Corrosion Science xxx (2014) xxx–xxx

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Hydrogen absorption associated with the corrosion mechanism of 316L

stainless steels in primary medium of Pressurized Water Reactor (PWR)
Marie Dumerval a,e, Stéphane Perrin a,⇑, Loïc Marchetti b, Michel Tabarant c, François Jomard d,
Yves Wouters e
a
CEA, DEN, DPC, SCCME, Laboratoire d’Étude de la Corrosion Aqueuse, F-91191 Gif-sur-Yvette, France
b
CEA, DEN, DTCD, SECM, Laboratoire d’étude du Comportement à Long Terme des matériaux de conditionnement, F-30207 Bagnols-sur-Cèze, France
c
CEA, DEN, DPC, SEARS, Laboratoire d’Ingénierie des Surfaces et Lasers, F-91191 Gif-sur-Yvette, France
d
CNRS, Groupe d’Etude de la MAtière Condensée, F-78035 Versailles, France
e
Université de Grenoble, SIMaP, F-38402 Saint Martin d’Hères, France

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

Article history: Samples of 316L were exposed at 325 °C to PWR primary water labelled with deuterium and oxygen 18.
Received 26 February 2014 The SIMS and GD-OES analysis has revealed the presence of deuterium in the internal oxide layer and in
Accepted 19 April 2014 the underlying alloy. Two-stage corrosion experiments have shown that the oxygen and hydrogen trans-
Available online xxxx
port in the oxide layer is not coupled and that the short-circuit diffusion coefficient of 18O in the oxide
scale: Dsc = (9 ± 1)1017 cm2 s1. These results are used to propose a mechanism describing the anionic
Keywords: growth of the protective oxide layer and the concomitant adsorption of hydrogen in the alloy.
A. Stainless steel
Ó 2014 Elsevier Ltd. All rights reserved.
B. SIMS
C. Oxidation
C. Reactor conditions
C. Hydrogen absorption

1. Introduction with a composition close to (Ni,Fe)Fe2O4. These two layers are

Austenitic stainless steels are commonly used for the construc-
tion of structural elements in nuclear reactors. Although these
materials exhibit corrosion resistant properties, some stress corro-
sion cracks on baffle and bolts have been observed since the eight-
ies. In PWR the austenitic stainless steels are exposed to primary
medium, which is an aqueous solution containing dissolved hydro-
gen at a temperature between 290 °C and 325 °C. These materials
are subjected not only to a corrosive environment and mechanical
and thermal stresses but also to the neutron flux emitted by the
reactor core, this can lead to possible damages by stress corrosion
cracking (SCC) possibly assisted by irradiation (IASCC). Oxide film
rupture is the first step in this corrosion process and thereby the
nature and the structure of oxide scale formed on SS 316L are
key parameters relative to SCC initiation.
In literature, the oxide scale formed is described as having a
duplex structure with an inner layer of Cr-rich oxide and an outer
layer rich in Fe; both evidence a spinel structure [1–8]. The internal
layer is described as continuous and protective and is composed of
(Ni,Fe)(Fe,Cr)2O4 whereas the external layer is made of crystallites
⇑ Corresponding author.
E-mail address: steph.perrin@cea.fr (S. Perrin).
formed by different mechanisms. Some authors propose an anionic
growth [6,9,10] linked to oxygen diffusion at the grain boundaries
of the oxide for the inner oxide layer [10] whereas for the external
layer, a cationic diffusion followed by a release in the medium and
precipitation processes has been proposed [2,10]. Besides the
nature and the structure of the oxide scale, the oxide growth mech-
anism could also play an important role in SCC initiation.
In the case of alloy 600 exposed to simulated PWR primary
medium, Jambon et al. [12,13] have isotopically labelled hydrogen
and oxygen atoms, using deuterium and oxygen 18, coming from
water molecules or dissolved hydrogen in order to investigate
the link between concomitant hydrogen absorption and the corro-
sion processes. SIMS (Secondary Ion Mass Spectrometry) analysis,
reported in these studies, highlighted that: (i) the hydrogen uptake
during corrosion processes is associated with the reduction of
water molecules and (ii) the transport of O and H across the oxide
scale is through the formation of a hydroxide ion, thereby initiating
a link between hydrogen absorption and oxidation kinetics.
Some authors studied the effect of the dissolved hydrogen con-
centration in PWR primary media on SCC initiation and propaga-
tion [14–17]. In all cases, they observed an effect of dissolved
hydrogen concentration on crack growth rate and on grain bound-
ary fracture ratio, on the mechanical stress and on electrochemical

http://dx.doi.org/10.1016/j.corsci.2014.04.025
0010-938X/Ó 2014 Elsevier Ltd. All rights reserved.

Please cite this article in press as: M. Dumerval et al., Hydrogen absorption associated with the corrosion mechanism of 316L stainless steels in primary
medium of Pressurized Water Reactor (PWR), Corros. Sci. (2014), http://dx.doi.org/10.1016/j.corsci.2014.04.025
2 M. Dumerval et al. / Corrosion Science xxx (2014) xxx–xxx

behaviour. The aqueous dissolved hydrogen concentration, which Table 2

plays a role on corrosion processes, could also affect the hydrogen Experimental conditions used to make the deuterided Zy-4.

uptake by the alloy. That is why this study aims to investigate the Medium [D2SO4] = 0.5 M
possible links between hydrogen absorption and oxidation Temperature 25 °C
mechanisms in the case of austenitic stainless steels exposed to Time 95 h
Current density 7.5 mA cm2
PWR primary medium. For that purpose two complementary
characterization methods, coupled with isotopic labeling, have
been used in this work:
1.5
(a) SIMS in order to investigate the distribution of hydrogen and D peak
oxygen through the oxide scale,
H peak
(b) GD-OES (Glow-Discharge Optical Emission Spectrometry) in
order to characterize hydrogen absorption in the alloy
underlying the oxide. 1

Intensity (a.u.)
2. Materials and methods

2.1. Sample preparation

0.5
2.1.1. Corrosion experiment sample preparation
The elementary composition of 316L austenitic stainless steel
used in this study is given in Table 1. Plates of this alloy were
heated at 1050 °C for 2 h, quenched in water, and then tempered
for 15 h at 300 °C. These plates were then cut by electro-discharge
machining into 20 mm  10 mm  2 mm coupons. Coupon edges 0
121.4 121.45 121.5 121.55 121.6 121.65 121.7
were mechanically ground using 400 grit SiC paper. All sample
faces were mechanically polished up to 0.04 lm colloidal silica Wavelength (nm)
suspension. Sample surfaces showed a mirror aspect with a surface
Fig. 1. GD-OES emission spectrum obtained on the deuterided Zy-4 reference
roughness (Ra, arithmetic mean value of the measured profile), sample (see Section 2.1.).
estimated by interferometry, of 13 nm.

2.1.2. Preparation of reference sample for GD-OES configuration Table 3

In order to detect deuterium by GD-OES, the spectrometer
needs to be shifted on D wavelength. In order to do this calibration,
a sample with a high concentration of deuterium is needed. The
experimental conditions to produce this sample, zircalloy-4
(Zy-4) with zirconium deuteride dispersed, are reported in Table 2
[18]. These conditions involve a process of cathodic charging
allowing the deuterium to be absorbed from the solution to the
metal. This process allows absorption of deuterium and creates a
stable phase: zirconium deuteride. It is therefore easier to shift
the spectrometer on the D wavelength thanks to the high intensity
of emission from D as shown in Fig. 1.
2.2. Corrosion experiments
2.2.1. One-stage corrosion experiments
The 316L specimens were exposed to either natural primary
medium (with a natural isotopic abundance) or deuterated pri-
mary water (in which the water was labelled with deuterium
under the form D2O with 99% of D) in a titanium static autoclave.
The experimental conditions are reported in Table 3. To study (i)
the interest of deuterium compared to hydrogen during GD-OES
analysis and (ii) the interest of liquid nitrogen preservation
between the corrosion experiment and the analysis, the coupons
were exposed for 130 h whereas the other sample was exposed
for 600 h in primary water. A previous study [12] has shown that
in the case of alloy 600 samples exposed to PWR primary medium
hydrogen absorption is mainly due to the dissociation of water
molecules during the corrosion process. It is supposed that
Experimental conditions used to simulate the primary medium.
Temperature 325 °C
Pressure 130 bar
Boron (H3BO3) 1000 wt. ppm
Lithium (LiOH) 2 wt. ppm
H2 (pressure) 0.28 bar at 325 °C
Calculated pH 7
hydrogen absorption by 316L during its exposition in PWR primary
water proceeds in a similar way that is why deuterium was only
used in this study as a hydrogen marker in water molecules.
After exposure to primary medium, the oxidized samples were
stored in liquid nitrogen until characterization. The storage of
samples in liquid nitrogen is necessary in the case of D loaded
austenitic steels [19] and is used, in this study, as a precaution in
order to prevent possible hydrogen isotopes diffusion or desorp-
tion during aging periods at room temperature [20].
2.2.2. Two-stages corrosion experiments
The objective of these experiments is to study the transport of
hydrogen and oxygen in the internal oxide layer in order to better
understand its formation mechanism and its link with the hydro-
gen absorption by the underlying alloy. The samples of 316L were
pre-oxidized for 600 h in a titanium static autoclave in natural pri-
mary water (experimental conditions presented in Table 3). These
samples were then exposed to PWR primary medium isotopically
labelled either with 18O (20%) or D (99%) to respectively study
the oxygen or hydrogen transport. The duration of this second

Table 1
Chemical composition (wt.%) of 316L alloy.

Fe Cr Ni Mo Mn Cu Si Co N P C S
68.18 16.6 10.2 2.21 1.82 0.43 0.3 0.11 0.056 0.033 0.03 0.028

Please cite this article in press as: M. Dumerval et al., Hydrogen absorption associated with the corrosion mechanism of 316L stainless steels in primary
medium of Pressurized Water Reactor (PWR), Corros. Sci. (2014), http://dx.doi.org/10.1016/j.corsci.2014.04.025
 M. Dumerval et al. / Corrosion Science xxx (2014) xxx–xxx
stage is limited to 16 h in order to limit the oxide growth and
measure a diffusion coefficient [21]. At the end of the corrosion
experiments, the samples were stored in liquid nitrogen until their
characterisation.
2.3. SIMS analysis
SIMS was used to determine the deuterium and oxygen profiles
in the oxide. This analysis was performed with a CAMECA IMS 7f
device. A primary Cs+ beam (5 nA) is sputtering a crater over
150  150 lm2, and the analysed area is limited to a 33 lm
diameter circle via a system of diaphragms.
The difference in ionization yield between the oxide and the
alloy has for consequence a strong decrease of the intensity at
the oxide/alloy interface and makes it impossible to draw conclu-
sion about the origin of variations in H and D signals near the
oxide/alloy interface [12]. Consequently, GD-OES has been used
to study H isotope absorption in the alloy underlying the oxide
scale.
2.4. GD-OES analysis
In order to study the hydrogen absorption by the alloy, GD-OES
analysis was performed. Experiments were done using a Horiba
Jobin Yvon GD-Profiler 2. A polychromator with 23 fixed optical
lines was installed and a monochromator was used to have the
choice of a new wavelength. The discharge lamp works with an
Argon partial pressure of about 800 Pa. The Cu anode diameter is
4 mm and the input power was adjusted to 40 W.
Hatano et al. have shown the possibility of both detecting and
analysing deuterium using GD-OES [22]. Their method has been
used in order to study deuterium absorption in this work. A
method in several steps was established to obtain the profile of
metallic elements, deuterium, and hydrogen in the sample.
(i) The polychromator was shifted on the deuterium wave-
length (121.517 nm) and a profile of D was obtained in these
conditions. A sample of deuterided Zy-4 (see Section 2.1.2)
was used to configure the system.
(ii) Then, the polychromator was adjusted to the hydrogen
wavelength (121.586 nm) with a certified standard (NIST
1155). A profile of hydrogen and metallic elements was
made in these conditions.
During the two stages, a Cr profile was made with the mono-
chromator (shift on the Cr wavelength: 425.439 nm) to be sure
that the sample was homogeneous between the two analysis zone.
This second analysis technique has been employed in order to
avoid the ionization yield difference between the oxide and the
alloy, further enabling the study of the hydrogen concentration
profile in the oxide, the alloy, and at the interface.
2.5. Nuclear reaction analysis (NRA)
In order to convert the sputtering time into depth for SIMS
analysis, the oxide scale thickness has been measured by NRA. This
analysis technique allowed us to determine the quantity of oxygen
through studying the reaction, called 16O(d,p1)17O:
16 þ 17 þ
OþD  OþH
The Van de Graaf accelerator used enables the creation of a D+ beam
with an energy of 900 keV. The protons emitted by the reaction
between these ions and the oxygen present in the sample, at an
energy of 1258 keV, are collected and analysed with at an angle of
150°. To filter the backscattered deuterons, a Mylar (C10H8O4) foil
Please cite this article in press as: M. Dumerval et al., Hydrogen absorption associated with the corrosion mechanism of 316L stainless steels in primary
medium of Pressurized Water Reactor (PWR), Corros. Sci. (2014), http://dx.doi.org/10.1016/j.corsci.2014.04.025
3
with a thickness of 12 lm has been used. The oxygen calibration
was done using samples of oxidized tantalum with a known thick-
ness of Ta2O5. The nuclear reaction analyses were done at JANNuS
(Joint Accelerators for Nano-science and Nuclear Simulation) in
Saclay, France.
3. Results and discussion
3.1. Remarks about GD-OES analysis of hydrogen
Two samples of 316L were oxidised for 130 h in primary med-
ium: one in classical water H2O and one in deuterated water
D2O. The observed hydrogen signal result mainly from three
sources: the water adsorbed on different surface of the analysis
chamber (for example the glow discharge source), the condensa-
tion of water on the sample surface due to the nitrogen conserva-
tion and the most interesting part of the signal stemmed from
hydrogen absorption in the sample. Among these three separate
hydrogen sources, the two first one are highly dependent of the
analysis procedure and often lead to unreproducible results, partic-
ularly when studying materials in which the hydrogen absorption
remains weak. Then, the use of deuterium as an isotopic tracer of H
during corrosion tests, allows the isolation of the signal due to H
isotope uptake by the sample during it exposure to PWR primary
medium [12]. The hydrogen profile in both sample exposed to
classical and deuterated primary water and the deuterium profile
in the sample exposed to D2O medium are compared in Fig. 2,
and highlights the interest of using deuterium to study hydrogen
by GD-OES. A part of this hydrogen enrichment was previously
hidden by the hydrogen signal due to condensation and/or
adsorption on analysis chamber surfaces, whereas the deuterium
profile shows a well-defined peak due to absorption by the sample,
without hydrogen external sources effects.
3.2. Deuterium absorption in oxide
After 600 h of oxidation, the profiles of the main metallic
elements (iron and chromium), deuterium, and oxygen obtained
by SIMS analysis are presented in Fig. 3.
The oxygen intensity is plotted in order to show the oxide film
location. The metallic elements profiles are reported to delimit the
outer and the inner layers. This delimitation of the internal and the
external interface are marked by the dotted lines in Fig. 3 and has
0.35 2
D - Exp to D2O medium
H - Exp to D O medium
2
0.3
H - Exp to H2O medium
Intensity of D and H exposed
D 1.5
to D O medium (a.u.)
0.25
Intensity of H (a.u.)
0.2
1
0.15 H
2
0.1
0.5
0.05 H
ð1Þ
0 0
0 5 10 15 20 25
Sputter time (s)
Fig. 2. Comparison of hydrogen and deuterium GD-OES profiles recorded on 316L
stainless steel exposed 130 h to deuterated primary medium to hydrogen profile
preformed on 316L sample exposed 130 h to natural primary water.
4 M. Dumerval et al. / Corrosion Science xxx (2014) xxx–xxx

0 1000 2000 3000 4000 5000 6000 and metallic element profiles are used to localize the two layers
6
1,4 10 composing the oxide film. The delimitation of internal and external
16 interfaces is made in the same way as for SIMS profile, by the
O 5000

Intensity of Cr, Fe and D (counts/s)

1,2 10
6
reduction of Cr signal of 50%. These interfaces are marked by
dotted lines in Fig. 4. A deuterium peak appears after the chro-
Intensity of O (counts/s)

6 4000 mium peak i.e. near the oxide/alloy interface. As a consequence,

1 10
an accumulation of absorbed deuterium is observed in the alloy
5
underlying the oxide. This localization of absorbed hydrogen in
8 10 3000 the corroded sample is considered in the oxidation mechanism
D
16

proposed in Section 3.5.

5
6 10 It can be noted that, in the case of oxidised samples, coupling
2000 SIMS and GD-OES analysis allowed studying hydrogen isotopes
4 10
5 absorption not only in the oxide but also in the alloy beneath.
Indeed, during SIMS analysis, the collected signal can be strongly
5
Fe 1000 different depending on the nature of the matrix (oxide or metal)
2 10
[12]. For a given concentration of a species analysed, the signal
Cr at the metal/oxide interface collapse because of the strong depen-
0 0 dence of the ionization and/or sputtering yields on the nature of
0 1000 2000 3000 4000 5000 6000
the matrix. Therefore a slight enrichment at the interface can be
Sputter time (s)
hidden by this strong signal decay. On the contrary, the variations
Fig. 3. SIMS profiles recorded on 316L sample exposed 600 h to deuterated primary of signals due to H isotopes around the oxide/alloy interface can be
medium: intensity of the main elements versus time. From left to right, the dotted recorded accurately using GD-OES, because this type of analyse
lines highlight respectively external oxide/internal oxide and internal oxide/alloy does not involve an ionization process.
interfaces.

been determined by the reduction of Cr signal of 50%. Indeed, as 3.4. Oxygen and hydrogen transport through the oxide scale
mentioned in Section 2, the external crystallites are mainly
composed of iron and nickel whereas the inner layer is enriched SIMS profiles of oxygen and hydrogen markers (18O and D
in chromium. Thereby, the deuterium enrichment could be located respectively) after the 2-stage corrosion experiments are presented
by comparing the oxide layers. The deuterium peak appears to be in Fig. 5. The Cr intensity is used to localize the two interface by the
correlated to chromium enrichment. These results show the method presented in Sections 3.2 and 3.3. These interfaces are
deuterium is located in the inner oxide layer and could be associ- marked by dotted lines for the two kinds of experiments in the
ated with the dissociation of water molecules during corrosion Fig. 5. The localisation of this interface shows the reproducibility
processes. Moreover, deuterium does not seem to be present in between the two experiments (second sequence with 18O or D).
the external layer. It is then possible to compare the profile of 18O and D linked to
the second sequence of oxidation.
Fig. 5 shows that the 18O and D profiles in oxide scale formed on
3.3. Deuterium absorption in alloy 316L are different whereas the 16O profiles are similar. Indeed, the
18
O signal presents a characteristic diffusion profile whereas the D
Quantitative profiles of metallic elements obtained by GD-OES profile shows a plateau. This result proves that hydrogen diffusion
are presented in Fig. 4. The specimen was corroded under the same in the oxide is faster compared to oxygen diffusion. Moreover,
conditions as those used for SIMS analysis. The oxygen intensity these profiles demonstrate that hydrogen and oxygen transports,

70 0.2 12 0.1

Fe
60
Ni
10 0.08
0.15
% Weight (Fe, Cr, Ni, O)

50
Intensity of D (a.u.)

Intensity of D (a.u.)
% Weight of Ni

8 0.06
40
0.1
30 D
6 0.04

20 Cr
0.05
4 0.02
Ni
10 D
O
0 0 2 0
0 5 10 15 20 25 30 0 5 10 15 20 25 30 35 40
Sputter time (s) Sputter time (s)

(a) (b)
Fig. 4. Quantitative profiles of metallic elements and oxygen (left axis) and qualitative one of deuterium (right axis), obtained by GD-OES on 316L sample corroded 600 h in
deuterated primary medium, and plotted against the sputtering time.(a) General graph. From left to right, the dotted lines highlight respectively external oxide/internal oxide
and internal oxide/alloy interfaces. (b) Zoom of (a) on the Ni and the D.

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 M. Dumerval et al. / Corrosion Science xxx (2014) xxx–xxx 5

6
0.04 1.5 10 6
1.6 10
16

Intensity of O and (Cr x 750) (counts/s)

16 2500 O
6 O 0.035
Intensity of O and (Cr x 790) (counts/s)

1.4 10

Intensity of D (counts/s)
6
1.2 10 0.03

Concentration of O
2000 D

16
1 10 6
6 Cr
1 10 0.025

18 1500
8 10
5 O 0.02

6 10
5 Fit 0.015 1000 5

18
5 10
16

5
4 10 0.01
500
2 10
5
0.005 Cr

0 0 0 0
0 20 40 60 80 100 120 140 0 20 40 60 80 100 120 140
Depth (nm) Depth (nm)

(a) (b)
Fig. 5. SIMS profiles, as a function of sputtering time, of the 18O and D distributions through the oxide scale formed during 2-stages (600 h + 16 h) corrosion experiments
leaded on 316L exposed at 325 °C to primary medium, isotopically labelled with 18O (a) or D (b) during the second stage. From left to right, the vertical dotted lines highlight
respectively external oxide/internal oxide and internal oxide/alloy interfaces. The black dashed line exhibits the fit of 18O concentration profile in the internal oxide layer,
according to Eq. (2).

through the oxide scale formed on 316L exposed to PWR primary
environment are probably not coupled in a single molecule. These
results differ from those obtained by Jambon et al. [13] in the case
of alloy 600 exposed to primary medium, in which a concomitant
diffusion of H and O in the oxide layer is reported, involving an
hydroxide ion in substitution in the anionic sublattice. Even if
the conditions of oxidation are the same between the two papers,
the materials, their microstructure and their preparation are differ-
ent. In Ref. [13], the specimens are single crystals like alloy 600,
and the samples are electro-polished. These differences can lead
to the formation of an oxide with transport properties which can
be different than those obtained in this study.
As it can be seen in Fig. 5a, the oxygen diffusion coefficient is
determined in the internal oxide layer only assuming a short-
circuit diffusion regime (C-regime) [23]. The oxide thickness,
determined by NRA, is equal to 43 nm and corresponds to the first
part of the profile until the oxide/alloy interface (evidenced by a
50% reduction of Cr signal). Furthermore, the total eroded depth
was determined by profilometry. These two measurements allow
for the conversion of the sputter time to depth both in the oxide
and in the alloy. Then, the 18O concentration profile is fitted
between 10 and 40 nm (corresponding to the internal oxide layer
in Fig. 5) with a C-regime equation modified to exclude the
external oxide scale:
 
x  lext
CðxÞ ¼ K erfc pffiffiffiffiffiffiffiffiffi
2 Dsc t
18
where C(x) is the
Ið OÞ 18
CðxÞ ¼
Ið18 OÞ þ Ið16 OÞ
K is a constant depending on the tracer concentration at the
surface and on the short circuit density, x is the recalculated
depth, lext is the external oxide thickness, Dsc the 18O short-circuit
diffusion coefficient and t the duration of the second sequence.
The value of short-circuit diffusion coefficient Dsc obtained is
(9 ± 1)1017 cm2 s1. This value is in the same order of magni-
tude than those reported in the literature for oxygen diffusion
in internal oxide scale formed on Ni-base and Fe-base alloys
during their exposure at 325 °C in primary water (cf. Table 4).
Table 4
Values of oxygen diffusion coefficients, in the internal oxide scale formed on Ni-base
and Fe-base alloys during their exposure at 325 °C in primary water, reported in the
literature.
Alloy Diffusion coefficient (cm2 s1) Refs.
316L 3  1016 [10]
A-690 2  1017 [24]
A-600 5  1017 [13]
According to deuterium profile which corresponds to a plateau
in the oxide, it is not possible to determine the diffusivity of D
on the basis of these experiments. Indeed, this levelling off is
characteristic of hydrogen accumulation in the oxide rather than
a diffusion profile in the oxide scale.
3.5. Links between hydrogen absorption and oxidation mechanism
during corrosion processes of 316L stainless steels in PWR primary
media
The localization of absorbed deuterium in 316L alloy, after
exposure to PWR primary medium, was investigated by SIMS and
GD-OES in the Sections 3.2 and 3.3. This absorption of hydrogen
(marked by deuterium) can be explained by the dissociation of
water molecules during oxidation. In the following paragraph,
ð2Þ interest is mainly devoted to propose a mechanism of the inner
oxide growth taking into account the link between hydrogen
O concentration defined as: uptake and corrosion of the alloy. The inner oxide is considered
to be a FeCr2O4-type spinel [1,2,4–6]. The notation hhAii refers to
ð3Þ the element A in solid solution in the 316L alloy. This mechanism
is written according to Kröger–Vink notations [25] for the point
defects description and defined:
(a) the adsorption of water molecules at the surface
(b) the internal oxide growth supported by OXO et Hi diffusion
through the oxide and uphill diffusion of oxygen vacancies
(c) the absorption of hydrogen in the alloy.
The reactions taking place at the solution/passive film interface
are:

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6 M. Dumerval et al. / Corrosion Science xxx (2014) xxx–xxx
(a) Water adsorption
H2 O þ s ¡ H2 O  s
(b) Oxygen vacancy consumption and water molecules dissoci-
ation, considering that the absorption site s is the same for
water molecules and protons
H2 O  s þ VO þ s ¡ OXO þ 2Hþ  s
(a) Absorption of a part of protons produced by water dissocia-
tion in the oxide
Hþ  s ¡ Hi þ s
(d) Proton reduction
þ 0
H  s þ e ¡ 1=2 H2 þ s
OXO and Hi
diffuse from the oxide/solution interface to the oxide/
alloy interface whereas VO diffuses in the opposite direction.
The reactions at the oxide/alloy interface are:
(e) Oxide growth
hhFeii þ 2hhCrii ¡ 2CrXCr þ FeXFe þ 4VO þ 8e0
(f) Hydrogen absorption by the metal
Hi þ e0 ¡ hhHii
Two scenarios could explain the hydrogen accumulation beneath
the oxide/alloy interface as seen in Fig. 4.
This accumulation could be attributed (i) to a slower diffusion
of hydrogen in 316L stainless steel than in the oxide scale or (ii)
in the case of faster hydrogen diffusion in the alloy, to hydrogen
trapping in the alloy underlying the oxide scale.
Indeed, the external layer is formed via a cationic diffusion pro-
cess through the internal layer [2,6,10] and the diffusion of Fe and
Ni in the oxide implies the injection of vacancies in the alloy
beneath the oxide/alloy interface. The area immediately under
the oxide/alloy interface is consequently a zone where hydrogen
could be trapped in vacancies [26]. Some authors have observed
nickel enrichment in the alloy underlying the oxide [5–11]. Kruska
et al. [27] observed, by Atom Probe Tomography, a segregation of
ions with a ratio (m/z) of 59 Da in the Ni-enriched regions and
expected that this mass-to-charge ratio is for (NiH)+1. They hypoth-
esize that H could be trapped by dislocations or vacancies in the
Ni-rich region. Fig. 4(b) confirms, on a global scale, this supposition
because it shows that the enrichment of Ni is correlated to that of
deuterium. The oxidation mechanism seems to create an area
enriched in Ni and H trapped by defects due to vacancy injection
by cationic diffusion.
Whatever the origin of this H accumulation in the alloy under-
lying the oxide scale, it is another evidence of the difference
between the H uptake mechanisms during corrosion of Ni-base
or Fe-base alloys in PWR primary media. In the case of Ni-base
alloy, the concomitant diffusion of O and H through the protective
oxide scale [13] implies this scale to act as diffusion barrier for H
absorption and consequently to play a role in rate determining
steps of H uptake kinetics. Conversely, in the case of diffusion
through the oxide scale formed on 316L stainless steel, O and H
transport is mainly not coupled, resulting in a faster diffusion of
H in the oxide, and this last step consequently do not play a deter-
mining role in kinetics of hydrogen absorption in this case.
The trapping of hydrogen in the alloy directly beneath the oxide
layer could play a role, at a local scale, on mechanical properties of
the metallic phase, due to hydrogen embrittlement mechanisms.
Please cite this article in press as: M. Dumerval et al., Hydrogen absorption associated with the corrosion mechanism of 316L stainless steels in primary
medium of Pressurized Water Reactor (PWR), Corros. Sci. (2014), http://dx.doi.org/10.1016/j.corsci.2014.04.025
This type of local effect of absorbed hydrogen applied to a crack
tip might affect the SCC processes.
ð4Þ It can also be remarked that a parallel can be establish between
(i) the differences of hydrogen transport mechanisms trough the
oxide formed on Ni-base and Fe-base alloys exposed to primary
medium and (ii) the differences between these two alloys regard-
ing the role of aqueous dissolved hydrogen concentration on the
ð5Þ crack growth rate, reported by Meng et al. [16]. Then, the discrep-
ancies in H absorption mechanisms could play a role in the partic-
ular SCC resistance of each two alloys.
ð6Þ 4. Conclusion
In order to better understand how hydrogen uptake is associ-
ated to the corrosion mechanism of stainless steels in PWR, sam-
ð7Þ
ples of 316L were exposed to a simulated primary medium
where hydrogen and/or oxygen was isotopically labelled with deu-
terium and/or 18O. The complementarity SIMS and GD-OES analy-
ses were used to localize the deuterium in the oxide and the
underlying alloy.
SIMS analysis has revealed the presence of deuterium in the
internal oxide layer. Furthermore, GD-OES profiles have shown
an enrichment of deuterium in the alloy underlying the oxide as
ð8Þ well as an evolution of the profile through this alloy. SIMS analyses
performed on pre-oxidized samples have indicated: (i) a mainly
non-coupled diffusion of hydrogen and oxygen through the oxide
ð9Þ scale (ii) the absence of a limiting stage in the oxide scale for the
hydrogen absorption kinetic in the alloy. According to these
results, a possible mechanism describing the internal oxide scale
growth and the hydrogen absorption has been proposed. This
study has shown discrepancies between the H absorption mecha-
nisms concomitant to corrosion processes of SS 316L and alloy
600 exposed to PWR primary media, which could play a role in
the SCC resistance due to the possible impact of hydrogen uptake
on cracking processes.
In order to explain the hydrogen accumulation beneath the
oxide/alloy interface, additional experiments to determine the dif-
fusion coefficient of D in a spinel-type oxide will be performed and
then compared to that obtained in the alloy. Furthermore, stan-
dards are currently being manufactured in order to allow for a
quantitative analysis of deuterium by GD-OES.
Acknowledgments
The authors would thank S. Vaubaillon for the NRA analysis, H.
Badji for GD-OES analysis and D. Besnard for his help in oxidation
experiments.
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