Corrosion Science 52 (2010) 1787–1795

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

Environmentally assisted cracking mechanism of pipeline steel in near-neutral pH

groundwater
B.T. Lu a,1, J.L. Luo a,*, P.R. Norton b
a
Department of Chemical and Materials Engineering, University of Alberta, Edmonton, Alberta, Canada T6G 2G6
b
Department of Chemistry, University of Western Ontario, London, Ontario, Canada N6A 5B7

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

Article history: A modified Devanathan dual cell was used in environmentally assisted cracking (EAC) tests to indepen-
Received 2 November 2009 dently control the concentration of dissolved hydrogen and anodic current density. The experimental
Accepted 6 February 2010 evidence indicates that the corrosion may reduce the micro-hardness of steel, suggesting a dissolu-
Available online 13 February 2010
tion-induced degradation of the mechanical properties in the surface layer. An EAC model is described
in which surface micro-plastic deformation can be enhanced by the dissolved hydrogen and anodic dis-
Keywords: solution, and plays a crucial role in cracking processes. The model can provide a reasonable prediction for
A. Steel
the dependence of the cracking resistance of pipeline steel on the applied potential.
B. Hydrogen permeation
C. Anodic films
Ó 2010 Elsevier Ltd. All rights reserved.
C. Effect of strain
C. Stress corrosion

1. Introduction hydrogen-induced cracking mechanism [5–7]. In the conventional

The near-neutral pH stress corrosion cracking (SCC) of pipelines
has received a lot of attention since the first case was found in Can-
ada in the 1980s [1,2]. This transgranular SCC occurs in dilute
groundwater (pH 5.5–7.5) and is distinct from classic intergranular
SCC that has been found in concentrated carbonate-bicarbonate
solutions (pH 9–11). Its most distinguishing features are: (1) it oc-
curs in an active dissolution system instead of an active-to-passive
transition system; (2) the lateral dissolution on the crack side is
substantial and (3) cyclic or dynamic loads are often necessary
for the occurrence of SCC [1,2], although limited experimental
observations indicated that the cracking was also detected under
the action of sustained load with high levels [2,3]. The classic inter-
granular SCC has been well recognized as being controlled by a
mechanism of preferential dissolution of grain boundaries and re-
peated rupture of passive films, but the mechanism of near-neutral
pH SCC still needs to be further explored.
Based on the fact that cathodic polarization or pre-charging
with hydrogen degrades the SCC resistance of pipeline steels mea-
sured in slow strain rate tests (SSRT) [4,5], some researchers
believed that the near-neutral pH SCC might be controlled by a
* Corresponding author. Tel.: +1 (780) 492 2232; fax: +1 (780) 492 2881.
E-mail addresses: baotong.lu@swri.org (B.T. Lu), jingli.luo@ualberta.ca (J.L. Luo).
1
Present address: Environmental Performance of Materials, Materials Engineering
Department, Mechanical Engineering Division, Southwest Research Institute, 6220
Culebra Road (78238-5166), P.O. Drawer 28510, San Antonio, TX 78228-0510, USA.
Tel.: +1 (210) 522 2721; fax: +1 (210) 522 5122.
SSRT test, the cathodic polarization is often used to increase the
dissolved hydrogen concentration in specimens [8,10]. Anodic dis-
solution on the specimen surface is suppressed whenever cathodic
polarization is applied to charge hydrogen into specimen; i.e., the
anodic dissolution rate on the test surface and the dissolved hydro-
gen concentration in the material are always interdependent. This
creates some difficulties to identify the exact contributions of
hydrogen and anodic dissolution to the SCC processes. Therefore,
an improvement in experimental techniques would be helpful to
understand the SCC mechanism.
Some laboratory data have shown that the SCC resistance does
not decrease monotonically by shifting the potential in the nega-
tive direction [8,9]. This phenomenon can be attributed to the ano-
dic dissolution in the SCC process. As pointed out by Parkins [8], ‘‘It
was inconclusive to say that the anodic dissolution observed on the
crack wall did not occur at the crack tip and, therefore, difficult to
ignore the involvement of dissolution in near-neutral pH SCC at the
potentials around the open circuit potential, so that both anodic
dissolution and hydrogen permeation are active and their (syner-
gic) combination gives rise to this particular kind of cracking”.
Although some researchers believed that both dissolved hydrogen
in steels and active dissolution present on the surface could affect
near-neutral pH SCC of pipelines [2,7–9], the roles of dissolved
hydrogen and active dissolution in near-neutral pH SCC are not
well understood. To incorporate the contributions of dissolved
hydrogen and anodic dissolution into the development of near-
neutral pH SCC, some researchers [9–11] believed that the SCC
was controlled by a so-called hydrogen-facilitated anodic dissolu-

0010-938X/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2010.02.020
1788 B.T. Lu et al. / Corrosion Science 52 (2010) 1787–1795

tion mechanism. According to this model, the active dissolution 20 DIA - 2HOLE
R12.5
must be significantly enhanced by the synergistic effect of dis-

20
solved hydrogen and the local stress field around the crack tip.
However, both thermodynamic analysis and experimental evi-

38
dence have indicated that the difference of anodic dissolution rates
between the tip and wall of a crack caused by the interaction of the
stress field and hydrogen is insufficient to prevent the crack from 62.5 12 30
30
losing its sharpness to become a pit [12]. Therefore, anodic disso-
50
lution must affect, if it does, the SCC of pipeline steel in the near- 50 87.5
neutral pH groundwater via some other mechanisms.
In the past, the bulk of the research effort was devoted to the 195
roles of hydrogen and anodic dissolution in the crack propagation
process [2,5,8,9]. Considerably less attention has been focused on

1.25
their effects on crack nucleation. It has been broadly accepted that

5
the crack advance mode during transgranular SCC is discontinuous
[7,13–15]. Hence, the importance of the crack nucleation stage be-
comes still more apparent from the fact that the same critical
R6.25
stress–environment interaction must take place in the crack prop-
agation at an accelerated pace, because of the high stress intensity
Fig. 1. Specimen geometry (all dimension in mm).
at the crack tip; i.e., each crack advance event can be regarded as a
re-nucleation process [16]. Therefore, a comprehensive under-
standing of the crack nucleation mechanism may be crucial to acetone. To reduce the influence of scratches produced in the sur-
resolving the transgranular crack propagation mechanism. A well face preparation on the crack nucleation, the grinding was always
known fact is that the incubation time for crack nucleation often in the longitudinal direction of the specimens. All the test solutions
comprises the major part of the service lifetime of pipelines [2,8]. were made with analytical reagents and de-ionized water. Since
Improved knowledge on the mechanism of crack nucleation is also pipeline steels exposed to the near-neutral pH groundwater are
practically important to permit the prediction of the service life- most susceptible to the cracking at room temperature, all the
time of pipelines, to improve the SCC resistance of steels and to experimental measurements were conducted at room temperature
optimize the protection techniques that are used. (22 ± 1 °C).
Since stationary stress required to cause the near-neutral pH
SCC of pipeline steels is close to yield strength of the steel that is
2.2. Tests to investigate cracking behavior
much higher than the operating stress level in pipelines, the inter-
nal pressure fluctuation during service of pipelines is believed to
The test solution present in both sides of the cells was NS4 solu-
play a key role in the development of cracking [1,2]. By definition
tion, which simulates the composition of water trapped on the pipe
this feature is quite different from that of the classic SCC. In the
surface under a disbonded coating. The chemical composition of
evaluation of service life of pipelines exposed to near-neutral pH
NS4 solution (mMol/L) was 1.64 KCl, 5.75 NaHCO3, 1.23 CaCl2
groundwater, the fatigue damage is often neglected because the
and 0.74 MgSO47H2O. The solution was deaerated by continuously
internal pressure fluctuations within the pipes have a very low fre-
bubbling, using a mixture of 5% CO2 + 95% N2 to create a test solu-
quency and a high stress ratio (>0.8) [1]. As pointed out by Parkins
tion with pH 6.7. To control the hydrogen concentration in speci-
et al. [2], the cyclic loads produced by the internal pressure fluctu-
mens and the anodic dissolution rate on the specimen surface
ations promote plastic deformation at the crack tip significantly
independently, a Devanathan cell illustrated in Fig. 2 was used in
and it plays a dominative role in the processes of cracking develop-
the SCC experiments. A specimen with a thickness of 1.2 mm in
ment. Until now, it is still difficult, in view of the damage mecha-
the test section was inserted between the dual cells. In each cell,
nism, to differentiate this type of SCC from corrosion fatigue,
a long platinum wire was used as the counter electrode and a
although some efforts have been made [17,18]. Therefore, in this
Saturated Calomel Electrode (SCE) was used as the reference
paper, the term ‘‘environmentally assisted cracking (EAC) in near-
neutral pH groundwater” instead of ‘‘near-neutral pH SCC” is used
thereafter.
In this study, the roles of dissolved hydrogen and anodic disso- Gas in Gas out Gas out
RE Gas in RE
lution in the EAC of pipeline steel were explored. With the aid of
the concept of chemo-mechanical interaction [7,19–21], an im-
proved corrosion-facilitated plasticity model is tentatively used
to interpret the mechanism of EAC. It is expected that the results
of the present study will expand the previous knowledge-base
about SCC mechanisms of pipelines.
H
2. Experimental procedures
CE CE
2.1. Test material and specimen preparation
Charging side
Oxidizing side
The test material was X60 pipeline steel. Its yield strength was
436 MPa and the ultimate tensile strength was 549 MPa. The geo-
metric size of specimens is shown in Fig. 1. Before testing, the spec- Cyclic loading
imens were ground with SiC abrasive papers of grits up to #1200,
and successively cleaned and rinsed with de-ionized water and Fig. 2. A Devanathan dual cell.
 B.T. Lu et al. / Corrosion Science 52 (2010) 1787–1795
electrode. The experiments were conducted using a Material Test-
ing System under the action of a cyclic load of constant amplitude.
To complete the experiments in a reasonable period, the maximum
stress rmax = 426 MPa, which is slightly below the yield strength of
steel, was adopted in the tests. The loading frequency utilized was
0.1 Hz and a stress ratio was 0.5.
The hydrogen concentration in the specimens was controlled by
means of applying a constant potential in a range from 0.6 to
1.2 VSCE with a potentiostat at the charging side. On the opposite
(oxidizing) side of the specimen, an anodic potential could be ap-
plied to control the anodic current density on the test surface. In
the present tests, only Ecorr (about 0.74 VSCE) was utilized. The
hydrogen atoms that were generated at the charging side would
penetrate the specimen via diffusion. Different from the conven-
tional hydrogen permeation experiments, the hydrogen atoms
reached the specimen surface of the oxidizing side would form
hydrogen bubbles instead of being oxidized because the value of
Ecorr was lower than the oxidizing potential of hydrogen (around
0.64 VSCE). The dissolved hydrogen concentrations under the sta-
ble conditions were largely controlled by the applied potential at
the charging side. The secondary ion mass spectrometry (SIMS)
measurements have indicated that the dissolved hydrogen concen-
tration of pipeline steels in the anaerobic NS4 solution increases
with decreasing applied potential [8,9,22]. Because of the low po-
tential at the oxidizing side and the relatively small specimen
thickness, the concentration gradient of diffusible hydrogen within
the testing section of the specimen was relatively small (1.2 mm).
After cracks nucleated at the specimen surfaces, the nominal
hydrogen concentration in the surface layer could increase be-
cause the crack tips can act as hydrogen traps. On average, the
cracks can be approximately considered as hydrogen traps of
the same depth, so that the average amount of hydrogen atoms
trapped in the area around the crack tips at both surfaces is close
after the system is stabilized under the potentiostatic condition.
Thus, the main difference between the two test surfaces was
the corrosion current densities present at the surfaces. The anodic
current densities at the oxidizing side were equal to the corrosion
current densities of X60 steel at the open circuit potential. Our
electrochemical measurements have indicated the difference in
the polarization resistance measured at the surface of oxidizing
side, when the different potentials are applied at the charging side
of the specimen, is less than the error of measurement [12].
Therefore, the anodic current density at the oxidizing side could
be approximately considered to be independent of the applied
potential at the charging side. At the charging side the anodic dis-
solution rates were controlled by the applied potential, which was
similar to the environmental conditions of the regular SSRT to
investigate the effect of electrochemical potential on the EAC
[2,4,5,9].
Before a cyclic load was applied, the specimen was electro-
chemically charged with hydrogen for more than 3 h until the
hydrogen permeation reached a stable condition, as indicated
by an independent hydrogen permeation experiment. The tests
were interrupted at various intervals for the crack measure-
ments; the number of cracks nucleated and the crack sizes were
measured by making use of the replica technique. During making
the replica, a constant tensile stress equal to the maximum
stress applied in the experiments (426 MPa) was applied to the
specimens to keep the cracks open. This will be helpful to pro-
duce clear crack images on the replica to facilitate the crack
measurements. In order to remove the corrosion products on
the test surface to produce the replica of good quality, the rep-
lica were made several times until no porous corrosion products
were observed on both the surfaces of specimen and the replica.
The tests stopped before the cracks penetrated the specimen
thickness.
1789
2.3. Hydrogen permeation measurement
The hydrogen permeation rates through the specimen were also
measured with the same dual cell as used for the EAC test. To cre-
ate a hydrogen concentration close to that in steel pipes in the
crack nucleation stage, the solution in the charging cell was the
anaerobic NS4 solution, and the applied potentials were in the
same range as those adopted in the SCC tests. The solution in the
oxidizing cell was 0.3 M H3BO3 + 0.075 M Na2B4O7 with pH 8.4. A
fraction of the hydrogen atoms that were generated on the charg-
ing side diffused through the specimen and were electrochemically
oxidized on the opposite side where the potential was maintained
at 0.2 VSCE. The hydrogen permeation rate was determined from
the experimentally measured current density at the oxidizing side.
Since this value is approximately proportional to the hydrogen per-
meation current density [8], it serves as the indicator of the
amount of hydrogen dissolved in the steel during the hydrogen-
charging.
2.4. Active dissolution of cyclic loaded and hydrogen-charged steel
In order to demonstrate the effects of dissolved hydrogen and
applied stress on active dissolution, the anodic current densities
of the steel specimen at 0.7 VSCE using the same dual cell as
shown in Fig. 1 were measured under four different conditions,
namely: (1) non-hydrogen-charged and non-loaded; (2) non-
hydrogen-charged but cyclically loaded; (3) hydrogen-charged
but non-loaded and (4), hydrogen-charged and cyclically loaded.
To simulate the effect of large plastic deformation at the crack
tip, a maximum cyclic stress rmax = 462 MPa with the minimum/
maximum stress ratio R = 0.1 and the loading frequency
f = 0.1 Hz, was applied so that a significant amount of plastic defor-
mation was introduced. The test solution in the cells of oxidizing
sides was the anaerobic NS4 solution and the electrolyte at the
charging side was 0.1 M H2SO4 + 250 ppm As2O3. All measure-
ments were conducted at the oxidizing side in the anaerobic NS4
solution after the steady state hydrogen permeation condition
was reached. Continuous hydrogen-charging with a charging
current density (iH-charging) of 100 A/m2 was utilized to create a high
hydrogen concentration and to simulate the conditions at the crack
tip. The dissolved hydrogen concentration under this condition
measured by SIMS technique was about 20 ppm [22]. The electro-
chemical measurement was conducted after 3 h of pre-charging
and was completed within 2 h to avoid the impact of hydrogen
damage, since blistering would be observed if the total charging
duration exceeded 24 h.
3. Crack nucleation and propagation behavior
When the stress cycles reached a critical number, cracks began
appearing on the specimen surface. After that time, both the crack
density, Dc, defined as the number of cracks observed in a unit area,
and the maximum surface length of cracks, cmax increased with the
test duration, as shown in Figs. 3 and 4.
In order to evaluate the crack nucleation kinetics, the crack
nucleation rate, D_ crack , was defined as dDc/dt. As indicated by the
limited data in Fig. 5, the crack nucleation rates within the test
duration are roughly independent of the test duration. The rela-
tionship between the average crack nucleation rate and the applied
potential is shown in Fig. 6. The crack nucleation rate increases, in
general, as the applied potential is shifted to the negative direction.
This implies that the hydrogen dissolved in the steel promotes
crack nucleation, since the test results of hydrogen permeation
indicated that the concentration of hydrogen dissolved in the
material increases with decreasing applied potential [8,9,22].
1790 B.T. Lu et al. / Corrosion Science 52 (2010) 1787–1795

(a) 0.8 Eapp (VSCE) (a) 0.5 Eapp (VSCE)

0.7 -0.6 -0.6
-0.65 0.4 -0.65
0.6 -0.7 -0.7
-0.74
-0.74

Cmax (10 m)
Dc (10 m )

0.5 -0.8
-2

-0.8 0.3

-3
-1.0
6

0.4 -1.0 -1.2

-1.2 0.2
0.3

0.2
0.1
0.1
Oxidizing side Oxidizing side
0.0 0.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0
t (Ms) t (Ms)

(b) 0.8 (b) 0.4 Eapp (VSCE)

Eapp (VSCE)
0.7 -0.6
-0.6
-0.65
0.6 -0.65 0.3 -0.74
-0.7
-0.7

Cmax (10 m)
Dc (10 m )

0.5 -0.74
-2

-0.8
-0.8 -3
6

0.4 0.2 -1.0

-1.0
-1.2
0.3 -1.2

0.2 0.1

0.1
Charging side
Charging side
0.0 0.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0
t (Ms) t (Ms)

Fig. 3. Dependence of crack density on test duration. Fig. 4. Dependence of maximum crack size on test duration.

4
When Eapp < Ecorr, the higher crack nucleation rate at the oxidizing σmax/SMYS =1.05
side indicates that anodic dissolution also facilitates crack nucle- ν = 0.1Hz, R=0.5
ation. When Eapp > Ecorr, the crack nucleation rates at the both sides
are almost the same. 3
Dc rack (m s )

In the present study, the incubation time for crack nucleation ti

-2 -1

was determined by extrapolating the curves of crack density vs test

duration to zero crack density. The data in Fig. 6 show clearly that
2
the crack nucleation lifetime at the oxidizing side, where the aver-
age rate of anodic dissolution is almost unchanged, is reduced
monotonically with the increase of the dissolved hydrogen concen-
tration. However, the trend of crack nucleation lifetime at the 1 Oxidizing side
charging side is different. When the applied potential Eapp is no
Charging side
more than 0.8 VSCE, the values of ti at the oxidizing side are lower Ecorr
than those at the charging side. It is worthy to note that the dis- 0
solved hydrogen concentration in the surface layer of oxidizing -1.4 -1.2 -1.0 -0.8 -0.6 -0.4
side should be a little bit lower than that at the charging side be- Eapp (VSCE)
cause the concentration gradient of dissolved hydrogen within
the specimen is unavoidable, no matter how small it is. Hence, if Fig. 5. Effect of applied potential on crack nucleation rate.
the anodic dissolution were absent, the crack nucleation lifetime
at the oxidizing side would be not lower than that at the charging
side. The lower crack nucleation lifetime at the oxidizing side with- increases slightly. This suggests that the crack nucleation is de-
in the potential region below the Ecorr must result from the anodic layed by the dissolution of crack nuclei because of the relatively
dissolution occurring on the surface. At a potential around the Ecorr higher rate of anodic dissolution.
the steel displays a lower crack nucleation lifetime that is close to In the present investigation, the crack propagation rate was de-
the value of ti at the opposite side. This is mainly because the ano- fined as the slope for the curve of the maximum surface crack size
dic dissolutions rates at each side are very similar in this potential vs test duration (Fig. 3). The crack propagation rates (dcmax/dt) so
range. At a potential range more positive than the Ecorr, the crack determined are shown in Fig. 7. The crack propagation rates on
nucleation lifetime measured on the oxidizing side further the both sides increase, in general, when the potential is moved
 B.T. Lu et al. / Corrosion Science 52 (2010) 1787–1795 1791

Side Oxidizing Charging around the crack tip to maintain the sharpness of crack tip, as dem-
ti onstrated by the hydrogen-facilitated anodic dissolution model [9–
11]. In line with our previous thermodynamic analysis [12], the ef-
Crack initiation life (10 s)

1.6
6

fects of dissolved hydrogen and applied stresses, as well as their

interaction on the active dissolution, can be evaluated using the ac-
tive current density ratios of hydrogen-charged or stressed elec-
1.2 trode to that of uncharged/unloaded specimen. The hydrogen
factor kH is defined as the anodic current density ratio of the hydro-
gen-charged electrode ia(H) to the uncharged under the stress-free
condition, ia,
0.8
 
ia ðHÞ DU H  T DSH
kH ¼ ¼ exp a ð1Þ
Ecorr ia RT
0.4 where a is the electric charge transfer coefficient for the interface
-1.4 -1.2 -1.0 -0.8 -0.6 -0.4
reaction, R is the gas constant and T is the absolute temperature,
Eapp (VSCE) DUH and DSH are the increments of internal energy and the entropy
of steel electrode due to incorporation of dissolved hydrogen,
Fig. 6. Effect of applied potential on crack nucleation lifetime.
respectively. The stress factor kr is the ratio of the anodic current
density of the loaded electrode ia(r) to that of the non-loaded one ia
1.6
" !#
Oxidizing side i a ð rÞ 3Mð1  2mÞr2h M rh ep V p;max Mep
Charging side kr ¼ ¼ exp a þ þ
ia Eq RT ef q RT q RT
¼ ke kp ð2Þ
dcmax/dt (10 m/s)

1.2

M, q, E and m are the atomic mass, density, Young’s modulus and

-10

P
Poisson’s ratio of electrode material, rh ¼ 13 3j¼1 rjj is the hydro-
0.8 static stress, and rjj ðj ¼ 1; 2; 3Þ are the principle stresses, ep and
ep are the plastic strain and the stored strain energy caused by
the plastic deformation, respectively, ef and V p;max are the fracture
0.4 ductility of the material and the maximum volume expansion due
σmax/SMYS =1.05 to the damage produced by plastic deformation. As indicated by Eq.
ν = 0.1Hz, R=0.5 Ecorr (2), the stress factor can be expressed as the product of the elastic
0.0 deformation factor ke and the plastic deformation factor kp. They
-1.4 -1.2 -1.0 -0.8 -0.6 -0.4 are given by
Eapp (VSCE)  
3Mð1  2mÞr2h
ke ¼ exp a ð3Þ
Fig. 7. Effect of applied potential on the crack propagation rate. Eq RT
" !#
Mep M rh ep V p;max
in the negative direction. When the applied potential was lower kp ¼ exp a þ ð4Þ
q RT ef q RT
than 0.8 VSCE, the crack propagation rates at the oxidizing side
were higher than at the charging side, indicating the contribution The synergistic factor kS is used to evaluated the effect due to
of anodic dissolution to the crack growth. However, at the poten- the interaction of dissolved hydrogen and stress field.
tials around the Ecorr, the difference in the crack growth rates under " #
the same potential was so marked as that observed in the crack ia ðr; HÞ rh C H V H
Ks ¼ exp a ð5Þ
nucleation lifetime. This result implies that the crack propagation kH kr ia RT
process is mainly dominated by the dissolved hydrogen concentra-
tion and is less influenced by anodic dissolution. This is not sur- where ia(r, H) is the anodic current density of the loaded and hydro-
prising because the local hydrogen concentration at the crack tip gen-charged electrode, CH is the dissolved hydrogen concentration
is much higher than that at the free surface. and V H is the partial molar volume of hydrogen in the metallic elec-
The EAC tendency on the charging side shown in Figs. 3–7 trode. The experimental data in Table 1 shows that, although the
agrees well with the results of slow strain rate tensile tests re- dissolved hydrogen and applied stress can increase the anodic cur-
ported in the literature [2,4,8,9]. Since both anodic dissolution rent density slightly, their effects are very limited. In particular, the
and dissolved hydrogen can promote the EAC of pipeline steel, synergistic effect of applied stress and dissolved hydrogen is negli-
their roles in EAC of pipeline steel in near-neutral pH groundwater gible. It is noteworthy to point out that the kp value for a specific
will be further examined. material relies heavily on the dislocation structure formed in plastic

4. Effects of dissolved hydrogen and local stress field on active Table 1

Effects of dissolved hydrogen and applied stress on anodic current density at 0.7 VSCE.
dissolution at crack tip
Unstressed/ Stressed/ Unstressed/ Stressed/
A large number of experimental observations have indicated the uncharged uncharged charged charged
(ia/Am2) (ia(r)/Am2) (ia(Y)/Am2) (ia(r,Y)/Am2)
substantial anodic dissolution at the crack wall [1,2,24]. If the ano-
dic dissolution dominates the cracking, the anodic dissolution at 0.0169 0.0241 0.0206 0.0302
– kr = ia(r)/ia kH = ia(Y)/ia kS = ia(r,Y)/(kHkria)
the crack tip must be enhanced by the interaction between the
– 1.43 1.22 1.02
local stress field and enriched dissolved hydrogen concentration
1792 B.T. Lu et al. / Corrosion Science 52 (2010) 1787–1795
deformation processes. The detailed analysis was given elsewhere
[12]. The experimental data in Table 1 are in good agreement with
the thermodynamic analysis [12].
At a crack tip, the local stress level is much higher than that
used in our experiment. However, our theoretical analysis has indi-
cated that for pipeline steels, the maximum ratio of the anodic cur-
rent density at the crack tip and the crack wall is not larger than 2.3
[12]. This value is not large enough to prevent the crack from losing
its sharpness if the crack propagation is controlled by anodic disso-
lution at the crack tip. Because of the substantial lateral dissolution
on the crack side-walls, the crack tip will be blunted. This reduces
the stress concentration at the crack tip and, in turn slows down
the anodic dissolution at the crack tip. Eventually, the blunt crack
will likely stop propagating. The synergistic impact of dissolved
hydrogen and applied stress is expected to be even less marked
during crack nucleation, because both lower hydrogen concentra-
tions and lower levels of local stresses are involved. Therefore,
the cracking of pipeline steels in the anaerobic groundwater of
near-neutral pH is unlikely to be governed by a mechanism of ano-
dic dissolution type and the anodic dissolution must affect the EAC
via some other mechanisms.
5. Roles of dissolved hydrogen, anodic dissolution and plasticity
in EAC
It has been found that the cracks in pipeline steel, when it is
cyclically loaded in the simulated near-neutral pH groundwater,
are more likely to nucleate at the edge of the specimens [24]. It
is well known that the confinement of the plastic deformation
is weakest at the edge of an un-notched specimen. Hence, mi-
cro-plastic deformation may occur preferentially at these loca-
tions, when the cyclic stress is below the yield strength [23].
This implies that localized micro-plastic deformation plays a
crucial role in the crack nucleation process. SEM analysis has re-
vealed a trace of plastic tearing on the fracture surface of cleav-
age-like transgranular SCC [24,25]. Several theoretical models
have been developed to correlate the transgranular cracking and
the local stress caused by the development of dislocation pile-
ups [25,26]. Parkins et al. [2,8,27] pointed out that the SCC pro-
cess might be controlled by the local plastic strain rate and/or
creep at the crack tip, and that cracks would be dormant if the
plastic strain rate at the crack tip cannot maintain crack propaga-
tion. The experimental evidence has revealed that the action of a
cyclic load can accelerate room temperature creep of pipeline
steels [2,8,28]. Garbtta et al. [29] believed that the strain rate at
the crack tip was a key factor controlling the crack propagation
of pipeline steels in near-neutral pH groundwater, and its influ-
ence was much stronger than the solution chemistry, including
the dissolved species and pH. The fact that the EAC of pipeline
steels in the anaerobic groundwater with near-neutral pH takes
place preferably under the action of cyclic or dynamic loads indi-
cates that the cyclic load-promoted creep may play an important
role in the EAC processes.
Figs. 6 and 7 indicate that the crack propagation rate increases
generally with an increase in the concentration of dissolved hydro-
gen in the steel and that the crack nucleation lifetime at the oxidiz-
ing side, where the anodic dissolution rate is essentially unchanged,
is reduced almost monotonically with decreasing the applied poten-
tial. These phenomena suggest the dominative role of dissolved
hydrogen in the EAC processes. It is well known that the ingress of
hydrogen will reduce the internal cohesive strength of metals
[7,30]. Actually, the occurrence of localized micro-plastic deforma-
tion is also necessary to nucleate cleavage cracking in non-corrosive
environments [31]. The enhanced mobility of dislocations due to the
hydrogen–dislocation interaction is likely to promote cracking
because the cracking occurs when the local fracture toughness is
reached [7,26], especially if the local fracture toughness is lowered
by the adsorption of hydrogen along the slip plane[32]. The fact that
the hydrogen-induced cracking behavior of pipeline steel obeys von
Mises criterion [33] suggests strongly that the dissolved hydrogen
in the steel is likely to affect the cracking process via the mechanism
of hydrogen-induced plasticity. Dissolved hydrogen-promoted creep
has been found in iron and carbon steels [34–37]. In each case, the
creep behavior returned to its original condition after the hydrogen
was removed from the hydrogen-charged materials. When a stress
gradient existed, dissolved hydrogen reduced the flow stress of the
material and facilitated localized surface plastic deformation
[38,39]. Hydrogen enrichment can promote the development of lo-
cal stress and tri-axial stress gradients [34] but the plastic deforma-
tion can also accelerate hydrogen release [40]. Hydrogen-induced
surface plasticity has also been detected by the nanoindentation
technique [41]. These observations suggest that hydrogen-induced
plasticity may be an important contributor to a possible cracking
mechanism for the EAC of pipeline steels, i.e., localized plastic defor-
mation is enhanced with an increasing concentration of dissolved
hydrogen and gives rise to cracking, although more direct experi-
mental proof is still required.
According to the data in Figs. 4–6, not only the dissolved hydro-
gen, but also the anodic dissolution promotes the cracking pro-
cesses, especially in the potential region below the open circuit
potential. Magnin et al. [26] proposed a SCC model of corrosion-en-
hanced plasticity, based on many experimental observations in FCC
metals. According to this model, the local plasticity will be en-
hanced by localized anodic dissolution and dissolved hydrogen.
Wei et al. [42] measured the plastic deformation at crack tips of
copper during corrosion fatigue in 3.5% NaCl solution using
speckle-interferometry technique, and found the anodic dissolu-
tion could promote plastic deformation. Magnin et al. [26] have
studied the hydrogen–dislocation interactions using numerical
simulation. However, the mechanism for the anodic dissolution-in-
duced plasticity needs to be further examined. It is natural to relate
the effect of anodic dissolution on the crack nucleation, to the pits
formed in the corrosion processes, because pits can offer both the
stress concentrators and the local environmental conditions which
facilitate crack nucleation [43]. In laboratory investigations, two
types of cracks have been detected in near-neutral pH SCC, namely,
pit-cracks and non-pit-cracks [24,44]. The former nucleated from
pits but the latter were related to the localized plastic deformation
instead of pits. The number of non-pit-cracks found on the speci-
mens with original external pipe surface conditions was much
higher than that of pit-cracks [24]. In the present investigation, pits
were rarely found and a lot of crack nucleation was not related to
pits. Therefore, another mechanism for anodic dissolution-pro-
moted SCC should be considered, besides the pitting-induced
cracking.
According to Jones and Jankowski [20,45], Lian and Meletis [16]
and Duquette [46], anodic dissolution on the surface could increase
the mobility of dislocations in the surface layer and therefore pro-
mote the localized surface plasticity. Similar to the hydrogen-in-
duced plasticity, the anodic dissolution-induced plasticity is
expected to play a role in crack nucleation [20,47]. Gutman [19]
pointed out that when anodic current was present at the surface,
the flow stress in the surface layer would decrease because of
the chemo-mechanical interaction. With the aid of theories of
non-equilibrium thermodynamics and dislocation kinetics, the
authors found that the dependence of the decrease in the shear
flow stress induced by the anodic dissolution Dsa on the anodic
dissolution current density ia, was approximately formulated as
follows [21]
 
kT ianodic
Dsa ¼  ln ð6Þ
vd ith
 B.T. Lu et al. / Corrosion Science 52 (2010) 1787–1795
where k is the Boltzman constant, T the temperature, vd the average
activated volume of dislocation sources and ith the threshold anodic
current density to cause the corrosion-induced plasticity effect.
Note that the anodic dissolution-induced plasticity is only re-
stricted to a thin layer underneath the surface exposed to the cor-
rosive medium, the thickness of which is less than the mean free
path of dislocations. It is therefore very difficult to experimentally
measure the decrease in the flow stress induced by anodic
dissolution.
An alternative way has to be utilized to characterize the anodic
dissolution-induced plasticity [19,48,49]. It is well known that the
hardness of steels are approximately proportional to the flow
stress. To a first approximation, the relative decrease of hardness
(DHv/Hv) can be correlated to the anodic current density via the
following expression [21]
 
DH m ianodic
¼ B log
Hv ith
where DHv = Hv  Hv0, Hv and Hv0 are the hardness values with
and without the presence of anodic dissolution, B is an experimen-
tal constant. The validity of Eq. (7) is confirmed by the test data in
Fig. 8. The experimental facilities and methods to measure the hard-
ness while anodic current is applied is given elsewhere [21].
Although some experimental evidence has implied the existence
of the anodic dissolution-induced plasticity, its mechanism is not
yet well known. Some researchers believed that the anodic dissolu-
tion-induced plasticity would attenuate the strain-hardening of the
subsurface region, and that it might result from the formation and
diffusion of vacancies in the surface layer, which was produced by
the anodic dissolution [20,45]. Anodic dissolution-induced localized
plasticity has been observed in low carbon steel [50], brass [51] and
titanium alloy [52]. Magnin et al. [26] pointed out that the weaken-
ing of inter-atomic bonds due to the subsurface vacancies would
lead to a local reduction in the energy barrier for dislocation nucle-
ation. The chemical potential gradient in the surface layer may lead
to an increase in the mobility of dislocations within surface layer
[19]. This is demonstrated by the accelerated creep of metals while
anodic current is applied on the surface. The increment of creep rate
caused by the anodic dissolution e_ Ac can be expressed as [19,21]
c_ Ac ¼ Lia
L is an experimental constant. The phenomenon of anodic dissolu-
tion-promoted creep has been found in austenitic stainless steels
[53,54], copper [55,56], magnesium [57], cadium [19] and brass
[51]. The creep rate increases as anodic current is applied and
0.00
-0.04
-0.08
ΔHv/Hv
-0.12
-0.16
-0.20 X60
NS4 solution
-0.24
-3 -2 -1 0 1 2
10 10 10 10 10 10
2
ianodic (A/m )
Fig. 8. Effect of anodic dissolution current density on hardness.
1793
recovers its original value after the current is shut-off [19,53]. It is
known that the mean free path of a dislocation possesses a value
no larger than the grain size of a material, and only the dislocations
situated in the surface layer at a depth less than or equal to the
mean free path can reach the surface [19]. Therefore, the anodic dis-
solution–promoted creep is more likely to be observed in stressed
thin wire or foil [19,53].
Duquette [46] and Lian and Meletis [16] found that both the
intensity and localization of surface plastic deformation were en-
hanced by anodic dissolution and the slip bands were more likely
to be attacked. Consequently, the synergistic action of hydrogen-
and anodic dissolution-induced plasticity may be a possible EAC
mechanism of pipeline steels in near-neutral pH groundwater.
6. A modified model of corrosion-facilitated plasticity for EAC
ð7Þ According to the above analysis, a modified model of corrosion-
facilitated plasticity for the EAC of pipeline steel in near-neutral pH
groundwater is tentatively described and is illustrated in Fig. 9,
where the cracking process of steel comprises the following steps.
(1) Localized plastic deformation in the surface layer is induced
by the cyclic load and the effect of dislocations slipping out
of the outmost surface and producing fresh bare metal sur-
face which is exposed to the corrosive environment [58].
(2) The localized plastic deformation resulting from the forma-
tion of slip bands, (a single slip band is schematically illus-
trated for clarity), and/or the dislocation slip within the
slip bands is promoted by the anodic dissolution on the sur-
face, leading to the anodic dissolution-induced plasticity.
Meanwhile, the micro-plastic deformation in the surface
layer is likely to be more non-uniform because the fresh bare
metal surface is prone to being attacked by the corrosive
species [16,46,59]. The localized plastic deformation is more
likely to concentrate at certain locations where the micro-
structure and mechanical behavior is non-uniform, such as
the boundaries of ferrite and pearlite.
(3) The local stress gradients at the surface discontinuity pro-
duced by the slip bands can promote the diffusion of dis-
solved hydrogen into the localized plastic zones. The
ð8Þ localized plastic deformation can accelerate the reduction
of hydrogen ions due to the formation of fresh surface
[34,35,60] and the movement of dislocations can also assist
the ingress of hydrogen atoms into the slip bands [34]. The
enrichment of hydrogen in the slip bands or the adsorption
Fe2+
H
H H
H
H
H H
H H H
H
H
Fe2+
H H
Fe2+ H
H H
Fe2+
Fig. 9. Schematic illustration of chemo-mechanical model for SCC.
1794 B.T. Lu et al. / Corrosion Science 52 (2010) 1787–1795

of hydrogen on a slip plane [26], will in turn promote the
movement of dislocations in the slip bands, as well as the
development of the local stress and stress gradients [34].
In this way, the localized surface plasticity will be further
enhanced. Steps 2 and 3 can occur simultaneously.
(4) When the accumulated micro-plastic deformation at critical
points reaches a threshold value which should be a material
property, a crack will nucleate or re-nucleate. The former
occurs at the free surface exposed to the corrosive medium
and the latter occurs at the crack tip.
(5) After crack nucleation, the crack tip enters an unaffected
zone and a new plastic zone will form at the crack tip
because of the stress concentration. The above process will
be repeated to bring about the crack propagation.
Because both the level and gradient of tri-axial stresses at the
crack tip are much higher than that within the slip band on the
un-notched specimen surface, it results in a much higher local
hydrogen concentration at the crack tip [9,22]. Therefore, hydro-
gen-inducing cracking becomes the dominant mechanism for the
crack growth process and the anodic dissolution does not play as
important a role there as in the crack nucleation stage. Although
anodic dissolution-induced plasticity may contribute to the crack-
ing processes, the crack growth rate cannot be correlated to corro-
sion current density using Faraday’s law.
As a consequence, the localized damage in the near-neutral pH
SCC process results from the cyclic loads (fatigue damage DF),
hydrogen-induced plasticity (DHIP) and anodic dissolution-induced
plasticity (DADIP). The total damage D is the sum of these three
components
D ¼ DF þ DHIP þ DADIP
At the initial state free of damage, the total damage, and its
three components as well, are equal to zero. The conditions of
ties of the material. Since the fatigue damage results mainly from
mechanical force, D_ F is approximately independent of potential.
Thus we have D_ F  108 s1.
The values of D_ HIP and D_ ADIP at various potentials can be esti-
mated using the following procedures.
(1) At 1.2 VSCE and 1 VSCE, the sample surface at the charging
side is under the fully cathodic protection and, hence
D_ ADIP ¼ 0 for the suppression of anodic dissolution. In this
case, t i;ch arg ing ¼ 1=ðD_ F þ D_ HIP Þ. Meanwhile, the surface at
the oxidizing side is at the OCP and the anodic dissolution
rate is governed by the self-corrosion current density of
material. Because the hydrogen concentrations at both side
surfaces are similar, the D_ HIP on both surfaces at any given
potential can be approximately regarded as the same. Thus,
the value of D_ ADIP at the oxidizing side, denoted as
D_ ADIP;oxidizing ; can be given by D_ ADIP:ch arg ing ¼ t1 1
i;oxidizing  t i;ch arg ing .
(2) Since the effects hydrogen and applied stress on the anodic
dissolution rate are limited, we can approximately take the
D_ ADIP;ch arg ing value as a constant and its value is estimated
to be around 6.0  106 s1. The value of D_ HIP at the oxidiz-
ing side under the other potentials can be estimated by
D_ HIP ¼ t 1 _ _
i;oxidizing  DADIP;ch arg ing  DF .
(3) Since the D_ HIP values of both sides at a given potential are
approximately the same, the D_ ADIP value at the charging side
can be estimated from the values of ti,charging and D _ HIP at same
potential: D_ ADIP ¼ t 1 _ _
i;ch arg ing  DHIP  DF .
3 t
.i 1.6
D.
ð9Þ DHIP
.
DADIP 1.2
.
2 DF
D (10 s )
-6 -1

ti (10 s)
DF = 1, DHIP = 1 and DADIP = 1 correspond to the crack nucleation in-
duced solely by fatigue, hydrogen-induced plasticity and anodic 0.8
.

6
dissolution-induced plasticity, respectively. When the pipeline
steel is subjected to the cyclic load and exposed to near-neutral 1
pH groundwater, the damage accumulates with time and the 0.4
nucleation of EAC will occur so long as D = 1. The evolution rate
of each damage component is D_ F ; D_ HIP and D_ ADIP ; respectively. As
a first approximation, we assume that the damage evolution rates
0 0.0
depend only on the test conditions but are independent of time, so -1.2 -1.1 -1.0 -0.9 -0.8 -0.7 -0.6 -0.5
that they are constant during testing if the test conditions are held E (VSCE)
unchanged. Hence, Eq. (4) can be written as
_ ¼ D_ F t þ D_ HIP t þ D_ ADIP t (a) Effects of potential on the crack initiation time
D ¼ Dt ð10Þ and the evolution of damage
The damage evolution rate can be related to the crack incuba-
0
tion time ti as follows 10

D_ ¼ t1
i ð11Þ -2
10
In the following analysis, we denote ti,oxidizing and ti,charging as the
iH-permeation (A/m )
2

ianodic (A/m )

cracking incubation time at the oxidizing side and the charging iH-permeation
side, respectively. -1
10
The experimental results [61] indicated that the cyclic stress le- ianodic
vel adopted in the current experiments was close to the endurance
2

limit of the material, and the mean fatigue crack nucleation life of
samples under such a stress level is about 107cycles. The fatigue 10
-3

damage under cyclic loads with constant amplitude is a function Ecorr

-2
of the number of stress cycles N. If the loading frequency f is con- 10
stant, N = ft, then -1.2 -1.1 -1.0 -0.9 -0.8 -0.7 -0.6 -0.5
E (VSCE)
dDF dN dDF
D_ F ¼ ¼f ð12Þ (b) Dependence of hydrogen permeation rate and
dN dt dN
anodic current densities on applied potential
D_ F will increase with the loading frequency and dDF/dN is a Fig. 10. Dependence of damage evolution rates during the EAC on the dissolved
function the cyclic loading conditions and the mechanical proper- hydrogen concentration and anodic dissolution rate.
 B.T. Lu et al. / Corrosion Science 52 (2010) 1787–1795
The evolution rates of overall damage and each component on
the charging side, together with the crack nucleation lifetime
determined at the same side, are plotted against the potential in
Fig. 10a. It suggests that the contribution of fatigue to the total
damage, under the current test condition, is negligible. To evaluate
the dependence of D_ HIP and D_ ADIP on potential, the anodic current
density and the hydrogen permeation current density on the ap-
plied potential is illustrated in Fig. 10b. The true anodic dissolution
current density ianodic in Fig. 9b is approximately estimated from
the anodic polarization curve. The hydrogen permeation current
density, iHpermeation, can serve as an indicator of dissolved hydrogen
concentration [8]. The damage evolution rate due to the hydrogen-
induced plasticity, D_ HIP , increases monotonically as the potential
shifts in the negative direction. This is because the dissolved
hydrogen concentration in steel, as indicated by the hydrogen per-
meation current density (iHpermeation) in Fig. 9b, increases with
decreasing potential. An increase in the dissolved hydrogen con-
centration will promote the hydrogen-induced plasticity. At poten-
tials below 0.8 VSCE, the damage resulting from the anodic
dissolution-induced plasticity is negligible because of the suppres-
sion of anodic dissolution. When the potential is higher than 0.8
_ ADIP initially increases with the potential, because the anodic
VSCE, D
dissolution-induced plasticity is enhanced by increased anodic dis-
solution current density (ianodic). However, the effect of anodic dis-
solution on the crack nucleation possesses a two-fold character. It
is known that even in uniform corrosion, the anodic dissolution
takes place preferentially at certain active sites on the electrode
surface, but the locations of the active sites changes all the time.
Some of the active sites like slip bands may be the potential loca-
tions for crack nucleation. If the anodic current density is suffi-
ciently large, it will cause dissolution of potential crack nuclei, so
that the crack nucleation will be delayed, and may even be sup-
pressed. Therefore, the dependence of D_ ADIP on applied potential
is a bell-shaped curve and the contribution of anodic dissolution-
induced plasticity reaches a peak at the potential around the
OCP. When the potential is low than 0.8 VSCE, the crack nucleation
is dominated by the mechanism of hydrogen-induced plasticity. At
the potentials around the OCP, both hydrogen-induced plasticity
and anodic dissolution-induced plasticity contribute to the damage
accumulation.
7. Conclusions
(1) The Devanathan dual cell technique can be used as a useful
tool in SCC tests to control the dissolved hydrogen concen-
tration in specimens and the anodic current density on the
test surface independently.
(2) The dissolved hydrogen in pipeline steel promotes the EAC
in near-neutral pH groundwater but the effect of anodic dis-
solution depends on the value of the anodic current density.
At potentials below the open circuit potential, anodic disso-
lution facilitates crack nucleation. However, if the anodic
current density is too high, crack nucleation is delayed
because of the dissolution of crack nuclei.
(3) The crack propagation of pipeline steel in near-neutral pH
groundwater is mainly dominated by the dissolved hydrogen
concentration and is less influenced by anodic dissolution.
(4) The dependence the resistance of pipeline to the EAC in
near-neutral pH groundwater can be interpreted using an
improved corrosion-facilitated plasticity model. At the
potentials around the OCP, both the hydrogen- and anodic
dissolution-induced plasticity play important roles in the
crack nucleation process.
1795
Acknowledgements
This project was supported by a Strategic Project Grant of the
Natural Sciences and Engineering Research Council of Canada, Syn-
crude Canada Ltd., Dow, IPSCO and NOVA. Dr. R. Eadie’s discussion
is also appreciated.
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