR(U) (g m2 days1)
0.1
0.01
0.001
0.0001
2
(c)
8
pH
10
12
14
Figure 5 Results of static tests at 50 C in solutions with () 10 000 kg m3 Cl, ( ) 1000 kg m3 Cl, and () without added
NaCl: NL(U) at (a) pH 4 and (b) pH 8, and (c) average release rates NR(U) through 70 days for tests at various pH values in
solutions with 1000 kg m3 Cl. Data from Ebert, W. L.; Lewis, M. A.; Barber, T. L.; DiSanto, T.; Johnson, S. G. Static Leach
Tests with the EBR II Metallic Waste Form; Argonne National Laboratory Report ANL-03/29; Argonne National Laboratory:
Argonne, IL, 2003.
then reform. This moderation of the passivating

effect is due to the absence of direct evidence regarding the long-term stability of the oxide layers. The
model presumes a common time dependence of the
oxidation and dissolution reactions for releasing constituents to solution and growing the oxide layer. If
the corrosion and release rates decrease exponentially due to growth of the oxide layers, then the
cumulative release of all constituents should follow
the logarithmic form:
Cumulative constitute release a ln1 bt 3
where a and b are fitting parameters and t is time. For
sparingly soluble oxides, the thickness of the layers
should increase following the same equation. The
fitting parameters a and b have the following significance59: the product a b gives the initial release rate
prior to formation of the layer, 1/b gives the
characteristic time required to passivate the surface

(i.e., until the release rate becomes negligible compared to experimental uncertainty), and a represents
the extent of corrosion necessary for the layer to
significantly slow the release to solution. The metallic waste form does not dissolve stoichiometrically in
laboratory tests because of differences in the oxidation rates of individual elements, their solubility limits, and their sequestration in alteration phases.
Although there is no experimental evidence that
the slowing effect of the oxide layers will not persist
over long times, for example due to the layers sloughing off, application of the model to the EBR-II MWF
was conservatively limited to 1-year periods, which is
the longest duration over which most test series were
conducted. The average release rate over the time
interval Te that the oxide layer remains an effective
barrier is:
Release rate
amax ln1 bt
Te
4
The term amax is used to indicate that the element

released the fastest under particular conditions was
used to fit the model. Values of the model parameters
amax and b capture the dependencies on temperature
( C), pH, and the Cl concentration (kg m3).
Expressions were determined by assuming a simple
linear or quadratic dependence on these variables,
using a least-squares fit of the experimental data,
and minimizing the number of free parameter combinations. The dependencies, which were determined
by fitting experimental results,48,53 are given in eqns
[5] and [6] (see Bauer et al.58,59):
ln b amax 0:10105 0:015112
5:8201 106
Cl T 0:69848 pH 5
and
ln amax 7:9812 2:3938 104 Cl
1:2273 pH
6
The fitted dependencies given in eqns [5] and [6] are

not unique relationships, but they provide physically
sensible fits for conditions relevant to a geological
disposal site. The modeled rate increases with
increasing temperature and Cl concentration, and
decreases with increasing pH. Equation [4] can be
rewritten in terms of the fitted dependencies as

amax ln 1 b amaxamax t
7
Bounding release rate
Te
where the cumulative release over the interval Te can
be used to provide a conservative time-independent
rate that can be compared with the rates calculated
for other waste forms. Note that the rate equation
given in eqn [7] represents release from a metallic
waste form having the specific phase composition and
chemical composition for treated EBR-II spent fuel.
Rate equations for other compositions would require
conducting separate suites of tests to determine
parameter values for each composition.
5.20.8.6
Repository Model
The EBR-II waste forms were not included in the

performance assessment calculations conducted in
support of the Yucca Mountain repository license
application for construction. To evaluate the likely
533
acceptability of the EBR-II MWF, the source term

for metal waste form degradation using eqn [7] was
compared to that for HLW glass.60 The radionuclide
release rates used in performance assessment calculations are calculated as the product of the release rate
from the waste form degradation model, the radionuclide inventory, and the reacted surface area.61 The
products of the degradation rate, inventory, and surface area for each waste form can be compared to
estimate the impact of replacing some of the HLW
glass with EBR-II MWF on repository performance.
For both the EBR-II MWF and the HLW glass, the
release rates of all radionuclides are modeled to be
equal to the waste form degradation rate. Solubility
and transport limits are based on individual radionuclides and independent of the source.
The effects of temperature and pH on the degradation rate of the EBR-II metal waste form can be
compared to the temperature and pH dependence of
the defense HLW glass degradation model developed
for use in the Yucca Mountain performance assessment calculations. Because the glass model does not
include a term for the effects of Cl (HLW glass
dissolution is not affected by dissolved Cl), the
metal waste form model rates were calculated using
the highest anticipated Cl concentration for comparison with the glass model. The Cl concentration
is treated as a constant rather than a variable for the
purpose of comparison with the glass model. The
concept for disposing EBR-II wastes is to codispose
ceramic waste forms with metal waste forms in the
same canister to distribute the weight of the metal
waste forms among several canisters and waste
packages. Degradation of the ceramic waste form
would provide Cl to groundwater contacting the
metal waste form. It was estimated that a maximum
of 620 kg m3 Cl could be dissolved in the water
inside a breached canister based on the volume and
surface area of ceramic waste form available to infiltrating water.
The model predictions can also be compared with
the rates measured in modified ASTM C 1220 tests
conducted with leachants spiked with NaCl (these
were discussed in Section 5.20.8.4). The dissolution
rates of a SS15Zr10U alloy were measured in
tests conducted at 50, 70, and 90 C over a range of
pH values using buffer solutions spiked with NaCl to
attain 1000 kg m3 Cl. The cumulative amount of
U released over 70 days was used to calculate the
average dissolution rate for comparison with the
HLW glass and EBR-II metal waste form models.60
The rates from tests conducted at 50 and 90 C are
534
plotted in Figure 6 along with the lines showing the

maximum rates from the defense HLW glass models
at these temperatures over the full pH range. The
dashed lines in Figure 6 show the rates calculated
with the empirical metal waste form model given in
eqn [6] calculated at 50 and 90 C with 620 kg m3
Cl and a time interval Te 1 year; the rates calculated with 1000 kg m3 Cl are only slightly higher.
The EBR-II MWF model is representative of the
measured rates in acidic and neutral solutions, but
underestimates the rates measured in alkaline solutions by more than an order of magnitude. The poor
fit in alkaline solutions calls into question the simple
pH dependence that is used in the EBR-II MWF
model.
The key finding demonstrated in Figure 6 is that
the rates calculated with the defense HLW glass
model bound both the rates calculated with the
EBR-II MWF model and the rates measured in the
modified ASTM C 1220 tests (solution exchange
tests) over the entire pH range, including the rates
in alkaline solutions. One exception is the rate
measured in the test at 50 C and pH 9, which was
slightly higher than the glass model. It is important to
note that the MWF model pessimistically ignores the
likely long-term stability of the oxide layers that will
probably protect the MWF surface throughout the
service life of the repository. The oxide layers
log rate g (m2 days1)
MWF immersion 90 C
MWF immersion 50 C
HLW glass
model at 90 C
HLW glass
model at 50 C
0
1
5.20.8.7 Metallic Waste Form Product

Consistency
EBR-II MWF
2 model at 90 C
3
4
0
EBR-II MWF
model at 50 C
likewise have a minor effect on the rates determined

from the short-term modified ASTM C 1220 tests.
In effect, the EBR-II MWF model assumes that
the oxide layers disappear and reform on an annual
basis, such that the average degradation rate from the
model becomes increasingly conservative over time.
The surface area of HLW glasses available for
degradation in performance assessment calculations
is based on the dimensions of the glass pour canisters
and a cracking factor. The exposed surface area of an
average HLW glass log is taken to be 30 m2 for
comparison with the EBR-II MWF, which will be
cast as ingots having a right cylinder geometry
0.350.41 m (1416 in.) in diameter and 0.050.13 m
(25 in.) thick. One or two ingots will likely be codisposed with two ceramic waste form monoliths in a
disposal canister. The ingots are not expected to fracture due to cooling or impact, so the geometric surface
area represents the maximum surface area that can be
exposed to water. The surface area of a representative
ingot 0.4 m (16 in.) in diameter and 0.1 m (4 in.) thick is
about 0.38 m2, so the surface area of two EBR-II
MWF ingots in a breached canister is about 0.76 m2.
This is about 2.5% of the glass surface area.
The total inventory of radionuclides in the EBR-II
MWF is only about 0.1% of the total inventory of
HLW glass, on a per canister basis. The predominant
radionuclides are 1.92 1012 Bq 63Ni, 7.77 1011 Bq
99
Tc, 9.99 1010 Bq 60Co, and 6.66 1010 Bq 59Ni.
(The total inventory of the EBR-II ceramic waste
form is about 16% of the HLW glass inventory, on a
per canister basis.) Based on comparison of the combined release rate, inventory, and surface area, the
performance of the EBR-II MWF is conservatively
bounded by the performance of HLW glass in total
system performance assessments.
10
12
14
pH
Figure 6 Comparison of measured MWF degradation
rates (data points), rates from empirical MWF model
(dashed lines), and rates from HLW glass degradation
model (solid lines) at 50 and 90 C. Data from Ebert, W. L.
Testing to Evaluate the Suitability of Waste Forms
Developed for Electrometallurgically Treated Spent SodiumBonded Nuclear Fuel for Disposal in the Yucca Mountain
Repository; Argonne National Laboratory Report ANL-05/
43; Argonne National Laboratory: Argonne, IL, 2005.
The objective of tracking the consistency of waste

form products is to link the controls applied to
waste form production with predictable performance
in a disposal system (see Section 5.20.5.2). The narrow range of waste stream compositions anticipated
from the EBR-II spent fuel inventory simplified the
task of tracking waste form product consistency.
The control limits placed on the feed compositions
are 111 mass% total U and 520 mass% Zr with
targets of 10 mass% total U and 15 mass% Zr.
The composition Fe15Zr results in nearly equal
amounts of the steel and Fe2Zr intermetallic phases
being formed, and variations in the amount of Zr in

the alloy will change the relative amounts of each
phase. Acceptable performance requires that the
waste form contains at least the minimum amount
of the Fe2Zr intermetallic phase required to sequester
the actinides present in the waste. It was determined
that 5 mass% Zr in the alloy is adequate to produce
enough intermetallic phase to accommodate the
maximum amount of actinides that could be present
in the waste. Most waste streams will contain <5 mass
% Zr, and additional Zr must be added to generate an
adequate volume of intermetallic phase.
The addition of Zr is a critical step in waste
processing. Because Zr is not soluble in the steel
phase and the actinides substitute for Zr in the intermetallic,44 the Zr content of the waste form provides
a reliable measure of the amount of intermetallic
phase that will form. It is expected that waste streams
from several electrorefining runs will be blended to
control the U enrichment in the EBR-II MWF. The
Zr content will be tracked, but not optimized. In
practice, 5 mass% Zr can be added to any waste
mixture to ensure that the total Zr will exceed the
minimum content of 5 mass% by the amount of Zr
present in the fuel wastes stream. Measurement of the
Zr content can be used to track waste form consistency by verifying enough Zr is present.42 Based on
the FeZr binary phase diagram and scoping tests,
about 30 mass% Zr can be accommodated in the
phase structure of the waste form, although the temperature required to reactively dissolve the Zr will
increase with the Zr content of the mixture. However,
scoping tests showed that alloys with that much Zr
were brittle, so an upper limit of 20 mass% Zr is
imposed to provide enough of the steel phase to
maintain the physical integrity of the alloy. As part
of this approach, it must be demonstrated that the
composition analysis of small samples taken from
waste forms having the fine-grained microstructure
of the SS15Zr alloy will provide a sufficiently accurate measure of the Zr content. This can be done by
comparing the analytical results of various sample
sizes to bulk compositions based on known formulations or analysis of larger aliquants.
5.20.9 Summary
Metallic waste forms are appropriate for waste
streams that include significant amounts of metallic
components or contain radionuclides that are most
effectively processed and immobilized as metals. The
current design of metallic waste forms is based on the
535
compatibility of the waste stream with the targeted

assemblage of phases that form from the waste and
added metals. Other metals can be added to facilitate
melting the waste metals or forming phases that
effectively immobilize the waste components in a
consistent assemblage of phases. Binary phase diagrams provide useful insights regarding the likely
melting temperatures, eutectic melting compositions,
likely phase compositions and assemblages, and solubilities for various mixtures of wastes and additives.
The degradation behaviors of radionuclidebearing alloy phases must be modeled to predict
radionuclide release and migration over very long
times in performance assessment calculations. These
calculations are used to demonstrate that regulatory
requirements will be met over the service life of the
disposal system as the waste forms degrade. This
requires testing to understand and quantify radionuclide release rates under the range of conditions
anticipated in a disposal facility and those possible
under extreme conditions. Long-term predictions
based on mechanistic models are more reliable than
those based on empirical models, but mechanistic
models are very difficult to develop. An empirical
model with mechanistic underpinnings has been
developed for the specific metal waste form composition formulated and designed to immobilize metallic wastes from the electrometallurgical treatment of
spent EBR-II fuel. Tests and analyses of the EBR-II
MWF provide valuable insight regarding the disposition of radionuclides in component phases and their
releases as those phases degrade. They also show the
difficulties of quantifying a complicated and coupled
corrosion process. Development of a mechanistic
model for the degradation of alloyed waste forms is
probably the most important research need, especially a term to represent the effect of the phase
composition.
Qualification of metallic waste forms for disposal
will likely require evidence that acceptable waste
form performance (i.e., controlling the radionuclide
release) can be expected based on how the waste form
is produced. That is, controlling the gross composition of waste streams and additives and controlling
the processing conditions (processing temperature,
furnace atmosphere, etc.) will result in a waste form
with predictable phase assemblage and radionuclide
disposition that can be related to waste form performance. Because a very large number of waste forms
will be made over long times with varying waste
stream compositions, controlling waste form performance through processing controls is a very
536
important aspect of waste form design. This is necessary to provide confidence that the performances of
all waste forms produced are bounded by the radionuclide release rates used in the performance assessment calculations.
A variety of test methods is required to provide the
range of data needed to determine the radionuclide
release mechanism(s), the influence of environmental
variables and waste form composition on the release
rate (both the chemical and phase composition),
develop and parameterize a model for calculating
radionuclide release over very long times, and establish process control limits for making consistent products. The electrochemical and immersion test
methods used to characterize the EBR-II MWF
have provided an extensive database to support its
qualification for disposal in the proposed Yucca
Mountain repository. Lacking a mechanistic model
for radionuclide release, the approach taken was to
show that the impact of disposing EBR-II waste forms
would be dwarfed by the impact of commercial fuel
and HLW glass and bounded by performance assessment calculations. A mechanistic model of radionuclide release is an important goal for advancing the
development of metal waste forms. From the conceptual model of sequential oxidation and dissolution
steps, new test methods coupling electrochemical
techniques with test methods that accelerate corrosion are probably needed to characterize radionuclide release under a range of conditions. The
oxidation step may also complicate coupling waste
form degradation with the transport models used in
performance assessments. For example, the need to
take into account galvanic couples within the waste
from and between the waste form and other metals
may require additional terms in transport models.
Methods to accelerate metal corrosion processes are
also needed to help understand long-term performance, support waste form modeling, and lead to
acceptance for disposal.
Testing and modeling completed to date indicates that metallic waste forms provide a preferable
option for several existing and anticipated waste
streams from fuel treatment and recycling processes.
Several challenges remain in development of metallic waste forms for high-level and low-activity
radioactive waste streams in the areas of performance and consistency testing, developing waste
form degradation and radionuclide release models,
and integrating those into performance assessments.
Innovative research in electrochemical measurements and modeling is needed to support continued
model development and waste form formulations,

and replace the current empirical approaches with
sound mechanistic models. (See also Chapter 3.01,
Metal Fuel; Chapter 5.14, Spent Fuel Dissolution
and Reprocessing Processes; Chapter 5.16, Spent
Fuel as Waste Material; Chapter 5.18, Waste
Glass and Chapter 5.19, Ceramic Waste Forms).
Acknowledgments
The submitted manuscript has been created by
UChicago Argonne, LLC, Operator of Argonne
National Laboratory (Argonne). Argonne, a U.S.
Department of Energy Office of Science laboratory, is
operated under Contract No. DE-AC02-06CH11357.
The U.S. Government retains for itself, and others
acting on its behalf, a paid-up nonexclusive, irrevocable worldwide license in said article to reproduce,
prepare derivative works, distribute copies to the
public, and perform publicly and display publicly, by
or on behalf of the Government.
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Goff, K. M.; Benedict, R. W.; Teske, G. M.; Johnson, T. J.
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ID, 2007.
Vaden, D.; Li, S. X.; Johnson, T. A. In Proceedings of the
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Fissile Materials Management, Charleston, SC, Sept
1720, 2002; American Nuclear Society: La Grange, IL,
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Scr. Mater. 1997, 37, 239244.
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Mater. Sci. Eng. 1997, A239240, 658664.
McDeavitt, S. M.; Abraham, D. P.; Park, J. Y. J. Nucl.
Mater. 1998, 257, 2134.
Ebert, W. L. Testing to Evaluate the Suitability of Waste
Forms Developed for Electrometallurgically Treated Spent
Sodium-Bonded Nuclear Fuel for Disposal in the Yucca
Mountain Repository; Argonne National Laboratory Report
ANL-05/43; Argonne National Laboratory: Argonne, IL,
2005.
Ebert, W. L. Immobilizing GNEP Wastes in Pyrochemical
Process Waste Forms; US Department of Energy Report
GNEP-WAST-PMO-MI-DV-2008-000150; Idaho National
Gerhold, W. F.; Escalante, E.; Sanderson, B. T. The
Corrosion Behavior of Selected Stainless Steels in Soil
Environments; National Bureau of Standards Report
NBSIR 81-2228; National Bureau of Standards:
Washington, DC, 1981.
Abraham, D. P.; Richardson, J. W. Phase stability of
laves intermetallics in a stainless steelzirconium alloy.
In Proceedings of the Long Term Stability of High
Temperature Materials Conference, Warrendale, PA;
Fuchs, G. E., Dannemann, K. A., Deragon, T. C., Eds.;
1999; pp 169179.
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Radioactive Waste Management. Waste Acceptance
System Requirements Document, Rev. 5; US Department
of Energy Office of Civilian Radioactive Waste
Management Report DOE/RW-0351 Rev. 05, May 2007;
US Department of Energy: Washington, DC, 2007.
Bacon, D. H.; White, M. D.; McGrail, B. P. Subsurface
Transport over Reactive Multiphases (STORM): A Parallel,
Coupled, Nonisothermal Multiphase Flow, Reactive
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Version 3.0. Users Guide; Pacific Northwest National
Laboratory Report PNNL-14783; Pacific Northwest
National Laboratory: Richland, WA, 2004.
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Stansbury, E. E.; Buchanan, R. A. Fundamentals of
Electrochemical Corrosion; ASM International: Materials
Park, OH, 2000.
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Ebert, W. L.; Bates, J. K.; Bourcier, W. L. Waste Manag.
1991, 11, 205221.
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testApplication to vitrified matrixes for high-level
radioactive waste; International Standard ISO
16797:2004; International Standard Organization:
Geneva, Switzerland, 2008.
Wronkiewicz, D. J.; Bates, J. K.; Gerding, T. J.;
Veleckis, E.; Tani, B. S. J. Nucl. Mater. 1992, 190,
107127.
McGrail, B. P.; Martin, P. F.; Lindenmeier, C. W.
In Scientific Basis for Nuclear Waste Management XX,
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Symposium, Boston, MA, Dec 26, 1996; Gray, W. J.,
Triay, I. R., Eds.; Materials Research Society: Pittsburgh,
PA, 1997; Vol. 465, pp 253260.
Pierce, E. M.; McGrail, B. P.; Valenta, M. M.; Strachan,
D. M. Nucl. Technol. 2005, 155(2), 149165.
White, A. F.; Brantley, S. L. Chem. Geol. 2003, 202,
479506.
Fuhrmann, M.; Schoonen, M. Leaching of Slag from Steel
Recycling: Radionuclides and Stable Elements;
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Brookhaven National Laboratory: Upton, NY, 1997.
Arnold, G.; Colombo, P.; Doty, R. M.; et al. Lysimeter
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Plodinec, M. J. J. Nucl. Mater. 2008, 378, 244256.
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Performance Modeling to Support Safety Assessment of
Low and Intermediate-Level Radioactive Waste Disposal;
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and Management of Sodium-Bonded Spent Nuclear Fuel,
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Diagrams of Binary Iron Alloys; Okamoto, H., Ed.; ASM
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Johnson, S. G. Static Leach Tests with the EBR II Metallic
Waste Form; Argonne National Laboratory Report
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2003.
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Johnson, S. G.; Wigeland, R. A. In Proceedings of the
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5.21
Graphite
J. Fachinger
Furnaces Nuclear Applications Grenoble ZU Hanau Research and Development, Hanau, Germany
5.21.1
Introduction
540
5.21.2
5.21.2.1
5.21.2.2
5.21.2.3
5.21.2.4
5.21.2.5
5.21.3
5.21.4
5.21.4.1
5.21.4.1.1
5.21.4.2
5.21.4.2.1
5.21.4.2.2
5.21.5
5.21.5.1
5.21.5.2
5.21.5.3
5.21.5.4
5.21.6
5.21.6.1
5.21.6.2
5.21.6.3
5.21.6.4
5.21.7
5.21.8
References
Appendix 1
Amounts of i-Graphite and Its Origin

Russia
United Kingdom
France
United States
Others
Retrieval of i-Graphite
Graphite Properties
Physical Properties
Wigner energy
Chemical Properties
Oxidation in gaseous phases
Graphite reactions with liquids
Graphite Radioactivity
Formation of 3H
Formation of 14C
Formation of 36Cl
Diffusion of Radionuclides in Graphite
Graphite Treatment for Disposal or Recycling
Waste Packages and Encapsulation
Thermal Treatment
The Russian Self-Propagating High-Temperature Synthesis SHS
Recycling of i-Graphite
Final Disposal
Summary
540
540
541
541
541
542
542
542
542
543
543
543
545
545
546
546
547
549
550
550
551
552
553
553
556
557
558
Amounts of Irradiated Graphite in Different Countries
Abbreviations
AGR
AM-1
AMB
AVR
b
BEPO
CP1
EDF
EL2
FRJ-1
Advanced gas-cooled reactor

Prototype of RBMK
Ao Mp oo
Allgemeiner Versuchsreaktor (a small
HTR prototype reactor in Germany)
Barn (1024 cm2)
British experimental pile 0
Chicago pile-1
Electricite de France SA
Graphite moderated test pile in
France
Research Reactor Julich 1
GLEEP
Graphite low energy experimental

pile
HTGR
High-temperature gas-cooled reactor
HTR
High-temperature reactor
IAEA
International Atomic Energy Agency
MAGNOX Magnesium alloy graphite moderated
gas cooled uranium oxide reactor
RBMK
Reaktor Bolschoi Moschtschnosti
Kanalny
THTR
Thorium high-temperature reactor
UNGG
Uranium naturel graphite gaz reactor
WAGR
Windscales advanced gas-cooled
reactor
539
540
Graphite
5.21.1 Introduction
Graphite has been used in nuclear technology since
the birth of this technology. The first artificial nuclear
reactor, the Chicago Pile-1, consisted of a pile of
uranium and graphite.
It was the fundament for future developments in
the different graphite-moderated nuclear power
reactors such as the Uranium Naturel Graphite Gaz
reactors (UNGG) in France, Magnox and advanced
gas-cooled reactors (AGR) in the United Kingdom,
or RBMK in Russia. The culmination of this development was the high-temperature reactor, for example, the Fort Saint Vrain reactor in the United States
or the Thorium-Hochtemperaturreaktor (THTR) in
Germany.
Worldwide, more than 230 000 tons of irradiated
graphite (i-graphite) exist, which will eventually
need to be managed as radioactive waste.1 The major
part of i-graphite is still in operational or shutdown
nuclear power reactors. Actually, the reactor cores
have been removed from Fort Saint Vrain, GLEEP,
and BEPO. The removal of the core from the Allgemeiner Versuchsreaktor (AVR) is proposed for the next
few years.
Smaller quantities of i-graphite result additionally from operation, in the form of graphite sleeves,
which have to be replaced during operation, and
from different kinds of research reactors. The total
amount of i-graphite is assumed to be in the range of
220 000250 000 tons. A more detailed overview of
the amount of i-graphite is given in Section 5.21.2.
Graphite changes its properties during irradiation
in a nuclear reactor. Most important for the treatment and disposal of i-graphite is the possibility
of storing energy in the form of structural defects,
the so-called Wigner energy. The entire Wigner
energy could be released rapidly after an initial
local release. Furthermore, the graphite will be contaminated by radionuclides. They result from the
activation of 13C and impurities in the graphite
matrix as well as from the depletion of fission products released from the fuel elements. This is
described in Section 5.21.5.
Various treatment methods have been developed
or are under development to decontaminate i-graphite
or to optimize the disposal volume and behavior,
respectively. Section 5.21.6 gives a short overview
of all these developments. A major issue is the establishment of a close graphite cycle, which is essential
for the future development of graphite-moderated
nuclear reactors.
The last section is dedicated to the final disposal

options for i-graphite and the behavior of i-graphite
under different disposal conditions.
5.21.2 Amounts of i-Graphite and

Its Origin
Generally, one can distinguish between four different
types of nuclear reactors that utilize graphite as neutron moderator and reflector.
Aircooled graphite piles with a low power density
as test facilities, prototypes, and first-generation
plutonium production reactors.
Carbon-dioxide-cooled reactors (Magnox and
UNGG) for electricity supply and/or plutonium
production.
Helium-cooled high-temperature reactors for
electricity generation and process heat generation.
Graphite-moderated water-cooled reactors for plutonium production and/or electricity generation.
The last feature, electricity generation, has been
optimized especially in the Russian RBMK reactors.
5.21.2.1
Russia
The main sources of i-graphite are the RBMK nuclear

power plants as well as high-capacity plutonium production reactors. Five RBMK power plants with 11
reactors are still in operation in Russia.2,3 The original
license foresaw a lifetime of 30 years. However, lifetime extensions are already licensed or envisaged.
Therefore, the first shutdowns are expected in 2013,
with a replacement program starting in 2015.3
The amount of graphite from these reactors is
given in Table A.1. An important fact about this
graphite-moderated water-cooled reactor type is
that a heliumnitrogen mixture gives the graphite
moderator a protective atmosphere, which will
have an important impact on the generation of 14C.4
Four more graphite-moderated power reactors,
Bilibino-14, are in operation. These dual purpose
reactors for electricity and heat contain 133 tons of
graphite each.3
The AMB-1 and -2 in Beloyarsk, and the AM-1,
prototypes of the RMBK reactors, were shutdown in
1981, 1989, and 2004 respectively. The fuel has been
removed from the reactor core and stored in cooling
basins. The reactor units with the graphite core are
under safe storage conditions of IAEA Stage I, under
surveillance; further dismantling is planned.
Graphite
Besides these graphite-moderated power plants,

13 high-capacity plutonium power reactors had
been in operation in Russia. All of them were shutdown between 1987 and 2008. The reactor units with
the graphite core are under safe storage conditions of
IAEA Stage II. The first dismantling concepts proposed the transformation of the reactor shafts into a
final radwaste repository. However, this disposal concept is not in accordance with the new Russian waste
disposal regulations.5 Therefore, a further 21 000 tons
of graphite internals of the reactor units, as well as
8000 tons of graphite rings at on-site storage facilities,
have to be managed as radioactive waste in Russia.
An additional source of i-graphite are research
reactors and other critical assemblies. The determination of the exact number of these reactors and
assemblies is complicated. However, it can be assumed
that more than 110 such facilities exist in Russia.
Furthermore, it was not possible to figure out which
moderator had been used in these facilities and therefore the amount of i-graphite could not be evaluated.
5.21.2.2
United Kingdom
The United Kingdom has the largest amount of

i-graphite that has to be managed as radioactive
waste1,6 because most of the British nuclear power
plants are gas-cooled graphite-moderated reactors as
opposed to those in other countries, which utilize
water-moderated reactors as an alternative. The
Magnox reactor type was utilized after test reactor
and prototype development in the late 1950s. The
name was derived from the fuel cladding made from a
magnesiumaluminum alloy. The last Magnox reactor was commissioned in 1971. The next generation
of gas-cooled reactors were the AGR, commissioned
between 1976 and 1989. Both reactor types were
graphite-moderated and cooled with CO2. Totally
about 80 000 tons of graphite have to be handled as
radioactive waste now or in the next two decades after
the shutdown of the still operational AGR reactors.
An overview of the amount of graphite in the different
UK reactors is given in Table A.2 in the Appendix.
5.21.2.3
France
The first graphite-moderated reactor in France was

the pile EL2 built at Saclay in 1952.7,8 It was an
experimental reactor like the EL3 built in 1957.
The total mass of graphite in these two reactors was
109 tons. The operation of these reactors ended in
1965 and 1979, respectively.
541
The first UNGG were built and operated by CEA

in Marcoule as plutonium production reactors for the
French nuclear deterrent forces. The main characteristics of these reactors are given in Table A.3. While
the G1 was still air cooled, all other UNGG used CO2
as cooling gas. The graphite bricks, used as moderator
as well as shielding for the internal walls of the reactor,
were mounted to a horizontal reactor core. The
decommissioning has achieved IAEA level 2.
Six more UNGG reactors have been built and
operated by EDF for electricity production. The
main characteristics of these reactors are also given
in Table A.3. All of them are under decommissioning. With the exception of Chinon A1 the design
was changed from a horizontal to a vertical shaft for
improved fuel handling. However, the fuel cartridges had to be protected by graphite sleeves to
withstand the mechanical forces of the upper fuel
cartridges. These graphite sleeves are temporarily
stored in silos except those from Buggy, which have
been disposed at the final disposal sites at Manche
and Aube.
5.21.2.4
United States
The development of nuclear reactors started in the

United States with the graphite-moderated pile 1
(CP1) in Chicago. The largest amounts of i-graphite
in the United States are from the plutonium production reactors at the Hanford site. The Hanford
B-Reactor was the first large-scale plutonium production reactor in the world. The reactor was graphite
moderated and water cooled. It consisted of an
8.5 11 m horizontal tube and contained 1100 tons
of graphite.9 All reactors at the Hanford site were
intended for plutonium production. In all, nine plutonium production reactors were operated at the Hanford site. The reactors were shutdown between 1964
and 1971 after an average life span, except the lastbuilt N Reactor (1963), a dual purpose facility for civil
electricity generation (shutdown in 1987). Most of the
reactors have been entombed after defueling and act
as interim storage for the graphite moderator and
structural materials to allow the decay of radioactive
material until dismantling is possible with a low dose
risk. Reactors exclusively for civil application were
the HTGR at Peach Bottom and Fort Saint Vrain
with a graphite block as moderator. Both were shutdown after a relatively short operational time of 7 and
13 years, respectively. An overview of the amount of
graphite in the different reactors is given in Table A.4
in the Appendix.
542
Graphite
5.21.2.5
Others
Table A.5 gives an overview of graphite-moderated

reactors in other countries. Most of them are RBMK
reactors in countries of the former Soviet Union or
Magnox reactors. High-temperature reactors have
been constructed in China, Germany, and Japan.
Two graphite-moderated high-temperature reactors,
the AVR and the THTR, were operated in Germany.
About 1000 metric tons of i-graphite and irradiated
carbon bricks have to be managed as radioactive
waste. Furthermore, about 1 million irradiated fuel
pebbles were produced during the operational time
of these reactors. They consist mainly of a graphite
matrix that contains about 10 000 so-called coated
particles (see Chapter 3.06, TRISO Fuel Production and Chapter 3.07, TRISO-Coated Particle
Fuel Performance). These particles safely enclose
the nuclear fuel and the major part of the fission
products. The AVR is under dismantling to the
green field. Therefore the reactor vessel with the
graphite core will be pulled out as one piece and
transferred to an interim storage facility. It will stay
there for about 80 years before further treatment.
The development in Japan is based on a graphite
block core similar to that in the United States. The
Chinese HTR-10 is a pebble HTR like the one in
Germany.
whole reactor core was flooded before cutting the

graphite internals. This procedure provides two advantages. First, the water acts as shielding, which minimizes the dose rate of the employees, and second, the
water prevents the formation of graphite dust. However, water purification requires additional effort.
A third approach is being used for dismantling the
AVR in Julich, Germany. The whole reactor vessel,
including the graphite internals, built as one part, has
been lifted out of the reactor and transferred to an
interim storage. Before lifting, the reactor core was
filled with light concrete to consolidate the internals
and to reduce impacts, in case the vessel falls down
during the lifting procedure. Further dismantling will
be performed after the decay of the main part of
g-emitters, especially 60Co. This method represents
a way between complete dismantling and long-term
safe storage and enables fast cleanup of a site.
The choice of the best applicable retrieval method
depends on several site-specific facts and therefore
there is no best procedure. They include the mechanical and physical properties of the graphite, the dose
rate of the graphite, and the surrounding structures, as
well as the specific side constructions, which determine
the space available for the installation of equipment.
A detailed overview of retrieval and available procedures and tools is under compilation by an expert team
of the European Carbowaste project.10
5.21.3 Retrieval of i-Graphite

5.21.4 Graphite Properties
The retrieval of i-graphite is based on two main
principles, dry and wet retrieval.10 Dry retrieval has
been chosen for the decommissioning of WAGR and
GLEEP. GLEEP was a low-energy and low-radiation
test reactor. The resulting total activity was so low
that the graphite could be removed manually without
shielding. Only protective overalls and gloves were
required to avoid incorporation. The graphite should
be treated in an industrial incinerator that is licensed
for the discharge of small amounts of radioactivity. It
was noted that the graphite blocks showed only small
effects after treatment at 1400 K for 3 h in air. Less then
2% of the graphite was lost during the process. However, about 87% of 3H and 63% of 14C were released
from the graphite.
The activity and dose rate were so high that a
manual retrieval of the graphite was not acceptable
for the WAGR. A remote removal system was developed for the retrieval of the graphite stack.
Wet retrieval was utilized for dismantling the hightemperature reactor at Fort Saint Vrain. Therefore, the
5.21.4.1
Physical Properties
The properties of graphite are related to its polycrystalline structure (see Chapter 2.10, Graphite: Properties and Characteristics). Graphite crystallites are
built by graphite planes, which are loosely bound by
van der Waals forces. The single planes consist of
carbon six rings with a sp2 electron configuration of
the carbon atoms and a dislocated p-system on both
sides of the plane. Therefore the properties of the
crystallites are anisotropic with respect to the orientation parallel or vertical to the planes. Irradiation
induces damages in these graphite crystallites, which
lead to anisotropic effects in the crystallites. A good
example is a radiation-induced expansion in one
direction and shrinkage in the other direction. Therefore the macroscopic changes can be anisotropic, if
the crystallites have an overall preferred orientation
direction, or isotropic, if the crystallites are randomly
distributed. This depends on the shape of the crystallites as well as on the production process. For example,
Graphite
extruded graphite shrinks parallel to the extrusion

direction and expands perpendicular to the extrusion direction at temperatures below 300 C and
shrinks in both directions at higher temperatures.
More isotropic molded graphite initially exhibits
shrinkage in all directions under all irradiation conditions. The irradiation-induced shrinkage proceeds to a
point of maximal density. Further irradiation causes an
expansion to the original density and beyond. Besides
being important for reactor operation, this effect is
also a key issue for waste management. It affects the
mechanical stability, which has a large influence on the
retrieval of graphite piles from the reactor for decommissioning. Furthermore, the density and porosity may
influence the radionuclide release in intermediate storage and especially in final disposal.
Another important parameter for disposal is the
reduction of the thermal conductivity. Small amounts
of fast neutrons will reduce thermal conductivity
and can be decreased further by 2 orders of magnitude to 2 W m1 K1, depending on neutron dose
and irradiation temperature.
Another very important property for disposal is
porosity, which allows the penetration of aqueous
phases into the graphite matrix and therefore an
undisturbed transport of radionuclides through the
graphite matrix.
5.21.4.1.1 Wigner energy
The Wigner effect is named after its discoverer Eugene

Paul Wigner. This effect describes the displacement of
atoms in a solid caused by neutron irradiation, which
can occur in any solid. However, it has a special importance for solid moderator materials such as graphite.
An atom can be moved from its position in a
crystal lattice by collision with neutrons, if they
have energies above 25 eV. Therefore, high-energy
neutron, for example, 1 MeV, causes cascades of
damages with about 900 displacements in a graphite
moderator. Not all of the displacements lead to lattice
defects because the displaced atoms could also
fill lattice vacancies. Atoms that cannot be placed in
lattice vacancies remain as interstitial atoms between
the lattice planes and therefore they are associated
with a higher energy.11 When such an atom has
sufficient thermal energy, it is able to move to normal
lattice position and release excess energy if the position energy is higher than the energy required for the
return to a lattice place. If such a process has been
initiated, the hole-stored Wigner energy can be
released immediately and heat up a graphite pile.
This was the cause of the Windscale fire accident.12
543
Wigner energy can cause the following problems

related to the management of i-graphite:
1. Initiation of an uncontrolled release of Wigner
energy during retrieval.
2. Sawing or cutting of the graphite core can lead
to a local heat increase, which may lead to an
uncontrolled release of Wigner energy. Therefore
such operations should be performed with sufficient cooling.
3. Release of the Wigner energy during final disposal.
4. The temperature of the final disposal sites for lowand medium-level wastes is normally strictly limited. These limits depend on corrosion processes or
microbial degradation, and higher temperatures
may disturb the integrity of the disposal or increase
the reaction rates of release mechanisms. Therefore,
the Wigner energy should be dissipated before storage by annealing the graphite at temperatures above
250 C or it has to be demonstrated that the disposal
site will not be affected by such an energy release.
This has been tried by NIREX but they concluded
that Wigner energy is not adequately understood to
guarantee that a release of Wigner energy cannot
affect the safety of a disposal site.13
Despite this potential risk, only low amounts of
i-graphite have considerable amounts of Wigner
energy. They are related to reactors operated at low
temperatures, for example, reflectors of material test
reactors. High reactor operation temperatures, for
example, achieved in an AGR would directly cause
the annealing of the graphite.13
5.21.4.2
Chemical Properties
Burning of radioactive graphite has been in public

discussion since the accident at Chernobyl. But graphite has an extremely low chemical reactivity, which
explains its geochemical stability, proved by the presence of natural graphite ores in the earths crust.
Graphite needs extremely powerful oxidation agents
to convert it into the thermodynamic-favored carbon
dioxide. This also allows the utilization of graphite
under extreme conditions in industrial processes, for
example, as electrode in arc melting at temperatures up
to 3000 C or its use as fire extinguisher.
5.21.4.2.1 Oxidation in gaseous phases
Graphite can react with gases such as O2, CO2, H2O,

and H2 at elevated temperatures and the temperature
depends on the perfection of the graphites crystal
structure14 and therefore on the amount of impurity.
544
Graphite
Generally, heterogeneous reactions involving a

porous solid and a gas can be controlled by one or
more of three idealized steps:
1. Mass transport of the reacting gas from gas stream
to the exterior graphite surface.
2. Mass transport of the reacting gas from the exterior surface to an active site and mass transport of
the products in the opposite direction.
3. Chemical reaction at the active sites.
The variation of the reaction rate with temperature for gascarbon reactions can be divided into
three main zones (Figure 1).
In the low-temperature zone (zone I), the reaction
is controlled by the chemical reactivity of the solid
(step 3). There will be almost no concentration gradient of reacting gases throughout the whole volume
of the sample because of low reaction rate, and this
provides uniform access to the interior surface of
porous materials. For graphite oxygen reaction,
the upper limit for temperature will be 500 C, and
for graphitesteam system, it will be 850 C.15
In the intermediate-temperature zone (zone II),
step 2 becomes important. The diffusion of reactants
in pores will influence the oxidation rate of material.
At higher temperatures, the concentration gradient of
the reacting gas becomes steeper within graphite and
the gas concentration becomes zero at a distance R
nearer the surface. The activation energy Ea in this
zone amounts to half of the true activation energy Et.
For graphitesteam reaction, this temperature region is
characterized by a temperature range of 8501350 C
and graphite oxygen reaction, by 500900 C.
In the high-temperature zone (>900 C for graphite oxygen and >12501400 C for graphitewater
steam) zone III the concentration of the reacting
gas is low at the exterior of the solid and the rate is
controlled by step 1. As bulk gas-transfer processes

have low activation energies, the apparent activation
energy for gascarbon reactions in zone III is low.
The reactions occurring in the gasgraphite
system are
Reaction with oxygen
r H : standard enthalpy of reaction at 25 C
1
2
Ln (reaction rate)
II
r H 283:0 kJmol1
COg 1=2O2 g!CO2 g
3
Reaction with carbon dioxide

Boudouard reaction :
Cs CO2 g ! 2CO
r H 172:5 kJ mol1
4
The equilibrium can be shifted with increasing

CO pressure16,17 or in the presence of a catalyst.
Reaction with water
CsH2Og!COgH2g
r H 131:3 kJ mol1
5
COg H2 Og ! CO2 g H2 g
r H 213:7 kJ mol1
6
The hydrogen and CO2 produced can then react

with carbon
C H2g ! CH4 g
r H 110:5 kJmol1
Cs 1=2O2 g!COg
C CO2g ! 2COg
III
r H 394:5 kJmol1
Cs O2 g ! CO2 g
r H 172:5 kJ mol1
4
r H 71:81 kJ mol1 7
The presence of hydrogen can shift reaction [5]

left [4].
Reaction with hydrogen
I
1/ T
Figure 1 Ideal reaction zones in graphite: I reaction

rate is controlled by chemical reactivity of the sample;
II reaction rate is controlled by diffusion in pores;
III reaction rate is controlled by gas transport to the
exterior surface of the sample; a and b are transition zones.
C H2g ! CH4 g r H 71:81 kJ mol
7
The mechanism and kinetics of these reactions are

described by Walker15.
The approximate relative rates of gascarbon
reactions at 800 C and 0.1 atm. are given in Table 1.
Graphite
Table 1
Approximate relative rates of gascarbon
reactions at 800 C and 0.1 atm. pressure
Reaction
Relative rate
CO2
CH2O
CCO2
CH2
1 105
3
1
3 103
In the literature, there are a number of investigations of nuclear graphite reactivity in different oxidation conditions. Results of oxidation of HTR-10
nuclear graphite IG-1118 exhibited three regimes:
400600 C with an activation energy of 158.56 kJ
mol1, 600800 C, at which the activation energy
was 72.05 kJ mol1, and the third-zone, over 800 C
regime with a very low oxidation energy. The comparison of reactivity of the two types of graphite used
in HTR in oxygen and air at 650900 C (regime II)
leads to the conclusion that there is no difference in
the behavior of matrix graphite (A3-27) and standard
graphite V483T during oxidation.19 At the same
time, at a lower temperature (400 C, regime I) matrix
graphite is more reactive with respect to air. For the
temperature range 350520 C, the activation energy
Ea for A3-3 graphite matrix amounts to 110 kJ mol1.20
The oxidation in air and moisture has to be considered for dismantling and interim storage, whereas
the reaction with humidity and aquatic phases is
important for final disposal.
Several investigations into virgin and irradiated
graphite have been carried out, mostly in air at
ambient pressure. A comprehensive review was
made by Stairmand,21 who concluded that significant
graphite oxidation can be excluded at temperatures
below 350 C.
However, graphite oxidation in air can occur in
high irradiation fields. Duwe et al.22 showed the consumption of oxygen and the production of carbon
dioxide during the interim storage of HTR fuel pebbles in sealed cans. But the dose of the irradiation
field from freshly irradiated fuel pebbles is normally
not relevant to the interim storage or final disposal of
i-graphite.
5.21.4.2.2 Graphite reactions with liquids
Graphite does not react with alkaline and acidic

solutions if no oxidizing agent is present. Dissolved
oxidants such as nitric acid, ozone, hypochlorides,
and hydrogen peroxide attack graphite to different
degrees.2326 An important factor is the surface area,
which depends mainly on pore volume and pore size.
545
The reaction with oxidizing agents, for example,

concentrated nitric acid, leads finally to the evolution
of carbon dioxide:
C 4HNO3 ! 2H2 O 4NO2 CO2
However, different stable intermediate reaction
products can be formed: graphitic oxide (C7H2O4),
mellitic acid (C6(CO2H)6), and hydrocyanic acid
(HCN). The yield of these products and carbon
dioxide depends on the reaction conditions and the
nature of the graphite material.
Contact of i-graphite with aqueous phases during
interim storage or final disposal cannot be excluded
with an absolute certainty. In such a case, the oxidation of i-graphite depends mainly on the irradiationinduced production of highly reactive species by
radiolysis of the aqueous phase and the accessible
graphite surface. Corrosion experiments with A3-3
graphite show that the corrosion rate of graphite is
increased in final repository relevant aqueous phases
by external g-irradiation with a dose rate of 2 kGy
h1.27 The obtained corrosion rates are in the range
from 105 down to 107 g m2 day. High chloride
concentrations accelerate the graphite corrosion
probably by the formation of hypochlorides. This
clearly indicates that irradiation-induced corrosion
processes are relevant to the final disposal of graphite.
However, this is an extremely high dose rate not
relevant to the disposal of i-graphite. The first attempt
to determine the relation between the dose rate and
the corrosion rate was made in the framework of the
European RAPHAEL project.28 However, the low
number of performed measurements and the scattering of the obtained data did not allow the derivation of
a validated data set for such a correlation.
5.21.5 Graphite Radioactivity

The utilization of graphite in a reactor leads to two
different types of radioactive contamination in the
graphite material, the contaminants being
Activated impurities in the bulk graphite material
Radioactive isotopes occurring in the reactor circuit
The activation products are more or less homogenously distributed in the graphite, depending on
the original location of the impurities, as well as on
the possibility of their migrating in the graphite by
thermal gradients induced by the reactor conditions
and repulse effects during the activation process
itself. The radioactive isotopes from the reactor
546
Graphite
circuit are located (adsorbed) primarily at the graphite surface and migration into the bulk material
requires a transport force, which could be a thermal
gradient. The depleted isotopes have different
origins:
Activation products of the coolant.
Impurities in the coolant.
Corrosion products from steel constructions of the
reactor distributed in the coolant and activated in
the reactor core.
Release of fission products from fuel elements with
a cladding failure.
These different sources of the radioactive contamination indicate that the activities of i-graphite depend
on the reactor type, the type of the utilized virgin
graphite material, and the operational conditions of
the reactor. Therefore, even i-graphite of similar reactor types can show different contamination levels and
different isotope ratios and a detailed characterization
of i-graphite is required before retrieval from a specific reactor in addition to calculated radionuclide
inventories. A good example of such an approach was
the compilation of the so-called Aktivitatsatlas des
AVR29 which was calculated and validated on the
basis of radiochemical analysis of i-graphite from different locations in the reactor core.
However, a detailed consideration of the different
i-graphite materials from different reactor types
and different graphite types will not be helpful. Furthermore, the amount of detailed information would
definitely be out of the scope of this review and not
indicate the significant general problems of the waste
management of i-graphite.
The dose rate, one of the key parameters for the
retrieval and interim storage of i-graphite, depends
mainly on the 60Co activity. 60Co has a half-life of
5.3 years. The main source of 60Co in i-graphite is the
abrasion of fine metal parts from the pebble loop
system, which has been built up in the pipes by
neutron activation. Therefore, waiting for some
decay periods can be helpful to reduce the dose per
person for the workers at dismantling. Another
important parameter for retrieval is the release of
radionuclides into air. This could occur in the form
of contaminated dust, which can be handled by adequate exhausting methods. More problematic is the
release of tritium as gaseous component. However, it
must be ensured that information specific to the
reactor is retained during this period.
For final disposal, 14C and 36Cl have been identified as key nuclides with respect to the long-term
safety, due to their long half-life, mobility, and biocompatibility.

5.21.5.1
Formation of 3H
The radionuclide 3H, tritium has a half-life of

12.3 years. The contribution of radioactivity in nuclear
graphite resulting from tritium is significant.2931 It is
produced by the following reactions:
Fission reactions of uranium impurities in
the graphite and fuel cladding failure, such as
235
U(n,f) 3H reactions.
Lithium impurities in the graphite via 6Li(n,a)
3
H reactions.
3He (n,p) 3H in HTR reactors, which utilize
helium as coolant.
10B (n,2a) 3H reactions in absorber rods (negligible
for designs without core rods).
The chemical properties of tritium are essentially
the same as those of ordinary hydrogen. Tritium
generated from lithium impurities is produced
mostly in graphite bulk. The release of tritium is
controlled by its diffusion out of the grain boundaries
and into the pore system.
5.21.5.2
Formation of 14C
Three routes, shown in Table 2, have to be considered for the formation of 14C. In the reactor core
materials, nitrogen is present only as an impurity,
whereas carbon and oxygen are in some cases major
constituent elements of the coolant, moderator, or
fuel. In spite of this fact, the 14N activation reaction
is usually more important for 14C production due to
its large cross-section. Therefore, the location and the
chemical form of nitrogen are important for the location of the formed 14C. Nitrogen levels vary widely
from 10 to 100 ppm in different reactor graphite
types30 and sometimes they are not known very precisely. A comprehensive study of 14C has been carried
out by Marsden et al.31 Calculations showed that
about 70% of the 14C originates from nitrogen impurities with an assumed amount of 50 ppm by weight.
Table 2
Activation reactions generation 14C
Reaction
Abundance of isotope
in natural element (%)
Capture crosssection (barn)
14
99.63
1.07
0.04
1.81
0.0009
0.235
N(n,p)14C
C(n,g)14C
17
O(n,a)14C
13
Graphite
Another source of 14C is the oxygen pathway from

the coolant. A birth ratio of 14C has been calculated
for an AGR from 17O:14N:13C as 25:21:1, assuming
50 ppm nitrogen.
Besides the level, the location of nitrogen impurity
in reactor core materials is an important parameter.
The nitrogen content of graphite is reduced during
manufacture by several high-temperature treatment
steps. However, the different heating and cooling processes cause the formation of cracks and closed pores,
which could be filled with air. Therefore, the absorption of nitrogen on graphite surfaces as well as the
nitrogen diffusion in the graphite matrix is one of the
major parameters for the local distribution of 14C in
i-graphite. Takahashi et al. reported that the nitrogen
content in graphite depends on the surface area of the
graphite and decreases from the surface to a depth of
about 30 nm32 and that 14C produced from nitrogen
will remain at its original position. This is in agreement
with the 14C distribution of HTR fuel pebbles from
the German AVR33 (Figure 2) and with the observation of a preferential release of 14C by surface oxidation
of i-graphite from the German high-temperature reactor AVR in a nitrogen/steam atmosphere.36
Takahashi et al.32 reported that the kinetic energy
of the formed 14C atom is about 470 kJ mol1, which
is in the range of covalent carbon bonding energies
and therefore the 14C atom will be attached to nodes
of the carbon lattice. They suggested that 14C will not
be released by radiolytic oxidation of the graphite.
Ci g1(C)
547
However, this is also a surface-related reaction and a

similar release should be assumed as observed for
thermal surface oxidation. This is in contradiction
to Finn reporting a backscattering energy of 40 keV
(4 106 kJ mol1) for 14C formation.37 This would
be significantly above any chemical bonding energy
and would lead to movements in the lattice and the
formation of new species. This high backscattering
energy as well as the large number of displacements
of carbon atoms during irradiation should lead to
a more homogenous distribution of 14C. However, the
displacements are in the range of 12 mm so that 500
displacements in one direction would be required for
a transport of 1 mm. So generally, it can be assumed
that 14C produced by activation of 13C is more or less
homogenously distributed as opposed to 14C generated
from 14N which is located in near-surface areas.
However, it cannot be concluded in general that
the 14C in i-graphite at the end of the reactor life is
generated mainly by nitrogen activation. Surface oxidation of i-graphite irradiated in carbon dioxide during reactor operation could reduce surface-bound
14
C. This reaction, as well as low amounts of nitrogen
impurities, could result in the remaining 14C inventory
being generated mainly by activation of 13C. Activation calculation for the Bugey 1 reactor shows that
the 13C activation leads to 96% of the measured
inventory 14C in i-graphite and only 4% of the
inventory must be addressed to nitrogen activation.38
This would also be in agreement with the results
obtained by Pichon,39 which show a fast release of
about 0.1% of the 14C inventory followed by a negligible leaching phase (Figure 3). A possible explanation could be a covalent bonding of 14C resulting
from 13C activation in the graphite matrix and leachable 14C fraction from nitrogen activation loosely
absorbed at the surface.
5.21.5.3
10
20
30
mm
Figure 2 Distribution of 14C in an high-temperature

reactor (HTR) pebble fuel element. Adapted from
Schmidt, P. Alternativen zur Verminderung der C-14-Emission
bei der Wiederaufarbeitung von HTR-Brennelementen;
Forschungszentrum Julich: Julich, 1979.
Formation of 36Cl
The dominant formation of 36Cl is by the neutron

activation of 39K (2.2 barn), the main stable natural
chlorine isotope with an occurrence of about 75%.
Chlorine itself is used for the removal of metal impurities in graphite by the formation of volatile chlorides. However, residual amounts of chlorine remain
in the graphite. Therefore, new cleaning methods for
nuclear graphite avoid the utilization of chlorine.
Furthermore 36Cl can be built by n,a-reaction of
39
K (4.3 mbarn) or from 34S via an n,g-reaction to
35
S (2.3 barn) followed by a b-decay to 35Cl. But these
reactions have no significant relevance.
548
Graphite
Cumulative released
fraction of 14C (%)
0.08
N 8 Lime water
0.07
N 10 Lime water
N 9 Pure water
0.06
0.05
0.04
0.03
0.02
0.01
0
0
50
100
150
200
250
300
Time (days)
350
400
450
500
Figure 3 Leaching behavior of 14C from French G2. Adapted from Pichon, C.; Guy, C.; Comte, J. Cl-36 and C-14 behaviour
in UNGG graphite during leaching experiments, 2008.
Fraction of data less than concentration
1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
Measured by NAA
Inferred from 36Cl
0.2
0.1
0
0
0.2
0.4
0.6
0.8
1.2
Initial chlorine concentration (ppm)

Figure 4 Initial chlorine concentration in Oldbury moderator graphite as measured by NAA and as inferred from
36
Cl activation. Adapted from Brown, F.; Palmer, J.; Wood, P. Derivation of a radionuclide inventory for irradiated
graphite-chlorine-36 inventory determination. In IAEA Technical Committee Meeting on Nuclear Graphite Waste
Management, Manchester, UK, 1999.
An investigation of core graphite from the Oldbury reactor shows the correlation of the initial chlorine impurities and the 36Cl inventory (Figure 4).40
Furthermore, the investigation shows chlorine loss
during irradiation. This is explained by the release
of chlorine from open pores and an activation of
chlorine in the closed pores. However, radiolytic
oxidation during operation will open the closed
pores by graphite oxidation, which results in an additional release path for 36Cl (see Figure 5).
Leaching experiments with French i-graphite
from G2 showed that a major amount of 8085%
will be leached from the graphite in 1 month.

A further 510% will be leached in a period of
about 1 years (Figure 6).39 This is in agreement
with the proposed chloride form of 36Cl located at
water-accessible surfaces and its high solubility.
A small part of 510% 36Cl remained in the graphite.
This could be explained by 36Cl located in graphite
areas that are not in contact with the leaching media,
for example, closed pores, or by covalent bonds
between the chloride and the carbon atoms of the
graphite lattice. Further investigations are required
to clarify the nature of the nonleachable 36Cl.
Graphite
Closed porosity
35Cl
Open porosity
Oxidation
Activation
549
Primary circuit
Release
35Cl
35Cl
Activation
Oxidation
36Cl
Release
36Cl
36Cl
Figure 5 Schematic of activation and release of chlorine in graphite.
Cumulative released fraction of

36Cl (%)
100
90
80
70
N 5 Lime water
N 10 Lime water
N 8 Lime water
60
50
N 6 Pure water
N 9 Pure water
N 2 Pure water
40
0
100
200
300
400
500
Time (days)
Figure 6 Leaching behavior of 36Cl from French G2. Adapted from Pichon, C.; Guy, C.; Comte, J. Cl-36 and C-14 behaviour
in UNGG graphite during leaching experiments, 2008.
5.21.5.4 Diffusion of Radionuclides in

Graphite
Diffusion in polycrystalline graphite is a complex
topic strongly related to the structure of the graphite.
The three general diffusion types, listed in the order
of increasing diffusion velocity, are:
Volume diffusion by movements of atoms due to
the presence of lattice defects or exchange of lattice positions.41
Diffusion along grain boundaries.
Pore diffusion.
All the three different diffusion types can occur in
graphite: Volume diffusion in the graphite crystallites,
grain boundary diffusion at the micropores between the
crystallites, and pore diffusion in the pores between
the graphite particles. Self-diffusion of carbon in graphite occurs at temperatures about 2000 C42 and may be
important for central zones of HTR fuel elements.
Diffusion of fission products in graphite has

been studied intensively with respect to radionuclide release from HTR fuel elements. All these
processes become effective at higher temperatures
and can be neglected at temperature ranges relevant
to retrieval, interim storage, and final disposal.
However, they might be interesting for decontamination processes, especially for tritium. Table 3
shows some diffusion coefficients measured for
A3-3 graphite from HTR fuel pebbles, pitch coke
(AS1-500), and petrol coke (AL2-500) after
irradiation.43,44
The diffusion and release processes of radionuclides in i-graphite depend strongly on the nature of
the graphite and especially on the anisotropy of the
graphite.45,46
Tritium can be released from graphite more or
less completely by thermal treatment under inert
atmosphere at temperatures in the order of
1300 C.36
550
Graphite
Table 3
Diffusion coefficients of tritium nuclear graphite

Type of
graphite
Temperature ( C)
Diffusion coefficient,
D0 (s1)
A3a
A3a
A3a
A3b
AS1-500b
AL2-500b
800
850
900
1000
1050
1025
1.72 109
9.09 109
6.89 108
8.18 109
9.83 1011
1.83 1010
Irradiation at temperatures < 100 C.

Irradiation at temperatures 500 C.
5.21.6 Graphite Treatment for

Disposal or Recycling
5.21.6.1 Waste Packages and
Encapsulation
Containers or drums are used as a packaging option
for i-graphite, mainly for safe handling in the operational phase of waste management and not as a barrier for long-term safety aspects. No special designs
of containers or drums have been made for i-graphite
and standards from common waste management are
applied. Therefore, this aspect is not covered in this
chapter. However, it must be mentioned that graphite can act as a noble metal and accelerate the
galvanic corrosion of stainless steel containers and
measures should be implemented to isolate the
graphite from the container or container materials
with a guaranteed lifetime until final disposal
should be used.
Another problem may arise while filling the waste
container, especially if more or less rectangular
graphite bricks are filled into drums. The disposal
costs depend on the classification and volume of the
radioactive waste and not on the weight. Therefore
different methods have been developed to achieve a
high packing density but all methods will generate
secondary wastes in the form of graphite dust.
Bach et al. compared grinding, plasma cutting, jet
cutting, wire sawing, and hydraulic breaking of
graphite, especially with respect to the related release
of graphite dust.
The encapsulation aims at a safe enclosure of the
waste by retardation or immobilization of radionuclides to avoid a release into the environment or at
least to reduce the release to an unobjectionable
level. Generally two options exist for encapsulation.
Embedding in a matrix material.
Impregnation of the graphite to fill the open pores.
The reference waste package concept for graphite

waste envisages the embedding of i-graphite in
cement pastes. The cement will establish an alkaline
environment in the pore water, which will reduce the
solubility of many key nuclides. Especially 14C will
form insoluble carbonates if it is oxidized to CO2 by
radiolysis processes. Further, the different cement
phases combined with a large pore surface area will
be able to absorb radionuclides or build insoluble
secondary phases. On the other hand, the porous
structure will not hinder the contact between aquatic
phases and the waste and therefore a radionuclide
release cannot be excluded, especially for 36Cl, which
shows no significant retardation by cement.
Alternative embedding materials could be glass,
polymers or resins, bitumen, low-melting metals, or
ceramics. The organic materials would all result in a
dense waste package that protects the graphite from
leaching. However, the production process and the
handling are related to a potential fire hazard. Furthermore, the long-term stability could be less than
the half-life of the key nuclides due to radiolysis or
ageing processes and therefore water exclusion cannot be guaranteed for the final disposal time scale.
Low-melting metals may have sufficient corrosion
stability, which has not been sufficiently determined
for disposal conditions. However, their own toxicity
may create a problem. For example, the license for
the German low-level waste underground disposal
site Konrad allows only the disposal of 72 Mg tin,
539 Mg zinc and 33 400 Mg lead due to the water
protection law of Lower Saxony.
The vitrification of graphite will result in a wellknown product similar to vitrified high-level waste.
Besides the known problems of the final disposal of
high-level waste such as fracturing, the graphite may
react with the glass melt and form dispersed gas
pebbles (bubbles?), which is known from the embedding of coated particles from HTR fuel.
The closing of the open pore system of graphite
has been successfully tested by impregnation with
bitumen, epoxy resins, and tar. Therefore, the graphite has to be evacuated and then immersed in bitumen
or resin under high pressure at elevated temperatures
to obtain a sufficient fluidity. Leaching tests with such
an impregnated material have proved the high immobilization potential of this procedure. However, this
would lead to problems similar to those already
described for materials used as embedding.
A new approach to fill the pore system of i-graphite
is a process that can be classified between embedding
and impregnation. It foresees the granulation of the
Graphite
i-graphite and a high-temperature compaction after

mixing with glass in an amount equal to the pore volume. First attempts show a density of about 2.2 cm3 g1,
which is close to the theoretical density, and that the
glass does not increase the total volume. Furthermore,
this method would lead to volume-optimized waste
packages because the produced block dimensions can
be adjusted to the waste container dimensions. However,
the proposed good leaching resistance and mechanical
properties are yet to be demonstrated.
5.21.6.2
551
Centre, Julich (former KFA Julich). This development was related to the reprocessing of HTR fuel
pebbles. Another process, based on inductive heating,
has been developed by Westinghouse for graphite
fuel compacts.
However, the incineration of graphite would
result in a total release of 14C as CO2 together with
the bulk 12CO2, which may causes local increases of
the 14C activity in the surrounding area of the incineration plant. Therefore no public acceptance could be
achieved for such a graphite treatment option, even if
the released 14C activity would be negligible in comparison with the natural 14C amounts. The trapping of
CO2 is no alternative. Solidification of the CO2 as
insoluble calcium carbonate from 1.2 tons of graphite
(0.7 m3) would produce 10 tons CaCO3 (3.7 m3).
However, such a process has the advantage that the
14
C has been transferred into a defined species and will
have a more or less homogenous distribution.
An advanced thermal treatment method has been
developed first at the Research Centre, Julich. It was
shown that the majority of the carbon 14C inventory
could be removed from the AVR reflector and fuel
graphite and graphite from the thermal column of the
research reactor FRJ-1 by partial oxidation.34 The AVR
Graphite was irradiated at a high temperature in an
inert helium atmosphere and the other graphite at room
temperature in an air atmosphere. The thermal treatment process for 14C separation was performed in
nitrogen or argon plus 2% oxygen or humidified nitrogen or argon. First examinations by Podruzhina showed
a 14C release of about 70% with a total graphite oxidation in the range of 20 to 30%.34 This results were
Thermal Treatment
The most effective volume reduction would be the

complete oxidation of the i-graphite with a small ash
residue which contains the nonvolatile radionuclides.
Volatile radionuclides like tritium, 36Cl, or 137Cs may
cause some problems but could be trapped from the
off-gas and solidified for final disposal. (Tritium in
the form of HTO could be used for the production of
cement paste used as embedding material for radioactive waste.) Another problem is the incineration of
nuclear graphite due to its chemical purity. The high
thermal conductivity will conduct the heat from the
surface into the bulk material, which inhibits incineration. The poor combustibility of graphite was
shown by the first attempt of CEA, utilizing a coal
stove. Therefore, the material must be crushed before
incineration. Milling can be performed technically
without dust release but requires great effort. The
burning itself could be performed in furnaces or
in fluidized bed reactors. The burning of crushed
graphite has been demonstrated at the Research
100
Release rate (%)
80
60
14
C release rate; nitrogen + steam

Total carbon release rate; nitrogen + steam
C release rate; nitrogen + 2% oxygen
Total carbon release rate; nitrogen + 2% oxygen
14
40
20
0
0
Figure 7
14
50
100
150
200
Time (min)
250
300
350
C release and total carbon oxidation by thermal treatment of Allgemeiner Versuchsreaktor graphite at 1230 C.
552
Graphite
confirmed by Jansen.35 Higher release rates were

obtained by Florjan.36 Up to 60% of 14C will be released
within the first 60 min followed by a slower release of
2030% in the next 27 h (Figure 7). The best 14C
release rates have been obtained at temperatures of
about 1200 C, whereas the separation of 12C and 14C
is better at lower temperatures (Tables 4 and 5). But the
release rates of Florjan could not be repeated until now.
Furthermore, these results show the different 14C
release behavior of the different graphite types under
similar treatment conditions. The best results have been
obtained with AVR graphite. This is explained by the
inhomogenous distribution of 14C with higher 14C concentrations on the surface and the existence of more
reactive 14C containing species. This indicates that the
irradiation conditions have an important influence on
this process and that further investigations will show
whether this process can be applied to CO2-cooled
reactors or RMBK reactors. However, this process
could be an alternative waste treatment option only
when 5% of the graphite materials have to be oxidized
and captured as CaCO3, if sufficient decontamination
factors can be achieved with these graphite types.
The removal of 14C from graphite has been considered the main problem in decontaminating graphite. However, the separation of radionuclides other
than 14C has to be managed, which can be performed
by different methods.
Table 4
5.21.6.3 The Russian Self-Propagating

High-Temperature Synthesis SHS
Graphite is homogenously mixed aluminum and titanium dioxide. The amounts are related to the following reaction:
3C 4Al 3 TiO2 ! 2 Al2 O3 3TiC
The exothermic reaction is self-propagating and
only an initial start is required. The formed stable
14
C release by thermal treatment in N2 + 2% O2
Sample
R7
Origin
AVR
Treatment time (h)

Temperature ( C)
Total carbon release (%)
14
C release (%)
Separation factor
Table 5
An option would be the complete incineration of

the residual graphite, which would result in two more
waste streams. The residual 14C including the CO2
stream could be released in the environment if sufficient decontamination rates can be achieved or
fixated as CaCO3, which can be sent to a surface
disposal site. The second waste stream will be a
very small quantity of high active ashes and filter
dust which must be disposed as high-level waste
after an appropriate fixation. A typical volume reduction would be in the range of 160 for an incineration
process for nuclear graphite.1
A second option would be direct disposal in a nearsurface disposal site. However, this would require a
sufficient reduction of the 36Cl inventory (see Chapter
1.06, The Effects of Helium in Irradiated Structural
Alloys), which has not been investigated yet.
R8
K8
K9
M3
M4
FRJ2
Reflector graphite
Fuel graphite
3
900
2.85
61.0
21
3
900
2.69
62.2
23
3
1230
2.94
78.8
27
3
900
1.87
43.2
23
3
1230
2.32
64.4
28
K5
K6
M2
MS2
3
1230
4.04
79.8
20
Thermal column
14
C release by thermal treatment in N2 + steam
Sample
R6
Origin of graphite
AVR
Treatment time (h)

Temperature ( C)
Total carbon release (%)
14
C release (%)
Separation factor
R10
FRJ2
Reflector graphite
Fuel graphite
7
900
0.85
41.0
48
7
900
1.48
70.0
47
7
900
1.55
45.0
29
Thermal column
7
1280
5.40
92.6
17
7
900
4.12
69.8
17
7
900
0.02
49.0
2250
Graphite
titanium carbide contains 14C and the other radionuclides incorporated into the corundum and titanium carbide lattice. Additional confining additives
can be added to the reaction mixture, for example,
zirconium, which build even more stable crystalline
phases with selected radionuclides such as uranium
and plutonium. Furthermore, additives are used to
improve the final product quality and to minimize the
volatilization of radionuclides.
Therefore, this process is also suitable for graphite
contaminated with actinides from the Russian production reactors. The process requires a carefully controlled regime to minimize the radionuclide release.
5.21.6.4
Recycling of i-Graphite
The reuse of i-graphite may open a waste management route that has the potential to reduce the
amount of i-graphite for disposal.
The easiest attempt would be the direct use of
i-graphite without any treatment for the production of new materials for the nuclear industry.
Generally, it is known that used graphite can be
recycled as additive material for graphite production.
However, this cannot be done with i-graphite in
the existing graphite production facilities. Even lowcontaminated graphite must be handled in a closed
manufacturing unit to avoid the release of contaminated graphite dust. Furthermore, the amount of
i-graphite suitable for direct reuse is small in comparison with the total amount of i-graphite. Therefore
reuse will be associated with decontamination of
i-graphite. The success of the decontamination
depends on the achievable decontamination factors,
especially of 14C.
In principle, two methods could be proposed for
decontamination:
The wet method of leaching the graphite with
suitable decontamination agents such as mineral
acids or alkaline solutions.
Decontamination by thermal treatment in steam
or diluted oxygen atmosphere.
Both options are under investigation in the European Carbowaste project.47 At the moment, there
are not enough results from the leaching process to
evaluate the feasibility of this method, whereas the
thermal treatment mentioned in Section 5.21.6.2
has already proved its potential to remove 14C from
the i-graphite matrix. Figure 8 shows potential
routes to obtain feedstock material for graphite recycling. Two options can be considered after thermal
553
14
C decontamination. The first option is the total

oxidation of the residual graphite to find out if the
remaining 14C amount in the graphite would allow a
free release of the off-gas into the atmosphere. The
expected residues are in the range of a few kilograms
per Mg graphite. The alternative is treatment with
graphite cleaning methods known from the graphite
industry to remove the residual nonvolatile radionuclides to a level that can be handled in further
production steps. Potential products could be silicon
carbide, waste additives, and feedstock material for
new graphite materials in the nuclear industry.
The production of materials will definitely be
cheaper if fresh feedstock materials are used, but
the benefit will be the reduced waste volume (see
next section).
Another interesting aspect of the separation of the
14
C is the option to replace 14C production as tracer
material for scientific purposes by irradiation of nitrates.
5.21.7 Final Disposal

Figure 9 shows the general routes for radioactive
waste classification in different countries. Among
the European Union states, the Belgian and French
schemes are very similar and are closely related to
the EU classification scheme, which is based on the
general IAEA recommendations. These schemes formally recognize the lifetimes of the predominant
radionuclides within waste packages, and segregate
low- and intermediate-level waste into short-lived
and long-lived categories, on the basis of whether
the half-lives of these nuclides are less than or greater
than 30 years respectively.
Generally i-graphite can be assumed to be low- or
medium-level radioactive waste by these regulations,
whereby the classification for final disposal of
i-graphite is determined mainly by the inventory
of long-living radionuclides 14C and 36Cl. The high
bio-compatibility and the good solubility of 36Cl if it
occurs as chloride and therefore its high mobility
require larger efforts to provide a safe enclosure
from the environment.
The French surface disposal site Centre de lAube
has a total limit for the disposal of 0.4 TBq for 36Cl.
Figure 10 shows a calculation of the 36Cl inventory of
the stack of Bugey 1 plus some measured data. The
graphite core of the reactor Bugey 1 would have a 36Cl
inventory of about 0.1 TBq, assuming an average level of
50 Bq 36Cl g1, which is probably too low as shown in
Figure 10. Measured values for Bugey 1 reveal an
554
Graphite
i-graphite
Disposal
Solidification
14
C depleted
i-graphite
Partial oxidation in
steam or diluted oxygen
14
C enriched
off-gas in the
form of CO or CO2
14
C separation
14
C products
Option 1
Total oxidation
Option 2
Free release of the off-gas

(depending on the
residual 14C inventory)
Reconversion of CO and
CO2 off-gas to carbon
Solidification and disposal
Further graphite cleaning by high temperature

treatment may be in presence of halogens as
decontamination agent
Other carbon-based products

(e.g., SiC, lamp black, waste
additives)
Additive for new graphite
products
Figure 8 Process scheme of a potential process for thermal treatment of i-graphite.
average of about 200 Bq g1. Furthermore 36Cl is easily

leached, which has been discussed in Section 5.21.5.3.
Therefore, a near-surface disposal of graphite is not an
acceptable waste management option in France.
The situation in the United Kingdom is similar. An
estimate of the total 36Cl inventory is given by David
Lever.48 It is in the range of 23 TBq for the British
i-graphite. This 36Cl inventory will not allow the
near-surface disposal at the Drigg site if the release
could not be excluded over geological time scales.
A further aspect of UK reactors is the release of

C if it is in the form of methane. Figure 11 shows a
risk analysis of such a release if all the 14C is released
as methane. The assumption will not be true for
i-graphite; however, no quantitative results that give
a clear figure about the relation between 14CO2, 14CO,
and 14CH4 in the long-term release of 14C under
disposal conditions are available. However, there is
some evidence that organic 14C compounds cannot be
neglected. Leaching of HTR fuel spheres shows a
14
Belgium
France
VLLW < 100
Bq g-1
Cal A low
concentrations
short half-lives
(Criteria X and Y)
LLW
Short-lived halflives < 30 years;
activity between 100
and 105 Bq g-1
ILW
Short-lived halflives < 30 years;
activity between
105 and 108 Bq g-1
European Union
Transition waste
IAEA
United Kingdom
EW Exempt waste
VLLW less than 400

kBq of b/g
activity per 0.1 m3
material
LILW-SL
LILW-SL
Short-lived half-lives
< 30 years
Short-lived half-lives
< 30 years
LLW
Long-lived halflives > 30 years;
Cal B medium or activity between 100
LILW-LL
long half-lives in
and 105 Bq g-1
relatively high
Long-lived half-lives
ILW
concentrations
> 30 years
Long-lived halfpower < 20 W m-3
lives > 30 years;
LILW-LL
Long-lived half-lives
> 30 years
activity between
105 and 108 Bq g-1
Cal C substantial
HLW;
amounts of b- and
activity between 108
a-emitters
and 1010 Bq g-1
power > 20 W m-3
HLW
HLW
Figure 9 Comparison of radioactive waste classification schemes.
Spent nuclear fuel

Waste with negligible
heat generation
LLW < 4
GBq t-1 of
a and
<12 GBq t-1
of b/g
activity
Landfill/free disposal
Surface disposal
Geological disposal
High-level waste (HLW)

similar to European
definitions; arises mainly
from manufacture of nuclear
weapons
Transuranic waste (TRU):
radioactive waste containing
more than 3.7 103 Bq g1
(100 nCi g1) of a-emitting
transuranic isotopes with
half-lives > 20 years
nuclear weapons
ILW >4
GBq t-1 of
a or >12
GBq t-1 of
b/g activity, no
heating
consideration
in storage
HLW as ILW and with
cooling in storage
facilities
United States
Uranium mill tailings

Naturally occurring
radioactive material
Heat-generating waste
Low-level radioactive
waste (LLW): by definition:
everything else
Graphite
Generic disposal routes
Germany
555
556
Graphite
1.00E + 03
Bq g de 36Cl
1.00E + 02
Measures
C2J6
C1K7
B319
C4H2
B8J0
C2L4 = C2G6
ABlB
C3F9
D9Jl = A619
Risque = 50.00%
Risque = 2.50%
Risque = 0.10%
Initial centre
Initial + 2 sygma
1.00E + 01
1.00E + 00
36Cl
measurements
Activation
calculation results
for each channel
where the
samples come
from
1.00E 01
11
13
15
17
19
21
Height (m) in the graphite stack (cooling gas flow direction)
23
Figure 10 Activation calculation results on BU1 stack with data assimilation method: 36Cl.
1E 02
1E 03
1E 04
Total
Magnox spheres
1E 05
1E 06
1E 07
Uranium spheres
Stainless steel spheres
Carbon steel spheres
1E 08
Organic degradation
1E 09
1E 10
Radiolysis organics
Release from graphite
Risk target
1E 11
1E 12
1E 13
1E + 00
1E + 01 1E + 02
1E + 03 1E + 04
1E + 05
1E + 06
Years postclosure (postclosure starts calendar year 2150)
Figure 11 Radiological risk versus time for 14CH4 by contributory sources. Adapted from Lever, D. Graphite Wastes:
Disposal Issues; Manchester, UK, 2006.
higher release of organic 14C than 14CO2, but as dissolved organic species and not as gaseous species.49
In Germany, radioactive waste is divided into two
classes: waste with and without significant heat development. Deep underground disposal is planned for
both types. The former Konrad iron mine has been
designated as the disposal site for the nonheat developing waste and is proposed to be ready for waste disposal
in 2013. The graphite from the reactor core of the AVR
and THTR clearly belongs to the category of non heat
developing waste and therefore could be disposed of at
this site. However, the 14C inventory of about
2.9 1014 Bq for the ceramic core interior from the
AVR will claim a major share of the licensed
C inventory (4 1014 Bq) of this disposal site and

will limit the disposal of other radioactive waste. Furthermore, the actual interim storage stage will extend
beyond the proposed operational time of this disposal
site and therefore alternatives are required.
14
5.21.8 Summary
A general solution for the management of i-graphite
has not been established yet. Only France has an ambitious final disposal plan for its i-graphite, with the
proposal of the near-surface underground disposal
site at a depth of about 200 m. Other countries like
Graphite
the United Kingdom have not made a final decision for

a reference waste management route until now.
Three main challenges have been identified for
the waste management of i-graphite.
The first is the retrieval of the major amounts of
i-graphite from the reactor cores. Some experience is
available from the decommissioning of the BEPO,
GLEEP, and Fort Saint Vrain reactors. However, no
general methodology can be recommended because
the retrieval depends on many site-specific factors.
A major concern is the need for more data on
i-graphite. This includes data on property changes of
the structure and mechanical properties due to irradiation and the radionuclide inventory, as well as fundamental data concerning the behavior of i-graphite
during treatment procedures, and disposal behavior.
Future research should focus also on the speciation of
the chemical form of radionuclides because the chemical form determines the long-term release behavior
under final disposal conditions. Furthermore, the localization of the key nuclides 14C and 36Cl at a nano-scale is
a major challenge because a near-surface distribution
and a homogenous distribution in the bulk would lead to
completely different release characteristics.
Another challenge is the development of a safe waste
management route. Generally, two principal methodologies could be utilized: the decontamination of
i-graphite by chemical or thermal treatment to obtain
a carbonaceous material for further use in nuclear technology or the final disposal of i-graphite. The most
advanced plan for a final disposal has been achieved
by France, which is planning an underground disposal
site for low-level radioactive waste containing longliving radionuclides, especially 36Cl, 14C, and radium.
Therefore, i-graphite will be grouted in drums or containers and disposed of afterward. This could be
assumed as the actual reference concept. Other conditioning methods, which ensure the safe long-term
enclosure of 36Cl and 14C as the Russian RSH method
or a long-term stable sealing of the graphite pore system, for example, with glass,50 may be alternatives to
enable a near-surface disposal of i-graphite from reactor cores.
4.
5.
6.
7.
8.
9.
10.
11.
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14.
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Holt, G. The decommissioning of commercial magnox
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Bastien, D. (CEA Centre dEtudes Nucleaires de Saclay,
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Delle, W.; Koizlik, K.; Nickel, H. Graphitische Werkstoffe
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Verbrennungs-Head-Ends fur HTR-Brennelemente,
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Duwe, R.; Brucher, H.; Fachinger, J. R&D on Intermediate
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Gomez-Serrano, V.; Acedo-Ramos, M. A.;
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Appendix 1 Amounts of Irradiated

Graphite in Different Countries
Table A.1
Graphite-moderated reactors in Russia
Reactor
Graphite amount (Mg)
Scheduled
shutdown
Kursk 1
Kursk 2
Kursk 3
Kursk 4
Leningrad 1
Leningrad 2
Leningrad 3
Leningrad 4
Smolensk 1
Smolensk 2
Smolensk 3
Total
2000
2000
2000
2000
2638
1798
1798
1798
2158
1798
1798
19 988
2021
2024
2013
2015
2018
2020
2009 + 20 years
2011 + 20 years
2013
2020
Graphite
Table A.2
559
Graphite-moderated reactors in United Kingdom
Location
Reactor
Type
Graphite in reactor (tons)
Graphite total (tons)
Dungeness
Dungeness
Hartlepool
Hartlepool
Heysham
Heysham
Heysham
Heysham
Hunterston
Hunterston
Hinkley Point
Hinkley Point
Torness
Torness
Bradwell
Bradwell
Calder Hall
Calder Hall
Calder Hall
Calder Hall
Chapelcross
Chapelcross
Chapelcross
Chapelcross
Dungeness
Dungeness
Hinkley Point
Hinkley Point
Oldbury
Oldbury
Sizewell
Sizewell
Wylfa
Wylfa
Berkeley
Berkeley
Hunterston
Hunterston
Trawsfynydd
Trawsfynydd
Windscale
Winfrith
Windscale
Windscale
Harwell
Harwell
Total
B-1
B-2
1
2
Unit I-1
Unit I-2
Unit II-1
Unit II-2
B1
B2
B1
B2
1
2
Unit 1
Unit 2
Unit 1
Unit 2
Unit 3
Unit 4
Unit 1
Unit 2
Unit 3
Unit 4
A1
A2
A1
A2
Unit 1
Unit 2
A1
A2
A1
A2
Unit 1
Unit 2
A1
A2
Unit 1
Unit 2
WAGR
Dragon
Pile 1
Pile 2
BEPO
GLEEP
AGR
AGR
AGR
AGR
AGR
AGR
AGR
AGR
AGR
AGR
AGR
AGR
AGR
AGR
Magnox
Magnox
Magnox
Magnox
Magnox
Magnox
Magnox
Magnox
Magnox
Magnox
Magnox
Magnox
Magnox
Magnox
Magnox
Magnox
Magnox
Magnox
Magnox
Magnox
Magnox
Magnox
Magnox
Magnox
Magnox
Magnox
AGR
HTR
Air cooled
Air cooled
Air cooled
Air cooled
850
850
1360
1360
1520
1520
1520
1520
970
970
970
970
1520
1520
1810
1810
1164
1164
1164
1164
1164
1164
1164
1164
2150
2150
2210
3310
2061
2061
2237
2237
3470
3470
1938
1938
1780
1780
1900
1900
285
40
<2000
2000
766
505
65 080
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
1931
1931
1630
1630
1630
1630
1630
1630
1630
1630
2237
2237
2457
2457
2090
2090
2240
2240
3740
3740
1650
1650
2150
2150
1980
1980
285
40
<2000
2000
766
505
77 000
560
Graphite
Table A.3
Graphite-moderated reactors in France
Location
Reactor
Type
Marcoule
Marcoule
Marcoule
Loyettes
Avoine
Avoine
Avoine
Orleans
Orleans
Total
G1
G2
G3
Bugey 1
Chinon A1
Chinon A2
Chinon A3
St. Laurent A1
St. Laurent A2
Air cooled
UNGG
UNGG
UNGG
UNGG
UNGG
UNGG
UNGG
UNGG
1200
1207
1207
2039
1050
2200
2530
2572
2440
16 445
1200
1207
1207
3600
1060
2500
4000
4240
4100
23 114
Table A.4
Graphite-moderated reactors in United States
Location
Reactor
Type
Platteville, CO
Peach Bottom, PA
Hanford
Hanford
Hanford
Hanford
Hanford
Hanford
Hanford
Hanford
Hanford
Savannah River
Savannah River
Oak Ridge
Brookhaven
Chicago
Pacific North West Labs
Pacific North West Labs
Argonne National Laboratory
Fort Saint Vrain

Peach Bottom
B
D
F
DR
H
C
KW
KE
N
SR-305
SP
8 GR (X-10)
BGRR
CP1
HTLTR
HTR
CP2
HTGR
HTGR
LWGR
LWGR
LWGR
LWGR
LWGR
LWGR
LWGR
LWGR
LWGR
Test
ND
ND
1080
1080
1080
1080
1080
1080
1080
1080
1080
ND
ND
ND
440
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Air cooled
Test
Test
Air cooled
United States
Graphite pile
Graphite
Table A.5
Germany
Belgium
Italy
Japan
North Korea
Lithuania
Spain
Ukraine
China
561
Graphite-moderated reactors in other countries

Location
Reactor
Type
Graphite in reactor
(tons)
Graphite total
(tons)
Shutdown
date
Juelich
Uentrop
Mol
Borgo Sabotino
Tokai
Oarai
Nyongbyon
Visaginas
Visaginas
Hospitalet de
lInfant
Chernobyl
Chernobyl
Chernobyl
Chernobyl
INET
AVR
THTR 300
BR-1
Latina
Tokai 1
HTTR
Nyongbyon 1
Ignalina 1
Ignalina 2
Vandellos
HTGR
HTGR
Air cooled
Magnox
Magnox
HTTR
Magnox
LWGR
LWGR
Magnox
225
300
472
2065
920
ND
ND
1700
1700
2440
ND
300
472
ND
1600
ND
ND
2000
2000
ND
1988
1989 S
Unit 1
Unit 2
Unit 3
Unit 4
Tsinghua
HTR-10
ND
ND
ND
LWGR
LWGR
LWGR
LWGR
HTR
1700
1700
1700
<1700
111
2000
2000
2000
<2000
2000
1996 S
1991 S
2000 S
1986 S
Air cooled
LWGR
LWGR
ND
ND
ND
ND
ND
ND
Baotou
Jiuquian
Guangyuan
1987 S
1998 S
1990 S
5.22
Minerals and Natural Analogues
G. R. Lumpkin
Australian Nuclear Science and Technology Organisation, Kirrawee, NSW, Australia
T. Geisler-Wierwille
Universitat Bonn, Bonn, Germany
Crown Copyright 2012 Published by Elsevier Ltd. All rights reserved.
5.22.1
5.22.2
5.22.3
5.22.3.1
5.22.3.2
5.22.3.3
5.22.3.4
5.22.3.5
5.22.3.6
5.22.3.7
5.22.3.8
5.22.4
5.22.4.1
5.22.4.2
5.22.4.3
5.22.4.4
5.22.5
5.22.5.1
5.22.5.2
5.22.5.3
5.22.5.4
5.22.6
5.22.6.1
5.22.6.2
5.22.6.3
5.22.6.4
5.22.7
References
Appendix:
Introduction
a-Decay Damage in Minerals
Oxides
Pyrochlore Group
Zirconolite
Brannerite
Perovskite
Baddeleyite
Crichtonite
ABO4 and AB2O6 Minerals (B Nb, Ta, and Ti)
Hollandite
Silicates
Zircon
Thorite
Titanite (Sphene)
Allanite
Phosphates
Monazite
Apatite Group
Kosnarite and Related NZP Materials
Xenotime
Ore Deposits: Analogs for Spent Fuel
Preamble
General Aspects of Uraninite Alteration in Natural Systems
Natural Fission Reactors in Gabon
Uranium Migration in the Koongarra Ore Deposit
Conclusions
List of Mineral Names and Compositions
Oxides
Silicates
Phosphates, Arsenates, Vanadates
Carbonates, Fluorocarbonates, Fluorides
Sulfides
Uranyl Minerals (Section 5.22.6)
Abbreviations
apfu
AES
AFM
Atoms per formula unit

Auger electron spectroscopy
Atomic force microscopy
BSE
DTA
564
565
565
565
570
574
575
578
578
579
580
581
581
585
585
586
587
587
588
590
590
591
591
591
592
593
594
595
599
599
599
599
599
600
600
Backscattered electron, an imaging

mode in SEM, sensitive to mean
atomic number
Differential thermal analysis
563
564
EDX
EELS
EPMA
EXAFS
HLW
ICP-OES
IMF
IR
Ln
MM
MO
MOM
MOX
NZP
RDF
SEM
Synroc
Synroc-C
Synroc-F
TEM
TOF-SIMS
Urf6
vpfu
XANES
XPS
XRD
Energy dispersive X-ray analysis

Electron energy loss spectroscopy
Electron probe microanalysis,
quantitative X-ray analysis with
crystal spectrometers
Extended X-ray absorption fine
structure
High level waste
Inductively coupled plasma-optical
emission spectrometry
Inert matrix fuel
Infrared, a type of vibrational
spectroscopy complementary to
Raman spectroscopy
Lanthanide series elements, LaLu
Metalmetal distance in a crystal or
amorphous material
Metaloxygen distance in a crystal or
amorphous material
Metaloxygenmetal angle
Mixed oxide fuel, composed of
uranium and plutonium oxide
Sodium zirconium phosphate
Radial distribution function, a way of
describing MO and MM distances
Synthetic rock
Hollandite + perovskite + rutile +
zirconolite-based material for HLW
Pyrochlore + uraninite ceramic for
partially reprocessed fuel
Time-of-flight-secondary ion mass
spectrometry
A uranyl group with six equatorial
oxygen atoms
Vacancies per formula unit
X-ray absorption near edge structure
X-ray photoelectron spectroscopy
X-ray diffraction
5.22.1 Introduction
The immobilization and long-term disposal of
nuclear waste is one of the greatest challenges that
modern society faces today. Various types of high level
waste (HLW) have been generated from nuclear
operations around the world; for example, spent fuel
from commercial nuclear power stations, liquid waste
from the reprocessing of spent fuel, and waste from the
production of nuclear weapons and weapons grade

plutonium resulting from nuclear disarmament
treaties between the United States and Russia. Some
plutonium, particularly in France, has been used
in mixed oxide fuel (MOX, composed of uranium
and plutonium oxide) in place of the standard uranium
oxide fuel. Previous US policy adopted the strategy of
a once-through fuel cycle followed by direct disposal
of the spent fuel; however, recent changes have seen
a move toward more effective use of uranium-based
fuels in programs that combine reprocessing, transmutation, and separations technology in advanced fuel
cycles (e.g., Generation IV nuclear power systems).
Borosilicate glass is the currently accepted waste
form of choice for many countries that reprocess
their commercial spent fuel (see Chapter 5.18,
Waste Glass), but there exists a significant fraction
of legacy waste and other nuclear materials that are
very complex in physical form and chemical composition (e.g., the Na-, Al-, and Zr-rich waste stored in
tanks at sites in the United States). These complex
waste materials, together with impure plutonium, and
the separated fission products and actinides generated
from the various partitioning strategies may be better
suited for existing or new types of high-performance
crystalline waste forms or glass-ceramics (see Chapter
5.19, Ceramic Waste Forms). Some of these materials, for example, inert matrix fuels (IMFs), are being
designed for recycling of reactor-grade plutonium and
minor actinides in commercial power stations, followed by geological disposal, an attractive option that
does not generate new plutonium.1
As envisaged by G.J. McCarthy, A.E. Ringwood,
and others in the 1970s, there exist alternative crystalline waste forms that may be capable of providing
a much higher level of chemical durability than
borosilicate glass or directly disposed spent fuel.
Many of these materials have been extensively developed over the previous 2025 years, while others are
relatively new. Materials such as tailored ceramics,2
the synthetic rock (Synroc) polyphase titanate waste
forms,3,4 and related special purpose waste forms are
reasonably well developed and have been the subject
of extensive leach testing and radiation damage studies. Pyrochlore is the major component of Synroc-F, a
polyphase ceramic designed for partially reprocessed
nuclear fuel5 and later appeared as the principal host
phase for excess weapons Pu and U in a crystalline
titanate ceramic form. Zirconolite has also been proposed as an ideal host phase for actinides due to a
combination of crystal chemical flexibility and very
high durability in aqueous fluids,6 and hollandite
may provide an excellent host material for separated

long-lived radioactive Cs for similar reasons.7
Additional special purpose waste forms for actinides
include zircon,8 monazite,9 and zirconium-based materials having the fluorite, defect fluorite, or pyrochlore
structures.10,11 Except for zircon, none of these materials has been studied to the same extent as the titanate
waste forms. Nevertheless, monazite and Zr-based
materials are promising in view of their resistance to
amorphization and excellent chemical durability.
Nuclear waste form materials must meet several requirements in order to reach final consideration for use
in a repository, including a high level of durability in
aqueous fluids, crystal chemical flexibility allowing the
material to cope with variations in the composition of
the waste stream, reasonably high waste loadings, volume reduction, and reliable and cost-effective processing technologies. Information derived from minerals
can be used to assess all but the latter criterion. Furthermore, studies of U ore deposits are useful in the assessment of the performance of spent fuel, including
transport of U away from the repository.
The purpose of this chapter is to summarize the
performance of minerals in terms of their response to
a-decay damage and their interactions with natural
aqueous fluids in geological environments. For comparison, we also discuss some of the relevant literature
results involving accelerated radiation damage of synthetic compounds doped with short-lived actinides,
controlled laboratory experiments on the dissolution
of synthetic materials with and without short-lived
actinides, and dissolution of radiation-damaged natural samples. Following a brief introduction to uraninite
and its alteration products in natural systems, we conclude with an overview that uranium ore deposits as
analogs for spent fuel under repository conditions,
including aspects of the natural fission reactors in
Gabon and uranium migration around the Koongarra
ore body, Northern Territory, Australia.
5.22.2 a-Decay Damage in Minerals

In this section, we briefly summarize the effects of
a-decay damage on the structures of some of the
more important natural analogs. Here, it is important
to point out that a-decay involves two concurrent
processes, the release of a high energy (45 MeV)
a-particle together with a low energy (70100 keV)
recoil atom. The process can be expressed in the
following general way:
A n
ZP
n2 4
!A4
2 He2
Z2 R
I
565
In this expression, P is the parent isotope, R is the

recoiling daughter isotope, and the charged He atom
is the emitted a-particle. The symbols A, Z, and n
represent the mass, atomic number, and nuclear
charge, respectively. The massive recoil nucleus has
a range of 2025 nm and typically displaces on the
order of 1000 atoms primarily by nuclear stopping
processes; whereas, the a-particle has a range of
about 1015 mm and loses most of its energy through
electronic interactions before displacing on the order
of 100 atoms near the end of its track. The valence
states of the a-particle and recoil atom are rapidly
reconfigured in the solid to produce 4He and to return
the recoil atom to a more stable state. This charge
reconfiguration process may be complex in the case of
U that can exist as the U4+, U5+, and U6+ ions in solids
or in general if there are other elements present with
variable valence states such as the transition metals
(see Section 5.22.4.3).
The important parent isotopes in minerals are
238
U, 235U, and 232Th. These isotopes decay to the
stable isotopes 206Pb, 207Pb, and 208Pb through their
respective decay series. Based on each decay series,
the total a-decay dose D can be calculated using the
following equation:
D 8N238 el238 t 1 7N235 el235 t 1
6N232 el232 t 1
1
In this equation, t is the geological age, N represents

the present-day concentration of the parent isotope,
and l is the decay constant. This equation is strictly
applicable to samples wherein the isotopic composition
of the U has been determined. In situations where
only the Th and U elemental concentrations have
been determined, one may assume that the U isotopic
composition consists of 99.28% 238U and 0.72% 235U.
Alternatively, the second term in the equation may be
ignored without major consequence, as the associated
error is usually smaller than the uncertainty in the
geological age. In this chapter, we give all dose values
in units of 1016 a-decays per milligram (this is
because 1 1016 a-decays per milligram is approximately equivalent to one displacement per atom in
minerals).
5.22.3 Oxides
5.22.3.1
Pyrochlore Group
Pyrochlore is an anion-deficient derivative of the

fluorite structure type with a doubled a cell
566
parameter and change in space group from Fm3 m to

Fd3 m.1214 Minerals of the pyrochlore group conform to the general formula A2mB2X6wY1npH2O,
where A represents cations in eightfold coordination,
B represents cations in sixfold coordination, and
X and Y are anion sites. The basic structural element
of pyrochlore is the framework of corner-sharing
octahedra. Within this framework, continuous tunnels
exist parallel to the h110i directions. Both the A-site
cations and Y-site anions are located in these tunnels.
In synthetic systems, some A-site cation exchange
capacity has been demonstrated in defect pyrochlores,
in which the values of m in the general formula can be
quite large.
Most natural pyrochlores form under magmatic
conditions in granitic pegmatites, nepheline syenite
pegmatites, and carbonatites, or late-stage veins associated with these rock types. The composition of
common pyrochlore usually approaches the stoichiometric form (Na, Ca, Ln, U)2(Nb, Ta, Ti)2O6(F, OH, O),
but the structure type is extremely flexible in
terms of the sheer number of elements that can
be incorporated and is particularly amenable to the
incorporation of actinides. Natural samples are known
to contain up to 30 wt% UO2, 9 wt% ThO2, and 16 wt%
Ln2O3, an important consideration for the issue of
nuclear criticality. However, as shown by the general
formula, the crystal chemistry of pyrochlore is complicated by the potential for vacancies at the A-, X-,
and Y-sites (m 0.01.7, w 0.00.7, and n 0.01.0)
and the incorporation of water molecules (p 02)
in the vacant tunnel sites. The total water content
of the natural defect pyrochlores may be as high as
1015 wt% H2O (with speciation as both water molecules and OH groups).
In a little known but classic paper, Krivokoneva
and Sidorenko15 examined a suite of Russian pyrochlores using X-ray diffraction (XRD) methods. An
analysis of the line broadening showed that strain
increased from 0.0009 to 0.0035 as crystallite dimensions decreased from 100120 nm down to 3540 nm
in the initial stages of damage, a decrease to 15 nm
was observed in the latter stages of damage. These
authors also carried out an analysis of the radial
distribution function (RDF) of an amorphous sample
and showed that there was no long-range order present beyond the second coordination sphere. However,
peaks in the RDF representing the major MO and
MM distances showed that the fundamental structural units (e.g., the coordination polyhedra) still
existed in the amorphous state. Lumpkin and
Ewing16 also used XRD to determine both the
beginning (Di) of the crystallineamorphous transformation and the critical amorphization dose (Dc) for a
large suite of pyrochlores from different localities.
They showed that the transformation zone increased
in dose as a function of the geological age of the
samples. Both dose curves are well-described by an
equation of the form:
Di;c D0 etK
2
In this expression, D0 is the intercept dose for Di or

Dc and K is a rate constant. Analysis of the dose-age
data gives a value of D0 1.4 1016 a per milligram
for the amorphization dose curve and K 1.7 109
year1.17 The Bragg peak intensities of a subset of
these samples were fitted to an equation of the form:
I =I0 eBD
3
Here, I/I0 represents the total intensity of all

observable Bragg peaks divided by the total intensity
obtained from an undamaged sample of similar
composition and B is a constant related to the amount
of material damaged by each a-decay event. Equation
[3] gives an excellent fit to the data with
B 2.6 1016 mg per a-particle, corresponding to
an average cascade radius of 2.3 nm in which a maximum of 2600 atoms are displaced. An analysis of line
broadening in these samples showed that crystallite
dimensions decreased from about 500 to 15 nm with
increasing dose. Strain initially increased with dose
and reached a maximum of 0.003 before falling to
values below 0.0005 at higher dose levels, consistent
with a description of the crystallineamorphous
transformation as a type of percolation transition.18
With increasing a-decay dose, transmission electron
microscopy (TEM) images reveal mottled image
contrast due to strain, followed by the appearance of
local amorphous domains that increase in volume and
begin to overlap to produce larger amorphous areas
until they are connected throughout the material.
This is the first percolation transition. With further
increases in dose, the crystalline areas diminish in
volume until they become isolated, giving way to a
microstructure dominated by amorphous pyrochlore.16
This is the second percolation transition.
During the 1980s, Greegor and coworkers1922
carried out several studies of the local structure and
bonding around Ti, Nb, Ta, and U atoms in pyrochlore using EXAFSXANES (extended X-ray
absorption fine structureX-ray absorption near
edge structure). Results of these studies demonstrated that the MO coordination polyhedra of
amorphous pyrochlore exhibit reduced bond
567
Zircon
Apatite
Pyrochlore
Zirconolite
14
12
DV/ V0 (%)
distances, reduced coordination number, and

increased distortion relative to the undamaged crystalline structure. Furthermore, there was no periodicity in evidence beyond the second coordination
sphere, with some disruption of the MM distances.
From these studies, it was realized that only a slight
increase in the mean MM distance was required in
order to explain the overall increase in volume
caused by a-decay damage and that this could be
facilitated by increased MOM angles. The thermal
behavior of radiation-damaged natural pyrochlore
was investigated using differential thermal analysis
(DTA) and XRD.23,24 Results of this study indicated
that the samples recrystallized in the range of
400700 C, depending upon the composition and
degree of crystallinity. Measured values of the recrystallization energy are 125200 J g1 and are inversely
correlated with the level of crystallinity.
In the early to mid-1980s, Clinard and his colleagues conducted an extensive set of experiments
on cubic zirconolite CaPuTi2O7 in which the Zr
is completely replaced by 238Pu (t1/2 87.7 years).
This material is actually a pyrochlore compound
similar to synthetic CaUTi2O7. In their first publication, Clinard et al.25 reported that CaPuTi2O7 has a
total volume expansion of 4.7%, an apparent lattice
volume expansion of 2.2%, and a critical amorphization dose of 0.3 1016 a per milligram based on XRD
analysis. Further analysis of the data showed that
CaPuTi2O7 exhibits a bulk volume expansion of
5.4% at ambient temperature and becomes amorphous at a dose of 0.5 1016 a per milligram based
on bulk swelling curves. For samples held at 302 C,
the bulk swelling saturates at 4.3%, and the material
becomes amorphous at a dose of 1 1016 a per milligram as estimated from the swelling data. This is a
very significant result, as it indicates that the critical
dose for an experiment lasting 3 years at 302 C
is roughly equivalent to what nature produces in
107109 years. When stored at a temperature of 602 C,
CaPuTi2O7 did not become amorphous; however, the
material showed a bulk expansion of 0.4% consistent
with accumulation of lattice point defects.26 In retrospect, this is a stunning result and represents the first
and only realistic bracket for the critical temperature
for amorphization of a nuclear waste form material.
Also during the 1980s, Weber et al.27 investigated synthetic Gd2Ti2O7 doped with 3 wt%
244
Cm (t1/2 18.1 years) and determined the amorphization dose of 0.4 1016 a per milligram with
B 4.4 1016 mg per a-particle, a total volume
expansion of 5.1% at saturation (Figure 1), and
10
8
6
4
2
0.1
0.2
0.3
0.4
0.5
0.6
0.7
Dose (1016 a per milligram)

Figure 1 Plot showing total volume expansion of
synthetic pyrochlore Gd2Ti2O7 doped with 244Cm,
zirconolite CaZrTi2O7 doped with 244Cm, apatite (e.g.,
britholite) CaNd4(SiO4)3O doped with 244Cm, and zircon
(ZrSiO4 doped with 238Pu) as a function of increasing
a-decay dose.
an increase in fracture toughness together with a

decrease in hardness and elastic modulus. Changes
in microstructure with increasing dose mimic the
results for natural pyrochlores described earlier.
Based on the results of DTA experiments, an activation energy of Ea 3.8 eV was determined for recrystallization of this pyrochlore. A recrystallization
temperature of 700800 C was determined by isochronal annealing. The authors also performed leach
tests on single-phase Cm-doped Gd2Ti2O7 pyrochlore samples. In this work, the leach tests were
limited to annealed, fully crystalline and fully amorphous samples, and were exercised at 90 C in pure
water for 14 days. The experiments revealed weight
losses of 0.02% and 0.05% for the crystalline and
amorphous pyrochlore samples, respectively. The
results of this study also indicated that the leach
rate of Cm increased by a factor of 17 as a consequence of amorphization.
More recently, Strachan and coworkers28 investigated the effect of 238Pu on the structure of four
synthetic pyrochlore samples with variable amounts
of Al, Gd, Hf, and U. The results of detailed XRD and
bulk swelling measurements indicate that the critical
dose for amorphization is (0.20.4) 1016 a per
milligram and is associated with a total volume
expansion of <6%. Based on changes in the cubic
lattice parameter with time, it appears that the unit
568
cell expansion of the pyrochlore phase is on the order

of 2.94.7%. Using purpose-built equipment for flow
through dissolution tests, Strachan et al.28 examined
the behavior of 238Pu-doped pyrochlore at pH 212
and 8590 C. They found very low release rates
based on Pu and to a lesser extent U, possibly due
to solubility controls on these elements. Experiments
carried out on amorphous and recrystallized samples
demonstrated very similar release rates for Gd at
pH 2 and 85 C. This is a very important conclusion of this major research project and, together
with the observation that the materials did not
develop cracks with increasing dose, lends substantial
credence to the use of these ceramics as nuclear waste
forms. Following a careful analysis of the effects
of flow rate and specimen surface area, forward dissolution rates of (0.71.3) 103 g m2 day1 were
obtained for two different samples. Other experiments have been conducted in order to determine
the kinetics of U release from pyrochlore, (Ca,Gd,Ce,
Hf,U)2Ti2O7, but without the complicating effects of
short-lived actinides.29,30 Both studies report that the
pH dependence follows a shallow v-shaped pattern
with a minimum near neutral pH. The release rates
for U, converted from the limiting rate constants
given by Zhang et al.,30 range from 6 107 to
7 105 g m2 day1 for all experimental conditions
(e.g., T 2575 C and pH 212).
Geisler et al.3133 performed hydrothermal experiments with a natural, crystalline Ta-based pyrochlore
(microlite) from Lueshe near Lake Kivu of the
Democratic Republic of Congo in pure water and
acidic solutions (pH 0) at 175 and 200 C. The
hydrothermal treatment in the acidic solutions causes
the partial replacement of the microlite by a new defect
pyrochlore that is characterized by a larger unit cell
volume, a large number of vacancies at the A-site
(A Ca, Na) and anion vacancies, by molecular
water, and possibly, OH groups. Analyses of the
experimental fluid further revealed that U was lost
to the solution. TEM investigations of the interface
between the new defect pyrochlore and the unreacted
microlite revealed a topotactic relationship between
both pyrochlore phases. Furthermore, the interface
between both phases was found to be sharp on the
nanoscale with a sharp, step-like decrease of the Ca
and Na content at the interface toward the defect
pyrochlore. Time-of-flight-secondary ion mass spectrometry (TOF-SIMS) and confocal micro-Raman
mapping of the defect pyrochlore produced in an
acidic solution that was enriched with 18O (47.5 at.%)
revealed that the defect pyrochlore is strongly
enriched with 18O with a sharp 18O gradient to relict

unreacted areas. The authors suggested that the
replacement of microlite by a defect pyrochlore
occurs by a pseudomorphic reaction that involves
the dissolution of the pyrochlore parent accompanied
by the simultaneous reprecipitation of a defect pyrochlore at a moving dissolutionreprecipitation front;
a process that has been named interface-coupled
dissolutionreprecipitation process. It is noteworthy
that the treatment in pure water for 14 days at 175 C
did not produce reaction zones detectable by backscattered electron (BSE) imaging. However, significant spectral changes in powder infrared (IR) spectra
of the reaction product and the detection of Na and
Ca in the experimental solution indicated that the
microlite has also reacted in pure water. The experimental, chemical, and textural alteration features bear a
remarkable resemblance to those seen in naturally
altered microlite samples (see Figure 2 and subsequent
discussion).
Later, Poml et al.34 studied the hydrothermal
alteration of a natural, heavily radiation-damaged
pyrochlore (betafite) from a rare earth pegmatite
from Lindvigskollen near Krager, South Norway
and a synthetic titanate-based pyrochlore ceramic
[(Ca0.76Ce0.75Gd0.23Hf0.21)Ti2O7] produced at the
Lawrence Livermore National Laboratory, USA.
The authors treated cuboids of both samples with
edge lengths of 3.3 mm in a 1 M HCl solution containing 43.5 at.% 18O at 250 C for 72 h. During the
experiments, both samples were transformed mainly
into rutile with subordinate anatase. The degree of
transformation was significantly higher for the natural
radiation-damaged pyrochlore; for example, 18O was
highly enriched with the reaction products of both
samples with a sharp gradient (on a micrometer scale)
toward the unreacted pyrochlore and no apparent
diffusion profile. The replacement reaction retained
even fine-scale morphological features typical for
pseudomorphs. Based on these observations, the
authors suggested that the dissolution of pyrochlore
is spatially and temporally coupled with the precipitation of stable (metastable) TiO2 phases at an
inwardly moving reaction front, a mechanism that is
essentially the same as proposed for the experimental
replacement of crystalline microlite by a defect pyrochlore as discussed in the previous paragraph. The
authors pointed out that their results produced under
relatively extreme batch-experimental conditions show
similarities with nature as well as with results derived
from experiments conducted under moderate conditions rather expected in a nuclear repository.
(a)
(b)
20 mm Na+
BSE
(c)
(d)
Ca+
18O-/O-
0
Reaction rim / new pyrochlore phase
Unaltered core / untreated microlite
Altered natural microlite
Unaltered natural microlite
A
0.00
0.25
1.00
0.25
0.50
0.75
0.00
1.00
A+
0.75
0.50
(e)
0.25
1.00
O5
(f)
0.00
0.3
1.00
0.75
0.25
1.00
0.00
A+2
0.00
0.2
0.50
0.50
0.75
0.1
+
0.25
0.75
0.50
569
0.25
0.50
0.75
0.00
1.00
Figure 2 Experimental hydrothermal aqueous alteration of a natural pyrochlore (e.g., Ta-rich variety known as microlite) in
highly acidic solution at 200 C. Backscattered electron image (a) indicates increased average atomic number in altered
(brighter) areas, due to selective loss of the light cations Na (b) and Ca (c), and enrichment in 18O (d). Triangular diagrams also
indicate that changes in cation (e) and anion (f) compositions are similar to those observed in nature.
Numerous investigations have demonstrated that

natural pyrochlores are susceptible to alteration via
reaction with aqueous fluids over a range of conditions
involving pressure, temperature, and fluid composition.
At higher temperatures (300650 C, <400 MPa) in
highly evolved late-stage magmatic fluids, Ca enrichment is commonly observed; whereas, the main effect of
alteration at moderate temperatures under hydrothermal conditions (200350 C, <200 MPa) is the loss
of Na and F, often combined with cation exchange for
Sr, Ba, REE, and Fe. Further removal of Na, F, Ca, and
O may occur in low temperature hydrothermal or
weathering environments, resulting in the maximum
numbers of A-site, Y-site, and X-site vacancies, maximum hydration levels, and more limited exchange large
cations such as K, Sr, Cs, Ba, Ce, and Pb in certain
environments.3545
Ti-rich pyrochlore (betafite) from hydrothermal
veins (Figure 3) in the contact metamorphic zone
adjacent to the Adamello igneous massif in northern
Italy contain 2934 wt% UO2 and are chemically the
closest natural analogs presently known for nuclear
waste forms. Electron microscopy and microanalytical work have revealed that these pyrochlore samples
Figure 3 Photograph showing dark-colored Ti-rich

hydrothermal veins in marble from the contact metamorphic
zone of the Adamello igneous massif in northern Italy. These
veins have transported U, Th, and lanthanide elements as
demonstrated by the presence of pyrochlore (e.g., Ti-rich type
known as betafite) and zirconolite. Width of image 10 cm.
have only suffered a minor late-stage hydration event

as evidenced by lower backscattered electron image
contrast around the rims of the grains (Figure 4).
570
of the U-rich rim. During this alteration, which is the

result of exposure to tropical conditions, Na, Ca, and
F were removed from the pyrochlore, thus leading to
increased A-site vacancies (up to about 1.8 A-site vpfu).
The alteration also led to localized redistribution of
radiogenic Pb and to hydration, but U remained immobile. Although U loss has been documented in certain
geological environments, it appears that U is highly
stable on the A-site of the pyrochlore structure. As
natural pyrochlore can accommodate U6+ in significant
amounts, it is possible that the geometry of the A-site,
which is similar to the Urf6 topology in uranyl minerals
with two short bonds and six long equatorial bonds,49
plays a role in the geochemistry of pyrochlore.
Figure 4 Backscattered electron image of pyrochlore
(betafite) and zirconolite from Ti-rich veins, Adamello, Italy.
Pyrochlore occurs as overgrowths on highly zoned
zirconolite crystals. Note the slightly darker rim on the
pyrochlore, due to minor loss of Na, F, and increased
hydration. Zirconolite was unaffected by this alteration
event. Width of image 60 mm.
Results of this study demonstrate quantitative retention of U and Th for time periods of 40 Ma, even
though the crystals experienced cumulative total
a-decay doses of 34 1016 a per milligram.46 In
two samples from Bancroft, Ontario, Canada, Lumpkin
and Ewing39 had previously concluded that the major
result of alteration was hydration, with only minor
changes in elemental composition, apart from the precipitation of galena due to mobility of radiogenic Pb. In
contrast to these examples, the Ti- and U-rich pyrochlores from granitic pegmatites in Madagascar exhibit
a range of alteration effects, including relatively hightemperature, postmagmatic hydrothermal processes,
and lower temperature alteration.39,47 If the Ca content falls below 0.20.3 apfu, these Ti-rich pyrochlores
may exhibit various levels of recrystallization to liandratite rutile (or anatase). In the most severe cases
documented, this may be accompanied by a loss of up
to 2030% of the original amount of U and local
redistribution of the radiogenic Pb.
A recent study of a 440 Ma pyrochlore from
Mozambique provides qualitative information on
the effect of radiation damage on the alteration of
pyrochlore.48 These pyrochlore crystals exhibit a distinct growth zoning, characterized by a U-free core
and a U-rich rim (up to 17 wt% UO2). Following
uplift and cooling, groundwater penetrated these
fractured crystals and led to the deposition of clay
minerals along both fractures and cleavage planes.
This low-temperature process also led to chemical
alteration of the pyrochlore but only within the zone
5.22.3.2
Zirconolite
The structure of zirconolite14 is also considered to be

an anion-deficient derivative of the fluorite structure
type and can be viewed as a volumetrically condensed, layered version of pyrochlore with reduced
symmetry and several polytypic forms (monoclinic
2 M or 4 M, both with space group C2/c; orthorhombic 3O with space group Acam, hexagonal 3T with
space group P3121). The chemical composition of
zirconolite 2 M corresponds to CaZrTi2O7, but in
nature, it commonly deviates from this end-member
composition due to extensive substitution of Y, Ln,
Th, and U for Ca and Nb, Fe, and Mg for Ti.50,51 In
natural samples, Zr is subject to only limited substitution by other elements (e.g., minor amounts of Y,
Ln, U, and Ti). Experimental work has shown that
extensive substitution of REE, Th, and U generally
results in a polytypic phase transformation from
monoclinic 2 M to trigonal 3T or from monoclinic
2 M to monoclinic 4 M. Zirconolite is an important,
highly durable host phase for actinides and fission
products, with the ability to incorporate up to 24 wt%
UO2, 22 wt% ThO2, and 32 wt% Ln2O3 in natural
systems.
Lumpkin et al.23,24 discussed the results of an
extensive study of amorphous and annealed zirconolite
from Sri Lanka using a variety of methods, including
XRD, EXAFSXANES, TEM, and DTA. Electron
diffraction and high-resolution TEM studies suggested that amorphous zirconolite lacked periodicity
beyond the second coordination sphere, consistent
with a random network model of the amorphous state.
EXAFSXANES results provided more detailed
information for the Ti- and Ca-sites and indicated
that amorphous zirconolite lacked periodicity beyond
the first coordination sphere, with reduced MO
bond lengths, reduced coordination number, and

increased distortion of the TiO polyhedra (determined from a prominent pre-edge feature in the
XANES results). Farges et al.52 provided additional
results for the Zr-, Th-, and U-sites and reported
nearly identical coordination numbers and bond
lengths for the amorphous and annealed samples.
However, a significant increase in the range of ZrO
and ThO distances was observed, leading the authors
to conclude that slight variation of the MOM
angles can have a profound effect on long-range
periodicity and medium-range order. Later work
also confirmed the reduced coordination of Ti in
the amorphous samples, pointing specifically to a
fivefold coordination environment.53
Annealing studies of the amorphous zirconolites
from Sri Lanka were performed using DTA and showed
exotherms at 780 C due to recrystallization.23,24 For
two different samples, the energy release associated
with recrystallization was 43 and 48 J g1. TEM
investigation of samples annealed at 1100 C showed
that the structure recovered to monoclinic zirconolite2 M, but the material was highly twinned and
contained some stacking faults and intergrowths of
other polytypes on (001). A few polycrystalline grains
were also observed, which gave electron diffraction
patterns consistent with the fluorite structure type.
From these observations, it was suggested that amorphous zirconolite initially recrystallizes to a disordered, defect fluorite structure.
A detailed study of highly zoned zirconolite samples from the contact metamorphic zones of the
Bergell intrusion (30 Ma) on the SwissItalian border and the Adamello igneous complex (40 Ma) in
northern Italy provided the first detailed results on
the crystallineamorphous transformation in natural
zirconolites.54 The crystals from both localities contain a wide range of ThO2 and UO2 concentrations up
to a combined maximum of over 20 wt%, thus ensuring a substantial range of a-decay dose (see Figure 4).
Due to the small grain size, the two suites of samples
were characterized by analytical electron microscopy.
In particular, a series of TEM dark field images
revealed the percolation-like behavior with increasing
dose: (1) the appearance of mottled diffraction contrast
(0.08 1016 a per milligram), (2) extensive development of amorphous domains in a crystalline matrix
(0.30.5 1016 a per milligram), and (3) overlap of
collision cascades to produce larger amorphous areas
that eventually dominate the structure as crystalline
domains diminish in size to <10 nm (0.70.9 1016
a per milligram).
571
A study of seven suites of zirconolite samples ranging in age from 16 to 2060 Ma and with a-decay doses
of 0.008 1016 to 24 1016 a per milligram has also
been reported.55,56 For each suite of samples, the
beginning of the crystallineamorphous transformation (onset dose) was defined as the first appearance
of mottled diffraction contrast in bright field images.
The end of the transformation (critical amorphization dose) was defined by the complete disappearance
of Bragg diffraction spots, leaving only diffuse rings
at 3.0 and 1.8 A in diffraction patterns. These dose
brackets were used to construct a plot of dose versus
age, revealing a pattern of upward curvature with
increasing age for both the onset dose and critical
dose. As in the previous work on pyrochlore, this
upward curvature was interpreted as evidence for
long-term annealing of isolated a-recoil collision
cascades back to the crystalline structure. The data
were fitted using eqn [2] in order to determine the
intercept dose and annealing rate constant. Curve fits
gave values of D0 0.11 1016 a per milligram and
K 1.0 109 year1 for the onset dose curve; and
D0 0.94 1016 a per milligram and K 0.98 109
year1 for the critical dose curve.
Due to potential dose rate effects and other factors, it is instructive to compare the work summarized earlier with actinide doping experiments. Weber
et al.27 published a detailed body of work on radiation
damage in CaZrTi2O7 doped with 3 wt% 244Cm.
Synthetic zirconolite becomes amorphous at a dose
of 0.5 1016 a per milligram with a total volume
expansion of 6.0% at saturation (Figure 1) and
B 4 1016 mg per a-particle for the amount of
material damaged in the collision cascade. The crystallineamorphous transformation in this material
also leads to an increase in fracture toughness and a
decrease in hardness and elastic modulus. DTA studies show that the fully amorphous material exhibits
exothermic reactions at 500530 and 680700 C
and releases about 13 and 114 J g1 of stored energy,
respectively, in the two exotherms. Isochronal annealing indicated that the main phase of recrystallization
occurs at 500700 C; however, the zirconolite initially
forms as a pseudocubic (rhombohedral) structure before
transformation to monoclinic zirconolite at about
900 C. As shown in Figure 5, this material exhibits
anisotropic lattice expansion with increasing dose
(data from Wald and Offermann57). The a lattice
parameter increases by 0.3% and exhibits saturation
behavior at higher doses, the b parameter increases
marginally by 0.1% at low dose and then remains
nearly constant, whereas the c cell dimension
572
1.25
0.729
1.248
b (nm)
a (nm)
1.249
0.728
1.247
0.727
1.246
(a)
(b)
1.035
1.155
1.145
Vc (nm3)
c (nm)
1.03
1.15
1.02
1.14
(c)
1.025
1.015
(d)
0.5
1.5
2.5
Dose (1015 a per milligram)

Figure 5 Plots showing anisotropic lattice expansion in zirconolite (CaZrTi2O7) doped with 244Cm. As shown in (a) and (b),
the a and b parameters exhibit normal saturation behavior and increase by 0.32% and 0.14%, respectively. The c cell
parameter does not show saturation and increases by 1.6% up to the maximum dose of the experiment. The total unit cell
volume expansion (d) is 2.0%.
continues to expand with dose and reaches a maximum value of 1.5% relative to the undamaged zirconolite. In a concurrent study of synthetic zirconolite
doped with 238Pu, Clinard et al.58 reported a total
volume expansion of 5.5% and a critical amorphization dose of 0.5 1016 a per milligram.
In a recent study of radiation damage via actinide
doping experiments, Strachan and coworkers59 investigated the effect of 238Pu on the structure of three synthetic zirconolites that also contained variable amounts
of Al, Gd, Hf, and U but no Zr. Although these are
not pure single-phase specimens, detailed XRD and
bulk swelling measurements indicate that the critical
dose for amorphization is (0.30.5) 1016 a per
milligram and is associated with a total volume expansion of 5%. By employing similar procedures to
those used in their previous study of 238Pu-doped
pyrochlore (Section 5.22.3.1), Strachan et al.59
showed that the forward dissolution rate of radiation-damaged zirconolite is 1.7 103 g m2 day1
at pH 2 and 90 C. The dissolution tests exhibited
very little dependence on pH, were not dependent on
the level of radiation damage, and no cracking was

observed in the zirconolite specimens.
The dissolution of synthetic zirconolite without
short-lived actinides has been determined as a function of pH using pure water in single pass flow through
tests at temperatures of 75 C and lower.29,30 These
authors have independently studied a CeGdHf zirconolite containing about 16 wt% UO2 and the results
of the two studies are similar. Release rates determined
by Zhang et al.30 for Ti and U indicate that zirconolite
dissolves congruently after about 20 days following an
initial period where U is released at a somewhat faster
rate than Ti. The limiting rate constants are equivalent
to U release rates of 6.4 107 to 1.3 105 g m2
day2 for zirconolite over the entire pH range of 212
and temperature range of 2575 C. The dissolution
rate of zirconolite is characterized by a shallow
v-shaped pattern with a minimum near pH 8, similar to the results obtained for pyrochlore.
Isotopic age dating work by Oversby and Ringwood60
and electron microscopy studies by Ewing et al.61
have shown that natural zirconolite exhibits closed
system behavior for U, Th, and Pb for up to 650 Ma

with little, if any, evidence for geochemical alteration.
More recently, Rasmussen and Fletcher62 proposed
that zirconolite may become the principal mineral for
age dating in mafic igneous rocks due to its ability to
retain radiogenic Pb. Their analysis of 1200 Ma dolerite
intrusive rocks from Western Australia demonstrated
that zirconolite returned the same 207Pb/206Pb age as
zircon and baddeleyite, but the zirconolite age was
much more precise (by factors of 3.3 and 13, respectively). Lumpkin et al.17 and Hart et al.63 have described
the alteration of amorphous zirconolite from the
2060 Ma carbonatite complex of Phalaborwa, South
Africa in somewhat greater detail. Electron microprobe analyses, element mapping, and backscattered
electron images demonstrate that the alteration is
localized along cracks and resulted in the incorporation of Si and loss of Ti, Ca, and Fe. However, in these
samples, the Ln, Y, Th, and U contents remained
relatively constant across the alteration zones. Radiogenic Pb appears to have been mobile and precipitated mainly within the altered areas as galena. In
carbonatites, zirconolite may be replaced along
cracks and within micron-sized domains by an
unidentified BaTiZrNbACT silicate phase, suggesting that zirconolite may not be stable in the
presence of relatively low temperature hydrothermal
fluids enriched with aqueous silicate species.64,65
At higher temperature and pressure in magmatic,
hydrothermal, or metamorphic systems, zirconolite
may be altered by dissolutionreprecipitation or
replacement mechanisms. Giere and Williams66
have described zoned zirconolites from Adamello,
Italy, which exhibit corrosion and replacement by
a new generation of zirconolite together with loss
of Th and U to a hydrothermal fluid. Importantly,
a thermodynamic analysis of the mineral assemblages
was performed in this work and indicated that the
zirconolite crystallization and corrosion occurred at
500600 C in a reducing hydrothermal fluid rich in
H2S, HCl, HF, and P and relatively poor in CO2. Pan67
has also described the breakdown of zirconolite to a
new mineral assemblage consisting of zircon, titanite,
and rutile in metamorphosed ferromagnesian silicate
rocks at Manitouwadge, Canada. This reaction can be
expressed as follows (modified slightly from Pan67):
CaZrTi2 O7 2SiO2 ZrSiO4 CaTiSiO5 TiO2
II
This reaction illustrates the potential instability of zirconolite at high temperature and pressure in silica-rich
573
systems; however, the phase relations of zirconolite and

other minerals in the system CaOSiO2TiO2ZrO2
H2OCO2 remain elusive, especially at low temperature and pressure.
Malmstrom68 investigated the performance of
several zirconolite compositions under hydrothermal
conditions (150700 C, 50200 MPa) in fluids containing different concentrations of HCl, NaOH, H3PO4,
silicate, or carbonate, in addition to pure water. Starting
materials consisted of near end-member CaZrTi2O7,
together with single-phase samples doped with Nd, Al,
U, Ce, Gd, and Hf. The results of these experiments
demonstrate that zirconolite is most highly reactive in
the NaOH-bearing fluids, but temperatures in excess of
500 C are required to produce a continuous alteration
layer consisting of perovskite calzirtite at 50 MPa or
perovskite baddeleyite at 200 MPa. In the case of
HCl, similar temperatures are required to produce an
alteration layer consisting of rutile and anatase. Somewhat surprisingly, scanning electron microscopy (SEM)
observations revealed that the silicate and carbonate
fluids had no visible effect on the zirconolite surface
after experimental runs at 550 C and 50 MPa. Only
limited reaction was observed in pure water or H3PO4
fluids at the same temperature and pressure, with rutile
and monazite appearing as products on the surface.
Recently Poml,69 experimentally investigated the
hydrothermal alteration of a crystalline 239Pu-doped
and an X-ray amorphous 238Pu-doped (D 7 1018
a-decay per gram) zirconolite ceramics with the
composition Ca0.87Pu0.13ZrTi1.74Al0.26O7. A disk of
each ceramic sample was treated in a Teflon# vessel
with 2 ml of 1 M HCl at 200 C for 3 days under
autogeneous pressure. The analyses of the experimental fluids by inductively coupled plasma-optical
emission spectrometry (ICPOES) revealed that significantly higher Ca, Al, and Pu concentrations were
released into solution from the 238Pu-doped than
from the crystalline 239Pu-doped sample. Optical
and SEM investigations of the 239Pu-doped sample
after the experiment revealed no signs of alteration,
while the X-ray amorphous 238Pu-doped sample
showed strong alteration features even under the optical microscope. Parts of the disc were covered by a
carpet of TiO2 crystals. Energy dispersive X-ray
(EDX) analyses further showed that the uncovered
areas lost Ca, Pu, and Al and have a composition
close to ZrTiO4. Surface areas yielding the original
composition could not be found. Such an observation
indicates a diffusion-controlled leaching process from
the X-ray amorphous 238Pu-doped zirconolite. However, further research is necessary before any
conclusion about the alteration mechanism can be

made. Regardless of what details constitute the alteration process, the comparative experiments clearly
demonstrated that self-irradiation damage has a
strong effect on the aqueous stability of zirconolite.
In addition, further hydrothermal experiments
were conducted with powders of different Ce-doped
zirconolite ceramics (XCe 00.225 apfu) at temperatures between 100 and 300 C, with different
surface-area-to-fluid volume ratios, and different
solution compositions (1 M HCl, 2 M NaCl, 1 M
NaOH, 35% H2O2, 1 M NH3, pure H2O). Experiments at temperatures >200 C were carried out in
silver and nickel reactors, while for those at lower
temperatures, Teflon vessels were used. The results
of the different experimental series can be summarized
as follows: (1) The alteration rate was insignificant for
all solutions other than the 1 M HCl solution. A 1 M
HCl solution was therefore used for all other experimental series. (2) Rutile (and anatase) and baddeleyite replaced the zirconolite grains to varying
degrees in the 1M HCl solution, that is, zirconolite
dissolution was found to be incongruent. (3) No clear
correlation between the Ce-doping level and the
degree of alteration could be observed. (4) The degree
of alteration increased only slightly with increasing
temperature. (5) The alteration rate was found to be
independent on the surface-to-volume ratio. (6) Ag
dissolved from the silver reactors dramatically increased
the reaction rate, while Ni from the Ni reactors reduced
the solubility of Ti and Zr in the HCl solution, indicating that background cations have a strong effect on the
alteration rate. In summary, considering that only the
1 M HCl solution caused any significant alteration
at temperatures between 100 and 300 C, crystalline
zirconolite proved to be extremely stable in aqueous
solutions.
5.22.3.3
Brannerite
The crystal structure of brannerite, ideally UTi2O6,

is based on a distorted array of hexagonal closepacked oxygens. The structure is monoclinic, space
group C2/m, and consists of layers of Ti octahedra
connected by columns of U octahedra.70,71 Natural
and synthetic brannerites can incorporate substantial
amounts of Ca, Ln, Th, and other elements. In both
cases, the incorporation of lower valence elements on
the A-site may be charge-balanced by partial oxidation of U4+ to U5+ and/or U6+ ions.72,73 Lumpkin
et al.74 have examined a small suite of brannerites
from different localities by SEMEDX, showing
Calibration
B4 brannerite
B10 brannerite
B12 brannerite
0.7
M5/(M4 + M5)
574
0.68
0.66
0.64
4.5
5.5
Average U valence
Figure 6 This diagram shows the electron energy loss
spectroscopy branching ratios M5/(M4 + M5) obtained from
the U M4,5 spectra of three natural brannerite samples.
Calibration data indicate average valence states between
about 4.3 and 4.8, for example, significant amounts of
U5+ and/or U6+ are present.
that unaltered areas of the samples contain up to

7 wt% CaO, 8 wt% Ln2O3, 7 wt% PbO, and 15 wt%
ThO2, together with minor amounts of Al, Si, Mn, Fe,
Ni, and Nb. Using electron energy loss spectroscopy,73 measured the UM4,5 spectra of three of
these samples and reported average U valence states
of 4.44.8 based on the individual M5/(M4 M5)
branching ratios (Figure 6). Amorphous brannerite
may contain nanocrystal inclusions of uraninite. All
natural brannerite samples with ages greater than
20 Ma appear to be amorphous due to a-decay
damage. Electron diffraction patterns of relatively
unaltered areas of the brannerite samples typically
consist of two broad, diffuse rings characteristic of
amorphous materials. Unaltered natural brannerites
have average a-decay doses of (2170) 1016 a per
milligram in part due to the very high U content.74
A partially crystalline brannerite from Binntal, Switzerland,75 allows the critical dose to be estimated
at 1 1016 a per milligram, a value similar to geologically young pyrochlore and zirconolite samples.
Geochemical alteration of brannerite is common
and appears to increase in severity with geological
age, although the PTX conditions are poorly
understood.76 Alteration usually occurs around the
rim of the brannerite or along cracks and may involve
the formation secondary such as anatase, galena, and
thorite. As reported for pyrochlore and zirconolite,
the galena may precipitate due to the combined

effects of radiogenic Pb migration and the presence
of S species in the aqueous fluid. Altered brannerite
typically loses U, and the concentration may fall
to 1 wt% UO2 in the most heavily altered areas.
The loss of U may be compensated in part by the
incorporation of up to 18 wt% SiO2 and 16 wt% FeO,
together with significant amounts of P2O5, As2O5,
and Al2O3 in certain examples. In some cases,
the associated rock or mineral matrix surrounding
the brannerite may be highly fractured, providing
pathways for the migration of U, evidenced by the
precipitation of secondary U minerals.74
Several important experimental studies of synthetic and natural brannerite have been conducted
and are summarized as follows: For temperatures of
2050 C and pH values in the range of 212, Zhang
et al.30 reported limiting rate constants for U equivalent to dissolution rates of about 103 to 105 g m2
day1. The lowest dissolution rate was obtained at
20 C and pH 5.6. However, the pH dependence
was examined in detail at 70 C, and the results show
a shallow v-shaped pattern similar to that of pyrochlore and zirconolite, although the release rates of
U from these two phases are 12 orders of magnitude
less than that of brannerite.
In further detailed work, Zhang et al.77 demonstrated that the U release rate is strongly dependent
on bicarbonate concentration and that bicarbonate
does not interact strongly with titanium, either on
the solid surface or in solution. The dissolution of
brannerite is incongruent and a preferential release
100
U/ Ti atomic
pH = 2
pH = 11
10
0.1
10
15
20
Time (days)
25
Figure 7 Experimental aqueous dissolution of synthetic

brannerite showing how the U/Ti atomic ratio in solution
changes with time in acidic (pH 2) and alkaline (pH 11)
solutions. The experiment at pH 2 mimics the U loss
observed in natural brannerite samples.
575
of uranium occurs at pH 2 (Figure 7). TEM examination after the experiment identified a relatively
small amount of secondary TiO2 (anatase brookite)
containing variable amounts of U and trace amounts
of other elements. Overall, the dissolution of the
brannerite at pH 11 is nearly congruent, and
TEM examination after the experiment shows that
the sample develops large areas of an amorphous
secondary phase. X-ray photoelectron spectroscopy
(XPS) analyses indicate the existence of oxidized U5+
and U6+ species on specimens both before and after
leaching, and U6+ was the dominant component on
the specimen leached in the pH 11 solution.
Zhang et al.78 also conducted thermal annealing
studies of amorphous brannerite in Ar at 500, 700,
900, and 1100 C followed by batch dissolution
experiments in solution at pH 4 at 30 C. XRD
analysis indicates that the major recrystallization of
the sample occurs at 9001100 C, but detailed TEM
examination revealed that partial recrystallization
started at 700 C. Analysis of the starting material
showed that it contained small amounts of Al and Si
due to alteration and nanocrystals of UO2+x within the
amorphous matrix. Interestingly, the authors found
that the dissolution rate increases with annealing temperature, and this is attributed to the growth of UO2+x
and to the formation of an aluminosilicate glass phase
at the highest temperature. Relative to synthetic
brannerite,30 the dissolution rate of the amorphous
brannerite is about one order of magnitude higher.
5.22.3.4
Perovskite
Perovskite is an ABX3 structure type based around

a framework of corner sharing, octahedral B-site
cations with B Ti, Fe, and Nb, together with
minor amounts of Mg, Al, Zr, and Ta, depending on
bulk rock chemistry and mineralogy. The large A-site
cations occupy the center of a large cavity formed by
8 B-site octahedra and are coordinated to 12 oxygens
in the ideal cubic structure. Most perovskites are
distorted via octahedral tilting and generally have
lower symmetry. In nature, only near end-member
SrTiO3 is cubic, most other compositions are orthorhombic.79 The major A-site cations in natural perovskites are Na, Ca, Sr, and REE, with minor
amounts of K, Ba, and U. The concentration of Th
is usually low, but may reach levels as high as 18 wt%
ThO2 in certain alkaline rocks.80,81
Only a limited amount of information is available
on radiation damage in natural perovskite. In one
study, TEM methods were used to examine the
microstructure and electron scattering properties of a

large suite of samples having a range of geological
ages.55,56 Perovskite grains containing 1.43.1 wt%
ThO2 indicate that the beginning of the transformation
is at a dose of 0.30.6 1016 a per milligram for
t 295520 Ma. A preliminary analysis of the data
using eqn [2] gave D0 0.19 1016 a per milligram
and K 2.3 109 year1. Perovskite from Bratthagen,
Norway, contains up to 6.0 wt% ThO2, equivalent to
a-decay doses of (0.81.2) 1016 a per milligram.
These grains are partially damaged based on the
appearance of a weak diffuse ring in electron diffraction patterns. During this study, it was discovered that
the perovskite crystals contain a hydrothermal alteration phase known as lucasite. Although lucasite has a
slightly higher Th content relative to the associated
perovskite, it is completely electron diffraction amorphous at a dose of (1.51.7) 1016 a per milligram,
suggesting a lower radiation tolerance than the host
perovskite. Th-rich perovskites from the Khibina
alkaline complex, Russia, have been studied by electron probe microanalysis (EPMA) and XRD.80,81 The
crystals are zoned and contain 2.318.5 wt% ThO2,
increasing from core to rim. XRD results indicate that
the cores (2.37.4 wt% ThO2) retain some crystallinity, but the rims (8.718.5 wt% ThO2) are completely
amorphous. These data are consistent with a critical
dose of 2 1016 a per milligram based on the maximum and minimum Th contents of the cores and rims,
respectively.
There have also been very few laboratory studies
of radiation damage in perovskite by doping with
short-lived actinides. Mosley82 studied CmAlO3, in
which about 95% of the actinide content is 244Cm,
and determined that the material is amorphous by
XRD after 8 days of the experiment, from which we
estimate a dose of 0.150.2 1016 a per milligram
(equivalent to 0.20.3 dpa). Although the critical
dose may be slightly higher than the X-ray value,
it is still substantially lower than the value estimated
for natural perovskite. Using Mosleys lattice parameter versus time data, we have plotted the unit cell
volume expansion, DVc/Vc0, as a function of the
estimated dose (Figure 8). This plot indicates that
the lattice volume expansion may be as high as 8.8%
at saturation based on the curve fit; however, the last
data point indicates a lattice volume expansion
of 6% prior to amorphization. The latter value is
close to the total volume swelling observed in pyrochlore and zirconolite doped with 238Pu or 244Cm.
Perovskite commonly releases Ca in aqueous
fluids even at low temperature, breaking down to
0.06
0.05
DVc / V0
576
0.04
0.03
0.02
0.01
0.05
Dose (10
0.1
16
a per milligram)
Figure 8 Unit cell volume expansion of CmAlO3

plotted as a function of a-decay dose. The total
expansion at saturation is 8.8%; however, the highest
measured expansion is 6.0%. These data suggest
that the total macroscopic swelling could be in excess of
10 vol.%.
one or more polymorphs of TiO2 (generally anatase

brookite or TiO2B). This is well illustrated by the
alteration of perovskite to anatase, cerianite, monazite, and crandallite group minerals during severe
weathering of carbonatites in Brazil.83 Using electron
microscopy, Banfield and Veblen84 have proposed
that the perovskiteanatase reaction mechanism
involves topotactic inheritance of layers of the perovskite TiO framework. In hydrothermal systems,
Mitchell and Chakhmouradian80,81 have described
the alteration of perovskite to kassite, anatase, titanite,
calcite, and ilmenite in the presence of a CO2- and
SiO2-rich fluid phase at temperatures of 250600 C
in alkaline rocks. These observations are consistent
with the thermodynamic properties of perovskite and
related minerals. Nesbitt et al.85 have shown that
perovskite is unstable with respect to titanite, rutile,
calcite, and quartz in many hydrothermal fluids and
groundwaters at 25300 C.
Lumpkin et al.55,56 and Chakhmouradian et al.86
described the hydrothermal alteration of Na-bearing
perovskite (ideally Na0.5Ln0.5TiO3) in alkaline igneous rocks. The primary result of this alteration is
removal of Na from the original perovskite, producing lucasite, LnTi2O6x(OH,F)xH2O. Lucasite is isostructural with kassite, CaTi2O4(OH)2H2O, another
alteration product of perovskite (CaTiO3). The simplified reaction relationships for perovskite, kassite,
and lucasite are shown subsequently:
2H H2 O 2CaTiO3
CaTi2 O4 OH2 H2 O Ca2
III
H H2 O 2Na0:5 Ln0:5 TiO3

LnTi2 O5 OH H2 O Na
IV
In both cases, the replacement product is usually

reported as having a distinctly fibrous or prismatic
morphology, a feature that can be observed by SEM
(Figure 9). In the following paragraphs, we will discuss
some of the important experimental data on perovskite
dissolution.
Thermodynamic calculations and data for natural
groundwaters and hydrothermal fluids (up to 300 C)
revealed that perovskite is generally unstable with
respect to titanite, titanite quartz, rutile, or rutile
calcite.85 Measurements of the dissolution rates of
two natural perovskites and synthetic SrTiO3 and
BaTiO3 samples were obtained in pure water at
25300 C, indicating that elemental release rates
are 101 to 103 g m2 day1 for Ca, Sr, and for
Ba. Kamizono et al.87 have also examined Ce, Nd, and
Sr-doped CaZrO3 in acidic (HCl, pH 1) and near
neutral (deionized water, pH 5.6) solutions at
90 C. In the acidic solution, the dissolution rates of
the impurity elements were near 0.1 g m2 day1;
whereas Ca and Zr were released at rates on the
order of 103 and 103 g m2 day1, respectively.
Leach rates were about two orders of magnitude
lower in the experiment using deionized water.
6729
577
Surface analytical studies of synthetic perovskite

after leaching at 150250 C in silica-saturated aqueous fluids were reported by Myhra et al.88 These
authors, using a combination of Auger electron spectroscopy (AES), SEMEDX, and XPS techniques,
identified the presence of a surface reaction layer
ranging in thickness from a few monolayers to several
hundred nanometers, depending on the leaching conditions. The alteration layer was composed mainly of
crystalline TiO2, a thin siliceous layer, and possible
calcium carbonate or hydroxide species. Following
this work, Myhra et al.89 reported additional results
for CaTiO3 and BaTiO3 leached at 300 C in pure
water. They determined release rates after 14 days of
1.4 102 g m2 day1 for Ca and 3.3 102 g m2
day1 for Ba from the two samples, respectively.
Surface analytical work showed that Ca and Ba
were depleted to a depth of about 200 nm and that
oxygen was enriched near the surface, consistent with
the release of Ca and Ba to solution and the formation of a crystalline TiO2 layer.
The studies noted earlier were extended to lower
temperatures of 20100 C by Pham and coworkers,90,91 who showed that near surface decreases in
the Ca/Ti ratio determined by XPS are accompanied
by the formation of an amorphous Ti-rich layer up to
10-nm thick, as observed by TEM. The authors proposed a base catalyzed hydrolysis and ion exchange
model to account for their observations, whereby
surface Ca2+ is released to solution via exchange
with H+ and TiOTi surface species are converted
to TiOH species via reaction with OH and H2O.
The overall reaction can be written as follows90:
CaTiO3 6 xH Ca2 TiOHx4x
3 xH2 O
50 mm
Figure 9 Example of hydrothermal alteration of natural
perovksite in alkaline rocks from Bratthagen, Norway. This
backscattered electron image shows partial replacement of
a large perovskite (e.g., Na-rich variety known as loparite)
single crystal by a brighter, fibrous secondary phase,
lucasite.
V
This reaction indicates that the aqueous Ca2+/H+

ratio and the presence of TiOH surface species
control the dissolution of perovskite. The presence
and buildup of the amorphous TiOH surface film at
low temperatures may be due to kinetic factors, as
crystalline anatase or rutile are thermodynamically
favored at low temperatures.90
McGlinn et al.92 have investigated the pH dependence
of the release of Ca from two perovskite samples: endmember CaTiO3 and Ca0.78Sr0.04Nd0.18Ti0.82Al0.18O3.
Results of this study, performed at 90 C with pH
ranging from 2.1 to 12.9, demonstrated that the
Ca release rates generally decrease with increasing
pH. After 43 days of leaching, the Ca release rate
for the end-member perovskite decreased from
578
8.9 102 g m2 day1 at pH 2.1 to 2.2 103 g

m2 day1 at pH 12.9. Similar results were obtained
for the doped perovskite. SEM imaging clearly showed
the development of agglomerated, submicron, titanaceous particles on the perovskite surface after the dissolution experiments performed in acidic aqueous
solutions.
In a more recent study by Zhang et al.,93 thermally
annealed perovskite (CaTiO3) surfaces were characterized by SEM, TEM, XPS, and atomic force
microscopy (AFM) techniques before and after aqueous dissolution testing in deionized water at room
temperature, 90 C, and 150 C. Results of this work
demonstrated that, although mechanical damage
caused higher Ca release initially, it did not affect
the long-term Ca dissolution rate. However, the
removal of surface damage by annealing did lead to
the subsequent spatial ordering of the alteration
product, which was identified as anatase (TiO2) by
both X-ray and electron diffraction, on CaTiO3 surfaces after dissolution testing at 150 C. The effect of
Ca2+ in the leachant on the dissolution reaction of
perovskite at 150 C was also investigated, and the
results suggest that under repository conditions, the
release of Ca from perovskite is likely to be significantly slower if Ca2+ is present in groundwater.
5.22.3.5
Baddeleyite
The monoclinic form of ZrO2, baddeleyite is the only

natural analog for the proposed cubic zirconia waste
forms. A recent literature review by Lumpkin94
shows that, even though baddeleyite is rather widespread as a trace phase in natural systems, it has a
limited composition range of 8799 wt% ZrO2, with
most of the remainder comprised of FeO, TiO2, and
HfO2. Natural baddeleyite has a distorted fluorite
structure due to the low concentrations of other
large cations such as Ca and REEs. The total concentration of Th and U is usually <2000 ppm by weight;
nevertheless, the cumulative a-decay dose is in the
range of (0.11.1) 1016 a per milligram for samples
with ages of 11001200 Ma. Natural samples of baddeleyite appear to remain crystalline even at the
highest observed a-decay dose levels. A case study
of baddeleyite from the Jacupiranga carbonatite complex of southern Brazil shows that the mineral can
incorporate up to 4.1 wt% Nb2O5 and 1.2 wt%
Ta2O5.94 Incorporation of Nb5+ and Ta5+ is partially
compensated by the incorporation of up to 0.4 wt%
MgO and 0.3 wt% FeO in a charge-balanced substitution of the form 3Zr 2(Nb, Ta) (Mg, Fe).
These samples are also resistant to hydrothermal

alteration which affected associated pyrochlore crystals, even though the baddeleyite crystals received
a-particle doses as high as (34.5) 1016 a per milligram along common grain boundaries with a U-rich
pyrochlore phase.94 These observations are consistent with results from hydrothermal experiments on
zirconolite ceramics, wherein zirconolite is often
replaced by baddeleyite.68,69
5.22.3.6
Crichtonite
Minerals of the crichtonite group conform to the general formula A1xM21O38 and are generally found in
maficultramafic and granitic igneous rocks. In these
minerals, A Na, Ca, Sr, Pb, and the larger Ln elements (e.g., La, Ce, Pr, and Nd) and M Ti with
variable amounts of Mg, Al, V, Cr, Mn, and Zr. They
are of some interest here due to the ability to incorporate substantial amounts of U in the mineral davidite.
Based on a review of the literature, Gong et al.95 proposed that this structure type may be an effective host
phase for a range of fission products and actinides in
high-level nuclear waste. One member of the group,
loveringite, commonly occurs in titanate-based nuclear
waste forms as a minor phase. Very little is known about
the radiation effects of this mineral; however, we report
here some previously unpublished data from our laboratory for samples (five davidite, one crichtonite).
SEMEDX analyses demonstrate that the chemical composition varies considerably from sample to
sample, but individual samples are relatively uniform
in composition with only limited evidence for zoning.
The U content ranges from 0.2 to 9.5 wt% UO2
(0.020.65 apfu). The Th content is much lower, ranging from <0.1 to 1.3 wt% ThO2 (<0.010.09 apfu).
Maximum amounts of other notable cations include
3.7 wt% V2O3, 4.1 wt% Cr2O3, 2.5 wt% Y2O3, 5.6 wt%
La2O3, 6.0 wt% Ce2O3, 4.0 wt% MnO, 2.4 wt% ZnO,
2.7 wt% SrO, and 4.9 wt% PbO. Estimates of the
geological age are available for these samples, giving
a dose range of (0.342) 1016 a per milligram using
eqn [1]. At present, the critical amorphization dose
is poorly constrained, but is probably somewhere
between 0.5 1016 and 2 1016 a per milligram
based on our TEM observations. This is consistent
with recent data for a 270 Ma davidite sample from
Bektau-Ata, Kazakhstan, which is heavily damaged at a
dose of 1.5 1016 a per milligram in a recent study by
Malczewski et al.96 Two of our samples showed evidence for alteration in the form of replacement by an
assemblage of rutile ilmenite or rutile titanite.
579
5.22.3.7 ABO4 and AB2O6 Minerals

(B Nb, Ta, and Ti)
A number of other oxide minerals are known to contain substantial amounts of Th and U and are interesting from the point of view of the effect of structure
type and composition on response to a-decay damage.
Minerals in this category are principally fergusonite,
aeschynite, euxenite, samarskite, and to a lesser
extent, columbitetantalite. Fergusonite, ideally
YNbO4, may contain substantial amounts of heavy
Ln, Th, and U on the Y-site together with Ti and Ta
on the Nb site.97 This rare element oxide mineral
is commonly reported to be amorphous as a result of
a-decay damage. Giere et al.97 have given a detailed
description of the chemistry and radiation damage of
fergusonite occurring in a 40 Ma granitic pegmatite
from Adamello, Italy. These authors used a combination of quantitative EPMA, TEMEDX, and microRaman analyses to provide an upper limit on the
critical amorphization dose of 1 1016 a per milligram for a sample characterized by TEMEDX. This
is consistent with previous work on amorphous fergusonite from Norway, containing 4.9 wt% UO2,98
and having an estimated a-decay dose of 4 1016
a per milligram based on an assumed age of 320 Ma.
By way of comparison, amorphous fergusonite from
the Rutherford pegmatite, Amelia, Virginia, has a
well-defined age of 289 Ma, and contains 2.24.7 wt%
ThO2 and 1.57.4 wt% UO2, giving a dose range of
(27) 1016 a per milligram.99 Fergusonite from this
locality is commonly altered along grain boundaries
and cracks, accompanied by loss of most of the Y and
Ln elements and uptake of Ta, Ca, Fe, and some Th
(Figure 10).
The orthorhombic AB2O6 oxides aeschynite,
euxenite, and polycrase (with idealized compositions
CeNbTiO6 or YNbTiO6) typically occur in granitic
pegmatites where they incorporate Y and a range
Ln series elements, together with Ta, Th, and U,
and small amounts of Ca and Fe. Ewing100 investigated a suite of AB2O6 oxide minerals and reported
all of them to be amorphous or metamict due to
a-decay damage. Based on Ewings carefully measured compositions, we have estimated that these
samples received a-decay doses of (221) 1016 a
per milligram wherein the lowest dose provides a
good upper limit for amorphization of samples with
ages of 250 Ma. According to Ewing, the AB2O6
oxides are commonly altered by hydrothermal fluids
whereupon they show a consistent increase in the Ca
content together with OH and H2O, generally at the
Figure 10 Backscattered electron image showing

hydrothermal alteration of natural fergusonite (left) and
monazite (right) from the Rutherford #2 granitic pegmatite,
Amelia County, Virginia. Fergusonite is heavily altered to
calciotantite + fersmite, thereby losing Y and heavy
lanthanides to the fluid phase. The adjacent monazite
crystal has also been partially altered during this process,
but in this case, the alteration involves minor chemical
exchange with the fluid phase. Width of image 0.2 mm.
expense of Y, Ln, Th, and U. At lower temperatures,

for example, during weathering processes, A-site
cations tend to be globally depleted. Due to the
complications imposed by alteration, radiation damage, and potential phase transformations between
AB2O6 minerals, thermal annealing is generally complex. The observations of Ewing and Ehlmann101
show that, in the simplest case, the aeschynite structure type is the first phase to form beginning
at 400 C, followed by transformation to the higher
temperature euxenite form at 700750 C. However,
pyrochlore and rutile are commonly formed in many
samples. Lumpkin et al.23,24 examined a small group
of amorphous NbTaTi oxide minerals with stoichiometries of ABO4 and AB2O6 and reported
recrystallization energies in the range of 4085 J g1.
Rare examples of columbitetantalite, ideally
(Mn,Fe)(Nb,Ta)2O6, were reported to contain enough
U to induce amorphization (see Lumpkin102 and
references to previous work). These 1800 Ma samples are zoned in both the TiO2 (2.24.8 wt%) and
UO2 (0.22.6 wt%) contents and exhibit a critical
amorphization dose of 8 1016 a per milligram for
specimens examined by electron microscopy. This
unusually high dose was attributed to long-term
annealing of a-recoil collision cascades back to the
original structure. We have recently found zoned
columbitetantalite crystals from the High Peak mine,
580
in the Elk Mountain district of northern New Mexico.

These zoned crystals have U-rich cores with up to
2.5 wt% UO2 and U-poor rims. The rims, however,
contain inclusions of amorphous AB2O6 oxides resulting in cracking due to differential swelling (Figure 11).
This example provides dramatic evidence for mechanical failure and subsequent geochemical alteration in
course-grained materials with inclusions rich in
U and Th. Columbitetantalite is commonly altered
to a secondary assemblage consisting of pyrochlore
(NaCaTa2O6F), fersmite (CaNb2O6), or calciotantite
(CaTa4O11) during postmagmatic hydrothermal
activity, depending upon the activities of Na, Ca2,
Fe2, H, and HF in the fluid medium (see Lumpkin
and Ewing38 and references therein).
EXAFS and XANES studies generally indicate
that the fully amorphous structures of these radiation-damaged minerals do not possess atomic periodicity beyond the second coordination environment
(MM distances), and in some cases, there is evidence for disruption of the second coordination
sphere. The first coordination sphere (MO distances) remains intact albeit with minor changes in
the bond lengths and degree of distortion of the MO
polyhedra. In the case of fergusonite, the NbO bond
lengths of two longer bonds in the crystalline phase
appear to decrease slightly in the amorphous material, consistent with a reduced preedge feature in the
NbK edge.103 Thus, the distorted 4 2 coordination
geometry of fergusonite is somewhat homogenized
Figure 11 Backscattered electron image showing

cracking and geochemical alteration of U-rich amorphous
AB2O6 mineral inclusions in U-poor columbitetantalite from
the High Peak pegmatite, Elk Mountain, New Mexico. The
cracking is clearly induced by differential swelling of the
inclusions and the host phase, allowing aqueous fluid to
migrate through the cracks. Width of image 0.5 mm.
by a-decay damage. Apart from the loss of and considerable disruption of the second coordination
sphere, Nakai et al.103 found little difference in the
mean bond length and distortion of the Nb site in
euxenite. This result differs somewhat from the analysis of the Ti-site geometry in amorphous and annealed
aeschynite and euxenite presented by Greegor et al.104
Although the disruption of the second coordination
sphere is a common feature of both studies, it was
found that amorphization produced a slight reduction
in both the mean TiO bond length and coordination
number of these minerals, primarily due to displacement of the longer TiO bonds.104
5.22.3.8
Hollandite
Although they do not contain actinides in natural or

synthetic systems, minerals of the hollandite group
are extremely important for the encapsulation of the
relatively short-lived heat-generating radionuclides
90
Sr and 137Cs and long-lived 135Cs. The crystal
structure of hollandite, A1.11.7B8O16, is similar to
that of rutile and consists of edge-sharing chains of
octahedra connected via corner sharing to form a
three-dimensional framework. Hollandite, however,
has two octahedral chains connected by edge sharing
instead of the single chain found in rutile, resulting in
a rather large 2 2 tunnel capable of accommodating
large A-site cations like K, Rb, Cs, and Ba.105107
These cations exhibit various ordering sequences over
the available tunnel sites, commonly resulting in superlattice peaks in X-ray or electron diffraction patterns.
The space group is typically I4/m or C2/m depending
upon the A/B cation radius ratio. Numerous synthetic
samples have been produced with Ti, Mn, Mo, noble
metals, or Sn as the most common major elements and
with Mg, Al, V, Fe, Co, Ni, Zn, and Sb, among others, as
minor elements on the B-site. The composition of
hollandite in titanate-based waste forms is generally
4
given as Bax Csy Ti; Al3
2xy Ti82xy O16 in which
charge compensation for Ba and Cs is usually provided
by Al or Ti3.108
In natural samples, typical B-site cations are Ti, V,
Cr, Fe, Mn2, and especially tetravalent Mn4. It is of
interest to mention here one geological occurrence in
particular, the Mn-rich metamorphic rocks Le Coreaux, Belgium, where deep purple and violet metasedimentary layers are host to quartz veins that
contain BaSr hollandite and other Mn minerals.109
These stable hollandites formed at a pressure of
12 kbar and temperature below 360380 C, they
contain 198 wt% BaO and 0.38 wt% SrO, and Sr is

the dominant cation in the tunnels at concentrations
above 6 wt% SrO. This suggests that hollandite
may also be considered as a potential host phase for
radioactive Sr in nuclear waste forms. The closest
natural analog for synthetic titanium hollandite is
the mineral priderite that occurs in Western Australia
and elsewhere and has a composition of approximately (Ba,K)1.21.6[Ti,Fe,Mg]8O16.110,111
Very little information exists on the geochemical
behavior of hollandite in natural systems, therefore,
in this section, we will briefly outline some of the
relevant experimental studies. Pham et al.112 carried
out experimental work on synthetic Ba-hollandite
doped with Cs and containing Al on the B-site for
charge balance. These authors suggested that, following the initial release of Cs and Ba from reactive
surface sites, the first few monolayers of the structure
rapidly dissolved due to the release of Al and consequent precipitation of AlOH species, driving solution pH to lower values. However, the alteration
process was mediated via the formation of a continuous Al- and Ti-rich surface layer. Further evidence
for selective removal of Ba and enrichment of Al and
Ti on the surface of hollandite leached at 250300 C
was presented by Myhra et al.108 These conclusions
were largely based on the incongruent release of Ba
(0.113 g m2 day1), Al (6.6 103 g m2 day1), and
Ti (<8 104 g m2 day1) after 14 days of leaching,
combined with XPS analyses of the altered surfaces.
In a study combining dissolution experiments and
detailed characterization by electron microscopy,
Carter et al.7 demonstrated that the release rates of
Ba and Cs from hollandite are nearly identical,
whereas Al and Ti are below the detection limits at
90 C and only Al was detected at 150 C (however,
only by a factor of 23 above the detection limit).
This is similar to previous observations; however,
SEM work revealed the presence of nodular secondary phases on the surface of the hollandite at both
temperatures. This was confirmed by TEM, which
identified both Ti-rich and Al-rich nodules in a ratio
of about 10 to 1, respectively. Furthermore, XPS
analysis of the hollandite surfaces after the dissolution experiments indicated the presence of an Al-rich
layer but only for the samples used in the experiments at 150 C. These authors also examined the pH
dependence of the elemental release rates at 90 C,
finding that the release of Ba decreases linearly from
about 2 103 g m2 day1 at pH 2.5 down to
4 104 g m2 day1 at pH 12.9.
581
5.22.4 Silicates
5.22.4.1
Zircon
Zircon is classified as an ABO4 type orthosilicate (space

group I41/amd) due to the presence of isolated SiO4
tetrahedra, which constitute the B-site, but the structure actually consists of a framework of edge-sharing
silicate tetrahedra and eight coordinated A-sites.113
In nature, the composition of zircon often approaches
ideal ZrSiO4 and is a common accessory mineral
found in a variety of geological environments. Natural
zircon may contain trace amounts of Ca, Ln, Hf, Th,
and U on the A-site and P on the B-site. Some or all of
these elements may be enriched significantly in zircon
specimens from highly fractionated granitic rocks and
especially in granitic pegmatites. Maximum concentrations of 26 wt% Ln2O3, 10 wt% ThO2, 10 wt%
UO2, and 5 wt% CaO have been reported in zircon,
but these values are exceptional. Natural zircons may
also contain both OH and H2O species, some of
which may be incorporated as a means of providing
local charge balance at radiation damage sites.114
It is of interest to note here that U-rich zircon,
containing up to 12.9 wt% U (0.1 U per formula
unit) occurs in the silicate melt that formed during
the accident at the Chernobyl nuclear plant in
1986.115 This melt, often referred to as Chernobyl
lava, resulted from partial melting of the nuclear fuel,
related structural materials, and other materials
dropped into the reactor area by helicopter. The
presence of zircon, together with (Zr,U)Ox and UOx
phases and globules of Fe(Cr,Ni) metal, proved to be
important in determining the sequence of events.
Based on a consideration of the phase relations,
Burakov et al.116 suggested that in the initial phase
of the accident, nuclear fuel interacted with Zr metal
as temperatures increased to 2500 C just prior
to the explosion, followed later on by silicate lava
flow and emplacement of the melt below the reactor at temperatures of <1700 C. Geisler et al.117
conducted a detailed electron microprobe and
micro-Raman spectroscopic investigation of the compositionally zoned Chernobyl zircons and reported
that the UO2 content ranges from 0.8 to 15.8 wt%,
equivalent to 0.0050.115 U atoms per formula unit.
Because the compositions of these remarkable zircons are confined to the system Zr1xUxSiO4, they
provide an important benchmark for the analysis of
observable Raman bands. To summarize briefly, the
frequencies of the SiO4 stretching modes decrease
by 0.670.75 cm1 per formula unit of U as a direct
582
result of increasing SiO bond length with increasing

U content. Similar results are found for the lattice
modes, but the SiO4 bending modes remain relatively
constant in terms of the Raman frequency shift. Line
broadening is significant for the lattice modes due to
the ionic size difference between Zr4 (rVIII 0.072 nm)
and U4 (rVIII 1.00 nm) and the resulting microscopic strain fields induced by substitution of Zr by
U. A detailed analysis of the lattice vibrational modes
indicates that the microscopic strain is larger in the
(001) plane than along the c axis, consistent with the
structure of zircon.117
In a pioneering study of natural zircons from
several different localities, Hurley and Fairbairn118
demonstrated that the mineral experiences a transformation from the crystalline to the amorphous state
and they determined that the diffraction angle of the
(112) reflection decreased from 35.635 2y to 35.1
2y up to 0.4 1016 a per milligram. The data were
found to follow an exponential function that related
the fractional disorder to the a-activity, the number
of atoms displaced per a-decay event, and an annealing parameter. From the data, Hurley and Fairbairn
determined a value of B 2.3 1016 mg per
a-particle and calculated that 4500 atoms were displaced by each a-decay event. Closely following this
work, Holland and Gottfried119 published their classic paper on the density, refractive indices, and unit
cell parameters of zircon as a function of dose. Using
a suite of samples from Sri Lanka, they showed that
the density decreased systematically from <4.70
to 3.96 g cm3 at a dose above 1.2 1016 a per
milligram. These data showed that the density of
zircon decreased by 16%, the largest change of any
potential waste form material. Refractive indices also
decreased systematically and approached a single isotropic value of 1.81 over a similar dose range defined
by the density measurements. XRD work revealed
that the a and c cell parameters both increased rapidly,
but anisotropically, as a function of dose before leveling off at 0.6 1016 a per milligram. Holland and
Gottfried concluded their paper with an analysis of
the fractions of crystalline zircon, an intermediate
phase, and amorphous zircon as a function of dose.
Analysis of the data for the crystalline fraction showed
that B 3.8 1016 mg per a-particle.
Murakami et al.120 showed that certain XRD peaks
of zircon samples from Sri Lanka could be separated
into Bragg and diffuse scattering components with
increasing dose. This procedure enabled a more
accurate determination of the anisotropic expansion
with increasing dose, giving expansions of 1.5% along
the a axis, 1.8% along the c axis, and a lattice volume

expansion of 4.7% (total volume expansion is 18%).
Further work, including density measurements and
TEM observations, delineated three stages of damage
in the natural zircon samples. At dose levels below
0.3 1016 a per milligram, the damage is characterized by the accumulation of point defects, unit
cell expansion, and lattice distortion. Within an intermediate dose range of (0.30.8) 1016 a per milligram, there is a progressive overlap of a-recoil tracks
to produce larger amorphous domains with increasing dose. Above 0.8 1016 a per milligram, the zircon
is completely X-ray and electron diffraction amorphous. Weber et al.121 have also suggested a long-term
annealing rate of 1 109 year1 for zircon from
Sri Lanka, a value that is similar to that reported for
natural zirconolite.
Changes in the mechanical properties of zircon as
a function of dose are extremely important. This is
not surprising in view of the large total volume
expansion and anisotropic unit cell expansion documented earlier. Using a single specimen from Sri
Lanka, Chakoumakos et al.122 provided a dramatic
illustration of the fracture properties of a zoned zircon sample from Sri Lanka. Even though the total
ThO2 UO2 concentration only varied by about
0.40.5 wt% between the 5400-mm thick growth
zones, the variation in dose was sufficient to cause
microfracturing of the more brittle, low dose zones.
The fractures were pinned in the high dose zones,
indicating an increase in fracture toughness for
these actinide-enriched layers. Following this work,
Chakoumakos et al.123 revisited the sample and examined in detail the changes in chemistry and mechanical properties using electron microprobe data and
a mechanical properties microprobe. Results of this
study demonstrated that the hardness and elastic
modulus of natural zircon decreased by 40% and
25%, respectively, for a-decay doses ranging from
0.3 1016 to 1.0 1016 a per milligram. Zircon samples from Sri Lanka were also used in an important
study of the energetics of radiation damage as a
function of dose.124 In this study, the results of temperature calorimetry revealed that the enthalpy of annealing at room temperature follows a sigmoidal trend
with increasing dose, reaching a saturation value above
0.5 1016 a per milligram with DH 59 kJ mol1,
consistent with structural changes at the subnanometer
scale. The magnitude of this value exceeds DH for
tetragonal ZrO2 SiO2 glass by 1859 kJ mol1 and
baddeleyite quartz by 33 kJ mol1, indicating that
these assemblages may form upon thermal annealing of
583
fa 1 eBD
4
The best fit of eqn [4] to the data gives a value of

B 2.7 1016 mg per a-particle, consistent with
amorphous cascades having radii of 2.5 nm. Although
there has been some controversy surrounding
the damage accumulation model, a recent article by
Palenik et al.129 indicates that sensitive measurement
techniques, such as diffuse X-ray scattering, IR spectroscopy, and NMR spectroscopy, are capable of direct
determination of the amorphous fraction and provide
support for damage accumulation via the direct impact
model. Using available data, the components of volume
expansion are plotted in Figure 12, where we see that
expansion of the crystalline fraction (e.g., unit cell)
dominates at lower dose levels, but saturates at about
5 vol.%. Subsequent expansion is dominated by accumulation of amorphous domains.
The structure of the amorphous state in natural
zircon has been examined using EXAFSXANES by
Farges and Calas130 who found that the average ZrO
distance 0.1 A less than that of crystalline zircon.
They were also able to determine that the coordination
number of Zr decreases from 8 to 7, indicating that
O atoms are displaced from the ZrO8 coordination
sphere during a-decay damage. Although long-range
periodicity is lost, the ZrZr distances are still observed
Total
Unit cell
Difference
15
DV/ V0 (%)
amorphous zircon (see McLaren et al.125 for a detailed

study and implications for age dating by ion microprobe techniques).
Significant progress has been made in the understanding of a-decay damage in zircon through a comparison of natural samples and synthetic specimens
doped with short-lived 238Pu.120,126,127 It was initially
reported that the critical dose for amorphization of
238
Pu-doped zircon is 1.0 1016 a per milligram,
and a multiple cascade overlap model was proposed to explain the accumulation of amorphous
domains.126,127 Detailed analysis of the dose dependence of the crystalline fraction, derived from XRD
analysis of the Bragg peak intensities, gives a value
of B 5.8 1016 mg per a-particle for the amount of
material damaged per a-decay event.127 The volume
expansion is 16% (Figure 1), similar to the natural
zircons. Until recently, the fraction of amorphous
material as a function of dose has never been directly
measured. Ros et al.128 accomplished this by directly
measuring the amorphous fraction by careful determination of the diffuse scattering component in a suite of
zircon samples from Sri Lanka, wherein the dose
dependence of the amorphous fraction fa is shown to
follow a direct impact model of amorphization:
10
0.1
0.2
Dose
0.3
0.4
(1016
0.5
0.6
a per milligram)
0.7
Figure 12 Plot showing the components of

volume expansion in zircon doped with 238Pu as a
function of a-decay dose. Unit cell expansion dominates
at low dose, but saturates at about 5 vol.%. At higher
doses, the total macroscopic swelling is dominated
by volume expansion due to amorphous domains in the
material.
in amorphous zircon, but on average they appear to

decrease by 0.3 A relative to crystalline zircon. Interestingly, these authors also found that Hf and Th retain
eightfold coordination in amorphous zircon, but
U appears to exist in a sixfold coordination geometry.
Later work on synthetic zircon samples doped with
trivalent 238Pu and 239Pu (t1/2 2.42 104 years)
revealed that the amorphous 238Pu-doped samples
retained a distorted zircon structure and composition
on the subnanometer scale after 18 years, equivalent to
D 2.8 1016 a per milligram.131 Thermal annealing
of these samples in air revealed that the zircon structure is restored for T
1200 C, but with oxidation of
Pu3 to Pu4, together with minor PuO2 formation.
Below this temperature, the samples recrystallize to a
mixture of ZrO2, SiO2, and PuO2, generally consistent
with the thermodynamic data of Ellsworth et al.124 The
239
Pu-doped samples remained crystalline after a
cumulative dose of 0.012 1016 a per milligram due
to the longer half-life of 239Pu. Thermal annealing
of these samples at 1200 C in air also resulted in
oxidation of Pu3 to Pu4, decreased lattice distortion,
and formation of some PuO2 in the ceramic.
Wayne and Sinha132 were among the first investigators to show that the cracks in zircon, caused by
radiation damage and differential swelling of different compositional zones, serve as pathways for
584
migration of aqueous fluids. These fluids were able to

penetrate into the zircon crystals, resulting in preferential leaching of radiation-damaged zones at temperatures of 450500 C during deformation of
the host rocks. Furthermore, Geisler et al.133 have
provided a detailed description of the hydrothermal
alteration of 619 Ma zircon from a posttectonic granite, Eastern Desert, Egypt, at temperatures on the
order of 100200 C. The zircon crystals exhibit
oscillatory zoning and cracking arising from anisotropic, differential volume expansion. These cracks
provided pathways for fluid migration and chemical
exchange with the solid zircon, resulting in preferential alteration of the U and Th rich zones. Geisler
et al.133 have determined that the more heavily damaged, higher dose zones, are enriched with Al, Ca,
Mn, Fe, light Ln (e.g., LaNd), and H2O species, and
have lost Zr, Si, and radiogenic Pb.
Due to the importance of zircon in geological age
dating, numerous experiments have been conducted
on both natural and synthetic samples. Pidgeon
et al.134 conducted hydrothermal experiments on
X-ray amorphous natural zircon from Sri Lanka containing 0.6 wt% U. They showed that up to 61% of
the original amount of radiogenic Pb was lost after
treatment with an aqueous solution of 2 M NaCl at
500 C and 100 MPa fluid pressure. Later studies
carried out by Sinha et al.135 show that crystalline
zircon loses 3551% Pb and 3047% U when treated
with 2 M NaCl at 600 C and 600 MPa. Under the
same conditions, partially damaged zircon lost 87%
and 52% of the original amounts of Pb and U, respectively. Experiments were also conducted using
the crystalline sample in a fluid with 2% HNO3
at 600 MPa and two different temperatures. In these
experiments, the zircon lost 1325% Pb and
0.54.3% U at 300 C and 3033% Pb and 5.712%
U at 600 C. A study by Rizvanova et al.136 demonstrated that Pb and U are released from amorphous zircon at temperatures as low as 200 C at
100500 MPa in 2 M Na2CO3; however, crystalline
zircon required higher temperatures of at least
650 C to produce significant levels of Pb and U
loss in this aqueous system. At such a high temperature, crystalline zircon was replaced by baddeleyite in
the silica-undersaturated solution.
Using natural, radiation-damaged zircon samples
from Sri Lanka,133,137140 conducted a series of hydrothermal experiments at temperatures between 75
and 650 C in 2 M AlCl3, 2 M CaCl2, 0.1 M HCl, 0.1
and 3 M KOH, pure water, and complex aqueous
solutions at pressures between 50 bar and 2.5 kbar.
The authors observed inward penetrating, irregular

alteration fronts, which resemble those found in natural zircon. The experimentally altered areas are
characterized by a lowered backscattered and an
increased cathodoluminescence intensity and sometimes show complex internal nonequilibrium textures. Their thickness was found to be dependent on
temperature as well as on the duration and pH of the
experiments. Nanosized baddeleyite could be identified in some reaction zones by TEM and IR spectroscopy. The experiments also documented the uptake
of hydrogen (mainly as OH) and of cations such as
Ca, Ba, Mg, and Al from the fluid, combined with
release of variable amounts of Zr, Si, Hf, Ln, Pb, Th,
and U from the altered zircon. The loss of trace
elements and the degree of structural recovery
(including nucleation and growth of new zircon
from the amorphous phase and the removal of defects
in the crystalline remnants) was found to be temperature-dependent. At experimental fluid temperatures
between 75 and 200 C, recrystallization of the amorphous phase was not activated and loss of REEs, U,
Th, and radiogenic Pb was severe, while at higher
fluid temperatures, limited loss of trace elements
have been observed. This observation was interpreted
to reflect a competition between the kinetics of longrange diffusion and ion exchange and the kinetics of
the short-range diffusion necessary for the structural
recovery processes, which significantly reduce the
molar volume of the reacted domains. This creates,
on the one hand, stress that is partly released by
fracturing and, on the other hand, a nanoporous
microstructure, as observed by TEM, providing
pathways for fast chemical exchange between the
reaction front and the fluid. Based on these results,
the authors postulated a diffusion-reaction model
for the alteration of radiation-damaged zircon
whereby moving recovery/recrystallization fronts
are driven by the diffusion of hydrogen species into
the amorphous zircon structure.
In an effort to determine the effect of radiation
damage on the dissolution of zircon, Ewing et al.141
performed experiments using natural zircon samples
at 87 C in an aqueous solution containing 5 wt%
KHCO3. Results of this study indicate that the dissolution rate increases by nearly two orders of magnitude from 3 108 up to 2 106 g m2 day1 for
a-decay doses up to 1.0 1016 a per milligram, for
example, the zircon samples range from highly crystalline to completely amorphous. Helean et al.142
determined the forward dissolution rate of zircon at
120250 C. Using the elemental release rate of Si as
a guide, these authors found that the dissolution rate

of zircon increases from 1.7 104 g m2 day1 at
120 C to 4.1 104 g m2 day1 at 250 C.
The impact of self-irradiation damage in zircon on
its aqueous durability was also studied by Geisler
et al.143 These authors performed a hydrothermal
experiment in a 2 M CaCl2 solution at 600 C and
100 MPa with 16 variably radiation-damaged, that is,
amorphized natural zircon samples from Sri Lanka.
They found a dramatic increase in the alteration rate,
monitored by the penetration of Ca and a lowered
backscattered electron intensity from the reacted
areas, at two critical fractions of amorphous domains.
Molecular-dynamics (MD) simulations showed that
the recoil cascades consist of a core depleted in
matter surrounded by a densified and polymerized
boundary.144 Simulations of a second and third recoil
event further revealed that the low-density regions
form percolating regions inside the amorphous cascades.143 The existence of such a nonuniform amorphous structure was confirmed experimentally by
low-angle X-ray scattering experiments. MD simulations of multiple events further reveal that strongly
overlapping cascades produce connected regions of
depleted matter (e.g., low atomic density), which
likely serve as fast-diffusion pathways. The authors
suggested that the first dramatic increase in the alteration rate marks the first percolation point where
the amorphous domains form infinite clusters. However, at this stage, the polymerized boundary regions
still exist as barriers to diffusion and have to be
overcome by hydrolysis and hydration reactions during the alteration process. The second dramatic
increase is interpreted to be a direct consequence of
the formation of interconnected regions of depleted
matter, allowing invasion-like penetration of Ca and
water over macroscopic length scales.
Geisler et al.145 have performed a comparative
experiment with a radiation-damaged natural zircon
from Sri Lanka and a synthetic 238Pu-doped zircon
(4.7 wt% of 238Pu) in an acidic solution at 175 C.
Both zircon samples have suffered a similar degree of
radiation damage, as given by their degree of amorphization. XRD measurements of the experimental
run products revealed that during the hydrothermal
treatment, only the disordered crystalline remnants
recovered in the natural zircon, whereas in the
238
Pu-doped zircon, the amorphous phase strongly
recrystallized. Such a different alteration behavior
of natural and Pu-doped zircon suggests two
fundamentally different alteration mechanisms. The
authors postulated that the alteration of natural
585
radiation-damaged zircon with a low doping level

of U and Th is controlled by diffusion-reaction processes as discussed earlier, but that the high degree of
recrystallization observed in the 238Pu-doped zircon
doped is more compatible with the concept of an
interface-coupled dissolutionreprecipitation process, where congruent dissolution is assumed to be
spatially and temporally coupled to the reprecipitation of new zircon (poorer in Pu) at an inward moving
reaction interface.
5.22.4.2
Thorite
Thorite (ideally ThSiO4) is isostructural with zircon

and contains 1719 wt% SiO2 and 5575 wt%
ThO2, depending upon the age and content of radiogenic Pb. In some natural systems, thorite may contain
up to 4 wt% P2O5, 6 wt% CaO, 5 wt% ZrO2, 2 wt%
As2O5, 21 wt% Ln2O3, 25 wt% UO2, and 516 wt%
total H2O (see Farges and Calas,130 Foord et al.,146 and
Lumpkin and Chakoumakos147 and references therein).
Thorite samples from the Harding pegmatite, New
Mexico, exhibit extensive solid solution toward the
end-members, Ca0.5Th0.5PO4, Ca0.5Th0.5VO4, and to a
lesser extent, YPO4. Rare, yellow thorites were also
found with a significant Ca0.5U0.5SiO4 component in
which the U is postulated to be hexavalent.147 Geologically young thorite crystals with a well-defined age of
67 Ma have been reported to be completely amorphous,146 providing an upper limit on the critical dose
of 0.8 1016 a per milligram, consistent with data for
natural zircon discussed in the previous section. However, Lumpkin and Chakoumakos147 found that the
P and V thorites from the Harding pegmatite retained
substantial crystallinity even after sustained doses of
40120 1016 a per milligram (Figure 13). Based on
a simple comparison of bond energies, they proposed
that thorites rich in P and V have a lower energy barrier
to recrystallization than samples that are closer to
ThSiO4 in composition. Earlier work has shown that
thorite is subject to extensive alteration in natural systems, generally resulting in hydration, loss of Si, and loss
of radiogenic Pb, often forming secondary galena in the
presence of S-bearing fluids.148,149
5.22.4.3
Titanite (Sphene)
Titanite, ideally CaTi(SiO4)O crystallizing in monoclinic space group C2/c, may incorporate minor
Na, lanthanides, and low levels of actinides on the
Ca site, together with Fe, Al, and Nb on the Ti site.
Additionally, significant amounts of F and OH may
586
Figure 13 Optical micrograph showing the presence of

crystallinity in P and V-rich thorite from the Harding granitic
pegmatite, Taos County, New Mexico. This image, taken
with crossed polarizers, reveals crystalline domains as
brightly colored spheroidal regions, suggesting
recrystallization of radiation damage thorite over time.
Width of image 1 mm.
replace O on the anion site that is not bonded to Si.

The amounts of actinides incorporated in the structure are generally below 500 ppm Th and 3000 ppm U.
Due to limited solubility of lanthanides and actinides
in the structure, the titanite has seen limited use
in waste forms apart from the titanite-based glassceramics developed for Canadian waste.150 Heavily
damaged samples studied by Hawthorne et al.151 from
the Cardiff mine, Ontario, Canada, indicate that the
critical dose is somewhat higher than (0.30.4) 1016
a per milligram if we assume an age of 1000 Ma for
this locality. This is in good agreement with a major
study conducted by Vance and Metson,152 which
showed that the critical dose is 0.5 1016 a per
milligram and that the crystallineamorphous transformation results in a density decrease of 8%. General features of a-decay damage in titanite with
increasing dose include increasing thermal vibration
parameters of the cations and anions, increasing unit
cell volume up to about 3% in the most heavily
damaged samples, and possible reduction of some
Fe3 to Fe2 during electron transfer processes associated with the radioactive decay (see Section 5.22.2).
5.22.4.4
Allanite
Minerals of the epidote group conform to the general

structural formula A2M3(SiO4)(Si2O7)(O,F)(OH)
with A Ca, Sr, Pb, Mn, Th, Y, Ln, and U, and
M Al, Fe, Mn, Mg, Cr, and V. In this section,
we are mainly interested in the mineral allanite,

characterized by the presence of light Ln elements
and Th on the A-sites together with Al, Fe3, Fe2,
and Mg on the M-sites. Allanite typically occurs as an
accessory mineral in felsic igneous rocks, granitic
pegmatites, volcanic rocks, and metamorphic systems, among others. It has assumed some importance
as a tracer of geochemical processes and has proved
to be useful for geological age dating. Only limited
data are available with regard to radiation damage
effects in allanite; however, it is clear that the mineral
becomes optically isotropic due to a-decay damage.
The most consistent data sets also indicate that the
density decreases by 8.510.5%, giving a reasonable
indication that the volume expansion is well below
that of zircon.153,154
Janeczek and Eby153 investigated three samples
from different geological localities and provided
a detailed assessment of the composition, microstructure, and annealing behavior. Based on careful
EPMA, XRD, and TEM studies of samples with
reasonably established geological ages, it appears
from this work that the critical amorphization dose is
somewhat >0.5 1016 a per milligram for two samples
from the Appalachian orogen (200400 Ma). A third
sample from Arizona has an age of 1400 Ma and exhibits a slightly higher level of crystallinity in the bulk
XRD pattern. The critical amorphization dose of this
sample is slightly >5 1016 a per milligram, suggesting that a long-term annealing mechanism may be
operative in allanite. Thermal recovery of allanite
occurs above 500 C and the mineral decomposes
above 850 C. Lattice parameter changes are anisotropic during recovery and the unit cell volume
decreases by 2% at a temperature of 800 C.
Allanite is subject to hydrothermal and low temperature alteration and breakdown to new phase
assemblages. It is commonly replaced at low temperatures by fluorocarbonate minerals (e.g., bastnaesite,
LnCO3F), clay minerals, and thorite. Breakdown during weathering to cerianite (CeO2), monazite, clays,
and goethite has also been reported.154 Wood and
Ricketts155 described in some detail the alteration of
igneous allanite by low temperature (100200 C)
hydrothermal F and P containing fluids circulating
in the Casto pluton, Idaho. The alteration occurs
along the rims of crystals and along fractures and
is accompanied by some Th enrichment and loss of
Ln elements. The most severe alteration resulted in
breakdown of allanite to fluorite, monazite, and other
secondary phases. Figure 14 shows an example of
hydrothermal alteration of natural allanite from the
Figure 14 Backscattered electron image at low

magnification showing progressive alteration of allanite from
the Rutherford #2 granitic pegmatite, Amelia County,
Virginia. The lower, lighter gray area is unaltered allanite.
Darker gray zones in the middle of the image represent
allaniteepidoteclinozoisite alteration, for example,
chemically altered allanite possibly of hydrothermal origin.
The heavily altered dark area in the upper part of the image
consists of a complex assemblage of silicate, lanthanide,
and iron minerals probably formed at lower temperature.
Width of image 1 mm.
Rutherford #2 granitic pegmatite, Amelia County,

Virginia. This image reveals an outer zone of progressive alteration of allanite to an assemblage of late stage
silicate, lanthanide, and iron minerals.
5.22.5 Phosphates
5.22.5.1
Monazite
Like zircon and thorite, monazite also has ABO4

stoichiometry, but the crystal structure is monoclinic
(space group P21/n) and consists of chains of alternating BO4 tetrahedra and AO9 polyhedral sites.156
These chains are cross-linked by edge sharing with
the AO9 polyhedra, effectively closing off open tunnels and creating a structure that is 10% more
dense than the zircon structure type. Orthophosphates with Nd, Pr, Ce, La, Am, or Pu on the
A-site adopt the monazite structure; whereas, those
with the heavier and smaller Ln elements Lu, Yb,
Tm, Er, Ho, and Y adopt the tetragonal xenotime
structure, which is isostructural with zircon. In natural systems, the formula of monazite is generally
given as (Ln,Th,U,Ca)(Si,P)O4, representing a
solid solution of the ideal end-members LnPO4,
Ca0.5Th0.5PO4, Ca0.5U0.5PO4, and ThSiO4. Natural
587
monazite may contain up to 16 wt% UO2 and

52 wt% ThO2,156,157 and has recently been found in
alkaline rocks containing over 8 wt% SrO, indicating
solid solution toward an end-member of the form
Sr0.5Th0.5PO4.42 Therefore, the mineral may be considered as a potential host phase for actinides and a
range of fission products, including Sr. Natural monazite remains crystalline even up to a-decay doses
approaching 7 1016 a per milligram, a feature that
makes synthetic monazite-based materials very
attractive for nuclear waste encapsulation. The radiation stability of synthetic (La,Pu)PO4 and PuPO4
doped with 8.1 and 7.2 wt% 238Pu, respectively, has
been investigated by Burakov et al.158 These authors
discovered that (La,Pu)PO4 remains crystalline up to
a dose of (0.20.3) 1016 a per milligram, albeit
with a decrease in the intensity of the measured XRD
peaks. In contrast to this result, the PuPO4 ceramic
sample is heavily damaged at a dose of only
0.1 1016 a per milligram, and exhibits substantial
volume swelling and cracking.
A number of studies have documented alteration
of monazite during interaction with various hydrothermal fluids.159164 An important study was conducted by Mathieu et al.162 on natural monazite
occurring in Lower Proterozoic sandstones of the
Franceville basin, Gabon (see Section 5.22.6.3).
The results of this work demonstrate that monazite
was altered to a microcrystalline Th-silicate phase
by interaction with a low temperature (<200 C,
100 MPa) diagenetic brine (NaClCaCl2, with Li,
Br, and SO4), resulting in loss of light Ln elements
and U. Several monazite alteration mechanisms
have been identified, including chemical exchange,
dissolutionreprecipitation, dissolution and replacement by a different mineral, and, in rare cases, selective Th removal (see Figure 10). In their detailed
study, Poitrasson et al.160 documented that while the
light Ln are typically released from monazite, U, Y,
and the heavy Ln were retained during hydrothermal
alteration at temperatures of 260340 C and in fluids
with salinities ranging from 3 to 18 wt% NaCl equivalent. In a study of monazite from the Steenkampskraal mine, South Africa, Read et al.164 showed that
the light Ln elements are retained in altered monazite, the heavy Ln and Y are being released and
precipitated locally as secondary phosphate minerals,
and U is released to the fluid phase and removed
from the system. In general, Th is typically less
mobile than the lanthanide and Y, and is concentrated
into Th-bearing alteration products.165,166 More
recently, Hetherington and Harlov167 demonstrated
588
that monazite is subjected to a chemical refinement

process during interaction with an evolving granitic
pegmatite fluid. These relatively high temperature,
H2O-rich fluids contained Na, K, F, and minor Cl and
reacted with high CaThUSi monazite via a coupled
dissolutionreprecipitation mechanism to produce
near end-member LnPO4 monazite and precipitates
of thorite and uraninite.
Experimental data indicate that monazite is highly
insoluble in most hydrothermal and low temperature
fluids; however, the solubility may be enhanced in
aqueous fluids with low pH, low phosphate content,
or high F concentrations which can lead to the formation of REE-fluoride complexes.168,169 Thermodynamic calculations suggest that an increase in pH
from 3.5 to 5.0 will decrease the solubility of monazite by about two orders of magnitude at 300 C.
A similar decrease in solubility is expected if the
total PO4 concentration decreases from about 107.5
to 105.5 molal.169 At temperatures below 250 C, the
solubility of monazite in aqueous solutions decreases
with increasing temperature,156 and this has attractive implications for geological disposal. Recent work
by Oelkers and Poitrasson170 provided important
results on the steady-state dissolution rates of monazite at temperatures of 50230 C and pH ranging
from 1.5 to 10 with variable flow rate and surface
area. Using a natural sample as the starting material,
these authors show that the release rates of the REEs
and U are essentially congruent for all experimental
conditions. The Th concentration in solution was
stoichiometric only in the basic solutions and was
detected at lower than stoichiometric ratios in acidic
solutions, probably due to precipitation of a Th-rich
secondary phase.
A few experiments have been performed at elevated temperature and pressure in order to assess the
behavior of the UThPb system in monazite.171,172
Teufel and Heinrich,171 by means of hydrothermal
experiments at 400750 C and 300 MPa, demonstrated substantial Pb loss in monazite powder at
temperatures as low as 400 C. The mechanism of
Pb loss involved dissolution and reprecipitation of
the monazite at these high temperatures. In contrast,
Seydoux-Guillaume et al.172 found no evidence for
Pb loss in their experiments in pure water at
8001200 C and 700 MPa, even though some dissolution and recrystallization was observed on the margins of the monazite grains. Additional experiments
were conducted at 1000 C using NaCl, CaCl2, SrCl2,
and Pb-bearing fluids. Significant changes in the
UThPb system were only observed in the CaCl2
and SrCl2 hydrothermal fluids, with a Pb loss discordance of 68% and 16%, respectively. Nevertheless,
no Pb diffusion profiles were observed and the
discordance observed in these experiments was attributed to the dissolutionreprecipitation mechanism.
5.22.5.2
Apatite Group
An important feature of this rather larger structural

group is the ability to incorporate a range of substitutions on the Ca and P sites, including solid solution
toward britholite that contains Si on the tetrahedral
sites. The general formula of the group, consisting of
more than 20 mineral species, can be expressed as
M5(ZO4)3X with M Ca, Sr, Ba, Pb, Na, Mn, Y, and
Ln; Z P, S, V, As, and Si; and X F, Cl, and OH.173
There are also more than 80 synthetic compounds
that crystallize with the apatite structure. The common rock-forming minerals of the apatite group
(fluor-, chlor-, and hydroxyapatite) are described by
the formula Ca5(PO4)3(F,Cl,OH) and crystallize in
space group P63/m (X F) or P21/b (X Cl, OH).
In most rocks, these minerals generally contain low
levels of Th and U, for example, <0.2 wt%
Th U and have limited value for radiation damage
studies. However, in more highly evolved rocks, there
may be extensive solid solution toward britholite,
ideally Ln4Ca(SiO4)3O, wherein the ability to substitute Si on the tetrahedral sites and O on the anion site
normally occupied by halogens or OH groups allows
for incorporation of actinides on the Ca/Ln sites.
The rare apatite minerals of the pyromorphite
vanadinitemimetite series, Pb5(PO4)3ClPb5(VO4)3
ClPb5(AsO4)3Cl, are also important as potential
analogs for materials designed to encapsulate longlived radioactive 129I in nuclear wastes. Synthetic
apatites can also contain Sr on the Ca-site and may
be considered as a possible host phase for short-lived
90
Sr. It is of interest to note that fluorapatite occurs in
the alteration zones of the Oklo natural fission reactors, where the mineral contains Nd and Sm isotopes
of fission origin.174 One sample also showed a slightly
elevated 235U/238U ratio, possibly due to incorporation of 239Pu derived from the fission reactors at
the time of formation. This has been confirmed
by Hidaka,175 who measured 235U/238U isotopic
ratios of up to 0.0171 for apatite coexisting with
uraninite with slightly depleted 235U/238U 0.0066
(see Section 5.22.6.3).
Although technically a silicate mineral, britholite
is discussed here as part of the group. Britholite from
pegmatitic segregations in felsic igneous rocks of the
Eden Lake complex in Manitoba, Canada, has been

studied in some detail.176 These silicate apatites contain about 0.91.3 wt% ThO2 and 0.71.0 wt% UO2
together with 5255 wt% Ln2O3, 1217 wt% CaO,
15 wt% P2O5, and 24 wt% F. The crystals are
optically isotropic but weakly crystalline according
to XRD analysis; however, in this case, the observed
diffraction could be due to inclusions of associated
minerals. Assuming an age of 1700 Ma for the host
rocks, the estimated a-decay dose is (47) 1016 a
per milligram and probably represents an upper limit
for the critical dose for amorphization. For comparison, the results of Carpena et al.177 on a series of
2100 Ma apatitebritholite samples from Ouzzal
Mole, Algeria, indicate that the critical dose is
2 1016 a per milligram. This suggestion is reasonably consistent with the recent work of Yudintseva,178
who examined six natural britholite samples from
alkaline rocks in Russia, ranging in age from 320 to
2600 Ma and containing up to 12 wt% ThO2 and
UO2. Detailed XRD and TEM work on these samples
places the critical dose for amorphization at a value
close to 0.9 1016 a per milligram. Thermal annealing of fully amorphous samples indicated recrystallization temperatures of 500600 C by XRD.178
Apatite is one of the few minerals studied by actinide
doping experiments in the laboratory.179,180 For example, the synthetic britholite CaNd4(SiO4)3O becomes
completely amorphous at a dose of 0.3 1016 a per
milligram when doped with 1.2 wt% 244Cm. This is
about a factor 3 lower than the critical dose required
to render natural samples amorphous and is generally in
keeping with observations on the other minerals discussed in previous sections of this chapter. The crystallineamorphous transformation in this compound
results in a bulk volume expansion of 8.08.5% (see
Figure 1) in which the calculated damage volume
B 200 nm3, corresponding to a spherical track radius
of about 3.6 nm. DTA showed that the amorphous
Cm-doped britholite recrystallized at temperatures of
600700 C, releasing 130 J g1 of stored energy and
activation energy of 3.1 0.2 eV.179
Boudreau and McCallum181 reported significant
findings on the alteration of Ln-rich chlorapatite
from the Stillwater igneous complex in Montana.
This alteration event is associated with the hydrothermal alteration of the mafic host rocks as olivine
was replaced by serpentine magnetite calcite
during infiltration of meteoric water at low temperatures (100 C) and near-neutral pH. Under these
conditions, the chlorapatite was partially replaced by
hydroxyapatite and small grains of monazite. Based
589
on the results of electron microprobe analyses, the

authors suggest that Si was lost from the magmatic
chlorapatite and that CO2 and minor amounts of
other elements (e.g., Fe) may be incorporated in
the hydroxyapatite alteration product. Arden and
Halden176 also reported that apatites from Eden
Lake, Manitoba, exhibit evidence for hydrothermal
alteration in which La, Ce, and F were lost and Cl,
and possibly OH, were gained. The temperature during the hydrothermal alteration event may have been
as low as 200 C. This study is interesting in view of
the dissolution experiments performed on the Cmdoped synthetic britholite CaNd4(SiO4)3O.179 The
tests described in this study were conducted on
fully amorphous and recrystallized samples using
deionized water at 90 C for 14 days. In general, the
results indicate that radiation damage induced amorphization and volume swelling lead to an increase in
the dissolution rate by approximately one order of
magnitude. However, the release of Nd was below
detection limits in all of the experiments, suggesting
that it had reprecipitated on the surface of the specimens as a secondary oxide phase.
Valsami-Jones et al.182 noted that, although phosphate mineral dissolution has not been studied in
detail, they are known to have very low solubility
products in aqueous solution. Based on a series of
laboratory experiments on synthetic hydroxylapatite
and natural fluorapatite at 25 C and pH 27, they
proposed that apatite dissolves according to the following dissolution reactions:
Ca5 PO4 3 OH 7H 5Ca2 3H2 PO
4 H2 O VI

Ca5 PO4 3 F 6H 5Ca2 3H2 PO
4 F
VII
Experimental data indicate that the dissolution rates

of both phases increased with decreasing initial pH of
the buffered solution, in accordance with the reactions shown earlier.
A similar experimental study was recently
reported for synthetic apatite having the composition
Ca4.5Nd0.5(P2.5Si0.5O4)3F, conducted at 25 C and
pH 312.183 Results of this work also showed a
negative correlation between the dissolution rate
and pH for pH 27, but a constant rate was
observed for pH > 8. In these experiments, the
authors discovered that the Nd release rates are
slower than those of Ca, P, and F and attributed
the result to the precipitation of a secondary phase,
possibly rhabdophane, NdPO4nH2O. Apatite samples doped with Nd, Th, and U were examined by
590
Terra et al.,184 who measured release rates of 4 104

g m2 day1 for Nd and 1.3 104 g m2 day1 for
Th in single-phase NdTh samples in experiments
with 104 M HNO3 at 90 C. In comparison, the
release rate of U was found to be 2 102 g m2
day1 for NdU-doped apatite under the same conditions. This was attributed to the oxidizing conditions of the experiment and the presence of a second
U phase in the NdU-doped material.
5.22.5.3 Kosnarite and Related NZP
Materials
Kosnarite, ideally KZr2(PO4)3, crystallizing in space
group R3c, is a relatively rare mineral occurring in granitic pegmatites where it occurs in association with late stage, secondary phosphate mineral
assemblages.185 A synthetic analogue of kosnarite,
NaZr2(PO4)3, otherwise known as sodium zirconium
phosphate (NZP), is the prototype for a large family
of synthetic compounds that can be described by the
general formula A1xB2(PO4)3 with A monovalent
Na and K, divalent Ca, Sr, Cd, Ba, and Pb, or trivalent
Ln elements; and B tetravalent Ti, Zr, Hf, Sn, Th,
and U or trivalent Cr, Fe, Ga, and In, etc.186189 These
materials exhibit low thermal expansion properties and
have potential applications as fast ion conductors,
redox insertion/extraction materials, and as a host
phase for nuclear waste immobilization. In the latter
case, it is the crystal chemical flexibility and durability
in aqueous solutions that have attracted the most attention to this interesting family of compounds.190,191
In comparison to the available data on other
minerals and synthetic compounds summarized in
this chapter, very little work has been published on
a-decay damage in NZP compounds, and natural
kosnarite has not been reported with detectable
amounts of Th and U. However, Russian scientists
have succeeded in the synthesis of NaPu2(PO4)3 containing 239Pu or 238Pu. After 2 years of storage, the
239
Pu sample accumulated a dose of 0.0091 1016
a per milligram and showed no evidence of degradation; whereas, the 238Pu sample became amorphous at
a dose of 0.93 1016 a per milligram (conference
abstract by Orlova et al. 1993, cited by Zyryanov and
Vance192).
There have been several studies of the aqueous
dissolution behavior, one of the earliest was conducted by Roy et al.190 who prepared CsZr2(PO4)3
and reported a release rate of 0.2 g m2 day1 for
Cs after a hydrothermal experiment in deionized
water for 14 days at 300 C and 30 MPa. Analyses of
the solution following the experiment indicate the

release rates on the order of 0.1 g m2 day1 for
P and 2 103 g m2 day1 for Zr. A second experiment was conducted using a brine containing 5 wt%
NaCl, 5 wt% KCl, 10 wt% MgCl2, and 10 wt%
CaCl2 at the same temperature and pressure. In this
case, the Cs release rate was higher by a factor of
three, while the release rates of P and Zr were similar
to those of the experiment with deionized water.
Furthermore, in the latter experiment, baddeleyite
was observed as an alteration product.
Zyryanov and Vance192 conducted dissolution
tests on undoped NaZr2(PO4)3, several NZP samples
containing Cs, Sr, Y, Nd, Gd, and Ca, and a sample
containing 20 wt% simulated Purex type waste.
Although the samples were hot pressed, the tests
were conducted on 3763 mm powders at 90 C in
an aqueous solution with pH 5 and a solid surface-area-to-solution-volume ratio close to 1.0.
After 28 days, the test results gave elemental release
rates of 0.0020.03 g m2 day1 for Na, 0.13 107
g m2 day1 for Zr, and 0.0020.1 g m2 day1 for P.
The release rates of Cs and Sr were 0.002 and
0.003 g m2 day1, respectively, whereas Y, Nd, and
Gd were released at rates similar to that of Zr.
Based on the measured weight losses, the authors
suspected that reprecipitation had occurred during
the experiments, but this was not proven. In the
sample prepared with simulated waste, release of Zr,
P, Ce, Nd, and Ag were similar to those of Synroc-C,
whereas other elements in the NZP showed release
rates typically 12 orders of magnitude higher than
the Synroc sample under the same conditions.
More recently, Bois et al.193 synthesized
La0.33Zr2(PO4)3 and LaPO4 (monazite) ceramics and
determined the elemental release rates at a temperature of 96 C. For experiments conducted with a solid
surface-area-to-solution-volume ratio of 0.1, the
authors report a minimum release rate of 103 g m2
day1 for P, while the release rates of La and Zr were
both <105 g m2 day1. In a parallel experiment,
they determined that the release rates of La and
P from the monazite ceramic were about one order
of magnitude lower than the NZP type compound.
5.22.5.4
Xenotime
Ideally YPO4 with heavy lanthanide elements (e.g.,

DyLu) replacing some of the Y, xenotime is an important accessory mineral in igneous and metamorphic
rocks where it may be a very useful mineral for UPb
age dating and for geothermometrygeobarometry in
conjunction with coexisting monazite and garnet.194,195

Like monazite, xenotime has never been reported in the
amorphous state even though it has the zircon crystal
structure. Typical concentrations of Th and U in xenotime are 0.10.3 wt%; however, xenotime samples
from evolved granitic rocks and pegmatites may contain
up to 6.0 wt% ThO2 and 7.5 wt% UO2.167,196 Based on
several analyses of xenotime with high Th and
U concentrations from host rocks with reasonably constrained geological ages, we estimate that they have
received a-decay doses of (1.414) 1016 a per milligram. The principal study of relevance to radiation
damage is the accelerated radiation damage study of
Luo and Liu,197 wherein flux grown crystals of LuPO4
were doped with 1.0 wt% 244Cm and stored for 18 years.
In this time, the crystals reached a cumulative dose of
5 1016 a per milligram which is within the range of the
high ThU natural xenotime samples noted earlier, but
they remained in a highly crystalline state according to
electron microscope observations. However, the authors
did observe 510 nm defect clusters with associated
strain fields and 520 nm voids assumed to contain He
due to the high a-particle dose. The importance of this
study lies in the demonstration of radiation resistance in
Yand lanthanide orthophosphates with the zircon structure type and, at least to a certain extent, substantiates
the observations on the recovery of radiation damage in
P-bearing natural thorites discussed earlier (Section
5.22.4.2). Hetherington and Harlov167 have also
described a chemical refinement type of alteration in
high ThUSi xenotime, wherein a fluid-driven coupled dissolutionreprecipitation mechanism produced
near end-member (Y,Ln)PO4 xenotime, thorite, and
uraninite.
oxidizing conditions is given in the next section,

followed by two examples of U ore deposits that
have been studied quite extensively as natural analogs: the natural fission reactors of Gabon and a
description of U migration at Koongarra, Australia.
5.22.6.2 General Aspects of Uraninite
Alteration in Natural Systems
Uraninite, ideally UO2, is a cubic (fluorite structure,
Fm3m) mineral crystallizing in granitic rocks, granitic pegmatites, volcanic rocks, metamorphic systems, and sedimentary environments. All natural
uraninites remain crystalline to a-decay doses reaching values in excess of 100 1016 a per milligram.
Natural uraninite is always slightly oxidized and can
be described by the formula UO2x with x < 0.3.199
This is achieved through the slight oxidation of
U4 to U6 in natural samples. Other elements
incorporated during crystallization include Th, Ca,
and Ln elements with similar ionic radii to that of U.
The amounts of radiogenic Pb accumulated in
uraninite can be quite high, but this element is not
compatible with the fluorite structure and is commonly depleted due to long-term diffusion or episodic geological events. Under reducing conditions,
the solubility of uraninite is extremely low; however,
this is moderated to some extent by the presence
of minor U6 and radiogenic Pb2 in the structure,
the latter increasing substantially with time. Perhaps
the most important alteration mechanism of uraninite under reducing conditions is replacement by
coffinite (USiO4) and this proceeds according to the
reaction:
UO2x SiO2 USiO4 0:5xO2
5.22.6 Ore Deposits: Analogs for

Spent Fuel
5.22.6.1
Preamble
Although this chapter mainly deals with ThU

minerals as natural analogs for alternative ceramic
nuclear waste forms, some of these polyphase materials may contain significant amounts of UO2 in addition to the targeted phases. Considering this and the
fact that direct disposal of spent fuel is still an option,
the purpose of this section is to introduce the reader
to some of the geological and mineralogical aspects of
U ore deposits as natural analogs (see Wronkiewicz
and Buck198 for a more detailed review of this topic).
A brief discussion of the general aspects of the geochemical alteration of uraninite under reducing and
591
VIII
From this reaction, we can see that an increasing

silica activity promotes coffinite formation, whereas
increasingly oxidizing fluids tend to stabilize uraninite. If dissolved H2S is present, then radiogenic Pb
released from uraninite may lead to the formation of
galena as a byproduct of eqn [VIII].
Under oxidizing conditions, the uranyl oxyhydroxides play an important role in the early stages of
uraninite alteration in relatively acidic and dilute
aqueous systems. According to Finch and Murakami199, this important uranyl mineral group can
be described by the general formula Mn[(UO2)x
Oy(OH)z](H2O)m with M Ca, Sr, Ba, Pb, and K.
Schoepite and studtite are the main phases with
n 0 and ianthinite is an interesting oxy-hydroxide
592
in which M U4. In relatively basic aqueous systems

with dissolved silica, there are several important uranyl silicates, including soddyite (UO2)2SiO4(H2O)2,
members of the uranophane group Mn[(UO2)
(SiO4OH)]n(H2O)m, and members of the weeksite
group M(UO2)2(Si5O13)(H2O)4. In more complex
aqueous systems, a number of relatively insoluble uranyl phases may form as alteration products of uraninite. The general formula of many of these minerals
can be written as Mn[(UO2)(XO4)]2(H2O)m where
M Na, Mg, K, Ca, Mn, Fe, Co, Ni, Cu, Zn, Ba, and
Pb, and X P, V, or As. Minerals described by this
formula include members of the autunite group, metaautunite group, a large number of vanadates, such as
carnotite and curienite, and certain arsenates.49
The alteration of uraninite commonly proceeds
through the early-formed metastable uranyl oxyhydroxides, such as schoepite, becquerelite, vandendriesscheite, and fourmarierite, to silicates such as
soddyite, curite, and uranophane. Certain uranyl carbonate minerals (e.g., rutherfordine) may also be
present as part of the assemblage of secondary
U minerals provided that there is enough dissolved
CO2 in the system. Uranyl phosphate minerals are
commonly the last to form in this alteration sequence.
Wronkiewicz and Buck198 presented an informative
comparison between a laboratory experiment involving the dissolution of synthetic UO2 in an aqueous
solution designed to simulate conditions imposed by
volcanic rocks at the Yucca Mountain repository in
Nevada and the uranyl mineral paragenesis observed
in the Nopal I ore deposit, a geologically young
(8 Ma) occurrence with low radiogenic Pb, hosted
by a similar suite of volcanic rocks in the Pena district, Chihuahua, Mexico. With minor variations, for
example, the Na/Ca ratio of the experiment versus
the groundwater composition of the natural system
and the relative amounts of the uranyl phases Naboltwoodite and uranophane, the laboratory experiment (lasting 8 years) closely followed the observed
mineral paragenesis at the Nopal I deposit.
5.22.6.3
Natural Fission Reactors in Gabon
The western African country of Gabon is host to a

number of sedimentary U deposits that formed
around 2000 Ma in the Franceville basin and
remained unmetamorphosed, reaching a maximum
temperature of 200 C during diagenesis (see
Janeczek200 and references therein). There are six
known U ore deposits, three of which (Oklo, Okelobondo, Bangombe) are known to have sustained
nuclear fission in 16 different reactor zones soon

after formation. These natural fission reactors may
have operated for several thousand years, driving the
235
U/238U ratio of the uraninite fuel to values as low
as 0.0038. In a careful study of the mineral florencite
occurring as inclusions in uraninite, Meshik et al.201
found elevated levels of fission Zr, Ce, Sr, Xe, and Kr.
Based on analysis of the isotopic signature of Xe,
they determined that the natural reactor operated
in a cyclic pattern, 30 min on and 2.5 h off. Radiogenic heat production during this time may have
caused the temperature to increase locally to values
as high as 450 C. As a direct result of the elevated
temperatures, hydrothermal alteration occurred
locally around the reactors, leading to dissolution
of quartz and growth of clay minerals together
with small amounts of apatite (see Section 5.22.5.2)
and zircon.
The Oklo deposits are located stratigraphically
near the upper part of a geological formation consisting of sandstone and conglomerate, and are overlain by black shales (typical reducing environment).
Uraninite is the major U ore mineral in all of the
deposits in the region. The Th content is very low
(<0.3 wt% ThO2), the amounts of SiO2, TiO2, ZrO2,
FeO, and Ln2O3 are generally <1 wt% each, and the
maximum CaO content is 23 wt%. The major impurity element is radiogenic Pb. Most analyses show
PbO contents of 47 wt%, but this may approach a
value of 22 wt% in some samples. Based on an age of
2000 Ma for the uraninite mineralization, the calculated maximum amount of radiogenic Pb is about
22.5 wt% PbO; thus, the uraninites from these deposits have typically lost up to 7080% of the expected
quantity of radiogenic Pb. The localized hydrothermal alteration that occurred during the operation of
the fission reactors is attributed to the presence of
generally reducing and moderately saline aqueous
fluids. A second period of hydrothermal alteration is
associated with 14001600 Ma groundwater circulation in the Franceville basin, leading to mobilization
of radiogenic Pb in the reactor zones and precipitation of Sb-rich galena and other sulfides (e.g., pyrite).
The major phase of Pb loss from uraninite is related
to the intrusion of dolerite dikes in the region at
780 Ma, during a third period of aqueous fluid flow
through the rocks, resulting in widespread sulfide
mineralization and precipitation of much of the
radiogenic Pb in galena.
For the most part, reducing conditions prevailed
during the low temperature hydrothermal activity
described earlier, with some dissolution and
replacement of uraninite by coffinite, but this does

not preclude the possibility of more oxidizing conditions near the ore bodies due to radiolysis of water.
Oxidizing conditions certainly prevail for ore bodies
located nearer the surface during recent weathering
of the region, resulting in U transport and precipitation as uranyl minerals or sorption on goethite, florencite, anatase, and chlorite. The main uranyl phases
identified in and around the reactor zones are torbernite, fourmarierite, francevillite, francoisite, and schoepite.200,202 Plutonium and lanthanide elements released
by dissolution of uraninite were precipitated mainly in
phosphate minerals. Other fission and decay products,
such as Pb, Tc, platinum group elements, were predominantly released by diffusion, were fixed in sulfide
minerals. In general, most of these relatively insoluble
elements, together with the actinides, were probably
retained locally with 1020 m of the ore bodies.
It appears that Cs, Rb, Sr, Ba, Xe, Kr, and I produced
during the fission cycles were also lost by diffusion
processes; however, these soluble elements were transported out of the system for unknown distances.
5.22.6.4 Uranium Migration in the
Koongarra Ore Deposit
The Koongarra U ore deposit is one of several located
in the Northern Territory of Australia. Much like the
deposits described earlier, Koongarra is of sedimentary
origin having formed at about 1600 Ma, but experienced a significantly higher level of metamorphism.
Due to the substantial influence of meteoric water
circulation and weathering, this deposit has served as
a case study for U migration in the environment.203,204
The tropical climate of this geographic region produces 1.7 m of rainfall annually, leading to a distinctive dispersion of secondary uranyl minerals around
the primary ore body above and below the weathering
baseline, lying at a depth of about 2030 m below the
surface. This pattern has developed over the previous
13 Ma and includes a dispersed fan of U associated
with Fe minerals in the weathered zone, extending up
to 200 m from the primary ore body.
The groundwater flow pattern in the Koongarra
area is primarily from northwest to southeast.
A deeper penetration of groundwater occurs along
the Koongarra fault and rises to the southeast to
intermix with groundwater in the weathered zone
after passing through the area of the primary ore
body. Chemically, the groundwaters are neutral to
slightly acidic and characterized by dilute concentrations of MgHCO3 and SiO2 due to the dissolution of
593
chlorite in the host rocks.205 Alteration of chlorite

leads to the formation of vermiculite and ultimately
to kaolinite and oxidized Fe minerals such as goethite
in the weathered zone. Below the weathered zone,
primarily between the Koongarra fault and the main
ore body, there is a zone of dispersed secondary uranyl silicate mineralization, consisting of sklodowskite,
Mg[(UO2)(SiO4OH)]2(H2O)6. Directly above the ore
body and the secondary silicate mineralized zone,
saleeite, Mg[(UO2)(PO4)]2(H2O)10 is the major
uranyl mineral where it replaces sklodowskite and
apatite.199,203 However, the nature of the U association in the weathered zone changes with flow direction and distance away from the ore deposit as
saleeite gives way to secondary Fe minerals with
significant adsorbed U contents. These Fe minerals
are predominantly goethite (FeOOH), hematite
(Fe2O3), and ferrihydrite (Fe5HO84H2O) and they
occur as vein fillings, discrete nodules, and in intimate association with clay minerals. Detailed electron microscopy indicates that there is very little
sorption of U on clay minerals. The highest concentrations of U are found in association with goethite in
the nodules, but this is complicated by a correlation
with minor metal cations such as P and Cu, suggesting that precipitation of a uranyl phase such as torbernite may also play a role in the fixation of U.204
Considerable experimentation has been reported
with regard to the adsorption of U on Fe mineral
surfaces as a function of pH and the availability of
complexing ligands.206,207 In U sorption experiments
performed directly on weathered schist from Koongarra, it was demonstrated, via a chemical reagent technique, that selective removal of Fe oxides caused a large
decrease in the sorptive capacity of the material.206 This
confirmed in later sorption experiments whereby
the material was characterized by analytical electron
microscopy,208 revealing selective U sorption on goethite at levels 20 times higher than associated clay
minerals (Figure 15). Payne et al.206 also studied the
effect of synthetic ferrihydrite transformation to hematite or goethite on both the adsorption and desorption of
U. Using amorphous ferrihydrite with adsorbed 238U,
sorption/desorption tests were conducted with 236U as
a tracer in solution. Results of these tests revealed that
crystallization of hematite and goethite reduced the
sorptive capacity of the material and also immobilized
a significant amount of the 238U initially adsorbed on
the ferrihydrite. In a related study that is of particular
relevance to Koongarra, the authors showed that the
addition of phosphate to the system resulted in a significant shift to lower pH in the sorption of U by
594
pyrochlore, zirconolite, and apatite doped with

Pu or 244Cm. In the specific case of zircon, the
effect of long-term annealing is certainly present, but
appears to have less effect on the critical dose, which
may be on the order of 67 1016 a per milligram or
even higher. Thus, for most of these minerals, the
observation of increased critical dose over time can
be attributed to partial annealing of collision cascade
damage on geological time scales (there is a difference in dose rate on the order of 107109 year1
between the laboratory experiments and natures
own work). The long-term annealing rate is consistently reported to be on the order of 109 year1 for
natural samples of pyrochlore, zirconolite, perovskite,
and zircon. Within this group of minerals, total
volume expansion associated with amorphization is
lowest for pyrochlore and zirconolite (5%) and
greatest for zircon (18%). Monazite is the only
potential waste form phase considered herein that
remains crystalline to very high a-decay dose levels.
Today, more than 30 years since the late Ted
Ringwood began to develop Synroc based upon his
knowledge of minerals and geological processes,
there have also been significant advances in research
on the geochemistry of some of the minerals noted
earlier. In terms of the low measured dissolution rate
as a function of pH and minimal alteration in natural
systems, zirconolite remains as a promising host
phase for actinides and certain fission products.
Experimental studies show that titanate pyrochlore
has a slightly higher dissolution rate across the same
range of pH and is also more susceptible to alteration
by hydrothermal and low temperature fluids in
nature. Nevertheless, quantitative retention of Th
and U is a characteristic feature of pyrochlores from
many different geological environments. Although
zirconate pyrochlores do not occur in natural systems, we note that they may exhibit dissolution rates
similar to zirconolite while having the attractive
property of radiation resistance. However, these pyrochlores may lack the crystal chemical flexibility of
the titanates (they also require higher processing
temperatures). Monazite also has low dissolution
rates in laboratory experiments, but several investigations of natural samples have presented evidence of
alteration at relatively low temperatures in geological
environments. In view of the radiation resistance of
this structure type and the ability to incorporate
actinides, lanthanides, and Sr, it would be useful to
investigate the aqueous geochemistry in greater
detail. Other phases such as apatite and hollandite
have considerable potential for use in applications
238
Figure 15 Transmission electron microscopy image of

goethite-clay intergrowths from weathered rocks near the
Koongarra uranium ore body, Northern Territory, Australia.
This sample came from outside the U dispersion zone.
When these natural substrates are used in laboratory
U sorption experiments, transmission electron microscopy
energy dispersive X-ray analyses demonstrate that most of
the U is adsorbed by the goethite phase. Similar
observations have been made for samples taken directly
from the U dispersion zone, for example, goethite and
other Fe minerals adsorb U in the dispersion zone above
the ore body. Width of image 2.4 mm.
ferrihydrite. The increased sorption of U was attributed

to the formation of ternary surface complexes involving
2
PO3
4 and UO2 on ferrihydrite. Similar results were
reported for the uptake of U in the presence of humic
acid but, in general, both types of complexing ligands
may be affected by the U concentration and the ionic
strength of the aqueous solution.207
5.22.7 Conclusions
With regard to radiation damage effects, it is clear
that many of the oxide and silicate minerals currently
of interest as analogs for nuclear waste immobilization become amorphous due to the cumulative effects
of a-decay damage on the structure. This includes
minerals of the pyrochlore group, zirconolite, perovskite group, brannerite, various ABO4 and AB2O6
oxides, zircon, titanite, and silicate apatite (britholite). The critical amorphization doses of these
minerals are typically around 1016 a per milligram
(1 dpa) for samples with ages below 600 Ma. This
compares with typical critical doses of 0.30.5 1016
a per milligram (0.20.4 dpa) for synthetic
requiring immobilization of Sr, Cs, and I in isolation

from actinides and other fission products. New materials based on these phases may be in considerable
demand for Generation IV nuclear power systems.
Studies of uranium deposits as natural analogs for
spent fuel have provided valuable information bearing on the alteration of uraninite in hydrothermal and
low temperature groundwaters. Recent investigations, in particular, have provided a new perspective
on the kinetics and mechanisms of uraninite alteration in oxidizing aqueous systems. In nature, it
appears that the higher U oxides such as U3O8 and
U4O9 are kinetically inhibited in oxidizing fluids
such that the initial alteration stage of uraninite
involves replacement by uranyl oxyhydroxides. The
oxyhydroxide phases are then replaced during successive stages of alteration, depending on (a) the
activity ratios of the large metal cations in solution,
[M/H] and (b) the activities of aqueous silicate,
carbonate, phosphate, and other species. The uranium ore deposits in Gabon (e.g., Oklo) and in the
Northern Territory of Australia (e.g., Koongarra) are
very similar with regard to many of their geological
features. However, conditions were ideal for cyclic
natural fission reactions to occur in the former due to
the scale of the ore bodies and concentration of
U within them, the presence of water as a moderator,
the host sandstone as a neutron reflector, and the
absence of neutron absorbers. The natural fission
reactors have provided an ideal laboratory for the
study of fission and decay products in a sedimentary
basin. In the case of Koongarra, differences in the
water content and the amounts of neutron absorbers
(e.g., Gd) present in the rocks probably played a
major role in preventing the ores from reaching criticality. The extensive weathering and consistent
groundwater flow pattern in the area resulted in a
distinctive fan of secondary U mineralization and
adsorption in the weathered zone extending up to
200 m from the primary ore deposit.
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Appendix: List of Mineral Names and

Compositions
Oxides
Aeschynite, (Ce,Nd,Y,Fe)(Ti,Nb,Ta)2(O,OH)6.
Anatase, Brookite, and Rutile, TiO2. Rutile,
in particular, may contain V, Cr, and Fe.
Baddeleyite, ZrO2.
Brannerite, (U,Th,Ca)Ti2O6.
Calciotantite, CaTa4O11.
Calzirtite, CaTi2Zr5O16.
Cerianite, CeO2.
Columbitetantalite, (Mn,Fe)(Nb,Ta,Ti)2O6.
Crichtonite, (Sr,La,Ce,Y)(Ti,Fe,Mn)21O38.
Davidite, (La,Ce,Ca)(Y,U)(Ti,Fe,Mn)20O38.
Euxenite, (Y,Ca,Ce)(Ti,Nb,Ta)2O6.
Fergusonite, (Y,Yb,Gd,Nd,Ce)(Nb,Ta)O4.
Ferrihydrite, Fe5HO84H2O.
Fersmite, CaNb2O6.
Goethite, FeOOH.
Hematite, Fe2O3.
599
Hollandite, (Ba,Pb,K,Na)(Mn,Fe,Ti,Al)8O16.
Ilmenite, FeTiO3.
Kassite, CaTi2O4(OH)2H2O.
Liandratite, UNb2O8.
Lucasite, (La,Ce,Nd,Pr)Ti2O6x(OH,F)xH2O.
Magnetite, Fe3O4.
Perovskite, (Ca,Ba,Na,La,Ce,Nd)(Ti,Nb,Fe)O3.
Polycrase, (Y,Ca,Ce,U,Th)(Ti,Nb,Ta)2O6.
Pyrochlore, (Na,Ca,Ce,Th,U)(Nb,Ta,Ti,Zr,Sn)2O6.
Priderite, (K,Ba)(Ti,Fe)8O16.
Samarskite, (Y,Dy,Er,Yb,U,Fe)(Nb,Ta,Ti)O4.
Uraninite, UO2.
Zirconolite, (Ca,Nd,Gd,Th,U)(Zr,Hf,Y)(Ti,Nb,
Fe,Al)2O7.
Silicates
Allanite, (La,Ce,Ca,Y)(Al,Fe)3(SiO4)3(OH).
Chlorite, (Mg,Fe,Al)6Si3AlO10(OH,O)8.
Clinozoisite, CaAl3(SiO4)3(OH).
Coffinite, USiO4.
Epidote, CaFe3(SiO4)3(OH).
Kaolinite, Al2Si2O5(OH)4.
Olivine, (Mg,Fe)SiO4.
Quartz, SiO2.
Serpentine, (Mg,Fe)3Si2O5(OH)4, there are several
polymorphs.
Thorite, ThSiO4.
Titanite, CaTiSiO5.
Vermiculite, (Mg,Fe,Al)3(Si,Al)4O10(OH)24H2O.
Zircon, ZrSiO4.
Phosphates, Arsenates, Vanadates
Chlorapatite, Ca5(PO4)3Cl.
Florencite, (La,Ce,Nd,Pr)Al3(PO4)2(OH)6.
Fluorapatite, Ca5(PO4)3F.
Hydroxyapatite, Ca5(PO4)3OH.
Kosnarite, KZr2(PO4)3.
Mimetite, Pb5(AsO4)3Cl.
Monazite, (La,Ce,Nd,Pr,Ca,Th,U)(P,Si)O4.
Pyromorphite, Pb5(PO4)3Cl.
Rhabdophane, (La,Ce,Nd,Pr)PO4nH2O.
Vanadinite, Pb5(VO4)3Cl.
Xenotime, (Y,Dy,Er,Yb)PO4.
Carbonates, Fluorocarbonates, Fluorides
Bastnaesite, (La,Ce,Nd,Pr)CO3F.
Calcite, CaCO3.
Fluorite, CaF2.
600
Sulfides
Galena, PbS.
Pyrite, FeS2.
Uranyl Minerals (Section 5.22.6)
Autunite, Ca[(UO2)(PO4)]2(H2O)1012.
Becquerelite, Ca[(UO2)6O4(OH)6](H2O)8.
Boltwoodite, (K,Na)(UO2)(SiO3OH)(H2O)1.5.
Carnotite, K2[(UO2)(VO4)]2(H2O)3.
Curienite, Pb[(UO2)(VO4)]2(H2O)5.
Curite, Pb1.5x(UO2)4O42x(OH)32x(H2O).
Fourmarierite, Pb(UO2)4O3(OH)4(H2O)4.
Francevillite, Ba[(UO2)(VO4)]2(H2O)5.
Francoisite, (Ce,Nd,Sm,Y)(UO2)3(PO4)2O(OH)
(H2O)6.
Ianthinite, U4(UO2)O4(OH)6(H2O)9.
Meta-autunite, Ca[(UO2)(PO4)]2(H2O)6.
Rutherfordine, UO2CO3.
Saleeite, Mg[(UO2)(PO4)]2(H2O)10.
Schoepite, (UO2)8O2(OH)12(H2O)12.
Sklodowskite, Mg(UO2)2(SiO3OH)2(H2O)6.
Soddyite, (UO2)2(SiO4)(H2O)2.
Studtite, UO44H2O.
Torbernite, Cu[(UO2)(PO4)]2(H2O)8.
Uranophane, Ca(UO2)2(SiO3OH)2(H2O)5.
Vandendriesscheite,
Pb1.57(UO2)10O6(OH)11(H2O)11.
Weeksite, (K,Na) (UO2)2Si5O13 (H2O)4.

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Comprehensive nuclear materials

Editorial : Gemma Mattingley

Roger Stoller is currently a Distinguished Research Staff Member in the

Todd Allen is an Associate Professor in the Department of Engineering

Shinsuke Yamanaka is a professor in Division of Sustainable Energy and

Figure 39 of Carbon as a Fusion Plasma-Facing Material

Figure 5 of Radiation Effects in UO2

Figure 10d of Atomic-Level Dislocation Dynamics in Irradiated Metals

Corrosion and Compatibility

2012 Elsevier Ltd. All rights reserved.

Boiling water reactor

Corrosion and Compatibility

DCp Change in standard partial molar heat

Mars Fontana identified eight forms of corrosion in

and corrosion mechanisms. For example, intergranular

Half Cell Reactions

The electrochemical interface is characterized by an

Corrosion and Compatibility

Because the system cannot store charge, the electrons

Acid: O2 4H 4e ) 2H2 O

Base: O2 2H2 O 4e ) 4OH

From eqns [I] and [III], the general corrosion of an

For any chemical reaction the driving force, the

Figure 2 Diagram of what the anodic and cathodic

Voltaic cells in which a spontaneous reaction occurs

where Fe(OH)2 is the corrosion product.

where DG0 is the standard Gibbs energy, Q is the

where n is the number of electrons participating

Corrosion and Compatibility

The reaction quotient, Q (starting conditions) becomes:

where fH2 is the fugacity of hydrogen gas. Substituting

5.01.1.4 Reference Electrodes and Their

and the overall reaction being:

The Nernst equation for eqn [XI] is equal to:

where aCl is the activity of chloride and for which

Corrosion and Compatibility

Figure 4 A diagram of a pressure-balanced reference

potential deviations owing to the solubility of AgCl

Corrosion and Compatibility

where the subscript i denotes a species that may be

reactions with two soluble species

solubility of iron and its oxides

2Fe2 3H2 O Fe2 O3 6H 2e

E 0 0:493 0:089pH 0:0295logHFeO

5.01.1.5 The Thermodynamics of Corrosion

E 0 1:819 0:029pH 0:088logHFeO

reaction of two solid substances

2Fe3 O4 H2 O 3Fe2 O3 H 2e

An example of a simplified Pourbaix diagram for Fe

Corrosion and Compatibility

EH2 (200 C) (V)

EH (25 C) (V)

where DS is the standard entropy change and DC p is

Figure 5 A simplified potentialpH diagram for the

Figure 6 The potentialpH diagram for the FeH2O

the most notable change in the diagram is at high pH

Corrosion and Compatibility

Figure 7 PotentialpH diagram for chromium species in

thus, not considered. The diagrams assumed that the

decreasing the barrier, that is, not all of the applied

For small applied potentials around Ecorr , the Stern

where b is the symmetry factor and reflects the fact

where ba and bc are defined as the anodic and

Ga2 Ga1 1 bnF f E0

3:27 103 icorr EW