Engineering Failure Analysis 119 (2021) 104969

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Engineering Failure Analysis

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

The potential significance of tempering treatment in alleviating

the hydrogen embrittlement susceptibility of a hot-rolled and
intercritically annealed medium-Mn steel
Xiaoli Zhao a, Yongjian Zhang a, Weijing Hui a, *, Chengwei Shao b, Cunyu Wang c,
Han Dong d
a
School of Mechanical, Electronic and Control Engineering, Beijing Jiaotong University, Beijing 100044, PR China
b
China Aero-Polytechnology Establishment, Beijing 100028, PR China
c
Central Iron and Steel Research Institute Group, Beijing 10008, PR China
d
School of Materials Science and Engineering, Shanghai University, Shanghai 200444, PR China

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

Keywords: The influence of tempering on the hydrogen embrittlement (HE) behavior of a hot-rolled and
Hydrogen embrittlement intercritically annealed medium-Mn steel (0.1C-5Mn) was investigated by slow strain rate tensile
Medium-Mn steel testing. It was observed that the absorbed diffusible hydrogen content remained almost un­
Tempering
changed with increasing tempering temperature. The susceptibility to HE evaluated by the
Mechanical properties
Microstructure
relative total elongation loss is most significant for the as-annealed specimen, while tempering
treatment can notably alleviate it. It is nearly immune to HE when the tempering temperature was
increased up to 500 ◦ C. The fraction of hydrogen-induced brittle fracture decreases with
increasing tempering temperature. The enhanced resistance to HE of the tested steel is primarily
ascribed to the microstructural evolution of retained austenite and cementite during the
tempering process. It is thus proposed that the HE susceptibility of medium-Mn steel could be
significantly reduced through suitable tempering treatment after intercritical annealing provided
no notable loss of its superior strength-ductility balance.

1. Introduction

The need of light weight, low cost and safety improvement of modern automobile has spurred increased interest in the development
of advanced high strength steels (AHSSs). In recent years, AHSS sheets with ultimate tensile strength (UTS) over 1000 MPa grade have
been increasingly used to manufacture many automobile body parts for the purpose of achieving further weight reduction and
improving the impact safety of vehicles [1–3]. However, there is an increasing danger that hydrogen-induced degradation of me­
chanical properties, often terms hydrogen embrittlement (HE), due to hydrogen absorbed during product production and/or lifecycle
might occur under service environments with increasing steel strength grade for structural steels [4–6]. The susceptibility to HE could
represent one of the main limitations to the application of higher strength AHHS sheets in the auto body-in-white and therefore,
increasing studies have been carried out both experimentaly and numerically on the HE behavior of AHSSs in recent years [5–16].
Although no consensus about the basic mechanisms responsible for HE is reached yet, two mechanisms, that is, hydrogen-enhanced

* Corresponding author.
E-mail address: [email protected] (W. Hui).

https://doi.org/10.1016/j.engfailanal.2020.104969
Received 25 February 2020; Received in revised form 23 September 2020; Accepted 27 September 2020
Available online 29 September 2020
1350-6307/© 2020 Elsevier Ltd. All rights reserved.
X. Zhao et al. Engineering Failure Analysis 119 (2021) 104969

Table 1
Chemical composition (wt%) and the Ae1 and Ae3 temperatures of the steel used.
C Mn P S N Ae1 Ae3

0.10 5.0 <0.005 0.002 0.005 610 ◦ C 740 ◦ C

Fig. 1. Schematic diagram of heat treatment schedule.

localized plasticity (HELP) [17,18] and hydrogen-enhanced decohesion (HEDE) [19], have been advanced as the more accepted and
cited ones for the case of hydrogen-related degradation in steel in literature [13]. The HELP mechanism proposes a hydrogen-promoted
dislocation mobility and planar slip around a crack tip and usually accounts for highly localized plastic-like deformation in fracture
surfaces and slip-band cracking [9,18]. However, there exists contradictory results and there is no direct connection between this
mechanism and actual embrittlement [15]. The HEDE mechanism postulates that interstitial hydrogen lowers the cohesive bond
strength between the metal atoms by dilatation of the atomic lattice and causes brittle cracking in the absence of significant local
deformation [9,20]. Practically, sometimes a synergistic action of these proposed mechanisms may be responsible for degradation and
embrittlement of steel rather a single one [20,21]. Recently, a novel and unified HELP + HEDE model concerning the synergistic action
of hydrogen-enhanced plasticity and decohesion in steels was proposed, and the dominance of one of the mechanism (HELP or HEDE)
depends on the hydrogen concentration and the material-stress state-environment factors [20,22,23].
Medium-Mn steel has recently been suggested as one promising candidate for the third generation AHSS for its excellent strength-
ductility balance [24–26]. The most widely studied microstructure of this type of steel consists of ultrafine grained ferrite and retained
austenite (RA), which is usually obtained by austenite reverted transformation (ART) annealing in the α + γ region [27,28]. RA is a key
factor in governing the excellent mechanical properties of medium-Mn steel, which generally originate from the transformation-
induced plasticity (TRIP) effect of RA providing persistent work-hardening and postponed localized deformation [24–26]. As the
UTS of medium-Mn steels reported in literature is normally ranges from ~900 MPa to 1500 MPa [24,25], it raises concerns of a
susceptibility to HE. Moreover, due to inevitable plastic deformation during the fabrication processes of automotive parts, a portion of
the high fraction metastable RA might transform to martensite [24,29,30]. Thus, considering that the transformed fresh untempered
martensite is most susceptible to HE as well as the higher strength level, it is regarded that medium-Mn steels might be more vulnerable
to the hydrogen compared with conventional TRIP steels and special attention should be given [24]. However, only a few works have
been focused on this problem till now [30–38]. These existing investigations clearly demonstrate that this type of steel exhibited a
relatively high susceptibility to HE. For example, a HE index (relative total elongation (TEL) loss, HEI) of 64.9% was obtained in a cold-
rolled 0.2C–4.9Mn–3.1Al–0.6Si (all in wt%) steel when it was intercritically annealed at the temperature obtaining maximum strength-
ductility balance [36]. Similar HEI of 74–87% was also found in a 0.1C–7Mn steel [31]. Therefore, it is really necessary to explore
methods of alleviating the susceptibility to HE of this type of steel.
Elevated temperatures might be experienced during the manufacturing and in service applications of medium-Mn steel sheets, for
example, automotive steel sheets are usually heated up to ~170 ◦ C in the paint baking process and as high as ~400–500 ◦ C for the
galvanizing in order to improve the corrosion resistance [39]. It has been long known the beneficial influence of tempering treatment
on enhancing the resistance to HE of high-strength steels [40–44]. However, until now, no reports have explored the influence of
tempering on the HE behavior of medium-Mn steels. Thus, the purpose of this paper is to explore the potential of different tempering
treatment (200–500 ◦ C) in alleviating the HE susceptibility of one extensively studied and least alloyed medium-Mn steel with ~5 wt%
Mn by electrochemical hydrogen-charging and slow strain rate tensile (SSRT) testing.

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Fig. 2. TEM micrographs showing (a,c,d) variations of duplex microstructure with tempering temperature and (f) the in situ decomposing of blocky
RA. (a,b) ART-annealed; (c) AT200; (d,e,f) AT500. (inserts in (a) and (b): indexed SAED patterns of austenite and cementite, respectively).

2. Experimental material and methods

The material used was an industrial trial of hot-rolled 6-mm-thick sheets of medium-Mn steel (0.1C-5Mn) with its chemical
composition listed in Table 1. Its critical temperatures of Ae1 and Ae3 calculated based on the Thermal-Calc (TCFE8) software are also
presented in Table 1. For the purpose of homogenizing the initial microstructure, the hot-rolled sheets were soaked at 800 ◦ C for 30
min, quenched in an oil bath. After quenching, the sheets were ART-annealed at 650 ◦ C for 30 min followed by air cooling. The se­
lection of this ART-annealing parameter was based on previous investigations of similar medium-Mn steels [27,35]. Subsequently, a
part of the sheets were tempered at 200 ◦ C, 400 ◦ C and 500 ◦ C for 60 min and then air cooled to ambient temperature. Fig. 1 gives the
schematic diagram of the heat treatment schedule. Flat tensile specimens (1.5 mm thickness, 5 mm width and 15 mm gauge length)
were cut longitudinally to the prior rolling direction using a wire cutting machine. These specimens which were cut from the 200 ◦ C,
400 ◦ C and 500 ◦ C tempered sheets were hereafter referred to as the AT200, AT400 and AT500 according to the tempering temperature
(Ttemp), respectively.

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Fig. 3. XRD spectra and the RA fraction of the tested steel sheets at different conditions before and after SSRT tests. (a,b) XRD spectra; (c) RA
volume fraction.

Hydrogen was electrochemically charged into the specimens in an aqueous solution of 0.25 mol/L H2SO4 containing 0.5 g/L
thiourea at 0.2 mA/cm2 for 60 min at ambient temperature. SSRT tests were conducted at a nominal strain rate of 4.2 × 10− 5 s− 1 for
both the hydrogen-charged and uncharged specimens. The hydrogen-charged specimens were tensile strained within 10 min after
hydrogen-charging and the total testing duration time was no longer than 120 min. Each test was repeated at least three times. HE
index (HEI), which was defined as the relative TEL loss, is expressed as:
HEI(%) = (1 − TELH /TEL0 ) × 100% (1)

where TEL0 and TELH are the TEL for the uncharged and hydrogen-charged specimens, respectively.
Hydrogen content was measured by thermal desorption spectrometry (TDS) at a heating rate of 100 ◦ C/h. According to ISO
17801–2004(E) standard, a modified Devanathan-Stachurski device was used to conduct the electrochemical hydrogen permeation
tests. The device includes two parts: a hydrogen charging side, which contained 0.25 mol/L H2SO4 solution with 0.5 g/L thiourea, and
a hydrogen oxidation detection side, which contained 0.1 mol/L NaOH aqueous solution. Details of the tests see reference [45]. The
following equation was used to calculate the effective hydrogen diffusion coefficient (Deff) [45]:

Deff = L2 /6tL (2)

where L is the sample thickness (1 mm), tL is the time-lag defined as 0.63 times the steady-state current in the permeation curve.
Microstructure characterization was performed using a transmission electron microscopy (TEM) at an operating voltage of 200 kV.
An alcohol solution with 5% perchloric acid was used for the preparation of TEM thin foils in a twin-jet electropolishing apparatus. X-
rays diffraction (XRD) was used to analysis the volume fraction of RA using a Cu-Kα X-ray source. After standard grinding and pol­
ishing, the surfaces normal to the rolling direction and the fractured surfaces of the SSRT specimens were etched in a 3% nital solution
for cracks observation by an optical microscopy (OM) and a scanning electron microscopy (SEM) operating at 20 kV. The fracture
surfaces of the fractured specimens were also observed by SEM.

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Fig. 4. (a) Hydrogen desorption curves of hydrogen-charged specimens and (b) variations of diffusible hydrogen contents of both the hydrogen-
charged and uncharged specimens with tempering temperature.

Fig. 5. Hydrogen permeation curve of the ART-annealed specimen.

3. Results

3.1. Microstructural characteristics

The TEM micrographs of the tested steel sheets ART-annealed and tempered at different temperatures are presented in Fig. 2. All
the specimens exhibit an ultrafine duplex microstructure consisting of black- and white-colored laths and blocks (Fig. 2(a), 2(c) and 2
(d)). The analysis of selected area diffraction (SAD) patterns further identified that the white-colored lath is ferrite phase while the
black-colored is RA [27,35]. This primarily lath-shaped microstructure is mainly because the reverted austenite grew along the
original martensitic laths and block boundaries before the recrystallization of the martensitic matrix [31], as was also found in other
hot-rolled/forged and ART-annealed medium-Mn steels [27,28,31,35]. XRD analysis shows that the RA fraction is 18.6 vol% for the
ATR-annealed specimen, and then an increase in Ttemp leads to a gradual decrease of the RA fraction as shown Fig. 3; especially when
the specimen was tempered at 500 ◦ C, the large blocky-type RA became thermally unstable and decomposed in situ into a mixture of
ferrite and cementite particles (Fig. 2(f)), causing a remarkable decrease (~6.6 vol%) of the RA fraction.
It is noteworthy that there are many rod-shaped cementite particles precipitated along the ferritic lath boundaries and within the
laths in the ART-annealed specimen, as was also found in previous investigations of short time ART-annealed 0.1C-5Mn and 0.2C-5Mn
steels [27,35,46]. Both TEM observations and numerical simulations showed that the precipitation of cementite during the ART-
annealing treatment of Mn-alloyed martensitic steels seems to be unavoidable [47,48]; more explanations about this phenomenon
are detailed in our previous work [46]. During the subsequent tempering process, the cementite particles retained in the ART-annealed
specimen grew gradually, while new cementite particles precipitated simultaneously (Fig. 2(c), 2(d) and 2(e)).

3.2. Hydrogen desorption and permeation behavior

Fig. 4(a) gives typical thermal desorption curves of the hydrogen-charged ART-annealed and tempered specimens. All the curves

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Fig. 6. (a) Engineering stress-strain curves of ART-annealed and tempered specimens before and after hydrogen-charging; and (b) variations of HEI
with tempering temperature.

exhibit a significant low-temperature peak at around 130 ◦ C and a weak high-temperature peak at around 370 ◦ C. This type of
hydrogen desorption curve is similar to those of other medium-Mn steels in literature [30–36]. Moreover, the low-temperature peak
temperature (TPI) of the ART-annealed, AT200, AT400 and AT500 are 136 ◦ C, 128 ◦ C, 112 ◦ C and 110 ◦ C, respectively, i.e., it tends to
decrease with an increase in Ttemp. This result indicates that the hydrogen trap activation energy of the low-temperature peak exhibits a
decreasing tendency with increasing Ttemp. An in-depth analysis of the peak of desorption curve of a 0.1C-7Mn-0.5Si steel with dual-
phase microstructure of RA + ferrite revealed that its low-temperature desorption peak could be separated into two different peaks
corresponding to α phase with lower peak temperature of ~65 ◦ C and to γ phase with higher peak temperature of ~110 ◦ C [31].
Therefore, the decrease of the RA fraction with an increase in Ttemp is mainly responsible for the decrease of the TPI.
It is usually regarded that hydrogen released lower than ~300 ◦ C is responsible for the HE of high-strength steels [49,50]. Thus, the
hydrogen which desorbed up to 300 ◦ C was defined as diffusible or weak trapped hydrogen (HD). Obviously, almost all the hydrogen of
each specimen corresponds to HD. Fig. 4(b) presents the variations of HD of the tested specimens at as-ART-annealed and tempered
conditions. For the uncharged specimens, the HD of the ART-annealed is ~0.1 ppm, and it remains almost unchanged with an increase
in Ttemp. For the hydrogen-charged specimens, the HD of the ART-annealed is 2.17 ppm; there is a slight variation of HD for the AT200,
AT400 and AT500 specimens.
Fig. 5 shows the hydrogen permeation curve of the ART-annealed specimen. The obtained Deff is 2.92 × 10− 7 cm2/s, which is rather
close to the one in low-alloy martensitic steels (Deff = 3.70 × 10− 7 cm2/s) [31]. The obtained Deff is much higher than that in duplex
stainless steels with ~40–50 vol% austenite (Deff ≈ 10− 11–10− 9 cm2/s) [51]. This is can be explained as follow. For the ART-annealed
specimen, its RA fraction (18.6 vol%) is much lower than ferrite, so the RA is embedded in the ferritic matrix. As ferrite has much
higher hydrogen diffusivity than austenite, the three-dimensional ferritic network would provide an efficient and quick path for
hydrogen transport [37], and thus the influence of the RA on hydrogen diffusivity would be rather limited. Based on (6Dt)1/2 [35] and a
charging time of 60 min, the hydrogen diffusion distance can be estimated to be 0.79 mm, which is slightly larger than the half-
thickness (0.75 mm) of the tested sheet specimen. Therefore, it is regarded that a steady-state hydrogen distribution was estab­
lished within the tested specimens.

3.3. HE susceptibility

Fig. 6(a) gives the typical engineering stress-strain curves of the tested steel at different conditions. For the uncharged specimens,
the UTS increases slightly while the TEL decreases with increasing Ttemp, which are more notable for the AT500 specimen. This result is
mainly related to the thermal stability of the RA during tempering treatment, and it is referred to reference [46] for details about this
variation of tensile properties with Ttemp.
The engineering strain was lowered after hydrogen-charging, and this decreasing tendency is more remarkable for the ART-
annealed and lower temperature tempered specimens. The hydrogen-charged ART-annealed and AT200 specimens exhibited signif­
icant premature fracture without necking. As shown in Fig. 6(b), it is clear that the susceptibility to HE evaluated by the relative TEL
loss (HEI) decreases significantly with increasing Ttemp. This result reveals that the susceptibility to HE is most significant for the ART-
annealed specimen, while tempering treatment can significantly alleviate it. For the AT500 specimen, its HEI is lower than 5%,
suggesting that it is almost immune to HE.

3.4. HE fracture surface characteristics

Both the macroscopic and microscopic SSRT tensile fracture surfaces were carefully observed by SEM to clarify the cause of the
degradation of mechanical properties for the tested steel due to hydrogen. The fractographs of both the uncharged and hydrogen-
charged ART-annealed specimens are shown in Fig. 7. The fracture surface is rough and shows noticeable necking for the

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(caption on next page)

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X. Zhao et al. Engineering Failure Analysis 119 (2021) 104969

Fig. 7. SEM micrographs of (a,b) uncharged and (c,d,e,f,g) hydrogen-charged ART-annealed specimens, showing a view of (a,c) low magnification
and (b,d,e,f,g) morphology at high magnification in regions as marked B, D, E, F, G in (a,c,f).

Fig. 8. SEM micrographs of the fracture surfaces of hydrogen-charged (a,b) AT200, (c,d) AT400 and (e,f) AT500 specimens. The graphs (a) and (c)
and (e) are the macroscopic view of the fracture surfaces, and (b), (d) and (f) are the corresponding details of the fracture surfaces in (a), (c) and (e)
marked B.

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Fracture surface

(a) (b)
AT500

RD AT400

AT200

ART-annealed

Fig. 9. (a) Schematic illustration of the observation surface (the red dot box) in the fractured SSRT specimen, and (b) optical macroscopic view of
cracks at the edges of hydrogen-charged specimens. RD refers to rolling and tensile deformation direction. (For interpretation of the references to
colour in this figure legend, the reader is referred to the web version of this article.)

Fig. 10. SEM micrographs taken at the normal direction of the fractured hydrogen-charged ART-annealed specimen, showing (a,b) internal cracks,
(c) cracks propagated along prior austenite grain boundaries (rectangle white box in (b)) and (d) voids initiated at the α/γ interfaces. Green circles
highlighted voids. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

uncharged specimen (Fig. 7(a)), while the fracture surface is more even and exhibits limited necking for the hydrogen-charged one
(Fig. 7(c)). Further SEM examination with high magnification revealed that the facture is primarily characterized by fine dimples,
revealing a ductile fracture mode for the uncharged (Fig. 7(b)). For the hydrogen-charged specimen, however, there are some flat
fractured areas in the edges of the fracture surface (region I) (Fig. 7(c)). These flat fractured areas are primarily characterized by
hydrogen-induced quasi-cleavage (QC) fracture mixed with intergranular fracture (IG) and some secondary cracks (Fig. 7(d)), which is
an indication of loss of ductility and is consistent with the SSRT result shown in Fig. 6. The region next to these flat areas (region II) are
mainly QC fracture with some secondary cracks and shallow dimples (Fig. 7(e)), while the central part of the fracture surface (region
III) is a mixed mode fracture of empty dimples and dimples filled with grains (Fig. 7(f,g)).
As seen from Fig. 8(a), the fraction of the brittle flat area notably decreases for the hydrogen-charged AT200 specimen compared

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Fig. 11. SEM micrographs taken at the normal direction of the fractured hydrogen-charged AT500 specimen, showing (a,b) no internal cracks can
be found at low magnification and (c) fine voids initiated at the α/γ interfaces. Green circles highlighted voids. (For interpretation of the references
to colour in this figure legend, the reader is referred to the web version of this article.)

with that of the ART-annealed one (Fig. 7(c)). The fraction of the brittle flat area further decreases for AT400 specimen (Fig. 8(c)),
while it nearly disappeared for the AT500 specimen (Fig. 8(e)). The fracture surfaces of the flat fractured area are dominated by QC
fracture for the hydrogen-charged AT200 and AT400 specimens (Fig. 8(b) and 8(d)), while the fracture mode is primarily ductile
dimple fracture for the hydrogen-charged AT500 (Fig. 8 (f)).

3.5. Hydrogen-induced crack initiation and propagation

The surface normal to the rolling and fracture surface as illustrated in Fig. 9(a) was observed by OM in an attempt to unveil the
underlying hydrogen influences with respect to microstructure. As shown in Fig. 9(b), many macroscopic cracks can be observed at
both edges of the fractured SSRT specimens except the AT500. The number of cracks decreases with an increase in Ttemp and no cracks
can be found in the AT500 specimen.
Fig. 10(a) and 10(b) show that some successive large cracks indicating the crack propagation are also found in the center region
neighborhood to the facture surface of the hydrogen-charged ART-annealed specimen. Further observation of the microstructure
ahead of the crack tip showed that it seems likely that voids were primarily initiated at the interphase boundaries between RA
(martensite) and ferrite as shown in Fig. 10(c) and 10(d), whereas no voids can be found within the ferrite. It should be noted that
during ART-annealing, the reverted austenite was preferentially nucleated at prior austenite grain boundaries, thus part of the voids
were also initiated at and propagated along the prior austenite grain boundaries (Fig. 10(c)), which was also found by Han et al. [31].
Thus the fracture mode of the hydrogen-charged ART-annealed specimen is mixed with intergranular fracture as shown in Fig. 7(d). In
contrast, no cracks can be found in the center region neighborhood to the facture surface of the AT500 specimen (Fig. 11(a) and 11(b)),
although much fine voids were still found to be primarily located at the RA/ferrite interfaces, but these voids seemed staying isolated
from each other and did not form cracks (Fig. 11(c)).

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4. Discussion

4.1. Influence of tempering treatment on HE susceptibility

It is widely regarded that increasing steel strength level usually causes an increase in HE susceptibility [12,52]. A systematic
investigation of the HE of several high-strength steels with different microstructures and hardness (strength) levels ranging from 327 to
544 HVN revealed that the foremost factor influencing the HE susceptibility is strength level [52]. However, numerous experimental
and practical results show that this general tendency is true especially for UTS being higher than about 1000 MPa [53], which suggests
that strength is not the only primary factor influencing the HE of various steels with lower strength level, that is to say, the micro­
structure of such steels plays a predominant role [54]. The experimental results of this research reveal that the AT500 specimen
exhibits the lowest value of HEI, although it has the highest strength level (~840 MPa) (Fig. 6(a)). Therefore, other factors should be
considered for the explanation of this experimental result.
When Ttemp is lower than ~400 ◦ C, it is still a little lower to permit the necessary large diffusion of carbon, and thus the thinning of
the RA laths primarily accounts for the slight decrease of the RA fraction [46]. There is a notable decrease of the RA fraction primarily
due to the decomposing of the large block RA when the steel was tempered at 500 ◦ C. Therefore, as mentioned in section 3.1, the
significant microstructural changes during tempering of the ART-annealed specimen could be regarded as the evolution of the RA and
cementite particles. It has been confirmed that both RA and cementite particles are strong hydrogen traps and the trap activation
energy of hydrogen desorption of RA is higher than that of cementite [4,55–57], thus it causes a decreasing of TPI with increasing Ttemp
(Fig. 4). Therefore, during subsequent hydrogen-charging, the decrease of the RA fraction causes a decrease of the HD trapped by RA
with increasing Ttemp, while the increase of the amount of cementite particles causes an increase of the HD. Thus, the HD remains almost
unchanged with increasing Ttemp up to 500 ◦ C (Fig. 4(b)). Moreover, it is rational to suppose that more and more hydrogen was trapped
by cementite particles with increasing Ttemp considering the nearly unchanged HD and the decreasing RA fraction.
It has been pointed out that metastable RA which transforms to martensite during deformation is detrimental to the resistance to HE
primarily because the hydrogen trapped by RA was inherited into martensite and hydrogen-enriched fresh martensite was so brittle
that it provided a nucleation site for micro-crack [30,31,45]. That is to say, TRIP effect is detrimental to the resistance to HE of TRIP-
assisted high-strength steels. After the SSRT tests, the remaining RA fractions are less than 3% (Fig. 3(c)), i.e., most of the RA (>85%)
transformed to martensite. It is obvious that the transformed RA fraction decreases with increasing Ttemp (Fig. 3(c)), for example, the
volume fractions of transformed RA are 16.8%, 11.2% for the ART-annealed and AT500 specimens, respectively. This is mainly
because the thinning of the lath width of the RA with increasing Ttemp increases its mechanical stability [46]. Given that most cracks
are associated with the martensitic transformation, the susceptibility to HE decreases with increasing Ttemp as revealed in Fig. 6. And
more importantly, the large blocky-type RA, which primarily nucleated along prior austenite grain boundaries (Fig. 2), transformed to
martensite at the early stage of the SSRT test, and thus would promote the crack initiation and propagation in the presence of hydrogen
as shown in Fig. 10. Thus, it is the large blocky-type RA which is mainly responsible for the IG fracture of the ART-annealed specimen,
as was also pointed out by Han et al. [31]. Therefore, the decrease of the fraction of the RA especially the large blocky-type RA due to
its lower thermal stability with an increase in Ttemp causes a decrease of the fraction of brittle IG fracture (Figs. 7 and 8) and thus
enhanced resistance to HE.
In addition to the change of the RA, tempering treatment also changed the characteristics of carbide of the tested steel. As the
precipitation of cementite particles during the ART-annealing of Mn-alloyed martensitic steel seems to be unavoidable [47,48], a short
duration of intercritical annealing (30 min) at 650 ◦ C would unavoidable lead to undissolved cementite particles as shown in Fig. 2(b).
During the subsequent tempering treatment, these cementite particles grew gradually, while new cementite particles would precipitate
along ferritic lath boundaries or within laths or through the decomposition of the RA by a diffusion mechanism or directly from the RA
at a higher Ttemp (Fig. 2(c)-2(f)). This process is similar to that of the tempering process of quenched martensitic steel, and thus is
beneficial to the enhancement of the HE resistance of the tested steel [40,52,55]. Moreover, the increasing uniform distribution of fine
cementite particles could also improve the HE resistance under plastic deformation as it would change the state of hydrogen trap at
cementite, i.e., from low-energy to high-energy by forming strained interfaces between matrix and cementite [58].

4.2. Influence of tempering treatment on HE fracture surface characteristics

As shown in Fig. 7, the SSRT fracture surface of the ART-annealed specimen could be roughly divided into three regions. As for the
flat brittle region near the specimen surface (region I), it is macroscopic brittle transgranular (TG) with the presence of IG and some
secondary cracks. As mentioned above, the existence of large block-type RA is mainly responsible for the IG fracture in the presence of
hydrogen. This is because the preferred enriched hydrogen would reduce the cohesive bonding energy between lattice atoms, that is to
say, the IG fracture mode is due to the predominant decohesion – HEDE mechanism activity initiated due to high local hydrogen
concentration in the vicinity of specimen surface [20,59]. As for the inward region next to region I (region II), it is a mixed fracture of
brittle QC and ductile microvoid coalescence (MVC). The local MVC fracture indicates localized plasticity and the HELP mechanism
activity, and this is in the accordance with the HELP + HEDE model about the synergistic action of both HELP and HEDE mechanism
[20]. As for the central part of the fracture surface (region III), one significant characteristic is the presence of a small fraction of
dimples filled with grains besides pure ductile empty dimples, the former was also found in other medium-Mn steels [31,33,34,36]. It
has been verified that these “grains” are deformation-induced martensites from the RA and this type of fracture is initiated by IG
cracking along the RA grain boundaries and/or the interfaces of RA and ferrite in the presence of hydrogen by the HEDE mechanism
[31,33,34,36]. Thus, dimples filled with grains are by nature an IG fracture.

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Table 2
Summaries of tensile properties and HEI of the tested medium-Mn steel at different conditions.
Tempering temperature (◦ C) UTS (MPa) TEL (%) UTS × TEL (GPa⋅%) HEI (%)

ART-annealed 783 41.9 32.8 62.3 ± 4.3

200 789 39.9 31.4 31.9 ± 15.1
400 786 39.8 31.3 16.4 ± 4.9
500 838 34.9 29.3 3.6 ± 1.0

From above considerations, it is seen that the HEDE mechanism dominates in region I (HEDE > HELP), the HELP mechanism
dominates in region III (HELP > HEDE), and the synergistic action of both HELP and HEDE mechanism in the transition area (region II)
(HELP + HEDE). The transition between HE mechanisms depends on hydrogen concentration and applied stress conditions [20]. The
decrease of the metastable RA fraction with increasing Ttemp causes the decrease of the fraction of region I (Figs. 7 and 8), and when the
steel was tempered at 500 ◦ C, it almost disappeared (Fig. 8). More detailed studies are still necessary to clarify this HE fracture
mechanism in medium-Mn steels.

4.3. Influence of tempering treatment on strength-ductility balance

The product of UTS to TEL (UTS × TEL) is now widely adopted to assess the strength and ductility combination of AHSSs for
automobiles, and the target value of UTS × TEL for the third-generation AHSS grades is higher than ~30 GPa⋅% [1,26]. As seen from
Table 2, almost all the values of UTS × TEL meet that requirement for the Ttemp range investigated although it slightly decreases with
increasing Ttemp. Interestingly, the decrease of the value of HEI is much more significant compared to the slight decrease tendency of
the value of UTS × TEL. For example, the increase of Ttemp up to 200 ◦ C leads to a 48.8% decrease of HEI while only a 4.3% decrease of
the value of UTS × TEL; the increase of Ttemp up to 500 ◦ C leads to a 94.2% decrease of HEI while only a 10.7% decrease of the value of
UTS × TEL. This result suggests that low temperature tempering like that used in the paint baking process could notably lower the
susceptibility to HE, and that high temperature tempering like that used in the galvanizing process could significantly reducing the
susceptibility to HE or even make it immune to HE.
It should be noted that the HEI of the ART-annealed specimen (~62%) of the present study is similar to those of the hot/cold-rolled
plus ART-annealed (74–87%) of a 0.1C–7Mn steel [31], which indicates that a risk to HE fracture might exist for the ART-annealed
medium-Mn steels. It is thus proposed that tempering treatment combining with paint baking and/or galvanizing processes might
provide a promising way to lower the susceptibility to HE of medium-Mn steels with relatively lower decreasing in the strength-
ductility balance, although further investigation is still needed.

5. Conclusions

(1) The susceptibility to HE evaluated by the relative total elongation loss decreases continuously with increasing Ttemp, and it is
nearly immune to HE for the specimen tempered at 500 ◦ C. The diffusible hydrogen contents for both uncharged and hydrogen-
charged specimens remain almost unchanged with increasing Ttemp up to 500 ◦ C. These results are ascribed primarily to the
microstructural evolution of the RA and cementite during tempering.
(2) The SSRT fracture surface of the ART-annealed specimen can be divided into three regions with different fracture characteristics
including IG, QC and MVC fracture, and corresponding HE mechanism changes from HEDE dominates to the synergistic action
of both HELP and HEDE mechanism to HELP dominates from specimen surface layer to interior. The fraction of the brittle
fracture especially IG fracture decreases with an increase in Ttemp, while it nearly disappeared with further increasing Ttemp up
to 500 ◦ C.
(3) A novel strategy is proposed, i.e., tempering treatment after ART-annealing might provide a promising way to lower the HE
susceptibility of medium-Mn steel at little expense of lowering its strength-ductility balance, and this treatment could be
combined with the paint baking and/or galvanizing processes usually applied to enhance the corrosion resistance of automotive
steel sheets.

Declaration of Competing Interest

The authors declare no conflict of interest to this work.

Acknowledgements

This research was financially supported by the National Key Research & Development Program of China [grant No.
2017YFB0304401] and the High-level Scientific Research Foundation for the Introduction of Talent of Beijing Jiaotong University
(grant number: M14RC00010).

12
X. Zhao et al. Engineering Failure Analysis 119 (2021) 104969

Data Availability

Data will be made available on request.

Appendix A. Supplementary material

Supplementary data to this article can be found online at https://doi.org/10.1016/j.engfailanal.2020.104969.

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