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The Effect of Absorbed Hydrogen on the Corrosion of Steels: Review,

Discussion, and Implications

Article in CORROSION · January 2017

DOI: 10.5006/2242

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RESEARCH TOPICAL SYMPOSIUM

The Effect of Absorbed Hydrogen on the

Corrosion of Steels: Review, Discussion,
and Implications

S. Thomas,‡,* G. Sundararajan,** P.D. White,*,*** and N. Birbilis*

ABSTRACT
The presence of absorbed hydrogen (H) within pure iron and
most steels (including carbon and stainless steels) has been
found to increase their corrosion. Historically, the enhanced
corrosion of H-charged steels has been attributed to the ability of
H to destabilize the passive film formed upon the metal.
However, recent works have revealed that absorbed H can
promote Fe dissolution even in non-passivating solutions.
This indicates that the effect of H on metal corrosion could be
“intrinsic,” rather than through “extrinsic” mechanisms in-
volving solely the destabilization of the passive film. In this
review, the impact of absorbed H on the corrosion of different
types of steels has been collated, summarized, and discussed.
The influence of H on the pitting and environmentally assisted
cracking mechanisms of steels has been elaborated. Some
implications of H-assisted corrosion from an engineering
perspective have also been discussed.
INTRODUCTION
Atomic hydrogen (H) can enter metals during expo-
sure to hydrogen (H2) gas and also during corrosion,
when the hydrogen evolution reaction (HER) takes
place upon the metal surface.1-4 The HER has
several elementary steps (Equations [1] through [3]),5
including H adsorption (Equation [1]) and H re-
combination to form molecular H2 (Equation [2]).
Some adsorbed H atoms may be absorbed into the steel
lattice (Equation [3]).
M þ Hþ þ e− → MHðadsÞ (1)
MHðadsÞ þ MHðadsÞ → 2M þ H2 (2)

KEY WORDS: corrosion, hydrogen, hydrogen assisted MHðadsÞ → MHðabsÞ (3)

cracking, hydrogen-induced corrosion pitting, steel, sulfide
stress cracking
The HER occurs upon steels during corrosion
in acidic or poorly aerated environments, over-
polarization from cathodic protection, and also dur-
ing the pitting of steels.1-4 Therefore, there is a likelihood
of H absorption into steels under such conditions. In
hydrogen sulfide (H2S) containing environments, the
Submitted for publication: August 29, 2016. Revised and accepted:
January 10, 2017. Preprint available online: January 10, 2017,
absorption of H into steels is more favored because
http://dx.doi.org/10.5006/2242. Based on a presentation given at the adsorbed sulfide species serve to “poison” the H re-
the Research Topical Symposium on at CORROSION 2016 in combination reaction (Equation [2]).6-8 The H solu-
Vancouver, British Columbia, Canada.
‡
Corresponding author. E-mail: Sebastian.Thomas@monash.edu.
bility in pure Fe is reported to be between 0.001 ppm
*
Department of Materials Science and Engineering, Monash and 0.01 ppm for temperatures less than 100°C.9-12
University, Clayton, Victoria 3800, Australia. Absorbed H atoms, therefore, may spontaneously dif-
**
GE Global Research, Bangalore 560066, India.
***
Aerospace Division, Defence Science and Technology Group, 506 fuse through the steel lattice, depending upon local
Lorimer Street, Fishermans Bend 3207, Australia. concentration gradients.13-14 The introduction of H into
ISSN 0010-9312 (print), 1938-159X (online)
426 17/000073/$5.00+$0.50/0 © 2017, NACE International CORROSION—APRIL 2017

steel could also increase the mobility of dislocations
within the steel lattice,15 with dislocations themselves
serving to transport H through the steel (known as
dislocation drag).16 The presence of H has been found to
aggravate the corrosion of steels,17-20 and this aspect
is the major focus of this review.
H transport through steel usually occurs by in-
terstitial lattice diffusion, which is described by the ideal
lattice diffusivity (DL). DL relates to the activation
energy required by H to surmount the minimum energy
barrier (EM) for diffusion between different interstitial
lattice positions.21-22 For pure iron (Fe) at 25°C, DL
is approximately 1.3 × 10−5 cm2/s and EM is around
7 kJ/mol (0.07 eV/atom).22 Microstructural features
such as grain boundaries, carbides, dislocations, and
nonmetallic particles can impede interstitial lattice H
diffusion. The H atoms are “trapped” at such sites,
depending on the depth of the potential energy well and
the binding energy of H (EB) at the particular “trap”
site.21-22 The trap sites can be classified as irreversible
trap sites and reversible trap sites, depending on EB.
In the case of irreversible trapping, the depth of the
potential energy well at the trap site is too deep (EB is
too high), that at a given temperature H does not possess
enough thermal energy to surmount the barrier. The
irreversibly trapped H concentration within steels is
usually determined by thermal desorption spec-
trometry.22 For reversible trapping, the rate of H
transport through the steel depends upon the EB at
the trap site. If EB > EM, the effective diffusivity of
H through steel (DH) will be lower than DL, thus
correspondingly lowering the diffusion rate of H through
steel. The lattice H and reversibly trapped H atoms
constitute the net diffusible H atoms within the steel, at
a given temperature. The diffusible H atoms are the
resident “mobile” H atoms within the steel that can
interact with the passive film, exit the metal to
participate in interfacial reactions, and also can readily
diffuse toward crack tips under the influence of
stress-fields. The diffusible H concentration (CH,Diff)
therefore is an important parameter used to define
the resident mobile H atoms within a steel lattice.
However, besides diffusible H atoms, adsorbed H
atoms can also influence interfacial processes taking
place upon the steel surface.23 Surface H atoms that
are trapped within the first few atomic layers of a steel
surface23 could also influence the electrochemistry of
the steel.
In research studies, H is usually introduced into
steels by cathodic charging, wherein one of the steel
faces is held at a cathodic potential (for the HER to
take place) in a slightly alkaline solution. The absorbed
H atoms diffuse through the steel and emerge at the
exit faces, where they can be oxidized by applying an
anodic potential.13 The anodic current densities that
correspond to the H oxidation reaction can be used to
determine CH,Diff.13 A palladium coating is usually
applied to the steel at the entry and exit faces, so that
CORROSION—Vol. 73, No. 4
RESEARCH TOPICAL SYMPOSIUM
steel surface does not participate in any electro-
chemical reactions and basically serves as a “mem-
brane” for H permeation. Alternatively, the so-called
barnacle cell, where the absorbed H is oxidized at the
entry face itself (after H-charging), is also another
typical method (owing to its simplicity) used to deter-
mine CH,Diff.24 The absorbed H concentration and
surface H concentration cannot be readily determined
using conventional experimental techniques.
The presence of H in steel is also known to cause
hydrogen embrittlement (HE). Several mechanisms
have been proposed to rationalize the ability of
absorbed H to weaken steel, with some prominent
mechanisms being: hydrogen enhanced localized
plasticity (HELP), hydrogen enhanced decohesion
mechanism (HEDE), and adsorption induced dislo-
cation emission (AIDE).25 A comprehensive review on
the different H embrittlement mechanisms may be
found elsewhere.25-26 One may rationalize that the
presence of H within steel should also increase its
corrosion, as the activation energy for metal dissolution
should decrease with any form of decohesion in the
metal lattice. Also, H is mobile and is a strong reducing
agent.27-28 The presence of absorbed H atoms could
therefore significantly influence the corrosion and
electrochemistry of steels. This review elaborates on
the impact of absorbed H on the corrosion of different
types of steels. It also addresses the current knowl-
edge gaps in literature, with an aim to refine the un-
derstanding of the influence of H on the corrosion
of steel.
EXPERIMENTAL OBSERVATIONS
Pure Iron
Pyun, et al.,17 studied the pit initiation charac-
teristics of H-charged, passivated Fe surfaces in boric
acid/borate solutions. The metal surface was exposed
to H2 gas (at the entry face), with the H2 partial pressure
varied in the range of 0.009 MPa to 0.1 MPa in order to
achieve H-charging. The exit face (exposed to the borate
buffer solution) was held at 300 mVSCE for 10 h to first
passivate the surface and then to monitor the H oxi-
dation current corresponding to the flux of H atoms
exiting the metal lattice by diffusion. Dilute NaCl so-
lution was injected into the borate buffer solution
after H permeation had reached a steady-state to study
the pit initiation characteristics upon the H-charged
Fe surface. It was observed that for the uncharged
sample, the anodic current density did not increase
with the addition of Cl− ions. However, for the H charged
samples, there was a rapid surge in the anodic cur-
rent densities after about 30 min (Figure 1).17 The pit
induction time was found to decrease with increasing
inlet H2 gas pressure and to increase with the delay in
the introduction of Cl− ions into the borate buffer
solution. Pitting potential (Epit) was also determined to
become less noble for H-charged specimens. It was
427
RESEARCH TOPICAL SYMPOSIUM
0.4
Sample: Pure Fe
µA/cm2)
H-charged sample
(increasing anodic
0.3 current)
Anodic Current Density (µ
0.2
– ties).31-32 The destabilization of the passive film
Addition of 0.005 M Cl
0.1 H-charging
0.0
0 200 400 600
Time (min)
FIGURE 1. The changes in the anodic current density with time for
pure Fe, after the sudden addition of 0.005 M NaCl solution into a
borate buffer solution. The tests were conducted for H-charged and
uncharged Fe specimens. The anodic current density from the
H-charged Fe specimens, increased rapidly after the addition of
Cl− ions into the solution. Adapted and replotted from Pyun, et al.17
concluded that the presence of H undermines Fe
passivity and correspondingly increases the suscep-
tibility of Fe to pitting. The effect of H on pit initiation
was also found to be reversible. It was postulated that
once the H atoms enter the passive film, they convert
(reduce) the O−2 ions to OH− ions, and the OH− ions to
H2O molecules. The converted species could then
favorably exchange with the Cl− ions in the solution
and consequently allow them to penetrate and desta-
bilize the passive film.17
Similarly, Yu, et al.,29 used a combination of elec-
trochemical noise methods and the scanning refer-
ence electrode techniques (SRET) to evaluate the
metastable and stable pitting characteristics of un-
charged and H-charged Fe samples. The electrolyte
used was the borate buffer solution (pH 8.4). The
electrochemical noise measurements revealed that the
presence of H resulted in a large number of measured
current fluctuations, indicating that there were more
metastable pitting events occurring on the surfaces of
H-charged steels. SRET revealed that pits were formed
upon the H-charged Fe surfaces much sooner than
upon the uncharged Fe surfaces, suggesting that
H-charged samples have a higher susceptibility to-
ward pitting than uncharged samples. Subsequently,
analytical techniques such as Auger electron spec-
troscopy, secondary ion mass spectrometry, and nu-
clear reaction analysis were used to characterize the
passive films formed upon H-charged Fe surfaces.30 It
was observed that the presence of H decreases the
(1)
UNS numbers are listed in Metals and Alloys in the Unified Num-
bering System, published by the Society of Automotive Engineers
(SAE International) and cosponsored by ASTM International.
428
thickness of the passive film, increases the Fe2+ content,
and decreases the oxygen content within the film. The
passive film formed upon Fe was assumed to be a
semiconducting Fe2O3 film, having predominantly
n-type semiconducting characteristics. It was proposed
that H-charging altered the chemical composition of
the passive film, thus shifting it away from its ideal
stoichiometry and also altering its electronic prop-
Uncharged erties (as a result of changes in the local donor densi-
sample
formed upon Fe was attributed to the changes in the
electronic properties of the passive film, induced by
H-charging.
The influence of H on the passive film formed
upon Fe was also studied in borate buffer solution using
scanning electrochemical microscopy (SECM) and
800 1,000
x-ray near edge absorption spectroscopy.33 It was pro-
posed that H reduces the passive film formed upon Fe
and also increases the Fe2+ concentration in the film.
A thin conductive passive film with high Fe2+ con-
centration was detected upon the Fe surface following
H-charging, which subsequently influences the
electrochemical characteristics of the surface. Williams,
et al.,34 used the scanning Kelvin probe (SKP) to
investigate the impact of permeating atomic H on the
oxide film covering the Fe surface. The H-charging
was performed on the reverse face of the Fe sample,
while the Volta potential of the Fe surface was
mapped by SKP. The oxygen partial pressure within the
SKP environmental chamber was also varied during
the experiments. It was observed that for the H-charged
samples, the Volta potentials fluctuated with the
oxygen partial pressure. It was correspondingly pro-
posed that permeating atomic H reduces the Fe3+
species to Fe2+ species within the oxide film, which are
then re-oxidized by oxygen in the chamber,34 thus
causing the observed Volta potential fluctuations. In
non-passivating solutions, such as dilute sodium
sulfate solutions, Ejaz, et al.,35 observed that the
presence of H increases the corrosion rate of the Fe
and also influences the nature of the corrosion products
formed upon the surface.
As in part summarized by the above appraisal of
various works to date, for pure Fe there is consensus in
literature that H-charging results in the metal having
a less noble corrosion potential (Ecorr) and Epit. The
H-charged samples also have a higher corrosion rate
than the uncharged samples. It has been postulated by
several researchers that absorbed H destabilizes the
passive film formed upon Fe by altering its electronic
properties and chemical composition. Atomic H could
reduce the passive film and also species such as Fe3+,
O−2 , and OH− within the film, which could conse-
quently undermine Fe passivity.
Austenitic Stainless Steels
Osawa, et al.,36 observed that for the austenitic
stainless steels (SS) 304 (UNS S30400(1)) and 316 (UNS
CORROSION—APRIL 2017

S31600), H-charged specimens had a higher sus-
ceptibility toward pitting in 6% FeCl3 solution when
compared to uncharged specimens. They postulated
that the presence of H destabilizes the passive film
formed upon such stainless steels. Similarly for 304
and 310 (UNS S31000) SS, the presence of absorbed H
was found to increase the stress corrosion cracking
(SCC) rates in boiling MgCl2 solution.37 Qiao, et al.,18
studied the corrosion of 310 and 304 SS specimens
under both H-charged and uncharged conditions, in
0.5 M H2SO4 + 0.1 M HCl. These tests were performed
to rationalize the influence of absorbed H on the SCC
rates of both these steels. The presence of H in the
steel specimens was found to increase the anodic dis-
solution rate, lower Epit, and also increase the current
densities associated with the active to passive transition
(refer to Figure 2). They also detected that the chro-
mium (Cr) enrichment was much lower in the surface
films formed upon the H-charged specimens, thus
making the specimens more prone to pitting.18 The
authors of that work also proposed that the presence
of absorbed H induces local martensitic transformation
in the austenitic steel, thus making it more suscep-
tible to localized attack.18 A similar explanation was also
proposed by Yashiro, et al.,38 for 304 SS, wherein the
presence of absorbed H was also found to make the steel
more susceptible to pitting. They inferred using x-ray
photoelectron spectroscopy that the cationic fractions of
Cr present within the passive films formed upon the
H-charged specimens were much lower than those of
the uncharged specimens.38 For 316L (UNS S31603),
Ningshen, et al.,39 observed that H-charging decreased
the Epit and increased the passivation current
densities (ipass) of the steel. They claimed that this effect
was a result of the ability of atomic H to alter the
chemical composition of the passive film. Dong, et al.,40
1.2
Steel: 304 SS
Uncharged
0.8 20 mA/cm2
Potential (VSCE)
H-charged samples 40 mA/cm2
lower Epit 50 mA/cm2
0.4
H-charged sample
(higher anodic currents at active
0.0 to passive transition)
–0.4
0.00 0.15 0.30 0.45 0.60 0.75
Current (mA)
FIGURE 2. The impacts of H-charging on the potentiodynamic
polarization behavior of 304 SS, in 0.5 M H2SO4 + 0.1 M HCl. The
presence of H decreases Epit and increases the current densities
associated with the active-to-passive transition of the steel. Adapted
and replotted from Qiao, et al.18
CORROSION—Vol. 73, No. 4
RESEARCH TOPICAL SYMPOSIUM
investigated the impact of dissolved hydrogen on the
corrosion of 316NG SS in high-temperature, hydroge-
nated water. The dissolved hydrogen concentration
introduced into the SS varied from 150 ppb to 600 ppb.
The 316NG SS samples were exposed to the hydro-
genated water for 500 h at a temperature of 285°C and a
pressure of 8.5 MPa,40 with corrosion rate (or weight
gain) found to increase with the dissolved hydrogen
content.40 The characterization of the oxide layers
formed upon the 316NG SS after exposure indicated
that there was a decrease in the Cr content in the
inner oxide layer and an increase in the Fe content in
same layer for the samples containing dissolved hy-
drogen.40 It was postulated that accelerated diffusion of
Fe into the inner oxide layer was a result of the
presence of dissolved hydrogen.40
The synergistic impact of applied stress, absorbed
H, and Cl− concentration ([Cl−]) on the pitting char-
acteristics of 304 SS was studied by Yang, et al.41 The
tensile stresses were applied in the range 50 MPa to
150 MPa, which was less than half the yield stress of 304
SS. The [Cl−] was varied in the range 100 ppm to
10,000 ppm. The samples were also charged at several
different cathodic current densities ranging from
1 mA/cm2 to 10 mA/cm2 for 2 h in a solution containing
0.5 M H2SO4 + 250 ppm As2O3. It was observed that
the breakdown potential (akin to Epit) did not signifi-
cantly change with increasing applied stress, for a low
[Cl−] (100 ppm). However, Epit was found to significantly
decrease with increasing applied stress, when the
[Cl−] was 10,000 ppm. For the H-charged specimens,
even when the [Cl−] concentration was 100 ppm, Epit
was found to significantly decrease both with and
without applied stress. A second-order exponential
decay equation was found to fit the Epit values, as a
function of the applied cathodic charging current
densities (at a fixed applied stress). The relationship
between Epit and applied stress was also found to be
linear (for a particular cathodic charging current den-
sity). The synergy between absorbed H, [Cl−], and
applied stress on the pit initiation characteristics of 304
SS was therefore elaborated in that study. It was also
clarified that the presence of absorbed H enhances the
pitting susceptibility of 304 SS.
The SCC mechanisms of austenitic steels can
be classified into two predominant types: hydrogen-
induced cracking (HIC) and anodic path cracking
(APC).18,37 The HIC mechanism is more prominent
when the austenitic steels are exposed to environ-
ments such as H2S-containing brines. Crack
propagation by HIC commences only when the H
0.90
concentration at the crack tip exceeds a certain
threshold value.18,37 The APC mechanism primarily
occurs in chloride-containing environments, wherein
the crack growth rate is governed by the anodic
dissolution rate at the crack tip. The crack velocity could
be thus estimated from the Faraday’s laws. Qiao,
et al.,18 postulated that the presence of absorbed H
429
RESEARCH TOPICAL SYMPOSIUM
increases the SCC rates of austenitic steels pre-
dominantly by the APC mechanism, as absorbed H
decreases the pitting resistance and increases the
anodic dissolution rate of the steels.
Martensitic Stainless Steels
Martensitic stainless steels, such as AISI 410
(UNS S41000), are widely used in chloride-containing
H2S environments.42-43 These steels possess ade-
quate resistance to sulfide stress cracking (SSC) in such
“sour” environments. Thomas, et al.,44 studied the
corrosion of H-charged and uncharged AISI 410 steel
specimens in 0.1 M NaCl solution with pH 3.5. The
duration of cathodic H-charging was varied from 6 h to
72 h to evaluate the synergistic effect of absorbed H
and Cl− ions on the pitting characteristics of AISI 410
(Figure 3). The Ecorr and Epit values of AISI 410 were
found to become less noble, with an increase in
the duration of cathodic charging.44 ipass was also
found to increase for the H-charged specimens when
compared to the uncharged steel specimens. This
study clarified that presence of absorbed H also lowers
the pitting and corrosion resistance of martensitic
stainless steels.
Duplex Stainless Steels
The corrosion characteristics of H-charged and
uncharged duplex 2205 (UNS S32205) SS specimens in
a borate buffer solution, were studied by Yao, et al.45
The medium used for cathodic charging was 0.5 M
H2SO4 + 0.25 g/L thiourea, and the cathodic charging
current densities were varied from 0.5 mA/cm2 to
10 mA/cm2. The samples were all charged for 2 h
prior to electrochemical testing. It was observed that the
presence of absorbed H lowers Ecorr and Epit of the
duplex 2205 specimens (refer to Figure 4). Absorbed H
1.0
Uncharged
0.8 H pre-charged for 6 h
72 h
0.6 24 h
48 h
0.4
Steel: AISI 410 (Martensitic SS)
0.2
E (VSCE)
H-charged samples
0.0 lower Epit
Lower Ecorr
with H-charging
–0.2
–0.4
–0.6
–0.8
10–8 10–7 10–6 10–5 10–4
i (A/cm2)
FIGURE 3. The impacts of H-charging on the potentiodynamic
polarization characteristics of the martensitic stainless steel AISI
410, in 0.1 M NaCl at pH 3.5. The presence of H decreases Epit,
Ecorr, and increases the passive current densities (ipass). Adapted
from Thomas, et al.44
430
1.2 Uncharged
0.5 mA
0.8 1 mA
2 mA
5 mA
0.4 10 mA
Lower Epit
Peak B with H-charging
E (VSCE)
Steel: 2205 duplex SS
0.0
Lower Ecorr
with H-charging Peak A
–0.4
–0.8 Higher icorr/ipass
with H-charging
–1.2
–6.0 –4.5 –3.0 –1.5 0.0
log |<I>/mA|
FIGURE 4. The effects of H-charging on the potentiodynamic polari-
zation curves of the duplex stainless steel 2205 SS, in borate buffer
solution with 3.5 wt% NaCl. The presence of H decreases Epit and
Ecorr, and increases ipass. Adapted from Yao, et al.45
also increases the corrosion current density (icorr) of
the 2205 SS. It was postulated based on a Mott-
Schottky analysis of the passive film formed upon the
H-charged 2205 SS that absorbed H alters the elec-
tronic properties of the passive film and also increases
its n-type characteristics. These factors contribute to
the destabilization of the passive film formed upon
this steel. In a separate study, Guo, et al.,46 tested both
uncharged and H-charged 2507 (UNS S32750) SS
specimens for pitting resistance in 6% FeCl3 solution.
Pits were observed upon the H-charged specimens
within 6 d of immersion in the solution. The uncharged
specimens did not show any visible pits for up to 30 d
of exposure. They also observed that initially the pits
preferably formed in the austenite zones, then at the
ferrite/austenite boundaries, and finally within the
ferritic regions. These observations were rationalized
by the fact that the austenitic phase has a higher H
solubility and lower H diffusivity compared to the
other phases.
Other Steels
Zeng, et al.,19 studied the corrosion character-
istics of the uncharged and H-charged X70 steel
specimens in 0.5 M sodium bicarbonate (NaHCO3)
solution. It was observed that the presence of absorbed
H did not significantly impact the Ecorr and Epit of the
X70 steel in 0.5 M NaHCO3 solution. However, when Cl−
H-charged ions were added to the NaHCO3 solution, the anodic
samples
higher ipass
dissolution rates of H-charged specimens were found to
be much higher than that of the uncharged speci-
mens. The presence of absorbed H was also found to
10–3 10–2 increase the rate of crevice corrosion of the X70 steel.
Yuan, et al.,47 used SECM to study the pitting char-
acteristics of H-charged and uncharged X70 speci-
mens, in neutral chloride-containing solutions. The pit
densities of the H-charged specimens were found to
be much higher than those of the uncharged X70
specimens. They postulated that atomic H undergoes
CORROSION—APRIL 2017
 RESEARCH TOPICAL SYMPOSIUM

oxidation at the steel/solution interface, releasing

DISCUSSION
copious quantities of protons (H+) into the solution.
These released protons could cause local acidification
The Different Effects of Absorbed H on Steels
of the electrolyte and thus could correspondingly
The presence of absorbed H is found to aggravate
favor the pitting of the steel. Similarly, He, et al.,48
corrosion of most types of steels (as discussed in the
observed that H-charged X80 steel samples experi-
previous section). The different effects of the H atoms
enced more corrosion than uncharged samples. In
on steel are presented in a schematic shown in Figure 6.
ferritic steels, Hasegawa, et al.,49 observed that the
The H atoms first adsorb onto the steel surface at the
mass losses of the H-charged specimens in acidic
onset of the HER upon steel. They then enter the steel
solutions were much higher than that of the un-
and immediately enrich the first few atomic layers of
charged steel specimens. Similarly for interstitial-free
the steel surface, resulting from the presence of several
steels, the corrosion rates were found to increase for
high energy trap sites at the surface.23 The HER takes
H-charged specimens when compared to uncharged
place at potentials below −1.2 VSCE wherein the passive
specimens. It was also inferred from the salt fog
film is reduced; in any case, the effect of H on the
experiments that the formation of pits and rusts was
passive film (and vice-versa) at the entry face has been
much faster upon the H-charged specimens than the
considered to be negligible. The passive film is thus
uncharged steel specimens.50
not depicted in the entry face (refer to Figure 6). The
Recently, Thomas, et al.,20 studied the impact of
absorption of H into the steel can also result in the
absorbed H on the corrosion of the 1018 steel (UNS
formation of vacancies51 and super-abundant vacan-
G10180) using atomic emission spectroelectro-
cies in the metal.52 Local phase transformations
chemistry (AESEC). This technique enabled the real-
(such as austenite to martensite transformation) in the
time reconciliation of metal dissolution, using online
steel may also occur as a result of H-enrichment in
inductively coupled plasma-AESEC. A flowing non-
certain areas within the metal.53 The presence
passivating electrolyte (0.6 M NaCl at pH 1.95) was
of absorbed H atoms within steel also increases the
used in this study. The presence of absorbed H in steel
mobility of dislocations.15 H atoms could also be
was found to “intrinsically” increase Fe corrosion, as
transported through the steel lattice via the motion of
inferred from the detection of the Fe2+ ions by the
dislocations.16
inductively coupled plasma optical emission spec-
H transport through the steel occurs by diffusion
trometry (ICP-OES) system (refer to Figure 5). This work
and through the motion of H-containing dislocations.
first clarified that the influence of absorbed H is not
Initially the diffusion rate of H through the steel
just confined to undermining metal passivity and, in
(characterized by DH) could be low, as many H atoms
fact, absorbed H can “intrinsically” promote the cor-
may be trapped at the irreversible trap sites.21,43
rosion of steel. This observation was rationalized by
However, once the trap sites within the steel are
atomistic modeling, which indicated that the pres-
saturated with the H atoms, the rate of H diffusion
ence of interstitial H in the Fe lattice weakens local
through the steel steadily increases and eventually
metallic bonding. The H atoms were found to draw
attains a steady-state (as defined by Fick’s first law of
electrons from the first and second nearest neighbor
diffusion). The CH,Diff can be deduced from the steady
Fe atoms.
state H diffusion flux, emanating from the steel lattice at
the exit faces. The H atoms emerging from the steel
–100 Steel (potentiostat current) make contact with the passive film (either Fe2O3 in the
Steel (Fe current from ICP)
case of Fe and carbon steels, or Cr2O3 in the case of
H-charged steel (potentiostat current)
–200 SS). The interaction of H with the passive film results in
H-charged steel (Fe current from ICP)
destabilization of the passive film. The resultant effect
Steel: 1018 carbon steel
–300 is that at the steel/solution interface, the Ecorr/Epit of
E (mVSCE)

Higher Fe dissolution from the steel decreases and icorr increases. This effect is
–400 H-charged steel, detected
by the potentiostat reversible, as once the absorbed H atoms exit the steel,
the Ecorr and Epit values recover to those corre-
–500 sponding to an uncharged pristine steel surface.
Higher Fe dissolution from
H-charged steel, detected Several mechanisms have been proposed to
by ICP-OES
–600 explain the destabilization of the passive film on its
interaction with the H atoms. H is a strong reducing
10–5 10–4 10–3 10–2 agent27 and can reduce oxygen,28 the passive film
i (A/cm2)
itself,33 and also oxygen-containing species such as
FIGURE 5. The effects of H-charging on the potentiodynamic polari- O−2 and OH− within the passive film.17 Absorbed H thus
zation curves of 1018 carbon steel samples, in 0.6 M NaCl at pH alters the chemical composition of the passive film
1.95. The current densities determined by AESEC using real time formed upon steels. This could alter the dielectric
ICP-OES are overlaid upon the current densities measured by the
constant and the electronic properties of the passive
potentiostat. Adapted from Thomas, et al.20
film, thus promoting its destabilization.31,54-55 The

CORROSION—Vol. 73, No. 4 431

RESEARCH TOPICAL SYMPOSIUM
H entry H transport
Metal
Permeation
Dislocation drag
HER
Diffusion
Surface Bulk
Absorbed H Surface H
Atomic H Dislocations
Metal vacancy H-induced phase transformations
FIGURE 6. A schematic representation of the different processes occurring within steel during the interactions with
adsorbed/absorbed H atoms.
impact of H on Fe corrosion was historically consid-
ered to be “extrinsic”: related to the impact of H on the
passive film formed upon steel. However, Thomas,
et al.,20 showed that absorbed H promotes Fe dissolu-
tion even in non-passivating solutions, indicating
that there may be other “intrinsic” mechanisms which
promote the corrosion of H-charged steels.
Current Knowledge Gaps
Although the electrochemistry of H absorption
has been well quantified, there still remains gaps in the
understanding of absorbed H atoms and surface H
atoms. In particular, ab initio calculations have shown
that the ideal fracture energy of the Fe surface was
found to decrease linearly with H coverage.56 It was
found to decrease by about 45% when the Fe surface
is covered by one-half monolayer of H atoms.56 The
effects of adsorbed H and surface H on the corrosion
of steel have still not been completely realized, as it is
difficult to measure the adsorbed and surface H
concentrations using traditional techniques.
The mechanistic aspects of the H-assisted de-
stabilization of the passive films formed upon steels
have not been clearly understood. It was proposed by
Song, et al.,54-55 that atomic H undergoes oxidation to
form a proton (H+), as it enters the passive film.
However, interstitial H and substitutional H have been
recently identified as point defects within the oxides of
metals such as Zn.57-58 Such point defects could in-
fluence the electronic properties of the oxide film and
could consequently promote its destabilization. H could
432
H exit
Film Solution
H+solution Pitting
For Fe: +
Hsolution
2+
[Fe ]film
–
[O2 ]film Ecorr
H+film
Epit
H+film
icorr
For SS:
[Cr]film
Surface
Interstitial H Destabilization of the
passive film
Irreversibly trapped H
Reversibly trapped H
be transported through the passive film in the form of
such point defects; however, the energetics of such
processes have never been explored. The CH,Diff within
steels is currently determined from H permeation
techniques which assume a steady-state diffusion of
H atoms from within the steel lattice. However,
H/proton transport through the passive film occurs
both by diffusion and also by migration55 as there is a
potential drop across the passive film, especially
when a potential is applied across the metal/oxide/
electrolyte system. Because H can participate in
reactions with other species in the passive film (such as
O−2 and OH−), the diffusivity of H is around 1012 times
slower through the passive film than through the
metal.55 It is not clarified whether the measured
CH,Diff corresponds to the H concentration within the
passive film or the H transport through the passive
film. The estimation of the H concentration within the
passive film will be an important step toward un-
derstanding the different mechanisms of destabilization
of the passive film by the absorbed H atoms.
The presence of absorbed H atoms could also
cause several “intrinsic” changes within the steels. The
absorbed H atoms could weaken metallic bonding,59
promote the formation/transport of metal vacancies,
form H-vacancy complexes,60 and could also cause
H-dislocation interactions61 within the metal. Absorbed
H atoms also increase the electron densities at the
vacancies and tetrahedral sites within Fe, which could
correspondingly increase the mobility of dislocations
and contribute to HELP.61 Atomistic modeling has
CORROSION—APRIL 2017

shown that at high H concentrations, screw disloca-
tions trap more H than edge dislocations. This leads to a
reduction in cross-slip, thus causing increased brit-
tleness.61 H could also locally disrupt the metal lattice
by causing amorphization near stressed crack tips.26
These atomic level effects could influence the micro-
structural properties of the metal and could conse-
quently influence its corrosion characteristics. The
impact of some of the above “intrinsic” effects on
metal corrosion are currently not well understood and
will be an important direction for future research. The
cathodic charging current densities used to introduce H
into steels in many of the past works has not been
benchmarked in the context of the relevant practical
situations and applications, as experienced in field
exposures. This is an important aspect which will need
to be considered in laboratory-based experiments,
wherein H is introduced into steels by cathodic
charging.
IMPLICATIONS
The electrochemical models that describe the
pitting of steels62-64 do not take into consideration the
impact of H on both pit initiation and pit propagation.
Such models therefore may not effectively predict the
degradation of steels in H-containing environments. If
the Epit of a given steel is above the equilibrium electrode
potential (EH+/H2) of Reaction (4) at a given pH (Re-
action [5]),65 then H will be readily oxidized according to
Reaction (4). The impact of absorbed H on the pit
propagation rate of the steel in this case may not be
significant. However, when the Epit of a given steel is
much lower than (EH+/H2), then more H atoms may be
retained within the steel and could promote pit
propagation.
H2 → 2Hþ þ 2e−
EHþ =H2 = − 0.244 − 0.0591 pH − 0.00295log ρH2
The H-assisted cracking mechanisms of steels
can be classified into two types, namely hydrogen en-
vironment assisted cracking and internal hydrogen
assisted cracking. In both of these mechanisms, the
crack growth rate (da/dt) is governed by the diffusion
rate of H to the fracture process zone (FPZ). The upper
limit for the diffusion controlled crack growth rate
(da/dt)Diff controlled is related to the FPZ length (xcrit) and
DH,eff by the following relation:66
   
da
=4 ×
DH,ef f
dt Diff controlled xcrit
The electrochemical crack growth rate for a given
metal (da/dt)electrochemical can be estimated by Faraday’s
laws using Reaction (7), wherein MWFe corresponds to
CORROSION—Vol. 73, No. 4
RESEARCH TOPICAL SYMPOSIUM
the atomic weight of Fe and ρFe corresponds to the
density of steel.
   
da MWFe
= icorr (7)
dt electrochemical 2 × F × ρFe
The presence of absorbed H atoms within steel
could first increase (da/dt)electrochemical and also corre-
spondingly increase the HER rate upon the steel. This
could increase the H concentration entering the steel
lattice and thus the FPZ within the steel. An increase
in the H concentration within the FPZ will increase
(da/dt)Diff controlled. Absorbed H could destabilize and
reduce the passive film at the crack tips and thus could
serve to sustain environmentally assisted cracking
(EAC) of steels. The impact of absorbed H atoms on both
the pitting and EAC of steels will therefore need to be
considered in future modeling efforts.
For SS systems, the precursor to cracking is
usually pitting. As absorbed H, pH, and [Cl−] could all
promote pitting of SS, it is important to understand
their synergistic effects in pit propagation and EAC in a
given environment. Such scenarios typically are
experienced in H2S/Cl− environments wherein
absorbed H enters the steels as a result of H2S poi-
soning the H recombination reaction6-8 and participates
with the Cl− ions in the environment to attack the
metal. Kane, et al.,67 reviewed corrosion/cracking
propensities of steels, stainless steels, and Ni-based
alloys in H2S containing environments. The work
highlighted that the presence of H2S could cause
different forms of H embrittlement, including internal
hydrogen blistering, HIC, and stress-oriented HIC of
carbon steel plate and pipe material. It can also
contribute toward the SSC, localized corrosion, and
anodic SCC of stainless steels and Ni-based alloys.
Rhodes, et al.,68 reported the EAC propensities of
(4) martensitic SS, duplex SS, austenitic SS, and also
Ni-Cr-Mo alloys exposed to H2S/Cl− containing
environments (in temperatures ranging from ambient to
(5)
232°C), revealing such metals were more susceptible
to SCC in a H2S/Cl− containing environment as opposed
to a Cl− environment—indicating a H2S/Cl− syner-
gism influences the EAC of such metals. The effect of
H2S/Cl− environments on the EAC of Ni-based alloys
was proposed to be a combination of the following
important effects:68 (a) increased H absorption into
the metal, (b) an increased corrosion rate of the metal,
(c) an increase in the local acidity resulting from
Reaction (8), and finally (d) the deposition of NiS-rich
precipitates at crack tips and other corroded areas.
(6) Ni2þ þ H2 S → NiS þ 2Hþ þ 2e− (8)
The synergy of absorbed H and [Cl−] in causing
the SSC of 17-4 PH is presented in Figure 7 (adapted
from Vitale69). The 17-4 PH specimens were subject to
the NACE Standard TM0177-96 test with varying pH,
433
RESEARCH TOPICAL SYMPOSIUM

103 7
Steel: 17-4 pH
pH: 3.5
102 Test: TM0177 (NACE) Pass—no cracking
H2S Partial Pressure (bar)

(Resistance to SSC) 6 or corrosion

High H2S
101 Pass/Fail
depends

pH
5 –
on [Cl ]
100 – Fail—cracking
Maximum [Cl ] or unacceptable
tested corrosion
10–1 4
–
Low Cl –
Minimum [Cl ]
10–2 Pass
tested
Fail 3
Increasing pH2S
10–3
10–1 100 101 102 103 104 105 FIGURE 8. A schematic presenting the domain of failure/no failure for
Chloride (ppm) the martensitic stainless steel 17-4 PH, when subject to NACE
standard test (TM0177-96) for testing the resistance to SSC. The
FIGURE 7. The domain of failure/no failure for the martensitic stain-
pH and pH2S were varied to identify their synergistic impacts on the
less steel 17-4 PH, when subject to NACE standard test (TM0177-96)
susceptibility of 17-4 PH to SSC. Adapted from Vitale, et al.69
for testing the resistance to SSC. The chloride concentration and
pH2S were varied to identify their synergistic impacts on the sus-
ceptibility of 17-4 PH to SSC. Adapted from Vitale, et al.69

Steel: Modified 13% Cr SS

Yield strength: 618 MPa
− 69 10–1
pH2S, and [Cl ] in that study. The absorbed H pH: 4.5
concentration within the steel increases with increasing 5% NaCl solution
Critical pH2S (MPa)

pH2S.8 The specimens were found to fail by SSC,

under two independent conditions: one with low pH2S/ 10–2
high [Cl−] and the other with high pH2S/low [Cl−].
Similarly, the synergistic impact of pH and pH2S on the
SSC of 17-4 PH is presented in Figure 8. The failure of 10–3
17-4 PH specimens by SSC was found to occur both in
the low pH/high pH2S and high pH/low pH2S con-
ditions.69 Several researchers have proposed models 10–4
considering the synergistic effect of pH2S/[Cl−] on the
localized corrosion of pure Fe70 and also austenitic 0 25 50 75 100 125 150
stainless steels.71 However, the impact of absorbed H Temperature (°C)
on the electrochemistry and corrosion of the metal has FIGURE 9. The effect of temperature on the critical H2S partial
not been addressed in such modeling efforts. The pressure (pH2S) for SSC of a modified 13% Cr stainless steel, in
temperature of the environment influences the 5% NaCl at pH 4.5. The results were inferred from V-notched four
point bent beam tests, with the specimen loaded at 100% yield
absorbed H concentration within the steel. Sakamoto,
strength. Adapted from Sakamoto, et al.72
et al.,72 observed that the SSC susceptibility of
13% Cr SS decreases with increasing temperature
(Figure 9). This effect could be attributed to the de-
creased H-trapping within these steels at higher pH is 4 and pH2S is 10 mbar (1,000 Pa) (as determined
temperatures.42 by the TM0177 tests).69-73 Nickel-based alloys such
A thorough understanding of the impact of absorbed as the Inconel 718† alloy (UNS N07718) are used in such
H and also its synergistic effects in combination with components when the [Cl−] and pH2S are above these
pH and [Cl−] is a necessary precursor in facilitating the prescribed limits. A comprehensive understanding of
development of new alloys/materials, which could be the synergistic effects of pH, pH2S, and [Cl−] on
used in chloride containing “sour” environments. Such the SSC of SS could provide pathways to develop novel
aspects are beyond the present review; however, for alloys/materials which are more cost-effective than
context, oil and gas equipment used in such environ- Ni-based alloys. It would also create an impetus
ments include centrifugal compressors, subsea for appending standards such as NACE Standard
manifolds/trees, well-heads, downhole drilling ma- MR-0175 for alloy selection in oil and gas environments.
chinery, etc. Currently for martensitic SS (used in
centrifugal compressors), the maximum permissible SUMMARY
limit for exposure to chlorides is 600 ppm, when the
The presence of absorbed H within most steels
†
Trade name. appears to have some “universal” effect on their

434 CORROSION—APRIL 2017


corrosion, based on a critical review of the historic
literature. Absorbed H has been shown to increase
measured corrosion rates and has been shown to
result in less noble Ecorr and Epit values for steels. For
stainless steels (SS) and pure iron (Fe) (in a passiv-
ating borate buffer solution), there appears to be a
consensus in the literature that H-enhanced corro-
sion is attributed to the destabilization of the passive
film formed upon the metal.
The destabilization of the passive film formed
upon pure Fe could occur via several mechanisms.
H could directly reduce the passive film (comprising
Fe2O3) and/or could reduce the O−2 and OH− species
within the film to the OH− and H2O species, respec-
tively. Such species could preferably exchange with the
aggressive Cl− ions in solution, leading to destabili-
zation of the passive film. The interaction of the passive
film with the H atoms could also increase the Fe2+
content while lowering the oxygen content within the
film, consequently altering the electronic properties of
the semiconducting passive film to promote destabili-
zation. For SS, the presence of absorbed H is likely to
deplete the Cr content within the passive film and thus
permit more ready corrosion of SS. However, the
mechanistic aspects of the interactions between the
passive film and the H atoms are not well understood.
The state of the H atom within the passive film, the
H concentration within the passive film, and also its
reactions within the oxides of metals are important
aspects that are also currently not well understood,
albeit complex to study empirically. A clarification of
these aspects would, however, serve toward a more
unambiguous understanding of the mechanisms of
passive film destabilization by H atoms.
In non-passivating solutions (in the absence of a
passive film) it has been observed that absorbed H can
still increase the corrosion rate of steel. This indicates
that absorbed H can “intrinsically” promote Fe disso-
lution, rather than via destabilization of a passive
film. This impact of H in increasing the dissolution rate
of steel, may be a result of several factors. These
include decohesion of metallic bonding within the metal,
increased mobility of dislocations in the metal lattice,
H-induced phase transformations, and even the for-
mation of metal vacancies (and possibly so-called
super-abundant vacancies) within the metal.
The effects of H on the corrosion and cracking of
steels are primarily attributed to the diffusible H con-
centration (CH,Diff) within the steels. CH,Diff is a pa-
rameter which defines the resident “mobile” H atoms
present within the steel, after H-charging. However,
the adsorbed H and surface H are noted to play a more
important role on the corrosion of steels. The mea-
surement of surface H/adsorbed H and studies on their
influence on metal corrosion will be an important
aspect to be investigated in future work on this topic. The
impact of H on the corrosion/electrochemistry of steels
is currently not considered—perhaps surprisingly—in
CORROSION—Vol. 73, No. 4
RESEARCH TOPICAL SYMPOSIUM
classical pitting and environmentally assisted
cracking models, and this is necessary to effectively
predict the degradation of steels in H-containing
environments.
ACKNOWLEDGMENTS
This article is dedicated to the memory of Prof. R.A.
Oriani.
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CORROSION—APRIL 2017