Applied Surface Science 511 (2020) 145550

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Applied Surface Science

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Full Length Article

High temperature deformation behaviors of hot dip 55 wt% Al-Zn coated T

steel
⁎
Jun-Kai Changa, Chao-Sung Lina, , Woei-Ren Wangb, Shun-Yi Jianc
a
Department of Materials Science and Engineering, National Taiwan University, 1, Roosevelt Road, Section 4, Taipei 106, Taiwan
b
Department of Additive Manufacturing Materials & Applications, Division of Metallic Materials Research, Material and Chemical Research Laboratories, Industrial
Technology Research Institute, Tainan 709, Taiwan
c
Department of Chemical and Materials Engineering, National Defense University, Dasi District, Taoyuan 335, Taiwan

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

Keywords: The high temperature tensile test of hot dip 55 wt% Al-Zn coated steel was performed to study the fracture
Hot dip 55 wt% Al-Zn coating behaviors of hot dip 55 wt% Al-Zn coating as a protective coating for hot-stamping steel. During austenitization,
Cracking the 55 wt% Al-Zn coating had transformed to an alloy layer composed an Fe2Al5Znx (with few FeAl and Zn) outer
Fe-Al intermetallic phase layer and an FeAl inner layer. When the austenitization heat treatment was fixed at 5 min, the sample heated at a
High temperature tensile test
higher heating rate (20 K/s) was subjected to a longer soaking time at 900 °C. This resulted in a thicker FeAl
Hot stamping
inner layer at the steel/Fe2Al5Znx (FeAl, Zn) interface. During the initial stages of deformation, cracks formed in
Fe2Al5Znx (FeAl, Zn) layer. Subsequently, cracks developed in the FeAl inner layer. With continued deformation,
cracks widened and debonding occurred at the FeAl/Fe2Al5Znx (FeAl, Zn) interface for the samples heated at
lower heating rates (5 K/s or 10/s). Finally, crack widening accelerated the exposure and subsequent oxidation
of the steel substrate. The absence of debonding can be beneficial for reducing the susceptibility to powdering
during hot stamping.

1. Introduction
Reducing the emission of greenhouse gases, enhancing the effi-
ciency of fuel-consumption and improving the safety of passengers are
simultaneously practiced in present ecological demands. Applications
of hot-stamped steel components is increasing in automobile industries
due to their superior strength to weight ratios [1,2]. Press-hardening
steel (PHS), such as Mn-B steel, is the most commonly-used advanced
high-strength steel, which is processed into structural components using
the hot stamping process [3,4]. During the hot stamping process, a PHS
blank is heated at 850–950 °C for 3–10 min to obtain a fully austenite
structure first and is transferred to a forming die where the forming is
conducted, followed by subsequent die quenching [4–6]. The strength
of PHS is enhanced to approximately 1500 MPa via martensitic trans-
formation upon die quenching [6–9]. During the austenitization heat
treatment, the PHS is exposed to ambient atmosphere, where oxidation
and decarburization take place. To avoid oxidation and decarburiza-
tion, a protective coating on PHS is a necessity [6,10].
An Al-10 wt% Si coating, also patented as Usibor® by ArcelorMittal,
has been widely employed for PHS as an effective protective coating. A
hot-stamped Al-10 wt% Si coated PHS mainly consists of Fe2Al5 and
FeAl phases with a compact and continuous Al2O3 layer on the surface.
As a result, the Al-10 wt% Si coating is resistant to high-temperature
oxidation [11]. However, Fe2Al5 and FeAl phases are brittle and pro-
vide inadequate corrosion resistance during service [11–16]. Moreover,
microcracks form during the forming and cooling stages, and may cause
debonding of the coating from the steel substrate, resulting in pow-
dering [11,17,18]. Hydrogen embrittlement of the Al-Si coating on PHS
has also been reported [19,20]. By taking corrosion resistance into
consideration, Zn coating is an ideal coating due to its barrier protec-
tion and sacrificial protection to the underlying steel. Hot dip Zn
coating is thus a widespread protection coating on steel for archi-
tectures and automobiles [21–25]. Recently, hot dip Zn coating has
been reported as an effective coating for PHS with reduced sensitivity of
hydrogen embrittlement [26]. However, oxidation and liquid mental
embrittlement (LME) are still major concerns. After hot stamping, an
hot dip Zn coating usually transforms to Zn-saturated ferrite (α-Fe(Zn))
and Г-Fe3Zn10 phase with a thick ZnO scale on the surface [11,27,28].
This ZnO layer adversely affects the resistance spot welding [29,30].
LME is the most critical issue for hot dip Zn coated PHS. During the hot
stamping process, the austenitization heat treatment temperature is
higher than the Fe-Zn peritectic reaction temperature, such as Г-

⁎
Corresponding author.
E-mail address: csclin@ntu.edu.tw (C.-S. Lin).

https://doi.org/10.1016/j.apsusc.2020.145550
Received 15 October 2019; Received in revised form 16 January 2020; Accepted 27 January 2020
Available online 29 January 2020
0169-4332/ © 2020 Elsevier B.V. All rights reserved.
J.-K. Chang, et al.
Fe3Zn10 → α-Fe(Zn) + Zn(l) occurring at 782 °C [21]. As a result, liquid
Zn forms in the coating. When liquid Zn wets the grain boundaries of
the steel substrate (austenite), intergranular fracture occurs with
stresses imposed during die forming and is known as LME
[10,29,31–40]. During the cooling stage via die quenching, liquid Zn
reacts with α-Fe(Zn) to transform back to Г-Fe3Zn10. Lee et al. [41]
demonstrated that the presence of Г-Fe3Zn10 phase on hot-stamped hot
dip Zn coated PHS is a critical criterion for evaluating the susceptibility
to LME. LME can thus be avoided when liquid Zn is nearly consumed
during austenitization heat treatment, specifically longer austenitiza-
tion times at higher temperatures. Takahashi et al. [37] investigated the
effect of austenitization time on the fraction of Г-Fe3Zn10 phase and the
LME susceptibility of hot-stamped galvannealed PHS. They found that
LME occurred during hot stamping when liquid Zn was present in the
coating layer. Although the elimination of Г-Fe3Zn10 phase avoids LME,
the corrosion resistance of the alloy layer is likely to be reduced,
especially the sacrificial protection provided by Zn. Increasing the Fe
content in the Zn coating prior to austenitization via galvannealing can
also avoid LME [36], but the presence of Fe in the coating accelerates
oxidation [42–44]. In contrast, the addition of Al to Zn coating to form
Galfan® (5 wt% Al-Zn) and Galvalume® (55 wt% Al-Zn) coating [21]
can be beneficial for suppression of high-temperature oxidation. After
the austenitization heat treatment, the 5 wt% Al-Zn coating transforms
to typical α-Fe(Zn) and Г-Fe3Zn10 phase and the presence of Al results
in the formation of a protective Al2O3 surface layer [44,45]. After the
austenitization heat treatment, the 55 wt% Al-Zn coating transforms to
FeAl, Fe2Al5Znx (Zn as solid solutes in Fe2Al5), and Zn [40,43]. As a
result, during austenitization both 5 wt% Al-Zn and 55 wt% Al-Zn
coatings suffer less oxidation compared to hot dip Zn coating. More-
over, the presence of 5 wt% or 55 wt% Al in Zn also reduces the LME
susceptibility during hot stamping [33,41,46].
Previous studies have shown that hop dip 55 wt% Al-Zn coated PHS
does not suffer LME during high-temperature deformation [46]. This is
due to the fact that during hot stamping, liquid Zn is restrained in the
grain boundaries of Fe-Al phases and does not contact and wet the grain
boundaries of the steel substrate [41,46]. However, little focus has been
made on the cracking behaviors and interface debonding of hop dip
55 wt% Al-Zn coated PHS during hot stamping. Gui et al. [47] studied
the cracking mechanism of Al-10 wt% Si coating during high-tem-
perature tensile and found that cracking initially began at the Fe-Al
coating, followed by interface debonding. During hot stamping, pow-
dering of the coating is generally related to the fracture behavior of the
coating. Powdering of the coating tends to damage the surface of
forming dies and reduce the corrosion resistance of hot-stamped PHS
parts. Understanding the fracture behavior of protective coating on PHS
is thus of great importance. In this present study, a hop dip 55 wt% Al-
Zn coating was used to study the phase evolution and cracking beha-
viors of the coating during austenitization heat treatment and high
temperature tensile test.
2. Experimental procedure
2.1. Materials and high-temperature tensile test
Hot dip 55 wt% Al-Zn coated steel was received from the continuous
hot dip 55 wt% Al-Zn production line of Yieh-Phui Enterprise
Corporation, Kaohsiung, Taiwan. Additional 1.5 wt% Si was added in
the 55 wt% Al-Zn bath to avoid fierce Al-Zn and steel substrate alloy
reaction during the hot dip process [48–50] and to reduce the viscosity
of Zn bath [51]. The thickness of hot dip 55 wt% Al-Zn coated steel was
1.4 mm and the composition of the steel substrate is listed in Table 1.
The phase of the as-received coating was Al and Zn, as identified by
XRD (Fig. 1(a)). The thickness of the coating was about 40 μm, as
shown by the cross-sectional SEM micrograph in Fig. 1(b). The bulk Al
was the principle phase and Zn presented as a dendrite-like structure in
the grain boundaries of bulk Al.
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Applied Surface Science 511 (2020) 145550
Table 1
The element composition of the steel substrate used in this study.
Element content (wt.%) C Mn Si P S Fe
0.2 1.2 0.01 0.013 0.004 Bal.
A Gleeble 3500 thermo-mechanical process simulator was used to
conduct the heat treatment and high-temperature tensile test. The
geometry of the sample for tensile test was prepared based on the ASTM
standard [52,53], which was also used in our previous study [43,44].
The hot dip 55 wt% Al-Zn coated steel panel was heated by electrical
resistance heating. The temperature was monitored continuously by
using a K-type thermocouple welded to the center of the back of the
panel, where the coating had been removed by emery paper. The gauge
length of the sample was 10 mm. Fig. 1(c) presents the thermal history
and tensile deformation conditions. The heating rate was 5 K/s, 10 K/s,
and 20 K/s, while the soaking temperature was fixed at 900 °C in
stagnant air to study the effect of heating rate on microstructure evo-
lution and fracture behaviors. The tensile test was performed when the
total heat treatment time, including heating time and soaking time,
reached to 5 min. Finally, a stream of compressed air was injected to
cool down the sample with a cooling rate of approximately −80 K/s.
2.2. Materials characterization
An X-ray Diffractometer (XRD, Rigaku TTRAX 3) was used to
identify the phase of hot dip 55 wt% Al-Zn coating using monochro-
matic Cu Kα (λ = 1.54439 Å) radiation at 30 kV and 50 mA. The
scanning speed was set at 4°/min. All XRD diffraction peaks were
characterized via the crystallographica search-match 2.1 software to-
gether with the PDF-2 JCPDS-ICCD database [54]. A field-emission gun
scanning electron microscope (FEG-SEM, JOEL JSM 7800F PRIME) was
used to investigate the cross section of hot dip 55 wt% Al-Zn coated
steel panels. The cross section was investigated under the backscattered
electron (BSE) mode at 20 kV to characterize the various phases. The
chemical composition of the coating and oxides was analyzed using the
energy dispersive spectrometry (EDS) equipped in the FEG-SEM. The
electron backscatter diffraction (EBSD) equipped in the FEG-SEM was
also employed to identify the phase distribution in the coating after
austenitization. The Oxford EBSD acquisition system with Aztec soft-
ware was used for the EBSD analysis, which was conducted at an op-
erating voltage of 20 kV and an emission current of 37 μA. The crys-
tallographic information to identify the phases and crystals in the
coating was referenced to the Inorganic Crystal Structure Database
(ICSD) [55] and NIMS Materials Database (NatNavi) [56]. Table 2 lists
the information of the distinct phases employed for EBSD analysis. At
least 6 Kikuchi lines with 1.5° angular tolerances were applied to index
the electron backscatter patterns (EBSPs) in order to reduce mis-
identification. During the recording of EBSD mapping, the EDS map-
ping was also conducted to measure the element distribution in the
coating. Finally, the phase map was also undertaken using the HKL-
Channel 5™ software package.
3. Results and discussion
3.1. Microstructure evolution during austenitization
To investigate the phase evolution of hot dip 55 wt% Al-Zn coating
during the heating stage, the steel panel was heated to 900 °C at a
heating rate of 10 K/s and was immediately cooled down to room
temperature at a cooling rate of −80 K/s via compressed air injection.
Fig. 2 shows the XRD patterns, cross-sectional SEM micrograph, and
EBSD phase identification of this heat-treated sample. The XRD patterns
(Fig. 2(a)) revealed that the coating of heat-treated sample was com-
posed of Al and Zn phases, which are similar to that of the as-received
hot dip 55 wt% Al-Zn coating (Fig. 1(a)). Fig. 2(b) shows that the
J.-K. Chang, et al. Applied Surface Science 511 (2020) 145550

Fig. 1. (a) XRD patterns, (b) cross-sectional SEM micrograph of the as-received hot dip 55 wt% Al-Zn coating, and (c) the thermal history and tensile deformation
conditions.

Table 2 the occupant sites of Zn solutes [57–61]. The Zn content in FeAl3 and
The crystal structure, space group, and lattice parameters of the various phases Fe2Al5 is consistent with the results made by Chen et al. [62], who
employed for this study [55,56]. established the Fe-Al-Zn ternary phase diagram at 450 °C, on which the
Phase Structure Space Lattice parameters solubility of Zn in Fe2Al5, FeAl3, and FeAl is approximately 20.9 wt%,
Group 5.3 wt% Zn, and 2.0 wt%. The results in Fig. 2 and Table 3 also imply
that during the heating stage, the Al in the coating reacts with the steel
Al Face-Center Cubic Fm-3m a = b = c = 4.05 Å;
to form Fe2Al5Znx and FeAl3 and the remnant Al-Zn is present at the
(FCC) α = β = γ = 90°
Zn Hexagonal P63/ a = b = 2.67 Å, c = 4.95 Å; outer part of the coating. The increase in the thickness thus results from
mmc α = β = 90°, γ = 120° the alloying reaction between the Al-Zn coating and the steel substrate.
Fe2Al5Znx Orthorhombic Cmcm a = b = 2.67 Å, c = 4.95 Å;
α = β = 90°, γ = 120°
FeAl3 Monoclinic C2/m a = 15.49 Å, b = 8.08 Å, 3.2. Cracking behaviors of hot dip 55 wt% Al-Zn coating during isothermal
c = 12.47 Å; α = γ = 90°, tensile deformation
β = 107.69°
FeAl Body-Center Cubic Pm-3m a = b = c = 2.91 Å;
(BCC) α = β = γ = 90°
Prior to tensile testing, the microstructure of hot dip 55 wt% Al-Zn
α-Fe Body-Center Cubic Pm-3m a = b = c = 2.87 Å; coating after 5 min of heating and soaking at 900 °C was characterized
(BCC) α = β = γ = 90° by using SEM and EBSD, as shown in Fig. 3. The thickness of the coating
Martensite Body-Center- I4/ a = b = 2.87 Å, c = 2.89 Å; increased to 63 μm and the outer layer was mainly composed of
Tetragonal (BCT) mmm α = β = γ = 90°
Fe2Al5Znx grains with FeAl and metallic Zn as minor phases, as shown
by EBSD phase identification and EDS element distribution results.
According to the information in Table 2, the crystal structure and lattice
thickness of the coating was approximately 52 μm, which is larger than
parameters of FeAl and lath martensite are too similar to be dis-
that of the as-received coating (~40 μm). Moreover, the coating
criminated by EBSD analyses, i.e. FeAl with BCC structure of
evolved into two layers, including an outer bright layer and an inner
a = b = c = 2.91 Å and martensite with BCT structure of
dark layer seen under the BSE mode. The outer bright layer displayed a
a = b = 2.87 Å, c = 2.89 Å. Therefore, the lath martensitic structure
morphology similar to the as-received coating, which consists of dark
could be identified as the FeAl phase. However, with the assistance of
bulk Al and bright Zn. After being polished using alkaline SiO2 sus-
corresponding EDS mapping, the boundary of FeAl and lath martensite
pension solution of pH ≈ 10, the sample was further analyzed via
could be distinguished. Herein, this outer layer was denoted as
EBSD. The bright part of outer bright layer corroded in alkaline solution
Fe2Al5Znx (FeAl, Zn). The metallic Zn was kept in the grain boundaries
and became concave, which made EBSD characterization impossible,
of Fe2Al5Znx or FeAl phases. This agrees well with the results made by
although EBSD is powerful to distinguish the phase distribution in the
Lee et al. [41,46]. The inner layer was identified as FeAl phase with
coating. Fig. 2(c) is the EBSD phase mapping, EDS element mapping,
teeth-like grain morphology neatly arranging in between the Fe2Al5Znx
and pole figure of Fe2Al5 phase. In the EBSD phase mapping, the outer
(FeAl, Zn) outer layer and the martensite substrate, as showing in the
dark region was identified as Al phase, which contained 77.2 wt% Al
IPF crystal orientation mapping. In the EDS mapping results, the ob-
and 22.8 wt% Zn, as measured by EDS (point ➀ in Fig. 2(c) and
vious difference of Zn distribution was found between the Fe2Al5Znx
Table 3). In addition, the branch-like structures marked as points ➂ and
and FeAl phases. The solubility of Zn in FeAl is approximately 2–12 wt
➃ in Fig. 2(c) were identified as FeAl3, which averagely contained
% and that in Fe2Al5 is 14–23 wt% [62,63]. As a result, Zn is largely
58.2 wt% Al, 35.9 wt% Fe, and 5.9 wt% Zn present as solutes. The inner
expelled out of the FeAl phase to form metallic Zn pockets residing in
dark layer was identified as Fe2Al5 by EBSD. Moreover, this Fe2Al5
the grain boundaries of Fe2Al5Znx.
phase contained around 13.6 wt% Zn as solutes, as shown by the EDS
Fig. 4 presents the engineering strain-stress curve and the simulta-
analysis of point of ➄ in Fig. 2(c) and Table 3. The pole figure further
neous video images during the isothermal tensile deformation at 900 °C
identified that the c-axis ([0 0 1]) of Fe2Al5 was vertical to the steel
to different engineering strains. As shown in Fig. 4(a), the total strain
substrate. The c-axis of Fe2Al5 can act as the path for Al and Fe inter-
until fracture was approximately 0.6 and the ultimate tensile strength
diffusion along [0 0 1] direction and the vacancies along c-axis provide
(UTS) was about 120 MPa. Moreover, LME did not occur during

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J.-K. Chang, et al. Applied Surface Science 511 (2020) 145550

Fig. 2. (a) XRD patterns, (b) cross-sectional SEM micrograph, and (c) EDS and EBSD phase identification of the hot dip 55 wt% Al-Zn coating after being heated to
900 °C at a heating rate of 10 K/s without soaking.

Table 3 deformation at 900 °C, the sample was pulled to a specific engineering
The EDS analysis results of the corresponding points in Fig. 2(c). strain marked in Fig. 4(a). After rapid cooling to room temperature, the
Corresponding point in Fig. 2(c) Element content (wt.%)
sample was characterized via cross-sectional SEM specimen, as shown
in Fig. 5. Prior to tensile deformation (0% strain), the coating was
Al Fe Zn Phase composed of Fe2Al5Znx, FeAl, and Zn. After 5% strain of isothermal
tensile deformation, obvious cracks were observed between coarse
➀ 77.2 0.5 23.3 Al
➁ 33.4 3.1 63.5 Zn
Fe2Al5Znx grains in the Fe2Al5Znx (FeAl, Zn) outer layer, which was
➂ 57.6 37.5 4.9 FeAl3 denoted as coating cracking. At a larger strain, another cracking type
➃ 58.8 34.3 6.9 FeAl3 was observed primarily in the FeAl inner layer. Under 10% strain, this
➄ 42.8 43.6 13.6 Fe2Al5 type of cracking happened in the FeAl inner layer and was defined as
interface cracking. With continued deformation, cracks of the coating
cracking widened and cracks of the interface cracking expanded. Under
isothermal tensile test at 900 °C. Fig. 4(b) shows the simultaneous video
30% strain, expanded cracks of the interface cracking resulted in the
images recorded at different strains. During the tensile deformation
debonding between the Fe2Al5Znx (FeAl, Zn) outer layer and the inner
process, firing was observed once plastic deformation took place. It is
FeAl layer. This expansion continued with further deformation to 40%
likely that upon plastic deformation, cracking of the coating occurred
strain and caused exposure and oxidation of the underlying martensite
and led the exposure of liquid Zn to ambient air, causing flash fires.
substrate.
Therefore, liquid Zn in cracking region had no time to wet the grain
Fig. 6 shows the detailed cross-sectional microstructure of hot dip
boundaries of austenite. Liquid Zn pockets, which resided at the grain
55 wt% Al-Zn coating after isothermal tensile deformation at 900 °C to
boundaries of Fe2Al5Znx and FeAl phases, also did not contact with the
40% strain. As seen in Fig. 6(a), oxide scales were found at the cracking
underlying austenite substrate. Both avoids the occurrence of LME.
region of the FeAl inner layer after the Fe2Al5Znx (FeAl, Zn) outer layer
In order to study the cracking behaviors during isothermal tensile
detached (i.e., debonding) from the FeAl inner layer. Fig. 6(b) confirms

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J.-K. Chang, et al. Applied Surface Science 511 (2020) 145550

Fig. 3. The cross-sectional SEM and EBSD phase mapping as well as EDS element mapping of Al, Fe and Zn of hot dip 55 wt% Al-Zn coating after heating at a rate of
10 K/s to 900 °C and isothermally holding at 900 °C to a total heat treatment time of 5 min.

that an Fe oxide scale formed in the crack opening region after coating
debonding took place and cracking of the FeAl inner layer had led the
exposure of the underlying martensite substrate to air.
3.3. Effect of heating rate prior to isothermal tensile test on cracking
behavior
Fig. 7 shows the effect of heating rates on the engineering strain-
stress curves recorded at 900 °C. Note the total heat treatment time
before tensile deformation was set at 5 min, including heating time and
isothermal soaking time. At a higher heating rate, the fracture strain
was slightly larger, but the UTS was hardly changed, i.e., approximately
120 MPa. Moreover, LME was not observed and the total elongation
until fracture reached to approximately 0.6, which was larger than the
hot dip Zn coated PHS having elongation less than 0.1 when LME took
place [36]. According to the studies of Lee et al. [36,46], the elongation
of LME-free Zn and 55 wt% Al-Zn coated PHS during elevated-tem-
perature tensile test would reach to a value of 0.4 at which no cracks
were found to penetrate into the steel substrate.
Fig. 8 presents the EBSD phase, crystal orientation, and EDS element
mapping of hot dip 55 wt% Al-Zn coating after a total heat treatment
time of 5 min, including heating to 900 °C at different heating rates and
isothermal soaking at 900 °C. Since the total heat treatment time was
fixed, the soaking time was longer at a higher heating rate. As a result,
the alloying reaction between the coating and the steel substrate pro-
ceeded to larger extents at a higher heating rate. Fig. 8(a) shows the
results at a heating rate of 5 K/s. The thickness of the coating was
around 55 μm and the coating was primarily composed of Fe2Al5Znx
phase, as evident from the results of EBSD phase identification. More-
over, the topmost columnar grains in the Fe2Al5Znx outer layer were
smaller than the rest of coarse Fe2Al5Znx columnar grains. The FeAl
inner layer between the Fe2Al5Znx (Zn) outer layer and the martensite
substrate was thinner compared to the sample heated at 10 K/s, as
shown by comparing Fig. 8(a) to Fig. 3. As the heating rate was in-
creased to 20 K/s, the total thickness of the coating increased to about
88 μm and the inner layer became thicker (Fig. 8(b)). Moreover,

Fig. 4. (a) The engineering strain–stress curve of hot dip 55 wt% Al-Zn coating recorded after heating at a rate of 10 K/s to 900 °C and isothermally holding at 900 °C
to a total heat treatment time of 5 min, (b) simultaneous video images during isothermal tensile deformation at 900 °C.

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J.-K. Chang, et al. Applied Surface Science 511 (2020) 145550

Fig. 5. Cross-sectional SEM characterization of hot dip 55 wt% Al-Zn coating after isothermal deformation at 900 °C to different engineering strains.

dispersive FeAl grains were also observed in the outer layer. Table 4
summarizes the thickness of the total alloy layer and the FeAl inner
layer formed at different heating rates. The thickness of both the
Fe2Al5Znx (FeAl, Zn) outer layer and the FeAl inner layer increased with
increasing heating rate. Apparently, the longer soaking time associated
with higher heating rate contributes to larger extents of alloy reaction,
which, in turn, promotes the growth of the Fe2Al5Znx (FeAl, Zn) outer
layer and the FeAl inner layer.
Fig. 9 shows the cross-sectional SEM micrographs of hot dip 55 wt%
Al-Zn coating heated to 900 °C at 5 K/s and 20 K/s, hold at 900 °C for a
total heat treatment time of 5 min, followed by tensile deformation to
different engineering strains. For the sample heated at 5 K/s, metallic
Zn phase shown with white contrast was observed among dark coarse
Fe2Al5Znx grains. During tensile deformation, coating cracking was
observed at 5% strain. Then, interface cracking was observed at 20%
strain. With continued deformation, interface cracking continued and
cracks expanded further. As for the sample heated at 20 K/s, metallic Zn
phase was only observed in between the outer layer and the inner layer.
Several crevices and voids were found in the outer layer and at the Fig. 7. The engineering strain-stress curves of hot dip 55 wt% Al-Zn coaitng
interface between the outer layer and the inner layer. Once the de- tested at 900 °C showing the effect of heating rate.
formation commenced, cracking occurred and several cracks penetrated
into the inner layer. Then, both coating cracking and interface cracking increasing strains. Compared to the sample heated at 5 K/s, the sample
were observed at 5% strain. Moreover, oxide scales were observed at heated at 20 K/s appeared to have larger crack openings and obvious
the regions where cracks of the interface cracking expanded with oxide scales.

Fig. 6. (a) The cross-sectional microstructure of hot dip 55 wt% Al-Zn coating after isothermal tensile deformation at 900 °C to 40% strain and (b) the EDS spectrum
of oxide scales in Fig. 6(a).

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J.-K. Chang, et al.
Fig. 8. The EBSD phase, crystal orientation, and EDS element mapping of hot dip 55 wt% Al-Zn coaitng heated at a heating rate of (a) 5 K/s and (b) 20 K/s to 900 °C
for a total heat treatment time of 5 min.
Table 4
The thickness of the total alloy layer and FeAl inner layer formed at different
heating rates to 900 °C for a total heat treatment time of 5 min.
Heating rate Total alloy layer thickness (μm) FeAl inner layer thickness (μm)
5 K/s 55.1 ± 2.5 8.3 ± 1.5
10 K/s 63.5 ± 1.7 12.8 ± 1.1
20 K/s 88.2 ± 5.1 15.4 ± 1.3
After the fracture of the samples tensile tested at 900 °C, the surface
morphology and fracture surface of the samples were characterized by
using SEM, as shown in Fig. 10. The surface morphology shows that the
cracking opening increased as the heating rate was increased from 5 K/s
to 10 K/s. Further increase in the heating rate resulted in a slight
change in the cracking opening. The fracture surface observation re-
vealed that debonding between the Fe2Al5Znx (Zn) or Fe2Al5Znx (FeAl,
Zn) outer layer and the FeAl inner layer occurred in the samples heated
at 5 K/s and 10 K/s, as marked by the arrow in Fig. 10. In contrast, for
the sample heated at 20 K/s, the interface between the outer layer and
the inner layer was almost intact after fracture, as shown by the double
arrows in Fig. 10.
Fig. 11 shows the crack density as a function of strain and the
evolution of crack propagation for hot dip 55 wt% Al-Zn coating tensile
tested at 900 °C. Coating cracking represented the cracks formed and
propagated in the Fe2Al5Znx (Zn), or Fe2Al5Znx (FeAl, Zn) outer layer,
whereas interface cracking was associated with the cracks developed in
the FeAl inner layer. Both the population density of coating cracking
and interface cracking increased with increasing engineering strains
regardless of the heating rate. The population density of coating
cracking was larger than that of interface cracking for the samples
heated at 5 K/s and 10 K/s. In contrast, the sample heated at 20 K/s had
a comparable population density of coating cracking and interface
cracking. Moreover, the sample heated at 5 K/s had the largest popu-
lation density of coating cracking and interface cracking. As shown in
Table 4, the sample heated at 5 K/s has the thinnest FeAl layer. It is thus
likely that the intensive cracking of the sample heated at 5 K/s to 900 °C
is due to the presence of brittle Fe2Al5Znx layer underlying which the
relatively ductile FeAl layer is thinnest. Since the thermal history
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Applied Surface Science 511 (2020) 145550
employed for this present study allows a longer period of soaking at
900 °C for the sample heated at a higher heating rate, the formation and
growth of ductile FeAl phase will be promoted at higher heating rates.
Therefore, the sample heated at 20 K/s undergoes least cracking during
tensile testing at 900 °C. As a result, the prevalence in alloying reaction
occurring at higher heating rates prior to soaking can reduce de-
bonding, which, in turn, decreases the susceptibility of powdering.
Golem et al. [64] studied the effect of austenitization parameters on the
fracture behaviors of Al-10 wt% Si coating on PHS by using smooth-
sided tensile testing, DENT testing, and free bending testing, including
austenitization temperature and treatment time. They found that at the
same austenitization temperature, a longer holding time caused the
coarsening of prior austenite grains, and more importantly, the growth
of the alloying layer. Moreover, a full austenitization treatment occur-
ring at high temperature or long holding time promoted brittle fracture
behaviors arising from the Fe-Al alloy layer. This is because the Fe-Al
alloy layer is more brittle compared to the PHS substrate.
The fact that the austenitization parameters affect the fracture be-
haviors can be explained via the evolution of the various Fe-Al phases
during the austenitization treatment. In this present study, a higher
heating rate corresponds to a longer isothermal soaking time when the
total heat treatment time is fixed. Under this circumstance, a thicker
FeAl inner layer forms due to larger extents of Fe/Al interdiffusion.
Table 5 lists the mechanical properties of Fe2Al5 and FeAl phases
[65–71]. The fracture toughness of Fe2Al5 is 1.2 MPa m1/2, which is
lower than that of FeAl ~ 26 MPa m1/2 measured in room temperature
[66–68]. Windmann et al. [68] studied the mechanical properties of
Fe2Al5 and FeAl by using wear test and high-temperature hardness
measurement. They concluded that Fe2Al5 has lower fracture toughness
than FeAl, but has higher hardness than FeAl even at high temperature.
They also showed that at higher temperature, the FeAl phase grew and
improved the abrasive wear resistance and coating adhesion. The
sample heated at 20 K/s has the thickest FeAl inner layer (Table 4) and
the least population density of both coating cracking and interface
cracking (Fig. 11). Apparently, the formation of relatively ductile FeAl
as an interlayer between the brittle Fe2Al5Znx (FeAl, Zn) outer layer and
the ductile austenite substrate reduces cracking of the alloy layer. This
is beneficial for reducing the susceptibility of powdering. However,
crack opening of the relatively ductile FeAl inner layer expands with
J.-K. Chang, et al.
Fig. 9. The cross-sectional SEM micrographs of hot dip 55 wt% Al-Zn coating heated to 900 °C at 5 K/s and 20 K/s, hold at 900 °C for a total heat treatment time of
5 min, and tensile deformed to a specific engineering strain.
continued tensile deformation, which causes exposure and oxidation of
the austenite substrate. This is different from the results made on hot
dip Zn coated PHS showing that a higher heating rate prior to soaking
leads to the formation of a thin Al2O3 layer, which effectively inhibits
the oxidation of the PHS substrate [72].
4. Conclusions
The cracking behaviors of hot dip 55 wt% Al-Zn coating during the
tensile test at 900 °C were studied, with emphasis on the effect of
heating rate prior to isothermal deformation. Several key findings are
summarized as the following:
(1) When the hot dip 55 wt% Al-Zn coating was heated at 10 K/s to
900 °C, an Fe2Al5Znx layer formed between the remnant Al-Zn
coating and the steel substrate. The Fe2Al5Znx layer displayed a
columnar grain structure with [0 0 1] preferred orientation.
Branch-like FeAl3 grains were also observed in the remnant Al-Zn
coating layer.
(2) Further soaking at 900 °C resulted in the growth of Fe2Al5Znx layer
at the expense of Al-Zn coating; meanwhile, FeAl phase evolved at
the interface between the Fe2Al5Znx layer and the steel substrate, as
well as the grain boundaries of Fe2Al5Znx. Zn was present as solutes
in Fe2Al5Znx and FeAl phases with a larger solubility in Fe2Al5Znx.
8
Applied Surface Science 511 (2020) 145550
The Zn, which was expelled during phase transformation, presented
as metallic Zn mainly residing along the grain boundaries of
Fe2Al5Znx.
(3) For the thermal history studied, a higher heating rate was asso-
ciated with a longer isothermal holding time for austenitization.
The hot dip 55 wt% Al-Zn coating heated at 20 K/s had the thickest
FeAl layer. This is because a longer isothermal holding time pro-
moted the extent of Fe/Al interdiffusion.
(4) During tensile deformation at 900 °C, cracking was observed solely
in the alloy coating. Compared to the various Fe-Al intermetallic
phases, the austenite is ductile. Moreover, cracks developed and
propagated in Fe2Al5Znx (FeAl, Zn) outer layer during the initial
stages of tensile deformation. With continued deformation, cracks
formed in the FeAl inner layer and their propagation were confined
inside the FeAl inner layer, but cracks in the Fe2Al5Znx (FeAl, Zn)
outer layer had penetrated to the FeAl inner layer. With increasing
tensile strains, the width of crack opening extended in both the
Fe2Al5Znx (FeAl, Zn) outer layer and FeAl inner layer. Finally,
cracking in the FeAl inner layer resulted in the exposure of the steel
substrate, which underwent further oxidation.
(5) More complete austenitization, such as a higher heating rate at a
fixed time for the austenitization heat treatment, resulted in a
thicker FeAl inner layer. Such a thicker FeAl inner layer was ad-
herent to the Fe2Al5Znx (FeAl, Zn) outer layer after the sample was
J.-K. Chang, et al. Applied Surface Science 511 (2020) 145550

Fig. 10. The surface morphology and fracture surface of hot dip 55 wt% Al-Zn coaitng heated to 900 °C at different heating rates and subjected to tensile deformation
to the fracutre of the sample.

Fig. 11. The evolution of the crack population

density of coating cracking and interface
cracking of hot dip 55 wt% Al-Zn coating after
5 min heat treatment via different heatig rates
and during isothermal tensile deformation of
various strains. The schematic diagram shows
the types of coating cracking and interface
cracking, which are marked by the long-dashed
square and short-dashed square, respectively.

Table 5
The melting point and mechanical properties of FeAl and Fe2Al5 phases [65–71].
Fe-Al phase Melting point (°C) [65] Hardness (HV)* [66–68] Fracture toughness (MPa m0.5) [69,70] Young’s modulus (GPa)** [69,71]

Fe2Al5 1171 950–1100 1.2 240

FeAl 1215 450–520 25 260

* Note: measured by Vickers hardness, test force of 50 gf.

** Measured by nanoindentation.

deformed to fracture. This is beneficial for reducing the suscept-
ibility to powdering during hot stamping.
CRediT authorship contribution statement
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.

Jun-Kai Chang: Investigation, Writing - original draft. Chao-Sung

Lin: Supervision. Woei-Ren Wang: Investigation, Resources. Shun-Yi Acknowledgements
Jian: Visualization.
This study was supported by the Ministry of Science and

9
J.-K. Chang, et al. Applied Surface Science 511 (2020) 145550

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