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CORROSION SCIENCE SECTION

Effect of Environmental Variables


on Localized Corrosion of Carbon Steel
C.S. Brossia and G.A. Cragnolino*

ABSTRACT
Environmental conditions under which localized corrosion of
carbon steel could take place in simulated groundwater were
examined. Using specimens with crevices, it was determined
that at potentials above the repassivation potential, the ratio
of the chloride concentration to the total carbonate concentration, solution pH, and solution temperature played critical
roles in establishing conditions that promote localized corrosion, as well as in influencing the rate of propagation.
Preoxidation in air at 200C for short times improved the resistance to localized corrosion, but was detrimental for longer
times. Monitoring of the open-circuit potential of samples with
crevices in air-saturated, alkaline (pH 11) solutions revealed
that the repassivation potential could be exceeded and localized corrosion can occur under free corrosion conditions.
Factors important to the use of carbon steel as a construction
material for high-level radioactive waste disposal containers
were discussed.
KEY WORDS: carbon steel, localized corrosion, open-circuit
potential, pH, repassivation

INTRODUCTION
Carbon steels are among the most widely utilized
engineering materials for structural applications. As
such, their corrosion performance under a wide variety of environmental conditions has been examined,
and in many cases, only uniform corrosion has been
Submitted for publication April 1999; in revised form, January
2000.
* Center for Nuclear Waste Regulatory Analyses, Southwest
Research Institute, 6220 Culebra Road, San Antonio, TX 782385166.

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observed. Because carbon steel generally undergoes


relatively predictable uniform dissolution in many
environments and is a widely utilized engineered material in structural applications, it was chosen by the
U.S. Department of Energy (DOE) as a potential candidate corrosion-allowance material for high-level
nuclear waste (HLW) disposal containers.1-2 There are
a number of environmental factors, however, that can
cause carbon steel to undergo rapid, localized corrosion instead of relatively slow, uniform corrosion.
For localized corrosion, pit initiation potential
(Epit), commonly measured by scanning or stepping
the potential, is the potential above which stable pit
growth is detected.3 Even though pits may be initiated well below this potential, spontaneous
repassivation occurs and pits fail to continue propagating, thus leading to their classification as
metastable pits. Metastable pitting is of fundamental
importance to the understanding of localized corrosion dynamics. Generally, it is not important for life
prediction as these pits do not lead to perforation of
the structure. Furthermore, the potential to
repassivate stably growing pits (repassivation potential, Erp) is approximately equal to Epit, provided the
former is measured for deep pits under slow, backward scan rates and the latter is measured under
extremely long exposure conditions.4 Thus, Erp can
serve as a conservative estimate of the minimum
potential necessary for nucleation and stabilization
of localized corrosion. Erp and Epit generally are used
to evaluate effects of environmental variables on the
localized corrosion behavior of materials during
short-term tests.

0010-9312/00/000097/$5.00+$0.50/0
2000, NACE International

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CORROSION SCIENCE SECTION

The pH of the solution has been shown to play a


key role in determining the corrosion mode of carbon
steels. Below a critical pH (pHcrit), only uniform corrosion is observed; whereas above pHcrit, localized
corrosion is possible. This behavior arises because of
the dependence of the formation and stability of the
passive film of iron on pH.5 The pHcrit for the transition
from general corrosion to passivity has been reported
to be between 8 and 10.5, depending on the temperature and concentration of ionic species present in
solution.5-9 For example, in chloride-free carbonate
(CO32)/bicarbonate solutions, pHcrit was a function of
the total CO32 concentration, with increasing total
CO32 concentrations leading to decreases in pHcrit.6 In
the presence of chloride, pHcrit tended to be greater
than in chloride-free solutions.8-9 Higher temperatures tended to have the opposite effect on pHcrit, with
increasing temperatures decreasing pHcrit.7,9
The pH also has been observed to affect Epit of
iron and carbon steels once passivity is established
and localized corrosion is possible. Alvarez and
Galvele observed a dependence of Epit for iron on pH,
but only when the pH was > 10 (the pH dependence
was slight, only 20 mV/pH).10 At pH values < 10, Epit
was independent of pH. It was proposed that at the
higher pH values, the bulk solution tended to buffer
the developing acidified solution within the occluded
region, thereby raising Epit.10 Simard, et al., observed
that at pH > 8.9, Epit for 1024 mild steel (UNS
G10240)(1) increased by 125 mV for every unit
increase in pH.11
The presence and concentration of chloride and
solution temperature also play key roles in determining whether localized corrosion of carbon steel occurs.
The effect of chloride concentration ([Cl]) on Epit of
iron and carbon steel has been examined by several
investigators and summarized by SzklarskaSmialowska.12 In general, once sufficient concentration
of chloride is present such that localized corrosion is
possible (for carbon steels, this concentration has
been reported to be between 0.3 mM and 3 mM12),
the effect of [Cl] on Epit follows the relationship
shown in Equation (1), where E0pit is the pitting potential at 1 M chloride concentration, B is the slope of
Epit dependence on [Cl], and T is temperature:

[ ]

E pit ( T ) = E 0pit ( T ) + B( T ) log Cl

(1)

Alvarez and Galvele reported that Epit for iron decreased at a rate of 64 mV/decade increase in
[Cl].10 Newman, et al., using simulated one-dimensional pits on iron, confirmed that the dependence of
Epit on chloride was 66 mV/decade of [Cl ].13 These
values, reported in the experimental investigations by
(1)

UNS numbers are listed in Metals and Alloys in the Unified


Numbering System, published by the Society of Automotive
Engineers (SAE) and cosponsored by ASTM.

506

Alvarez and Galvele10 and Newman, et al.,13 are very


close to the theoretical value defined by 2.303 RT/F
of ~ 59.5 mV/decade of [Cl], with differences arising
as a result of ohmic drop in the pit,11 assuming active
dissolution of iron in the pit solution as predicted by
Galveles model.10 Many times, the effect of chloride
on Epit has been reported in terms of the concentration ratio between chloride and another species
present in the solution, such as hydroxide8 or total
CO32.6,14 Similar to [Cl], increasing the temperature
generally results in decreasing Epit.12
In previous work examining the pitting behavior
of carbon steel in bicarbonate solutions containing
chloride, it was found that Erp can be expressed by
an equation identical to the form of Equation (1).15 The
following relationships for E0pit and E0rp (mV) as a function of [Cl] (M) and temperature (C) were developed:
E 0pit ( T ) = 584.8 + 3.92 T; B pit ( T ) = 24.5 1.1T

(2)

E 0rp ( T ) = 620.3 + 0.47 T; B rp ( T ) = 95.2 0.88 T

(3)

Once the pH, temperature, and [Cl] are conducive to the onset of localized corrosion, the redox
potential of the environment, and as a consequence,
the corrosion potential, become critical factors. If the
corrosion potential is higher than Erp, it is assumed
that localized corrosion would occur, even though
initiation could be delayed significantly. The utility of
the Erp as a critical parameter for assessing the susceptibility to pitting and crevice corrosion for carbon
steels has been demonstrated by Akashi and coworkers6,9,16 and has been shown to be effective for
predicting the onset of stress corrosion cracking in
addition to localized corrosion for other materials.4,17-20
Unlike the case of Ni-Cr-Mo alloys, however, carbon
steels typically do not undergo deep penetration by
localized corrosion and exhibit rather weak protective
passive films. Hence, the applicability of this approach to carbon steels and the conditions under
which passivity and localized corrosion are possible
were examined in this paper.
The objective of this work was to build on previous work examining pitting corrosion of carbon
steel15 and further define conditions under which
crevice corrosion of carbon steel occurs. Critical parameters for initiating crevice corrosion such as pH,
[Cl], and the repassivation potential for crevice corrosion (Ercrev), also were sought to develop long-term
predictive models of material performance under a
variety of conditions.21 Furthermore, examination of
conditions and critical parameters conducive to localized corrosion of carbon steel in light of the expected
conditions at the proposed geologic repository at
Yucca Mountain (YM) is crucial to evaluate the
important factors in using carbon steel as a corrosion-allowance material.2

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TABLE 1
Composition of A516 Steel (wt%)
C

Mn

Si

Cr

Mo

Ni

0.18

1.00

0.23

0.03

0.01

0.01

0.009

0.014

EXPERIMENTAL PROCEDURES
All tests were performed on a single heat of A516
carbon steel (UNS K02100). The composition is
shown in Table 1. All specimens were machined from
mill-annealed, 12.5-mm thick plate in the form of
cylinders (6.3 mm in diameter and 48.6 mm in
length) or in the form of standard crevice specimens22
that were constructed by pressing serrated
polytetrafluoroethylene (PTFE) crevice formers
against the flat portion of a block specimen at a
torque of 0.28 N/m. All specimens were polished to a
600-grit finish prior to testing. All test solutions were
made from reagent-grade sodium salts (sodium chloride [NaCl], sodium carbonate [Na2CO3], sodium
bicarbonate [NaHCO3]) and 18 M-cm water. [Cl] examined ranged from 0.0012 mM to 1.2 M with total
CO32 concentrations of 12 mM or 120 mM. After the
bulk solution was made, the initial pH was determined at room temperature and the solution was
introduced into the test cell. The solution then was
purged with high-purity N2 as the solution was
heated to the desired temperature. The specimen
was introduced to the cell, and the test was initiated.
After testing was complete, the final pH of the test
solution was measured at room temperature. To
modify the solution pH, concentrations of Na2CO3
and NaHCO3 were varied such that the pH ranged
from 8.4 to 11.2.
Cyclic potentiodynamic and potentiostatic polarization tests were performed to examine conditions
under which localized corrosion of carbon steel took
place. All tests were conducted using a saturated
calomel reference electrode (SCE) connected to the
cell through a salt bridge/Luggin probe filled with a
30-mM chloride solution to maintain the reference
electrode at room temperature. A platinum foil or a
graphite rod was used as a counter electrode. Cyclic
polarization tests were initiated at the open-circuit
potential after the specimen had been immersed in
solution for 1 h and a nominally steady-state corrosion potential had been reached. A scan rate of
0.167 mV/s was used, and scans were reversed at a
current density of 5 mA/cm2.
Potentiostatic polarization was performed at
a sampling rate of 10 Hz. The minimum current
resolution with the system utilized was 0.125 A,
which represents a current density of 6 nA/cm2 to
16 nA/cm2, depending on the specimen geometry.
The potential applied was based on the midpoint between Erp and Epit determined from Equations (2) and

CORROSIONVol. 56, No. 5

(3). As a result, the applied potential varied from test


to test depending on [Cl] and temperature being
evaluated. After testing, specimens were examined
visually at low magnification for evidence of localized
corrosion. Based on the measured weight loss, dissolution rate, and visual examination of the entire
specimen, specimens with and without crevices were
assigned a subjective rating of minor, moderate, or
severe attack. Severe attack typically corresponded to
dissolution rates > 0.5 mA/cm2 and minor attack
corresponded to dissolution rates < 1 A/cm2, with
moderate attack corresponding to dissolution rates in
between. These values were chosen as representative
of current densities associated with rapid attack and
passive dissolution, respectively.

RESULTS
Based on relationships developed for the critical
potentials as a function of temperature, pH, and [Cl]
(Equations [2] and [3]), a series of potentiostatic tests
on boldly exposed samples were performed at potentials between Erp and Epit in an attempt to understand
better the effects of solution composition and temperature on localized corrosion of A516 steel.14
Results from these tests showed no clear dependence
of the severity or mode of attack (localized vs general)
on the environment.
Because of the lack of a clear dependence between the environment and the extent and type of
attack observed on samples without crevices, tests
on specimens with crevices were performed
potentiostatically between Erp and Epit (based on
Equations [2] and [3]) in solutions that had initial
and final pH of 11 0.3. A clearer dependence of the
degree of attack on the environmental parameters
was observed (Figure 1). As would be expected, an
increase in the temperature and [Cl] increased the
severity of attack. In some cases, the transition from
less severe to more severe was quite sharp. For example, at 65C, minor crevice corrosion was observed
at a chloride/total CO32 concentration ratio of 0.020,
whereas moderate attack was observed at a ratio of
0.024.
The actual area of attack under the crevice feet
that displayed corrosion was determined after polarization, and using the current measured at the end of
the experiment, the local dissolution rate was calculated. The effect of environmental variables on local
dissolution rate is shown in Figure 2 with lines delineating the regions of passive dissolution and crevice

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FIGURE 1. Effect of solution composition and temperature on the


severity of crevice corrosion observed after 24-h potentiostatic tests.
The applied potential ranged between 200 mVSCE and 300 mVSCE,
depending upon temperature and [Cl].

FIGURE 2. Effect of solution composition and temperature on the


dissolution rate calculated from 24-h potentiostatic crevice tests.
Delineation between passive dissolution and crevice corrosion was
performed by visual observation.

corrosion based on post-test visual examination. For


a given CO32 concentration, increasing the temperature and [Cl] caused the local dissolution rate to
increase. The initial CO32 concentration did not have
any significant effect on measured dissolution rates
for solutions with the same chloride/total CO32 concentration ratio.14
The effect of pH on the corrosion behavior of
A516 steel is summarized in Figure 3. In these ex-

508

periments, the bulk solution had an initial pH of


8.3 0.5. The pH at the end of the experiment (which
was the pH attained prior to polarization of the specimens), however, varied widely as a result of
exsolution of carbon dioxide (CO2), especially at temperatures > 65C, where the solubility of CO2 was
lower.19 A clear dependence of the mode of corrosion
on the final solution pH measured at room temperature was seen. When the final pH was < 9.3, only
general corrosion was observed with no localized
attack under the crevice former. At these pH values
(< 9.3), increasing [Cl] and temperature generally did
not increase the severity of attack nor the weight loss
measured. At a final pH > 9.6, crevice corrosion was
observed with increases in temperature and [Cl] resulted in increases in the severity of attack (Figures 1
and 2). For example, at 95C, increasing the chloride/total CO32 concentration ratio from 0.01 to 0.1
increased the severity of attack with an almost 3
orders-of-magnitude increase in the dissolution rate.
Similarly, increasing the temperature from 65C to
95C at a constant chloride/total CO32 concentration
ratio also increased the dissolution rate, but only by
1 order of magnitude. Interestingly, at 25C, no
localized corrosion was observed below a chloride/
CO32 ratio of 0.1 as the final solution pH remained
below 9.3.
Effects of [Cl] and temperature on the initiation
potential for crevice corrosion (Ecrev) and Ercrev for
carbon steel in a deaerated, pH 11 solution are summarized in Figure 4. This figure shows Ecrev at 95, 80,
and 65C and Ercrev at 95C. Below [Cl] of 0.12 mM,
no localized corrosion of carbon steel was observed
independent of temperature. At [Cl] > 1.2 mM, Ecrev
and Ercrev decreased linearly with log [Cl], and
B = 162 mV/decade [Cl] for Ecrev and 54 mV/decade [Cl] for Ercrev. Because no replicate experiments
were performed, it was unclear if differences observed with temperature were within the variability
of tests or were real effects. Therefore, the results at
all temperatures were combined into a composite
regression line with respect to [Cl]. The critical chloride concentration ([Cl]crit) for the occurrence of
localized corrosion also appeared to be independent,
within an order of magnitude of temperature. Furthermore, as [Cl] was increased from [Cl]crit, the
location of corrosion attack moved from exclusively
under the PTFE feet of the crevice former to under
the feet of the crevice former and on the boldly exposed surfaces of the specimen. A salt film also was
observed at the sites of corrosion attack outside the
crevice former.
The open-circuit potential (Ecorr) of specimens
with crevices under freely corroding conditions in airsaturated solutions of 0.0012 mM to 12 mM chloride
at pH 8.5 and 11 and temperatures of 65C and 95C
was monitored for a period of up to 6 weeks. Representative data taken at pH 11 with 1.2 mM chloride

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at 95C is shown in Figure 5. Also shown in the


figure are Ecrev and Ercrev for carbon steel at 1.2 mM
chloride at pH 11 and 95C. The potential initially
increased from near 0.62 to a peak value of
0.15 VSCE within the first 62 h of monitoring. Ecorr
subsequently decreased and attained a nominally
steady-state value of 0.3 for the next 340 h, then
further decreased to 0.4 VSCE for the remainder of
the experiment. Throughout the monitoring period,
Ecorr of the specimen with crevices exceeded the Ercrev
measured potentiodynamically in the same environment. Furthermore, Ecrev also was exceeded for a time
as well. At the end of the experiments, specimens
were observed to have experienced crevice attack at
pH 11 and general corrosion at pH 8.5. Limited opencircuit monitoring tests also were conducted in
simulated J-13 well water(2) at 65C and 95C (pH
7.4) under actively aerated conditions. Although no
crevice corrosion was observed in these tests, pitting
attack in the vapor phase region of the specimens
was detected.
Because waste packages are predicted to experience an initial environment that is relatively dry and
> 100C,1 the effect of thermal preoxidation in air at
200C on localized corrosion was examined.
Potentiostatic crevice tests at potentials representing
the midpoint between Epit and Erp (0 VSCE to
0.225 VSCE depending on [Cl]) were performed at
95C in solutions of differing [Cl] at pH 11, and the
effect of preoxidation time on the actual area of crevice attack was determined (Figure 6). At low [Cl ]
(chloride/total CO32 concentration = 0.01), little effect
of preoxidation was observed until preoxidation times
> 500 h. At higher [Cl], an initial drop in the attack
area was observed at short preoxidation times, but at
longer times, the extent of attack increased. For
example, in the chloride/total CO32 concentration =
0.10 solution, after a 24-h preoxidation treatment,
the attacked area measured 12 mm2. After 672 h,
the attacked area measured 86 mm2. Additionally,
extensive general corrosion also was observed on
some samples in the high-chloride solution after long
preoxidation times.

FIGURE 3. Effect of pH on the severity and type of corrosion


observed on samples with crevices at 20, 65, and 95C in chloride/
bicarbonate solutions. Final pH was measured at room temperature.

FIGURE 4. Effect of [Cl] on E crev and E rcrev measured from


potentiodynamic polarization curves at 65, 80, and 95C. Ercrev is
shown for all temperatures, whereas Ercrev is shown only at 95C for
simplicity.

DISCUSSION
Based on cyclic potentiodynamic polarization
curves, effects of temperature and [Cl] on Epit and Erp
for carbon steel were determined in deaerated CO32/
bicarbonate solutions of pH 11 and 9.5 and temperatures of 65C and 95C.15,24 It was confirmed that Epit
followed the well-recognized logarithmic dependence
on [Cl].12,15 Erp similarly followed this relationship,
which typically is not reported. To verify that Erp can
(2)

Nominal composition: 0.2 mM calcium sulfate (CaSO42H2O),


0.01 mM calcium nitrate (Ca[NO3]2), 0.04 mM potassium chloride
(KCl), 0.07 mM magnesium chloride (MgCl26H2O), 2 mM NaHCO3,
and 0.1 mM sodium fluoride (NaF).23

CORROSIONVol. 56, No. 5

be used as an enabling potential for localized corrosion, potentiostatic tests were performed at
potentials above Erp but below Epit under conditions
thought to be conducive to pitting corrosion. No clear
dependence between extent or type of attack and experimental conditions was observed.14 In fact, under
very similar conditions, general and localized corrosion were observed in subsequent tests. Results of
potentiostatic pitting tests and the lack of a discernible pattern seems to be indicative of the stochastic
nature of pit initiation,12,25 and thus, further work
examining the application of statistical analyses to
pit initiation times is warranted.

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FIGURE 5. Corrosion potential as a function of time for a carbon steel


specimen with crevices in air-saturated, pH 11 solution with 1.2 mM
chloride at 95C. Also indicated are values for Ecrev and Ercrev measured
from potentiodynamic polarization curves of carbon steel in the same
environment.

Because of the stochastic nature of pitting


corrosion, an attempt was made to increase the consistency of results using crevice specimens tested as
a function of solution composition and temperature.
From these tests (Figure 1), it was clear that increases in temperature and [Cl] led to an increase in
the severity of attack and local dissolution rates.
Results were consistent with the extensive body of
literature on the effects of chloride and temperature
on localized corrosion as summarized by SzklarskaSmialowska.12 Further, it was clear that the presence
of the crevice former aided in the initiation of localized attack, as would be expected.12 This effect arises
because of the restriction in mass transport into and
out of the occluded site by the crevice former, as development of a critical solution chemistry generally
has been accepted as a critical factor in initiating
localized corrosion. Under identical concentration
ratios (and bulk solution pH), the corrosion behavior
and local dissolution rates observed in 120-mM CO32
solutions were essentially the same as those observed in 12-mM CO32 solutions.14 This further
highlights the importance of the chloride/total CO32
concentration ratio rather than absolute concentration of CO32 in solution for conditions under which
the pH is nominally constant.
The pH of the solution also played a critical role
in the corrosion behavior of carbon steel, in that it
defined the regions in which localized corrosion, as
opposed to general corrosion, occurred (Figure 3).
Below pH 9.3, only general corrosion was observed
with no corrosion under the crevice former. Above pH
9.6, however, only crevice corrosion was observed on
the samples. It seemed that pH values > 9.6 promoted
the formation of a passive film on iron, especially at
elevated temperatures, which in the presence of chlo-

510

ride suffers localized breakdown. Similar results have


been reported by others who found that pHcrit for localized corrosion on carbon steel in CO32/bicarbonate
solutions was 9.4.6,9 Based on the work by Marsh
and Taylor, who developed a series of potential-pH
diagrams for carbon steel in CO32/bicarbonate solutions at 50C, pitting should be possible at pH values
as low as 9 at the lower [Cl] examined.7 Furthermore,
they observed extensive pitting in pH 8.4 solutions
containing up to 1,000 ppm chloride after 10,000 h
of testing. The observation in the present work that
localized corrosion only occurred at pH > 9.6 could
be explained by the short experimental times used
(24 h). If tests were allowed to proceed for longer
times, perhaps nucleation of crevice corrosion would
have taken place as this process may require longer
incubation periods in the lower pH range (8 to 9).
Examination of effects of [Cl] on the crevice corrosion behavior of carbon steel revealed that a [Cl]crit
existed, below which crevice corrosion did not occur
and above which crevice corrosion was possible. At
[Cl] 0.12 mM, no crevice corrosion was observed
(Figure 4). Based on experiments using a platinum
electrode, it was confirmed that the current increase
observed near 700 mVSCE was a result of oxygen evolution. Based on an experimentally measured Tafel
slope of 90 mV on platinum, extrapolation of the
reaction to the reversible potential for oxygen evolution yielded an exchange current density of 5
109 A/cm2. The measured Tafel slope on platinum
and the extrapolated exchange current density were
in good agreement with values reported in the literature.26-27 A similar increase in the current density at
~ 700 mVSCE also was observed by Makar and
Tromans for iron in a chloride-free, pH 10.5 buffer
solution.5 The [Cl]crit necessary for the onset of localized corrosion also agreed well with values reported
in the literature of 0.3 mM to 3 mM.12 Increases in
[Cl] above [Cl]crit resulted in steady decreases in Ecrev
and Ercrev, following a relationship similar to that for
Epit shown in Equation (1), as would be expected. Values of B experimentally measured for Ecrev and Ercrev
also agreed well with values reported in the literature.6
Increases in [Cl] also appeared to increase the
severity of attack observed, particularly at 65C,
and the local dissolution rate calculated from the
current and actual area of attack (Figures 1 and 2).
This increase was accompanied by a shift in the location of corrosion attack from underneath the feet of
the crevice former to the boldly exposed surfaces,
probably as a result of the increase in the number of
initiation sites available with increasing [Cl]. Under
such conditions, the attack readily was initiated on
the open surface without requiring the restricted
mass transport expected inside an area with crevices.
Temperature also was observed to affect the
extent of attack and dissolution rates for localized
corrosion of carbon steel as well as the measured

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critical potentials. At constant [Cl] and pH, increases


in temperature resulted in increases in the extent of
attack (area of attack) and greater dissolution rates
(Figures 1 and 2). The apparent dependence of dissolution rate on temperature might have been a result
of the dependence of reaction kinetics on temperature. However, it also might have been a result of a
decrease in the incubation time for nucleation of
localized corrosion.12 If the experiments were conducted for a long enough period of time, dissolution
rates at each temperature likely would have converged. Temperature also might have affected the
critical potentials measured during crevice experiments on carbon steel (Figures 5 and 6). Increasing
the temperature from 65C to 95C tended to decrease the critical potentials at [Cl] < 1.2 M, in
apparent agreement with what was reported by
Postlethwaite, et al., who observed a decrease in Epit
of iron in chloride-containing alkaline solutions as
the temperature increased from 25C to 100C.28
Given that in the current work, replicate experiments
were not performed, it is still somewhat uncertain if
the observed effect of temperature on the critical
potentials was real or an artifact that could be attributed to variability in test results.
Temperature also might have had an influence
on the value of B (Equation [1]). Based on experimental work at 25C, Galvele proposed that B for iron
was given by 2.303 RT/F.29 In Galveles model, it was
assumed that the critical factor for pit stabilization
was the product of the pit depth (x) and the current
density (i).29 Based on this relationship, the electrical
potential inside the pit necessary to achieve the critical x i to sustain propagation accounted for
changes in Epit with [Cl]. This model has been verified experimentally for iron by Alvarez and Galvele10
and Newman, et al.13 However, values of B measured
at elevated temperatures in previous work on pitting
corrosion15 and in the present work on crevice corrosion are larger than those predicted by Galveles
equation. This may result from variations with temperature of the kinetics for the active dissolution of
iron in the pit-like solution that is not accounted for
explicitly by Galvele.29 Another possibility, in light of
the work done by Pickering and coworkers examining
crevice corrosion of iron,30-33 in which the potential of
the metal falls into the active regime because of the
ohmic drop in the occluded site, is that the larger
values of B measured here also could have been a
result of changes in the Flade potential and the peak
current density in the active range with temperature.
Clearly, pH, [Cl], and temperature play important roles in determining the corrosion behavior of
carbon steels. Of additional importance is the redox
potential of the environment, and as a consequence,
Ecorr of the steel. Assuming that the pH is high
enough to promote passivation and [Cl] exceeds the
critical concentration such that localized corrosion is

CORROSIONVol. 56, No. 5

FIGURE 6. Effect of preoxidation at 200C on the extent of attack


measured after 24 h potentiostatic polarization in solutions of differing
chloride/total CO2
3 concentration ratio at 95C.

possible, if the Ecorr of the material in the environment can exceed Erp, then localized corrosion can
occur. Of further technological importance, if Erp can
be exceeded under open-circuit conditions, then the
likelihood of localized corrosion during engineering
service increases significantly. Open-circuit tests
using crevice samples revealed that under aerated
conditions, Ercrev was exceeded (Figure 5) and localized corrosion occurred. Similar results were
reported by Fukuda and Akashi in which Erp for carbon steel in pH 10.5 CO32 solutions was less than the
open-circuit potential in aerated solutions.6 Only
when the solution was deaerated did Ecorr fall below
Erp.6 Only general corrosion was observed in the submerged regions of samples exposed to simulated J-13
well water (pH ~ 7.4), with limited pitting attack in
the vapor phase. Similar observations of general corrosion after 1 year exposure to simulated J-13 well
water (pH < 7.4) have been reported and on pH modified (pH 9.6) J-13 with [Cl] < 103 M.2 These
results, again, highlight the importance of pH, [Cl],
and Ecorr in determining if localized corrosion of carbon steel will occur.
Preoxidation in air at 200C prior to crevice testing initially resulted in a decrease in the area of
attack measured (Figure 6). It seems likely that this
arises as a result of the oxide film thickening on the
carbon steel surface, thus partially delaying initiation
of crevice corrosion. At longer times, however,
preoxidation had a detrimental influence on crevice
corrosion. Jurek and Szklarska-Smialowska similarly
observed a decrease in pitting corrosion resistance
after thermally oxidizing carbon steel at temperatures between 100C and 200C.34 In their work, the
largest and deepest pits were observed after oxidation
in air in this temperature range. It was postulated
that a magnetite (Fe3O4) film was formed on the iron
surface, which led to the decrease in resistance to

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CORROSION SCIENCE SECTION

pitting. In the present and Jurek and SzklarskaSmialowskas works, no attempts were made to verify
experimentally the composition of the oxide on the
carbon steel samples. It probably was composed of
Fe3O4 covered by an outer hematite (-Fe2O3) layer.
Another possible explanation is that, as the
preoxidation time increased and the oxide film thickened, bulk defects such as cracks and pores were
introduced into the oxide film making the material
more susceptible to localized corrosion. Additional
work will examine this further. Even though it is unclear what the mechanistic role of preoxidation was
on corrosion of carbon steel, these results again
highlighted the important role that [Cl] played in
determining the extent of attack observed.
Corrosion performance of carbon steel in the
proposed HLW repository at YM is affected by several
factors, as discussed previously. The chemistry of the
water in contact with the waste package (WP) is a key
factor in that the chemistry can dictate if localized
corrosion of carbon steel is possible, which then
effects overall repository performance.35 In the J-13
well water chemistry used as a reference water chemistry in the DOE corrosion testing program,2,36 the
dominant dissolved carbon species is bicarbonate,
and thus the pH measured was on the order of 7.4 at
room temperature. At this pH, it is expected that
general corrosion rather than localized corrosion of
carbon steel will take place. As a result of water
leaching through the proposed concrete drift wall and
dripping onto a heated WP, the pH is expected to rise
to ~ 10 or even higher and [Cl] is expected to increase
as a result of water evaporation.2,21 If the solution
contacting the WP can attain sufficient [Cl] and pH
through interaction with the proposed concrete liner
and contact with a heated WP,21 then carbon steel
likely could suffer localized corrosion rather than the
intended general corrosion characteristics that led to
the selection of carbon steel as a corrosion-allowance
material.37 If localized corrosion occurs, any predictive modeling that assumes general corrosion of
carbon steel may be nonconservative.
McCright recently reported on tests using carbon
steel in modified J-13 well water at pH values as high
as 9.6 with no localized corrosion evident after 1 year
of exposure.38 In this case, however, [Cl] was below
the critical minimum concentration observed in the
present work, and thus, it is understandable why localized corrosion was not observed. Furthermore, no
efforts were made to monitor the potential. Even if
chloride was present in sufficient concentration, it
would be unknown if Erp was exceeded.
There are a number of anionic species present in
J-13 well water that are known as localized corrosion
inhibitors for iron and carbon steel in chloride media,
including nitrate and sulfate,12 which also were
present in the tests reported by McCright.38 Thus, inhibition of localized corrosion of carbon steel in the

512

repository may occur if these anionic species are concentrated sufficiently. Based on further experimental
work, however, the presence of other anionic species
in J-13 at their respective J-13 concentrations (total
anionic inhibitor concentration ~ 2.2 104 M) did
not affect measured critical potentials for crevice corrosion if pHcrit and [Cl] were met. Similar results
were observed by Zapp and Van Zee, who found that
[Cl]crit increased from 3 104 M to 3 103 M when
0.11 M nitrite was added.39 Thus, given the likely
concentrations of inhibitory anion present in the
groundwater, localized corrosion perhaps could be
delayed but not prevented if pHcrit, [Cl], and potential
criteria are met.
Localized dissolution rates observed in the current work were relatively high, in some cases
approaching 0.05 A/cm2. Based on the prevailing
groundwater chemistry near the proposed repository,
the chloride/total CO32 concentration ratio is
0.07.23,38 Depending on temperature, the local
dissolution rates at this ratio would range from
0.1 A/cm2 to 0.5 mA/cm 2 (9.3 103 mm/y to
4.6 mm/y). At higher chloride/total CO32 concentration ratios, as may be expected to develop as the
water chemistry in contact with the WP evolves,
dissolution rates as high as 30 mA/cm2 (278 mm/y)
theoretically may be reached. Based on longer tests
of up to 3-year durations, expressions for the pit
depth on carbon steel as a function of time have been
developed:7,40-41
P = At n

(4)

and take the form shown in Equation (4), where P is


the pit depth (mm), A is a constant, and t is time
(years). From the expressions generated, penetration
times for a 10-cm thick carbon steel plate ranged
from 78 years (A = 4.16, n = 0.7340) to 7.4 106 years
(A = 3.08, n = 0.2241). Clearly, a wide variance exists
in predicted lifetimes (nearly 5 orders of magnitude)
from these expressions, but each assumes continued
pit growth and does not account for the possibility of
pit arrest.
High propagation rates measured in the current
work and predicted by others likely would not be
sustainable for several reasons, including the broadening of the pit mouth and potential ohmic drop
effects in the pit.7 Based on the work of Beavers and
Thompson, who observed that high rates of attack
were limited to regions near the pit mouth on simulated pits of iron with reactive pit walls,42 ohmic drop
in the pit solution should minimize polarization in
the deeper areas of the pit. Furthermore, this will
have a broadening effect in that the pits will tend to
grow laterally rather than increase in depth, as has
been observed in numerous industrial applications of
carbon steels.43 Additional modeling by Marsh indicates that the potential of the external cathodic

CORROSIONMAY 2000

CORROSION SCIENCE SECTION

passive surface only remains positive relative to the


localized corrosion sites as long as the flux of oxidizing species to the cathodic site balances the anodic
current.44 Based on a granitic tunnel repository
design with backfill, Marsh predicted that this only
would occur for the first 125 years after emplacement, thereby restricting the time during which
localized corrosion of carbon steel was possible.44
Lastly, it cannot be overlooked that preoxidation
in air at 200C appeared to be detrimental to material performance. Similar high-temperature (T >
100C) exposure is predicted to occur in the repository for possibly up to several hundred years.2 Such
preoxidation could lead to easier initiation of localized corrosion as was observed. It is unclear,
however, if continued oxidation at 200C beyond the
times examined here (672 h) would lead to enhanced
localized corrosion. Based on the mechanisms discussed for the effect of preoxidation and the
observation that some general corrosion was observed at longer times could indicate that enhanced
general corrosion could occur or that localized corrosion could become broader and more shallow.
Without further work, it is difficult to predict what
affect long-term preoxidation will have on the corrosion performance of carbon steel.

CONCLUSIONS
At temperatures approaching the boiling point of
water, the corrosion of carbon steel is a complex
function of environmental conditions, including pH,
[Cl], and temperature.
Two critical environmental variables acted as enabling parameters for localized corrosion of carbon
steel: a pHcrit of 9.3 to 9.6, above which localized corrosion of carbon steel took place and below which
general corrosion was observed; and a [Cl]crit between
0.12 mM and 1.2 mM, below which localized corrosion of carbon steel did not take place in pH 11
solutions.
Localized corrosion of carbon steel, in the form of
crevice corrosion, was observed under open-circuit
conditions in air-saturated, pH 11 solutions at 95C
with [Cl] as low as 1.2 mM.
Uncertainty, however, still exists with respect to
sustainable localized corrosion propagation rates for
thick-section carbon steel structures.

ACKNOWLEDGMENTS
This work was funded by the U.S. Nuclear Regulatory Commission (NRC), Office of Nuclear Material
Safety and Safeguards, Division of Waste Management
under contract no. NRC-02-97-009. The technical assistance of S. Clay (Materials Division, Southwest
Research Institute) and reviews performed by N.
Sridhar and B. Sagar (CNWRA) are acknowledged.

CORROSIONVol. 56, No. 5

REFERENCES
1. U.S. Department of Energy, Repository Safety Strategy: U.S.
Department of Energys Strategy to Protect Public Health and
Safety after Closure of a Yucca Mountain Repository, YMP/9601, rev. 1 (Washington, DC: U.S. Department of Energy, Office
of Civilian Radioactive Waste Management, 1998).
2. U.S. Department of Energy, Viability Assessment of a Repository at Yucca Mountain. Total System Performance
Assessment, vol. 3, DOE/RW0508 (Las Vegas, NV: Office of
Civilian Radioactive Waste Management, 1998).
3. N.J. Laycock, R.C. Newman, Corros. Sci. 39 (1997): p. 1,771.
4. D.S. Dunn, N. Sridhar, G.A. Cragnolino, Corrosion 52 (1996):
p. 115.
5. G.L. Makar, D. Tromans, Corrosion 52 (1996): p. 250.
6. T. Fukuda, M. Akashi, Mater. Res. Soc. Symp. 412 (1996):
p. 597.
7. G.P. Marsh, K.J. Taylor, Corros. Sci. 28 (1988): p. 289.
8. H.E.H. Bird, B.R. Pearson, P.A. Brook, Corros. Sci. 28 (1988):
p. 81.
9. G. Nakayama, M. Akashi, Mater. Res. Soc. Symp. 294 (1993):
p. 329.
10. M.G. Alvarez, J.R. Galvele, Corros. Sci. 24 (1984): p. 27.
11. S. Simard, H. Menard, L. Brossard, J. Appl. Electrochem. 28
(1998): p. 151.
12. Z. Szklarska-Smialowska, Pitting Corrosion of Metals (Houston,
TX: NACE International, 1986).
13. R.C. Newman, M.A.A. Ajjawi, H. Ezuber, S. Turgoose, Corros.
Sci. 28 (1988): p. 471.
14. C.S. Brossia, G.A. Cragnolino, Localized Corrosion of Carbon
Steel Outer Overpacks for Nuclear Waste Disposal, CORROSION/99, paper no. 468 (Houston, TX: NACE, 1999).
15. G.A. Cragnolino, D.S. Dunn, P. Angell, Y.-M. Pan, N. Sridhar,
Factors Influencing the Performance of Carbon Steel Overpacks in the Proposed High-Level Nuclear Waste Repository,
CORROSION/98, paper no. 147 (Houston, TX: NACE, 1998).
16. M. Akashi, T. Fukuda, H. Yoneyama, Mater. Res. Soc. Symp.
176 (1990): p. 525.
17. N. Sridhar, G.A. Cragnolino, D.S. Dunn, H.K. Manaktala, Review of Degradation Modes of Alternate Container Designs and
Materials, CNWRA 94-010 (San Antonio, TX: Center for
Nuclear Waste Regulatory Analyses, 1994).
18. G. Nakayama, C. Liang, M. Akashi, Corros. Eng. 45 (1996): p.
345.
19. N. Sridhar, G.A. Cragnolino, D. Dunn, Experimental Investigations of Localized Corrosion of High-Level Waste Container
Materials, CNWRA 93-004 (San Antonio, TX: Center for
Nuclear Waste Regulatory Analyses, 1993).
20. G. Cragnolino, D.S. Dunn, N. Sridhar, Corrosion 52 (1996):
p. 194.
21. S. Mohanty, G.A. Cragnolino, T. Ahn, D.S. Dunn, P.C. Lichtner,
R.D. Manteufel, N. Sridhar, Engineered Barrier System Performance Assessment Code: EBSPAC Version 1.1Technical
Description and Users Manual, CNWRA 97-006 (San Antonio,
TX: Center for Nuclear Waste Regulatory Analyses, 1997).
22. ASTM, Standard Test Methods for Pitting and Crevice Corrosion Resistance of Stainless Steels and Related Alloys by Use of
Ferric Chloride Solution, in Annual Book of Standards (West
Conshohocken, PA: ASTM, 1996).
23. G. Geesey, A Review of the Potential for Microbially Influenced
Corrosion of High-Level Nuclear Waste Containers, CNWRA 93014 (San Antonio, TX: Center for Nuclear Waste Regulatory
Analyses, 1994).
24. C.S. Brossia, D.S. Dunn, N. Sridhar, Effects of Environmental
Factors on Container Life, CNWRA 98-008 (San Antonio, TX:
Center for Nuclear Waste Regulatory Analyses, 1998).
25. T. Shibata, T. Takeyama, Corrosion 33 (1977): p. 243.
26. F.G. Will, The Oxygen Electrode: A Critical Assessment, report
no. 76CRD276 (Schenectady, NY: General Electric Company,
1976).
27. A.J. Arvia, M.C. Giordano, Electrocatalysis: Basic Aspects and
Its Applications (Buenos Aires, Argentina: Fundacion para la
Educacion, la Ciencia y la Cultura, 1982).
28. J. Postlethwaite, R.A. Brierley, M.J. Walmsley, S.C. Goh,
Localized Corrosion, NACE-3, 415 (Houston, TX: NACE,
1974).
29. J.R. Galvele, J. Electrochem. Soc. 123 (1976): p. 464.
30. H.W. Pickering, Advances in Localized Corrosion, NACE-9, 77
(Houston, TX: NACE, 1990).

513

CORROSION SCIENCE SECTION

31. A. Valdes, H.W. Pickering, Advances in Localized Corrosion,


NACE-9, 393 (Houston, TX: NACE, 1990).
32. K. Cho, H.W. Pickering, J. Electrochem. Soc. 137 (1990): p.
3,313.
33. K. Cho, H.W. Pickering, J. Electrochem. Soc. 138 (1991): p. L56.
34. J. Jurek, Z. Szklarska-Smialowska, Corrosion 32 (1976): p. 309.
35. U.S. Nuclear Regulatory Commission (USNRC), Container Life
and Source Term, rev. 2, Issue Resolution Status Report
(Washington, DC: USNRC, Division of Waste Management, Office of Nuclear Material Safety and Safeguards, 1999).
36. J.E. Harrar, J.F. Carley, W.F. Isherwood, E. Raber, Report of
the Committee to Review the Use of J-13 Well Water in Nevada
Nuclear Waste Storage Investigations, UCID-21867 (Livermore,
CA: Lawrence Livermore National Laboratory, 1990).
37. TRW Environmental Safety Systems, Total System Performance
AssessmentViability Assessment (TSPA-VA) Methods and Assumptions, B0000000001717220000193, rev. 01 (Las
Vegas, NV: TRW Environmental Safety Systems, Inc., 1997).

38. R.D. McCright, Engineered Materials Characterization Report,


vol. 3, Corrosion Data and Modeling, UCRL-ID-119564, rev. 1.1
(Livermore, CA: Lawrence Livermore National Laboratory,
1998).
39. P.E. Zapp, J.W. Van Zee, Electrochemical Studies of NitrateInduced Pitting in Carbon Steel, CORROSION/99, paper no.
471 (Houston, TX: NACE, 1999).
40. A. Hoch, A. Honda, H. Ishikawa, F. Porter, S. Sharland, N.
Taniguchi, Mater. Res. Soc. Symp. 353 (1995): p. 703.
41. G.P. Marsh, K.J. Taylor, A.H. Harker, The Kinetics of Pitting
Corrosion of Carbon Steel Applied to Evaluating Containers for
Nuclear Waste Disposal, SKB Technical Report no. 91-62
(Stockholm, Sweden: Swedish Nuclear Fuel and Waste Management Co., 1991).
42. J.A. Beavers, N.J. Thompson, Corrosion 43 (1987): p. 185.
43. M. Kowaka, Metal Corrosion Damage and Protection Technology
(New York, NY: Allerton Press, 1990).
44. G.P. Marsh, Mater. Res. Soc. Symp., 112 (1988): p. 85.

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