Materials Science & Engineering A 735 (2018) 448–455

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Materials Science & Engineering A

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

Influence of vanadium on the hydrogen embrittlement of aluminized ultra- T

high strength press hardening steel
⁎
Lawrence Choa, ,1, Eun Jung Seoa,2, Dimas H. Sulistiyoa, 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: Improved safety standards and reduced automotive body-in-white weight have led to a strong interest in mar-
Hydrogen embrittlement tensitic press hardening steel (PHS). As the sensitivity to hydrogen embrittlement of martensite increases at
Press hardening steel higher strength level, the very small uptake of diffusible hydrogen by aluminized PHS during the austenitization
Aluminizing stage of the hot press forming process is of concern. The hydrogen uptake was found to reduce the plasticity of
Vanadium
the PHS considerably. The PHS with a higher strength was more susceptible to hydrogen-induced brittle fracture.
The present work reports that vanadium additions, which serve to trap the hydrogen, considerably reduce the
negative impact of the hydrogen uptake in aluminized 1800 MPa and 2000 MPa PHSs. The contribution also
proposes a mechanism for the uptake of hydrogen during the processing of aluminized PHS.

1. Introduction the PHSs is associated with high temperature atmospheric corrosion by

Improved safety standards and reduced automotive body-in-white
weight have led to a strong interest in advanced high strength/ultra-
high strength steels. The use of ultra-high strength press hardening steel
(PHS) in structural safety-related parts has experienced a rapid growth
in the automotive industry [1,2]. The requirement of an ultra-high
strength has, however, led to concerns about the hydrogen embrittle-
ment as martensitic steel is increasingly sensitive to hydrogen-induced
cracking at high strength levels. It is now well known that the diffusible
hydrogen which diffuses out of the steel at room temperature, is re-
sponsible for the observation of a transient hydrogen-induced embrit-
tlement [3].
In the direct hot press forming (HPF) process, the press-hardened
components are produced by heating cold-rolled or coated steel blanks
to an austenitizing temperature in a furnace and subsequently
quenching them between water-cooled quenching dies (Fig. 1(a)). Al-
10%Si alloy coating is the coating system that is most commonly used
for PHSs.
It has been reported that PHSs absorb diffusible hydrogen during
the austenitization in the HPF process [4–6]. The hydrogen uptake of
water vapor [4–6]. Al-Si alloy coated (aluminized) PHS is more sensi-
tive to the hydrogen uptake and resultant hydrogen-induced cracking
than the uncoated PHS. Fig. 1(b) shows that 0.50 mass ppm of the
diffusible hydrogen was detected in an aluminized PHS after the in-
dustrial HPF process. A hydrogen desorption peak at 170 °C was clearly
observed in the thermal desorption analysis (TDA) curve for the alu-
minized PHS. In contrast, there is no hydrogen-uptake in the uncoated
PHS. The ductility of the aluminized PHS was clearly reduced due to the
hydrogen embrittlement (Fig. 1(c)). The hydrogen-induced cracking
noted for the PHSs exhibits characteristics very similar to the “con-
ventional” embrittlement phenomena in that the presence of hydrogen
in the PHS causes a transition from ductile microvoid coalescence to
brittle intergranular fracture, accompanied by a premature failure and
that the resulting loss of ductility is of a time-dependent, transient
nature [6].
Recent investigations have shown that the bake hardening heat
treatment reduces the diffusible hydrogen content of aluminized PHSs
[4–6]. There is however still a potential risk for the hydrogen-induced
cracking if a forming process is applied to the aluminized PHS during
vehicle assembly prior to the paint coating. Georges et al. [4] reported

⁎
Corresponding author.
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.2018.08.027
Received 24 May 2018; Received in revised form 9 August 2018; Accepted 9 August 2018
Available online 10 August 2018
0921-5093/ Published by Elsevier B.V.
L. Cho et al.
Hot press forming process
Uncoated or Furnace
Al-10%Si coated steel
TA=850-950 ºC
Ferrite + Pearlite Austenite
0.015
Uncoated PHS
Hydrogen Desorption Rate
Aluminized PHS
0.010
(ppm·min-1)
0.005
0.000
0 50 100 150 200 250
Temperature ( C)
(b)
that the control of the dew point of the gas atmosphere of the annealing
furnace, i.e. a reduction of the water vapor content in the furnace at-
mosphere was key to suppress the hydrogen uptake of the aluminized
PHS.
Micro-alloying with vanadium (V), which results in the precipita-
tion of hydrogen-trapping V carbides (VCs) or nitrides [7–10], can be
used as a method to mitigate the hydrogen embrittlement of aluminized
PHS. The present work was initiated to evaluate the effect of V addi-
tions to the PHS composition, as it does not require the control of the
gas atmosphere in the industrial austenitizing furnace. This was con-
sidered to be a more cost-effective approach to improving the hy-
drogen-embrittlement resistance of aluminized 1800 MPa and
2000 MPa PHS grades. The contribution also proposes a mechanism for
the uptake of hydrogen during the processing of aluminized PHS.
2. Experimental
Four PHSs were used for the present work. A 30MnB5 PHS grade
(1800 MPa) and a 35MnB5 PHS grade (2000 MPa) were chosen as re-
ference V-free PHSs. 0.2 wt% of V was added to the composition of each
reference PHS to evaluate the effect of V additions on the resistance of
the PHS to hydrogen embrittlement. Hereafter, the V-added PHSs are
called as a 0.2V-added 30MnB5 PHS and a 0.2V-added 35MnB5 PHS. In
all cases, 10–20 ppm B was added to the steel composition to enhance
their hardenability. The formation of BN was avoided by additions of
0.03 wt% Ti, which stabilize N as TiN [1].
Industrially cold-rolled, full hard PHSs were continuously annealed
in N2 + 5 vol% H2 gas atmosphere and hot dip aluminized at 680 °C in
an Al-10%Si bath. The thickness of the Al-Si coating was approximately
30 µm. The following procedure was used for the HPF simulation of the
aluminized PHSs. ASTM E8 standard size tensile specimens with a
gauge length of 50 mm were prepared. The initial ferrite-pearlite mi-
crostructure of the continuously annealed PHS specimen was first
austenitized by heating to an austenitizing temperature of 900 °C and
isothermal holding for 5 min in an electrically-heated furnace. No at-
tempt was made to control the furnace atmosphere, i.e. the furnace
atmosphere contained water vapor. The furnace atmosphere had a dew
point of approximately 5 °C at room temperature. After the
Materials Science & Engineering A 735 (2018) 448–455
Fig. 1. (a) Schematic of the HPF pro-
cess. (b) Hydrogen TDA curves of the
Water-cooled Uncoated or aluminized PHS uncoated and the aluminized 35MnB5
quenching dies PHSs in the press-hardened (as-deliv-
ered) condition, showing that the un-
coated PHS did not show a character-
istic H desorption rate peak in the
20–300 °C temperature range, while
the aluminized PHS exhibited a large
Lath martensite H-uptake. The TDA heating rate was
(a) 100 °C/hour. (c) Room temperature
tensile properties of the uncoated and
2500 the aluminized 35MnB5 PHSs, in-
Uncoated PHS dicative of a loss of the ductility of the
Engineering Stress (MPa)
Aluminized PHS aluminized PHS due to hydrogen em-
2000
brittlement.
1500
1000
500
0
300 0 2 4 6 8 10
Engineering Strain (%)
(c)
austenitizing treatment, the specimens were transferred to a laboratory
hydraulic HPF simulator where the specimens were quenched between
two flat water-cooled dies to room temperature. During the die-
quenching, the austenite was transformed to lath martensite. The me-
chanical properties of the specimens were measured in a Zwick/Roell
Z100 universal tensile testing machine.
The PHS microstructure was observed by means of field emission-
scanning electron microscopy (SEM), electron backscattering diffrac-
tion (EBSD), and field emission-transmission electron microscopy
(TEM). The SEM and EBSD analyses were done in an FEI Quanta 3D
FEG. The specimens used for the EBSD analysis were prepared by
electro-chemical polishing in a solution of 5% perchloric acid and 95%
acetic acid. Prior to the SEM observation, the electro-chemically po-
lished specimens were etched by using saturated aqueous picric acid at
85 °C to reveal the prior austenite grain boundaries. Thin TEM foils
were prepared at room temperature by twin-jet electro-polishing a
3 mm disc in a solution of 5% perchloric acid and 95% acetic acid. TEM
specimens were analyzed in a JEOL JEM-2100F field emission-TEM
operating at 200 keV. The precipitates formed in the steels were ana-
lyzed by means of energy-dispersive spectroscopy (EDS) using a nan-
ometer-sized electron beam. The precipitates formed in the steel matrix
were also extracted by an electrochemical method using a methanol
solution containing 10% acetylacetone and 1% tetramethyl ammonium
chloride. The precipitates-containing residue was filtered with a mesh
size of 0.2 µm ϕ. Quantitative analysis of the precipitates was carried
out by inductively coupled plasma atomic emission spectroscopy (ICP-
AES) analysis.
In previous investigations, several hydrogen charging methods have
been used, including electrolytic charging [8] and gaseous charging
[11]. It should be noted that the conventional hydrogen charging
methods were not used in the present case because the purpose of this
study was to simulate the hydrogen uptake of a PHS, which takes place
during the HPF process. In the present study, hydrogen was naturally
absorbed in the aluminized steel specimens during the austenitizing
heat treatment as a result of high temperature atmospheric corrosion of
the Al-Si coating due to the water vapor in the furnace atmosphere.
Further details about the hydrogen charging method can be found in a
recent study by the present authors [6]. Hydrogen analysis of the
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L. Cho et al. Materials Science & Engineering A 735 (2018) 448–455

hydrogen-charged specimens was carried out by means of TDA with a
carrier gas consisting of He and N2 using an Agilent 7890 A gas chro-
matograph. The dimensions of the aluminized PHS specimen for the
TDA were 10 mm x 100 mm x 1.0 mm. The hydrogen desorption rate of
the specimens was measured during heating to 300 °C using a heating
rate of 100 °C/hour.
PHSs is shown in Fig. 3. The SEM and EBSD results indicate that the
prior austenite grain size, packet size, and block size of the lath mar-
tensite were reduced with the V additions. VC is known to inhibit the
growth of the prior austenite grain [14]. This results in the refinement
of the martensite substructure.
3.2. Hydrogen thermal desorption analysis

3. Results and discussion Fig. 4 shows the hydrogen TDA curves of the aluminized V-free
35MnB5 PHS and aluminized 0.2V-added 35MnB5 PHS, both austeni-
3.1. Microstructure tized at 900 °C, die-quenched, and aged at room temperature. A hy-
drogen desorption peak was clearly observed at about 140 °C in the
The hot dip Al-Si alloy coating is affected by the austenitization and TDA curves for both PHSs immediately after quenching. The value of
the die-quenching. The evolution of the microstructural features of the the activation energy obtained from this desorption peak was de-
Al-Si alloy coating at high temperature has been reported earlier [12]. termined to be 22.1 kJ/mol in the previous study [6]. Table 2 lists the
During the heating to the austenitizing temperature, the Al-Si coating literature data for the hydrogen trapping energies associated with dif-
close to the surface is liquefied while the Al-Si coating on the side of the ferent trap sites in ferritic steels and martensitic steels [8,15–23]. The
steel/coating interface reacts with Fe to form a phase mixture consisting activation energy values of hydrogen-desorption for grain boundaries,
of Fe-Al-Si intermetallic phases and the Fe2Al5 phase. During the aus- dislocations, and micro-voids in steels are reported to be 17.2, 26.8 and
tenitizing, which lasts 5–10 min, the liquid Al-Si phase is fully replaced 35.2 kJ/mol, respectively [15]. Based on these values, the desorption
by a solid reaction layer due to the growth of the Fe-Al-Si intermetallic peak observed at 140 °C is associated with the hydrogen-trapping at
phases and the Fe2Al5 phase. either grain boundaries or dislocations. The intensity of the hydrogen
The precipitation behavior of Ti and V during the processing of the peak decreased and the temperature for the peak maximum shifted to
V-added PHSs was investigated by quantitative analysis using the higher temperature with aging at room temperature. These observa-
electrochemical extraction of the precipitates (Table 1). In both the V- tions indicate that hydrogen was trapped at reversible traps and that it
added PHSs (0.2V-added 30MnB5 and 0.2V-added 35MnB5 PHSs), TiN out-diffused during aging at room temperature. The hydrogen weakly
and TiC precipitates were formed during the hot rolling process. These trapped at martensitic matrix should, in principle, naturally escape
precipitates do not dissolve in the subsequent heat treatment processes. from the specimen in several days [8], but the observed desorption peak
Some of the V precipitated during hot rolling, but most of the V was did not completely disappear even after the room temperature aging for
found to remain in solid solution. It is reasonable to assume that the V 4 weeks (Fig. 4(a)). The slow kinetics of the hydrogen desorption during
containing precipitate was VC, since the N was stabilized by TiN for- the room temperature aging are clearly due to the alloy coating layer
mation. The density of the VC increased during the continuous an- that acts as a hydrogen diffusion barrier, as was discussed in the pre-
nealing. During heating of the continuously annealed PHS, cementite in vious study [6]. It should be noted that the Al-Si coating also influences
the pearlite regions first dissolved and the VC precipitated at this re- the hydrogen thermal desorption behavior. It was shown that the hy-
gion. The VC was also partially redissolved during the austenitization in drogen desorption peak obtained for an aluminized PHS specimen was
the HPF process due to its higher solubility in austenite [13]. 20–30% of observed at slightly higher temperature as compared to the corre-
the added V was precipitated as VC while most of the added Ti was sponding peaks of an uncoated PHS specimen [6]. The possible me-
precipitated in the PHSs in the press-hardened state (Table 1). Fig. 2(a) chanism of hydrogen absorption in the aluminized PHS during the HPF
shows scanning TEM (STEM) micrographs of Ti(C,N) and VC pre- process will be discussed in the Section 3.3.
cipitates formed in the as-cold rolled microstructure of the 0.2V-added For all conditions, the intensity of the hydrogen desorption peak in
35MnB5 PHS. Fig. 2(b) to (d) show the precipitates formed in the lath the TDA curve of the aluminized 0.2V-added PHS was higher as com-
martensitic microstructure of the 0.2V-added 35MnB5 PHS in the as- pared to that of the aluminized V-free PHS (Fig. 4), indicating that the V
quenched condition. In particular, fine VC precipitates were uniformly addition resulted in the absorption of more hydrogen. The activation
distributed in the lath martensitic matrix (Fig. 2(c)). Their diameter was energy values of hydrogen-desorption for VC in steels are reported to be
approximately 30 nm. A coarse Ti(C,N) precipitate of about 100 nm in 29–35 kJ/mol, slightly higher than that for grain boundaries (17.2 kJ/
diameter was also present in the lath martensitic matrix (Fig. 2(d)). mol) or the strain field of dislocations (26.8 kJ/mol), as indicated in
The effect of V additions on the microstructure of the aluminized Table 2. For a TDA heating rating of 100 °C/hour, the temperature for
the peak maximum associated with VC is reported to range from 110° to
Table 1 220°C, which is slightly higher compared to those related to grain
Results of quantitative analysis of the Ti and V precipitation (in wt%) in the V- boundaries or dislocations (approximately 100 °C) (Table 2). Wei et al.
added PHSs after cold rolling (CR), continuous annealing (CA), and hot press [24] showed that a desorption peak associated with VC does not appear
forming (HPF). above 250 °C. Therefore, the observed increase in the intensity of the
Alloy Precipitate Thermo-Mechanical Treatment hydrogen desorption peak (Fig. 4(b)) is associated with the hydrogen
trapping at VC precipitates. In addition, the refinement of martensite
After CR After After CR+CA+HPF
substructure, which creates more boundaries of prior austenite grain,
CR+CA
packet, and block, could have contributed to the increased amount of
0.2V-added Precipitated Ti 0.027 0.030 0.030 the hydrogen trapping sites.
30MnB5 (wt%)
PHS Precipitated V 0.091 0.13 0.052 3.3. Influence of V on hydrogen absorption and embrittlement
(wt%)
0.2V-added Precipitated Ti 0.029 0.029 0.031
35MnB5 (wt%) The V addition clearly suppressed the hydrogen embrittlement
PHS Precipitated V 0.089 0.13 0.055 during the tensile straining of the aluminized PHS at room temperature.
(wt%) The aluminized V-free 30MnB5 PHS fractured at an engineering strain
of 4.1% (Fig. 5(a)). The aluminized V-free 35MnB5 PHS fractured
earlier during tensile straining, i.e. at an engineering strain of 2.3%, as
expected due to its higher strength. This clearly illustrates that PHSs

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Fig. 2. (a) STEM micrographs of the ferrite and pearlite

microstructure of the 0.2V-added 35MnB5 PHS in the as-
cold rolled state. Ti(C, N) and VC precipitates present in a
ferrite grain are shown in (a). (b) STEM micrographs of the
fully martensitic microstructure after the HPF of the 0.2V-
added 35MnB5 PHS. (c) STEM micrograph and re-
presentative EDS spectrum of nanometer-size VC particles
in the lath martensite. (d) STEM micrograph and EDS
spectrum of a coarse Ti(C, N) precipitate in the lath mar-
tensite.

V-free 30MnB5 V-free 35MnB5 0.2V-added 30MnB5 0.2V-added 35MnB5

2 µm 2µm 2µ m 2 µm

TD 111
RD
001 101

5µm 5µ m 5 µm 5µ m

(a) (b) (c) (d)

Fig. 3. SEM micrographs (top row) and EBSD inverse pole figure maps (bottom row) of the fully martensitic microstructures after the HPF of the aluminized PHS. (a)
V-free 30MnB5 PHS, (b) V-free 35MnB5 PHS, (c) 0.2V-added 30MnB5 PHS, and (d) 0.2V-added 35MnB5 PHS. The martensitic microstructure is clearly refined in the
V-added PHSs.

with a higher strength are more susceptible to hydrogen embrittlement.
The 0.2V-added PHSs exhibited the normal ductile fracture behavior
with a significant improvement of the ductility. The total elongations of
the 0.2V-added PHSs were approximately 5.5% (Fig. 5(a)). An addi-
tional advantage of the V addition is the precipitate strengthening ef-
fect. The 0.2V-added PHSs were more resistant to hydrogen
embrittlement than the V-free PHSs despite the fact that their strength
was increased by up to 40 MPa (Fig. 5) as a result of the VC pre-
cipitation hardening (Fig. 2(c)) and the grain refinement (Fig. 3). In the
case of the aluminized V-free 30MnB5 PHS, the hydrogen embrittle-
ment was clearly a time-dependent temporary degradation because the
mechanical properties were recovered as the diffusible hydrogen

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Fig. 4. Changes in the hydrogen TDA curves with aging at room temperature of (a) the aluminized V-free 35MnB5 PHS and (b) the aluminized 0.2V-added 35MnB5
PHS austenitized for 5 min at 900 °C followed by water-cooled die-quenching. The TDA heating rate was 100 °C/hour.

Table 2
Literature data overview for the hydrogen trapping activation energies associated with different trapping sites in ferritic and martensitic steels.

Type of trap Peak temperature, °C (heating rate, °C/hour) Activation energy, kJ/mol Microstructure Reference

Reversible H traps
Grain boundary 105-162 (184-491) 17.2 Pure iron [15]
Grain boundary and dislocation strain field ~100 (100) 21.9 Ti-added ferritic steel [16]
Dislocation strain field 198-311 (83-506) 26.8 Pure iron [15]
Dislocation strain field ~100 (100) 27 Martensitic steel [17]
Microvoids 267-379 (83-488) 35.2 Pure iron [15]
VC (coherent) ~220 (100) 30 V-added martensitic steel [18]
VC (coherent) 110-150 (100) 33-35 V-added tempered martensitic steel [8]
VC (coherent) 190-210 (100) 29.2 V-added martensitic steel [19]
VC (coherent) 219 (100) - V-added high carbon martensitic steel [20]
TiC (semi-coherent) 220 - Ti-added ferritic steel [21]
Irreversible H traps
Dislocation core ~300 (100) 45 Martensitic steel [17]
Ferrite/Fe3C interface ~370 (200) 65.0 Medium carbon ferritic steel [22]
TiC (incoherent) 718-787 (150-360) 86.9 Ti-added ferritic steel [23]

partially out-diffused from the steel during the room temperature aging
(Fig. 5(b)). The plasticity of the aluminized V-free 30MnB5 PHS clearly
improved after the aging treatment, i.e. the aluminized V-free 30MnB5
PHS exhibited a normal tensile behavior. On the other hand, the alu-
minized V-free 35MnB5 PHS aged for one week still ruptured in the
early stages of tensile straining, confirming an increase of the suscept-
ibility to hydrogen embrittlement with increasing strength in PHSs.
The V addition also had a significant influence on the failure me-
chanism of the PHSs, as shown in Figs. 6 and 7. A distinct flat fracture
region was shown at the central region of the fracture surface of the
aluminized V-free 30MnB5 PHS in the as-quenched state (Fig. 6(a)).
The central flat fracture region displayed mainly quasi-cleavage frac-
ture, a mixed mechanism of ductile fracture and brittle cleavage frac-
ture (Fig. 6(b)). Intergranular cracks were also observed in the flat
fracture region. The region outside of the flat fracture exhibited entirely
ductile microvoid coalescence, or dimpled, fracture surface appearance
(Fig. 6(c)). The aluminized V-free 35MnB5 PHS specimen had a larger
area fraction of the flat fracture, consisting of quasi-cleavage feature
and intergranular cracks, compared to the aluminized V-free 30MnB5
PHS (Fig. 6(a) and (d)), which is also associated with the influence of
the material's strength. The observation of quasi-cleavage feature and
intergranular cracks clearly indicates that the sudden fracture without
any post uniform elongation observed for the aluminized V-free PHSs
(Fig. 5(a)) was due to the hydrogen-induced brittle fracture. In contrast,
the fractures of the aluminized 0.2V-added PHSs were ductile, as can be
inferred from the dimpled fracture surface appearances shown in Fig. 7.
No evidence of quasi-cleavage feature or intergranular cracks was ob-
served for the aluminized 0.2V-added PHSs.
A mechanism for the hydrogen uptake in the aluminized V-free PHS
and the aluminized V-added PHS is described in Fig. 8. During the HPF
process of aluminized V-free PHS (Fig. 8(a)), hydrogen is formed by the
reduction of the water vapor in the furnace atmosphere by the Al of the
alloy coating layer according to the following reaction: 2Al + 6H2O →
2Al(OH)3 + 3H2 or 2Al + 3H2O → Al2O3 + 3H2 [25]. It is known that
this reaction results in the formation of hydrogen-filled blisters in pure
Al metal at elevated temperatures [26]. The increased hydrogen uptake
in the aluminized PHS is due, in part, to the fact that the thermo-
dynamic driving force for the reduction of water vapor by Al is much
higher than the water vapor reduction by Fe (Table 3). This may result
in the faster generation of hydrogen on aluminized PHS as compared to
uncoated PHS. At elevated temperatures, hydrogen diffuses much faster
in liquid Al as compared to γ-Fe [27,28], while both the solubility and
the diffusivity of hydrogen in solid Al are extremely low at room tem-
perature [27,29]. This suggests that hydrogen can be rapidly absorbed
in the liquid coating and transferred to the γ-Fe matrix during the
austenitization. The hydrogen is then prevented from diffusion out of
the martensite after the die-quenching to room temperature by the re-
acted coating layer.
Comparatively, aluminized V-added PHS has a larger density of
hydrogen traps and retains slightly more hydrogen (Fig. 8(b)). A pre-
vious study showed that when V is added in martensitic steels, the in-
tensity of a hydrogen desorption peak in the temperature range of
70–150 °C is increased due to the hydrogen trapping at VC precipitates
[8]. The refinement of martensite substructure also increases the
amount of the hydrogen reversibly trapped to grain, packet and block
boundaries.
The V micro-alloying addition considerably improved the hydrogen-
embrittlement resistance of the aluminized PHSs despite the fact that it

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L. Cho et al. Materials Science & Engineering A 735 (2018) 448–455

As-quenched trapped in the dislocation strain field or the grain boundaries. In the
2000 0.2V-added 30MnB5 meanwhile, there have been questions on the remarkable hydrogen
Engineering Stress (MPa)

0.2V-added 35MnB5 trapping capacity of VC despite the exceptionally low trapping energy
1600 [30], which is only slightly higher compared to other weak traps such
V-free 30MnB5
1200 V-free 35MnB5 as dislocations or grain boundaries. In a recent study of Turk et al. [30],
the authors attributed this high hydrogen trapping capacity to the effect
800 of the dense dislocation structures surrounding VC particles. They based
400 their idea on the finding that the hydrogen trapping capacity of VC was
more pronounced in martensitic steels, which contain a high density of
0 dislocations, than in low carbon ferritic steels. It should however be
0 1 2 3 4 5 6 7 1 2 3 4 5 6 7
Engineering Strain (%) pointed out that no physical evidence of the synergistic effect of VCs
(a) and dislocations has been provided.
After 1 week Another important metallurgical effect of the V micro-alloying ad-
dition is the refinement of martensite substructure. This refinement
2000 0.2V-added 30MnB5
Engineering Stress (MPa)

creates many more block and packet boundaries, leading to the de-
0.2V-added 35MnB5
1600 V-free 30MnB5
pletion of the hydrogen content per unit boundary area [7,31]. As a
V-free 35MnB5 result, V micro-alloying effectively increases the critical diffusible hy-
1200 drogen concentration below which the hydrogen embrittlement does
800 not occur. These results are in agreement with a previous report by
Krutikova et al. [10] that V additions resulted in improvement of the
400 hydrogen resistance of high strength quenched and tempered bolt
0
steels. Krutikova et al. also attributed the improved hydrogen resistance
0 1 2 3 4 5 6 7 1 2 3 4 5 6 7 of the material to both the hydrogen trapping effect of V carbonitride
Engineering Strain (%) precipitates and the grain refinement achieved by the micro-alloying
(b) with V. It has similarly been reported that Nb additions effectively
Fig. 5. Influence of the V addition on the hydrogen embrittlement of the alu-
suppress the hydrogen-induced delayed fracture of a press hardened
minized PHSs. (a) Room temperature tensile properties of the aluminized V-free 22MnB5 steel because of the benefits associated with the micro-alloying
PHSs and the aluminized 0.2V-added PHSs in the as-quenched state, i.e. im- precipitates and the resultant grain refinement [7,32].
mediately after the HPF process. (b) Room temperature tensile properties of the
aluminized V-free PHSs and the aluminized 0.2V-added PHSs after aging at
4. Conclusions
room temperature for one week.

Diffusible hydrogen is introduced in aluminized PHS during the

also resulted in a slightly increased hydrogen uptake. This observation
suggests that the susceptibility to hydrogen embrittlement depends on
the distribution of the solute hydrogen in the microstructure rather than
the overall concentration of hydrogen. The key role of VC on the hy-
drogen-embrittlement behavior of steel is the enhancement of the hy-
drogen trapping capacity. The hydrogen trapping capacity of VC is
higher as compared to the dislocation strain field or the grain bound-
aries [3]. De-trapping of hydrogen is also slower in V-added steel than
V-free steel [3,8]. The hydrogen trapped to VC is therefore considered
to be less harmful to its mechanical properties than the hydrogen
austenitization stage of the HPF process. This is due to the reduction of
water vapor in furnace atmosphere by Al. The hydrogen is trapped in
the lath martensite and inhibited from escaping from the martensite
matrix by the presence of the reacted alloy coating layer at the surface.
This causes an early hydrogen-induced fracture of the aluminized PHS
at room temperature. PHS with a higher strength is more susceptible to
hydrogen-induce brittle fracture. While the V additions result in the
absorption of slightly more hydrogen due to an increased density of
hydrogen trapping sites and interface boundaries in the finer lath
martensite substructures, it considerably reduces the negative impact of

V-free 30MnB5 V-free 35MnB5

Microvoid coalescence fracture Microvoid coalescence fracture

Quasi-cleavage fracture

0.5mm Quasi-cleavage fracture 0.5mm

(a) (d)

5µm 5µ m 5 µm 5 µm

(b) (c) (e) (f)

Fig. 6. Fracture surfaces of the tensile specimens of the aluminized V-free PHSs in the as-quenched state. (a) Overview SEM micrograph of the fracture surface of
aluminized V-free 30MnB5 PHS. (b) Enlargement of the quasi-cleavage and intergranular fracture zone surrounded by the dashed line in (a). (c) Enlargement of the
microvoid coalescence fracture zone in (a). (d) Overview SEM micrograph of the fracture surface of aluminized V-free 35MnB5 PHS. (e) Enlargement of the quasi-
cleavage and intergranular fracture zone surrounded by the dashed line in (d). (f) Enlargement of the microvoid coalescence fracture zone in (d).

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L. Cho et al. Materials Science & Engineering A 735 (2018) 448–455

0.2V-added 30MnB5 0.2V-added 35MnB5

Microvoid coalescence Microvoid coalescence

fracture fracture
0.5mm 0.5mm

(a) (c)

2 µm 2 µm

(b) (d)
Fig. 7. Fracture surface of the tensile specimens of the aluminized 0.2V-added PHSs in the as-quenched state. (a) Overview SEM micrograph of the fracture surface of
the aluminized 0.2V-added 30MnB5 PHS. (b) Enlargement of the half thickness region of the fractured specimen of the aluminized 0.2V-added 30MnB5 PHS. (c)
Overview SEM micrograph of the fracture surface of the aluminized 0.2V-added 35MnB5 PHS. (d) Enlargement of the half thickness region of the fractured specimen
of the aluminized 0.2V-added 35MnB5 PHS.

Fig. 8. (a) Schematic illustrating the me-

chanism of hydrogen absorption in the alumi-
nized PHS during the HPF process. The hy-
drogen uptake is accelerated due to the Al
reduction of the water vapor in the furnace gas
atmosphere during the austenitization. The
diffusible hydrogen is prevented from escaping
from the martensitic matrix by the reacted
coating layer at room temperature. (b)
Schematic illustrating the influence of the V
addition on the hydrogen absorption in the
aluminized PHS. The VC precipitates inhibit
grain growth during austenitization and pro-
vide an effective trap site for hydrogen. This
leads to the absorption of slightly more hy-
drogen in the martensitic matrix.

Table 3 the hydrogen uptake on the mechanical properties of aluminized PHS.

Possible reduction reaction of a water vapor molecule (H2O) in the furnace
atmosphere during heating and austenitizing in the HPF process. FactSage Acknowledgement
(version 6.4) was used for the calculations [6].
Possible H2O reduction reactions T (°C) ΔG (kJ) The authors gratefully acknowledge the support of the POSCO
Technical Research Laboratories, Gwangyang, South Korea.
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
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3 Fe (s) + 4H2O (g) → Fe3O4 (s) + 4H2 (g) 900 − 6.905
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