International Journal of Pressure Vessels and Piping 99-100 (2012) 34e43

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International Journal of Pressure Vessels and Piping

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A possible explanation for the contradictory results of hydrogen effects on

macroscopic deformation
Reza Miresmaeili a, *, Lijun Liu b, Hiroshi Kanayama c
a
Department of Materials Engineering, Faculty of Engineering, Tarbiat Modares University, Jalal Ale Ahmad Highway, P.O. Box: 14115-143, Tehran, Iran
b
Department of Intelligent Machinery and Systems, Graduate School of Engineering, Kyushu University, 744, Motooka, Nishi-ku, Fukuoka 819-0395, Japan
c
Department of Mechanical Engineering, Faculty of Engineering, Kyushu University, 744, Motooka, Nishi-ku, Fukuoka 819-0395, Japan

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

Article history: Despite extensive research, there have been many controversies on whether hydrogen hardens or softens
Received 12 June 2012 iron and steels. Conventional application of hydrogen-enhanced localized plasticity (HELP) theory e
Received in revised form including a decrease in the local ow stress in the presence of hydrogen e results in an expansion in the
31 July 2012
plastic zone ahead of a blunting crack tip rather than the localization of plastic deformation. Therefore,
Accepted 1 August 2012
we propose a model to interpret the criterion for the application of local softening concept. According to
our physical model, called pinning-softening model, the hydrogen-induced softening merely occurs in
Keywords:
the large shear stress regions, e.g. in the vicinity of the crack tip. The remote areas from the stress raisers
Hydrogen embrittlement
Hydrogen-induced hardening/softening
do not satisfy the critical condition of slip; as such, hydrogen-induced hardening occurs. Our model not
Local ow stress only explains the contradictory results of hydrogen effects on the macroscopic deformation, but also
Coupled analysis gives more insight into the mechanistic understanding of hydrogen embrittlement phenomenon.
Plastic deformation 2012 Elsevier Ltd. All rights reserved.

1. Introduction experimental observations, there is no single mechanism that can

Hydrogen is the smallest and lightest of all atoms; therefore, it
diffuses through metals very easily. The high diffusivity of hydrogen
and its low solubility in steels makes it extremely difcult to
conduct physical experiments and to interpret the results.
In the presence of hydrogen, materials fail at lower load levels in
comparison with hydrogen-free materials. The failure is often
premature and catastrophic, sometimes occurring after many years
of service. Alp et al. [1], and Bernstein and Thompson [2] have re-
ported that the microstructure has signicant effects on a materials
susceptibility to hydrogen embrittlement. The severity of the
degradation depends on the characteristics of the particular
material, the amount of hydrogen occluded and the distribution of
the dissolved hydrogen [3], whereas the susceptibility to hydrogen
embrittlement is inuenced by operating conditions such as
hydrogen fugacity, strain rate and working temperature.
Despite extensive research, the mechanisms involved in
hydrogen embrittlement are still unclear. While there are several
viable mechanisms of hydrogen-plasticity which are supported by
explain all instances of hydrogen embrittlement e the search for
a single mechanism to explain all observations is likely to end in
failure [4,5]. In fact, it appears that different mechanisms apply to
different systems under various conditions. However, it has been
established that in general, the interaction of hydrogen with the
lattice and defects in the vicinity of a major crack is the basis of the
damage caused by hydrogen embrittlement. Of the many proposed
mechanisms, three appear to be more popular: stress-induced
hydride formation and cleavage [6e10], hydrogen-induced deco-
hesion [11,12] and hydrogen-enhanced localized plasticity (HELP)
[4]. The current work has been conducted in the frame work of
HELP theory; therefore, in the following section, we review the
literature on the plastic behavior of materials from hydrogen effect
on the local ow stress viewpoint.
2. Plastic behavior of materials in the presence of hydrogen
2.1. A review of hydrogen-induced softening and hardening in
metallic materials

* Corresponding author. Tel.: 98 21 8288 4357.
E-mail addresses: miresmaeili@modares.ac.ir, reza.miresmaeili@gmail.com,
miresmaeili@kyudai.jp (R. Miresmaeili), liu@cm.mech.kyushu-u.ac.jp (L. Liu),
kanayama@mech.kyushu-u.ac.jp (H. Kanayama).
Johnson et al. [13] and Troiano [14] have reported that hydrogen
embrittlement is controlled by the diffusion of hydrogen into the
crack tip region and is strongly inuenced by hydrostatic stress
gradients. Beachem [15] has presented a model for hydrogen-

0308-0161/$ e see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ijpvp.2012.08.001
 R. Miresmaeili et al. / International Journal of Pressure Vessels and Piping 99-100 (2012) 34e43
assisted cracking which explains the decreasing microscopic plas-
ticity due to decreasing stress intensities at crack tips during stress
corrosion cracking. According to his work, hydrogen inuences
hydrogen environment embrittlement (HEE) by reducing the local
stress required for dislocation motion. Bernstein [16] introduced
the concept of a highly localized plastic rupture mechanism.
Beachem [15] and Bernstein [16] found a reduction in the yield and
ow stress compared to uncharged material. The effects of
hydrogen on the softening of high purity iron were reported by
Matsui et al. [17,18], Moriya et al. [19] and Kimura et al. [20]. In
contrast to the softening behavior, hardening has been reported by
some researchers. Asano and Otsuka [21,22] have presented that
the ow stress of iron and steel always increases by introduction of
dissolved hydrogen during deformation. Oriani [23] reported the
hardening of carbon steels in the presence of hydrogen. Kimura
et al. [24], and Kimura and Matsui [25] consider that the hydrogen
induced hardening often reported for electrolytic iron, mild steels
and iron alloys is due to a combined effect of hydrogen-
soluteedislocation interaction. Oguri and Kimura [26] reported
a remarkable correlation between the solution softening due to
impurities, including carbon, and the effect of hydrogen, i.e. soft-
ening or hardening depending on the specimen purity.
To address the problem of how hydrogen affects the ow stress
of iron and steel, Matsumoto et al. [27] investigated the effects of
hydrogen on the dislocation behavior in nickel and reported an
enhancement of the dislocation motion due to the low level of
hydrogen in solid solution. Tabata and Birnbaum [28,29] reported
the effect of hydrogen on the behavior of dislocations in iron of
various purities by using an in situ deformation technique in the
environmental cell of a high voltage electron microscope. More-
over, they have reported that hydrogen enhanced fracture of iron
(having a wide range of purities) is caused by the localization of
plasticity and by the enhancement of dislocation motion and
generation.
2.2. Contradictory aspects of hydrogenedislocation interaction
While some macroscopic deformation observations appear to be
supportive of the direct observations of hydrogen enhanced dislo-
cation mobility, in many similar measurements, ow stress hard-
ening rather than softening is observed. Despite extensive research,
there have been many controversies on whether hydrogen hardens
or softens iron and steels. On the basis of experimental results,
Kimura and Matsui [30] have proposed that the hydrogen-induced
softening in high purity iron (200 Ke300 K) is caused by an
increased mobility of screw dislocations. Hydrogen modies the
Peierls potential of screw dislocations, thereby increasing their
mobility. While on the contrary, presence of large hydrogen
concentration at the dislocation core in low temperature results in
a pinning of kinks on screw dislocations, thereby inducing the
hardening in high purity iron.
Recently Murakami et al. [31] have reported that hydrogen can
have an effect against hydrogen embrittlement. This surprising
nding was achieved in which charging a supersaturated level of
hydrogen into specimens of austenitic stainless steels drastically
improved the fatigue crack growth resistance. They explained
a reason for this dramatic effect of hydrogen by considering two
contradictory aspects of hydrogenedislocation interaction as
pinning (or dragging) and enhancement of mobility. Competition
between these two factors determines whether the resulting
phenomenon is softening or hardening.
The purpose of this work is to contribute to a better under-
standing of the hydrogeneplasticity interactions in the body-
centered cubic (BCC) iron and austenitic stainless steel type 316L
by studying the macroscopic effect of hydrogen on the tensile
35
characteristics of materials. It is necessary to reconsider the appli-
cation of hydrogen-induced softening model [32e37] e which is
based on the reduction in the local ow stress by an increase in
the hydrogen concentration e to hydrogeneplasticity interaction
phenomena in correlation with the hydrogen content and the
stressestrain state of computational domain. The proposed model
in Section 3, which reconsiders the application of local softening
model, may prepare a possible explanation for the contradictory
results of hydrogen-induced softening/hardening effects on the
macroscopic deformation observations. Moreover, unlike the
conventional application of HELP theory (see Section 3), our new
physical model can describe the presence of narrower plastic
region ahead of the crack tip in a hydrogen-charged sample than
the one in the hydrogen-free sample.
3. Present study: a model for revising the application of
hydrogen-induced softening
The crack growth path in hydrogen-charged specimens is rela-
tively linear and a relatively few slip bands are observed, whereas
the crack growth path in the uncharged specimens is more zigzag
and numerous slip bands are widespread all over the fracture
surface [38]. Murakami et al. [39] have proposed a mechanism for
fatigue crack growth of ductile materials, in the presence of
hydrogen, based on striations formed by slip at a crack tip. The basic
mechanism is the diffusion of hydrogen to, and concentration of
hydrogen at, crack tip. This leads to the activation of hydrogen-
induced slip formation. Their model shows that, in the presence
of hydrogen, a growing fatigue crack has a smaller plastic zone size
and a smaller crack tip opening displacement than in the absence of
hydrogen effect.
In our previous numerical simulation [32], using a uniaxial
stressestrain relation of power law hardening, proposed by
Sofronis et al. [33], in which ow stress reduces by an increase in
the hydrogen concentration [32e37,40], we are unable to model
the reduction in the plastic zone size in the presence of hydrogen.
In fact, by using the local softening concept throughout a domain,
we merely observe an expansion in the plastic zone due to the
presence of hydrogen. The higher the hydrogen concentration, the
more the extension in the size of plastic zone ahead of the crack tip.
Close observation of our previous study [32] reveals that, when the
p
stress intensity factor KI at the crack tip is at 40 MPa m, an increase
in the initial hydrogen concentration, C0, from 0 to 1.94 mass ppm
increases the size of plastic zone in both x and y directions from
0.92 to 1.53 mm and 4.24 to 7.06 mm, respectively (see Fig. 8 of
Ref. [32]). This result is completely in opposite direction of the
experimental observations [38,39] and also is against the concept
of HELP theory which is based on the localization of slip bands.
Considering the above-mentioned ndings, we need to revise
the criterion for the application of local softening model in our
computations. We interpret that the local softening model acts
inside the domain in the vicinity of the crack tip and the zone
outside does not satisfy the critical condition of slip. We propose
a physical model to interpret the criterion for the application of
local softening in a computational domain. In fact, this model
illustrates an indirect application for the pinning/releasing inter-
action effects of dislocations and hydrogen atoms [17,30,31]. In our
physical model, called pinning-softening model, the local softening
only occurs in the vicinity of the crack tip. In such regions enough
shear stress exists to overcome the critical shear stress for dislo-
cation glide. As described in Murakami et al. [31], once a dislocation
is released from pinning by hydrogen at its core, its mobility is
increased. The remote areas from the crack tip do not satisfy the
critical condition of slip. In such regions, hydrogen trapped by
a dislocation increases the critical shear stress for dislocation glide.
36 R. Miresmaeili et al. / International Journal of Pressure Vessels and Piping 99-100 (2012) 34e43
Therefore, hydrogen atoms hinder dislocation motion by a pinning
effect. The higher the hydrogen concentration, the stronger the
pinning effect [17,30,31]. The pinning effect in the remote distance
from the crack tip contributes to increasing the strength of mate-
rials. Using such a physical model e which considers two contra-
dictory aspects of hydrogenedislocation interaction as pinning
(or dragging) and enhancement of mobility e can explain the
presence of smaller plastic zone size and smaller crack tip opening
displacement in the presence of hydrogen than the ones in the
absence of hydrogen.
To introduce the above-mentioned criterion, we assume
the local softening merely occurs at the crack tip region where the
maximum shear stress (smax s1  s3 =2 with s1 and s3 as the
largest and smallest principal stresses, respectively) is equal or
greater than a critical shear stress (scrit) for the dislocation glide, i.e.
smax  scrit. As can be seen in Fig. 1, the maximum shear stress has
its largest values in the vicinity of the crack tip. As such, crack tip
regions experience local softening based on the HELP theory while
remote areas from the crack tip, in which maximum shear stress is
always lower than the critical ones, i.e. smax < scrit, experience
dislocation pinning phenomenon. Therefore, hardening occurs at
the remote regions. We propose a hydrogen-concentration-
dependent function for the critical shear stress as a criterion for
transition from softening to hardening throughout the domain. Eq.
(1) shows the above-mentioned function and is interpreted by the
fact that a higher hydrogen concentration produces a stronger
pinning effect [17,30,31].
scrit s0 1 2c; (1)
where scrit is the critical shear stress for the dislocation glide,
s0 z G/500 is the Peierls stress with G as the shear modulus and
c (CL CT)/NL is the normalized total hydrogen concentration
with CL as the hydrogen concentration in lattice sites, CT as the
number of trapped hydrogen atoms per unit lattice volume and NL
as the number of interstitial lattice sites per unit lattice volume, and
2  0 is a parameter describing the extent of hydrogen-pinning
effect on dislocations.
A model of local ow stress was proposed by Sofronis et al. [33] as
 n
p Orianis expression [46], CT CLNTKT/(KTCL NL), with KT as an
sY s0 c 1 ; (2)
0 equilibrium constant, a transient hydrogen transport equation is
where p denotes the equivalent plastic strain, 0 s0/E is the initial
yield strain which corresponds to initial yield stress in the absence
of hydrogen (s0) with E being Youngs modulus and n, the work
hardening exponent. s0(c) is the yield stress in the presence of
hydrogen which, as suggested by Kotake et al. [34], is given in
a linear form:
Fig. 1. A contour plot of maximum shear stress smax (s1  s3)/2 in BCC iron when the
p
stress intensity factor KI at the crack tip is at 30 Mpa m.
s0 c xc 1s0
if smax at t  scrit at t 0hydrogen  induced softening0x < 0;
else if smax at t < scrit at t 0hydrogen  induced (3)
hardening0x>0
where x is a coupled effect parameter to represent the behavior of
yield stress in the presence of hydrogen. In our new physical model,
i.e. pinning-softening model, the coupled effect parameter x is set
to a negative value wherever smax  scrit in order to take into
consideration the hydrogen-induced softening effect on materials,
whereas the positive values of x are conserved for the regions in
which smax < scrit in order to introduce the hydrogen-induced
hardening effect into the materials.
4. Hydrogen transport equation
The diffusion formulation is based on Krom et al.s paper [41]
which modied Sofronis and McMeekings convection diffusion
equation [42]. A detailed description of the governing equation,
numerical schemes and the related discretizations can be found
elsewhere [41e43]. Here, the descriptions are limited to intro-
ducing the physics of hydrogen transport and the required
parameters for the hydrogen advection diffusion.
Transported hydrogen is assumed to reside either at normal
interstitial lattice sites (NILS) or at reversible trapping sites that are
microstructural defects generated by plastic deformation. We
assume, as per Sofronis and McMeeking [42] and Krom et al. [41],
that traps are isolated in that they do not form an extended
network. Hence, hydrogen is considered to move through materials
by NILS diffusion. In other words, the dislocation transport mode is
neglected in view of studies by Frankel and Latanision [44], and
Ladna and Birnbaum [45]. Moreover, only one type of trap e the
saturable and reversible type e is considered.
Hydrogen atoms expand the host lattice. The chemical potential
of hydrogen in regions of tensile hydrostatic stress is therefore
lower. As a result, there exist chemical potential gradients which
encourage hydrogen diffusion. Lattice sites under tensile hydro-
static stress attract hydrogen whereas those under compression
repel it to eliminate the gradients of the chemical potential. Using
then represented as follows:
!
CL CT 1  qT vCL C D V
V,DL VCL V, L L H Vsh
CL vt RT
(4)
dN vp
qT T 0:
dP vt
where qT denotes the occupancy of the available trap sites, i.e. qT is
the ratio of occupied sites to the total available ones, and NT is the
number of trapping sites per unit lattice volume. DL is the lattice
diffusion constant, R the gas constant and T the absolute temper-
ature. V H is the partial molar volume of hydrogen. sh denotes the
P
hydrostatic stress such that sh 1=3 3i 1 sii .
For BCC iron, we calculate the term of dNT/dp from the
following monotonic increasing function [41,42]:
log10 NT 23:26  2:33e5:5p ; (5)
in which, according to Kumnick and Johnsons paper [47], the trap
site density depends only upon the plastic strain P. While for the
austenitic stainless steel type 316L, we estimate the trap density by
using lattice parameter information. For example, in face-centered
cubic (FCC) systems, assuming one hydrogen trap per atomic plane
threaded by a dislocation, we may write [48]:
 R. Miresmaeili et al. / International Journal of Pressure Vessels and Piping 99-100 (2012) 34e43 37

rd 6.0E+24
NT ; (6)
d
5.0E+24
where pd is the distance between two (111) planes given as
d a= 3, a is the lattice parameter and rd the dislocation density. 4.0E+24
Hence,

NT (m-3)
p 3.0E+24
3
NT r : (7)
a d calculated from Feaugas' results [49]
2.0E+24
From Feaugas [49], we determine numerically the dislocation adopted Spline for computations
density rd against the equivalent plastic strain as indicated in 1.0E+24
Fig. 2. Using Eq. (7) with a (3.597  0.003)  1010 m for 316L
[50], we then draw the number of trap sites per unit lattice 0.0E+00
volume NT against the equivalent plastic strain. Fig. 3 illustrates 0 5 10 15 20 25 30 35 40
Equivalent plastic strain (%)
the proposed relationship between the trap density NT and the
equivalent plastic strain p. As illustrated in this gure, an adopted Fig. 3. Trap density of 316L at different amount of equivalent plastic strains and the
Spline-function approximates the calculated data from results adopted Spline-function for the computations.
given in Feaugas [49]. We then implement the Spline-function to
compute the term of dNT/dp for the austenitic stainless steel 6. Modeling, boundary conditions and material properties
type 316L.
We study the pinning-softening model (see Section 3) through
5. Coupled analysis specications its application to the different analyses of a blunting crack tip
[32,34,41e43] and a tensile specimen [35,51].
In this study, we establish a fully coupled analysis to evaluate
the hydrogen transport near a blunting crack tip by taking into 6.1. A model of blunting crack tip
consideration the effect of hydrogen on the material local soft-
ening/hardening as well as the effect of structural analysis on Finite element analyses are employed to solve the boundary
hydrogen diffusion phenomena at the lattice and trap sites value problems of large strain elasto-plasticity in the vicinity of
(as described in Sections 3 and 4, respectively). Fig. 4 illustrates a blunting crack tip under mode I (tensile) opening and small scale
a owchart of the coupled analysis in which the general purpose yielding conditions. Fig. 5 shows the half-symmetry 3D geometry
code MSC. Marc is used for structural analysis and an in-house domain and the boundary conditions used for structural and
nite element program is used for the hydrogen diffusion diffusion analyses. As shown in this gure, symmetry boundary
computations. We implement the structural analysis by assuming conditions are applied on the crack plane y 0 while the
an initial hydrogen concentration of C0. This leads to an initial displacements through the thickness are completely constrained
normalized total hydrogen concentration of c0 C0/NL which is (uz 0). The symmetry line q 0 is free of shear tractions and
used in the rst increment to calculate the initial yield stress in the displacements in the y direction are constrained (uy 0), while on
presence of hydrogen (see Eqs. (2) and (3)). We then implement the disc circumference, the displacements are known from the
the rst increment of diffusion analysis by data transferring from elastic solution, which is controlled by KI as per Eqs. (8) and (9).
the rst increment of structural analysis and considering required r  
1n R q
diffusion boundary conditions (see Section 6). At the start of each ux R; q KI cos 3  4n  cos q; (8)
structural analysis step, by using the last element-wise hydrogen E 2p 2
concentration, we update the critical shear stress scrit (see Eq. (1)). r  
1n R q
By comparing the maximum shear stress smax of the previous step uy R; q KI sin 3  4n  cos q (9)
E 2p 2
with the updated critical shear stress scrit (see Section 3), we then
determine the yield stress for the current step of structural
where KI is the stress intensity factor from the linear elastic crack
analysis. p
solution. Its maximum value is considered 30 Mpa m and is
reached by the step of 0.5 s in 75 s. q is the polar angle as shown in
1.2E+15 Fig. 5. E and n are, respectively, Youngs modulus and Poisson ratio
of the material and R is the radius of half-symmetry domain.
1.0E+15 The symmetry axis is isolated, i.e. the hydrogen ux is zero
Dislocation density (m-2)

whereas on the disc circumference and the crack surface, the

8.0E+14 hydrogen concentration in lattice sites is prescribed. The nite
element mesh is established in MSC. Marc for structural analysis
6.0E+14 which consists of 3706 nodes and 1776 8-node hexahedral
elements. This mesh is then converted to the mesh having 21,771
4.0E+14 nodes and 10,656 tetrahedral 10-node elements which is required
for our in-house hydrogen diffusion code. The material used in this
2.0E+14 simulation is BCC iron whose mechanical material properties and
hydrogen diffusion parameters are given in Table 1.
0.0E+00
0 5 10 15 20 25 30 35 40
6.2. A model of tensile specimen
Equivalent plastic strain (%)

Fig. 2. Dislocation density of 316L at different amounts of equivalent plastic strains Finite element analyses are employed to solve boundary value
(calculated from experimental data by Feaugas [49]). problems of large strain elasto-plasticity in the onset of necking in
38 R. Miresmaeili et al. / International Journal of Pressure Vessels and Piping 99-100 (2012) 34e43

Diffusion analysis Structural analysis

c (hydrogen
Large deformation elasto-plastic analysis at time t+dt
concentration) at time t
-Updated Lagrange method
time if ( max ) at t ( crit ) at t Softening < 0
else if ( max ) at t < ( crit ) at t Hardening > 0
G
where crit = 0 (1 + c) with 0 = and 0
500
max = ( 1 3 ) 0.5

Advection-diffusion analysis at u displacement at time t+dt

h hydrostatic stress at time t+dt
time t+dt p equivalent plastic strain at time t & t+dt
- Backward Euler method for time
integration

c (hydrogen Large deformation elasto-plastic

concentration) at time t+dt analysis at time t+2dt

Fig. 4. A owchart of the coupled hydrogen diffusion-structural analysis.

tension. In uniaxial tension, after attaining the maximum macro-
scopically applied load, the necking is triggered. To simulate the
onset of necking, we take a specimen that features an initial small
geometric imperfection. The model is illustrated in Fig. 6. The
specimen is pulled in the y direction by displacement controlled
loadings to attain 25% strain in 200 steps. Hydrogen is charged at
different levels of pre-straining to examine the effect of hydrogen
on material local hardening/softening.
We initiate all analyses by using hydrogen-free samples
(see part (a) of Fig. 6) and then charge hydrogen at different pre-
straining levels of 5%, 10% and 15% such that a uniform concen-
tration of C0 is established before reloading (see part (b) of Fig. 6).
The loading is continued from the pre-straining condition without
any unloading. During reloading period, all outer boundaries are
insulated so that the hydrogen ux on these boundaries is zero.
Fig. 6 illustrates the structural and diffusion boundary conditions
for both hydrogen-free and hydrogen-charged periods. The mate-
rials used in these simulations are BCC iron and austenitic stainless
steel type 316L whose mechanical material properties and
parameters of hydrogen advection diffusion analysis are given in
Table 1.
7. Numerical results and discussion
This section describes stress and strain elds and the hydrogen
concentrations in both the blunting crack model and the model of
tensile specimen. The rst subsection, using pinning-softening
model (see Section 3), investigates the size of plastic zone ahead
of the crack tip in order to explain the experimentally observed
narrower plastic zone in the presence of hydrogen than the one in
the absence of hydrogen and interprets the concept of HELP theory
which is based on the localization of slip bands. The second
subsection describes a possible transition from local softening to
local hardening ahead of the crack tip. The following subsections
examine the effect of hydrogen charging at different pre-strain
levels, and initial hydrogen concentration on the stressestrain
state in the tensile specimen in order to understand

Table 1
Mechanical material properties and parameters of hydrogen advection diffusion
analysis in BCC iron and austenitic stainless steel type 316L.

Parameter BCC iron [41e43] 316L

Youngs modulus, E 207  103 MPa 180  103 MPa
Ref. [52]
Poisson ratio, n 0.3 0.29 Ref. [53]
Initial yield stress, s0 250 MPa 319 MPa Ref. [31]
Work hardening 0.2 0.2
exponent, n
Lattice diffusivity, DL 1.27  108 m2 s1 2.8  1016 m2 s1
Ref. [54]
Gas constant, R 8.3144 J mol1 K1 8.3144 J mol1 K1
Temperature, T 300 K 300 K
Material density, r 7.87  103 kg m3 7.89  103 kg m3
Partial molar 2  106 m3 mol1 1.65  106 m3 mol1
volume of hydrogen, V H Ref. [55]
Lattice sites per 5.1  1029 m3 1.69  1029 m3
unit volume, NL
Trap binding energy, DET 60  103 J mol1 13.5  103 J mol1
Fig. 5. Boundary and initial conditions for the coupled diffusion and elasto-plastic Ref. [56]
problem of a model of blunting crack tip.
 R. Miresmaeili et al. / International Journal of Pressure Vessels and Piping 99-100 (2012) 34e43 39

y is, there is a corresponding critical shear stress which must be

(u y ) fin overcome in order for a region to experience softening. As such, we
y (u y )int choose 2 10,000 arbitrarily. However, one may be able to
B determine a suitable critical shear stress for the BCC iron through
B a set of experimental observations. The reduction in the size of
1 cm plastic zone has been previously reported by some researchers
[31,38,39]. However, we still should examine the localization of
plastic deformation in the vicinity of the crack tip as the concept of
C0 = C L 0 HELP theory in our proposed model. We use different initial
in lint = l0 + (u y )int
hydrogen concentrations of C0 0, 0.097, 0.485, 0.97, 1.164, 1.552
l0 = 10 cm and 1.8 mass ppm in order to investigate the effect of hydrogen on
the stressestrain state ahead of the crack tip. Fig. 7 shows, for
different initial hydrogen concentrations of C0, the hydrostatic
2 cm stress sh and the equivalent plastic strain P ahead of the crack on
the crack plane (q 0) drawn against the distance from the crack
0.9999 cm
2 cm tip in the undeformed conguration at the end of loading time of
A A 75 s. Distances are normalized by the initial crack opening
x x displacement b0. As can be seen in part (a) of Fig. 7, increasing the
a b initial hydrogen concentration, C0, decreases the amount of
hydrostatic stress. Part (b) of Fig. 7 illustrates the effect of C0 on the
Fig. 6. Boundary and initial conditions for the coupled diffusion and elasto-plastic
problem of a tensile model; (a) the quadrant of model during the hydrogen-free
equivalent plastic strain which increases as the hydrogen concen-
period for pre-straining, (b) the quadrant of model during the hydrogen-charged tration increases.
period for reloading (Figures are not to scale). As per results of the above-mentioned analyses, by revising the
application of local softening model, we have shown that by an
increase in the hydrogen concentration, a higher value of equiva-
mechanistically the contradictory results of hydrogen-induced lent plastic strain is distributed in a narrower plastic zone. There-
hardening/softening. fore, unlike the conventional application of HELP theory which uses
the local softening [32e37] throughout a domain, our new model
7.1. The size of plastic zone ahead of the crack tip in the presence of successfully satises the concept of HELP theory which is based on
hydrogen the localization of slip bands and increasing the amount of plastic
deformation that occurs in a localized region adjacent to the frac-
As shown in Section 3, by using the local softening model ture zone.
[32e37] throughout a domain, we are unable to model the reduc-
tion in the plastic zone size in the presence of hydrogen. Whereas,
using our new proposed model i.e. pinning-softening model, we
observe that, when the stress intensity factor KI at the crack tip is at
p
30 MPa m, an increase in the initial hydrogen concentration, C0,
from 0 to 1.8 mass ppm decreases the size of plastic zone in both x
and y directions from 0.423 to 0.327 mm and 1.971 to 1.527 mm,
respectively. Table 2 summarizes the computed size of plastic zones
at different hydrogen concentrations. In Eq. (1), we assume the
parameter 2 10,000 for the BCC iron, and we set the coupled
effect parameter x 10,000 for the softened region and
x 10,000 for the hardened region (see Section 3). The value of
coupled effect parameter for the case of softening in the BCC iron,
i.e. x 10,000, was rstly introduced by Kotake et al. [34] and
used previously by the authors of current paper [32,35]. We assume
that the magnitude of the effect of hydrogen in the case of hard-
ening for the BCC iron is equal to the one in the case of softening but
with the opposite sign, i.e. x 10,000. Whatever the parameter 2

Table 2
The size of plastic zone ahead of the crack tip in BCC iron at different initial hydrogen
concentration C0 after reconsidering the criterion for the application of local soft-
ening model.

Initial hydrogen concentration C0 Size of plastic zone Size of plastic

in the x direction zone in the y
direction
C0 0 (hydrogen-free sample) 0.423 mm 1.971 mm
C0 4.615  1023 m3 0.097 mass ppm 0.423 mm 1.971 mm
C0 2.308  1024 m3 0.485 mass ppm 0.327 mm 1.971 mm
C0 4.615  1024 m3 0.97 mass ppm 0.327 mm 1.527 mm
C0 5.538  1024 m3 1.164 mass ppm 0.327 mm 1.527 mm Fig. 7. Plots of; (a) hydrostatic stress sh and (b) equivalent plastic strain P vs.
C0 7.384  1024 m3 1.552 mass ppm 0.327 mm 1.527 mm normalized distance X/b0 after 75 s when the stress intensity factor KI at the crack tip is
p
C0 8.3  1024 m3 1.8 mass ppm 0.327 mm 1.527 mm at 30 Mpa m (X is the distance of the initial position of each node from the crack root
in the undeformed conguration and b0 is the initial crack opening displacement).
40 R. Miresmaeili et al. / International Journal of Pressure Vessels and Piping 99-100 (2012) 34e43

7.2. A transition from local softening to local hardening ahead of maximum hydrostatic stress region having maximum hydrogen
the crack tip concentration thereby maximum dislocation pinning effect (see
Section 3 and Eq. (1)). It is worthwhile to mention that for hard-
The contour plot in part (a) of Fig. 8 illustrates the distribution ening to occur the amount of maximum shear stress is a key factor.
of hydrostatic stress for the sample containing a uniformly Although the point B experiences the strongest pinning effect,
distributed initial hydrogen concentration C0 0.97 mass ppm depending on its shear stress state, may or may not show the
while Cb 0.97 mass ppm. Many researchers [32,41e43] have hydrogen-induced hardening. Point C is at a remote region in
previously shown that the contour plot of hydrogen concentration which there exists an insufcient maximum shear stress to over-
in lattice sites CL illustrates similar distributions to the one of come the critical shear stress for dislocation glide (see Section 3
hydrostatic stress. Since the amount of hydrogen concentration in and Eq. (1)). With the increase in plastic deformation at the
trap sites CT, when the initial hydrogen concentration crack tip, all three points A, B and C continuously move outward.
C0 0.97 mass ppm, is two order of magnitude smaller than the Using the pinning-softening model, the three above-mentioned
one in the lattice sites CL [32,34], the maximum of total hydrogen regions illustrate different softening and hardening behaviors.
concentration, i.e. C CL CT, occurs in the region of maximum We draw the equivalent of stress against the KI value at the crack
hydrostatic stress. This fact can be observed in part (b) of Fig. 8, tip for points A, B and C. The graphs in parts (c), (d) and (e) of Fig. 8
which shows that the total hydrogen concentration C at the region contain the results of three different models of softening, pinning-
of highest hydrostatic stress, i.e. at point B, is much greater than softening and hydrogen-free. The curve having hollow square
other regions. To investigate the stress-strain state in the compu- symbol with Softening series name indicates our previous results
tational domain, we closely observe the results in three different [32] in which ow stress reduces by an increase in the hydrogen
positions of the crack tip regions, the maximum hydrostatic stress concentration throughout the domain. While the solid-line curve
regions and the remote regions from the crack tip. Point A (see the with Pinning-Softening series name illustrates the results of our
contour plot in part (a) of Fig. 8) is at the crack tip having the current model with revising the application of local softening
maximum equivalent plastic strain and the highest value of concept. In parts (c), (d) and (e) of Fig. 8, we compare the results of
maximum shear stress (see also Fig. 1). Point B is located at the both softening and pinning-softening models with those of

1.55 800
Total hydrogen concentration (mass ppm)

1.45
b 700 c
Equivalent of stress (MPa)

600
1.35
500

1.25 400 at point A

300
1.15
At point A 200
Softening
1.05 At point B
100 Pinning-Softening
At point C
H-Free
0.95 0
0 5 10 15 20 25 30 0 5 10 15 20 25 30
KI (MPa.m0.5) KI (MPa.m0.5)

400 300

350 d 250
e
Equivalent of stress (MPa)

Equivalent of stress (MPa)

300
200
250

200 at point B 150 at point C

150
100
100
Softening Softening
50
50 Pinning-Softening Pinning-Softening
H-Free H-Free
0 0
0 5 10 15 20 25 30 0 5 10 15 20 25 30
KI (MPa.m0.5) KI (MPa.m0.5)

Fig. 8. Stress and hydrogen concentration elds ahead of the crack tip in BCC iron: (a) a contour plot of hydrostatic stress; (b) total hydrogen concentration ahead of the crack tip vs.
the KI value at the crack tip; (c), (d) and (e) plots of equivalent of stress, respectively, for points A, B and C for three different models of hydrogen-free materials, Softening and
Pinning-Softening drawn against the KI value at the crack tip.
 R. Miresmaeili et al. / International Journal of Pressure Vessels and Piping 99-100 (2012) 34e43 41

hydrogen-free materials indicated by the dashed curves and the
series name of H-Free.
As can be seen in Fig. 8, the softening model shows hydrogen-
induced softening for all three above-mentioned regions when its
results are compared with the ones of hydrogen-free materials,
while the pinning-softening model illustrates completely different
behaviors depending on the regions. At point A, due to the highest
value of maximum shear stress, even at the early stages of loading,
there exists enough shear stress to overcome the critical one.
Therefore, according to the pinning-softening model, softening
occurs from an early stage of analysis such that the results of soft-
ening and pinning-softening models are very similar. At point B,
owing to the highest hydrogen concentration, there exists the
strongest pinning effect which results in the highest critical shear
stress. As such, at the early stages of loading the shear stress is
insufcient to overcome the critical one so that the hydrogen-
induced hardening occurs. By increasing the load, at a certain time,
the required shear stress is produced so that a transition from local
hardening to local softening occurs. At point C, the shear stress is too
low to overcome the strong pinning effect. Therefore, hydrogen-
induced hardening appears at the remote regions from the crack tip.
7.3. The effect of hydrogen charging in the tensile model
As described in Section 6.2, we charge hydrogen into the tensile
sample of Fig. 6 at different pre-strain levels of 5%, 10% and 15%.
Since the total time to attain the maximum load is set to be 100 s,
the total hydrogen diffusion times for the above-mentioned pre-
strain levels are 82 s, 63 s, and 43 s, respectively.
Fig. 9 illustrates the effect of hydrogen charging on the
stressestrain curves of BCC iron. Hydrogen charging starts at the
different pre-strains of 5%, 10% and 15% in three different samples
whose initial uniform hydrogen concentration before reloading is
assumed to be C0 0.97 mass ppm. From Fig. 9, we observe that the
ow stress decreases very rapidly after starting the hydrogen
charging. According to Matsui et al. [17], in pure iron, the amount of
stress decrease can be as large as 50% of the ow stress level
immediately before charging at above 190 K. As per Fig. 9, before
hydrogen charging, at each pre-strain level, the stressestrain curve is
in accordance with the one of hydrogen-free sample. While imme-
diately after charging, the ow stress decreases promptly and traces
in order to understand mechanistically the contradictory results of
hydrogen-induced local softening and hydrogen-induced local
hardening. Hydrogen charging starts at the pre-strain level of 5%. In
the case of BCC iron, we conduct three analyses with different
initial uniform hydrogen concentrations of 0, 0.97 and
1.94 mass ppm before reloading. While in the case of austenitic
stainless steel 316L, for making comparison with the experimental
observations, we follow Murakami et al. [31] and charge the initial
uniform hydrogen concentrations of 2.2, 10, 70.4 and
89.2 mass ppm. Large contents of hydrogen exist as supersaturated
contents in austenitic stainless steels [31]. In Eq. (1), we assume the
parameter 2 3000 for the stainless steel type 316L, and we set
the coupled effect parameter x 255 for the softened regions and
x 255 for the hardened region (see Section 3). These values of x
cause the variation of 1.58% as either reduction or increase in the
initial local ow stress of stainless steel 316L when the initial
uniform concentration, C0, is at 2.2 mass ppm. This concentration is
the nondiffusible hydrogen in uncharged solution-treated austen-
itic stainless steels [31]. The solubility of hydrogen in stainless steel
316L is much higher than the one in BCC iron. As such, considering
Eq. (3), in order for hydrogen to have a similar magnitude of soft-
ening (or hardening) effect on stainless steel 316L as the one on BCC
iron, we should use much smaller x value for 316L than the one for
BCC iron. It is worth to mention that according to Eq. (3) the
multiplication of x c determines the magnitude of hydrogen effect
on the local ow stress. For the same reason and by taking into
consideration Eq. (1), the value of 2 for stainless steel 316L should be
much smaller than the one of BCC iron. According to Eq. (1), the
multiplication of 2 c determines the magnitude of hydrogen
effect on the critical shear stress. However, one may be able to
measure a suitable coupled effect parameter and critical shear
stress for austenitic stainless steel through a set of experimental
observations.
Fig. 10 illustrates the effect of hydrogen contents on the local
ow stress. For the case of BCC iron (see part (a) of Fig. 10), as the
hydrogen concentration increases, the local ow stress decreases.
In other words, hydrogen e in its saturated contents for BCC iron e
causes softening in pure iron. This result is consistent with Matsui
a 800

the stressestrain curve of hydrogen-charged sample at 0% pre- 700 Hydrogen charging

Yield stress (MPa)

straining. 600
500
400
7.4. On the contradictory effects of hydrogen on the ow stress
300
C0=0 mass ppm
200
We examine the effect of initial hydrogen concentration before C0=0.97 mass ppm
reloading, i.e. C0, on the stressestrain state in the tensile specimen 100
0
BCC iron C0=1.94 mass ppm

0 5 10 15 20 25
Total equivalent plastic strain (%)
750
700 b 1600
650 1400
Yield stress (MPa)
Yield stress (MPa)

600 1200
550 1000
500
800
450
600 C0=2.2 mass ppm
400 H-Free
Charging at pre-strain 0% 400 C0=10 mass ppm
350 Charging at pre-strain 5%
Hydrogen charging
200 C0=70.4 mass ppm
300 Charging at pre-strain 10%
Charging at pre-strain 15% 0
316L C0=89.2 mass ppm
250
0 5 10 15 20 25 0 5 10 15 20 25
Total equivalent plastic strain (%) Total equivalent plastic strain (%)

Fig. 9. The effect of hydrogen charging at various pre-strain levels on the stress-strain Fig. 10. The effect of hydrogen charging at 5% pre-strain on the stress-strain curves of
curve of BCC iron. (a) BCC iron and (b) austenitic stainless steel type 316L.
42 R. Miresmaeili et al. / International Journal of Pressure Vessels and Piping 99-100 (2012) 34e43
et al. [17] who have experimentally investigated the effect of
hydrogen on the mechanical properties of high purity iron. For the
case of 316L (see part (b) of Fig. 10), depending on the hydrogen
contents, we can observe both softening and hardening. As the
hydrogen concentration increases from 2.2 to 10 mass ppm, the
local ow stress decrease so that hydrogen-induced softening
occurs. While for the supersaturated hydrogen contents, e.g. 70.4
and 89.2 mass ppm, the ow stresses are higher than the ones in
the hydrogen-free sample. In the supersaturation level, an increase
in the hydrogen contents of 316L results in an increase in the ow
stress.
In the pinning-softening model (see Section 3), there are two
key factors to determine whether the softening or hardening occurs
in macroscale. These two factors are the maximum shear stress smax
and the critical shear stress scrit which in turn is a function of
hydrogen content (see Eq. (1)). The local softening merely occurs at
regions where smax  scrit. Other regions, in which smax < scrit,
experience the hydrogen-induced hardening conditions. Close
observation of the results reveals that for the BCC iron at all
examined concentrations, the condition of smax  scrit is satised
thorough the domain so that hydrogen-induced softening occurs in
pure iron as the logical output of our proposed model. For instance,
at the end of loading, when the initial hydrogen concentration is
1.94 mass ppm for BCC iron, the maximum shear stress
smax 451 MPa while the critical shear stress scrit 177 MPa at the
central point A (see Fig. 6). These quantities for upper point B (see
Fig. 6) are 277 MPa and 177 MPa, respectively. For the case of 316L,
there exist different conditions depending upon the level of
hydrogen content. At a low concentration, e.g. 2.2 and 10 mass ppm,
the condition of smax  scrit is satised thorough the domain so that
hydrogen-induced softening occurs in 316L. While in the super-
saturation level, e.g. 70.4 and 89.2 mass ppm, owing to the presence
of large amount of hydrogen and considering the concentration-
dependent critical shear stress as Eq. (1), the condition of
smax < scrit is satised so that hydrogen-induced hardening occurs
throughout the domain. Close observation of the results for
10 mass ppm initial hydrogen content in 316L reveals that the
maximum shear stress smax 609 MPa while the critical shear
stress scrit 257 MPa at the central point A (see Fig. 6). These
quantities for upper point B (see Fig. 6) are 366 MPa and 257 MPa,
respectively. As can be seen, for 10 mass ppm initial concentration,
the conditions of smax  scrit is satised so that softening occurs (see
part (b) of Fig. 10). As opposed to softening, hardening occurs at the
supersaturation levels of 89.2 mass ppm initial hydrogen content,
in which smax 1075 MPa while scrit 1189 MPa at the central
point A (see Fig. 6). For upper point B, smax 642 MPa and
scrit 1189 MPa. Therefore, in the supersaturation level, the
condition of smax < scrit is satised and hardening occurs.
8. Conclusions
Our new model successfully satises the concept of HELP theory
for the localization of slip bands and increasing the amount of
plastic deformation in the vicinity of the fracture zone due to the
presence of hydrogen. According to this new model, called pinning-
softening model, both local softening and local hardening can occur
in a sample depending on the distribution of maximum shear stress
and hydrogen contents; softening at the crack tip and hardening at
the remote regions. During the loading, there exists a transition
from local hardening to local softening for the regions with high
value of hydrostatic stress ahead of the crack tip.
In the tensile model of BCC iron, before hydrogen charging, at
each pre-strain level, the stressestrain curve is in accordance with
the one of hydrogen-free sample. While immediately after
charging, the ow stress decreases promptly and traces the
stressestrain curve of hydrogen-charged sample at 0% pre-
straining.
We examine the effect of initial hydrogen concentration before
reloading, i.e. C0, on the stress-strain state in the tensile specimen
in order to understand mechanistically the contradictory results of
hydrogen-induced hardening/softening. For the case of BCC iron, as
the hydrogen concentration increases, the local ow stress
decreases. In other words, hydrogen e in its saturated contents for
BCC iron e causes softening in pure iron. For the case of 316L,
depending on the hydrogen contents, we can observe both soft-
ening and hardening. At a moderate hydrogen concentration, the
local ow stress decreases so that hydrogen-induced softening
occurs. While for the supersaturated hydrogen contents, the ow
stresses are higher than the ones in the hydrogen-free sample so
that the samples experience the hydrogen-induced hardening.
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