Engineering Fracture Mechanics 176 (2017) 116–125

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Engineering Fracture Mechanics

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

Influence of hydrogen on plasticity around the crack tip in high

strength steels
Kioshy S. de Assis a, Marcella Araujo Lage a, Geraldo Guttemberg b, Fabrício Pinheiro dos Santos b,
Oscar R. Mattos a,⇑
a
Laboratório de Ensaios Não Destrutivos, Corrosão e Soldagem – LNDC, COPPE, Universidade Federal do Rio de Janeiro – UFRJ, Cx. Postal 68505, Rio de Janeiro,
RJ CEP 21945-970, Brazil
b
PETROBRAS/CENPES/PDEP/TMEC, Av Horácio Macedo, 950-Cidade Universitária – Ilha do Fundão, Rio de Janeiro, RJ CEP 21941-598, Brazil

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

Article history: Fracture mechanics concepts applied to tests in aggressive environments are a challenge
Received 27 November 2016 for integrity analysis. Specifically about hydrogen, the concentration of this element in
Received in revised form 27 February 2017 defects or in trapping sites can cause unexpected failure. The present paper presents
Accepted 28 February 2017
results showing the influence of hydrogen in the reduction of fracture toughness and a dis-
Available online 1 March 2017
cussion about how to deal with it in high strength alloys. The results show that the hydro-
gen reduces the plasticity and consequently the applications of CTOD concepts are
Keywords:
questionable for the studied materials.
Fracture mechanics
Hydrogen embrittlement
Ó 2017 Elsevier Ltd. All rights reserved.
Toughness testing

1. Introduction

Many authors have studied the behaviour of hydrogen in metals [1–9]. Crack occurrence is mainly related with the critical
amount of hydrogen necessary to initiate the process [10]. In structures containing defects, hydrogen causes local changes in
the stress field and contributes to crack propagation, even for stresses below the yield limit. There are two accepted mech-
anisms for hydrogen embrittlement in metals. One is hydrogen enhanced local plasticity (HELP), which was first introduced
in the 1990s [11]. The other is hydrogen-induced decohesion (HEDE), which was first introduced in 1960 [12]. According to
HELP, atomic hydrogen enhances the mobility of dislocation through an elastic shielding effect causing local reduction of the
shear strength. The cracks occur by microvoid coalescence along preferred crystallography glide planes. HEDE refers to the
hypothesis that the atomic bonding ahead of the crack tip is weakened by dilatation of the atomic lattice due to the presence
of hydrogen and the fracture energy is reduced [3]. However, despite the importance of hydrogen in the fracture of metals,
there is no consolidated approach using linear elastic or elastoplastic theory to predict the critical defect size to be consid-
ered in integrity analysis. Indeed, R. P. Gangloff categorizes that the degradation process of the crack propagation resistance
occur due Internal Hydrogen Assisted Cracking (IHAC) or Hydrogen Assisted Cracking (HEAC) [7]. These phenomena are also
called Internal Hydrogen Embrittlement (IHE) and Hydrogen Environment Embrittlement (HEE), respectively [7]. However,
the influence of these concepts in fracture toughness tests approach using linear elastic or elastoplastic theory to predict the
critical defect size must to be more consolidated to be used in integrity analysis. Olden et al. [8] presented results of fracture
toughness using single edge notch tension specimens (SENT), with constant load tested in artificial sea water at 4 °C using
cathodic potential of
1050 mVSCE. The authors showed that whether the governing mechanism is HEDE or HELP, it can be

⇑ Corresponding author.
E-mail address: omattos@metalmat.ufrj.br (O.R. Mattos).

http://dx.doi.org/10.1016/j.engfracmech.2017.02.028
0013-7944/Ó 2017 Elsevier Ltd. All rights reserved.
 K.S. de Assis et al. / Engineering Fracture Mechanics 176 (2017) 116–125 117

argued that trapped hydrogen due to plastic strain is the main active hydrogen source and responsible for hydrogen induced
cracking in 25% Cr duplex stainless steel. Gyu et al. [9] assessed the effect of microstructure on hydrogen trapping efficiency
and hydrogen induced cracking of pipelines. The results showed a deleterious correlation between microconstituent
martensite-austenite (M-A) and the initiation of cracks induced by hydrogen. Furthermore, those authors presented results
showing that some microstructures are more sensible to hydrogen embrittlement, for example, bainite is more sensitive to
hydrogen induced cracking than the acicular ferrite phase. These results, although important, are not directly analysing the
main point if in presence of hydrogen it is or not possible to use the elastoplastic concepts to deals with crack propagation.
Indeed, according to Irwin [13] the brittle-ductile fracture transition can be understood as a change in the constraint of the
plastic zone from plane-strain to one in which the stresses govern the yield in the plastic zone. However, the constraint of the

Table 1
SMSS chemical composition.

C Mn Si Mo Cr Ni Fe
Elements (wt%)
0.008 0.47 0.18 2.44 12.08 6.47 Bal.

Table 2
FCS chemical composition.

C Mn Si Mo Cr Ni Fe
Elements (wt%)
0.299 0.698 0.259 0.337 0.775 0.703 Bal.

Table 3
Mechanical properties of materials.

Material rYS (MPa) rR0.2 (MPa) Elongation (%) Hardness Rockwell C

SMSS 680 ± 5 788 ± 8 25.8 ± 3.2 27.1 ± 1.1
FCS 1014 ± 60 1111 ± 39 14.9 ± 1.4 30.6 ± 0.9

Supermartensitic Stainless Steel

Forged Carbon Steel

Fig. 1. Dimension of pipes where different samples were extracted (all dimension in millimeters).

Fig. 2. Orientation of notch. X is parallel Y transverse and Z perpendicular to grain flow and Z is coincident with the thickness direction.
118 K.S. de Assis et al. / Engineering Fracture Mechanics 176 (2017) 116–125

plastic zone can change in the presence of hydrogen and in practical terms, crack instability may occur even for low plasticity
due to changes introduced in crack tip propagation. Bahrami et al. [14] addressed the effect of hydrogen in the fracture
toughness of superduplex stainless steel using critical tip opening displacement (d) and J integral tests with single-edge-
notch-bend (SENB) specimens. The authors evaluated the combined effect of strain rate under hydrogen charging condition.
The results showed a drastic reduction of d and J integral in the presence of hydrogen. Lage et al. [15] studied hydrogen influ-
ence on fracture toughness of the weld metal in superduplex stainless steel. The authors presented results showing a drastic
reduction of plasticity around the crack. The use of critical tip opening displacement approach (CTOD - d) in the presence of
hydrogen is criticized by the authors.
There is consensus involving the works above discussed: hydrogen embrittlement has higher deleterious effect in high
resistance and high alloy steels or in high strength and low alloy steels. However, there is no consensus in the literature
about which is the better methodology to evaluate the influence of hydrogen and provide safe parameters to be used in
terms of engineer critical analysis. Therefore, the present paper presents results involving fracture toughness tests of crack
tip opening displacement (CTOD - d), according to BS 7448-1 [16] and BS7448-2 [17] standards in two different parent mate-
rials: supermartensitic stainless steel (high resistance and high alloy steels) and one forged carbon steel (high strength and

Table 4
Dimension of samples (the length, in mm, is four times the thickness).

Sample Thickness (mm) - W Width (mm) - B Crack Length (mm)

SMSS 40 20 0.5 W
FCS 30 15

Fig. 3. Experimental apparatus. (a) Schematic and (b) experiment in progress.

 K.S. de Assis et al. / Engineering Fracture Mechanics 176 (2017) 116–125 119

low alloy steels). The influence of hydrogen in the reduction of plasticity around the crack is discussed. In addition the appli-
cability of CTOD approach to these materials is analyzed.

2. Materials and methodology

The materials used were: supermartensitic stainless steel (SMSS) and one forged carbon steel (FCS). They were used as
received and without extra heat treatment. The chemical composition and mechanical properties of the materials are pre-
sented in Tables 1–3, respectively.
The specimens were machined from two different pipes as described in Fig. 1.
Single-edge-notch-bend (SENB) specimens, from both, supermartensitic stainless steel and forged carbon steel, were
notched following orientation in relation to grain flow as outlined in Fig. 2 and in accordance with BS 7448-1 [16] standard.
The CTOD specimens were then submitted to fatigue pre-crack, following the BS 7448 [15] standard procedure, using a servo
hydraulic machine and maintaining a ratio a/W nearly 0.5 W.
The dimensions of specimens used are presented in Table 4. Fracture toughness tests were performed according to the
procedure described in BS 7448-1 [16] and BS 7448-2 [17] standards. The unique parameter that was adapted was the load-
ing rate. The value of loading rate used, established based in the literature [14,15] was 0.067 N mm3/2 s
1. This is the max-
imum value that allows that the diffusion of hydrogen occurs simultaneously with the loading during d tests.
Hydrogen was charged using a potential of
1100 mVSCE and 3.5% NaCl as electrolyte, with maximum variation of pH
maintained at 6.0 ± 0.2. The hydrogenation charging was 24 h for SMSS and 5 days for FCS before loading and it was main-
tained during the d test [15]. The hydrogenation time used had two objectives: first to determine the beginning of hydrogen
deleterious effect in the SMSS and second to assess the extension of the damage caused by hydrogen in the process zone from
crack tip in the FCS. Indeed, concerning the SMSS, the short hydrogenation time used imposed a low concentration of hydro-
gen trapped and restricted to the crack tip. Therefore, it was possible to evaluate the influence of hydrogen at the beginning
of the fracture process. On the other hand, the large hydrogenation time used in the FCS imposed a large content of hydrogen
trapped and not limited to the crack tip region, enabling to evaluate the extension of the damage caused by hydrogen.
The temperature of the test was 24 ± 2 °C during pre-charge hydrogenation and 5 ± 2 °C during the CTOD tests. The low
temperature (5 °C) complies the operational conditions of these materials. Room temperature during pre-charging was used
to accelerate hydrogen diffusion process. Five samples were used for each test. Another important aspect of the study was
the evaluation of the extension of damage. Thus, the tests were performed using two different criteria:

(1) For the initiation of the crack process the test was controlled by clip gauge opening and specific values of crack mouth
opening displacement (CMOD) were used to stop the test.
(2) For the extension of embrittlement from the crack tip and along the remaining ligament the tests were done using
CTOD maximum load (dm).

After the tests, the specimens were observed by stereoscopy, then cracked and the fracture observed by scanning electron
microscopy (SEM). The CTOD experimental apparatus is presented in Fig. 3.

3. Results and discussion

3.1. Hydrogen effect in the process zone

CTOD maximum load (dm) tests were performed in specimens obtained from FCS after hydrogenation for 5 days and two
graphic aspects were obtained as shown in Fig. 4. Five specimens were tested for each condition.

80000

70000
a
60000

50000
F [N]

40000
b
30000

20000

10000
c
0
0,0 0,5 1,0 1,5 2,0
[mm]

Fig. 4. Graphic aspects obtained from FCS tests. (a) Air test, (b) and (c) hydrogenated tests.
120 K.S. de Assis et al. / Engineering Fracture Mechanics 176 (2017) 116–125

Fig. 5. Analysis made after test of FCS specimen c. (a) Surface, (b) after break and heat tint (30 min to 300 °C and cooling in air) marking the steady growth
cracking due hydrogen embrittlement, (c) and (d) mechanisms of quasi-cleavage fracture.
 K.S. de Assis et al. / Engineering Fracture Mechanics 176 (2017) 116–125 121

Table 5
Evaluation of the K values obtained and validity to KIC.

Sample K (MPa m0.5) d (mm) a0 (m) B (m) W – a0 (m) Resulta

a 152.41 0.109 0.0207 0.020 0.0193 KQ (not valid)
b 126.97 0.052 0.0206 0.020 0.0193 KIC (Valid)
c 64.33 0.044 0.0205 0.020 0.0195 KIC (Valid)
a
The criterion of validity was established according BS7448-1 [16].

30000
(c)
25000

(b) (d)
20000
(a)
F [N]

15000 (e)

10000

5000

0
0 1 2 3 4 5
CMOD [mm]

Fig. 6. Fracture toughness tests controlling the opening of sensor. (a) Air (4 mm), (b) 0.4 mm, (c) 0.6 mm, (d) 0.8 mm and (e) 2.0 mm, after hydrogenation.

It is possible to observe that graphic instabilities were never obtained in the FCS specimens tested in air condition
(Fig. 4a), whereas in the hydrogenated specimens (Fig. 4b and c), graphic instabilities (pop-in) were always observed. The
pop-in effect is a strong indicative of the presence of hydrogen in the process zone during fracture toughness tests. An anal-
ysis of the damage extension from crack tip allows observing important aspects showing the effect of hydrogen in regions
around the crack tip and far from this region. In Fig. 5 the results of the fractographic analysis after test of FCS specimen c in
Fig. 4 are presented.
In Fig. 5a it is possible to observe three different regions: I, II and III. Region I is characteristic of steady growth crack prop-
agation, localized in the process zone around the crack tip. In this region, there is stress oriented by hydrogen induced crack-
ing combined with loading during d tests; region II presents possibly a synergistic effect of step wise cracking and stress
oriented hydrogen induced cracking together with loading. This characteristic is further enhanced due to the presence of
cracks in steps coalescing oriented by stress; finally, in region III, far from the crack tip, the aspect showing cracks in steps
suggest that the mechanism of cracking is step wise, with cracks appearing in stress levels within the elastic limit [15].
It is noteworthy that hydrogen reduces drastically the plasticity around the crack tip. It is important to emphasize that as
seen in Fig. 4, the instability of hydrogenated specimens occurs in the elastic stress range with no significant plasticity. More-
over, another aspect that deserves special attention is the steady crack propagation growth. The validity of this phenomenon
in fracture toughness is assured only if this propagation is controlled by J integral or d parameters. Observing Figs. 4b, c and 5
it is possible to observe that close the steady crack propagation growth region, the crack is effectively controlled by J integral
or d (region I). However, in the regions II and III, there are strong evidences of a non-steady crack propagation growth. In
these two regions the crack propagation are controlled by hydrogen, not governed by J or d control. Consequently, is it valid
to use elastoplastic parameters to evaluate toughness loss and estimating defect critical size within an engineering critical
analysis? Would not be more consistent to use the K [MPa m1/2] to determine the dm for hydrogenated specimens for this
purpose? These questions can be analysed calculating the K values associated with d and comparing them with the limit
KIC given by the standards.
According to BS7448-1 [16] the achievement of a valid KIC value must respect the following relation:
 2
KIC
a; B or ðw
aÞ P
rYS
where ‘‘a” is the crack length, ‘‘B” is the thickness, ‘‘(w-a)” is the uncracked region of the specimen, ‘‘rYS” is the 0.2% proof
strength and ‘‘KIC” would be the fracture toughness of the material. Taking into account the fracture toughness tests per-
formed and dimensions of specimens, tests were carried out to determine if K [MPa m1/2] obtained could validate the KIC
values. The results are presented in Table 5.
It is possible to observe that K values converge to a critical value of fracture toughness assisted by environment (KIEAC).
Thus, in this case, the plasticity is greatly reduced before failure. For practical purposes, these values cannot be called KIC
122 K.S. de Assis et al. / Engineering Fracture Mechanics 176 (2017) 116–125

(a) (b)

Steady growth cracking

(c)

(d) Steady growth cracking

(e)
Steady growth cracking

Fig. 7. Stereoscopy of samples. (a) Air, (b) 0.4 mm of opening, (c) 0.6 mm of opening, (d) 0.8 mm of opening and (e) 2.0 mm of opening.

because the tests were performed in aggressive environment. However, take into account the results obtained it is necessary
to establish a criterion seeking values of loading into the elastic region, above KIEAC of the material, which are not sufficient to
promote crack propagation (which could be called Klimit) instead of using the criterion based in the elastoplastic theory, shar-
ing the position claimed by [18,19]. The criterion of validity was established according BS7448-1 [16].
 K.S. de Assis et al. / Engineering Fracture Mechanics 176 (2017) 116–125 123

Table 6
d values, steady growth cracking by opening of
sensor.

Sample d (mm) Da (mm)

Air 0.871 ± 0.08 Not detected
0.4 0.124 ± 0.03 Not detected
0.6 0.228 ± 0.09 0.83
0.8 0.138 ± 0.10 1.02
2.0 0.157 ± 0.11 4.41

Fig. 8. Fractographic aspects of SMSS specimens that presented steady growth cracking. (a)–(b) Center and margin region, respectively, of specimen 0.6,
(c)–(d) center and margin region, respectively, of specimen 0.8 and (e)–(f) center and margin region, respectively, of specimen 2.0.

3.2. Effect of hydrogen in the initiation of the failure process

The supermartensitic stainless steel was subjected to the fracture toughness test where the control was determined by
the opening of a sensor used to measure the tip opening displacement. Through this, it was possible to establish stop criteria
124 K.S. de Assis et al. / Engineering Fracture Mechanics 176 (2017) 116–125

taking into account specific values of CMOD and consequently a small crack increment. In Fig. 6 the results obtained using
parent metal are presented.
The material presents different increments in steady cracking growth as a function of the CMOD value established to stop
the hydrogenated tests (CMOD values of 0.4 mm, 0.6 mm, 0.8 mm and 2.0 mm, according to Fig. 6). The results of different
values of steady cracking growth obtained are shown in Fig. 7 and Table 6.
In Fig. 6 it was possible to observe that for the specimen tested in air, Fig. 6a, even for maximum opening of the sensor, the
maximum value was not reached and steady crack growth was not detected, showing a great plasticity around the crack tip.
However, for the hydrogenated specimens, the maximum load was obtained corresponding to half the opening used in the
tests in air, Fig. 6e. Moreover, from the test opening of 0.6 mm (Fig. 6c and Table 6) it was possible to detect a great incre-
ment of steady crack growth (Da), corresponding to 0.83 mm. The plasticity necessary to initiate this increment was very
small, indicating that to extract the d value it is necessary to consider a drastic reduction of plasticity around the crack
tip. This reduction of plasticity is possibly caused by the presence of hydrogen trapped into the lattice and grain boundary
changing the local stress, even for low stress levels applied and small CMOD values.
To characterize the effect of hydrogen as being the responsible for the failure process, analyses using scanning electronic
microscopy (SEM) were performed. Fig. 8 shows SEM images about the hydrogen effect above discussed.

 As seen in Fig. 8, the mechanism of fracture is predominantly cleavage in both, center and margin region for all specimens
where it was observed a steady crack growth. It means that hydrogen acts restricting the plasticity near the region of ini-
tial critical tip open displacement (di), decreasing the crack mouth opening displacement and the energy to occur steady
growth cracking. Besides, the experimental procedure using the stopping criterion controlled by CMOD showed that the
hydrogen reduces the plasticity and the energy necessary for cracking even for small openings. This aspect is consistent
with the approach that the most appropriate methodology to assess the influence of hydrogen in the reduction of fracture
toughness must take into account a maximum applied load value that is not enough to promote crack propagation, con-
sidering a minimum or no plasticity around the crack tip, as claimed by [18,19]. The connection between hydrogen-
enhanced plasticity and the hydrogen-induced fracture mechanism was studied by Robertson et al. [20]. They showed
that in fact for very high resolution the quasi-cleavage fracture aspect associated with hydrogen can disappear and the
ductile aspect can be observed. However, it is interesting to emphasize that an actual industry structure is supposed
to work at least during twenty years. Indeed, during all this time the hydrogen will be act as discussed in the present
paper depending of the time and the quantity of hydrogen charged in the material. In these cases the main aspect claimed
in the present paper is that the criterion more adequate to test the high resistant steels must not be based in the elasto-
plastic concepts.

4. Conclusions

1. Hydrogen decreases drastically the plasticity around the crack tip the material (FCS and SMSS).
2. The extension of hydrogen embrittlement compromises the structural integrity of FCS, showing to be necessary the use of
more conservative criteria to assess fracture toughness (for example KIEAC).
3. In the region of initiation of steady crack growth, a small crack tip opening displacement is enough to promote a large
increment even near the elastic-plastic behaviour transition.

Acknowledgments

The authors would like to thank the Brazilian agencies CNPq, CAPES and FAPERJ for their financial support to this study.

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