Materials Science & Engineering A 716 (2018) 189–207

Contents lists available at ScienceDirect

Materials Science & Engineering A

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

A study on the susceptibility of high strength tempered martensite steels to T

hydrogen embrittlement (HE) based on incremental step load (ISL) testing
methodology
⁎
Tuhin Dasa, , Sriraman K. Rajagopalana,b, Salim V. Brahimia,b, Xiang Wangc, Stephen Yuea
a
Department of Mining and Materials Engineering, McGill University, Montreal, Quebec H3A 0C5, Canada
b
IBECA Technologies Corp, Montreal, Quebec H3H 1A8, Canada
c
Department of Materials Science and Engineering, McMaster University, Hamilton, Ontario L8S 4L7, Canada

A R T I C L E I N F O A B S T R A C T

Keywords: Incremental step load (ISL) technique was used to determine the material susceptibility of three different grades
Hydrogen embrittlement of tempered martensite steels 35CrMo4, 41Cr4 and 36NiCrMo4 to hydrogen embrittlement (HE). In addition to
Material susceptibility testing the steel grades in air, the environmental hydrogen embrittlement susceptibilities (EHE) of each material
Incremental step load test were determined by in-situ charging of hydrogen at three different cathodic potentials −0.85 VSCE, −1VSCE and
Transmission electron microscopy
−1.2VSCE to obtain the entire threshold curves for these materials. Overall investigation implies that 35CrMo4 is
Thermal desorption analysis
more susceptible than 41Cr4 and 36NiCrMo4. The fracture surface morphology in case of 35CrMo4 is entirely
intergranular at −1VSCE and −1.2VSCE showing the severity of embrittlement. The higher matrix-cementite
interfaces along with high cementite and low manganese sulphide (MnS) inclusion content of 36NiCrMo4 in-
fluencing the hydrogen transport kinetics within the material are responsible for the lower material suscept-
ibility. The thermal desorption analyses (TDA) further corroborate the observations.

1. Introduction especially fasteners [3]. On the other hand, b) environmental hydrogen

High strength tempered martensite steels are the frequent choice to
manufacture certain critical parts including fastener components in
several industries. For instance, mechanical fasteners manufactured
from high strength steels (tensile strength in the range of 1–2 GPa) are
often used as load bearing joints in automobile parts, ships and sub-
marines, aircraft frames, bridges and other structural components etc.
However, premature failures of these fastener components under ser-
vice environments due to hydrogen embrittlement (HE) can lead to
total loss of structural integrity. The consequences of those kind of
unpredictable failures could be more catastrophic. Thus, it is important
to identify the fundamental factors responsible for HE failure of these
materials. The presence of mobile hydrogen in the structure serves as the
primary reason. The hydrogen responsible for the damage could be
introduced into these materials right from steelmaking, followed by
other practices like coating, sacrificial corrosion etc. Depending on the
sources of hydrogen ingress into the steel structure, HE can be divided
into two broad categories [1,2]: a) internal hydrogen embrittlement
(IHE) which is a delayed failure, caused by residual hydrogen from
steelmaking, surface cleaning and electroplating etc. It has been a
pronounced problem while coating of high strength steel components,
embrittlement (EHE) which is classified as a subset of stress corrosion
cracking (SCC), occurs due to the introduction of hydrogen by sacrifi-
cial corrosion during service. Stress gradients generated during various
applications, control the hydrogen transport kinetics in materials [4].
However, the susceptibility of a material to HE is dictated by the mi-
crostructure. The global microstructure such as the total grain boundary
interface area, precipitates, inclusions etc. influences the hydrogen
diffusion to the high stress areas [5–7]. The roots of HE failure me-
chanisms involve the local microstructural evolution, i.e. dislocation
generation, hydrogen-dislocation interaction etc., at stress concentrated
regions [8,9]. Therefore, material susceptibility which is primarily a
function of microstructure could be identified as the decisive factor
because if the material is not susceptible then all other factors would be
irrelevant to a certain extent. A number of studies which report the
effect of various microstructural parameters on hydrogen diffusion and
trapping in complex microstructures such as tempered martensite steels
are available [5,10–16]. In spite of that, the specific role of individual
hydrogen trap states in this type of microstructures in relation to HE
failure remains unclear especially during real time applications. The
correlation of material susceptibility with HE failure of high strength
steel fastener components, which are designed to serve a wide range of

⁎
Corresponding author.
E-mail address: tuhin.das@mail.mcgill.ca (T. Das).

https://doi.org/10.1016/j.msea.2018.01.032
Received 3 October 2017; Received in revised form 6 January 2018; Accepted 8 January 2018
Available online 09 January 2018
0921-5093/ © 2018 Elsevier B.V. All rights reserved.
T. Das et al. Materials Science & Engineering A 716 (2018) 189–207

Table 1
Chemical composition of Steel grades.

Steel Grade (ISO) AISI C Mn Ni Cr Mo Si S P Cu Al Hardness (HRC)

35CrMo4 4130 0.30 0.78 0.13 1.13 0.21 0.27 0.02 0.011 0.15 0.023 43.8
41Cr4 5140 0.40 0.80 0.12 1.00 0.043 0.12 0.006 0.010 0.096 0.030 44.1
36NiCrMo4 4340 0.42 0.75 1.73 0.80 0.23 0.22 0.006 0.009 0.23 – 42.8

Fig. 1. Sample geometry according to ASTM F519

Type 1e standards used for ISL testing where L =
length and H = height of the sample, h = height of
the notch and R = radius of the notch root.

Fig. 2. (a), (b) and (c) SEM micrographs of 35CrMo4, 41Cr4 and 36NiCrMo4 respectively after 2% Nital etch at 4000× while (d) shows the schematic of a typical tempered martensite
structure [23].

engineering applications, needs further investigation through an ac- mechanical rupture within an optimum time period. Therefore, in the
celerated rigorous mechanical testing technique. During the mechanical present study an approach has been taken to understand HE failures in
testing procedure, the loading process should ensure that the crack relation to material susceptibility based on some modifications of ASTM
develops purely due to HE, without being overridden by pure F1624 standard test method [17]. The objective of this attempt is to

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Fig. 3. Bright field TEM images after mapping in 35CrMo4. Carbides are marked with
yellow arrows for illustration.

determine material susceptibility that can correlate to microstructure

and chemistry and direct hydrogen quantification using thermal deso-
rption analysis (TDA) technique. Moreover, keeping in mind the critical
applications of high strength steel fasteners, the present study also aims
to discuss complementary techniques for measuring the HE cracking
threshold stress of a material in a given environment of hydrogen ex-
posure.

2. Experimental methodology

2.1. Materials and heat treatment

Three different grades of high strength tempered martensite steels

35CrMo4, 41Cr4 and 36NiCrMo4 were selected for the study. Table 1
gives the compositions along with the corresponding ISO and AISI
grades. The materials were provided by Cetim Materials (France) in the
form of single edge notched square bars. Initially, the specimens were
manufactured from raw materials by cutting steel rod into square-
shaped blanks. The blanks were heated to 880 °C for 1 h and then
quenched. After quenching, tempering was carried at 415 °C for 1 h
except in case of 36NiCrMo4 which was tempered at 420 °C. The
hardness obtained in Rockwell C scale for 35CrMo4, 41Cr4 and
36NiCrMo4 are 43.8, 44.1 and 42.8 HRC, respectively. Hardness has an
important role in deciding the susceptibility to hydrogen embrittlement
(HE) [18] but it has little role to play in the current study since all the
steel grades have similar hardness values. After the heat treatment,
machining was performed as per ASTM F519 type 1e specifications [19]
to obtain the specimens in the form of square single edge notched bars
as shown in Fig. 1, where the stress concentration factor at the notch
was estimated to be around 4.27 ± 0.32 [19]. A wire electrical dis-
charge machining technique was employed to produce a rough-cut
notch within 0.5 mm of the final notch depth. The surface finish of the
notch was obtained in the order of 0.4 µm root square mean. The spe-
cimen dimensions and final notch depth were obtained by low-stress
grinding. No cleaning (mechanical or chemical) was performed after
the final machining. A stress relief heat treatment at a considerably low
temperature was performed as the last manufacturing step. Finally, the
specimens were coated with light oil to prevent corrosion during
transport or storage.
2.2. Mechanical testing
Incremental step load (ISL) testing based on ASTM F1624 [17] was
selected. One of the primary advantages of performing a four-point
bend ISL test is to increase the stress factor in the notch by 1.6 times to
that in case of pure tension for the given geometry [18]. The test
Fig. 4. Plots obtained from FactSage calculations showing the amount of precipitates and
inclusions in grams along y-axis vs temperature in degree Celsius along x-axis formed
during the equilibrium cooling of (a) 35CrMo4 [24], (b) 41Cr4 [24] and (c) 36NiCrMo4
respectively.
equipment used for this investigation was a RSL® loading frame, man-
ufactured by Fracture Diagnostics Inc. This computer-controlled four-
point bend displacement control frame can reach the target loads with
an accuracy of ± 1.78 N (0.4 lb) and can also hold the displacement
within ± 0.13 µm. The tests were conducted in air to determine the
effect of residual hydrogen introduced during processing i.e. internal
hydrogen embrittlement (IHE) susceptibility of the steels. The en-
vironmental hydrogen embrittlement (EHE) susceptibility was de-
termined by in-situ charging of hydrogen using 3.5 wt% NaCl electro-
lyte to determine the effect of hydrogen from external sources during
various engineering applications. The hydrogen charging was carried
out under potentiostatic control by imposing three different galvanic
cathodic potentials of −0.85VSCE, −1VSCE, −1.2VSCE at room tem-
perature. A saturated calomel electrode (SCE) was used as the reference
electrode (RE), a platinum wire of length 10 cm and 1 mm diameter
was used as the counter electrode (CE) and the material as the working

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Table 2 microscope (FEG-SEM) was used to perform microstructural char-

Quantitative prediction using FactSage. acterizations. Metallographic samples were ground using SiC papers
with mesh size upto 1200 and then diamond paste of 3 and 1 µm size
Precipitates Weight of precipitates Inclusions
(gm) was used for final polishing to observe the inclusions. The samples were
etched in 2–3% Nital solution for 5–10 s to observe martensitic laths.
35CrMo4 Cementite – MnS (0.055 g) Freshly prepared hot picral solution (95 ml saturated aqueous picric
M (Cr, Fe, Ni)23C6 1.1230
acid, 5 ml ethanol and 6 drops of Hydrochloric acid) was also used for
M (Cr, Mo)3C2 –
M (Cr, Fe, Mn)7C3 2.8171 25–30 s to reveal pre-austenitic grains. The calculated grain sizes of
41Cr4 Cementite 2.8033 MnS (< 0.001 g) 35CrMo4, 41Cr4 and 36NiCrMo4 are 9.95 ± 0.64, 10.2 ± 0.5 and
M (Cr, Fe, Ni)23C6 0.23389 11 ± 2 µm respectively. Thus, the grain sizes are close enough within
M (Cr, Mo)3C2 – the range of standard deviation. Henceforth, it could be anticipated that
M (Cr, Fe, Mn)7C3 2.3021
the grain boundary area will play similar roles irrespective of the ma-
36NiCrMo4 Cementite 4.3737 MnS (< 0.001 g)
M (Cr, Fe, Ni)23C6 1.2553 terial. The same instrument equipped with EDAX TEAM EDS analysis
M (Cr, Mo)3C2 – system and EDAX Octane Super 60 mm2 silicon drift detector (SDD) was
M (Cr, Fe, Mn)7C3 0.72549 utilized for elemental analysis of the inclusions.
The samples were thinned down to approximately 100 µm with the
help of SiC papers with mesh size upto 1200 starting from 400 in order
electrode (WE). The hydrogen charging condition at −1.2VSCE (room
to perform transmission electron microscopy (TEM) analysis. 3 mm
temperature) effectively reproduces the sacrificial cathodic protection
discs were then punched out for electro polishing. The electro-polishing
by zinc coating and could be considered as the most severe condition
treatment was carried out by using 10% perchloric acid in methanol at
conventionally.
around −40 °C and 16 V. Finally, the prepared foils were examined
A fast fracture test methodology was considered to determine the
using a PHILIP CM12 transmission electron microscope (TEM) at
baseline load measurements. A continuous loading rate of 445 N/min
120 kV.
(100 lbs/min) was applied until the specimen fractured and the load at
The fracture surfaces obtained at the end of the ISL tests were stu-
fracture was noted. This process was repeated at least four times and an
died in details using the same FEI Inspect F-50 Field Emission Gun-
average value of the fast fracture load was reported for each grade. Two
Scanning Electron Microscope (FEG-SEM) to perform fracture surface
different loading protocols namely 2%−2 h (10% increment in load in
mapping.
first one hour followed by another 10% in the next two hours & 2%
increments in load with two hours of holding time in the following
2.5. Thermal desorption analysis (TDA)
hours) and 2%−3 h (10% increment in load in first one hour followed
by another 10% in the next three hours & 2% increments in load with
The thermal desorption analyses (TDA) were carried out by using a
three hours of holding time in the following hours) were used to de-
thermal-desorption spectrometer, which was designed and assembled in
termine the most susceptible condition. The end of the test is identified
our lab. It is a well-established technique to quantify hydrogen in bulk
by a 5% drop in load indicating the onset of cracking. The percent notch
metals [21]. The technique is based on the fact that heating for a given
fracture strength (NFS%), which is the measure of the degree of material
period of time supplies a substantial amount of activation energy to
susceptibility to HE, was determined by Eq. (1):
drive out the diffusible and trapped hydrogen into the surrounding
Percent notch fracture strength (NFS%) atmosphere and can be detected within a closed vacuum system by
Fracture strength in H2 environment using an analytical instrument [22]. It is equipped with a quadrupole
= × 100 mass analyzer, which can be controlled by using a computer. It is fur-
Fast Fracture strength (1)
ther equipped with a specimen chamber, a lamp heating system as well
At least three tests were performed to obtain an average percent 1 as a vacuum system that is composed of turbo molecular pumps and
NFS (NFS%) value for each of the conditions. At the end of each ISL test, rotary pumps. Both the specimen chamber and the quadrupole mass
the fracture surfaces were preserved for fractographic analysis. analyzer were always kept in ultra-high vacuum in the order of 10−6 to
10−7 mbar pressure at room temperature. A specimen geometry of
2.3. Thermodynamic calculations (10.16*10.16*27.94) mm, approximately half of the dimension of the
samples used for ISL testing, was selected for TDA. The relatively large
Thermodynamic calculations were performed based on the steel specimen chamber also facilitates this experiment. Samples after the ISL
chemistries using the FSstel database of FactSage™ (version 6.4). This is tests at two different potentials of −1 VSCE and −1.2 VSCE were used
an integrated thermo-chemical software and works on the Gibbs energy for TDA experiments. Careful ultrasonic cleaning of the samples was
minimization principle [20]. FactSage™ was used to predict the for- performed using acetone before loading them into the specimen
mation of different microstructural features such as precipitates and chamber. The time period for this whole process was maintained to be
inclusions both qualitatively and quantitatively. As already mentioned, within 10 min approximately, to minimize the hydrogen loss as much as
a detailed understanding of these microstructural features is essential possible. The specimens for analysis were then loaded into the specimen
because they may act as potential trap sites for hydrogen, influencing chamber and an ultra-high vacuum (about 3*10−6 mbar pressure) was
the susceptibility of the materials. maintained within 15 min of the sample loading process. The sample
was then heated with the help of a lamp heater controlled by a PID
based control system. The sample temperature was recorded every 2 s
2.4. Material characterization
with help of a K type thermocouple fixed on the sample surface. The
maximum temperature for those experiments was 300 ± 2 °C which is
X-ray diffraction (XRD) was carried out by using Bruker Discover
well below the A3 temperature of the present steel samples, to elim-
D8–2D VANTEC 2000 ×-ray diffractometer (XRD) with Co Kα source
inate the chances of phase transformation. Finally, a spectrum in the
on polished faces of the samples (SiC paper upto 800 mesh) to identify
form of ion current vs time was recorded. The background desorption
the phases present.
rate spectrum was also measured without the sample, which was then
An FEI Inspect F-50 20 kV field emission gun-scanning electron
subtracted from each measured desorption spectrum for the quantifi-
cation purpose. The same set of procedures were repeated for each of
1
Average percent NFS will be represented as NFS% in future discussions. the steel specimens in an exact manner to minimize the chances of error

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Fig. 5. SEM images showing (a) and (b) inclusion distribution in 35CrMo4 from surface and cross-section respectively at 2000×, (c) and (d) inclusion distribution in 41Cr4 obtained from
a cross-section at 2000× and 16000× respectively, (e) and (f) inclusion distribution in 36NiCrMo4 obtained from a cross-section at 2000× and 16000× respectively.

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Fig. 6. EDS spectrum showing point scan on an inclusion surface in 35CrMo4.

Table 3
Quantitative analysis of the EDS spectrum (Fig. 6).

Element Weight % Atomic % Net Int. Error % K ratio Z R A F

SK 34.61 47.55 479.37 4.04 0.36 1.12 0.97 0.93 1.01

Mn K 65.39 52.45 96.62 8.17 0.62 0.93 1.01 1 1.02

while quantifying and comparing hydrogen content during the in-
vestigation.
3. Results
3.1. Microstructural characterization - I
Microstructural analysis is important as it provides an overview of
the potential hydrogen trap states at different scales, ranging from grain
boundary interfaces to dislocations. Fig. 2(a), (b) and (c) show the
scanning electron microscope (SEM) micrographs of 35CrMo4, 41Cr4
and 36NiCrMo4 respectively after 2% Nital etching. Etched micro-
structures of tempered martensite steels appear as a complex combi-
nation of laths, blocks and packets, where laths are the most intricate
structures [23], as shown in Fig. 2(d) [23] with the help of a schematic.
The needle-like shape or acicular shape of martensite is revealed as an
outcome of the etching process. It can be also observed that the grades
of steels comprise martensites due to similar heat treatment process. It
is extremely difficult to distinguish packets separately in the etched
microstructures, but due to different lath orientations the blocks of laths
are discernable. A more detailed understanding of these intricate fea-
tures and their relations with hydrogen embrittlement (HE) suscept-
ibility using higher electron microscopy techniques like transmission
electron microscopy (TEM) is required. But nevertheless, from Fig. 2 it
could be concluded that, as far as optical microstructure is concerned,
there is no significant difference among these steel grades.
X-ray diffraction (XRD) has been carried out to further establish the
fact. A successful indexing of the peaks also shows that all the three
steel grades comprise only martensitic phase and there is no presence of
retained austenite.
Detailed information about the complex microstructure of the ma-
terials are obtained from the bright-field transmission electron micro-
scope (TEM) images as shown in Fig. 3 in case of 35CrMo4 as an il-
lustration. Carbide and lath distributions could be observed by mapping
composite microstructures (Fig. 3). A homogenous distribution of car-
bides with a complex combination of laths of different shape, size and
orientation could be observed. The blocks are delineated to a large
extent in the microstructure. Moreover, a well distinguished pattern of
the stacks of needle and plate shaped laths of various widths has been
revealed. The inter lath boundaries could be observed whereas they

194
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Fig. 7. Bright field TEM images showing the carbide distribution in coarse plate martensite structures in (a) 35CrMo4 and (b) 41Cr4, (c) 36NiCrMo4 respectively.
disappear in some cases as well. The average length of lath in 35CrMo4
and 41Cr4 steels is around 3.3 ± 0.75 µm, while in case of 36NiCrMo4
it is 3.8 ± 0.42 µm. Sharp needle-like carbides could be observed along
the lath boundaries as well as within the laths.
3.2. Thermodynamic calculations using FactSage™
The thermodynamic calculations using FactSage [20], predict that
almost similar kinds of precipitates and inclusions are formed in case of
35CrMo4, 41Cr4 and 36NiCrMo4.
FactSage also provides a quantitative prediction of the precipitates
and inclusions forming. The attention was mainly paid to around 415 °C
temperature regime while performing calculations, as this was the
tempering temperature for these steel grades. Carbon diffuses out from
the body-centered tetragonal (BCT) martensite structures during tem-
pering to precipitate out in the form of a variety of carbides depending
on the steel chemistry. Thus, equilibrium predictions reveal a wide
spectrum of precipitates for these low alloy steels as shown in Fig. 4(a)
[24], (b) [24] and (c) while Table 2 accounts for each of the micro-
structural features quantitatively. It can be followed that, for the pre-
cipitation of carbides like M23C6, M3C2 and M7C3, 35CrMo4 is the
leading one, while for cementite, 36NiCrMo4 is dominant. In the case of
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Materials Science & Engineering A 716 (2018) 189–207
nonmetallic inclusions (NMI) like manganese sulphide (MnS), 35CrMo4
is dominant due to its high sulphur content while 41Cr4 and
36NiCrMo4 show negligible MnS content.
3.3. Microstructural characterization - II
The thermodynamic evaluations are based on Gibb's energy mini-
mization. However, the heat treatment process for these steel grades is
a non-equilibrium process producing non-equilibrium products like
martensite. Therefore, in addition to thermodynamic calculations fur-
ther microstructural characterization using higher magnifications is
important.
Fig. 5 shows the inclusion distribution in 35CrMo4, 41Cr4 and
36NiCrMo4 respectively. It can be observed, from Fig. 5(a), that elon-
gated stringer shaped NMIs appear in colonies or individually on the
surface and cross-section of 35CrMo4. Fig. 5(b) also shows that the
NMIs are distributed in a similar fashion in the cross-section as well.
Thus, from both types of observations, it can be concluded that the
numerous NMIs are distributed more or less uniformly throughout the
microstructure in 35CrMo4. On the other hand, almost no NMIs could
be observed in the case of 41Cr4 and 36NiCrMo4 at the same magni-
fication (Fig. 5(c), (e)), but very fine inclusions are observed at higher
T. Das et al.
Fig. 8. (a). Dark filed image obtained by using (0 1 3) Fe3C spot, corresponding SAED pattern (top right corner) in case of 35CrMo4. Bright field images and SAED pattern: (b) 41Cr4, (c)
36NiCrMo4 respectively.
magnification as shown in Fig. 5(d) and (f). This is primarily due to the
lower sulphur content of 36NiCrMo4 and 41Cr4 as compared to
35CrMo4. Again, energy-dispersive x-ray spectroscopy (EDS) was per-
formed on the inclusion surface to determine the type of inclusions
present in these steels.
It is observed that the NMIs are all MnS, as shown in Fig. 6 as an
illustration. Table 3 provides the quantitative analysis for the collected
EDS spectrum in Fig. 6. The number of inclusions per unit area was
calculated on a statistical basis, which shows that there are around
968 ± 159 no. of inclusions per square millimeter in case of 35CrMo4.
The average length and width of the NMIs found in case of 35CrMo4
were around 3.18 ± 0.8 and 0.95 ± 0.25 µm respectively with a few
exceptions where the NMIs were observed to be around 15–20 µm long.
Since very few inclusions were observed in case of 41Cr4 and
36NiCrMo4, no statistical evaluation could be obtained.
The carbides are known to a have a direct influence on the sus-
ceptibility of the material. Therefore, the carbide distribution and
morphology have been studied in detail both qualitatively and quan-
titatively using bright field and dark field TEM imaging techniques. The
carbides precipitate both at the lath boundaries as well within the laths
and their distribution is influenced by the presence of needle and plate
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Materials Science & Engineering A 716 (2018) 189–207
like laths. The coarsening of the lath structure, i.e. disappearance of
some lath boundaries present in the as-quenched martensite, could be
manifested by the presence of aligned carbide particles at those prior
lath boundaries. The plate martensite exhibits a coarse structure with
random orientation of carbides as shown in Fig. 7. The coarse particles
in 35CrMo4 could be recognized with the help of dark field imaging
(Fig. 8(a)) using (0 1 3) Fe3C spot as marked in the corresponding dif-
fraction pattern (top right corner in Fig. 8(a)). The incident beam is
approximately parallel to < 001 > direction of martensite. Thus, it has
been confirmed from selected area diffraction (SAED) pattern that these
carbide particles in 35CrMo4 having typical size of around 68 nm are
particularly cementite having an orthorhombic structure with lattice
parameters close to a = 0.452 nm, b = 0.509 nm and c = 0.674 nm
[25]. Similarly, in 41Cr4 and 36NiCrMo4 these coarse particles are
identified as cementite, as shown in Fig. 8(b) and (c).
As predicted from thermodynamic calculations, more cementite has
been observed in case of 36NiCrMo4 as compared to 41Cr4 and
35CrMo4 from TEM. In addition to cementite, very small sized pre-
cipitates having an approximate size less than 15 nm are observed in
large numbers in 35CrMo4 as shown in Fig. 9(a) and (c). The presence
of this type of small size precipitates is more predominant in case of
T. Das et al.
Fig. 9. Bright field TEM images showing the difference in size and morphology of precipitates in (a) 35CrMo4 and (b) 36NiCrMo4 respectively. (c) A high magnification image showing a
very small precipitate of approximately 10 nm size in 35CrMo4, corresponding SAED pattern of the particle (top left corner).
35CrMo4 as compared to 36NiCrMo4 and 41Cr4 (Fig. 9(a) and (b)). The
diffraction spots obtained from some of those small particles are weak
but nevertheless with careful observation of the dark field image could
be obtained by using (6 1 0) Fe2MoC spot. The particle is further iden-
tified as Fe2MoC (iron-molybdenum carbide) carbide from the SAED
pattern (top left corner in Fig. 9(c)) with orthorhombic structure having
lattice parameters close to a = 1.627 nm, b = 1.003 nm and c =
1.132 nm [25]. The frequency of carbide length distribution in
35CrMo4, 41Cr4 and 36NiCrMo4 are shown in Fig. 10 and the size
parameters of the particles are tabulated in Table 4.
3.4. Mechanical property test by increment step load (ISL) test method
The average fast fracture loads are 973.27 ± 16.3 N, 921.67 ± 6.6 N,
897.65 ± 5.84 N for 35CrMo4, 41Cr4 and 36NiCrMo4, respectively. A
plot (Fig. 11) of average percent notch fracture strength (NFS%) versus
cathodic potential (VSCE) of charging hydrogen at three different potentials
−0.85, −1, −1.2VSCE including air, shows the full threshold curves
(transition in NFS%) for the steel grades. The NFS% as well as the average
time to failure obtained from the ISL tests for the steel grades have been
reported in the form of a table (Table 5).
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Materials Science & Engineering A 716 (2018) 189–207
The NFS% shows a decreasing trend with increasing cathodic po-
tential of charging hydrogen and the transition behavior is quite similar
to that of the ductile-brittle transition behavior of steel if energy is
plotted against temperature. Therefore, in other words, it can be stated
that hydrogen introduces brittleness into the material and its influence
is dramatic beyond −0.85VSCE on increasing the cathodic potential of
charging hydrogen. But as far as individual performance is concerned,
36NiCrMo4 reveals better mechanical behavior as compared to
35CrMo4 and 41Cr4. The NFS% of 36NiCrMo4 are 52.2 ± 0.14 and
42.05 ± 0.07 at −1VSCE and −1.2VSCE respectively, which is higher as
compared to the values of both 35CrMo4 and 41Cr4.
At −0.85 VSCE, the NFS% values are similar but the time to failure
(Table 5) is highest in case of 36NiCrMo4 owing to the fact that
2%−3 h is the most susceptible loading condition for this material
under this particular hydrogen exposure environment. But for 35CrMo4
and 41Cr4, similar NFS% values were obtained irrespective of two hours
(2%−2 h) or three hours (2%−3 h) of holding time, hence the ac-
celerated protocol i.e. 2%−2 h has been identified as the most sus-
ceptible condition. Again, when the mechanical behaviors of 35CrMo4
and 41Cr4 are considered only, it can be observed that the NFS% de-
creases with increasing cathodic potential but the effect of hydrogen is
T. Das et al.
Fig. 10. Frequency of carbide length distribution in (a) 35CrMo4, (b) 41Cr4 and (c)
36NiCrMo4 respectively.
more pronounced in case of 35CrMo4 as compared to 41Cr4 beyond
−0.85VSCE. The NFS% is 46.4 ± 1.63 for 41Cr4 while it is 41.35 ± 1.34
for 35CrMo4 at −1VSCE. Again, at −1.2VSCE, 35CrMo4 and 41Cr4 have
almost similar NFS% values. But 41Cr4 can sustain higher load for a
longer period of time in the same environment as the values of average
time to failure are 10 h and 7 h more as compared to 35CrMo4 at
−1VSCE and −1.2 VSCE respectively. (Table 5). These values can be
more significant during real time engineering applications.
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Materials Science & Engineering A 716 (2018) 189–207
3.5. Fractography
A detailed analysis has been carried along with fracture surface
mapping to develop ideas on the fracture behavior of the steel grades.
Fig. 12 shows a typical fracture surface image of 35CrMo4 obtained
after the ISL testing in air. The fracture surface in Fig. 12 reveals the
different features those are typically present in case of a 4-point bend
tested specimen. The critical regions which are highlighted in the
fracture surface are the ‘notch region’, where the crack initiates, and the
‘center’ of the fracture surface, whereas the absence of certain macro
features like shear lips at the edges sometimes indicates the severity of
failure.
Fig. 13 shows the fracture surfaces of 35CrMo4 obtained after fast
fracture from the near notch region. It can be observed that Fig. 13
represents a normal fracture of rapid ductile failure mode, character-
ized by ductile-dimple morphology. The presence of micro void coa-
lescence (MVC) features could be observed throughout the surface
suggesting the complete absence of the influence of hydrogen in this
fracture process.
Fig. 14 (a) and (b) shows the fracture surfaces from the near notch
region and center of the fracture surface tested in air by ISL test
method. It is interesting to observe the differences in morphology be-
tween the fast fracture and ISL tested surfaces. As shown in Fig. 14(a), a
mainly ductile-dimple morphology is observed right at the notch where
the crack initiates, which transits into a transgranular mode on tra-
versing away from the notch towards the center. Hence, Fig. 14(b)
depicts a transgranular mode of fracture mostly along the martensite
laths accompanied by limited ductility. Again, in Fig. 14(c) the ductile
morphology is missing at the notch and is replaced by sheared coales-
cence of micro voids, marking the beginning of cleavage fracture at
−0.85VSCE. An intermingling morphology of intergranular and trans-
granular fracture with ‘quasi cleavage’ features are observed
throughout the center of the fracture surface as shown in Fig. 14(d).
The fracture surfaces obtained after ISL testing at −1 and −1.2VSCE are
shown in Fig. 14(e), (f), (g) and (h). It can be observed that there are
not many differences between them as it is all brittle-intergranular,
showing the severity of embrittlement, except in the case of −1VSCE,
where, at the notch (Fig. 14(e)), a very fine sheared-fibrous pattern
could be noticed on the flat facets of the grain surface under careful
observations.
The fracture morphology of 41Cr4 at −1VSCE has been shown in
Fig. 15(a) and (b). It can be observed that the morphology is noticeably
different as compared to 35CrMo4 under the same conditions. The
presence of a ductile morphology with features showing coalescence of
micro-voids is very common at the notch part. Some fine pockets re-
vealing intergranular features (IG) could also be noticed (Fig. 15(a)).
The center shows a drastic transition as intergranularity is combined
with quasi cleavage features (Fig. 15(b)). Again, flat facets of grains
mixed with cleavage are observed at the notch part of the fracture
surface at −1.2VSCE, as shown in Fig. 15(c). Secondary crack branching
in different directions could also be observed. Fig. 15(d) shows the
image from center of the fracture surface at −1.2VSCE. No significant
differences are noticed in morphology when compared to the notch
part.
The fracture surfaces of 36NiCrMo4 from different regions tested at
−1VSCE and −1.2VSCE are shown in Fig. 16. Fig. 16(a) shows the image
of the fracture surfaces at −1VSCE from the near notch part at 2000×.
The morphology is noticeably different from that of 35CrMo4 but re-
veals features similar to 41Cr4. But a drastic change in morphology
could be followed when the central region is compared with both
35CrMo4 and 41Cr4 (Fig. 16(b)). Interestingly, the intergranular mor-
phology was accompanied by ductility with no transgranular features at
all. Again, the images from the notch part at −1.2VSCE in Fig. 16(c)
varies distinctly. The morphology is entirely intergranular with sec-
ondary cracks showing up in some regions. But it is interesting to note
that the primary crack initiating from the notch strictly follows the
T. Das et al. Materials Science & Engineering A 716 (2018) 189–207

Table 4 obtained from the ISL tests as well as other observations and are dis-
Size parameters of carbides present in the microstructure of the steel grades obtained cussed in further details in the discussion section.
from TEM.

Sample Fine carbides Coarse/Elongated carbides 4. Discussion

Diameter (nm) Length (nm) Width (nm) 4.1. Influence of hydrogen activity during electrolytic charging
36NiCrMo4 5.6 ± 2.7 86 ± 59 20 ± 9
41Cr4 8±4 69 ± 47 20 ± 13 The incremental step load test (ISL) involves in-situ charging of
35CrMo4 8±5 68 ± 57 19 ± 11 hydrogen at different potentials. The influence of electrolytic charging
of hydrogen on subsurface hydrogen activity in high strength steels has
always been an area of interest in research; it still needs further at-
tention especially in neutral environments, as in this charging process,
which has been carried out in 3.5 wt% NaCl solution. In addition to
electrolytic charging conditions, hydrogen can be introduced into the
material with the aid of a gaseous environment as well. Some literatures
are already available [26–29] which clarify the charging of hydrogen in
both alkaline and acidic conditions along with gaseous environment.
But neutral solutions like 3.5 wt% NaCl in spite of yielding a low hy-
drogen activity as compared to that of acidic and alkaline solutions,
imitate the service environment most likely during sacrificial corrosion
of coatings [30,31]. The hydrogen discharge and evolution reaction on
a steel surface (M) has the following steps [32,33]:
H2 O + M + e− → MHads + OH− (2)

2MHads → H2 + 2M (3)

MHads → M + Habs (4)

Fig. 11. Average percent NFS (NFS%) versus imposed cathodic potential (VSCE) for the
three different steel grades 35CrMo4, 41Cr4 and 36NiCrMo4 obtained by Increment Step
Load (ISL) test method.
weakest boundaries instead of every grain boundary, as observed in
case of 35CrMo4. The morphology from the central part is again in-
tergranular with pockets of MVC ductile features as shown in Fig. 16(d)
and (e). It is to be noted that due to space constraints some selected
images have been presented but the fracture behavior remains mostly
invariant while comparing with other fracture surfaces as well, pro-
vided that the samples are tested under the same conditions.
3.6. Thermal desorption analysis (TDA)
After heating the samples to a temperature of 300 °C for approxi-
mately 2 h and 15 mins, the TDA spectra are obtained in the form of ion
current vs time as shown in Fig. 17(a), (b) and (c) for 35CrMo4, 41Cr4
and 36NiCrMo4 respectively. It can be observed from all three plots
that the measured ion current intensity is higher in case of −1.2VSCE as
compared to −1VSCE. Moreover, in case of 36NiCrMo4 the intensity is
highest in both the cases of −1VSCE and −1.2VSCE as compared to
41Cr4 and 35CrMo4. This trend could be correlated with the results
Eq. (2) represents the discharge of hydrogen from the solution and
its subsequent adsorption on the steel surface. Following Eq. (2), the
adsorbed hydrogen either gets absorbed or recombine to form a hy-
drogen gas molecule H2. Eq. (3) shows the combination of adsorbed
hydrogen atoms, to produce a H2 gas molecule and Eq. (4) represents
hydrogen absorption. The absorption or recombination process of hy-
drogen is dictated by the number of sites available for adsorption at the
surface of the material. Eq. (3) involving the recombination of hy-
drogen leading to the evolution of hydrogen is faster than the atomic
hydrogen absorption process (by Eq. (4)) [34]. As a result, Eq. (3)
dominates especially at low coverages. Therefore, it is the coverage
factor or the degree of coverage, θ [35], that acts as the rate controlling
factor and could be further manipulated by the imposed cathodic po-
tential or current as well as the surface impurities, promoters etc. A
detailed discussion is required to address those issues, which is beyond
the scope of the present discussion. Henceforth, further discussions are
based on a complete absence of the impurities on the steel surface.
Since all these reactions occur on the steel electrode surface, hence an
understanding of hydrogen activity in the solution is a necessity. For
that purpose, hydrogen fugacity, f 0 is a promising parameter. The re-
lation between hydrogen fugacity and cathodic electrochemical char-
ging overpotential, β has been developed for electrolytic charging with
different solutions [36–39]. One such relation in case of low interstitial
steels charged is given by [39]:

Table 5
ISL test results of 35CrMo4, 41Cr4 and 36NiCrMo4 steel grades.

35CrMo4 41Cr4 36NiCrMo4

Cathodic Potential (VSCE) Average percent NFS (NFS%) Error ( ± ) Average percent NFS (NFS%) Error ( ± ) Average percent NFS (NFS%) Error ( ± )
0 (Air) 94.4 1.06 97.9 2.26 97.97 1.85
−0.85 90.3 – 90 – 92 –
−1 41.35 1.34 46.4 1.63 52.2 0.14
−1.2 34.03 1.95 34.05 0.07 42.05 0.07
Cathodic Potential (VSCE) Average Failure Time (h) Error ( ± ) Average Failure Time (h) Error ( ± ) Average Failure Time (h) Error ( ± )
0 (Air) 114 1.73 119.5 2.12 118 3
−0.85 71.1 – 71.5 – 109.1 –
−1 30.7 2.69 40.4 0.14 49.55 0.21
−1.2 15.77 1.29 22.3 0.78 34.25 0.07

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T. Das et al.
Fig. 12. Shows the different regions of the fracture surface.
βF ⎞
f 0 = 10.9 exp ⎛−
⎝ 16.47RT ⎠
where F = Faraday constant, R = universal gas constant & the T =
Temperature in K, maintained during the charging procedure. Eq. (5)
renders some useful insights on hydrogen activity. Eq. (5) also em-
phasizes the aggressiveness of hydrogen activity on the steel electrode
surface with an increase in overpotential of charging hydrogen. More-
over, the equivalency of gaseous and electrolytic charging condition has
also been stated [33,36–39]. With these assumptions, together with the
Henrian behavior of hydrogen dissolved in steels [40], the amount of
interstitial hydrogen dissolved in the bulk material is given by,
CH = K S f °
This is the modified expression of Sievert's law [41] for electrolytic
charging where the hydrogen activity is expressed in terms of fugacity
instead of pressure [42,43]. In Eq. (6) KS is the solubility constant
having an approximate value of 3.8*10−3 mol m−3 atm−1/2 for pure Fe
in gaseous hydrogen charging environment [44]. Therefore, it can be
stated that, with the increase of electrochemical overpotential of
charging hydrogen in an electrolytic solution, there is exponential in-
crease of hydrogen concentration.
The interstitial hydrogen is again trapped by microstructural fea-
tures during diffusion inside the bulk matrix [45]. McNabb and Foster
[46] formulation and Oriani's local equilibrium approach states that
Fig. 13. Shows the fast fracture surface from the near notch region at two different magnifications of 2000× and 4000× respectively.
Materials Science & Engineering A 716 (2018) 189–207
hydrogen diffusion within the steel structure ultimately depends on the
density of the interstitial sites, trap sites and their respective interaction
with the hydrogen atoms.
4.2. Microstructural characterization
4.2.1. Effect of inclusions
The nature of trapping of hydrogen in the matrix-inclusion inter-
faces could be instrumental in degrading the mechanical behavior of
35CrMo4. The detrapping behavior of hydrogen from inclusion-steel
matrix interface is still confusing. Some researchers have considered
non-metallic inclusion interfaces including MnS as permanent traps for
hydrogen at room temperature [47,48]. Others have reported the re-
versible trapping of hydrogen by MnS [49–51]. This could be detri-
mental particularly in case of internal hydrogen embrittlement (IHE)
and less aggressive environments (i.e. −0.85VSCE in the present study).
The MnS trap sites can act as a local reservoir of hydrogen to other
vulnerable crack initiation sites like martensite lath boundaries, grain
boundaries etc. This is further manifested by the presence of inclusions
in the fracture surfaces as observed in Fig. 18. This effect of reversible
(5)
trapping by MnS could be neglected when the influx of hydrogen is
considerably higher at −1VSCE and −1.2VSCE. The high amount of
diffusible hydrogen at the notch region would be the triggering factor
responsible for both crack initiation and propagation. But MnS inclu-
sions are also potential sites for localized corrosion due to pit formation
followed by hydrogen generation [52]. Therefore, the presence of MnS
inclusions on 35CrMo4 steel surface may certainly facilitate absorption
of hydrogen into the bulk material leading to lower NFS% and lower
average time to failure as compared to 41Cr4 and 36NiCrMo4 at
−1VSCE and −1.2VSCE (aggressive charging conditions). The irrever-
sible trapping of hydrogen is considered beneficial under normal con-
(6) ditions as it hinders the movement of hydrogen to stress concentrated
regions. However, irreversible trapping by MnS would be catastrophic
as hydrogen in certain sensitive features, such as high triaxial stress
fields at sharp extremities or in microvoids formed in the vicinity of the
inclusions [53], as well as the interface between the inclusion and steel
matrix [51,53] can lead to immediate crack initiation resulting in
failure because sulphide inclusions having a different modulus of
elasticity with respect to the matrix inherently act as stress raisers
under highly stressed situations. Additionally, the degree of suscept-
ibility of steels to hydrogen assisted cracking is also influenced by the
density, size, shape as well as distribution of the inclusions in the steel
matrix [54–56].
Therefore, NMIs like manganese sulphide irrespective of their
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T. Das et al. Materials Science & Engineering A 716 (2018) 189–207

Fig. 14. (a), (c), (e) and (g) show SEM images
collected from the near notch regions of fracture
surfaces obtained after ISL testing in air and at
potentials of −0.85, −1, −1.2 VSCE respectively
in case of 35CrMo4. Similarly, (b), (d), (f) and (h)
show SEM images collected from the center of the
fracture surfaces. All images are obtained at the
same magnification of 2000×.

201
T. Das et al.
Fig. 15. (a) and (b) show SEM images collected from the near notch region and the center of a fracture surface obtained after ISL testing at −1VSCE while (c) and (d) show the same at
−1.2VSCE in case of 41Cr4. All images are obtained at the same magnification of 2000×.
trapping behavior within the bulk steel matrix along with their hy-
drogen generation/absorption capabilities at surface can directly in-
fluence the material susceptibility of 35CrMo4 which is also consistent
with other studies [57].
4.2.2. Effect of precipitates
TEM images revealed the presence of fine and coarse precipitates.
Precipitates depending on their size and distribution strengthen the
matrix by pinning the dislocation motion. Mobile hydrogen can also get
trapped at the matrix/precipitate interface or by the precipitates
themselves [58]. In the present study, based on the wide variety and
distribution of precipitates, the trap state could be detrimental or
beneficial depending on whether the traps are weak or strong. The
smaller precipitates in 35CrMo4, which are generally complex carbides
like Fe2MoC and having good coherency with matrix, can trap hy-
drogen reversibly [59]. Being reversible in nature, they may act as local
hydrogen sources to the stress concentrated regions, for instance, to the
notch tip, grain boundaries etc. The transport of hydrogen from these
trap states to the stress concentrated regions would be dictated by the
spacing between them. The movement of hydrogen atoms could also be
aided by faster diffusion process through the interconnected interstitial
sites due to the related crystal geometry of the material, as character-
ized by lower solubility and higher mobility of hydrogen in tempered
martensite steels [60]. This complete phenomenon involving hydrogen
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Materials Science & Engineering A 716 (2018) 189–207
trapping and transport explains the lower NFS% and a lower time to
failure value tested in air and at −0.85VSCE respectively in case of
35CrMo4.
As observed from TEM images and FactSage calculations, the
amount of cementite precipitated in case of 36NiCrMo4 is significantly
higher than 35CrMo4 as well as 41Cr4. The cementite-matrix interfaces
and the octahedral sites within cementite can act as strong traps for
hydrogen [61–63]. The cementite particles in 36NiCrMo4 will be
completely incoherent with the steel matrix due to their coarse sizes
and differences in crystal structure with the matrix. The high amount
disregistry at the matrix/precipitate interface will proportionately in-
crease the interfacial energy thereby attracting more hydrogen atoms to
the interface. Therefore, with the increase in cementite, the irreversible
trapping of hydrogen increases under stressed situation, which is ben-
eficial in reducing material susceptibility. Thus, the presence of large
sized cementite particles in higher volume fractions in 36NiCrMo4,
acting as sinks to the hydrogen atoms contributes towards the higher
NFS% at −1 VSCE and −1.2 VSCE as compared to 41Cr4 and 35CrMo4.
4.2.3. Fractography
The effect of hydrogen induced embrittlement is more pronounced
with increasing electrochemical potential of charging hydrogen, as
observed from fractography. The transition in morphology could be
distinctly observed through the fracture surfaces starting from air
T. Das et al. Materials Science & Engineering A 716 (2018) 189–207

Fig. 16. (a) and (b) show the SEM images collected from the near notch region and center of a fracture surface at 2000× obtained after ISL testing −1VSCE. Similarly, (c) and (d) show
the images at −1.2 VSCE in case of 36NiCrMo4 while (e) shows a high magnification image of (d) at 4000× highlighting some intricate features.

towards higher potential of charging hydrogen and is well correlated to
the decrease in NFS% in case of 35CrMo4. The difference in morphology
between the near notch and center region of the fracture surfaces
suggests a different mechanism responsible for the crack initiation and
crack propagation. The presence of micro void coalescence (MVC)
features representing ductile-dimple fracture at the near notch region of
the fracture surface in a predominant fashion while testing in air sug-
gests that the crack initiation process is external stress induced. The
transgranular morphology refers to typical hydrogen assisted crack
propagation along the tempered martensite lath boundaries, as in the
case of an internal hydrogen embrittlement (IHE) process. The flat re-
gion revealing the shearing of MVC in the near notch region shows that
crack initiation occurs due to plastic strain. The morphology at the
center part, which is somewhat distant from the notch root is a better
representative of hydrogen assisted crack propagation, and can be at-
tributed to the introduction of hydrogen at −0.85VSCE in presence of

203
T. Das et al.
Fig. 17. (a), (b) and (c) show the ion current vs time plots for 35CrMo4, 41Cr4 and
36NiCrMo4 respectively obtained after heating them to a temperature of around 300 °C
for around 2 h and 15 min.
peak hydrostatic stress in this region [64]. The morphologies of near
notch and center regions for both −1VSCE and −1.2VSCE in case of
35CrMo4 are quite similar, revealing complete brittle-intergranular
features showing the severity of hydrogen embrittlement failure.
Moreover, the existence of intergranular morphology from notch to
center also indicates that the crack initiation as well as propagation is
solely hydrogen induced. As can be observed from Fig. 19, the pre-
cipitation of carbides along the grain boundaries could be responsible
for the typical intergranular mode of failure in 35CrMo4 due to HE. The
fracture morphology of 41Cr4 and 36NiCrMo4 is different from
35CrMo4 at −1VSCE at the near notch part. As MVC features coexist
with intergranular morphology, the severity of hydrogen induced
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Materials Science & Engineering A 716 (2018) 189–207
embrittlement is expected to be less. The NFS% at this potential is
substantially high in case of 36NiCrMo4 and 41Cr4 as compared to
35CrMo4, implying that it can sustain higher loads for longer period of
time in the same environment. The morphology at the center in case of
36NiCrMo4 is conceivably different where more ductile features are
observed as compared to 41Cr4. This could be correlated with the
higher NFS% of 36NiCrMo4 as compared to 41Cr4 at the same potential,
implying the non-uniformity of damage from the notch root towards the
center between these two materials. Although, at −1.2VSCE there is no
significant difference in morphology that could be observed between
them, it is predominantly brittle-intergranular. But a difference in NFS%
and the average failure time indicates that either more diffusible hy-
drogen is required for crack initiation or the irreversible trapping effi-
ciency of hydrogen is better in case of 36NiCrMo4 followed by 41Cr4
and 35CrMo4. Cementite particles acting as sinks for hydrogen in these
materials turn into reservoirs of high hydrogen concentration due to
prolonged exposure to electrochemical charging. Again, due to the
elastic shielding effect under the influence of hydrogen, an increased
interaction among dislocations and in between dislocation-cementite
particles occurs, resulting in coalescence of leading dislocations at the
head of pile-up. Such local microstructural evolutions under the influ-
ence of stress and hydrogen may give rise to the formation of cracks
[65]. Once the crack initiates, it follows the weaker paths to propagate,
for instance grain boundaries. Therefore, the contribution of high ce-
mentite content towards crack initiation could be a possible explanation
of the brittle-intergranular features observed at aggressive potential of
charging hydrogen like −1.2VSCE in 36NiCrMo4.
4.2.4. Thermal desorption analysis (TDA)
The number of hydrogen molecules detected by this technique ba-
sically represents the interstitial hydrogen concentration along with
weakly trapped hydrogen, as the maximum temperature of desorption
was 300 °C [5]. The number of hydrogen molecules desorbed over a
period of time has been evaluated by using the Faraday cup equation
[66] which states that the ratio of the number of molecules, N to ion
current, I equals to the ratio of time, t to the charge of an electron, e, i.e.
N t
=
I e (7)
I×t
N=
e (8)
where, I × t in Eq. (8) is the area under the ion current versus time
plots. Fig. 20 shows the number of hydrogen molecules desorbed. The
trend of hydrogen desorption is the same as more number of hydrogen
molecules are detected at −1.2VSCE compared to −1.0VSCE, provided
that the time of the TDA experiment is constant. It suggests the fact that
−1.2VSCE is certainly a more aggressive environment of hydrogen ex-
posure. This observation also confirms the influence of hydrogen on
NFS% that has been discussed in the previous sections. Again, the
number of hydrogen molecules obtained at −1.0VSCE and −1.2VSCE is
higher in the case of 36NiCrMo4 as compared to 35CrMo4 and 41Cr4 as
36NiCrMo4 sustained higher loads in the same environment for longer
duration of time (Table 5). Thus, the TDA investigation further estab-
lishes that the amount of hydrogen necessary to trigger the same
amount of damage i.e. the critical hydrogen concentration requirement
is lower in case of 35CrMo4. In other words, 35CrMo4 is more sus-
ceptible to HE than 36NiCrMo4 and 41Cr4.
5. Conclusion(s)
1. All the three grades reveal very little internal hydrogen embrittle-
ment (IHE) according to the high values of NFS% obtained in air by
incremental step load (ISL) testing. Thus, the test results show that
amount of residual hydrogen due to steelmaking and other proces-
sing practices was low.
T. Das et al.
Fig. 18. (a) and (b) show the presence of manganese sulphide inclusions in the fracture surfaces of 35CrMo4 at 4000× and 16000× respectively.
Fig. 19. Shows the distribution of carbide particles (marked by red arrows) along the grain boundary (partially marked by dotted yellow lines for better visualization) of 35CrMo4
forming a garland like structure.
2. Although, 35CrMo4, 41Cr4 and 36NiCrMo4 are susceptible to EHE,
the degree of susceptibility varies in these materials. The NFS% and
total time to failure, both at −1.0 VSCE and −1.2VSCE in case of
36NiCrMo4 is higher as compared to 35CrMo4 and 41Cr4.
Therefore, based on ISL testing, it can be concluded that 36NiCrMo4
is more resistant to HE followed by 41Cr4 and 35CrMo4.
3. The higher susceptibility of 35CrMo4 is due to i) the trapping be-
havior and hydrogen generation/absorption capabilities of high
MnS inclusion content and ii) the presence of higher amount of fine
carbides like Fe2MoC in the matrix, which can act as local sources of
hydrogen to crack initiation sites to cause the damage.
4. The lower susceptibility of 36NiCrMo4 could be attributed to the
high cementite content and the irreversible nature of trapping by
cementite and cementite-matrix interfaces in this material.
5. Fractography results provide further confirmation of the above-
mentioned facts. The crack initiation and propagation process is
primarily hydrogen assisted in case 35CrMo4 at −1.0VSCE and
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Materials Science & Engineering A 716 (2018) 189–207
−1.2VSCE, which is not the obvious case for 41Cr4 and 36NiCrMo4.
Moreover, the fracture surface morphology is predominantly inter-
granular due to significant segregation of hydrogen at the grain
boundaries and other microstructural features like carbide particles
resulting in grain boundary embrittlement.
6. Hydrogen quantification results obtained from thermal desorption
analysis (TDA) technique provide direct experimental evidences that
the material susceptibility of 36NiCrMo4 is lowest followed by
41Cr4 and 35CrMo4.
Therefore, putting the facts together it can be stated that 35CrMo4
is a more susceptible to HE as compared to 41Cr4 and 36NiCrMo4,
owing to its microstructural features and chemistry. More importantly,
the ISL test methodology proves to be a successful technique in order to
investigate both IHE and EHE susceptibility, taking into account the
meticulous effect of individual microstructural constituents.
T. Das et al.
Fig. 20. Shows the number of molecules of hydrogen versus imposed cathodic potential
of charging hydrogen in case of 35CrMo4, 41Cr4 and 36NiCrMo4 at two different po-
tentials of −1VSCE and −1.2VSCE, obtained from the TDA plots.
Acknowledgements
The authors gratefully acknowledge Boeing Company (US) and
NSERC CRDPJ (grant number 428422) for their financial support in
carrying out the research work. The authors would like to thank Prof.
Hatem Zurob, McMaster University, Canada for allowing access to use
TEM at the CCEM facility in McMaster University. The authors would
also like to acknowledge Prof. In-Ho Jung, McGill University, Canada
for providing access to perform thermodynamic calculations using
FactSage.
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