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Applied Surface Science 392 (2017) 10261035

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Applied Surface Science


journal homepage: www.elsevier.com/locate/apsusc

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


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

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 1027

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 Fig. 1. Evolution of the hardness under a mass of 100 g along the diameter of the
a deterioration of the pitting corrosion resistance. The inuence of samples and effect of a subsequent recovery annealing at 450 C for 5 h (In the inset
the way used to produce nanocrystalline structures pointed on cor- is a general scheme of HPT experiments).
rosion properties has been recently reviewed in Ref. [23]. It clearly
appears that the corrosion behaviour of such alloys is not only (diameter 20 mm, thickness 1 mm) were processed under a pres-
dependent of the processing route, but also of the electrolyte and sure of 6 GPa, up to 10 revolutions at 400 C. They were then held
the experimental conditions. in temperature at 450 C for 5 h under vacuum for stabilizing the
Irradiation of austenitic stainless steels typically creates a high microstructure prior to irradiation experiments that were also
density of point defects. These defects tend to agglomerate, leading performed at this temperature. The hardness prole across the
to the formation of interstitial dislocation loops (Frank loops) that diameter of HPT discs (Fig. 1) shows a signicant gradient with a
contribute to irradiation hardening [24,25]. Due to the annihilation softer region in the center where the shear deformation was lower.
of point defects at sinks, intra- and inter-granular segregations are The post-processing annealing treatment leads to a very slight
usually observed in irradiated austenitic stainless steels [26]. In par- decrease in the hardness (about 10% but within the inaccuracy of
ticular, chromium depletion at grain boundaries is often reported measurements) outside the center area which might be attributed
in the literature [27]. In pressurized water reactors, the combi- to defect recovery mechanisms. All experiments given in the
nation of such irradiation hardening with chromium depletion present work were systematically carried out in the outer part of
at grain boundaries may therefore promote IASCC [6]. However, HPT discs (i.e. between 3 and 9 mm from disc center) where the
grain boundaries being also sinks for point defects, nanostructura- microstructure is homogeneous.
tion could lead to a better structural stability under irradiation Extruded and nanostructured samples were irradiated at
(by reducing the dislocation loop density) and therefore enhances JANNuS-Saclay (Joint Accelerators for Nanoscience and Nuclear
IASCC resistance. Such a scenario seems to be conrmed by recent Simulation), CEA, France, and supported by the French Network
studies about the microstructural evolution of nanocrystalline EMIR. Irradiation experiments were performed using 56 Fe5+ ions
stainless steels under irradiation [28,29]. However, so far the com- with energy of 10 MeV bombarding the sample with an angle of
plex interactions between nanostructuration, irradiation resistance incidence normal to the surface. Heavy ions like 56 Fe5+ produce
and corrosion properties of 316 stainless steels has not been sys- large displacement cascades that can be considered roughly repre-
tematically investigated. sentative of cascades produced by fast neutrons [31]. Irradiation by
The main goal of this work is to deepen the understanding of heavy ions was used in order to reach high doses in short times
such interactions by investigating the impacts of nanostructuration without any activation of the samples. The damage prole was
combined with irradiation on the hardening mechanisms together estimated using the S.R.I.M. software (Quick damage calculation
with the corrosion properties. Nanostructuration was obtained by option with a displacement energy threshold of 40 eV [32,33]). The
a High Pressure Torsion (HPT) procedure. The austenitic stainless maximum level of damage (damage peak) in term of displacements
steel, the methodology to obtain nanostructured and irradiated per atoms (dpa) is located at 2 m below the surface. The samples
samples, and experimental setups are presented in Section 2. were irradiated with a total average uence of 1.4 1016 ions/cm2 .
The evolution of the microstructure with irradiation, nanostruc- The average dose in the rst micrometer below the surface is about
turation, and corresponding experimental results of hardness and 2.7 dpa.
corrosion are given in Section 3. Finally the results are discussed in
Section 4, supported by electrochemical impedance spectroscopy 2.2. Metallurgical and electrochemical analysis
analysis.
Microstructural observations were performed thanks to con-
ventional metallurgical setups. The grain size distribution and
2. Material properties and experimental methods crystallographic texture of coarse grain specimen were analysed
by Scanning Electron Microscopy (SEM) coupled with Electron
2.1. Nanostructuration and irradiation procedures Backscatter Diffraction (EBSD) analysis. Microstructural observa-
tions of nanostructured samples were carried out by Transmission
A commercial extruded 316 stainless steel with a weight percent Electron Microscopy (TEM) with a JEOL 2010F microscope operat-
composition (Fe0.03C17Cr12.9Ni2.36Mo1.72Mn0.41Si0.01 ing at 200 kV. Plane view thin foils were prepared by mechanical
P0.03S) was used as starting material. Grain renement was polishing down to 80 m. They were then electropolished using a
achieved by severe plastic deformation using a HPT technique standard double-jet procedure. Cross section TEM thin foils were
[30]. Quenching at 1050 C for 1 h followed by air cooling was prepared either by FIB (Focused Ion Beam Helios Nanolab 660,
systematically performed before HPT processing. Discs samples 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 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.
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. 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
model alloys, previous results [40,41] report Cr concentration at irradiated samples. The rst is located near the surface layer and
GB higher than the bulk concentration. EDS proles through GB of is representative of oxidation of the extreme surface issued of
a mill annealed 316 steel also show Cr enrichment [6]. In all these irradiation procedures [51]. The hardness values considered in
papers, the reported Cr concentration at GB is about 15 at.% higher the following are therefore those obtained for depth greater than
in the bulk, which is in agreement with our observations. How- 50 nm [52]. The second peak is located at about 180 nm from the
ever, such tendency is not systematically depicted. For instance, surface for the coarse grained alloy and about 220 nm for the
neither enrichment nor depletion is reported in Refs. [40,42,43]. In nanocrystalline material. Hardness peak values are strongly dis-
particular, Tomozawa et al. [43] have shown by APT that neither persive, especially for coarse grain specimens, depending on the
enrichment nor depletion is observed in various random GBs and local surface state of the grains. The mean hardness (computed
3 GBs. As far as UFG steels are concerned, no difference between with the results of 25 distinct indents) is then measured at 1 m of
the Cr concentration at GB and in the matrix is found in a 316 stain- depth because it is representative of the intrinsic properties of the
less steel nanostructured by HPT at room temperature [44]. Thus, steels. The obtained values are reported in Fig. 6(a). As expected
in the present work, the processing temperature and subsequent and in accordance with previous results [53], nanostructurating
annealing (performed at 450 C) could be the main reason of the Cr by HPT strongly increases the in plane hardness. Also, the hard-
enrichment at GBs [45,46]. ness of the coarse grain material is signicantly affected by the
After irradiation, 17 GBs were intercepted during APT analysis. irradiation (leading to a gap of 0.86 GPa on average). However,
25% of them are still enriched in Cr, 10% exhibit at Cr concentration it is interesting to note that the hardness of the nanocrystalline
proles and the majority (65%) is depleted in Cr. As displayed in material is almost unchanged after irradiation, standing near 6 GPa,
Fig. 3(b), the Cr concentration prol through depleted GB does not with a small variation of 0.32 GPa. These results are consistent
exhibit a W shape. The minimum Cr concentration at GB is about with Vickers microhardness experiments (Fig. 6(b)), performed at
5 at.% lower than the matrix level in the depleted GB. Radiation corresponding depths two or three times higher than nanoinden-
induced depletion of Cr at GB in austenitic stainless steels or model tation ones. The increase in hardness is associated with an increase
alloys after irradiation with neutrons [41,47,48], protons [40,41,49] in elasticity modulus, as shown in Fig. 6(c). Complementary local
or heavy ions [26] has been widely reported. For a similar irradia- observation of nano-indents by confocal microscopy shows that
tion dose, a depletion of about 5 at.% is generally reported in coarse residual indent depths are greater in coarse grains than in nanocrys-
grain austenitic stainless steel. In coarse grain 316 alloy, segregated talline materials (see Supplementary material 1). This indicates a
loops and solute clusters are observed after irradiation with heavy large elastic springback connected to the hardening induced by
ions at similar dpa level [50]. Such features were not detected by nanostructuration, in good agreement with elastic modulus values.
APT in our nanocrystalline steel. TEM observations conrmed that Pile-up effects also appear around residual indentation imprints for
there are no visible defects or precipitates in nanograin samples irradiated and nanocrystalline materials, giving a lower accuracy in
after irradiation (Fig. 4). Such reduced irradiation damage could the estimation of hardness and elastic parameters [54].
be attributed to the increased proportion of sinks for point defects The high hardness depicted in nanocrystalline sample is then
at grain boundaries [44], despite the fact that a local depletion in linked to the high proportion of GBs that act as barrier for disloca-
chromium is evidenced. Irradiation could lead to a limited coars- tions. However, in irradiated materials, the high hardness is rather
ening of the grain (median diameter of 210 nm against 172 nm for connected to crystalline defects (like dislocation loops) resulting
unirradiated samples). However, this small discrepancy could be from the recombination of irradiation defects. There is little change
also due to a lack of statistic and a difference in the grain size related 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. 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.
3.3. Corrosion resistance in 3 wt.%NaCl solution Error bars give the standard deviation from 20 measurements.

Open circuit plots Eoc = f(t) are displayed in Fig. 7 for the four Examples of potentiodynamic polarization curves measured
specimens. After a short transient evolution depending on the after 15 h of immersion are given in Fig. 8 and the corresponding
initial surface state, open circuit potential of nanostructured sam- relevant parameters are listed in Table 1 (mean values obtained
ples rapidly stabilizes around 0.14 V/SCE for both irradiated and on ve distinct experiments). All samples exhibit more or less the
pristine states. Concerning coarse grain specimens, a small differ- behaviour of a passive material in a potential range L [Ep ; Epit ] with
ence exists between irradiated and unirradiated states after 15 h of Ep the passivation potential and Epit the pitting corrosion potential.
immersion (0.06 V/SCE against 0.11 V/SCE, respectively). How- Moreover, very slight values of the corrosion current density Jcor
ever, complementary experiments show that a common value of are obtained whatever the sample, well below 1 A/cm2 , indicat-
0.12 V/SCE is reached for the two states after 72 h of immersion for ing that the passivation of the surface is present for all specimens
coarse grain specimens, against 0.145 V/SCE for nanograin sam- after 15 h of immersion.
ples. Nanocrystalline 316 is therefore slightly less noble in open For coarse grain non irradiated specimens, corrosion (Jcor ) and
circuit conditions than coarse grain materials in 3 wt.% NaCl elec- passivation current density (Jp ) values are in agreement with results
trolyte, independently of the state (as received or irradiated). found in the literature [3,21]. Irradiation strongly deteriorates the
E. Hug et al. / Applied Surface Science 392 (2017) 10261035 1031

Table 1
Electrochemical parameters obtained from the polarization tests.

State Sample Eoc a (mV/SCE) Ecor (mV/SCE) Jcor (A/cm2 ) Rpol (k.cm2 ) Jp (A/cm2 ) Ep (mV/CSE) Epit (mV/CSE) L (mV/CSE)

Non irradiated Micro 120 73 0.34 37.01 0.96 133 282 149
Nanob 145 135 0.19 69.43 1.23 80 79 159
Irradiated Micro 120 47 0.55 22.95 1.83 7 183 190
Nanoc 145 158 0.17 73.38 1.47 91 59 150
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 .

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
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 was related to carbides precipitation at the conditions of irradiation
and 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
passive behaviour in this grain size range (Fig. 8(a)). Ecor remains higher value of Jp is closely related to a weaker pitting resistance
close to the same value, considering the natural dispersion of exper- of the nanocrystalline material because the higher density of grain
iments, but the good passivation state observed on pristine 316 boundaries increases the number of energetic unstable sites on the
is dramatically degraded when irradiated samples are considered. surface [20]. Metastable pits nucleate at higher rate on nanocrys-
Irradiation leads to a pseudo- passivation state in a lower potential talline surface samples, and grow up until being energetically stable
range, together with Jp values higher by a factor two. [57].
The nanostructuration of the stainless steel leads to the transla- HPT nanocrystalline samples exhibit a higher polarization resis-
tion of all values of potential towards less noble values (Fig. 8(b)). tance Rpol for both irradiated and unirradiated conditions just after
The passive potential range L is of the same order of value immersion of the fresh surfaces in 3 wt.% NaCl. The corresponding
(around 150160 mV/SCE) and Jp increases from 0.96 A/cm2 to value of Jcor is weak and the activation energy related to dissolu-
1.23 A/cm2 . A weak secondary passivity range is also system- tion mechanisms is more important, in accordance with previous
atically depicted for nanocrystalline specimens. Irradiation has results devoted to nickel [18,58]. The appearance of kinetic block-
a moderate inuence on the corrosion behaviour of nanostruc- ages on the growth mechanisms implies that the passive layer is
tured samples. All the representative corrosion parameters are not able to develop efciently for nanostructured samples. These
in the same range for both sample conditions (Table 1). The blockages are closely linked to the existence of compressive elastic
polarization resistance Rpol of the fresh surface is much higher microstrains in the surface region, in interconnection with the nec-
for the nanocrystalline material close to the corrosion potential essary geometrical dislocation substructure, as evidenced by the
(69 k cm2 against 37 k cm2 for coarse grains). Rpol moderately corresponding higher hardness level. These elastic microstrains can
decreases for irradiated coarse grain samples, and is grossly con- be benecial to corrosion resistance as for instance for electrode-
stant for nanostructured states. posited nanostructured nickel [18], or provide detrimental effects
Pitting corrosion resistance was measured by imposing a current as in this work. These two different processing routes could be origi-
density of 102 mA/cm2 for 2 h and observing the etched surface nating the opposite effects of nanostructuration but more generally
by traditional light microscopy. Representative pitting surfaces are elastic stresses play an important role on the oxidation behavior. A
shown in the photographs of Fig. 8. Complementary analysis by straightforward relation therefore exists between mechanical and
immersion for 24 h in a 6% FeCl3 solution (following ASTM G48 electrical properties of the free surfaces. When samples are just
procedure [22,55]) at a constant temperature of 30 C, followed by immerged in the electrolyte, the initial activity of the fresh surface,
a weight-loss measurement, completed the pitting analysis. The which is necessary for a good growth of the passive layer, is not suf-
total area of corrosion pits in irradiated coarse grain material is cient in small grain size samples. This leads to the development of
much larger than for others samples, consisting of very numer- a less good passive layer in terms of corrosion resistance, despite a
ous pits of small sizes. The corresponding corrosion rate is about local enrichment in chromium at grain boundaries, as indicated by
two/three times higher than for the non-irradiated state. Pitting 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 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
Fig. 9. Effect of nanostructuration and irradiation on the Nyquist plots of 316 stain- reduce signicantly the electrical conductivity of polycrystalline
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
metals [67,68]. This leads to a degraded passive layer, which in turn
obtain the best ts plotted in red (For interpretation of the references to colour in decreases the overall corrosion and pitting resistance of the mate-
this gure legend, the reader is referred to the web version of this article.). 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.
The impact of irradiation combined with nanostructuration on Besides, as the free surface of irradiated samples is also a possible
the initial electrical properties of surfaces of 316L stainless steel can efcient sink for irradiation defects, the irradiation process could
be successfully studied by EIS measurements. They were performed also eventually lead to a slight Cr depletion near the surface. Such a
after 15 h of immersion in open circuit conditions. Information on local change of the chemical composition might also affect the cor-
the resistive and capacitive properties of the passive layer can be rosion behavior. Some additional experiments are planned in the
obtained by Nyquist plots of impedance spectra (Fig. 9). All tests near future to quantify this effect and check this hypothesis. The
exhibit the same typical capacitive semi-loop shape which cov- enrichment of Cr at GB due to annealing of nanostructured samples
ers the entire frequency range [1 mHz10 kHz]. The existence of (prior to irradiation) delays the loss of Cr during irradiation, and
a single capacitive loop is representative at rst approximation to thus shows better corrosion resistance compared to coarse grain
a charge transfer resistance in parallel with a double-layer capaci- sample. The corrosion resistance of the nanostructured samples is
tance [59]. A simple Randles equivalent circuit as described in the less affected by the chromium depletion provoked by irradiation
second Supplementary material is often sufcient in this case to because their passive layer is already partly damaged by the HPT
represent the electrical interface between the electrode and the process.
electrolyte. However, in our study, the electrical properties of the
interface between the electrode and the aqueous solution are bet-
5. Conclusion
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,
The coupled inuence of the nanostructuration and irradiation
R is the electrolyte resistance and the respective inuence of the
passive metallic surface layer (represented by the resistance RP on the corrosion resistance of metals and alloys mainly depends
and the constant phase element CP ) and the electrochemical layer on the nature of the electrolyte and the process route with which
between the electrode outer surface and the electrolyte (charge nanostructuration has been obtained. In this work, nanostructur-
transfer resistance RCT and double layer capacity CDL ) can be ana- ing stainless 316 austenitic steel was successfully performed by a
lysed [59,61,62]. Best tting for the impedance data are obtained high pressure torsion procedure, giving a mean grain size of 172 nm
with numerical values given in Table 2 and are plotted in continu- against 65 m for the as-received material. The impact of this pro-
ous red lines in Fig. 9. cess combined with an irradiation by 56 Fe5+ ions of 10 MeV energy
R remains constant and low whatever the sample, indicat- on the hardness and corrosion resistance of the surface was investi-
ing the good reproducibility of the experimental set up. RCT and gated. The following conclusions can be drawn from this research:
CDL are representative of the kinetic blockages associated with
the diffusion mechanisms of ions through the diffusion Nernst Enrichment in chromium is depicted at a large majority of the
layer [63]. It can be observed that the electrical properties of the grain boundaries for nanostructured and annealed samples and
electrochemical double layer play a less important role than the a depletion is evidenced at most of the GBs after irradiation of
corresponding properties of the metallic passive layer: RCT is always these samples. A slow grain growth is observed after irradiation.
negligible compared to RP and CDL is weakly impacted by the Nanostructuration strongly increases the hardness both in sur-
nanostructuration and the irradiation. Nanostructuration moder- face and core of material. Nanocrystalline specimens are only
ately decreases the resistance RP of the passive layer and CP remains weakly affected by irradiation in terms of hardening.
grossly constant around 2535 F/cm2 , whatever the initial state The polarization resistance of nanocrystalline materials is higher
of the samples. However, for each metallurgical stage of the 316 and the corresponding corrosion current density lower. The pas-
steel (nanostructured or coarse grain specimens), the irradiation sive layer is not able to develop efciently for low grain size
strongly increases the value of RP , by a multiplicative factor of samples. The degradation of the kinetic properties of growth of
57. This constitutes the main result of the EIS measurements: the this layer could be due to the existence of compressive elastic
irradiation has a denitive impact on the electrical resistance of microstrains in the surface area.
the passive layer. Fresh surfaces of the irradiated austenitic steel The irradiation procedure has a strong impact on the electrical
are more electrically insulating and the passive lm is less able resistance of the passive layer of austenitic 316 stainless steels.
1034 E. Hug et al. / Applied Surface Science 392 (2017) 10261035

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Acknowledgments
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cavitation-annealing, Mater. Lett. 60 (2006) 24192422.
The authors acknowledge the nancial support of the french [22] P. Chui, K. Sun, C. Sun, X. Yang, T. Shan, Effect of surface nanocrystallization
Agence Nationale de la Recherche (ANR), through the program induced by fast multiple rotation rolling on hardness and corrosion behavior
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Investissements dAvenir(ANR-10-LABX-09-01), LabEx EMC3 . [23] R.K. Gupta, N. Birbilis, The inuence of nanocrystalline structure and
This project received a grant from the french state managed by the processing route on corrosion of stainless steel: a review, Corr. Sci. 92 (2015)
National Research Agency through the Investissements dAvenir 115.
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Network EMIR. N. Enikeev acknowledges partial support through Part II: irradiation induced hardening, J. Nucl. Mater. 326 (2004) 3037.
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659663.
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