Applied Surface Science 392 (2017) 10261035

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Applied Surface Science

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Full Length Article

Impact of the nanostructuration on the corrosion resistance and

hardness of irradiated 316 austenitic stainless steels
E. Hug a, , R. Prasath Babu b,d , I. Monnet c , A. Etienne d , F. Moisy c , V. Pralong a , N. Enikeev e,f ,
M. Abramova e , X. Sauvage d , B. Radiguet d
a
Laboratoire de Cristallographie et Sciences des Matriaux, Normandie Universit, CNRS UMR 6508, 6 Bd Marchal Juin, 14050 Caen, France
b
School of Materials, University of Manchester, M13 9PL, United Kingdom
c
Centre de recherches sur les Ions, les Matriaux et la Photonique CEA-CNRS, Normandie Universit, 6 Bd Marchal Juin, 14050 Caen, France
d
Groupe de Physique des Matriaux, UMR CNRS 6634, Universit et INSA de Rouen, Normandie Universit, Saint-Etienne du Rouvray Cedex, France
e
Institute of Physics of Advanced Materials, Ufa, Russian Federation
f
Saint Petersburg State University, Laboratory of the Mechanics of Bulk Nanostructured Materials, 198504 St. Petersburg, Russian Federation

a r t i c l e i n f o a b s t r a c t

Article history: The inuence of grain size and irradiation defects on the mechanical behavior and the corrosion resistance
Received 17 May 2016 of a 316 stainless steel have been investigated. Nanostructured samples were obtained by severe plastic
Received in revised form 7 September 2016 deformation using high pressure torsion. Both coarse grain and nanostructured samples were irradiated
Accepted 21 September 2016
with 10 MeV 56 Fe5+ ions. Microstructures were characterized using transmission electron microscopy
Available online 22 September 2016
and atom probe tomography. Surface mechanical properties were evaluated thanks to hardness mea-
surements and the corrosion resistance was studied in chloride environment. Nanostructuration by high
Keywords:
pressure torsion followed by annealing leads to enrichment in chromium at grain boundaries. However,
Stainless steel
Nanostructured grains
irradiation of nanostructured samples implies a chromium depletion of the same order than depicted
Irradiation resistance in coarse grain specimens but without metallurgical damage like segregated dislocation loops or clus-
High pressure torsion ters. Potentiodynamic polarization tests highlight a denitive deterioration of the corrosion resistance of
Corrosion resistance coarse grain steel with irradiation. Downsizing the grain to a few hundred of nanometers enhances the
corrosion resistance of irradiated samples, despite the fact that the hardness of nanocrystalline austenitic
steel is only weakly affected by irradiation. These new experimental results are discussed in the basis
of couplings between mechanical and electrical properties of the passivated layer thanks to impedance
spectroscopy measurements, hardness properties of the surfaces and local microstructure evolutions.
2016 Elsevier B.V. All rights reserved.

1. Introduction Despite the good formability and weldability of such stainless

316 austenitic stainless steels are currently used for their good
corrosion resistance, especially in acid [1] or chloride [25] envi-
ronments. In most of pressurized water reactors, the bafe bolts
of the internal structures are built with cold worked 316 stainless
steels. These components are used at temperatures typically rang-
ing from 280 C to 380 C and are submitted to a high neutron ux.
The observed cracks in some bolts are usually attributed to Irra-
diation Assisted Stress Corrosion Cracking (IASCC) [6] and can be
seen as a consequence of hardening assisted by irradiation when
these materials are loaded in a corrosive medium, with a possible
evolution of grain boundary chemistry [7].
Corresponding author.
E-mail address: eric.hug@ensicaen.fr (E. Hug).
steels, their mechanical properties remain modest, especially in
their full-annealed state. When employed in nuclear or aeronau-
tic industries, it is often mandatory to increase the strength of such
steel. Two traditional routes are available: conventional harden-
ing procedures [810] and solid solution hardening by interstitial
nitrogen [1113]. A reduction of the grain size in the submicron
range [14,15] may also lead to a signicant enhancement of the
strength [16] in accordance with the well-known Hall and Petch
law [17].
Nanostructuration processes also markedly modify the electro-
chemical reactions at the interface between metals and electrolyte.
Reported experiments show complex, and sometime contradic-
tory, evolution of the corresponding corrosion resistance, markedly
depending on the material and the solution. For instance, in H2 SO4
acid solution, electrodeposited nanocrystalline nickel exhibits a
progressive shift of potential values toward noble directions but
higher current densities compared to coarse grain metals [18]. This

http://dx.doi.org/10.1016/j.apsusc.2016.09.110
0169-4332/ 2016 Elsevier B.V. All rights reserved.
 E. Hug et al. / Applied Surface Science 392 (2017) 10261035
is satisfactorily explained by a competition between a general hin-
drance of corrosion in open circuit conditions and a deterioration
of the compacity of the passive layer. Also, ultrane grain tita-
nium produced by severe plastic deformation exhibits an increase
in surface hardness but a lower corrosion behaviour in 3 wt.%NaCl
electrolyte than the coarse grain traditional alloy [19].
Hardening of 316 stainless steel modies its corrosion resis-
tance, in close link with the evolution of compacity of the passive
layer [20]. Optimal conditions of surface treatments were found for
hardening by nitrogen solid solutions [3,4,12]. Kwok et al. report
an increase in corrosion resistance for nanostructured 316L tested
in 0.9 wt.%NaCl electrolyte [21]. However, it is interesting to note
that Chui et al. have shown that nanostructuring (and thus hard-
ening) a thin layer of stainless steel by a fast multiple rotations
rolling process leads to a signicant degradation of the corrosion
resistance [22]: lowering of the free corrosion potential and cor-
responding increase in the corrosion current density. This implies
a deterioration of the pitting corrosion resistance. The inuence of
the way used to produce nanocrystalline structures pointed on cor-
rosion properties has been recently reviewed in Ref. [23]. It clearly
appears that the corrosion behaviour of such alloys is not only
dependent of the processing route, but also of the electrolyte and
the experimental conditions.
Irradiation of austenitic stainless steels typically creates a high
density of point defects. These defects tend to agglomerate, leading
to the formation of interstitial dislocation loops (Frank loops) that
contribute to irradiation hardening [24,25]. Due to the annihilation
of point defects at sinks, intra- and inter-granular segregations are
usually observed in irradiated austenitic stainless steels [26]. In par-
ticular, chromium depletion at grain boundaries is often reported
in the literature [27]. In pressurized water reactors, the combi-
nation of such irradiation hardening with chromium depletion
at grain boundaries may therefore promote IASCC [6]. However,
grain boundaries being also sinks for point defects, nanostructura-
tion could lead to a better structural stability under irradiation
(by reducing the dislocation loop density) and therefore enhances
IASCC resistance. Such a scenario seems to be conrmed by recent
studies about the microstructural evolution of nanocrystalline
stainless steels under irradiation [28,29]. However, so far the com-
plex interactions between nanostructuration, irradiation resistance
and corrosion properties of 316 stainless steels has not been sys-
tematically investigated.
The main goal of this work is to deepen the understanding of
such interactions by investigating the impacts of nanostructuration
combined with irradiation on the hardening mechanisms together
with the corrosion properties. Nanostructuration was obtained by
a High Pressure Torsion (HPT) procedure. The austenitic stainless
steel, the methodology to obtain nanostructured and irradiated
samples, and experimental setups are presented in Section 2.
The evolution of the microstructure with irradiation, nanostruc-
turation, and corresponding experimental results of hardness and
corrosion are given in Section 3. Finally the results are discussed in
Section 4, supported by electrochemical impedance spectroscopy
analysis.
2. Material properties and experimental methods
2.1. Nanostructuration and irradiation procedures
A commercial extruded 316 stainless steel with a weight percent
composition (Fe0.03C17Cr12.9Ni2.36Mo1.72Mn0.41Si0.01
P0.03S) was used as starting material. Grain renement was
achieved by severe plastic deformation using a HPT technique
[30]. Quenching at 1050 C for 1 h followed by air cooling was
systematically performed before HPT processing. Discs samples
1027
Fig. 1. Evolution of the hardness under a mass of 100 g along the diameter of the
samples and effect of a subsequent recovery annealing at 450 C for 5 h (In the inset
is a general scheme of HPT experiments).
(diameter 20 mm, thickness 1 mm) were processed under a pres-
sure of 6 GPa, up to 10 revolutions at 400 C. They were then held
in temperature at 450 C for 5 h under vacuum for stabilizing the
microstructure prior to irradiation experiments that were also
performed at this temperature. The hardness prole across the
diameter of HPT discs (Fig. 1) shows a signicant gradient with a
softer region in the center where the shear deformation was lower.
The post-processing annealing treatment leads to a very slight
decrease in the hardness (about 10% but within the inaccuracy of
measurements) outside the center area which might be attributed
to defect recovery mechanisms. All experiments given in the
present work were systematically carried out in the outer part of
HPT discs (i.e. between 3 and 9 mm from disc center) where the
microstructure is homogeneous.
Extruded and nanostructured samples were irradiated at
JANNuS-Saclay (Joint Accelerators for Nanoscience and Nuclear
Simulation), CEA, France, and supported by the French Network
EMIR. Irradiation experiments were performed using 56 Fe5+ ions
with energy of 10 MeV bombarding the sample with an angle of
incidence normal to the surface. Heavy ions like 56 Fe5+ produce
large displacement cascades that can be considered roughly repre-
sentative of cascades produced by fast neutrons [31]. Irradiation by
heavy ions was used in order to reach high doses in short times
without any activation of the samples. The damage prole was
estimated using the S.R.I.M. software (Quick damage calculation
option with a displacement energy threshold of 40 eV [32,33]). The
maximum level of damage (damage peak) in term of displacements
per atoms (dpa) is located at 2 m below the surface. The samples
were irradiated with a total average uence of 1.4 1016 ions/cm2 .
The average dose in the rst micrometer below the surface is about
2.7 dpa.
2.2. Metallurgical and electrochemical analysis
Microstructural observations were performed thanks to con-
ventional metallurgical setups. The grain size distribution and
crystallographic texture of coarse grain specimen were analysed
by Scanning Electron Microscopy (SEM) coupled with Electron
Backscatter Diffraction (EBSD) analysis. Microstructural observa-
tions of nanostructured samples were carried out by Transmission
Electron Microscopy (TEM) with a JEOL 2010F microscope operat-
ing at 200 kV. Plane view thin foils were prepared by mechanical
polishing down to 80 m. They were then electropolished using a
standard double-jet procedure. Cross section TEM thin foils were
prepared either by FIB (Focused Ion Beam Helios Nanolab 660,
accelerating voltage of 5 keV and 2 keV for the nal stage to reduce
1028 E. Hug et al. / Applied Surface Science 392 (2017) 10261035

damages and gallium implantation), or by traditional methods

(dimples up to 510 m and ion milling with Ar+ 5 keV with a Gatan
PIPS).
Despite the fact that others elements (Ni, Si, . . .) could also segre-
gate at grain boundaries after nanostructuration and/or irradiation,
this work focus on the inuence of chromium content due to its key
role in corrosion properties of stainless steels. Chromium segrega-
tion at grain boundaries was analyzed by Atom Probe Tomography
(APT) with a Cameca FlexTAP instrument. APT samples were evap-
orated at 50 K using femtosecond UV laser pulses with an energy
giving an equivalent pulse fraction of 20% of the standing voltage.
Microstructural characterisation was performed with a new gen-
eration of atom probe (wide angle atom probe). This enhances the
statistical relevance of results because the investigated volumes are
quite large compared to grain size (so that a large number of grain
boundaries can be investigated). The non-irradiated APT samples
were prepared by microloop electropolishing technique. The irradi-
ated specimens were extracted from the uniform damaged layer (at
about 500 nm in depth) by lift out method and FIB annular milling
with a Zeiss NVision 40.
Vickers micro-hardness (under a mass of 100 g) was systemat-
ically measured for each sample. In plane nano-hardness proles
were obtained with a MTS XP nanoindentation device using the
continuous stiffness measurement mode. On each sample, a matrix
of 25 indents was performed with a Berkovich tip and a constant
indentation depth of 1 m was used. Nanohardness H and corre-
sponding elastic modulus E were measured using the Oliver and
Pharr methodology [34]. This method is useful for brittle materials
as evidenced by previous works on metallic glasses [35] and can be
applied for the study of hard metallic layers [3638]. After inden-
tation, indent depths were measured by laser confocal microscopy.
Open circuit potential measurements and potentiodynamic
polarization J(E) curves (J: current density and E: potential value)
were obtained using a standard three electrodes electrochemical
cell with Saturated Calomel Electrode (SCE) as potential reference
and a platinum grid as counter electrode. The electrolyte was a
3 wt.% NaCl neutral solution corresponding to a chloride ion con-
centration of 0.85 mol/L, freely aerated and maintained at room
temperature. Non-irradiated specimens were carefully polished
before measurements and irradiated samples were polished before Fig. 2. (a) EBSD inverse pole gure map of the coarse grain 316 sample in a section
normal to the rod. Inverse pole gures along axial (ND) and radial (RD) directions are
irradiation procedures. Five tests were performed on each sam-
displayed in inset. (b) Cross section TEM bright eld image of nano-grain 316. Very
ple in order to verify the repeatability of the results. Open circuit few stacking faults are observed (an example is shown by the star). SAED pattern
potential Eoc was rst measured during a period of 15 h, followed indicates a low texture of the nanostructure. Size histogram of grains is given in
by the potentiodynamic test performed with a variation of voltage inset.
of 0.166 mV/s from300 mV/SCE to 600 mV/SCE. The corrosion cur-
rent density Jcor was obtained by Tafel extrapolation of the cathodic
part of the J(E) curve. The initial polarization resistance Rpol of the size. EBSD observations reveal the existence of numerous twins
fresh surface was also captured by a linear polarization technique (Fig. 2(a)) and a weak crystallographic texture is identied with a
around the corrosion potential value Ecor (measurements per- dominant pole 001 parallel to the extrusion direction (ND direc-
formed directly after immersion of the samples). Electrochemical tion in the inset of Fig. 2(a)). The maximal density of the texture
Impedance Spectroscopy (EIS) measurements were nally carried is lower than 4 m.r.d. (multiple random distribution). The impact
out at E = Eoc after 15 h of immersion by applying an alternating of the initial texture on the experimental results of this work can
potential amplitude of 50 mV and frequency ranges from 1 mHz to be then neglected. As expected, the severe plastic deformation by
10 kHz with an acquisition rate of 15 points per decade. Polarization HPT leads to a signicant grain renement (Fig. 2(b)). A mixture
curves and Nyquist plots obtained by EIS are analysed by traditional of equiaxed grains and elongated grains (mostly the bigger ones)
tools [39] for access to the main parameters representative of the is evidenced, giving a mean grain size (diameter of a disk of the
corrosion properties of the samples. same area for elongated grains) of 172 nm (see histogram in inset of
Fig. 2(b)). Some sub-grain boundaries and very few stacking faults
are also identied.
3. Experimental results Thirteen Grain Boundaries (GB) were intercepted during APT
analyses performed in non irradiated nanostructured material. A
3.1. Microstructural analysis large majority (about 85% of them) are enriched in chromium
whereas the other ones do not show any tendency. A typical con-
The reference state material (coarse grain non irradiated 316 centration prole of one of the enriched GB is shown in Fig. 3. The
steel) was received in slightly cold working conditions. The mean local Cr concentration at GBs is 34 at.% higher than the matrix
grain size is 65 m with a standard deviation of half the grain level. In non-irradiated coarse grain austenitic stainless steels or
 E. Hug et al. / Applied Surface Science 392 (2017) 10261035
Fig. 3. (a) Atom probe tomography reconstructed volumes showing Cr distributions
in non-irradiated and irradiated samples of nanostructured 316 stainless steels.
Grain boundaries are highlighted by arrows. (b) Corresponding concentration pro-
les of Cr across the grain boundaries.
model alloys, previous results [40,41] report Cr concentration at
GB higher than the bulk concentration. EDS proles through GB of
a mill annealed 316 steel also show Cr enrichment [6]. In all these
papers, the reported Cr concentration at GB is about 15 at.% higher
in the bulk, which is in agreement with our observations. How-
ever, such tendency is not systematically depicted. For instance,
neither enrichment nor depletion is reported in Refs. [40,42,43]. In
particular, Tomozawa et al. [43] have shown by APT that neither
enrichment nor depletion is observed in various random GBs and
3 GBs. As far as UFG steels are concerned, no difference between
the Cr concentration at GB and in the matrix is found in a 316 stain-
less steel nanostructured by HPT at room temperature [44]. Thus,
in the present work, the processing temperature and subsequent
annealing (performed at 450 C) could be the main reason of the Cr
enrichment at GBs [45,46].
After irradiation, 17 GBs were intercepted during APT analysis.
25% of them are still enriched in Cr, 10% exhibit at Cr concentration
proles and the majority (65%) is depleted in Cr. As displayed in
Fig. 3(b), the Cr concentration prol through depleted GB does not
exhibit a W shape. The minimum Cr concentration at GB is about
5 at.% lower than the matrix level in the depleted GB. Radiation
induced depletion of Cr at GB in austenitic stainless steels or model
alloys after irradiation with neutrons [41,47,48], protons [40,41,49]
or heavy ions [26] has been widely reported. For a similar irradia-
tion dose, a depletion of about 5 at.% is generally reported in coarse
grain austenitic stainless steel. In coarse grain 316 alloy, segregated
loops and solute clusters are observed after irradiation with heavy
ions at similar dpa level [50]. Such features were not detected by
APT in our nanocrystalline steel. TEM observations conrmed that
there are no visible defects or precipitates in nanograin samples
after irradiation (Fig. 4). Such reduced irradiation damage could
be attributed to the increased proportion of sinks for point defects
at grain boundaries [44], despite the fact that a local depletion in
chromium is evidenced. Irradiation could lead to a limited coars-
ening of the grain (median diameter of 210 nm against 172 nm for
unirradiated samples). However, this small discrepancy could be
also due to a lack of statistic and a difference in the grain size related
1029
Fig. 4. Cross section of irradiated nanostructured 316 steel. The observed region is
just below the sample surface within the rst micrometer. SAED patterns and size
histogram of grains are given in insets.
to the localization of the thin foils, not at exactly the same distance
from the center of specimens.
3.2. Hardness properties of the surface layers
Fig. 5 shows examples of in plane hardness proles measured
on the four specimen states. Two peaks are clearly exhibited for
irradiated samples. The rst is located near the surface layer and
is representative of oxidation of the extreme surface issued of
irradiation procedures [51]. The hardness values considered in
the following are therefore those obtained for depth greater than
50 nm [52]. The second peak is located at about 180 nm from the
surface for the coarse grained alloy and about 220 nm for the
nanocrystalline material. Hardness peak values are strongly dis-
persive, especially for coarse grain specimens, depending on the
local surface state of the grains. The mean hardness (computed
with the results of 25 distinct indents) is then measured at 1 m of
depth because it is representative of the intrinsic properties of the
steels. The obtained values are reported in Fig. 6(a). As expected
and in accordance with previous results [53], nanostructurating
by HPT strongly increases the in plane hardness. Also, the hard-
ness of the coarse grain material is signicantly affected by the
irradiation (leading to a gap of 0.86 GPa on average). However,
it is interesting to note that the hardness of the nanocrystalline
material is almost unchanged after irradiation, standing near 6 GPa,
with a small variation of 0.32 GPa. These results are consistent
with Vickers microhardness experiments (Fig. 6(b)), performed at
corresponding depths two or three times higher than nanoinden-
tation ones. The increase in hardness is associated with an increase
in elasticity modulus, as shown in Fig. 6(c). Complementary local
observation of nano-indents by confocal microscopy shows that
residual indent depths are greater in coarse grains than in nanocrys-
talline materials (see Supplementary material 1). This indicates a
large elastic springback connected to the hardening induced by
nanostructuration, in good agreement with elastic modulus values.
Pile-up effects also appear around residual indentation imprints for
irradiated and nanocrystalline materials, giving a lower accuracy in
the estimation of hardness and elastic parameters [54].
The high hardness depicted in nanocrystalline sample is then
linked to the high proportion of GBs that act as barrier for disloca-
tions. However, in irradiated materials, the high hardness is rather
connected to crystalline defects (like dislocation loops) resulting
from the recombination of irradiation defects. There is little change
in the hardness value of the UFG steel because the contribution of
1030 E. Hug et al. / Applied Surface Science 392 (2017) 10261035
Fig. 5. Inuence of the irradiation on the typical hardness proles obtained by
nanoindentation measurements. (a) Coarse grains 316 steel, (b) nanostructured
samples.
GBs is already so large that additional defects due to irradiation do
not have a signicant effect on dislocation mobility.
3.3. Corrosion resistance in 3 wt.%NaCl solution
Open circuit plots Eoc = f(t) are displayed in Fig. 7 for the four
specimens. After a short transient evolution depending on the
initial surface state, open circuit potential of nanostructured sam-
ples rapidly stabilizes around 0.14 V/SCE for both irradiated and
pristine states. Concerning coarse grain specimens, a small differ-
ence exists between irradiated and unirradiated states after 15 h of
immersion (0.06 V/SCE against 0.11 V/SCE, respectively). How-
ever, complementary experiments show that a common value of
0.12 V/SCE is reached for the two states after 72 h of immersion for
coarse grain specimens, against 0.145 V/SCE for nanograin sam-
ples. Nanocrystalline 316 is therefore slightly less noble in open
circuit conditions than coarse grain materials in 3 wt.% NaCl elec-
trolyte, independently of the state (as received or irradiated).
Fig. 6. (a) Hardness values at 1000 nm of depth for the four states of 316. (b) Corre-
sponding mean values of Vickers microhardness (mean depths of indents are given
above each measurement). (c) Corresponding mean values of elasticity modulus.
Error bars give the standard deviation from 20 measurements.
Examples of potentiodynamic polarization curves measured
after 15 h of immersion are given in Fig. 8 and the corresponding
relevant parameters are listed in Table 1 (mean values obtained
on ve distinct experiments). All samples exhibit more or less the
behaviour of a passive material in a potential range L [Ep ; Epit ] with
Ep the passivation potential and Epit the pitting corrosion potential.
Moreover, very slight values of the corrosion current density Jcor
are obtained whatever the sample, well below 1 A/cm2 , indicat-
ing that the passivation of the surface is present for all specimens
after 15 h of immersion.
For coarse grain non irradiated specimens, corrosion (Jcor ) and
passivation current density (Jp ) values are in agreement with results
found in the literature [3,21]. Irradiation strongly deteriorates the
 E. Hug et al. / Applied Surface Science 392 (2017) 10261035
Table 1
Electrochemical parameters obtained from the polarization tests.
State Sample Eoc a (mV/SCE) Ecor (mV/SCE) Jcor (A/cm2 )
Non irradiated Micro 120 73 0.34
Nanob 145 135 0.19
Irradiated Micro 120 47 0.55
Nanoc 145 158 0.17
a
Open circuit potential after 72 h of immersion.
b
Secondary passivity: L = [107180] mV/SCE, J = 6.2 A/cm2 .
c
Secondary passivity: L = [334461] mV/SCE, J = 1.05 mA/cm2 .
Fig. 7. Evolution of the open circuit potential with time for 316 stainless steel
under immersion in 3 wt.%-NaCl solution. Combined effects of nanostructuration
and irradiation.
passive behaviour in this grain size range (Fig. 8(a)). Ecor remains
close to the same value, considering the natural dispersion of exper-
iments, but the good passivation state observed on pristine 316
is dramatically degraded when irradiated samples are considered.
Irradiation leads to a pseudo- passivation state in a lower potential
range, together with Jp values higher by a factor two.
The nanostructuration of the stainless steel leads to the transla-
tion of all values of potential towards less noble values (Fig. 8(b)).
The passive potential range L is of the same order of value
(around 150160 mV/SCE) and Jp increases from 0.96 A/cm2 to
1.23 A/cm2 . A weak secondary passivity range is also system-
atically depicted for nanocrystalline specimens. Irradiation has
a moderate inuence on the corrosion behaviour of nanostruc-
tured samples. All the representative corrosion parameters are
in the same range for both sample conditions (Table 1). The
polarization resistance Rpol of the fresh surface is much higher
for the nanocrystalline material close to the corrosion potential
(69 k cm2 against 37 k cm2 for coarse grains). Rpol moderately
decreases for irradiated coarse grain samples, and is grossly con-
stant for nanostructured states.
Pitting corrosion resistance was measured by imposing a current
density of 102 mA/cm2 for 2 h and observing the etched surface
by traditional light microscopy. Representative pitting surfaces are
shown in the photographs of Fig. 8. Complementary analysis by
immersion for 24 h in a 6% FeCl3 solution (following ASTM G48
procedure [22,55]) at a constant temperature of 30 C, followed by
a weight-loss measurement, completed the pitting analysis. The
total area of corrosion pits in irradiated coarse grain material is
much larger than for others samples, consisting of very numer-
ous pits of small sizes. The corresponding corrosion rate is about
two/three times higher than for the non-irradiated state. Pitting
1031
Rpol (k.cm2 ) Jp (A/cm2 ) Ep (mV/CSE) Epit (mV/CSE) L (mV/CSE)
37.01 0.96 133 282 149
69.43 1.23 80 79 159
22.95 1.83 7 183 190
73.38 1.47 91 59 150
mechanisms were also depicted for nanostructured materials. The
density of pits is slightly higher than in coarse grain samples.
However, the nanocrystalline samples, both in irradiated and non-
irradiated states, are more resistant in terms of pitting mechanisms
and weight loss than irradiated coarse grain steel.
In summary, the irradiation and the nanostructuration sig-
nicantly modify in a complex and not straightforward manner
the corrosion behaviour of pristine 316 steel. Irradiation strongly
impacts the value of current densities, but is less effective concern-
ing potential parameters, especially for nanostructured specimens.
Nanostructuration exhibits an opposite effect since the potential
values are translated towards less noble values whereas density
current values are less affected. Finally, the irradiation of nanos-
tructured samples does not markedly change the behaviour of 316
in terms of corrosion and pitting behaviours.
4. Discussion: electrical properties of the free surfaces
Recent experimental results [56] report a severe degradation of
the corrosion resistance for irradiated nanostructured steels. This
was related to carbides precipitation at the conditions of irradiation
experiment and to a bigger fraction of strain-induced martensite
after HPT at room temperature. Neither carbides precipitation nor
strain-induced martensite were evidenced in our experiments. The
higher value of Jp is closely related to a weaker pitting resistance
of the nanocrystalline material because the higher density of grain
boundaries increases the number of energetic unstable sites on the
surface [20]. Metastable pits nucleate at higher rate on nanocrys-
talline surface samples, and grow up until being energetically stable
[57].
HPT nanocrystalline samples exhibit a higher polarization resis-
tance Rpol for both irradiated and unirradiated conditions just after
immersion of the fresh surfaces in 3 wt.% NaCl. The corresponding
value of Jcor is weak and the activation energy related to dissolu-
tion mechanisms is more important, in accordance with previous
results devoted to nickel [18,58]. The appearance of kinetic block-
ages on the growth mechanisms implies that the passive layer is
not able to develop efciently for nanostructured samples. These
blockages are closely linked to the existence of compressive elastic
microstrains in the surface region, in interconnection with the nec-
essary geometrical dislocation substructure, as evidenced by the
corresponding higher hardness level. These elastic microstrains can
be benecial to corrosion resistance as for instance for electrode-
posited nanostructured nickel [18], or provide detrimental effects
as in this work. These two different processing routes could be origi-
nating the opposite effects of nanostructuration but more generally
elastic stresses play an important role on the oxidation behavior. A
straightforward relation therefore exists between mechanical and
electrical properties of the free surfaces. When samples are just
immerged in the electrolyte, the initial activity of the fresh surface,
which is necessary for a good growth of the passive layer, is not suf-
cient in small grain size samples. This leads to the development of
a less good passive layer in terms of corrosion resistance, despite a
local enrichment in chromium at grain boundaries, as indicated by
values of Jp and Epit .
1032 E. Hug et al. / Applied Surface Science 392 (2017) 10261035

Fig. 8. Effect of irradiation on the potentiodynamic polarization curves of 316 stainless steels. (a) Coarse grain samples. (b) Nanostructured samples. Pictures show pitting
observations after imposing a current density of 102 mA/cm2 for 2 h.

Table 2
Computed parameters issued from the simulation of EIS spectra measurements by a double time constant electrochemical model. Results are representative of the resistive
and capacitive properties of the passive metallic layer (RP , CP ) and of the electrochemical double layer (RCT , CDL ), respectively.

State Sample R ( cm2 ) RP (k cm2 ) CP (F/cm2 ) RCT ( cm2 ) CDL (F/cm2 )

Non irradiated Micro 27.19 5.531 36.2 12.32 18.5

Nano 25.68 2.970 33.7 364.60 40.7
Irradiated Micro 26.65 30.98 25.0 29.54 9.52
Nano 27.04 21.821 34.3 775.10 75.3
 E. Hug et al. / Applied Surface Science 392 (2017) 10261035
Fig. 9. Effect of nanostructuration and irradiation on the Nyquist plots of 316 stain-
less steel. Measurements performed at open circuit potential after 15 h of immersion
in 3 wt.%-NaCl solution. In the inset is shown the electric equivalent circuit used to
obtain the best ts plotted in red (For interpretation of the references to colour in
this gure legend, the reader is referred to the web version of this article.).
The impact of irradiation combined with nanostructuration on
the initial electrical properties of surfaces of 316L stainless steel can
be successfully studied by EIS measurements. They were performed
after 15 h of immersion in open circuit conditions. Information on
the resistive and capacitive properties of the passive layer can be
obtained by Nyquist plots of impedance spectra (Fig. 9). All tests
exhibit the same typical capacitive semi-loop shape which cov-
ers the entire frequency range [1 mHz10 kHz]. The existence of
a single capacitive loop is representative at rst approximation to
a charge transfer resistance in parallel with a double-layer capaci-
tance [59]. A simple Randles equivalent circuit as described in the
second Supplementary material is often sufcient in this case to
represent the electrical interface between the electrode and the
electrolyte. However, in our study, the electrical properties of the
interface between the electrode and the aqueous solution are bet-
ter captured by a two-time constants electrical equivalent circuit
[60] as this one given in the inset of Fig. 9. In this electrical model,
R is the electrolyte resistance and the respective inuence of the
passive metallic surface layer (represented by the resistance RP
and the constant phase element CP ) and the electrochemical layer
between the electrode outer surface and the electrolyte (charge
transfer resistance RCT and double layer capacity CDL ) can be ana-
lysed [59,61,62]. Best tting for the impedance data are obtained
with numerical values given in Table 2 and are plotted in continu-
ous red lines in Fig. 9.
R remains constant and low whatever the sample, indicat-
ing the good reproducibility of the experimental set up. RCT and
CDL are representative of the kinetic blockages associated with
the diffusion mechanisms of ions through the diffusion Nernst
layer [63]. It can be observed that the electrical properties of the
electrochemical double layer play a less important role than the
corresponding properties of the metallic passive layer: RCT is always
negligible compared to RP and CDL is weakly impacted by the
nanostructuration and the irradiation. Nanostructuration moder-
ately decreases the resistance RP of the passive layer and CP remains
grossly constant around 2535 F/cm2 , whatever the initial state
of the samples. However, for each metallurgical stage of the 316
steel (nanostructured or coarse grain specimens), the irradiation
strongly increases the value of RP , by a multiplicative factor of
57. This constitutes the main result of the EIS measurements: the
irradiation has a denitive impact on the electrical resistance of
the passive layer. Fresh surfaces of the irradiated austenitic steel
are more electrically insulating and the passive lm is less able
1033
to develop when samples are immerged in the electrolyte. Poten-
tiodynamic polarization values (J(E) curves in Fig. 8) then exhibit
degraded passivation properties for irradiated specimens together
with a high sensitivity to pitting mechanisms in chloride media.
This phenomenon is especially sensitive for coarse grain samples
and nanostructuration before irradiation tend to reduce this effect,
decreasing RP for both irradiated and non-irradiated samples.
The metallurgical origin of the evolution of RP could be found
in the intrinsic properties of the grain boundaries for each state
of the 316 austenitic steel. As already mentioned, mechanical and
electrical properties of the surface passive layer of the stainless
steel are intricately related. The neighbourhood of grain bound-
aries in nanostructured samples acts as pseudo-amorphous layers
(existence of an extended disordered region at grain boundaries
[64]) even if high resolution observations of GB conrm that crys-
tallinity often exists right up the boundary between grains [65].
These areas are mechanically harder [66] and GB are known to
reduce signicantly the electrical conductivity of polycrystalline
metals [67,68]. This leads to a degraded passive layer, which in turn
decreases the overall corrosion and pitting resistance of the mate-
rial. Furthermore, an important metallurgical impact of irradiation
is the depletion in chromium in grain boundaries which strongly
deteriorates the corrosion resistance of the coarse grain material.
Besides, as the free surface of irradiated samples is also a possible
efcient sink for irradiation defects, the irradiation process could
also eventually lead to a slight Cr depletion near the surface. Such a
local change of the chemical composition might also affect the cor-
rosion behavior. Some additional experiments are planned in the
near future to quantify this effect and check this hypothesis. The
enrichment of Cr at GB due to annealing of nanostructured samples
(prior to irradiation) delays the loss of Cr during irradiation, and
thus shows better corrosion resistance compared to coarse grain
sample. The corrosion resistance of the nanostructured samples is
less affected by the chromium depletion provoked by irradiation
because their passive layer is already partly damaged by the HPT
process.
5. Conclusion
The coupled inuence of the nanostructuration and irradiation
on the corrosion resistance of metals and alloys mainly depends
on the nature of the electrolyte and the process route with which
nanostructuration has been obtained. In this work, nanostructur-
ing stainless 316 austenitic steel was successfully performed by a
high pressure torsion procedure, giving a mean grain size of 172 nm
against 65 m for the as-received material. The impact of this pro-
cess combined with an irradiation by 56 Fe5+ ions of 10 MeV energy
on the hardness and corrosion resistance of the surface was investi-
gated. The following conclusions can be drawn from this research:
Enrichment in chromium is depicted at a large majority of the
grain boundaries for nanostructured and annealed samples and
a depletion is evidenced at most of the GBs after irradiation of
these samples. A slow grain growth is observed after irradiation.
Nanostructuration strongly increases the hardness both in sur-
face and core of material. Nanocrystalline specimens are only
weakly affected by irradiation in terms of hardening.
The polarization resistance of nanocrystalline materials is higher
and the corresponding corrosion current density lower. The pas-
sive layer is not able to develop efciently for low grain size
samples. The degradation of the kinetic properties of growth of
this layer could be due to the existence of compressive elastic
microstrains in the surface area.
The irradiation procedure has a strong impact on the electrical
resistance of the passive layer of austenitic 316 stainless steels.
1034 E. Hug et al. / Applied Surface Science 392 (2017) 10261035
Fresh surfaces are more electrically insulating and the passive
lm is less able to develop when samples are immerged in the
electrolyte. Degraded passivation properties for irradiated spec-
imens together with a high sensitivity to pitting mechanisms
in chloride media are reported, especially sensitive for coarse
grain samples. The nanostructuration before irradiation tends to
reduce this effect.
The neighbourhood of grain boundaries in nanostructured
samples is mechanically harder, more rigid, and electrically insu-
lating. The corresponding degraded passive layer decreases the
overall corrosion and pitting resistance. After irradiation, the
depletion in chromium in grain boundaries strongly deteriorates
the corrosion resistance of the coarse grain material.
In comparison, the corrosion resistance of the nanostructured and
irradiated samples is less affected by the chromium depletion.
Acknowledgments
The authors acknowledge the nancial support of the french
Agence Nationale de la Recherche (ANR), through the program
Investissements dAvenir(ANR-10-LABX-09-01), LabEx EMC3 .
This project received a grant from the french state managed by the
National Research Agency through the Investissements dAvenir
programme which reference is ANR-11-EQPX-0020. Experiment
done at JANNuS-Saclay (Joint Accelerators for Nanoscience and
Nuclear Simulation), CEA, France and supported by the French
Network EMIR. N. Enikeev acknowledges partial support through
Contract No. 14. B25.31.0017 dated 28.06.2013 by the Russian Min-
istry for Education and Science. Also many thanks to Gael Marnier,
GPM laboratory, for EBSD experiments on 316 initial samples.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.apsusc.2016.09.
110.
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