Materials Science & Engineering A 734 (2018) 416–426

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Materials Science & Engineering A

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

Hydrogen absorption and embrittlement of ultra-high strength aluminized T

press hardening steel
Lawrence Choa,1, Dimas H. Sulistiyoa, Eun Jung Seoa,2, Kyoung Rae Joa, Seong Woo Kimb,
Jin Keun Ohb, Yeol Rae Chob, Bruno C. De Coomana,3
a
Graduate Institute of Ferrous Technology, Pohang University of Science and Technology, Pohang 37673, South Korea
b
Technical Research Laboratories, POSCO, Gwangyang 57807, South Korea

A R T I C LE I N FO A B S T R A C T

Keywords: The use of press hardening steel (PHS) in structural safety-related parts has experienced a rapid growth in the
Hydrogen embrittlement automotive industry, due to increased passenger safety standards, which require an improved vehicle intrusion
Press hardening steel resistance. Very small concentrations of diffusible hydrogen in ultra-high strength PHS deteriorate their me-
Hot press forming chanical properties. The focus of the present study was the analysis of the diffusible hydrogen uptake during the
Aluminizing
hot press forming process of the aluminized PHS and its impact on the mechanical properties of PHS. The effect
of the paint baking on the properties of aluminized PHS was also evaluated by mechanical testing and hydrogen
thermal desorption analysis. A mechanism for the hydrogen absorption of aluminized PHS was proposed.

1. Introduction (3) The austenitized steel is subsequently quenched between water-

Hot press forming (HPF) also known as press hardening, hot
stamping, and die quenching, is a process to manufacture ultra-high
strength components, i.e. with a tensile strength (TS) > 1 GPa, with a
fully martensitic microstructure. The process also enables the produc-
tion of parts with a complex geometry without shape deviations re-
sulting from spring back. Hardenable boron steels, such as 22MnB5, are
generally used for the HPF process. Press hardened parts produced by
the HPF process are currently used in the automotive industry for the
production of A-pillars, B-pillars, bumpers, roof rails, rockers and tun-
nels [1]. The number of press hardening steel (PHS) parts used in au-
tomotive applications has increased sharply, and the percentage of PHS
parts in state-of-the-art car bodies, which currently stands at about
26%, could reach 40% in the future [1,2].
The HPF process consists of the following stages:
(1) A cold-rolled and annealed steel blank is heated to a soaking or
austenitizing temperature between 850 and 950 °C.
(2) The blank is held at the austenitizing temperature for 5–10 min.
During the heating process, the initial ferrite-pearlite micro-
structure transforms to austenite.
cooled dies. During the die-quenching stage, the blank is deformed
into the required shape and the austenitic microstructure trans-
forms fully into a lath martensitic microstructure.
Metallic coating systems are required to protect PHS from corro-
sions. In particular, the HPF process leads to significant oxide formation
on the surface of parts made from uncoated steel during the austeniti-
zation stage of the HPF process. This requires the removal of the oxide
scale on the stamped parts by shot blasting. Pre-coated steel blanks are
therefore preferred for HPF as these do not require an additional scale
removal stage. In addition, the protective alloy coating layer on the PHS
prevents the decarburization of the surface. The coating also improves
the in-service corrosion resistance. The most common coating for PHS is
the Al-10%Si alloy coating. The Al-10%Si alloy coating is applied to
cold-rolled steel by hot dip aluminizing. The typical composition of the
aluminizing bath is 87% aluminum, 10% silicon, and 3% iron [3].
The increased use of aluminized, i.e. Al-Si coated, PHS has led to
concerns about hydrogen (H) embrittlement. The risk of H embrittle-
ment is limiting the industrial application of ultra-high strength alu-
minized PHS with TS > 1.5 GPa.
Martensite, the main constituent of the matrix microstructure of

E-mail address: lawrence.cho@nist.gov (L. Cho).

1
Current address: National Institute of Standards and Technology, Boulder, CO 80305, USA.
2
Current address: Advanced Steel Processing and Products Research Center, Colorado School of Mines, Golden, CO 80401, USA.
3
Current address: R&D NLMK Group, Moscow, 119017, Russia.

https://doi.org/10.1016/j.msea.2018.08.003
Received 20 April 2018; Received in revised form 13 July 2018; Accepted 2 August 2018
Available online 07 August 2018
0921-5093/ Published by Elsevier B.V.
L. Cho et al.
PHS, has a pronounced susceptibility to H-related failure, as compared
to ferritic, bainitic, austenitic, and precipitation-hardened steel [4].
Previous studies have shown that the H-uptake occurs during the pro-
duction of PHS [5]. This H-uptake causes a severe, albeit transient,
reduction of the plasticity of PHS [5].
Aluminized PHS is considerably more sensitive to H-uptake and the
H-induced loss of plasticity than uncoated PHS [5]. The H-embrittle-
ment sensitivity of aluminized PHS has not been studied in detail. In
particular, the influence of the Al-Si coating on the H-uptake of the PHS
during the HPF process has not yet been studied systematically.
The present contribution aims to address the following questions:
(1) Which process in the industrial processing of PHS is responsible for
the H-uptake of the PHS?
(2) How does the aluminized coating accelerate the H-uptake of the
PHS?
(3) What is the impact of the H-uptake of the aluminized PHS on their
mechanical properties?
The present study focused on the analysis of the H-uptake during the
industrial processing of an ultra-high strength aluminized PHS and its
effect on the mechanical properties of this PHS. The H-uptake was
quantified by means of H thermal desorption analysis (H-TDA). The H-
uptake of uncoated PHS during the industrial processing was also in-
vestigated, for comparison purpose. Finally, a mechanism for the H-
uptake of the aluminized PHS was proposed.
2. Experimental procedure
An industrially produced, press-hardenable 35MnB5 steel was used
in the present study. The final cold-rolled thickness was 1.5 mm. The
steel in the press-hardened state has the ultimate tensile strength (UTS)
of approximately 2 GPa. The schematic shown in Fig. 1(a) illustrates the
sequence of processing stages for the uncoated PHS:
i) CA stage: A continuous annealing (CA) or recrystallization an-
nealing simulation was carried out at 800 °C for 1 min in an N2
+ 15% H2 gas atmosphere.
ii) HPF stage: During the HPF process simulation, a continuously an-
nealed specimen was austenitized at 900 °C for 5 min and quenched
between the water-cooled dies to room temperature. Note that no
attempt was made to control the furnace atmosphere, i.e. the fur-
nace atmosphere contained water vapor.
Fig. 1. Thermal cycles used for (a) uncoated and (b) aluminized PHS (CA:
continuous annealing, HPF: hot press forming, BH: bake hardening, and Al:
aluminizing).
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Materials Science & Engineering A 734 (2018) 416–426
iii) BH stage: During the bake hardening (BH) simulation, a press-
hardened specimen was isothermally held at 170 °C for 20 min. This
low-temperature tempering treatment simulates the paint baking of
an automotive part.
The uncoated specimens obtained after the CA, HPF, and BH stages
are labelled CA, CA+HPF, and CA+HPF+BH, respectively.
The schematic shown in Fig. 1(b) illustrates the sequence of pro-
cessing steps for the aluminized PHS. The specimen was continuously
annealed at 800 °C for 1 min in an N2 + 15% H2 gas atmosphere. The
specimen was then aluminized by hot dipping in an Al-10% Si liquid
alloy at 680 °C prior to cooling to room temperature in a hot dip alu-
minizing simulator. The aluminizing stage is referred to as “Al”. The
thickness of the Al-Si coating was approximately 30 µm. The thermal
cycles for the HPF and BH stages of the aluminized PHS used the same
thermal cycles as those used for the uncoated PHS (Fig. 1(a)). The
aluminized specimens obtained after CA and Al, HPF, and BH are la-
belled CA+Al, CA+Al+HPF, and CA+Al+HPF+BH, respectively.
The panels of the PHS after each stage (CA, CA+HPF, CA+HPF
+BH, CA+Al, CA+Al+HPF, and CA+Al+HPF+BH) were provided
by POSCO, Gwangyang. The dimensions of the industrially processed
PHS panels were 500 mm in width, 550 mm in length, and 1.5 mm in
thickness. It is important to note that, after the HPF, it took three days
to prepare the PHS panels for H-TDA and the mechanical testing, i.e. the
H-TDA and the mechanical testing were, in all cases, carried out 72 h
after each processing step.
In order to evaluate the H trapping states in both the uncoated PHS
and the aluminized PHS, a second set of H-TDA tests were carried out,
using a heating rate in the range of 4–30 °C/min. Since H has an ex-
tremely low solubility in α-Fe, weakly trapped H or diffusible H will
naturally escape from steel at room temperature. For these experiments,
a laboratory-scale HPF simulation was carried out. Prior to the la-
boratory-scale HPF simulation, the small coupons of 20 mm in width,
100 mm in length, and 1.5 mm in thickness were taken from the con-
tinuously annealed PHS panels and the aluminized PHS panels. The
PHS specimens were heated to 900 °C and isothermally held for 5 min in
an electrically-heated furnace. The specimens were then transferred to a
laboratory hydraulic HPF simulator where the specimens were quen-
ched between two flat water-cooled dies to room temperature. The die
temperature was maintained at room temperature by cooling the water
flowing through channels machined in the die. The thermal cycle used
for the laboratory-scale HPF simulation was same as the one used for
the HPF of the larger industrial PHS panels (Fig. 1). No attempt was
made to control the furnace atmosphere in the laboratory-scale HPF
simulations.
H analysis was carried out using a combination of two different H-
TDA instruments. The first H-TDA set up consisted of an infrared fur-
nace attached to an Agilent 7890A Gas Chromatograph. The dimensions
of the specimens for the H-TDA were 1.5 mm in thickness, 20 mm in
width, and 100 mm in length. The H desorption rate of the specimens
was measured during heating to 300 °C using a heating rate of 1.67 °C/
min. The specimens were analyzed at three-minute intervals using He as
carrier gas. The second H-TDA set up was the BRUKER G4 Phoenix
diffusible H analyzer. The H desorption rate of the specimens was
measured during heating to 800 °C using a constant heating rate. The
heating rate could be varied in the range of 4–30 °C/min. The carrier
gas was pure N2.
Uniaxial tensile tests and three-point bending tests were carried out
to observe the effect of H on the mechanical properties of the uncoated
and the aluminized PHS. The tensile tests were done with a Zwick/Roell
2100 universal tensile testing machine using a strain rate of 5 × 10−3
s−1. The ASTM E8 standard sized tensile specimens with a gauge length
of 50 mm used for this purpose were machined with their length par-
allel to the rolling direction. For each processing condition, three tensile
tests were performed. The three-point bending test equipment had a
punch radius of 0.4 mm. The punch speed was 20 mm/min. The
L. Cho et al.
Fig. 2. SEM images of the microstructure of the PHS specimens obtained after (a) continuous annealing, (b) hot press forming, and (c) bake hardening.
dimensions of the specimen used for the bending tests were 20 mm in
width, 80 mm in length, and 1.5 mm in thickness. One bending test per
each processing condition was performed.
The microstructure of the specimens was investigated by means of
field emission (FE) scanning electron microscopy (SEM), electron
backscattering diffraction (EBSD), and FE electron probe microanalysis
(EPMA). The SEM analysis was carried out in a ZEISS ULTRA-55 FE-
SEM. The EBSD analysis was conducted in an FEI Quanta 3D FEG FE-
SEM. The EPMA analysis was conducted in a JEOL JXA-8530F FE-
EPMA operated at 15 keV using a 50 nA beam current.
3. Results and discussion
3.1. Microstructure
Fig. 2 shows the PHS microstructure after CA, HPF, and BH. After
CA, the specimen microstructure consisted of a ferrite matrix and
pearlite islands, formed by alternating lamellae of ferrite and cementite
(Fig. 2(a)). The specimen after the HPF (CA+HPF) had a lath mar-
tensite microstructure. This lath martensite microstructure contained
fine carbide precipitates, which likely formed as a result of auto-tem-
pering during the die-quenching (Fig. 2(b)). The micrographs in
Fig. 2(c) show the tempered martensitic microstructure of the specimen
after the BH process (CA+HPF+BH). Tempering resulted in the for-
mation of relatively coarse carbide particles as can be seen in the inset
of Fig. 2(c).
The hot dip Al-Si alloy coating is affected by the austenitization and
the die-quenching stages in the HPF process. During heating to the
austenitizing temperature, the Al-Si coating close to the surface is li-
quefied while the Al-Si coating on the side of the steel/coating interface
reacts with Fe to form a phase mixture consisting of Fe-Al-Si inter-
metallic phases and the Fe2Al5 phase. During the austenitizing at
900 °C, the liquid Al-Si phase is fully replaced by a solid reaction layer
due to the growth of the Fe-Al-Si intermetallic phases and the Fe2Al5
phase.
Cross-sectional analysis of aluminized PHS after the HPF process
(CA+Al+HPF) was carried out by means of SEM, EBSD, and FE-EMPA.
Fig. 3 shows the surface and substructure of the aluminized PHS spe-
cimen in cross-section. Three regions are visible: a reacted surface
coating layer, a diffusion layer, and the lath martensitic matrix. The
reacted coating layer consisted of an Fe2Al5 and complex Fe-Al-Si in-
termetallic phases. Inside the reacted alloy coating area, the regions
with a black contrast in the EBSD phase map (Fig. 3(c)) correspond to a
complex Fe-Si-Al intermetallic phase. Al and Si were richer in the Fe-Si-
Al intermetallic phase than in the Fe2Al5 phase (Fig. 3(d)). This Si-rich
intermetallic constituent has been identified as Al2Fe3Si3 (τ1) phase in a
previous study [6]. The coarse-grained Al-diffused ferritic layer was
formed at the steel/coating interface. The diffusion layer was α-Fe(Al),
i.e. a solid solution of Al in BCC α-Fe. This region was not austenitized
due to its high Al and Si contents (Fig. 3(d)). The austenitized steel
matrix was transformed into martensite during the die-quenching
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Materials Science & Engineering A 734 (2018) 416–426
process. The martensite structure of the bulk PHS matrix is character-
ized by its characteristic lath martensite microstructure (Fig. 3(b) and
(c)).
3.2. Binding state of H absorbed in the PHS
Fig. 4 shows results of H-TDA tests for the uncoated PHS and the
aluminized PHS after each processing step. Note that, for the results
shown in Fig. 4, the H-TDA specimens were taken from the industrially
processed PHS panels and that the H-TDA test was performed three
days after each process. The uncoated specimens did not show a char-
acteristic H desorption rate peak in the 20–300 °C temperature range
(Fig. 4(a)). The total amounts of diffusible H measured for the uncoated
specimens after the CA, CA+HPF, and CA+HPF+BH stages were
0.036 ppm, 0.019 ppm and 0.020 ppm, respectively (Fig. 4(a)). The
TDA data for the aluminized specimen after aluminizing (CA+Al) did
also not show a H desorption rate peak in the 20–300 °C temperature
range (Fig. 4(b)). However, a H desorption rate peak was observed at
approximately 150 °C in the specimen after the HPF stage (CA+Al
+HPF) and after the BH stage (CA+Al+HPF+BH). The total contents
of diffusible H for the aluminized specimens after the CA+Al, CA+Al
+HPF, and CA+Al+HPF+BH stages were 0.055 ppm, 0.502 ppm and
0.369 ppm, respectively. This result implies that the aluminized PHS
exhibited a large H-uptake during the HPF. After the BH, the H content
in the specimen decreased, which suggests that the BH treatment acted
as a low temperature H out diffusion treatment.
In order to evaluate the H binding states in both the uncoated PHS
and the aluminized PHS, a second set of H-TDA tests were carried out
using different heating rates. Fig. 5 shows the H-TDA curves of the
uncoated PHS and the aluminized PHS, both austenitized at 900 °C for
5 min and die-quenched to room temperature. In this experimental set,
the H-TDA could be done immediately after the laboratory-scale HPF
simulation. A H desorption rate peak was clearly observed in the range
of 50–350 °C in the H-TDA curves of the uncoated PHS immediately
after the die-quenching (Fig. 5(a)). This low-temperature peak is la-
belled “Peak 1” in Fig. 5(a). The intensity of the H peak increased and
the temperature of the peak maximum shifted to higher temperatures
with increasing heating rate. A second H desorption peak was observed
in the range of 350–650 °C in the TDA curves of the uncoated PHS
(Fig. 5(a)). This high-temperature peak is labelled “Peak 2” in Fig. 5(a).
The intensity of this H peak increased and the temperature for the peak
maximum shifted to higher temperatures with increasing heating rate.
Enomoto et al. [7] analyzed the TDA curve for high strength martensitic
steel by means of numerical simulation and experiments. They also
observed two peaks in the TDA curve and demonstrated that the first
peak appearing at around 100 °C, which corresponds to Peak 1 in
Fig. 5(a), is due to H-atoms trapped in the stress field surrounding
dislocation. They reported that the second peak appearing at about
300 °C is due to H-atoms trapped in the dislocation cores. This peak
corresponds to Peak 2 in Fig. 5(a) of the present study.
The diffusible H content of the uncoated PHS was approximately
L. Cho et al. Materials Science & Engineering A 734 (2018) 416–426

Fig. 3. Cross-section of the aluminized PHS after hot press forming. (a) SEM image. (b) EBSD inverse pole figure map. (c) EBSD phase map. (d) SEM image and the
corresponding FE-EPMA elemental maps for Fe, Al, and Si.

Fig. 4. (a) H-TDA curves for the uncoated PHS

after continuous annealing (CA), hot press
forming (CA+HPF), and bake hardening
(CA+HPF+BH). (b) H-TDA curves for the
aluminized PHS after continuous annealing
and aluminizing (CA+Al), hot press forming
(CA+Al+HPF), and bake hardening (CA+Al
+HPF+BH). TDA was done three days after
each process using an Agilent 7890A Gas
Chromatograph. The TDA heating rate was
1.67 °C/min.

0.10 ppm. The term “diffusible H” refers to H that desorbs from a H- The trap activation energy of H (Ea) was obtained from the heating
charged specimen during aging at the moderately elevated temperature rate dependence of the peak maximum temperature, using the fol-
of approximately 300 °C [8] or even at room temperature [9]. In the lowing equation [10]:
present study, the diffusible H is defined as the H which desorbs at low
∂ ln(ϕ/ Tp2) Ea
temperature. It corresponds to the H-atoms which give rise to the Peak =−
1 desorption peak in the H-TDA curves. ∂ (1/ Tp) R (1)

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L. Cho et al. Materials Science & Engineering A 734 (2018) 416–426

Fig. 5. H-TDA curves for (a) the uncoated PHS and (b) the aluminized PHS, both austenitized at 900 °C for 5 min and die-quenched to room temperature. TDA was
done immediately after the HPF simulations using a Bruker G4 Phoenix Diffusible H analyzer. TDA heating rate ranged from 4° to 30 °C/min.

Here, ϕ is the heating rate used during the H-TDA test in K/s, Tp is
the peak maximum temperature in K, and R is the gas constant. The
values of the activation energy obtained from Peak 1 and Peak 2 are
22.1 kJ/mol and 74.7 kJ/mol, respectively. These values indicate that
the H-atoms giving rise to the desorption Peak 1 are weakly bound. The
H-atoms giving rise to the desorption Peak 2 are more strongly bound.
The “Peak 1” H-atoms diffuse easily at room temperature. The “Peak 2”
H-atoms remain bound at the trap site at room temperature. Table 1
lists the data of the present study and literature data [7,10–12] for the
trapping energies for H in ferritic steels and martensitic steels. The
activation energy values of H-desorption for grain boundaries, dis-
locations, and micro-voids in steels are reported to be 17.2, 26.8 and
35.3 kJ/mol [10]. Based on these values the desorption “Peak 1” is
associated with the H-trapping at either grain boundaries or the strain
field of dislocations.
Fig. 5(b) shows the H-TDA curves of aluminized PHS immediately
after die-quenching. Both the H-desorption rate peak “Peak 1” and the
H-desorption rate peak “Peak 2” were observed at slightly higher
temperatures as compared to the corresponding peaks of the uncoated
PHS. Peak 1 was in the 100–400 °C temperature range. Peak 2 was in
the 400–650 °C temperature range. The shift of the H desorption peaks
is likely caused by the presence of the Al coating, i.e. diffusion of H in
solid Al is very slow and thus, the Al coating can slow down the des-
orption process of H trapped at martensitic matrix during the TDA. The
diffusible H content of the aluminized PHS was approximately
0.30 ppm, i.e. much higher than that of the uncoated PHS (~ 0.10 ppm).
The intensity of both Peak 1 and Peak 2 was higher for the aluminized
PHS (Fig. 5(b)) as compared to the uncoated PHS (Fig. 5(a)), confirming
that the aluminized PHS is more sensitive to H-uptake than the un-
coated PHS.
It is noteworthy that an H desorption peak (Peak 1) was clearly
visible in the H-TDA curve of the uncoated PHS samples after the
laboratory-scale HPF simulation (Fig. 5(a)), while it did not appear in
the H-TDA curve for the uncoated PHS samples after the industrial HPF
process (CA+HPF) (Fig. 4(a)). This is due to that the fact that, in the
case of the PHS panels produced industrially, the H-TDA tests were
performed three days after the HPF process. This implies that most of
the absorbed H diffused out of the steel at room temperature. This is
consistent with the result of Hirakami et al. [13] that most of the dif-
fusible H diffused out of a H-charged, 0.35 wt% C martensitic steel at
room temperature in 2–4 days.
3.3. Effect of microstructure and H on the mechanical and fracture behavior
The results of the tensile tests, bending tests, and the TDS analysis
show a clear correlation between the deterioration of the plasticity of
the aluminized PHS and the H content. Table 2 indicates the room
temperature tensile properties of the uncoated PHS and aluminized PHS
specimens after the different process stages. Each value listed in Table 2
is the average value measured from three tensile tests. Fig. 6 shows the
representative engineering stress strain curves. Fig. 6(a) shows the
stress–strain curves of the H-free, uncoated PHS. The uncoated spe-
cimen after the CA stage had the ferrite-pearlite microstructure. Its
tensile properties exhibited a low yield strength (YS), a low UTS, and a
high total elongation (TE). The average YS, UTS, and TE for the spe-
cimen after CA were 410 MPa, 637 MPa, and 23.3%, respectively
(Table 2). After the HPF simulation (CA+HPF), the steel microstructure
was fully martensitic. The uncoated specimen after the CA+HPF stage
had a high YS (1234 MPa), a high UTS (1986 MPa), and a low TE
(6.3%). After the BH process (CA+HPF+BH), the YS increased to
1439 MPa, the UTS decreased to 1911 MPa and the TE increased
slightly to 7.2%. The increase in the YS by approximately 200 MPa
clearly indicates a strong BH response of the PHS. The BH behavior of
lath martensitic steel has been explained by dislocation locking caused

Table 1
Literature data overview for the trapping activation energies for H in ferritic steels and martensitic steels. Ferrite and martensite are labelled α and α′, respectively.
Type of trap Peak temperature, °C (heating rate, °C/min) Activation energy, kJ/mol Microstructure Reference

Reversible H traps
Grain boundary 105–162 (3.06–8.18) 17.2 Pure iron (α) Choo and Lee [24]
Grain boundary and dislocation strain field ~ 100 (1.67) 21.9 Ti-added steel (α) Wei et al. [25]
Dislocation strain field 198–311 (1.39–8.44) 26.8 Pure iron (α) Choo and Lee [24]
Dislocation strain field ~ 100 (1.67) 27 Martensitic steel (α′) Enomoto et al. [21]
Microvoids 267–379 (1.39–8.13) 35.2 Pure iron (α) Choo and Lee [24]
Irreversible H traps
Dislocation core ~ 300 (1.67) 45 Martensitic steel (α′) Enomoto et al. [21]
Ferrite/Fe3C interface ~ 370 (3.33) 65.0 Medium carbon steel (α) Takai and Watanuki [26]
Peak 1: dislocation strain field 110–250 (4–30) 22.1 PHS (α′) Present study
Peak 2: dislocation core 480–500 (4–30) 74.7 PHS (α′) –
Peak 1: dislocation strain field 200–300 (4–30) – Aluminized PHS (α′) –
Peak 2: dislocation core 480–520 (4–30) – Aluminized PHS (α′) –

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L. Cho et al. Materials Science & Engineering A 734 (2018) 416–426

Table 2 (a) (b)

CA CA+HPF CA+HPF+BH CA+Al CA+Al+HPF CA+Al+HPF+BH
Summary of tensile properties of the PHS after each process (CA: continuous
annealing, HPF: hot press forming, BH: bake hardening, and Al: aluminizing).
The reported results are averages of three repeated tests for each condition.
Process YS (MPa) UTS (MPa) TE (%)
62°

Uncoated PHS CA 410 ± 8.9 637 ± 8.4 23.3 ± 0.3

CA+HPF 1234 ± 2.0 1986 ± 7.5 6.3 ± 1.3
CA+HPF+BH 1439 ± 12 1911 ± 7.7 7.2 ± 0.6
Aluminized PHS CA+Al 441 ± 0.7 585 ± 3.3 24.1 ± 0.1 62°
CA+Al+HPF 1236 ± 20 1896 ± 46 2.8 ± 0.3
CA+Al+HPF+BH 1447 ± 7.7 1927 ± 17 6.9 ± 0.6

by the formation of Cottrell atmospheres, precipitation of iron carbides,

and softening of martensitic matrix due to the tempering [14].
Fig. 6(b) shows the stress–strain curves of the aluminized PHS. The
fracture behavior during the tensile test was clearly associated with the
amount of the diffusible H in the aluminized PHS. The average YS, UTS, Uncoated PHS Aluminized PHS
and TE for the aluminized specimen after the aluminizing (CA+Al)
Fig. 7. (a) Sample fracture after tensile test of uncoated PHS after continuous
stage were 441 MPa, 585 MPa, and 24.1%, respectively (Table 2). The
annealing (CA), hot press forming (CA+HPF), and bake hardening (CA+HPF
tensile properties of the aluminized specimen after the CA+Al stage
+BH) and (b) aluminized PHS after continuous annealing and aluminizing
were similar to those for the uncoated PHS after the CA stage because it
(CA+Al), hot press forming (CA+Al+HPF), and bake hardening (CA+Al
did not contain diffusible H (Fig. 4(b)). The aluminized specimen after +HPF+BH).
the HPF stage (CA+Al+HPF) had a YS of 1236 MPa and a UTS of
1896 MPa. The specimen fractured abruptly at an elongation of 2.8%.
martensite is associated with its high density of dislocations (~ 1015
Approximately 0.5 mass ppm of diffusible H was present in the alu-
m−2), which serve principal traps for H. Therefore, it is also possible
minized specimen after the CA+Al+HPF stage (Fig. 4(b)). The ducti-
that a slight reduction in the dislocation densities resulting from the
lity of the aluminized PHS was clearly reduced by H embrittlement. The
tempering of the martensitic PHS contributed to the improvement in
aluminized specimen after the BH treatment (CA+Al+HPF+BH) had a
the ductility shown in Fig. 6(b). While the BH treatment clearly resulted
YS of 1447 MPa, and a UTS of 1927 MPa. The TE was 6.9%, i.e. much
in a decrease of the diffusible H content of the aluminized PHS
larger than for the specimen after CA+Al+HPF. This improvement in
(Fig. 4(b)), the TE for the aluminized specimen after the CA+Al+HPF
the ductility is due partly to the fact that the BH process partially re-
+BH remained smaller than for the uncoated specimen after the
leased the diffusible H present in the aluminized PHS (Fig. 4(b)). The H
CA+HPF+BH stage. This implies that the BH process can only partially
susceptibility of lath martensitic steel is known to depend on the degree
mitigate the damage caused by H. It does not fully prevent the H em-
of tempering [15] and the dislocation density [16] as well as the dif-
brittlement.
fusible H content. In general, as-quenched martensitic steel is more
Fig. 7 shows macro images of the fractured tensile specimen. A
sensitive to H-induced brittle fracture than tempered martensitic steel
ductile fracture with diffuse necking occurred in the cases of the
[15]. Lee et al. [15] reported that the high H sensitivity of as-quenched

(a) i) CA ii) CA+HPF iii) CA+HPF+BH

2500
Engineering Stress, MPa

2000

1500

1000

500

0
0 5 10 15 20 0 2 4 6 8 0 2 4 6 8 10
Engineering Strain, % Engineering Strain, % Engineering Strain, %
(b) i) CA+Al ii) CA+Al+HPF iii) CA+Al+HPF+BH
2500
Engineering Stress, MPa

2000

1500

1000

500

0
0 5 10 15 20 0 2 4 6 8 0 2 4 6 8 10
Engineering Strain, % Engineering Strain, % Engineering Strain, %
Fig. 6. (a) Tensile properties of the uncoated PHS after continuous annealing (CA), hot press forming (CA+HPF), and bake hardening (CA+HPF+BH). (b) Tensile
properties of the aluminized PHS after continuous annealing and aluminizing (CA+Al), hot press forming (CA+Al+HPF), and bake hardening (CA+Al+HPF+BH).

421
L. Cho et al.
uncoated specimen after the CA (Fig. 7(a)). Both the uncoated speci-
mens after the HPF stage (CA+HPF) and after the BH treatment
(CA+HPF+BH) had a shear-type fracture with a fracture angle, θF, of
62°. A shear-type fracture is usually attributed to a very high strength,
which results in a decreased ratio of the average critical normal fracture
stress to shear fracture stress. Zhang and Eckert [17] have shown the
dependence of the tensile shear fracture angle on the ratio of the
average critical normal fracture stress to shear fracture stress. In high-
strength materials or nanostructured materials, θF is in the range of
45°–90°. In brittle materials with a very high hardness, the maximum
normal fracture stress controls the failure mode, resulting in a fracture
with a θF = 90°. The appearance of the fracture area for the aluminized
specimen after the aluminizing (CA+Al) was similar to that for the
uncoated specimen after the CA, i.e. they both exhibited diffuse necking
characteristics. However, a fracture with a θF = 90° occurred for the
aluminized specimens after the HPF stage (CA+Al+HPF) and after the
Fig. 8. SEM images of the fracture surface of tensile specimens. (a) The uncoated PHS after continuous annealing (CA), hot press forming (CA+HPF), and bake
hardening (CA+HPF+BH). (b) The aluminized PHS after continuous annealing and aluminizing (CA+Al), hot press forming (CA+Al+HPF), and bake hardening
(CA+Al+HPF+BH).
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Materials Science & Engineering A 734 (2018) 416–426
BH treatment (CA+Al+HPF+BH). A sudden fracture with a θF = 90°
due to limited plastic deformation was observed only for specimens
containing diffusible H. Therefore, this sudden fracture can be con-
sidered to be related to the H embrittlement.
Fig. 8 shows micrographs of the fracture surface of specimens after
tensile tests. It shows the region of the fractured surface up to 40 µm
below the surface. Fig. 8(a) reveals that for the uncoated specimens, the
fracture was always ductile, as can be inferred from dimpled fracture
surface appearance obtained in the CA, CA+HPF and CA+HPF+BH
specimens. In the case of aluminized specimens (CA+Al), the fracto-
graphic observation also revealed a dimpled fracture surface (Fig. 8(b)).
The aluminized specimen after the HPF stage (CA+Al+HPF) had a
mixed ductile and brittle fracture surface. This fracture surface con-
tained inter-granular cracks close to the coating. The presence of inter-
granular cracks is usually considered as direct evidence for brittle
fracture. Closer to the steel matrix, the fracture plane consisted of
L. Cho et al.
Fig. 9. (a) Bending test results of the uncoated PHS after continuous annealing (CA), hot press forming (CA+HPF), and bake hardening (CA+HPF+BH). (b) Bending
test results of the aluminized PHS after continuous annealing and aluminizing (CA+Al), hot press forming (CA+Al+HPF), and bake hardening (CA+Al+HPF+BH).
(a) CA CA+HPF CA+HPF+BH
(b) CA+Al CA+Al+HPF CA+Al+HPF+BH
20 mm
Fig. 10. Specimens after bending test. (a) The uncoated PHS after continuous
annealing (CA), hot press forming (CA+HPF), and bake hardening (CA+HPF
+BH). (b) The aluminized PHS after continuous annealing and aluminizing
(CA+Al), hot press forming (CA+Al+HPF), and bake hardening (CA+Al
+HPF+BH).
dimples. River marks, indicative of trans-granular fracture, were pre-
sent in the coating area of the fracture surface of the CA+Al+HPF
specimen. The trans-granular fracture feature is evidence that the re-
acted surface alloy coating was brittle. The dimple size for the alumi-
nized specimens after the HPF stage (CA+Al+HPF) and after the BH
treatment (CA+Al+HPF+BH) was much smaller than that for the
uncoated specimens.
The origin of the smaller dimple size observed on the fracture sur-
face on the aluminized specimens after HPF is very likely associated
with the presence of diffusible H. Decrease of the dimple size is, in
general, due to a very high void nucleation rate and a very small void
growth rate during the void coalescence process [18]. Lynch [19] has
shown that a dimpled fracture can be caused by adsorbed H atoms fa-
cilitating dislocation formation at crack tips, which promotes the coa-
lescence of cracks with voids.
The H-uptake during the HPF stage of the aluminized PHS also af-
fected the bending performance of the steel. Fig. 9 shows the bending
test results of the uncoated PHS and aluminized PHS specimens after
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Materials Science & Engineering A 734 (2018) 416–426
each processing step. The specimens were bent to a bending angle of
90° or 140°. The 140° bending was used for specimens after the CA stage
and after the CA+Al stage. The specimens after the HPF stage and after
the BH treatment were bent to a smaller bending angle (90°) since they
were less ductile as compared to the samples with a ferrite+pearlite
microstructure after the CA stage or the CA+Al stage. The bending
angle at maximum bending load, θB, for the uncoated specimens after
the CA, CA+HPF, and CA+HPF+BH stages was 97°, 67°, and 73°,
respectively (Fig. 9(a)). The value of θB for the aluminized specimens
after the CA+Al, CA+Al+HPF, and CA+Al+HPF+BH stages was 97°,
28°, and 46°, respectively (Fig. 9(b)). The aluminized specimen after the
CA+Al stage exhibited a bending performance similar to that of the
uncoated specimen after the CA stage. However, the bending perfor-
mance of the uncoated and the aluminized specimens after the HPF
stage was clearly different. After the BH treatment, the θB for the alu-
minized specimen increased to 46°, but it was smaller as compared to
the uncoated specimen after the CA+HPF+BH stage (73°). These re-
sults mirror those obtained by the tensile tests in that the BH process
partially mitigated the effect of the H embrittlement.
The effect of the H was also visible in the appearance of the speci-
mens after the bending tests. Fig. 10 shows images of the specimens
after the bending test. The uncoated specimen after the CA+HPF stage
had a single surface crack in the bend area. The aluminized specimen
after the CA+Al+HPF stage fully ruptured in the early stages of
bending. The aluminized specimen after the CA+Al+HPF+BH stage
had multiple cracks in the bend area.
It could be argued that the reduction of the ductility is caused by the
lower ductility of the reacted surface layer that consists mostly of the
brittle Fe2Al5 intermetallic compound, rather than the uptake of dif-
fusible H during the austenitization stage of the HPF process. The em-
brittlement phenomena shown in the present study can be attributed
mainly to H, because the degree of the embrittlement was dependent on
the amount of the diffusible H in the specimen. In addition, the BH
treatment, i.e. low-temperature tempering treatment, partially removed
the diffusible H, and it suppressed the embrittlement of the steel.
Moreover, the degradation of the mechanical properties is shown to be
transient phenomena (Supplementary materials).
L. Cho et al. Materials Science & Engineering A 734 (2018) 416–426

Table 3 water generates large amounts of H [20]. Al an Al-alloys have been

Possible reduction reaction of a water vapor molecule (H2O) in the furnace
atmosphere during heating and austenitizing in the HPF process.
Possible H2O reduction reactions T (°C) ΔG (kJ)
2 Al (l) + 3H2O (g) → Al2O3 (s) + 3H2 (g) 900 − 755.070
Fe (s) + H2O (g) → FeO (s) + H2 (g) 900 − 5.684
2 Fe (s) + 3H2O (g) → Fe2O3 (s) + 3H2 (g) 900 − 8.068
3 Fe (s) + 4H2O (g) → Fe3O4 (s) + 4H2 (g) 900 − 6.905
3.4. Mechanism of H-uptake
In the present study, the industrial process that is responsible for the
H-uptake of the PHS was determined by means of the H-TDA. The
diffusible H was not introduced into the steel in the CA stage via the
atmosphere which has a relatively high H2 content, i.e. 15 vol% (Fig. 4).
The specimen after the (CA+Al) stage did not contain diffusible H. The
H-uptake of the PHS took place during the austenitization stage of the
HPF process (Figs. 4 and 5). The furnace atmosphere during the HPF
process did not contain gaseous H2. However, water vapor in the fur-
nace gas reacted with the steel surface to form Fe oxides and H2 gas
during the heating to the austenitizing temperature [5]. This high
temperature atmospheric corrosion by water vapor results in the H
absorption. The water vapor in the furnace is formed by the combustion
of natural gas (mainly CH4) used to heat the furnace.
The aluminized PHS was more sensitive to H-uptake than the un-
coated PHS (Figs. 4 and 5). It is known that the reaction between Al and
used as H-generation materials [20]. The reaction of pure Al metal with
water at elevated temperatures is known to result in the formation of H-
filled blisters [21]. The thermodynamic driving force for the reduction
of water vapor by Al is much higher than the water vapor reduction by
Fe. The thermodynamic analysis shown in Table 3 illustrates the fact
that the water reduction reaction by Al, i.e. 2Al (s) + 3H2O (g) → Al2O3
(s) + 6 H (g), has the lower free energy as compared to the reaction
between Fe and water, e.g. Fe (s) + H2O (g) → FeO (s) + H2 (g). During
the austenitization stage, the Al of the alloy coating will therefore
promote the generation and absorption of H.
In addition to the accelerated H formation, the presence of the Al-Si
coating influences the permeability of H through the surface of the
alloy. Fig. 11(a) and (b) compare the temperature-dependent solubility
and diffusivity of H in pure Fe and pure Al [22–26]. The solubility data
revels that, at elevated temperature, H is significantly more soluble in
solid austenite (γ-Fe) as compared to the liquid Al. In the austenitiza-
tion stage of the HPF process, the H that is absorbed in the Al coating
will, therefore, be partitioned preferentially to the austenite. The
transfer of the H through liquid Al is very efficient because H diffuses
very rapidly in liquid Al. At temperatures lower than 600 °C, both the H
solubility and the H diffusivity are extremely low in solid Al as com-
pared to ferrite, α-Fe. This implies that the Al coating layer acts as a
strong diffusion barrier for H, keeping the H effectively in the Fe matrix
at room temperature.
It is important to note that during the austenitization stage of the
HPF process, the liquid Al phase rapidly reacts with Fe in the matrix to

Fig. 11. Temperature-dependence of (a) the solubility and (b) the diffusivity of H in Fe and Al (PH2 = 1 atm). Literature data of the H solubility in Fe and Al provided
by San-Martin and Manchester [22] and Qui et al. [23], respectively. The H diffusion coefficients in Fe and Al were calculated by the equations provided by Fast [24],
Kikuch and McLellan [25], and Jakse and Pasturel [26]. (c) Room temperature diffusivity of H in Fe-Al alloys as a function of Al content of the alloys [25,26,29–35].

424
L. Cho et al.
form Fe-Al or Fe-Al-Si intermetallics. In fact, Fe-Al intermetallics such
as Fe3Al and FeAl are also susceptible to the moisture-induced H up-
take, which can be explained by the same water reduction reaction
mechanism suggested for pure Al [27,28]. Therefore, the Fe-Al inter-
metallics in the reacted coating should also have contributed to the H
absorption of the Al-Si coated PHS during the austenitization stage.
However, temperature-dependence of the H behavior in Fe-Al or Fe-Al-
Si intermetallics is not known and thus, further investigation will be
needed to fully understand the role of the intermetallics in the H ab-
sorption and desorption of Al-Si coated PHS. Fig. 11(c) shows the lit-
erature data of the H diffusivity in Fe-Al alloys at room temperature,
indicating that the H diffusion is generally slower in Fe-Al alloys than in
pure Fe or lath martensitic steel [25,26,29–35]. This suggests that the
reacted coating layer of the Al-Si coated PHS, consisting mainly of the
Fe-Al intermetallics, likely lowers the permeability of H through the
surface of the alloy, preventing H from diffusing out of the martensite.
Fig. 12 illustrates the mechanism for the H-uptake in aluminized
PHS. After the aluminizing process, the PHS surface consists of Al-10%
Si alloy coating layer and an inhibition layer at the coating/steel in-
terface. The inhibition layer is formed during the hot dip aluminizing
process. Water vapor in the furnace is formed during the combustion of
the natural gas used to heat the furnace. During the heating to the
austenitizing temperature, the water vapor in the furnace reacts with
the Al of the Al-Si coating to form Al2O3 and H2. The H produced from
the reduction of H2O by the Al adsorbed into the coating layer. A me-
chanism for the transport of H through the Al oxide film has been
proposed by Draley and Ruther [36]. In this model, the H protons (H+)
diffuse through the oxide film to the metal. Their diffusion is balanced
by the diffusion of Al cations (Al3+) to the gas-oxide interface. The
protons are reduced to H atoms at the oxide-metal interface and H-
atoms diffuse into the metal. During the austenitization of the PHS at
900 °C for 5–10 min, the Al-10%Si alloy coating reacts with the steel
substrate. This results in the formation of Fe2Al5 and Fe-Al-Si inter-
metallic phases. After the austenitization, the PHS specimens are
transferred into water-cooled dies for HPF process. During cooling to
room temperature, most of the H is transferred into the steel matrix,
Fig. 12. Mechanism of the H-uptake of the aluminized PHS.
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Materials Science & Engineering A 734 (2018) 416–426
which has transformed to martensite. The H atoms are tapped in the
martensite, which has the high density of dislocation (1015–1016 m−2).
The H is prevented from diffusing out of the martensite by the reacted
coating layer that acts as a H-diffusion barrier.
4. Conclusions
The main conclusions of the present contribution are as follows:
1. Diffusible H is introduced in both uncoated PHS and aluminized PHS
during the HPF process. The H-uptake is due to the high temperature
atmospheric corrosion of the steel or the Al-Si coating in the aus-
tenitization stage of the HPF process.
2. The H-atoms introduced in the uncoated PHS naturally escape from
the steel at room temperature. Uncoated PHS aged at room tem-
perature exhibits a ductile tensile and bending performance.
3. The H-uptake is larger in aluminized PHS than in uncoated PHS.
Much larger amounts of diffusible H are absorbed in aluminized PHS
as compared to uncoated PHS. The Al-Si coating of PHS promotes
the generation of H. The water vapor in the furnace atmosphere
reacts with the Al in the alloy coating, generating H. The high H
solubility in austenite and the high H diffusivity in Al result in an
efficient partitioning of H to the PHS matrix during austenitization.
H is inhibited from diffusing out of the steel matrix by the reacted
Al-Si coating, which acts as a H-diffusion barrier.
4. Aluminized PHS is more sensitive to H embrittlement than uncoated
PHS. The H embrittlement of aluminized PHS is caused by diffusible
H-atoms weakly bound to dislocation or grain boundary. This em-
brittlement is characterized by a pronounced reduction of both the
tensile elongation and the bending angle at maximum load in three
point bending. The presence of diffusible H also causes inter-gran-
ular cracking and a refinement of the dimple size at the fracture
surface.
5. The BH treatment partially releases the H present in aluminized
PHS, and it suppresses the brittle fracture of aluminized PHS.
L. Cho et al.
Acknowledgment
The authors sincerely acknowledge the support of the POSCO
Technical Research Laboratories, Gwangyang.
Appendix A. Supplementary material
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.msea.2018.08.003
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