Microstructural Evaluation and Property Change

of 5 Wt Pct Al-Zn Coating on Press Hardening Steel

During Austenitization
JUN-KAI CHANG, CHAO-SUNG LIN, WOEI-REN WANG, and WEI-JEN CHENG

Microstructural evolution of a 5 wt pct Al-Zn coating on press hardening steel was studied in
comparison to hot-dip galvanized (GI) and galvannealed (GA) coatings. The results show that
the presence of 5 wt pct Al effectively suppresses oxidation during austenitization; meanwhile,
the presence of Fe resulting from galvannealing accelerates oxidation. Alloying with Al or Fe in
the coating prior to austenitization reduces the susceptibility to liquid metal embrittlement
(LME). The presence of Al in the as-coated Zn coating enhances the corrosion resistance in HCl
solution and reduces the cathodic kinetics in NaCl solution. However, for sacrificial protection,
the austenitized GI steel outperforms the other austenitized-coated steels. Nevertheless, the 5
wt pct Al-Zn coating exhibits better overall performance including high-temperature oxidation
resistance, less LME susceptibility, and cathodic protection.

https://doi.org/10.1007/s11661-018-4694-0
 The Minerals, Metals & Materials Society and ASM International 2018

I. INTRODUCTION decarburization occur.[12–14] Therefore, surface modifi-

cation to form a protective coating is essential for press
ADVANCED high-strength steels (AHSS), including hardening steel.
dual-phase steel, twinning-induced plasticity steel, com- Hot-dip aluminizing and galvanizing are commonly
plex phase steel, and martensitic ultrahigh-strength steel employed to fabricate corrosion protective coatings on
(MART steel), have found many applications in the sheet steels.[14–16] Al-10 wt pct Si coating is the widely
automobile industry for developing lightweight vehicles used coating on press hardening steel and has been
to meet demands of reduction in fuel consumption and patented as Usibor by ArcelorMittal Corporation.[17]
carbon dioxide emissions.[1–4] Specifically, the AHSS This coating can withstand oxidation and decarburiza-
sheets are applied in car cage parts, such as body-pillars, tion during the austenitization treatment via the forma-
bumpers, door beams, as well as roof rails, and tion of an Al2O3 layer.[17–19] Although the coating
passenger survival in crash events is better ensured.[5] formed after hot stamping offers barrier protection, it
Hot stamping process is used to fabricate MART steel only imparts limited sacrificial protection afforded by
parts to avoid springback associated with the conven- the resulting Fe-Al intermetallic phases.[20] The protec-
tional cold forming technology.[6,7] Press hardening tion of such a Fe-Al diffusion layer is not sufficient
steel, like MnB steel, has been increasingly used in the under harsh corrosion environments.[18–22]
automobile industry because its strength can be raised Zn-based coating on steel is known to provide both
from 400 MPa to 1500 ~ 1600 MPa after rapid cooling barrier protection and sacrificial protection.[14,23,24]
in the forming die.[8–13] Prior to press forming, the press However, the process temperature of austenitization is
hardening steel is generally heat treated at 880 ~ 950 C markedly higher than the melting point of Zn
for 3 ~ 10 minutes,[12,13] when severe oxidation and (419.5 C). The molten Zn layer suffers extensive oxi-
dation and evaporation.[25–27] The ZnO scale is evident
and deteriorates the resistance spot weldability of the
JUN-KAI CHANG and CHAO-SUNG LIN are with the steel parts.[14,28,29] Molten Zn(Fe) also quickly reacts
Department of Materials Science and Engineering, National Taiwan with the steel substrate, leading to the formation of
University, 1, Roosevelt Road, Section 4, Taipei 106, Taiwan. Contact Zn-saturated a-Fe [a-Fe(Zn)] and, if present, few
e-mail: [email protected] WOEI-REN WANG is with the Division of
Metallic Materials Research, Material and Chemical Research amounts of the Fe3Zn10 (C) phase. The Zn content of
Laboratories, Department of Additive Manufacturing Materials & the coating layer has been substantially reduced and the
Applications, Industrial Technology Research Institute, Tainan 709, sacrificial protection capability also decreases although
Taiwan. WEI-JEN CHENG is with the Department of Iron & Steel the coating layer still offers barrier protection.[17,25,26]
Research and Development, China Steel Corporation, 1, Chung Kang
Road, Kaohsiung 820, Taiwan.
Moreover, molten Zn (usually with dissolved Fe)
Manuscript submitted September 27, 2017. contacting the steel substrate can cause liquid metal
Article published online May 31, 2018

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 49A, AUGUST 2018—3715

embrittlement (LME) as a press forming load is bath, hot dipping, and galvannealing process. For
applied.[14,30–33] example, GI represented the coating made in the Zn
The 55 wt pct Al-Zn-coated steel[34,35] and 5 wt pct bath containing 0.14 wt pct Al and rapidly cooled to
Al-Zn[36–38]-coated steel are known as Galvalume and room temperature and 5Al-GA represented the coating
Galfan, respectively. The eutectic structure composed made in the Zn bath containing 5 wt pct Al and
of Al-rich and Zn-rich phases enhances the corrosion galvannealed at 773 K (500 C) isothermally for 25 sec-
resistance compared to the pure Zn coating. Galval- onds. Figure 1 shows the full temperature history of the
ume and Galfan are thus widely applied for archi- hot dipping and galvannealing process, as well as the
tectural and constructional steel structures.[24,34–38] various specimens produced.
Recently, the oxidation and phase transformation of a To simulate the austenitization treatment during the
55 wt pct Al-Zn coating on low-carbon steel and press hot stamping process, the coated steel was heat treated
hardening steel have been studied to evaluate its at 1183 K (910 C) in an electric furnace for 5 minutes.
practicability as a protective coating for press hardening After the heat treatment, all steels were withdrawn and
steel.[39–41] It has been shown that the coating has immediately placed on a cast iron block, which had been
transformed to Fe-Al phases and the Zn content has sprayed with liquid nitrogen, to simulate the rapid
been markedly reduced with Zn remnant residing along cooing in hot stamping.
the Fe-Al grain boundaries or present as solid solute in A Gleeble 3500 thermal-mechanical process simulator
Fe-Al phases.[40,41] The LME is thus avoided; however, was employed for the elevated temperature tensile test
the sacrificial protection of the resultant alloy layer has under ambient atmosphere. Figure 2 shows the geom-
not been fully explored. The eutectic reaction of Zn-Al etry of the specimen for the tensile test at elevated
binary alloy system occurs approximately at 382 C and temperatures reprinted from the ASTM standard.[42,43]
5.1 wt pct Al. As a result, the Galfan coating is A high-temperature axial extensometer was equipped in
generally processed at temperatures lower than those the center of the specimen. The gauge length of the
for Galvalume coating. In this study, the microstruc- specimen was 25 mm. The specimen was heated at a rate
tural evolution of a 5 wt pct Al-Zn coating on press of 20 K s 1 to 1183 K (910 C) and soaked until a total
hardening steel with and without galvannealing at heating time of 5 minutes, when the specimen was pulled
500 C for 25 seconds during austenitization was inves- at a strain rate of 0.5 s 1 until the specimen had
tigated. The feasibility of the 5 wt pct Al-Zn coating as a fractured.
protective coating for press hardening steel was evalu-
ated and discussed in detail.
B. Microstructure Analyses
The crystallinity and phase of the coating and
corrosion products (oxides) were identified using X-ray
II. EXPERIMENTAL PROCEDURE Diffraction (XRD, Rigaku TTRAX 3) with monochro-
matic Cu-Ka (k = 1.54439 Å) radiation at 30 kV and
A. Materials
50 mA. The scanning speed was 4 deg min 1. The
The steel studied was commercial cold-rolled press crystallographica search-match 2.1 software was
hardening steel with thickness of 1.2 mm produced by employed to analyze the characteristic peaks and each
the China Steel Corporation (CSC), Kaohsiung, Tai- phase was identified using the PDF-2 database.[44]
wan. The chemical composition of the press hardening To prepare the cross-sectional specimen for scanning
steel can be found elsewhere[9] and is typical of 22MnB5 electron microscope (SEM) characterization, two small
steel. The hot-dip galvanized press hardening steel was pieces of the coated steel were glued face-to-face with an
prepared using a hot-dip simulator of the CSC. The steel G1 epoxy and cured on a hot plate at 473 K (200 C) for
strip was annealed at 1073 K (800 C) for 60 seconds 30 minutes. Cross-sectional slices were then cut by a
under N2-10 pct H2 atmosphere with a dew point of low-speed diamond saw and mechanically ground using
213 K ~ 203 K ( 60 C to 70 C). The steel strip SiC paper up to 4000 grit, followed by polishing using
was then cooled down to 743 K (470 C), isothermally diamond paste down to 0.5 lm. Field-emission gun
held for 30 s, and subsequently dipped into a molten Zn SEM (FEG-SEM, Nova Nano SEM 450) was used to
bath containing 0.14 wt pct Al and 5 wt pct Al, respec- characterize the microstructure of the coated steels first.
tively, at 723 K (450 C) for 3 seconds. After being The cross section was characterized using backscattered
withdrawn from the Zn bath, one coupon was cooled to electron (BSE) mode at 25 kV. Chemical composition of
room temperature at a cooling rate of approximately the coating and corrosion products was analyzed using
– 10 K s 1 using nitrogen gas, and denoted as the GI the energy dispersive spectrometry (EDS) equipping in
specimen because commercial hot-dip Zn coating is the FEG-SEM. For the detailed element distribution on
commonly recognized as GI coating. The other one was the diffusion layer formed after austenitization, an
consecutively heated up to 773 K (500 C), isothermally electron probe X-ray microanalyzer (EPMA, JEOL
held for 25 seconds, then cooled down to room temper- JXA-8200) was also used to analyze the chemical
ature at – 10 K s 1 using nitrogen gas. This was denoted composition distribution by mapping at 15 kV and
as the GA specimen, where the GA stands for the 5 9 10 8 A.
galvannealing process employed in the industry to The cross-sectional transmission electron microscope
transform the pure Zn coating to a Fe-Zn alloy coating. (TEM) specimen was extracted from the panel using the
The specimen was denoted according to the type of Zn focused ion beam technique (FIB, FEI Helios 600i). The

3716—VOLUME 49A, AUGUST 2018 METALLURGICAL AND MATERIALS TRANSACTIONS A

Fig. 1—The temperature history of hot-dip galvanizing/galvannealing process and the various specimens studied.

Fig. 2—The geometry of the specimen for tensile test at elevated

temperatures (in accordance with the ASTM E8/E8M standard[43]).

characterization of the oxide layer was carried out using

a field-emission TEM (FE-TEM, FEI Tecnai G2 F20)
operating at 200 kV and the attached EDS.
An X-ray photoelectron spectroscope (XPS, AVG
Thermo K-Alpha) with an Al Ka monochromatic X-ray
Fig. 3—XRD patterns of the as-coated press hardening steels.
source was used for further studying the composition
and valence state of the surface oxide scale. The depth
profile was also obtained using argon sputtering at an electrodes, respectively. The polarization curve was
area of approximately 2 9 1 mm2. A total depth of measured by sweeping the potential from 250 to
approximately 200 nm was recorded in reference to an 500 mV relative to the open circuit potential (OCP) at a
etching rate of 0.31 nm s 1 for SiO2. scan rate of 0.167 mV s 1 after the steady OCP of the
tested specimen was reached, namely the potential
vibration was less than 5 mV over a time period of
C. Electrochemical Measurements 300 seconds.
The corrosion behavior of the coated press hardening
steel before and after austenitization was first evaluated
using an electrochemical stripping method. The test was III. RESULTS
performed via a PARSTAT 4000 potentiostat/galvanos-
tat using a conventional three-electrode cell in 4 wt pct A. Microstructure of the Coating Before Austenitization
HCl solution at 298 K (25 C).[45] The corrosion resis- Figure 3 shows the XRD patterns of the various
tance was further studied using potentiodynamic polar- as-coated steels. The GI coating was mainly composed
ization experiments in 0.1 M NaCl solution at 298 K of the Zn terminal solid solution (g-Zn phase); whereas
(25 C). The coated steel with an exposure area of the GA coating consisted of the FeZn10 (d-FeZn10
1.77 cm2 was employed as the working electrode, and a phase) as the major phase and the Fe3Zn10 (C-Fe3Zn10
platinum plate of 16 cm2 and a saturated calomel phase) as a minor phase, which results from the
electrode (SCE) were used as the counter and reference interdiffusion of Fe and Zn during galvannealing. All

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 49A, AUGUST 2018—3717

the peaks of the 5Al-GI coating can be identified to (Figure 4(a)). Similar result of the formation of a Fe-Al
result from the g phase. The peaks associated with the layer as an inhibition layer on commercial GI steel has
Al were not readily discerned and accurately identified. been well documented in the literature.[23,24,47,48] The
This is because there is a eutectic point at approximately GA coating was composed of Zn and Fe, with a slightly
5.1 wt pct Al and the Al terminal solid solution can higher Fe at the coating/substrate interface. This is
contain up to 83.1 wt pct Zn.[46] The presence of large consistent with the XRD results showing the presence of
amounts of Zn as a solute in the Al lattice can largely C-Fe3Zn10 phase as a minor phase in the GA coating
shift the diffraction angles of the Al solid solution. The (Figure 3). Moreover, the Al content was scanty in the
diffraction pattern of the 5Al-GA coating was identical coating and detected predominantly near the surface of
to that of the GA coating. Both were composed of the the coating. The cross section of the 5Al-GI coating
d-FeZn10 and C-Fe3Zn10 phases formed via the Fe-Zn displayed two distinct regions, including oval and
interdiffusion. The SEM/EDS analyses found that the lamellar structures. The element mappings further
Fe content of the GA and 5Al-GA coatings was revealed that the oval structure was the primary g-Zn
12.43 wt pct and 11.76 wt pct, respectively. This is phase and the lamellar structure was the g-Zn and b-Al
consistent with the results that both coatings are eutectic structure.[24,46] Moreover, a higher Al intensity
composed of the d-FeZn10 and C-Fe3Zn10 phases. was observed at the interface between the coating and
Figure 4 shows the cross-sectional characterization of substrate, indicating the presence of Fe-Al phases at the
the as-coated press hardening steels. The thickness of interface. Again, the element mapping result of the
each coating was reported as the average of ten 5Al-GA coating was similar to those of the GA coating,
measurements on three SEM micrographs. The average showing that the constituents of the coating were the
thickness of both the GI and 5Al-GI coatings was d-FeZn10 and C-Fe3Zn10 intermetallic phases. However,
12 ± 1.5 lm; meanwhile, that of the GA and 5Al-GA discrete Fe-Al patches were observed on the surface of
coatings was 15 ± 2 lm. The slightly larger thickness of the 5Al-GA coating, but not on the GA coating.
the GA and 5Al-GA coatings compared to the GI and
5Al-GI coatings is due to the Fe-Zn interdiffusion
B. Microstructure of the Coating After Austenitization
occurring during galvannealing.[24] The element map-
ping results show that the GI coating was mainly the To study the microstructural evolution during austen-
g-Zn phase and the Al signal was solely detected at the itization, the coated steels were heat treated at 1183 K
interface between the coating and the steel substrate (910 C) for 5 minutes. The XRD patterns show that

Fig. 4—SEM micrograph and EPMA mapping of the as-coated press hardening steels: (a) GI, (b) GA, (c) 5Al-GI, and (d) 5Al-GA.

3718—VOLUME 49A, AUGUST 2018 METALLURGICAL AND MATERIALS TRANSACTIONS A

except the 5Al-GI coating, the GI, GA, and 5Al-GA substitute of Fe by Zn, signifying that up to 46 wt pct
coatings had suffered severe oxidation, as evident from Zn can dissolve in a-Fe at 1055 K (782 C) correspond-
the obvious peaks of ZnO (Figure 5). Specifically, the ing to the a-Fe(Zn) + molten Zn peritectic reaction, but
austenitized GA steel had the highest relatively intensity the solubility of Zn in a-Fe decreases with increasing
of ZnO peaks, followed by the austenitized GI and temperatures exceeding 1055 K (782 C).[24] The
5Al-GA steels. a-Fe(Zn) in the present study has a Zn content markedly
In addition to Zn oxides, both the Zn-containing a-Fe larger than the solubility of the a-Fe(Zn) at room
[a-Fe(Zn)] and C-Fe3Zn10 phase were present in the temperature found in the Zn-Fe phase diagram, as will
alloy layer of the austenitized GI steel, whereas only be shown later in Table I. As a result, the a-Fe(Zn)
a-Fe(Zn) was present in that of the austenitized GA present in the austenitized Zn- and Zn-5Al-coated press
steel. The diffraction peaks of the a-Fe(Zn) can be hardening steels is metastable and can have a lattice
identified as a bcc structure, but shifted to smaller 2h constant larger than the stable counterpart existing in
values compared to those of the a-Fe. The lattice the phase diagram. This is consistent with the literatures
constant of the a-Fe(Zn) was calculated to be approx- showing that the metastable Zn-containing a-Fe pre-
imately 0.2914 nm for the austenitized GA, 5Al-GI, and pared by electroplating[51] and ball milling[52] (the
5Al-GA steels, as well as 0.2939 nm for the austenitized Fe—30 at. pct Zn alloy in Reference 52) has a lattice
GI steel, which corresponds to 1.67 and 2.55 pct larger constant larger than 0.2866 nm (the lattice constant of
than the lattice constant of the a-Fe. This is consistent a-Fe at room temperature).
with the fact that Zn has an atomic size larger than Figure 6 shows the overall cross-sectional microstruc-
Fe.[48] The shift of diffraction angles of the a-Fe(Zn) to ture of the various coated steels after austenitization at
smaller values was also noticed for austenitized GI 1183 K (910 C) for 5 minutes, illustrating the general
22MnB5 and Zn-Ni-electroplated 22MnB5 steels.[49] morphology of the surface oxide scale. The oxide scale
Mörtlbaueret et al. used in situ XRD to characterize was continuous on the austenitized GA steel; however,
the phase evolution of a GI steel during press hardening that on the austenitized GI steel had broken fragments
and found that the Zn-containing a-Fe formed at (Figures 6(a) and (b)). This is consistent with the results
1073 K and 1173 K (800 C and 900 C) exhibits a made by other researchers.[14,25,26,53] Conversely,
bcc structure with a lattice constant of 0.2963 nm.[50] insignificant oxidation was observed on the austenitized
Moreover, the thermal expansion is compensated by the 5Al-GI steel (Figure 6(c)). A discontinuous oxide layer
was observed on the austenitized 5Al-GA steel and was
thinner than on the austenitized GA steel, as evident by
comparing Figures 6(b) through (d). This indicates that
the presence of Al in the Zn coating has positive effect
on high-temperature oxidation resistance.
Figure 7 shows the detailed cross-sectional SEM and
EPMA characterizations of the coated steels after
austenitization. The alloy layer is denoted as the
diffusion layer herein to emphasize its formation via
extensive interdiffusion during austenitization. A con-
tinuous oxide layer (presumably ZnO) was observed on
the GI and GA steels after austenitization, as marked by
the arrows in Figures 7(a) and (b). The oxide layer on
the austenitized GA steel was evidently thicker than that
on the austenitized GI steel, consistent with the XRD
results. Moreover, the former adhered to the underlying
diffusion layer more completely than the latter, as
evident from the presence of gaps marked by the double
arrows in Figure 7(a). Instead of a continuous oxide
Fig. 5—XRD patterns of the coated press hardening steels after 5 layer, patches of particles were observed on the austen-
min of austenitization at 1183 K (910 C). itized 5Al-GA steel. EPMA mapping further revealed

Table I. Thickness and EPMA/WDS Analysis of the Diffusion Layer on the Coated Press Hardening Steels After Austenitization

Element Content (Weight Percent)

Sample Diffusion Layer Thickness (lm) Zn Al Fe Phase

GI 20.8 ± 1.2 70.40 ± 0.15 0.15 ± 0.03 29.45 ± 0.20 C-Fe3Zn10
34.01 ± 0.17 0.08 ± 0.01 65.91 ± 0.25 a-Fe(Zn)
GA 17.0 ± 1.5 29.18 ± 0.13 0.03 ± 0.01 70.81 ± 0.10 a-Fe(Zn)
5Al-GI 27.7 ± 1.1 29.90 ± 0.10 0.68 ± 0.12 69.42 ± 0.22 a-Fe(Zn)
5Al-GA 17.2 ± 1.8 29.42 ± 0.16 0.53 ± 0.05 70.05 ± 0.25 a-Fe(Zn)

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 49A, AUGUST 2018—3719

Fig. 6—Cross-sectional SEM micrograph at low magnifications of the coated press hardening steel after austenitization at 1183 K (910 C) for 5
min: (a) GI, (b) GA, (c) 5Al-GI, and (d) 5Al-GA. Note the red arrows indicate the oxide layer.

Fig. 7—SEM micrograph and EPMA mapping of the coated press hardening steels after 5 min of heating at 1183 K (910 C): (a) GI, (b) GA,
(c) 5Al-GI, and (d) 5Al-GA.

3720—VOLUME 49A, AUGUST 2018 METALLURGICAL AND MATERIALS TRANSACTIONS A

Fig. 8—The XPS depth profile of the coated press hardening steels after 5 min of heating at 1183 K (910 C): (a) GI, (b) GA, (c) 5Al-GI, and
(d) 5Al-GA.

the presence of ZnO patch (marked as the arrow in phase, and 34 wt pct Zn in a-Fe(Zn) in consistence with
Figure 7(d)), Fe-Al particles covering with an Al oxide the coexistence of the a-Fe(Zn) and C-Fe3Zn10 (the
layer (marked as the double arrows in Figure 7(d)), and XRD results in Figure 5). Moreover, the presence of
a discontinuous, thin Al oxide layer. Table I summarizes 5 wt pct Al in the coating markedly reduced the extent
the thickness and WDS composition of the individual of oxidation; thereby, more a-Fe(Zn) was retained after
Fe-Zn phase in the diffusion layer. It can be seen from austenitization.
Table I that (1) the thickness of the diffusion layer XPS was further employed to study the composition
increased with the presence of Al and the absence of Fe of the surface layer down to a depth of approximately
in the coating prior to austenitization; (2) the amount of 200 nm of the coated steel after austenitization
Zn in the diffusion layer, which can be approximately (Figure 8). The 200-nm-thick surface layer of the
estimated as the average Zn content multiplying the austenitized GI and 5Al-GA steels comprised, in the
thickness of the diffusion layer, also increased with the decreasing order, ZnO, Al2O3, and Fe3O4 (Figures 8(a)
presence of Al and the absence of Fe in the coating prior and (d)). The surface layer of the austenitized GA steel
to austenitization; (3) the Al was absent in the austen- was mainly composed of ZnO (Figure 8(b)). Conversely,
itized GI- and GA-coated steels; (4) the Al in the the austenitized 5Al-GI steel consisted of Al2O3 as the
diffusion layer was scant compared to the coating before major phase and ZnO as a minor phase. Moreover, at
austenitization. The diffusion layer of the austenitized 100 nm down to the surface of the austenitized 5Al-GI
GI steel contained around 70 wt pct Zn in C-Fe3Zn10 steel, a rapid increase in the Fe content was detected.

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 49A, AUGUST 2018—3721

 Fig. 10—Stress–strain curves of the bare and coated press hardening
steels tested at 1183 K (910 C).

thus beneficial in industrial implementations in terms of

the necessary surface pretreatment prior to resistance
spot welding.[28,29,54]

C. High-Temperature Tensile Test

Fig. 9—(a) A cross-sectional TEM micrograph and (b) the line Figure 10 shows the stress–strain curves of bare press
scanning results marked as the red arrow in (a) of the 5Al-GI steel hardening steel, and GI, GA, 5Al-GI, as well as 5Al-GA
after 5 min of austenitization at 1183 K (910 C).
press hardening steels tested at 1183 K (910 C) after a
total heating time of 5 minutes. The ultimate tensile
This indicates that the a-Fe(Zn) was present at around strength (UTS) and elongation of the bare press
100 nm down the surface. As a result, the oxide layer on hardening steel were approximately 120 MPa and 0.3,
the austenitized 5Al-GI steel was relatively thin, which is respectively. An obvious decrease in both the UTS and
in good consistence with the results of XRD, SEM, and elongation was observed for the GI steel. In contrast,
EPMA. A close investigation of the results in Figure 8 the GA, 5Al-GI, and 5Al-GA press hardening steels had
shows that (1) the presence of Al in the coating comparable UTS and slightly larger elongation com-
contributed to the formation of Al2O3 in the surface pared to the bare press hardening steel. As a result, the
layer; (2) the presence of Fe in the coating resulting from GI steel was prone to the LME, the other three coated
galvannealing reduced the amounts of Al2O3 in the steels were not.
surface layer; and (3) 5 wt pct Al in the Zn coating
without Fe was sufficient to ameliorate the severe
oxidation of the coating via the formation of a thin, D. Electrochemical Tests
continuous Al2O3 layer. Sacrificial protection of Zn-based coating on steel is
Figure 9 shows the cross-sectional TEM characteri- generally evaluated by the difference in the corrosion
zation of the 5Al-GI steel after austenitization. The potential of the coating and the steel substrate. Chem-
surface oxide layer was approximately 100 nm thick ical stripping test[45,54–56] was thus used to measure the
(Figure 9(a)). The EDS line scan across the surface potential difference between the coating and the sub-
oxide layer further confirmed that the oxide layer was strate in 4 wt pct HCl solution at 298 K (25 C),[45] as
mainly composed of Al2O3 with few ZnO (Figure 9(b)). shown in Figures 11(a) and (b) for the coated press
Moreover, the alloy layer right beneath the Al2O3 layer hardening steel before and after austenitization, respec-
was the a-Fe(Zn). Both the TEM and XPS results tively. Following a sharp increase in the potential upon
confirm the presence of approximately 100-nm-thick immersion, the potential of both the GI and 5Al-GI
Al2O3 with small amounts of ZnO on the surface of steels reached a plateau at 1.06 VSCE, which is a
austenitized 5Al-GI steel, signifying the effectiveness in characteristic of the chemical reactivity of Zn in HCl
preventing oxidation during austenitization. Oxide solution. The plateau potential lasted for 400 and
scales are commonly seen in hot-stamped parts made 2200 seconds for the GI and 5Al-GI steels, respectively.
of bare press hardening steels and those with commer- This is consistent with the results commonly seen in the
cial GI and GA coatings.[14,17] Thick oxide scales literature showing that the presence of Al in Zn coatings
generally deteriorate the resistance spot weldability enhances the corrosion resistance of the coating.[36–38]
and thus should be removed using sandblasting.[14] The potential then exhibited a sharp increase and
The thin oxide layer on the austenitized 5Al-GI steel is reached a second plateau at 0.5 VSCE associated with

3722—VOLUME 49A, AUGUST 2018 METALLURGICAL AND MATERIALS TRANSACTIONS A

Fig. 11—Potential evolution of (a) the as-coated press hardening steels and (b) the coated press hardening steels after austenitization measured in
4 wt pct HCl solution at 298 K (25 C).

the steel substrate when the coating had been completely the C-Fe3Zn10 phase did not complete during rapid
removed. As for the GA and 5Al-GA steels, the cooling for press hardening steel. At lower temperatures,
potential rose rapidly during the early stages of immer- the remnant Zn(Fe) melt can react with the C-Fe3Zn10
sion and soon reached the plateau potential of the steel phase to form the d-FeZn10 phase.[27] This agrees with
substrate compared to the GI and 5Al-GI steels. The the corrosion potential of the C-Fe3Zn10 and d-FeZn10
elapsed time reaching the exposure of the steel substrate phases measured in 100 g L 1 ZnSO4 and 200 g L 1
increased in the order of GA, 5Al-GA, GI, and 5Al-GI NaCl solution, i.e., 0.77 VSCE and 0.82 VSCE,
steels, indicating that (1) the presence of Al in the respectively.[54] Moreover, up to the intermediate stages
coating is beneficial for the corrosion resistance in HCl of immersion, the potential of the austenitized GI steel
solution; (2) the alloying with Fe deteriorates the was more negative to that of the other three austenitized
corrosion resistance in HCl solution; (3) the beneficial coated steels. This correlates to the existence of the
effect of Al is largely offset by the presence of Fe in the C-Fe3Zn10 phase in between the a-Fe(Zn) grains. As a
Zn-based coatings. result, the chemical stripping can be a quick, feasible
After austenitization, the potential of the coated steels method to evaluate whether or not the C-Fe3Zn10 phase
also evolved from a minimum value upon immersion in coexists with the a-Fe(Zn). This is important because the
4 wt pct HCl solution at 298 K (25 C) except for the presence of C-Fe3Zn10 phase is indicative of the exis-
austenitized GA steel. The potential of the austenitized tence of liquid Zn(Fe) phase during hot stamping, which
GA steel declined sharply upon immersion, reached a is one of the prerequisites causing the LME.[14,30–33,57,58]
lowest point, and rapidly rose again. This initial Nevertheless, the C-Fe3Zn10 and d-FeZn10 phases have
decrease in the potential is apparently due to the corrosion potentials negative to the steel substrate,
removal of surface oxides, which agrees with the result which is essential for the cathodic protection afforded by
that the austenitized GA steel had a thickest oxide layer the diffusion layer.
among the coated steels studied (Figures 7 and 8). A close comparison of the curves in Figure 11(b)
Moreover, the minimum potential increased (shifted in shows that (1) before reaching the plateau potential of
the positive direction) in order the of GI, GA, 5Al-GI, the steel substrate, the presence of Al in the coating
and 5Al-GA steels, as shown in the inset in Figure 11(b). shifted the potential along the positive direction and (2)
Following the minimum potential, the potential the alloying with Fe in the coating prior to austenitiza-
increased when chemically more active elements were tion also shifted the potential along the positive direc-
oxidized and removed first. Finally, the potential tion and slightly elevated the plateau potential. A
reached the plateau potential of the steel substrate. comparison between Figures 11(a) and (b) further
The potential of the austenitized GI steel evolved from shows that (1) the austenitization treatment markedly
0.83 VSCE, which is similar to that of the as-coated reduced the elapsed time to reach the plateau potential;
GA and 5Al-GA steels (Figures 11(a) and (b)). Because (2) the austenitization treatment reduced the difference
the coating of the as-coated GA and 5Al-GA steels in the potential vs time curves of the various coated
consisted of the d-FeZn10 phase as the major overlay, steels.
the d phase was likely to be present on the surface of the The corrosion resistance of the various coated steels
austenitized GI steel. The formation of the C-Fe3Zn10 was further studied using the potentiodynamic polar-
phase and d-FeZn10 phase proceeds via a peritectic ization method in 0.1 M NaCl solution at 298 K (25 C)
reaction at 782 C and 665 C, respectively.[24] The (Figure 12 and Table II). All the coated steels had Ecorr
peritectic reaction of a-Fe(Zn) + Zn(Fe) melt to form more negative than the bare steel, indicating the

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 49A, AUGUST 2018—3723

cathodic protection of the Zn and 5Al-Zn coatings. For of the bare steel, but its anodic and cathodic kinetics
the GI and GA steels, alloying with Fe retarded the were slower compared to the bare steel. This can be
anodic kinetics, but had a slight effect on the cathodic associated with the relatively thick, compact oxide layer
kinetics (Figure 12(a)). As a result, the GA steel had a present on the surface of the austenitized GA steel. The
nobler Ecorr than the GI steel. A similar trend was also polarization curves were similar for the other three
observed for the comparison of 5Al-GI vs 5Al-GA coated steels and the cathodic kinetics increased in the
steels. In contrast, the presence of Al in the coating order of 5Al-GI, 5Al-GA, and GI steels. It is likely that
inhibited the cathodic kinetics, but hardly influenced the the presence of a thin, compact Al2O3/ZnO(minor) layer
anodic kinetics, leading to a negative shift in the Ecorr. retards the cathodic reaction, which is known to be the
This is consistent with the fact that the corrosion reduction of oxygen in non-deaerated NaCl solu-
products of Zn-Al coating are more effective in retard- tion.[62,63] Finally, a scrutiny of Table II reveals that
ing the diffusion of reaction species of the test solution (1) the austenitization treatment ennobled the Ecorr
(1 M NaCl solution), but is not effective against the regardless of the coating composition; (2) the cathodic
dissolution in Cl--containing solutions during anodic kinetics were largely governed by the presence of the
polarization.[59–61] compact oxide layer; (3) the anodic kinetics were
As for the coated steels after austenitization, the primarily related to the composition of the coating or
austenitized GA steel had the Ecorr comparable to that the diffusion layer.

Table II. Potentiodynamic Polarization Results of the

Coated Press Hardening Steels
IV. DISCUSSION
The high-regarded design philosophy for the protec-
Before Austenitization
tive coating on press hardening steel is that the coating
Sample Ecorr (mVSCE) Icorr (lA/cm2) should offer resistance against high-temperature oxida-
tion and decarburization while it does not cause the
Press Hardening Steel 698 3.07 LME during press forming. The resulting alloy layer
GI 1053 7.92 (diffusion layer) after press hardening should also
GA 880 8.08 provide sufficient corrosion protection, including the
5Al-GI 1158 3.52
barrier and sacrificial protections. Furthermore, the
5Al-GA 949 2.09
surface scale cannot impair the resistance spot weldabil-
After Austenitization ity of the press hardened steel parts. Under this design
paradigm, the Al-Si coating meets most of the require-
Sample Ecorr (mVSCE) Icorr (lA/cm2) ments except the sacrificial corrosion protection.
Zn-based coating has advantages over the Al-Si coating
Press Hardening Steel 630 11.39
GI 730 14.28 due to the sacrificial protection afforded by the chem-
GA 629 13.78 ically active Zn. However, the Zn-based coating has
5Al-GI 733 3.05 oxidation resistance markedly inferior to the Al-Si
5Al-GA 725 5.43 coating and tends to cause the LME due to the presence
of Zn(Fe) melt that subsequently solidifies to form
Fe-Zn intermetallic phases (mainly the C-Fe3Zn10

Fig. 12—Polarization curve of (a) the as-coated press hardening steels and (b) the coated press hardening steels after austenitization measured in
0.1 M NaCl solution at 298 K (25 C).

3724—VOLUME 49A, AUGUST 2018 METALLURGICAL AND MATERIALS TRANSACTIONS A

Fig. 13—Cross-sectional SEM micrograph and related EPMA/WDS element distributions of the different coated steels (a) GI, (b) GA, (c)
5Al-GI, and (d) 5Al-GA after 5 min of isothermal holding at 1183 K (910 C) and subsequent tensile deformation. Note: Fig. 12(c) is presented
at a higher magnification to show the presence of a thin Al2O3 layer.

phase). The applicability of Zn-based coatings is thus austenitization, the Fe-Al phase transforms to the Fe-Zn
dependent on how to balance the overall performance of phases following the reaction paths commonly seen in
the coating via the composition design and process commercial GA coatings.[24]
control. Compared to the GI coating, the presence of It is apparent that most of the Al diffuses to the
5 wt pct Al in the Zn coating on press hardening steel surface to form Al2O3; thereby, the reduction in Gibbs
influences the phase evolution during austenitization, free energy via the Al2O3 formation prevails in the
which, in turn, determines the properties of the coating, 5 wt pct Al-Zn melt during austenitization. According
as discussed below. to the high-temperature oxidation theory of alloys,[65]
the spontaneity of oxidation is governed by the Gibbs
formation energy of oxides and the rate of oxidation is
A. Phase Evolution
determined by diffusion of reacting species. For the
5 wt pct Al in the Zn bath is effective to inhibit the Zn-based alloy coatings of this present study, Fe, Al,
formation of the Fe-Zn intermetallic phases during hot and Zn are all prone to oxidation during austenitization
dipping. However, the 5 wt pct Al has little effect on the under ambient atmosphere. The Gibbs free energy of
transformation of the Fe-Al inhibition layer to the formation for ZnO, Al2O3, and Fe3O4 at 1183 K
Fe-Zn intermetallic phases during subsequent galvan- (910 C) is 217, 872, and 677 kJ mol 1, respec-
nealing and austenitization. This indicates that the tively.[66] As a result, both Al and Fe are more
reaction between molten Zn and steel substrate proceeds susceptible to oxidation than Zn. Moreover, Al2O3 is
rapidly in a thin molten Zn-5 wt pct Al layer. This is more protective against oxidation than Fe3O4 because
different from the 55 wt pct Al-Zn coating on 22MnB5 the Pilling Bedworth ratio of Al and Fe is 1.29 and 2.1,
steel in which a Fe-Al diffusion layer forms after respectively.[65] Therefore, the hot-dip galvannealed
austenitization.[40,41] coating suffered larger extents of oxidation than the
A possible transformation path of the 5 wt pct Al-Zn galvanized coating regardless of the Al content in the
coating on press hardening steel during austenitization is coating (Figures 6 and 7). The presence of Fe in the
thus proposed. During the rapid heating up to the coating is thus detrimental to the high-temperature
austenitization temperature, the 5 wt pct Al-Zn coating oxidation resistance of Zn(Al)-based coatings on steels.
melts down before sufficient Fe diffuses to the coating. This is consistent with the studies showing that unlike
The Al in the melt diffuses down the chemical potential, the compact Al2O3 layer, Fe oxide scale is porous and
largely to the surface to form Al2O3, and, to less extents, fails to provide effective barrier for further oxida-
to the interface to support the growth of the Fe-Al tion.[14,17] Finally, the presence of compact Al2O3 layer
phase. Because the Fe-Al phases are absent after is of great importance for suppressing the vaporization

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 49A, AUGUST 2018—3725

of Zn and the intensive formation of ZnO. Conse- studied (Figure 11(b)), which is attributed to the pres-
quently, the presence of 5 wt pct Al contributes to the ence of C-Fe3Zn10.[25,26,30,31]
reduction in the thickness of oxide scales, which is Galvannealing after hot-dip galvanizing increases the
essential to ensure the resistance spot weldability. Fe content of Zn coatings such as GA and 5Al-GA
coatings. As a result, both GA and 5Al-GA coatings
have Ecorr higher than GI and 5Al-GI counterparts. It
B. The Liquid Metal Embrittlement Behavior has been shown previously that alloying Zn coating with
The typical difference between the coated press Fe ennobles the Ecorr owing to the standard reduction
hardening steel suffering the LME from that not potential of Fe ( 0.440 V) is nobler than that of Zn
suffering the LME is the presence of obvious C-Fe3Zn10 ( 0.763 V) and Al ( 1.662 V).[49] After the austeni-
phase after press hardening. This LME phenomenon tization heat treatment, more Fe diffuse to the Zn
and mechanism on Zn-coated steels has been studied in coating, further increasing the Ecorr of Zn(Al)-coated
detail.[14,30–33] Compared to the GI press hardening steels. For the Icorr, the austenitization treatment results
steel, the presence of 5 wt pct Al in the coating reduces in an increase in the Icorr, except the austenitized 5Al-GI
the amount of the C-Fe3Zn10 phase after press harden- steel (Table II). Furthermore, passivation behaviors
ing. The molten Zn(Fe) in the steel is thus not sufficient were not observed in both the austenitized 5Al-GI and
to wet the grain boundaries of the a-Fe(Zn); thereby, the 5Al-GA-coated steels. Lee et al.[40,41] and Lin et al.[68,69]
LME problem is ameliorated. This is further confirmed found that the presence of Fe-Al intermetallic phases in
using the EPMA characterization on the cross sections the austenitized 55 wt pct Al-Zn coating and hot-dip
of the coated press hardening steels after high-temper- galvanized 5 wt pct Al-Zn and 55 wt pct Al-Zn coatings
ature tensile test (Figure 13). Cracks with sharp tips resulted in passivation in 5 wt pct NaCl solution. In this
propagated down to the steel substrate for the GI steel study, both the austenitized 5Al-GI and 5Al-GA alloy
(Figure 13(a)). In contrast, crack propagation was layer mainly comprise a-Fe(Zn); thereby, they do not
confined in the diffusion layer for the GA, 5Al-GI, exhibit passivation in 0.1 M NaCl solution. Therefore,
and 5Al-GA steels (Figures 13(b) through (d)). These for short-term corrosion resistance tested in 0.1 M NaCl
cracks exhibited a typical U shape, indicative of the solution, the austenitized 5Al-GI press hardening steel
absence in wetting of the a grain boundaries by molten outperforms the other three steels in terms of the
Zn(Fe). The beneficial effect of the presence of Al in smallest Icorr. The retarded cathodic kinetics in the
Zn-1.6 wt pct Mg coating on LME for press hardening austenitized 5Al-GI press hardening steel indicates that
steel is also noted by De Cooman et al.[67] However, in the presence of 5 wt pct Al in the coating can be
this present study it is not immediately clear as why the beneficial for the barrier corrosion protection of the
amount of the C-Fe3Zn10 phase is reduced when press hardening steel in 0.1 M NaCl solution.[70,71]
5 wt pct Al is present. Approximately 0.6 wt pct Al
dissolves in the diffusion layer of the 5Al-GI steel in
D. The Overall Performance
contrast to the GI steel in which the content of Al is
below the detectable limit of the WDS (Table I). Further Alloying the Zn coating with Fe or Al is beneficial for
studies are needed to elucidate the major role of the Al reducing the LME susceptibility. However, pre-heating,
in Zn(Fe) melt in the wetting behavior along the like galvannealing, to promote the Fe-Zn interdiffusion
austenite grain boundaries during austenitization, which causes severe oxidation during subsequent austenitiza-
is considered to be a crucial mechanism by which Al tion. Conversely, the addition of 5 wt pct Al in the molten
suppresses the Zn penetration.[67] Zn bath is effective to reduce oxidation during austeni-
tization. This ensures the resistance spot weldability of the
press hardened steel parts. Moreover, the austenitized
C. Corrosion Protection 5Al-GI press hardening steel has slower cathodic kinetics
Zn-based coating is known for barrier protection and than the austenitized GI press hardening steel. However,
sacrificial/cathodic protection over steels. All the Fe-Zn the austenitized GI press hardening steel tends to outper-
intermetallic phases and the a-Fe(Zn) have corrosion form in terms of cathodic protection.
potentials negative to the press hardening steel In conclusion, to design effective Zn-based coating for
(Figure 12). As a result, the as-coated coating layer hot stamping application, the key point is the regulation
and the diffusion layer all can provide cathodic protec- of the Al composition in Zn bath. The ideal coating
tion over the steel substrate.[17] However, the effective composition is that the initial coating has adequate Al
sacrificial protection on deep-drawing quality spe- so that a thin, compact Al2O3 layer can form on the
cial-killed steel (a type of low-carbon steel) has been surface. Meanwhile, the presence of Al together with
measured to be an imposed potential of 0.725 proper austenitization treatments can regulate the Fe/Zn
VSCE.[64] Moreover, the protection in distance increases interdiffusion to modulate the volume fraction of molten
with the difference in the corrosion potential of the Zn(Fe) in the a-Fe(Zn) to avoid the LME, yet still
coating and the steel substrate. Consequently, the reserve sufficient Zn content (mainly C-Fe3Zn10 phase
austenitized GI steel has the best cathodic protection and perhaps few d-FeZn10 phase) to act as cathodic
capacity among the four coated press hardening steels protection.

3726—VOLUME 49A, AUGUST 2018 METALLURGICAL AND MATERIALS TRANSACTIONS A

 V. CONCLUSIONS ACKNOWLEDGMENT
Phase evolution of GI, GA, 5Al-GI, and 5Al-GA- The authors are grateful to the Ministry of Science
coated press hardening steels during austenitization was and Technology, Taiwan, and China Steel Corpora-
studied. The influence of the resultant phase constituents tion, Kaohsiung, Taiwan, for their financial supports
and microstructure of the diffusion layer on the prop- under Grant MOST 104-2622-8-006-001.
erties of steels was detailed. The key findings are
summarized as follows:
1. Both the GA and 5Al-GA coatings consist of the REFERENCE
d-FeZn10 and C-Fe3Zn10 phases, signifying that the 1. R. Kuziak, R. Kawalla, and S. Waengler: Arch. Civil Mech. Eng.,
presence of 5 wt pct Al in the Zn bath has little 2008, vol. 8, pp. 103–17.
effect on the phase evolution of the Zn coating 2. O. Bouaziz, H. Zurob, and M. Huang: Steel Res. Int., 2013,
vol. 84, pp. 937–47.
during subsequent galvannealing at 500 C for 25 3. J. Galan Lopez, L. Samek, P. Verleysen, K. Verbeken, and Y.
seconds. Houbaert: Rev. Metall., 2012, vol. 48, pp. 118–31.
2. The diffusion layer resulting from austenitization is 4. O. Kwon, K.Y. Lee, G.S. Kim, and K.G. Chin: Mater. Sci.
mainly composed of the a-Fe(Zn) regardless of the Forum., 2010, vol. 638, pp. 136–41.
5. N. Abedrabbo, R. Mayer, A. Thompson, C. Salisbury, M.
presence of 5 wt pct Al in the Zn coating prior to Worswick, and I. Van Riemsdijk: Int. J. Impact Eng., 2009, vol. 36,
austenitization. Moreover, the XRD diffraction pp. 1044–57.
peaks of the C-Fe3Zn10 phase were observed in the 6. W. Gan, S. Babu, N. Kapustka, and R.H. Wagoner: Metall.
austenitized GI steel only. Mater. Trans. A, 2006, vol. 37A, pp. 3221–31.
3. A loose ZnO scale was observed on the austenitized 7. J. Lin, F. Li, J. Min, J. Jin, H. Gu, Y. Liu, W. Zhang, H. Zhan, Y.
Ji, and L. Li: Advanced High Strength Steel and Press Hardening.
GI and GA steel. In contrast, a 100-nm-thick Al2O3 Proc. 2nd Int. Conf., Changsha, China, 2016, pp. 3–7.
layer was observed on top of the diffusion layer of 8. M. Geiger, M. Merklein, and C. Hoff: Adv. Mater. Res., 2005,
the austenitized 5Al-GI steel. As a result, the vols. 6–8, pp. 795–804.
presence of 5 wt pct Al in the coating markedly 9. J.F. Tu, Y.T. Pan, C.Y. Huang, and S.H. Hsieh: China Steel Tech.
Rep., 2009, vol. 22, pp. 7–12.
suppresses the oxidation of the coating during 10. L. Garcia Aranda, Y. Chastel, J. Fernández Pascual, and T. Dal
austenitization via the formation of a thin, contin- Negro: Adv. Technol. Plast., 2002, vol. 2 (2002), pp. 1135–40.
uous Al2O3 layer. 11. G. Berglund: First International Conference on Hot Sheet Metal Forming
4. The austenitized GA steel suffers oxidation more of High Performance Steel, Kassel, Germany (2008), pp, 175–77.
severely than the austenitized GI steel. Similar trend 12. D.W. Fan, H.S. Kim, and B.C. De Cooman: Steel Res. Int., 2009,
vol. 80, pp. 241–48.
is also noticed for the austenitized 5Al-GA steel and 13. H. Karbasian and A.E. Tekkaya: J. Mater. Process. Technol.,
5Al-GI steels. Pre-alloying the Zn coating with Fe 2010, vol. 210, pp. 2103–18.
via galvannealing is thus detrimental to the 14. D.W. Fan and B.C. De Cooman: Steel Res. Int., 2012, vol. 83,
high-temperature oxidation resistance of the coat- pp. 412–33.
ing regardless of the Al content of the coating. 15. E. Almeida: Ind. Eng. Chem. Res., 2001, vol. 40, pp. 3–14.
16. E. Almeida: Ind. Eng. Chem. Res., 2001, vol. 40, pp. 15–20.
5. The LME was observed in the austenitized GI steel, 17. L. Dosdat, J. Petitjean, T. Vietoris, and O. Clauzeau: Steel Res.
but not in the austenitized GA, 5Al-GI, and 5Al-GA Int., 2011, vol. 82, pp. 726–33.
steels. The C-Fe3Zn10 phase present in the austeni- 18. D.W. Fan and B.C. De Cooman: ISIJ Int., 2010, vol. 50,
tized GI steel can cause the LME as it is present as pp. 1713–18.
19. M. Windmann, A. Röttger, and W. Theisen: Surf. Coat. Technol.,
molten Zn(Fe) during austenitization. Moreover, the 2014, vol. 246, pp. 17–25.
electrochemical stripping test in 4 wt pct HCl solu- 20. C. Allély, L. Dosdat, O. Clauzeau, K. Ogle, and P. Volovitch:
tion is able to detect whether or not the presence of Surf. Coat. Technol., 2014, vol. 238, pp. 188–96.
the C-Fe3Zn10 phase in the austenitized Zn- and 21. K. Uda, A. Azushima, and A. Yanagida: J. Mater. Process.
Technol., 2016, vol. 228, pp. 112–16.
5Al-Zn-coated press hardening steels. 22. Z.X. Gui, W.K. Liang, Y. Liu, and Y.S. Zhang: Mater. Des., 2014,
6. The electrochemical stripping of the coated steels in vol. 60, pp. 26–33.
4 wt pct HCl solution reveals that the presence of 23. J. Mackowiak and N. Short: Int. Met. Rev., 1979, vol. 24,
Al and the absence of Fe enhances the corrosion pp. 1–19.
resistance of the as-coated press hardening steels in 24. A. Marder: Prog. Mater. Sci., 2000, vol. 45, pp. 191–271.
25. R. Autengruber, G. Luckeneder, S. Kolnberger, J. Faderl, and
4 wt pct HCl. Moreover, the 5Al-GI and 5Al-GA A.W. Hassel: Steel Res. Int., 2012, vol. 83, pp. 1005–11.
coatings have smaller Icorr tested in 0.1 M NaCl 26. R. Autengruber, G. Luckeneder, and A.W. Hassel: Corros. Sci.,
solution than their GI and GA counterparts. 2012, vol. 63, pp. 12–19.
7. The austenitized GI press hardening steel has more 27. C.W. Lee, W.S. Choi, Y.R. Cho, and B.C. De Cooman: ISIJ Int.,
2014, vol. 54, pp. 2364–68.
negative potentials during stripping in 4 wt pct HCl 28. O.L. Ighodaro, E. Biro, and Y.N. Zhou: J. Mater. Process.
solution, which correlates to the presence of the Technol., 2016, vol. 236, pp. 64–72.
C-Fe3Zn10 in the diffusion layer. 29. C.W. Ji, I. Jo, H. Lee, I.D. Choi, Y. do Kim, and Y.D. Park: J.
8. The presence of 5 wt pct Al in the Zn coating is Mech. Sci. Technol., 2015, vol. 28, pp. 4761–69.
beneficial for the overall properties of the austen- 30. C.W. Lee, D.W. Fan, I.R. Sohn, S.J. Lee, and B.C. De Cooman:
Metall. Mater. Trans. A, 2012, vol. 43A, pp. 5122–27.
itized coated press hardening steels, including sup- 31. C.W. Lee, W.S. Choi, L. Cho, Y.R. Cho, and B.C. De Cooman:
pression in oxidation and LME during hot press ISIJ Int., 2015, vol. 55, pp. 264–71.
forming, as well as reduction in Icorr in 0.1 M NaCl 32. L. Cho, H. Kang, C. Lee, and B.C. De Cooman: Scripta Mater.,
solution. 2014, vols. 90–91, pp. 25–28.

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 49A, AUGUST 2018—3727

33. H. Kang, L. Cho, C. Lee, and B.C. De Cooman: Metall. Mater. 51. X. Hu and T. Watanabe: Nano Plating-Microstructure Formation
Trans. A, 2016, vol. 47A, pp. 2885–2905. Theory of Plated Films and a Database of Plated Films, 1st ed.,
34. J. Selverian, M. Notis, and A. Marder: J. Mater. Eng., 1987, vol. 9, Elsevier, Oxford, 2004, pp. 577–88.
pp. 133–40. 52. R. Bensalem, O. Guergueb, S. Alleg, A. Younes, S. Souilah, M.
35. Y.H. Leng, Y.L. Feng, and M. Song: Adv. Mater. Res., 2012, Bououdina, and J. Suñol: Proc. Int. Conf. Nanomater.: Appl.
vol. 415, pp. 276–80. Prop., 2013, vol. 2, pp. 02PCN12-01–02PCN12-04.
36. H. Fujsawa, R. Kaneko, and H. Ishikawa: JFE Tech. Rep., 2009, 53. V. Janik, Y. Lan, P. Beentjes, D. Norman, G. Hensen, and S.
vol. 14, pp. 41–45. Sridhar: Metall. Mater. Trans. A, 2015, vol. 47A, pp. 400–11.
37. S.F. Radtke and D.C. Herrschaft: J. Less-Common Met., 1982, 54. M. Tumuluru: Weld. J., 2007, vol. 86, pp. 161–69.
vol. 93, pp. 253–59. 55. H. Lee and D. Hiam: Corrosion, 1989, vol. 45, pp. 852–56.
38. F. Rosalbino, E. Angelini, D. Maccio, A. Saccone, and S. Delfino: 56. X. Zhang and I. Bravo: Corrosion, 1994, vol. 50, pp. 308–17.
Electrochim. Acta, 2007, vol. 52, pp. 7107–14. 57. M. Nicholas and C. Old: J. Mater. Sci., 1979, vol. 14, pp. 1–18.
39. B. Zhou, F. Jin, Q. Luo, Q. Li, and K.C. Chou: Adv. Mater. Res., 58. P. Fernandes and D. Jones: Int. Mater. Rev., 1997, vol. 42,
2011, vols. 399–401, pp. 1998–2003. pp. 251–61.
40. C.W. Lee and B.C. De Cooman: Metall. Mater. Trans. A, 2014, 59. E. Tada and Y. Miura: ISIJ Int., 2016, vol. 56, pp. 444–51.
vol. 45A, pp. 4499–4509. 60. T.H. Shen, C.Y. Tsai, and C.S. Lin: Surf. Coat. Technol., 2016,
41. C.W. Lee, W.S. Choi, Y.R. Cho, and B.C. De Cooman: Surf. vol. 306, pp. 455–61.
Coat. Technol., 2015, vol. 281, pp. 35–43. 61. W. Chen, Q. Liu, Q. Liu, L. Zhu, and L. Wang: J. Alloy Compd.,
42. ASTM E21: Standard Test Methods for Elevated Temperature 2008, vol. 459, pp. 261–66.
Tension Tests of Metallic Materials, ASTM International, 62. M.M. Sadawy: Am. J. Mater. Res., 2014, vol. 4, pp. 53–58.
Philadelphia, 2003. 63. J. Masalski, J. Gluszek, J. Zabrzeski, K. Nitsch, and P. Gluszek:
43. ASTM E8/E8M: Standard Test Methods for Tension Testing of Thin Solid Films, 1999, vol. 349, pp. 186–90.
Metallic Materials, ASTM International, Philadelphia, 2003. 64. M. Budinski and B. Wilde: Corrosion, 1987, vol. 43, pp. 60–62.
44. ICDD: PDF-2 2002 Database, International Centre for Diffraction 65. A.S. Khanna: Introduction to High Temperature Oxidation and
Data, Newtown Square, PA, 2002. Corrosion, ASM International, Materials Park, 2002, pp. 80–81,
45. J.K. Chang and C.S. Lin: Metall. Mater. Trans. A, 2017, vol. 48A, 109–34.
pp. 3734–44. 66. D.R. Gaskel: Introduction to the Thermodynamics of Materials,
_
46. M. Zelechower, J. Kliś, E. Augustyn, J. Grzonka, D. Stró_z, T. CRC Press, Boca Raton, FL, 2008, pp. 305–586.
Rzychoń, and H. Woźnica: Arch. Metall. Mater., 2012, vol. 57, 67. B. C. De Cooman, W. Jung, K. R. Jo, D. H. Sulistiyo, L. Cho:
pp. 517–23. Galvatech 2017 Conf., Tokyo, Japan, 2017, pp. 790–95.
47. S. Shibli, B. Meena, and R. Remya: Surf. Coat. Technol., 2015, 68. K.L. Lin, C.F. Yang, and J.T. Lee: Corrosion, 1991, vol. 47,
vol. 262, pp. 210–15. pp. 9–17.
48. W.D. Callister and D.G. Rethwisch: Materials Science and Engi- 69. K.L. Lin, C.F. Yang, and J.T. Lee: Corrosion, 1991, vol. 47,
neering, 9th ed., Wiley, Hoboken, 2015, pp. 19–55. pp. 17–23.
49. J. Kondratiuk, P. Kuhn, E. Labrenz, and C. Bischoff: Surf. Coat. 70. C.J. Boxley, J.J. Watkins, and H.S. White: Solid-State Lett., 2003,
Technol., 2011, vol. 205, pp. 4141–53. vol. 6, pp. B38–B41.
50. T. Mörtlbauer, S. Kolnberger, and J. Faderl: Galvatech’15 Pro- 71. A.M. Lazar, W.P. Yespica, S. Marcelin, N. Pébère, D. Samélor, C.
ceedings, Toronto, Canada, 2015, pp. 861–67. Tendero, and C. Vahlas: Corros. Sci., 2014, vol. 81, pp. 125–31.

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