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State-of-the-Knowledge on Coating Systems for Hot Stamped Parts

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DOI: 10.1002/srin.201100292

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REVIEW

State-of-the-Knowledge on Coating Systems

for Hot Stamped Parts
Dong Wei Fan, and Bruno C. De Cooman

In the present contribution, recent developments of coatings for hot stamped steels are
reviewed. The use of bare steel in the initial hot stamping technology is discussed,
including the application of lubricant oils which are used as oxidation inhibitors on bare
steel surfaces. The aluminized coatings are introduced, focusing on the microstructure
evolution of aluminized coatings during the hot stamping process. An analysis of the
cracking of the coating, caused by the formation of brittle Fe–Al intermetallic phases and
their high temperature deformation, is presented. The development of a ductile aluminide
coating formed during the diffusion treatment of an aluminized coating is discussed. This
aluminide coating can endure both high temperature oxidation and severe plastic
deformation. The recently developed galvanized and galvannealed coatings are also
reviewed and the influence of the gas atmosphere during the heating cycle on the coating
stability is emphasized. The solutions which have been proposed to avoid liquid Zn-
induced embrittlement are analyzed. The use of Zn–Ni alloy coating, which is
characterized by a higher melting temperature, is reviewed. The behavior of sol–gel
hybrid coatings on hot stamped steels is discussed. The possible use of the recently
developed Al–Zn alloy coatings, dual layer Zn–Al and Zn–Al–Mg coatings is also
introduced. The application of Zn–Al–Mg post-process galvanizing is also discussed. In
each case, all available information related to the weldability, paintability, and corrosion
resistance of the coating systems is also reported. Finally, the advantages and technical
challenges associated with each type of coating are reviewed.

1. Introduction
The hot stamping process was originally developed to pro-
duce hardened parts for agricultural equipment. The process
was patented by the company Norrbottens Järnverk in 1973.
This company is today part of SSAB.[1,2] The original process
has been further developed to produce advanced high
strength steel parts for automotive applications. Hot
stamped steel parts were used in automotive applications
for the first time in 1984, when hot stamped door intrusion
beams were used in the SAAB 9000 passenger cars.[2]
The hot stamped steels are mainly used for anti-intru-
sion parts and structural reinforcements, such as side
impact beams, bumpers, A and B pillars, roof rails, cross
members, and tunnels. The use of hot stamped steels can
significantly increase the passenger safety in side-impact
[] Dr. D. W. Fan, Prof. B. C. De Cooman
Materials Design Laboratory, Graduate Institute of Ferrous
Technology, Pohang University of Science and Technology, 790-784
Pohang, South Korea
Email: decooman@postech.ac.kr
DOI: 10.1002/srin.201100292
and roll-over conditions. The use of hot stamped parts also
reduces vehicle weight, fuel consumption, and greenhouse
gas emissions. In addition, hot stamped parts do not
have the excessive springback which is characteristic of
the conventional high and ultra-high strength steels press-
formed at room temperature. Since 2000, the production of
hot stamped automotive parts has rapidly increased. The
annual production reached 107 million parts in 2007,[3] and
there were approximately 110 production lines worldwide
by 2009.[4] It has been estimated that the global annual
demand for hot stamped part will exceed 600 million parts
by 2015.[5]
At present the steel grade most commonly used in hot
stamping is DIN 22MnB5 steel (EN 1.5528). The chemical
composition of 22MnB5 is listed in Table 1. The steel is a
CMn steel with a small addition of B. C acts as an austenite
stabilizer and it strengthens the martensite effectively by
interstitial solute strengthening. Mn is an effective hard-
ening addition as it retards most austenite decomposition
reactions. B is added to hot stamping steel to increase the
hardenability as it retards the heterogeneous nucleation of
ferrite at austenite grain boundaries. Additions of Al and Ti
are often used to suppress the formation of BN, since AlN
or TiN precipitates are formed instead.

412 steel research int. 83 (2012) No. 5 ß 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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REVIEW
C Si Mn Cr B Al Ti

0.22 0.23 1.2 0.16 0.002 0.04 0.03

Table 1. Chemical composition of 22MnB5 hot stamped steel (wt%).

a Direct method: Heating Press forming

Decoiler Blanking furnace Cooling system

Die cooling
Press
b Indirect method: preforming

Figure 1. Schematic of the a) direct and b) indirect hot stamping process.

There are two main hot stamping methods: the direct with this initial microstructure are a combination of mod-
method and the indirect method. A schematic of the direct erate strength (600 MPa) and high ductility (25%). The steel
hot stamping process is shown in Figure 1a. Prior to the hot blank is heated in a furnace to a temperature range of 900–
stamping process the microstructure of steel consists of 9508C for 3–10 min. During the heating, the steel micro-
pearlite and ferrite. The mechanical properties of the steel structure becomes fully austenitic. In the high temperature
austenitic state the strength of the steel is soft (200 MPa)
and its ductility is high, with a total elongation of approxi-
mately about 40%. After being transferred into the press
Dr. Dongwei Fan graduated with a
forming equipment, the steel blank is pressformed in
bachelor degree in engineering from
the temperature range of 600–8008C and simultaneously
the University of Science and
quenched by the cooled dies until the temperature reaches
Technology Beijing. He majored in
about 2008C. The cooling rate is usually higher than
steel physical metallurgy at the
258C s 1. The steel microstructure becomes predominantly
Graduate Institute of Ferrous
martensitic during the quenching. At room temperature
Technology of Pohang University of
the hot stamped part has an ultra high strength (1500 MPa)
Science and Technology, where he
and a relatively low total elongation, typically about 6%.
received his doctorate for his research
In the indirect method, the blank is press-formed prior
on hot stamping technology. He is currently research
to the hot stamping process (Figure 1b). The steel sheet is
staff member of the ArcelorMittal Global R&D center in
deformed close to its final shape in a conventional die
East Chicago in the United States.
before heating. The indirect method makes it easier to
produce parts with larger dimensions and more compli-
Professor Bruno C. De Cooman
cated shapes. The indirect process also improves the con-
(PhD, Cornell University) started his
tact between the die and the formed part. This leads to a
academic career in steel research
reduction of the temperature inhomogeneity during cool-
as director of the Laboratory for
ing. In addition, the indirect method reduces the amount
Iron and Steelmaking at Ghent
of high temperature deformation of the coating. This helps
University in Belgium after 10 years
to reduce the risk of severe coating cracking.
in industrial materials research
In the hot stamping process, the steels are usually
and research management. He is
heated in the atmosphere containing oxygen. When bare
currently director of the Materials
steel is used, the steel surface is oxidized and decarburized.
Design Laboratory of the Graduate Institute of
In order to avoid these two phenomena, which have a
Ferrous Technology in Pohang, South Korea. His main
negative influence on both the surface appearance and
research interest is the development of advanced steels
the mechanical properties of hot stamped parts, coated
for automotive applications.
steels are widely used in the hot stamping process. The

ß 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim steel research int. 83 (2012) No. 5 413

REVIEW
coatings also enhance the corrosion resistance of the
parts.[6]
The aim of the present study is to review the different
types of coatings which are currently being used on hot
stamped steel, analyze their behavior during the hot
stamping, and evaluate their properties.
2. Bare Steel
2.1. Bare Steel Without Pretreatment
In the original hot stamping technology, bare steel was
utilized. Bare steel is sometimes still being used in the hot
stamping process. Iron oxide scale is formed on the steel
surface. The scale hinders the heat transfer between the
steel and the dies. The formation of scale also alters
the tribological properties of the steel surface. This affects
the friction between steel and the press dies during the
press forming stage. The oxide particles can also adhere to
the dies and this may cause die surface damage. After press
forming, the scale is removed by shot blasting or shot
peening. During this process spherical steel particles, with
a diameter of several hundred microns, are projected on
the steel surface by high pressure gas. The impact removes
the brittle surface oxides and introduces surface stresses
on the steel. In the case of hot stamped parts with a
complex shape, the oxide scales may still need to be
removed manually. When the scale is removed by
chromium shot blasting, a thin film of chromium and iron
is left on the surface. This approach eliminates the need for
re-oiling to prevent oxidation and corrosion.[7] After scale
removal, the hot stamped parts are passivated and coated
with primer paint.
In order to avoid excessive scale formation and decar-
burization, a hot stamping method carried out in a reduc-
ing gas atmosphere was proposed by Wiberg and
Laumen.[8] In this method the gas atmosphere is composed
of a mixture of N2 and CO (CO < 5 vol%). The gas atmos-
phere is free of hydrogen. This avoids the risk of increased
hydrogen contents in the steel and the associated hydro-
gen-induced embrittlement. No reports are available of the
steel surface condition after this process and it is also not
known whether the method is used in practice.
2.2. Bare Steel With Lubricant Oils
Mori and Ito[9] studied the possibility of suppressing the
surface oxidation of bare steel during hot stamping by
using lubricant oils. They compared two alkaline oils,
referred to as type A and type B, which are used as
lubricating oils for the warm stamping of stainless steel
and titanium, respectively. The type A lubricant oil was
composed of a boric acid solid lubricant, a fatty acid soap,
and a sequestering agent. The type B lubricant oil was
414 steel research int. 83 (2012) No. 5
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composed of boric acid, an oil-based fatty acid soap, phos-
phate solid lubricants, a metallic soap, and a sequestering
agent. A solid film was formed on the steel surface after
drying both lubricants. During heating at high tempera-
ture, this solid lubricant film transformed to a liquid film,
which retarded the oxidation. The type B oil was found
more effective in suppressing the oxidation, due to the
presence of compounds containing P and Ca. The oxi-
dation was further suppressed by the repeated application
(3–4 times) of the lubricant. Oxide scale was still formed on
the steel surface, but the amount of the scale was much less
than that on bare, unprotected steel. The oxide scale was
removed by a phosphoric acid treatment at 708C for
2 min.[9] The process lacks efficiency as it requires clean-
ing, repeated oil coating, and drying. In addition, the final
scale removal by means of an acid increases the risk for
hydrogen uptake and hydrogen-induced embrittlement.
3. Aluminized Coating
3.1. Initial Coating Structure
Two major types of hot dipped aluminized coatings are
currently produced industrially. Type 1 aluminized coating
consists of an Al–Si alloy with a near-eutectic composition
containing 7–11 wt% Si. This type of coating has an excel-
lent resistance to both corrosion and elevated temperature
oxidation. It is widely used as a coating on sheet steels for
manufacturing automotive exhaust systems, heat shields,
heating boilers, and cookers. Type 2 aluminized coating
consists of pure aluminum. Type 2 coatings are used
mainly for applications which require a highly reflective
surface appearance, such as building cladding panels and
ventilation systems.[10] A 25–30 mm thick type 1 aluminized
coating is widely used on hot stamped steel, and several
hot stamping methods based on the use of aluminized pre-
coated sheet steel have been developed.[11,12]
Usually the 22MnB5 steel is aluminized by hot dipping
into an molten Al alloy bath with a composition of approxi-
mately 88 wt% Al, 9 wt% Si, and 3 wt% Fe. The dipping
temperature is typically about 6758C. The purpose of the
Si addition in the type 1 aluminized coating is to form a t5
Fe2SiAl7 inhibition layer at the interface between the alloy
coating and the substrate steel. This inhibition layer pre-
vents the rapid formation of Fe2Al5 during the hot dip
aluminizing process and prevents the in-service formation
of intermetallic phases at temperatures below 5508C.[10]
The Si addition in the aluminized coating does not sup-
press the Fe–Al reaction effectively during the hot stamp-
ing process. In hot stamping, the heating temperature is
above 9008C, which is much higher than the normal service
temperature for aluminized coatings. As a consequence,
the Fe–Al reaction is much faster during hot stamping. In
the absence of Si, that is, in the case of type 2 aluminized
coating, there is a rapid growth of the brittle Fe2Al5 inter-
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www.steel-research.de
metallic phase. The growth of this compound into the steel
results in a wavy coating/steel interface at high tempera-
tures.[13] The Fe2Al5 phase is both very hard and brittle, and
its formation is detrimental to both coating adhesion and
formability. Si has been shown to prevent the inward
growth of the Fe–Al intermetallic phases. This leads to a
flat coating/steel interface and improved coating proper-
ties. The Si addition to aluminized coatings is also essential
to form a multi-layered microstructure, as will be dis-
cussed in a later section.
Figure 2 shows the cross-section of an as-produced type
1 aluminized coating. The coating microstructure has a
primary Al–Si eutectic matrix. A 5 mm thick Fe2SiAl7 inhi-
bition layer is present at the coating/steel interface. When
observed by high resolution microscopy, a thin layer of
Fe2Al5 and FeAl3 with a thickness of less than 1 mm can be
observed between the Fe2SiAl7 layer and substrate steel.
This is shown in the insert of Figure 2.
The heating temperature during hot stamping is higher
than 5778C, the melting temperature of the Al–Si alloy
coating. The coating melts during the heating stage of
the hot stamping process and the liquid coating adheres
to the furnace equipment. The molten coating reacts with
the conveying rollers of hot stamping production lines and
causes roller damage.[14] The molten coating also reacts
with the substrate steel and solid intermetallic phases are
formed which can reduce coating formability.
3.2. High Temperature Phase Evolution
The high temperature behavior of type 1 aluminized
coating on hot stamped steel was studied by
Drillet,[11]Grigorieva et al.,[15] Takagi et al.,[12] Suehiro
et al.,[16] Maki et al.,[17] Im et al.,[18] Fan et al.,[19] Jenner
et al.,[20] and Borsetto et al.[21]
The finding common to these studies is that the coating
reacts with the substrate steel and becomes gradually
Figure 2. Cross-sectional scanning electron microscope (SEM)
micrograph of a type 1 aluminized coating.
ß 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
REVIEW
enriched with Fe as the heating time or the temperature
increases. The coating thickness also increases with heat-
ing time and temperature. The heated coating is reported
to be composed of multiple layers.
The topmost part of the coating is an oxide layer. When
Al alloy coatings are heated at high temperature in air,
Al2O3 is formed at the surface. A compact Al2O3 layer
behaves as an external protective barrier and effectively
prevents the further oxidation of the coating. The layer can
also enhance the barrier corrosion resistance of the coating
at room temperature. The Al2O3 layer is very thin, as the
high temperature soaking at 900–9508C only lasts a few
minutes during the hot stamping process. The allomorphic
type of Al2O3 on the hot stamped aluminized coating has
not been reported. More advanced characterization will be
needed to identify whether a-Al2O3 or g-Al2O3 is formed
during heating above 9008C.
The coating structure under the oxide layer is complex.
The phase evolution in the coating is sensitive to the
process conditions, such as heating rate, heating time,
and initial coating thickness.
A multi-layered coating structure was reported by
Drillet[11] and Grigorieva et al.,[15] Takagi et al.,[12]
Suehiro[16] and Maki et al.,[17] and Im et al. [18] Figure 3a
shows an aluminized coating cross-section after heating
in air to 9308C with a heating rate of 108C s 1, followed by
a 5 min isothermal hold at 9308C. Five layers can be
identified by their composition obtained by energy disper-
sive spectrometry (EDS). The phase constituents were
determined by comparing their composition with those
reported in the Fe–Al and Fe–Si–Al phase diagrams.
The first layer has been identified as Fe2Al5 in the work
of Grigorieva and Drillet and co-workers,[15] Suehiro
et al.,[16] and Im et al. [18] Fan et al.,[19] however, identified
it as a FeAl2 layer resulting from the transformation of
Fe2Al5 due to the gradually increasing Fe content in the
coating. The second layer has been identified as t1 Fe2SiAl2.
This phase is also present in the form of particles in the first
layer close to the coating surface. This compound has been
identified as the t1 Fe2SiAl2 phase by Grigorieva et al.,[15]
Fan et al.,[19] and Jenner et al.,[20] but Suehiro et al.[16] and
Im et al.[18] report it to be the Si-enriched ordered FeAl
phase. The third layer was identified as FeAl2 by Suehiro
et al.,[16] Im et al.,[18] and Fan et al.[19]. It was identified as
Fe2Al5 by Grigorieva et al.[15] The fourth layer is similar to
the second layer. The fifth layer was identified as a diffu-
sion layer by both Takagi et al.[12] and Fan et al.[19] This
diffusion layer has a gradually increasing Fe content
toward to the substrate steel. In the work of Drillet
et al.[11] and Im et al.,[18] the fourth and fifth layer are
considered to be a single diffusion layer.
There are also differences in the morphology reported in
the literature of the intermetallic phases in hot stamped
aluminized coatings. This is especially the case for the
morphology of the second layer. A layered structure was
reported by Drillet et al.,[11] Grigorieva et al.[15] Takagi
et al.,[12] Suehiro et al.,[16] Maki et al.,[17] and Im et al.[18]
steel research int. 83 (2012) No. 5 415

REVIEW
Figure 3. Cross-sectional SEM micrographs of aluminized specimens heated at 9308C for 5 min, a) heating rate of 108C s
b) heating rate of 308C s 1 in vacuum. The hardness indentation was done with a 0.1 kg load.
Fan et al.[19] and Jenner et al.[20] report an island-type
morphology for the Fe2SiAl2 phase. It is possible that the
difference in the morphology of the Fe2SiAl2 phase is due a
difference in the heating rate. When the heating rate to
9308C is low, for example, 108C s 1, the Fe2SiAl2 phase
tends to form in a continuous layer, and only a few
Fe2SiAl2 particles are formed near the coating surface
(Figure 3a). The Si content in this continuous Fe2SiAl2 layer
is about 7.5 wt% (Figure 3a). The Si content of the layer was
reported to be 2–6 wt% in the work of Drillet et al.,[11] and
7 wt% in the work of Suehiro et al.[16] Figure 3b shows an
aluminized coating cross-section after heating to 9308C
using a heating rate of 308C s 1. The Fe2SiAl2 phase is
clearly island-type, with a Si content of 11–12 wt%.[19] It
is noteworthy that the Si content of the island-type Fe2SiAl2
phase is slightly higher. The slow heating rate might be able
to facilitate a more homogenous Si distribution and the
formation of a layered Fe2SiAl2 structure.
The layered structure of the first FeAl2/Fe2Al5 layer and
the second Fe2SiAl2 layer is reportedly beneficial for the
resistance spot welding (RSW) properties according to
Drillet et al.[11] They also mention that the fraction of
Fe2SiAl2 formed in the first layer should be less than
10 vol%. The first, second, and fifth layers also influence
the electrical resistance of the coating, due to their intrinsic
physical properties and their influence on the coating sur-
face roughness. The desired layered coating structure is
obtained when the heating rate is in the range of 4–
128C s 1.[11] In practice the aluminized blanks are usually
heated to 9008C within 3 min. The slow heating process
required to obtain a layered coating will therefore also
result in lower process efficiency.
The fifth diffusion layer has been identified as the
Fe3Al phase at room temperature on the basis of its com-
position.[18,20] At high temperature, this phase transforms
to a-Fe with Al and Si in solid solution. In this condition,
the layer is ductile during a high temperature deformation.
The diffusion layer has a much lower hardness than the
other layers in the coating. It is also softer than the
substrate martensitic steel.[18] It has been reported that
416 steel research int. 83 (2012) No. 5
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1
in air and
microcracks could therefore be arrested in the diffusion
layer.[12,18] This is illustrated in Figure 3a. As the heating
time is increased, the Fe2Al5, FeAl2, and Fe2SiAl2 phases
disappear, and the entire coating becomes a diffusion layer
consisting of a-Fe with Al and Si in solid solution.
3.3. Voids in the Coating
Voids are often observed in the coating after hot stamping.
Some small voids are formed directly under the oxide layer.
They are indicated by a rectangle in Figure 3a. As the
heating time increases, the coating surface becomes more
porous. When specimens heated in air (Figure 3a) and in
vacuum (Figure 3b) are compared, the surface is more
porous for the specimen heated in air. The voids formed
under the Al2O3 layer are possibly due to two processes: Al
atoms diffusing outwardly to form the surface oxide, and Al
atoms diffusing inwardly to form the Fe–Al intermetallic
phases. These two diffusion processes create Al vacancies
and the agglomeration of the vacancies results in the for-
mation of cavities.[22,23] An alternative explanation is that Al
atoms in the Fe–Al intermetallic phases react with moisture.
This results in the formation of H2 gas, which, in turn, causes
voids formation.[24] The precise mechanism of void for-
mation still needs to be clarified. The combined effects of
surface void formation and intermetallic phase formation
results in a surface with an increased roughness and a higher
friction coefficient. Jenner et al.[20] and Borsetto et al.[21]
have shown that the roughness and friction coefficient of
the coating increased with increasing coating Fe content.
Dessain et al.[25] studied the friction between aluminized
steel and press tools at high temperature. They reported a
friction coefficient in the range of 0.40–0.45. They also
reported that both the test temperature and the contact
pressure did not influence the friction coefficient.
Voids are also formed inside the coating, as indicated by
a circle in Figure 3b. These voids are mostly associated with
the ternary Fe2SiAl2 phase. It has been suggested that they
were formed by the removal of the hard Fe2SiAl2 interme-
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www.steel-research.de
tallic phases during sample preparation.[19,22] Jenner et al.,
however, prepared cross-sectional sample by means of the
focused ion beam (FIB) technique and found that these
voids were not due to sample preparation. They suggest
that these voids were related to the Kirkendall effect, that is,
the formation of voids resulting from a large difference in
the diffusivity of two atomic species.[20] Voids are also
observed in the diffusion zone at the coating/steel inter-
face. They are generally considered to be Kirkendall voids,
due to the different diffusivities of Fe or Al in the Fe2SiAl2
layer and the diffusion layer.[19,22]
3.4. Coating Brittleness
Figure 3a shows vertical through-coating cracks in an alu-
minized coating after a deformation-free hot stamping
thermal cycle. These cracks are formed during cooling
due to the difference in the thermal expansion coefficient
of the brittle intermetallic phases and the substrate
steel.[22] Figure 3b shows the coating in cross-section after
a hardness indentation with a load of 0.1 kg. The hardness
was estimated to be 769 Hv. Brittle cracks can be seen to
propagate from the indentation. This observation clearly
shows that the brittle coating can easily be damaged during
service and that coating powdering will be important. It
can also be seen that the cracks do not propagate beyond
the diffusion layer. Takagi et al.[12] reported that the dif-
fusion layer should make up 50% of the coating thickness,
in order to have a good crack propagation resistance.
Denner and Kim[26] reported that an aluminized coating
fractured by segmentation after 5–15% tensile deformation
after a thermal cycle at 8168C. Schießl[27] reported that the
coating was easily broken in the more heavily deformed
areas of a manufactured hot stamped part. Fan et al. have
shown that the coating was actually broken into segments
after a 30% plastic deformation at 8008C. They also
reported that the fracture pattern was strain rate depend-
ent with a higher density of finer cracks at higher strain
rates. In the cracked areas, the exposed steel is oxidized
and a thin oxide scale is formed on the exposed steel
surface during cooling in air.[19] Allely et al.[28] found that
hot stamped steel parts were more susceptible to corrosion
in areas where the coating was cracked.
The embrittlement of the coating is a important issue for
aluminized coatings on hot stamped steel as it leads to
coating fracture, which can occur during deformation both
at high temperature and at room temperature, that is,
during in-service use of the hot stamped part.
3.5. Properties
3.5.1. Weldability
In RSW, the welding current must always be within a
specific current range defined as Imax Imin, where Imax
is the maximum welding current required to weld the sheet
ß 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
REVIEW
without spatter formation, and Imin is the minimum weld-
ing current that results in the formation of a weld nugget
with a minimum diameter dmin equal to 4Ht, where t is the
sheet thickness. The current range Imax Imin should be
wide for practical operation. The welding forces are higher
for high strength hot stamped martensitic steels compared
to mild steel grades.[29]
As the Al2O3 layer on the heat treated aluminized coat-
ing is very thin, and as the Fe–Al intermetallic phases are all
electrically conductive, the electrical conductivity of heat-
treated aluminized coatings is generally compatible with
RSW. Drillet et al. have reported that to have a wide welding
current range of 1.4 kA, a layered coating structure was
essential. When the Fe2SiAl2 phase had a non-layered
morphology and when it was formed close to the surface,
the welding current range was strongly reduced.[11]
Suehiro et al. studied the spot weldability of aluminized
22MnB5. The heat treated aluminized steel was spot
welded to 400 MPa grade bare steel. The tests showed that
as the welding current increased, the welded nugget
diameter increased. This resulted in an increase of the
contact area. It also resulted in an increase of the tensile
shear strength and cross tensile strength. Typical values for
Imin and Imax for a 1.8 mm thick hot stamped steel are 8 and
10 kA, respectively. A welding current range of 2 kA is con-
sidered sufficient for practical applications. The welded
parts failed in the heat affected zones (HAZ), due to the
lower hardness of the HAZ. The high melting temperature
of the Fe–Al intermetallics in the coating resulted in a long
service life of the electrode and the consecutive weldability
was reportedly excellent.[16]
3.5.2. Paintability
A phosphate layer is usually deposited on steel used in
automotive applications prior to the application of a pri-
mer. In this process, the steel is dipped into a chemical
solution of zinc phosphate to form a phosphate film on the
steel surface. This process passivates the steel surface
and the microroughness of the phosphate layer greatly
improves paint adhesion. Suehiro et al. reported that
heat-treated aluminized coating surfaces are non-reactive
in phosphating solutions and that no phosphate layer is
formed on the surface. As the rough surface of the heat
treated coating offers adequate paint adhesion, the coating
can be directly painted without being phosphated.[16] Maki
et al.[17] have reported that phosphate can be formed
locally in areas where the oxide layer was broken due to
plastic deformation.
3.5.3. Corrosion Resistance
Fleischanderl and Faderl et al. have carried out electro-
chemical tests on hot stamped aluminized steel panels in a
chemical solution containing NaCl and ZnSO4, which is
usually used to characterize the corrosion resistance of Zn-
based coatings. They found that hot stamped aluminized
coatings had an electro-chemical potential similar to that
of the substrate steel.[30] However, the present authors
steel research int. 83 (2012) No. 5 417
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found that the coating composed of intermetallic phases layer thickness becomes insufficient for good coating
did not dissolve completely in the chemical solution of adhesion.[12]
NaCl and ZnSO4. Maki et al. conducted electro-chemical
tests in a NaCl solution and found that the first and third
3.6. Alternative Aluminized Precoating
Fe2Al5 layers in the coating had a slightly lower electro-
chemical potential than the substrate steel. The first Fe2Al5
In the hot stamping process the Fe–Al intermetallic coating
layer was preferentially corroded in the corrosion test.
is prone to fracture during deformation. The steel is there-
The entire coating had no significantly different electro-
fore sometimes pre-formed at room temperature prior to
chemical potential compared to the substrate steel.[17] This
the actual hot stamping process to reduce the amount of
implies that the aluminized coatings cannot offer any
strain during the press-forming at high temperature. This
cathodic corrosion protection. The uncoated regions of
process, commonly referred to as the indirect hot stamping
the aluminized steel, such as cut edges, are therefore not
method, is shown in Figure 1b. In the indirect hot stamping
protected against corrosion.
process, the blanks are mainly deformed in an initial pre-
Allely et al. have reported that the corrosion rate of hot
forming stage at room temperature. During hot stamping
stamped aluminized coating was very slow during a cyclic
process, the steel undergoes a much smaller deformation.
corrosion test. They explained this observation to the fact
Microcrack formation still takes place, but the cracks do
that a stable corrosion product consisting of the Fe–Si–Al
not propagate beyond the diffusion layer, and the substrate
compound filled the corrosion cavities, thereby, hindering
steel remains unexposed. This approach provides enough
the oxygen inward diffusion and the corrosion progress.[28]
oxidation and corrosion protection. During the pre-form-
Dosdat et al.[31] compared the corrosion resistance of alu-
ing stage, the metallic coating also cracks in the heavily
minized, galvanized (GI), and galvannealed (GA) coatings
deformed regions.[32] This is due to the presence of the
after hot stamping. The coated panels were phosphated
brittle Fe2SiAl7 intermetallic phase at the coating/steel
and painted. Cyclic corrosion tests were conducted on
interface. This intermetallic phase is always formed at
scratched panels. In the cosmetic corrosion test, the paint
the coating/steel interface during the hot dip aluminizing
blister width on hot stamped aluminized panels was
process, due to the fast reaction between Fe and the liquid
similar to that for GA interstitial free (IF) steel with a coat-
Al alloy. Whereas, Fe2SiAl7 is formed on type 1 coatings,
ing weight of 100 gm 2 (7.5 mm). The blister width on hot
Fe2Al5 is formed in the case of type 2 coatings. Alternative
stamped aluminized panels was, however, larger than for
coating techniques have been developed for hot stamped
hot stamped GI coatings. In a cut-edge corrosion test, the
steels in order to suppress the formation of intermetallic
hot stamped aluminized panels had inferior corrosion
phases.[32] Alternative coating methods include electro-
resistance results compared to hot stamped GI and GA
plating, chemical vapor deposition (CVD), physical vapor
coatings. In perforation corrosion tests, however, the maxi-
deposition (PVD), and co-rolling. The coated steel sheets
mum blister depth on the hot stamped aluminized panels
made by these methods have been reported to exhibit an
was similar to the case of hot stamped GI and GA coatings.
improved room temperature coating formability suitable
In the perforation tests on non-painted panels, the hot
for the indirect hot stamping process.
stamped aluminized steel had a mass loss and blister depth
similar to those of hot stamped GI and GA coated steels,
and much lower than that for a GA IF steel. Hot stamped 3.7. Aluminide Coating
aluminized coatings have a good cosmetic corrosion
resistance and perforation corrosion resistance, which is Formable aluminide coatings have been developed in
similar to that of hot stamped GI and GA coatings. order to solve the problem of coating brittleness. Kim
Hot stamped aluminized coatings, however, do not offer and Cho et al. reported that aluminized coatings contain
adequate cathodic corrosion resistance in cut-edge a large volume fraction of Fe2Al5 phase during hot stamp-
corrosion conditions. ing. This causes the coating to be brittle and have insuffi-
Maki et al.[17] report that during a corrosion test the cient barrier corrosion resistance. They also found that the
blister width depends on the thickness of the first Fe2Al5 iron-aluminides Fe3Al and FeAl were more formable, and
layer in the coating: the blister width decreases with an that they had a better corrosion resistance. These authors
increasing thickness of this Fe2Al5 layer. The corrosion proposed a method to obtain more formable aluminide
resistance of hot stamped aluminized coatings depend coatings consisting of Fe3Al and FeAl.[33,34] Their
on their Al content, which is in turn influenced by the heat approaches consists of the diffusion annealing of a type
treatment during hot stamping. It was shown that longer 1 aluminized coating, with a relatively thin initial coating
heating times or higher heating temperatures resulted in a thickness (4–7 mm, 20–40 gm 2). After heating at 9508C for
lower Al content in the coating and, as a consequence, a 5–10 min, the coating is entirely composed of a mixture of
larger corrosion depth.[17] Takagi et al. report that the coat- Fe3Al and FeAl (Figure 4a). As indicated on the Fe–Al phase
ing should contain at least 25 wt% Al after hot stamping in diagram shown in Figure 5,[35] the Fe content should be
order for it to offer a good corrosion resistance. If the higher than 65 wt% in order to form Fe3Al and FeAl at
coating has an Al content higher than 40 wt%, the diffusion 9508C. Note that the room temperature Fe3Al phase results

418 steel research int. 83 (2012) No. 5 ß 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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REVIEW
Figure 4. Cross-sectional SEM micrographs of an aluminide coating, a) the coating consisting of Fe3Al and FeAl after heating at
9308C for 10 min and b) the coating after bending test. Reproduced with permission of copyright holder (cf. ref. [33]).

from the transformation of the high temperature a-Fe
phase which contains Al in solid solution. The coating is
formable and it does not crack during high temperature
bending tests (Figure 4b).[33,34]
A similar aluminide coating suitable for hot stamping
was proposed by Fan and De Cooman.[36] The coating has
excellent high temperature ductility and thermal oxidation
resistance. Although FeAl is ductile at high temperature, it
becomes brittle below 8008C.[36] Kuc et al.[37] also reported
that FeAl cracks when it is deformed at temperatures below
8008C at a strain rate of 0.5 s 1. In contrast, the Fe3Al phase
is ductile in a wide temperature range.[36] The criterion for
ductile coating formation is that the coating should be the
0 10 20 30 40
1600
1538ºC
1400
1394ºC
(αFe)
1200
Temperature ºC
a-Fe phase with Al in solid solution at high temperature.
This a-Fe phase transforms to an ordered Fe3Al D03
structure upon cooling to room temperature. This room
temperature aluminide coating is readily formed by dif-
fusion annealing of an aluminized coating. In an example
study, a 10 mm coating was diffusion annealed at 10508C for
4 min. The surface Fe alloy content increased to 83 wt%,
and the coating consisted entirely of the a-Fe phase at high
temperature. This phase transformed to the Fe3Al phase
during cooling to room temperature.
Figure 6 shows cross-sectional views of a diffusion
annealed coating before and after deformation. During
the diffusion treatment, the coating thickness increases
from 10 to 30 mm (Figure 6a) and voids are formed close
Atomic Percent Aluminium
to the surface and in the center of coating. The near-
50 60 70 80 90 100
surface voids formation is similar to the surface voids
mentioned previously for hot stamped aluminized coat-
L ings, and they are indicated by a rectangle in Figure 6a. The
1310ºC voids near the center of the coating are Kirkendall voids.
1232 1165ºC
They are indicated by a circle in Figure 6a. During defor-
1169ºC ~1160ºC
ε
mation these voids are stretched and they become larger

(γFe)
Fan et al.
1102ºC

1000
Fe 83wt.%
(Figure 6b). Note that the deformation also resulted in the
Kim et al.
912ºC
Fe 65wt.% reduction of coating thickness to 25 mm, corresponding to
FeAl
a thicknesses strain of about 0.17. As steel substrate thick-
800
Fe2Al5

FeAl3
FeAl2

Tc
770ºC
ness simultaneously decreases from 1.65 to1.41 mm during
655ºC 660.452ºC
the deformation, that is, corresponding to a thickness
600
strain of 0.15, the equivalence of the thickness strain for
Fe3Al (Al)
the coating and the thickness strain for the substrate
400
0 10 20 30 40 50 60 70 80 90 100 implies that the coating deforms plastically with the sub-
Fe Weight Percent Aluminium Al
strate steel without loss of adherence or cracking.
Figure 5. The Fe–Al binary phase diagram (reproduced from The hardness of the conventional aluminized coating
ref. [35]). containing the FeAl2 phase is very high: 769 Hv (0.1 kg

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REVIEW
Figure 6. Cross-sectional SEM micrographs of an aluminide coating, a) as heat treated at 10508C for 4 min and b) 30% strain at
7008C, after heating at 10508C.
load). The hardness of the aluminide coating obtained
by diffusion annealing at 10508C is 222 Hv (0.05 kg
load). Figure 6a shows a hardness indent in the aluminide
coating. No cracks are observed around the indentation. In
addition, the indentation is asymmetric in the coating
thickness direction. This implies that the hardness
decreases from the surface to the coating/steel interface,
due to the gradually increasing Fe content in the thickness
direction. Both observations are clear indications that
the aluminide coatings remain ductile down to room
temperature.
Takagi et al.[12] mentioned that the corrosion resistance
of the coating was degraded when the Al content was less
than 25 wt%. Kim and Cho et al. reported that the Al con-
tent was 35 wt% at the surface and this content decreased
toward steel substrate. Kim and Cho et al. also found that
the aluminide coating had a better barrier corrosion resist-
ance than the conventional hot stamped aluminized coat-
ings during a salt spray test. In the conventional
aluminized coating, the brittle Fe2Al5 or FeAl2 intermetal-
lics contain many microcracks after the hot stamping
process. These cracks deteriorate the corrosion resistance.
In the aluminide coating, these microcracks are absent
and, consequently, the corrosion resistance is considerably
improved.[33,34] The corrosion resistance of iron-aluminide
can be further improved by small Cr-alloying additions.
The electro-chemical corrosion resistance of Fe3Al con-
taining 2–6 at% Cr and a small amount of Mo has been
reported to be comparable to that of 316 stainless steel.[38]
The addition of Cr has also been reported to improve the
ductility of Fe3Al at high temperature.[39]
4. Galvanized and Galvannealed Coatings
4.1. Initial Coating Structure
GI coatings are widely used on cold rolled sheet steel
products, due to their metallic appearance, adequate form-
420 steel research int. 83 (2012) No. 5
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ability, excellent barrier, cathodic corrosion protection,
and physiological harmlessness. GI coatings have also
been applied on hot stamped steels.[30] Hot dip pure Zn
GI coatings are sometimes given an additional heat
treatment in the 480–5208C temperature range, a process
known as galvannealing, to produce a Zn–Fe alloy or
‘‘Galvannealed’’ (GA) coating. GA sheet steel can also be
used in hot stamping.[40,41] During the hot stamping proc-
ess, the initial GI or GA coating reacts completely with the
substrate Fe, and the coating is replaced by Fe–Zn inter-
metallic compounds.
Approximately 0.2 wt% Al is usually added to the liquid
Zn bath of continuous hot dip galvanizing lines for the
production of GI coatings. The purpose of the Al addition is
first and foremost to form an Fe2Al5 xZnx inhibition layer
at the liquid Zn/steel interface during the hot dip process.
This layer can suppress the formation of brittle Fe–Zn
intermetallic phases and improve the coating formability
during deformation at room temperature. The addition of
Al also increases the reflectivity of the coating and reduces
the oxidation of the Zn bath. Al is added to the liquid Zn
bath in the range of 0.13–0.14 wt% for the production of GA
coatings. The relatively lower Al content facilitates the
formation of Fe–Zn intermetallic phases during the gal-
vannealing process, as no continuous Fe2Al5 inhibition
layer is formed at the coating/steel interface in this con-
dition.[42] In the hot stamping process, the presence of Al
leads to the formation an Al2O3 oxide surface layer, which
hinders the high temperature oxidation of the coating and
Zn evaporation. Low Al contents in the GA coating result in
a faster Fe–Zn reaction during hot stamping process.
Figure 7a shows the cross-section of an as-produced GI
coating. The coating thickness is about 17 mm. It consists of
two layers of Zn–Fe alloys, a h phase layer and a z phase
layer (Figure 7b). The Fe2Al5 xZnx can be clearly seen at the
coating/steel interface (Figure 7c). Fleischanderl et al.[30]
and Faderl[43] reported that a GI coating with initial thick-
ness of 10–15 mm resulted in an alloyed coating with thick-
ness of 20–30 mm after hot stamping. In the study of
Yoshikawa and Imai et al., the initial GA coating thickness
ß 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.steel-research.de
Figure 7. Cross-sectional SEM micrographs of as-produced GI coating, a) microstructure, b) Zn distribution, and c) Al distribution
obtained by wavelength dispersive spectroscopy (WDS).
was 4–5 mm (coating weight: 50–70 gm 2). The coating
thickness increased to 20 mm after hot stamping.[40] As
coatings with a different initial thickness have different
total amounts of Zn and Al, the amount and type of con-
stituent phases in the coating after the hot stamping are
expected to be different for GI and GA coatings. This will
eventually have an influence on the properties of the
coating.
4.2. High Temperature Phase Evolution
During the thermal cycle of the hot stamping process, the
Zn coating reacts with the substrate steel. The coating
gradually becomes enriched in Fe with increasing heating
time and temperature. The coating thickness also increases
with heating time and temperature. The coating has been
found to consist of the following three layers, from the
surface to interface: an oxide layer, a Fe–Zn intermetallic
layer, and a layer of a-Fe with Zn in solid solution. The Fe–
Zn intermetallic layer is gradually consumed by the Fe–Zn
solid solution layer, when the coating is kept for longer
time at a higher temperature, or when a thinner coating is
used.
Figure 8a shows the typical microstructure of a GI coat-
ing after hot stamping. The thickness increased from the
initial thickness of 17 mm to a final thickness of 30 mm. The
Figure 8. Cross-sectional SEM micrographs of a GI coating after heating at 9008C in air for 4 min, a) microstructure, b) Zn distri-
bution, and c) Al distribution obtained by WDS.
ß 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
REVIEW
surface oxides layer was about 1–2 mm thick. The Fe–Zn
intermetallic phase contained about 26 wt% Fe and it was
identified as the G1 phase. This phase is clearly visible
in Figure 8b. Its composition is indicated by a dot in the
Fe–Zn binary phase diagram (Figure 9).[44] It corresponds
to a mixture of liquid Zn and solid a-Fe phase, when the
temperature is above 7828C. This implies that during the
thermal cycle of hot stamping, the coating was partly
liquid. This would cause the Zn-adhesion to the furnace
rollers or to the press dies. Most importantly, the liquid
Zn can cause embrittlement of the substrate steel.
According to the phase diagram, during the cooling the
liquid Zn and some of the a-Fe transforms to the G1 phase.
Depending on the Fe content of the coating, different types
of Fe–Zn intermetallic phases can be formed during cool-
ing. The G2, d, and z phases are formed when the coating
has a low Fe content. The Fe content is affected by the
initial coating thickness, the initial Fe and Zn content, the
Al content in the coating and the heating conditions. Faderl
et al. reported that the G1 and d phases were formed after
heating a 10 mm GI coating above 8508C for several
minutes.[45,46] In another study, Fleischanderl et al.[30]
reported that a 15 mm coating containing 20 wt% Fe was
formed after heating at 9008C for 4.5 min. This composition
corresponds to the composition of the G2 phase as
indicated by the triangle in the Fe–Zn phase diagram
in Figure 9.
steel research int. 83 (2012) No. 5 421
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REVIEW

Atomic Percent Zinc peritectic transformation temperature is also lower, and

0 10 20 30 40 50 60 70 80 90 100
1600
liquid Zn can be present at low temperature. This may
1500
cause Zn penetration into the steel and lead to liquid metal
1400
L induced embrittlement (LMIE), which will be discussed
1300
(αFe)p αFe + L later. When the G1 or G2 phases are formed, both phases
1200 Fleischanderl and Faderl et al.
(γFe) are very hard and brittle, and they will easily fracture and
Temperature ºC

1100 Fe 20wt.%
Fleischanderl and Faderl et al. cause coating powdering, which may result in press dies
1000 Imai et al. present study present study
Zn 0-30wt.%
(αFe)p Zn 0-35wt.% Fe 26wt.% damage.
900
800 782ºC 75
The Fe or Zn content is also known to have an impact on
771ºC 93
46 the corrosion resistance of the coating obtained after hot
700 672ºC
(αFe)t Γ1 stamping. The electro-chemical potential decreases when
600 ~24 ~640ºC
550ºC 530ºC

500 δ the Zn content in Zn–Fe alloys decreases. A Zn-alloy coat-

420ºC
400 ζ ing should therefore have a sufficiently high Zn content
Γ2
300 to insure an adequate cathodic corrosion protection.
0 10 20 30 40 50 60 70 80 90 100
Fe Weight Percent Zinc Zn Fleischanderl and Faderl et al. reported that Fe–Zn inter-
metallic layer should have a Zn content in the range of 70–
Figure 9. Fe–Zn binary phase diagram (reproduced from 95 wt%. This composition range covers the Fe–Zn inter-
ref. [44]).
metallic phases G1, G2, d, and z. The a-Fe layer with Zn in
solid solution should have a Zn content in the range of 17–
The lower layer consists of the a-Fe phase with Zn in 44 wt%.[30] In the work of Imai et al.,[41] it was reported
solid solution. The Zn content of this layer gradually that a coating consisting entirely of a-Fe should have a
decreases toward the coating/steel interface. The maxi- Zn content above 10 wt% to guarantee a good cathodic
mum Zn content in this layer is 35 wt% (Figure 8b). This corrosion resistance.
is indicated by the solid arrows in the Fe–Zn binary phase
diagram in Figure 9.[44] A similar layer having 30 wt% of Zn
has also been observed by Fleischanderl et al.[30] In Imai’s 4.3. Evaporation of Zn
work, the GA coating was replaced by a Fe–Zn solid
solution containing less than 30 wt% Zn.[40] This phase is When GI 22MnB5 steel is tested in air, there is no evapor-
indicated in the Fe–Zn phase diagram (Figure 9) with small ation of the Zn. When the test is carried out in an inert Ar
arrows. atmosphere Zn evaporates when heated above 6008C.[46]
At 9008C there are two regions in the coating, an upper After heating in air, two layers are present in the coating: a
layer consisting of liquid Zn and a layer of a-Fe under this G1 layer and a a-Fe solid solution layer (Figure 8). Figure 10
first layer. During cooling below 7828C, the liquid Zn and shows cross-sections of a specimen heated in Ar. The
some of the a-Fe transform to the G1 phase. The remaining original coating thickness was about 17 mm. During the
a-Fe is stabilized to room temperature. The phase diagram heating at 9008C in Ar, the coating simultaneously evap-
shows that a-Fe has a very low solubility for Zn at lower orated and reacted with the substrate. After heating, the
temperatures and that Zn is strongly partitioned to the G1 coating thickness had decreased to less than 10 mm, and
phase. This is however not observed in practice. A single the coating was mostly replaced by a-Fe solid solution
layer of a-Fe with a high Zn content is observed at room (Figure 10).
temperature. This is very likely due to the fast cooling
which prevents the decomposition of the a-Fe with a high
Zn content.
At a temperature higher than 7828C, a solid–liquid reac-
tion takes place, in which the a-Fe solid solution grows at
the expense of liquid Zn. The a-Fe phase has the globular
morphology, characteristic of solid–liquid reactions. The
globular morphology is caused by the curved interface
between the upper G1 layer and the lower a-Fe layer.
This characteristic morphology has been referred to as a
‘‘leopard-patterned’’ morphology[30] and a ‘‘non-layered’’
morphology.[43]
The z phase or the d phase is formed when the coating
has a low Fe content after it undergoes a hot stamping
thermal cycle. The G2 or G1 phase is formed, if the annealed
coating has a higher Fe content. At very high Fe contents
the coating has completely transformed to a a-Fe solid Figure 10. Cross-sectional SEM micrograph of a GI coating after
solution. When the Fe content of the coating is low, the heating at 9008C in inert Ar atmosphere for 4 min.

422 steel research int. 83 (2012) No. 5 ß 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Lee and Fan et al. found that both ZnO and Al2O3 were
formed at the coating surface during heating in air. The Zn
evaporation was suppressed by the presence of this mixed
surface oxide layer.[46] Al, which was initially present in the
inhibition layer (Figure 7c), migrated from the coating/
steel interface to the coating top surface, where it formed
Al2O3 when the coating was heated to a temperature higher
than 6008C (Figure 8c). The presence of the surface layer of
Al2O3 is essential to suppress the Zn evaporation.[30]
Lee and Fan et al. reported that when the GI coating was
heated in the Ar atmosphere, the original coating was
replaced by a-Fe layer with Zn in solid solution
(Figure 10). A ZnO surface layer was formed due to the
reaction with the residual O2 in the testing chamber at
6008C. The amount of ZnO layer decreased with increasing
temperature, due to the sublimation of ZnO which decom-
posed it into gaseous Zn metal vapor and oxygen.[46] Zn
vapor is known to catalyze the decomposition of zinc
oxide.[47] The loss of Zn during heating in a protective
gas atmosphere is therefore due to a combination of Zn
evaporation and ZnO sublimation. Fe3O4 was also formed
at the surface, due to the high Fe content in the coating.
Fe3O4 was only observed when the heating temperature
was higher than 8008C (Figure 10c). The Zn remaining in
the coating after heating in Ar was due to the formation of a
Fe–Zn solid solution.
Al is clearly essential to the suppression of the Zn evap-
oration. In the study of Fleischanderl and Faderl et al., the
Zn coatings had an Al content in the range of 0.1–15 wt%.
As elements such as Mg, Si, and Ti have strong affinity for
oxygen, they can be added to Zn-coatings to form stable
surface oxides.[30] If the Al content in the coating is high,
Fe–Al intermetallic phases may be formed. It is unknown
whether Fe–Al intermetallic phases were formed in the
high Al coatings studied by Fleischanderl and Faderl et al.
In the study of Imai and Yoshikawa et al., the GA coating
was fully transformed to a Fe–Zn solid solution, and a 0.5–
2 mm ZnO layer was formed at the coating surface.[40] In
other work of the same authors, the initial GA coating had
an Al content of 0.25–0.3 wt% and Al2O3 was present on the
coating surface after hot stamping. Only ZnO was observed
at the surface when an Al-free GA coating was tested.[41] No
Zn evaporation was mentioned. It can be noticed that, as
the initial coating was only 4–5 mm, the diffusion distance
Engineering Stress [MPa]
for Fe was considerably smaller during the formation of
Fe–Zn solid solution and this may have prevented Zn loss
by the rapid formation of a Fe–Zn solid solution.
It is clear that the formation of surface oxides is essential
during hot stamping process as their presence suppresses
Zn evaporation. Al additions to the Zn coating are essential
to form the Al2O3 layer. The heat treatment should be
conducted in an oxidizing atmosphere, preferably in air.
This oxide layer will also act to separate the coating and
press dies during hot forming, avoiding the liquid Zn
adhesion to the dies.
The presence of surface oxides results in an increased
electrical contact resistance during RSW. It has therefore
ß 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
REVIEW
been suggested that the surface oxides should be removed
prior to RSW. The oxide removal can be done by abrasive
blasting with steel granulate, corundum, glass granulate, or
dry ice.[48] The surface oxides can also be removed by shot
blasting or liquid honing. In the liquid honing process, a
high pressure liquid containing a cleaning abrasive is used
to clean the surface.[41] Yoshikawa and Imai et al. found
that if the ZnO layer thickness was more than 2 mm, its
adhesion to the Fe–Zn coating was poor. This resulted in a
poor paint adhesion and the low corrosion resistance
for the entire coating system.[41] The formation of surface
oxide layer can be minimized by adjusting the heat treat-
ment during hot stamping. A shorter heating time or a
lower heating temperature will reduce the oxide formation
and reduce the contact resistance for RSW. Genderen et al.
reported that heating a GA coating at 9208C for 4 min
resulted in a reduction of oxide formation. The contact
resistance of 5 mV and a welding current range of 1 kA
could be obtained.[49] Akioka and Imai et al. showed
in a recent study that a thin ZnO layer had a negligible
influence on the weldability, phosphatability, and paint
adhesion. Their results suggest that ZnO surfaces layers
does not need to be removed prior to RSW.[50]
4.4. Liquid Metal Induced Embrittlement
Figure 11 shows stress–strain curves of 22MnB5 hot
stamping steel tensile specimens deformed in various test-
ing conditions. The steels were heated to 8508C for 4 min
and subsequently deformed to 40% engineering strain at a
strain rate of 0.5 s 1. At 8508C, the 22MnB5 steel is fully
austenitic. The uncoated steel had a ductile behavior and
the peak stress was about 150 MPa. A GI coated sample
tested in the same conditions fractured at an elongation of
8%. A sample heated at 8508C for 4 min and subsequently
deformed at 7008C, had a 40% elongation and a higher
ultimate tensile strength (UTS). These tests reveal that the
ductility of 22MnB5 steel is clearly dependent on the pres-
ence of the coating.
250
Coated 22MnB5, deformed at 700°C
200
Bare 22MnB5, deformed at 850°C
150
Coated 22MnB5, deformed at 850°C after 20min annealing
100 Coated 22MnB5, deformed at 850°C, LMIE
Bare IF steel, deformed at 850°C
50
Coated IF steel, deformed at 850°C, LIME
0
0.0 0.1 0.2 0.3 0.4
Engineer Strain
Figure 11. Stress–strain curves of deformed specimens.
steel research int. 83 (2012) No. 5 423

REVIEW
Figure 12. Zn distribution in a fractured GI specimen obtained
by WDS. The specimen was heated at 8508C for 4 min and
strained 40% at 8508C.
Figure 12 shows the Zn distribution for GI 22MnB5 steel
after deformation and fracture at 8508C. After the isother-
mal holding at 8508C for 4 min, the coating consists of a-Fe
and the G1 intermetallic phase. The G1 phase is formed
from the liquid Zn. The presence of G1 is the evidence for
the presence of liquid Zn at 8508C, which is higher than the
peritectic temperature (7828C). Figure 12 shows an area
close to the fractured region. The cracks clearly propagate
from the coating into the substrate steel. Zn is present
along the crack surface. After an isothermal holding at
8508C for 20 min, the coating is replaced by a layer of
a-Fe with Zn in solid solution and the steel has good
ductility (Figure 11). The existence of liquid Zn during
plastic deformation clearly caused the fracture of the steel.
This phenomenon can be identified as LMIE.
LMIE is usually observed between two metals with a low
mutual solubility, which do not form intermetallic com-
pounds. In hot stamping process, when the temperature is
above the peritectic temperature, Zn forms a solid solution
in -aFe, while there is still liquid Zn present in the coating.
Figure 13. Zn distributions obtained by WDS of a) galvanzied steel heated at 8508C for 4 min and subsequently strained 40% at
7008C and b) galvanzied steel heated at 8508C for 20 min and strained 40%.
424 steel research int. 83 (2012) No. 5
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The solubility of Zn in g-Fe is very low, and the liquid Zn
causes the embrittlement of the austenitic steel by weak-
ening grain boundaries and constantly wetting the freshly
exposed grain boundary fracture surface. The Zn is known
to embrittle austenitic stainless steels. It is generally
believed that LMIE is caused by the adsorption-induced
weakening of interatomic bonds at the tip of cracks. This
process facilitates the decohesion of grain boundaries.[51]
The Zn–Fe phase diagram (Figure 9) shows that Zn and
a-Fe have a relatively high mutual solubility at high
temperature. Liquid Zn induced embrittlement of a-Fe
was however also observed. Figure 11 shows a strain–stress
curve of a coated ferritic IF steel. During heating at 8508C
for 2 min, the IF steel is till fully ferritic and the coating
contains liquid Zn. In normal conditions the IF steel has a
20% elongation at 8508C. In contrast the elongation is only
about 10% for the coated IF steel.
The fracture process of the coated 22MnB5 steel can
therefore be estimated to take place in the following
manner. Liquid Zn is separated from the austenitic steel
substrate by the a-Fe layer (Figure 8b). During plastic
deformation, the liquid Zn penetrates along the a-Fe grain
boundaries. This causes the decrease of the ferrite grain
boundary cohesion. As the liquid Zn comes into direct
contact with the substrate austenite, it causes the
embrittlement in a similar manner. As the decohesion
process continues, cracks propagate as the tensile train
is increased and the specimen fractures in a brittle manner.
Several approaches have been proposed to avoid LMIE
in hot stamping. The deformation of hot stamping can be
conducted below the peritectic temperature. For example,
a specimen was heated at 8508C for 4 min and sub-
sequently deformed 40% at 7008C. Its stress–strain curve
is shown in Figure 11. At 8508C the coating contained liquid
Zn and a-Fe. When it was strained below the peritectic
temperature of 7828C, the liquid Zn transformed to solid G1
phase, and the steel showed good ductility. The G1 phase
was brittle, and it broke during deformation, as shown
in Figure 13a. But this broken coating is still able to offer
cathodic corrosion protection.
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It should be noted that, as indicated by bold lines in the
Fe–Zn equilibrium binary phase diagram (Figure 9), the
lower is the Fe content (or the higher its Zn content) in
the coating, the lower is the peritectic transformation
temperature. For example, if the coating has some d phase
(about 10 wt% Fe), the forming temperature for d phase
from liquid is 6728C. If the coating contains z phase (about
7 wt% Fe), the forming temperature for z phase from liquid
is 5308C. The deformation should therefore be conducted
below this temperature to avoid LMIE. This approach is
also confirmed by a study of Faderl[43] during which the
steel was deformed intentionally below 6608C in order to
avoid LMIE. The d phase was observed in the final coating.
Cooling of the steel during hot stamping process is
achieved by heat transfer between steel and cold dies.
As the cooling is continuous, the deformation start
temperature should be kept below the peritectic tempera-
ture. As the liquid metal may need some overcooling to
solidify, the actual deformation temperature should
actually be much lower than the peritectic temperature.
When the steel is deformed at lower temperature, ferrite is
formed in the steel and the strength of final product is
reduced. For example, when the 22MnB5 steel is left unde-
formed isothermally during a holding at 6508C, 4 vol%
ferrite is formed, and the UTS is 1420 MPa. A deformation
of 30% at 6508C results in a 15 vol% of ferrite, and a
decrease of the UTS to 1238 MPa.[52] As heavily deformed
areas of press formed parts usually have a smaller thick-
ness. The additional strength decrease due to strain-
induced ferrite formation should be considered when
the hot stamped part is designed.
Alternatively, Zn alloy coating with a higher melting
temperature can be used for hot stamped steels, for
example, the Zn–Ni alloy coating, which will be discussed
later.
Another technique is to completely eliminate the liquid
phase at high temperature. The liquid coating is trans-
formed to a solid a-Fe phase by increasing its Fe content.
This can be achieved by a diffusion annealing treatment of
the coating for long time, at higher temperature, or by
using a thinner coating to decrease the diffusion distance.
GA coating has advantages in this method because it has
higher initial Fe content (about 10 wt%) and usually has
lower Al content and absence of Fe2Al5 inhibition layer,
which can facilitate the Zn–Fe reactions. Figure 11 shows
the stress–strain curve for a GI specimen, which was heated
to 8508C and held for 20 min. During the heat treatment,
the coating was replaced by a a-Fe solid solution, and no
liquid Zn was present. The steel exhibited a good ductility.
The heating time can be reduced, if thinner coating is used.
This approach has been utilized by Imai and Yoshikawa
et al., who produced a coating which consisted entirely of
a-Fe with Zn in solid solution by heating a 5 mm thin GA
coating at 9008C for 5 min.[40] The a-Fe solid solution is a
soft phase, which can reduce the coating brittleness. The
elimination of the liquid Zn can both suppress both LMIE
and the formation of brittle Fe–Zn intermetallic phases.
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However, the coating consisted entirely of a-Fe solid
solution breaks unexpectedly during deformation at high
temperature, which can be seen in Figure 13b. This
phenomenon was also confirmed in the study of Kojima
et al.[53] It seems that the cracks form among the a-Fe
grains and the cracks stop at the steel surface. This broken
coating can still offer cathodic corrosion protection. It
should be noted that a high Fe content in the Fe–Zn solid
solution increases the electro-chemical potential of the
coating and this limits the cathodic corrosion protection
offered by the coating.
LMIE can also be avoided by reducing the amount of
deformation during hot stamping. In this case, the indirect
hot stamping process is the preferred technique. In the
indirect method, the steel sheet is heavily deformed in a
conventional cold press forming operation. In the sub-
sequent hot stamping process, the amount of strain is kept
small and LMIE is avoided. This method was reported in
the work of Faderl.[43]
It is a common misunderstanding that the Zn coated
steel can only be used in the indirect hot stamping process
due to LMIE.[54,55] The Zn coated steel can be used in the
direct process, providing there is no liquid Zn present in
the coating during actual press forming. As discussed pre-
viously, this can easily be achieved by hot forming below
the peritectic temperature, by using Zn alloy coating with
higher melting temperature, or by transforming the coat-
ing entirely to a solid a-Fe phase.
Besides the cracks caused by LMIE, there is the other
type of cracks formed in the steel. In the case of a-Fe(Zn)
solid solution consisted coating, the coating cracks during
deformation and these cracks propagated into the steel
with length less than 50 mm. Drillet et al. found that strain
induced ferrite or bainite was formed during press forming
and the cracks propagated from the coating into the steel
along the austenite/ferrite interface or austenite/bainite
interface. An effective way to solve this problem is to
reduce the friction by applying lubricant oil on the press
tool surface. The reduced friction can decrease the defor-
mation at the steel/coating interface, meanwhile the strain
induced transformation can also be limited. This method
can effectively avoid the cracks formation.[56]
4.5. Properties
4.5.1. Weldability
The resistance spot weldability of the GI steel after hot
stamping was investigated by Faderl.[43] The coating con-
sisted of Zn–Fe intermetallic phases and a-Fe phase with
Zn in solid solution. The presence of surface oxides
increased the contact resistance greatly. The surface must
therefore always be thoroughly cleaned. After dry ice clean-
ing, the welding resistance deceased to a value less than
1 mV. Some compact oxides remained on the coating sur-
face after cleaning. The presence of these residual oxides
resulted in an increased contact resistance. The heating
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cycle must therefore be optimized to minimize the for-
mation of the surface oxides. In a typical process, the
coated steel was furnace heated for 8 min, and the resulting
coating had an Imin and Imax of 5 and 7 kA for a welding
force of 3–5 kN. The welding current range is about 2 kA.[43]
The spot weldability of a stamped GA coating which
consisted of the Fe–Zn solid solution phase was studied by
Genderen et al.[49] The oxide formation was also reported
to be the reason of increased contact resistance. Short
annealing time could reduce oxide layer thickness and thus
reduce the resistance below 5 mV with a weldable current
range of 1 kA. Akioka and Imai et al. tested the mechanical
properties of welded steel blanks. They welded the blanks
with current of 5.5–10 kA but did not remove the surface
oxides. The tensile shear strength of the welds for hot
stamped GA steels and for bare hot stamped steels were
found to be very similar. This implies that the coating
apparently has no effect on the mechanical properties of
the welded parts.[50]
4.5.2. Paintability
Faderl[43] reported that after removing the surface oxides
and phosphating, the paintability of the GI coating after
hot stamping was similar to that of as produced GA coat-
ings and much better than that of as produced GI coating.
Akioka and Imai et al. reported that the hot stamped GA
coating could be directly phosphated and painted without
removing the surface oxides. The phosphate layer was
wavy due to the formation of ZnO. The phosphatability
was similar to the as produced GA coating. The paint
adhesion was reportedly also good.[50]
4.5.3. Corrosion Resistance
The high temperature formability is not a problem for the
Zn based coating, even when the coating cracks and the
steel substrate is exposed, the coating can still provide an
adequate cathodic corrosion protection.
In Fe–Zn alloys, the electro-chemical potential
decreases as the Zn concentration decreases.
Fleischanderl and Faderl et al. reported that in the hot
stamped GI coating, the upper Fe–Zn intermetallic layer
had an electro-chemical potential of approximately
0.75 V, and the that lower Fe–Zn solid solution layer
had about 0.6 V. These electro-chemical potentials are
higher than ordinary GI and GA coatings, but they are still
much lower than the electro-chemical potential of steel
( 0.42 V).[30] This implies that the coating still has good
cathodic corrosion protection ability.
Faderl et al. reported that the perforation corrosion
resistance of the GI coating after hot stamping was better
than the conventional pure Zn coating. This was due to its
more stable corrosion products induced by a slightly
higher electro-chemical potential. The coating exhibited
red corrosion products during corrosion tests due to the
high Fe content in the coating.[43] Akioka and Imai et al.
compared the corrosion resistance of hot stamped GA
coating with as produced GA coating by conducting cyclic
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corrosion tests. The hot stamped GA coating had similar
performance to the as produced GA specimen, but slightly
inferior than the as produced GA coating due to its higher
Fe content.[50] Dosdat et al.[31] studied the corrosion resist-
ance of aluminized coating, GI and GA coating after hot
stamping. The coated panels were phosphated and
painted. The cyclic corrosion tests were conducted on
scratched panels. In the cosmetic corrosion test, the mean
blister widths of hot stamped GI and GA coatings were
similar, and much smaller than that of hot stamped alumi-
nized coating. They were smaller than the GA IF steel
(100 gm 2, 7.5 mm), due to their larger thickness (about
25 mm) after hot stamping. This observation is different
from that of Akioka and Imai et al., it may be due to the
different thickness of the specimens, which affects the
corrosion performance largely. In the cut-edge corrosion
test, the hot stamped GI and GA coatings had superior
performance than the hot stamped aluminized coating,
because the Zn-based coating can protect the cut-edge
sacrificially. In perforation corrosion test, the maximum
blister depths of hot stamped GI and GA coatings were
similar to that of hot stamped aluminized, and slightly
larger than that of GA IF steel. In the perforation tests
on non-painted panels, the hot stamped GI and GA coated
steels had similar mass loss and blister depth to those of
hot stamped aluminized steel, and much lower than that of
the GA IF steel. This is also contributed by their lager
coating thickness after hot stamping. The hot stamped
GI and GA coatings have excellent cosmetic corrosion
resistance and perforation corrosion resistance, and they
also have sufficient cathodic corrosion resistance.
To ensure an adequate cathodic protection of the sub-
strate, the Zn content in the coating should be sufficient.
Fleischanderl and Faderl et al. reported that the Fe–Zn
intermetallic layer should have a Zn content in the range
of 70–95 wt% and that the a-Fe layer should have a Zn
content in the range of 17–44 wt%.[30] Imai et al.[40]
reported that in the fully a-Fe(Zn) consisted coating the
Zn content should be in the range of 20–30 wt%. It should
be noticed that the reported Zn contents in the a-Fe layer
are averaged values, since the Zn concentration is known
to gradually decrease to zero toward to the steel.
5. Zn–Ni Alloy Coating
A Zn–Ni alloy coating on hot stamped steels have been
developed by Kondratiuk et al.[54] and Kuhn et al.[57] The
coating is manufactured by electro-deposition. The coat-
ing composition is 11 wt%Zn, 0.6 wt%Fe, and balance Zn.
The coating is fully composed of a 10 mm thick g Zn21Ni5
phase. The solid–liquid transformation temperature for the
g Zn21Ni5 phase is 8818C. In equilibrium state, the g Zn21Ni5
phase can be formed when the Ni content is above 14 wt%,
in the process proposed by Kondratiuk et al.[54] and Kuhn
et al.[57] the metastable g phase with lower Ni content is
formed by electro-deposition. The lower Ni content can
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reduce the material cost and higher Zn content can guar-
antee a good corrosion resistance. The metastable g phase
has a simialr melting temperature of 8818C. And the Fe
diffusion into the coating during hot stamping process can
increase the melting temperature further.
In the work of Kondratiuk et al.[54], the steel was heat at
8808C to avoid any liquid phase formation. After holding at
8808C for 5 min, the coating thickness increased to 20 mm.
The top most part of the coating was an oxide layer con-
taining ZnO and MnO. The oxide layer was about 2.5 mm in
thickness.[54] In Figure 14, it seems that the oxide layer is
wavy and loosely adherent, but it is unknown whether the
oxide layer needs to be removed.
After the thermal cycle of hot stamping, the original
coating is replaced by a layer consisting of a-Fe phase with
Zn (26 wt%) and Ni (3 wt%) in solid solution. An additional
phase is present which has a similar composition and
morphology as a-Fe. This phase has a higher hardness.
It has been identified as martensite. The coating also con-
tained two types of g Zn–Ni–Fe phases with different Fe
contents. One of the compounds, located near the coating
surface, was Ni-rich g phase with 13 wt% Ni and 8 wt% Fe.
The other compound was a Fe–rich g phase embedded in
the a-Fe phase. It contained 13 wt% Ni and 13 wt% Fe.
Kondratiuk et al.[54] reported that Ni and Fe could be
substituted when forming these two g phases. The entire
coating transforms to a-Fe with Ni and Zn in solid solution
after an extended heating time.
5.1. Formability
The Zn–Ni intermetallic g phase is hard and brittle. It
cracks during conventional press forming at room
temperature. However, it has a much reduced flaking
and powdering property during forming compared to GA
coating.[58] The high temperature formability of g Zn–Ni–
Fe phases during hot stamping has not been reported
Figure 14. Cross-sectional SEM micrograph of the Zn–Ni alloy
coating after heating at 8808C for 5 min. Reproduced with per-
mission of Elsevier.
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REVIEW
during hot stamping. Considering that there is a large
fraction of a-Fe present in the coating, it may remain
ductile during plastic deformation. The coating will exhibit
less flaking and powdering at room temperature.
5.2. Weldability
Due to its higher hardness, higher melting temperature,
and lower coating weight, the weldability of the Zn–Ni alloy
coating is generally considered superior to the weldability
of GI and GA coatings. The electrode wear is reduced and
the welding current range is wider.[58] The hot stamped Zn–
Ni alloy coating is mostly replaced by a soft a-Fe phase
with Zn and Ni in solid solution. This increases the coating
weight and thickness, and it reduces the coating hardness.
Thus the weldability of the hot stamped coating may not be
as good as for the original Zn–Ni coating. But due to the
higher melting temperature, a smaller coating thickness
and the presence of the g Zn–Ni–Fe phase, the weldability
of the hot stamped Zn–Ni coating may still be good.
5.3. Paintability
It has been reported that the Zn–Ni alloy coating has some
paintability problems associated with the application of
the electrophoretic primer.[58] There is no information
available about the paintability of the coating after hot
stamping. Since the coating is replaced by large fraction
of a-Fe(Zn, Ni), it is expected that the paintability will be
improved comparable to that of the original coating.
5.4. Corrosion Resistance
Kondratiuk et al.[59] studied the corrosion performance of
the Zn–Ni alloyed coating after hot stamping. Hot stamped
Zn–Ni alloy coatings were evaluated by accelerated cor-
rosion tests, for example, cyclic corrosion test and salt
spray test. During the test the g Zn–Ni–Fe phases were
preferentially corroded. The electro-chemical potential
of a Zn–Ni alloy coating is about 500 mV lower than for
substrate steel, and the coating can offer cathodic cor-
rosion protection. Its corrosion resistance has been report-
edly to be better than that of hot stamped aluminized
coating and that of as-produced GI coating. The heating
time has no significant effect on its corrosion resistance,
which implies that the coated steel can be treated in a wide
heating range.
The corrosion resistance of the Zn–Ni alloyed coating
remains unclear. It was reported that Zn–Ni coating had a
better corrosion resistance than GI and GA coatings with
similar coating weights, when tests were conducted in an
accelerated corrosion condition, for example, cyclic cor-
rosion test, on unpainted panels.[60] In long-term and in-
service tests, the fully painted panels with Zn–Ni coating
had less cathodic corrosion protection and its corrosion
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resistance was poorer than that of GI and GA panels. This is
due to the gradual decrease of Zn content and increase of
the Ni content, in addition to the presence of microcracks
in the Zn–Ni intermetallic phase.[58] The corrosion resist-
ance of hot stamped Zn–Ni coatings in real service con-
ditions is still not well documented.
6. Hybrid Coatings
Hybrid coatings composed of organic and inorganic
materials were developed by Goedicke et al.[61,62] Several
generations of hybrid coatings have been developed. The
first generation was used to prevent oxidation during heat
treatment, and had to be removed after the hot stamping due
to its poor RSW performance. The second generation of
hybrid coatings achieved good welding properties by reduced
electrical resistance. However, the coating did not provide a
cathodic corrosion resistance after hot stamping. The third
generation offers protection from oxidation, good RSW per-
formance, and an adequate cathodic corrosion resistance.
The hybrid coating application process starts with a
strip cleaning stage, followed by a liquid paint spray proc-
ess and a paint drying step in a hot air atmosphere. The
paints are synthesized in a sol–gel reaction from organo-
silane precursors or organic monomers. After drying, the
coating is composed of an inorganic–organic matrix con-
taining Mg, Al particles, graphite, and wax components.
The graphite is added to improve the tribological property
during hot press forming, while the wax is added to
improve the tribological properties during cold press
pre-forming in the indirect hot stamping process. The
Mg addition is made to improve the cathodic corrosion
resistance after hot stamping. Its content should be more
than 30 wt%. The Mg particles were covered by a thin TiO2
film in order to prevent severe Mg oxidation during the
heat treatment. Figure 15a shows the cross-section of coat-
ing before hot stamping, and it can be seen that there are
lamellar dispersions of flat Mg particles and large Al
Figure 15. Cross-sectional SEM micrographs of hybrid coating a) before and b) after heating at 9508C for 5 min. Reproduced with
permission of copyright holder (cf. ref. [64]).
428 steel research int. 83 (2012) No. 5
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particles in the inorganic–organic matrix. The initial coat-
ing thickness is about 10–20 mm.[63] The melting tempera-
tures of Al (6608C) and Mg (6508C) were much lower than
the heating temperature in hot stamping process. They
may melt during heating and cause adhesion to furnace
rollers.
After hot stamping, the coating thickness is increased to
25–35 mm (Figure 15b). The Al reacted with the substrate
steel and formed Fe–Al alloy. The Fe–Al alloy is formed in
the coating, and also grows inward to the steel substrate.
The Fe–Al alloy improved the electrical conductivity of the
coating. It is estimated that the brittle Fe2Al5 or FeAl2
intermetallic phase is formed. The Mg transforms to a
mixture of Mg particles, MgO, and TiO2. The Mg particles
offer cathodic corrosion protection. Very little Al2O3 oxide
is present at the coating surface after hot stamping.[62,64]
The high Al content of hybrid coatings leads to a
reduced electrical resistance and an improved spot weld-
ability. When the coating contains an optimized amount of
Al, the electrical resistance decreases to 2 mV after heating
at 9508C for 4 min in air. The Imin was 7.0 kA and the Imax
was 8.1 kA for a welding force of 4.3 kN. The hybrid coating
has a good weldability in both laser welding and gas-metal-
arc welding.[29,62]
The third-generation of hybrid coating can offer catho-
dic corrosion protection. It was evaluated by conducting
salt spray tests on scratched specimens. The coating did
not exhibit corrosion during 96 h test.[62] Hybrid coatings
also have a good paintability. After phosphating and cata-
phoretic painting, the coating showed good paint adhesion
during an immersion test in salt water.[64]
7. Other Types of Coating
7.1. Al–Zn Alloy Coating
The 55 wt%Al–Zn alloy coating was tested for hot stamping
by Luther et al.[65] Commonly this type coating is named as
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Galvalume coating. Usually the coating has additional
1.6 wt% of Si. Si is added into the bath to prevent strong
reaction between the steel substrate and Al–Zn bath.[42]
Before hot stamping the coated steel firstly goes through a
pre-conditioning stage, where the coated steel is heat
treated at 550–7308C for 9–66 min. The Fe content
increases typically to above 60 wt%, which can stabilize
the coating metals during subsequent heating of hot
stamping. After hot stamping the coating surface becomes
porous, and two Fe–Al-rich phases are present, an Fe–Al(–
Si) phase and a Fe–Al(–Zn) phase. A diffusion layer with Al
enrichment was formed at the coating/steel interface.
Cracks are formed in the coating during bending test,
but cracks do not propagate into the steel.
The hot stamped Al–Zn coating has a weldable current
range of 1.1 kA for RSW. It also has good paint adhesion.
The phosphated and painted panels reportedly have better
corrosion resistance than that of hot stamped GA coating
in the cyclic corrosion test. This Al–Zn coating is still under
developing.
7.2. Dual Layer Zn–Al Coating
A dual Zn–Al layered coating for hot stamped steel has
been proposed by Lupp et al.[66] In this process the steel is
first hot-dip coated with a type 1 Al–10%Si aluminized
coating, and subsequently hot-dip coated with Zn
containing small addition of Al (<1 wt%). The final coating
is composed of a 5 mm Zn layer, a 15 mm Al–Si alloy
layer and a Fe2SiAl7 intermetallic layer at the coating/
steel interface. In addition, a phosphating process is
conducted prior to hot stamping. The phosphate layer
facilitates the formation of a surface oxide layer during
hot stamping.[67]
During the holding at 9008C for 5 min, inter-diffusion
takes place among the Zn layer, the Al–Si layer, and the
substrate steel. The final coating consists of two layers. The
Zn-rich upper layer composition is 80 wt%Zn, 16 wt%Al,
and 2 wt%Si. The Al-rich lower layer contains 40 wt%Al,
30 wt%Fe, 20 wt%Zn, and 5 wt%Si. The phase constituents
in the coating have not been reported.[66] The upper layer is
essentially a binary Zn–Al alloy, and it is expected to be
liquid at high temperature. This Zn-rich liquid may cause
the adhesion to press dies and the LMIE. The lower layer
can be considered to be a Zn–Al–Fe ternary alloy, and
complex intermetallic phases are very likely present in this
layer.
Lupp et al.[67] also proposed phosphating the Zn–Al dual
layer coating. He reported that Zn3(PO4)2H2O was formed
on the coating surface after phosphating, and that ZnO
and Al2O3 were present on the coating surface after heat
treatment. This oxides layer may be more effective at
suppressing Zn evaporation than the coating, that is, not
phosphated.
After heat treatment, the Zn–Al coating has a low elec-
tro-chemical potential of 0.75 V. This value is slightly
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REVIEW
lower than that of the hot stamped GI coating ( 0.70 V),
and much lower than that of steel ( 0.42 V).[66] It means
that the Zn–Al dual layer coating can provide cathodic
corrosion resistance.
7.3. Zn–Al–Mg Alloy Coating
The Zn–Al–Mg alloy coating on hot stamped steel was
studied by Genderen et al.[49] The coating composition is
unknown, but usually the Zn–Al–Mg alloying coating con-
tains about 6 wt% Al and 0.5–3 wt% Mg. It has superior
corrosion resistance compared to GI coating.
During hot stamping the coating fully reacts with the
substrate steel. LMIE can be avoided. Tiny cracks are
observed to propagate from coating to substrate steel,
which is similar to the cracks formed in the hot stamped
GA steel. Oxide layer is formed on the coating surface. The
contact resistance for RSW is below 5 mV, and the welding
current is within 1 kA. The phosphated and painted panels
reportedly show better corrosion resistance than that of
hot stamped GA coating. The surface Al and Mg oxides give
an extra barrier corrosion protection.
7.4. Zn–Al–Mg Post-Process Coating
A method to coat hot stamped parts by hot-dip galvanizing
has been developed by Merklinger et al.[68] In this method,
the bare steel is firstly hot stamped, and after a surface
cleaning process, the steel is hot dipped into the liquid Zn
bath. The steel is then hot-dip GI in a conventional Zn bath.
The process temperature is approximately 4508C. The mar-
tensitic steel is tempered during the coating process and its
tensile strength decreased from 1650 to 900 MPa. In order
to avoid this loss of strength, a Zn alloy with low melting
temperature was developed. This alloy was mainly alloyed
with Al and Mg, and its melting temperature was in the
range of 350–3758C. After dipping for 6 min the strength of
the steel decreases to 1300 MPa. This low temperature alloy
coating has a poor wetting performance with respect to the
substrate steel. A thin layer of Sn is therefore deposited on
the steel before galvanizing to increase the surface wetting.
The alloyed coating has a similar electro-chemical poten-
tial as a pure Zn coating, and it provides an excellent
cathodic corrosion protection.
The tempering effect of the hot dip galvanizing process
on the martensitic high strength steel can be in principle
avoided by electro-galvanizing. In the electro-galvanizing
process, the steel strip goes through a Zn containing sulfate
electrolyte and the Zn is electro-deposited on the strip.
Hydrogen uptake can occur during this process. An
increased H content makes the martensitic steel suscept-
ible to the hydrogen embrittlement and delayed fracture.
Up to now, there has been no report on the properties of
hot stamped steel which was subsequently electro-GI.
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8. Coating Comparison ing causes the adhesion of Zn to press dies and the LMIE of
the steel. The presence of the liquid Zn also results in
The major types of coating on hot stamped steels are formation of brittle Fe–Zn intermetallic phases. The for-
compared in Figure 16. The advantages, challenges, and mation of a coating consisting entirely fully of a-Fe(Zn) can
relevant references of each coating type are also listed alleviate this problem. This coating also cracks during
below each schematic. deformation, but cracked coating can still provide suffi-
In hot stamped aluminized coating and the aluminide cient cathodic corrosion protection. Hot stamped GI coat-
coating, the surface Al2O3 effectively protects the coating ings and GA coatings have similar corrosion performance.
from severe oxidation. The oxide layer is thinner than that In the hot stamped Zn–Ni alloy coating, the coating–
of other coating types, and it has no apparent effect on the steel reaction occurs in the solid state unlike to other types
contact resistance for RSW. This oxide layer also acts as a of coating. It does not have the problem of liquid Zn
barrier during corrosion. The hot stamped aluminized adhesion or LMIE due to higher melting temperature.
coating and the aluminide coating can only provide a The surface oxide is thick and wavy due to the formation
barrier corrosion resistance. The corrosion behavior is of loose ZnO and MnO. The formation of a large phase
excellent due to formation of stable corrosion products. fraction of a-Fe(Zn, Ni) reduces the coating brittleness
The hot stamped aluminized coating is brittle due to the compared to the original Zn–Ni coating. It is estimated
formation of Fe–Al intermetallic phases. The coating tends that Zn–Ni alloy coatings have a higher material cost due to
to break during plastic deformation. The aluminide coating Ni-alloying and the cost of the environmental regulations
can solve this problem by forming ductile phases in the associated with the use of Ni-containing electrolytes.
coating. The crack-free coating has better corrosion resist- In hybrid coatings, the Al2O3 is formed on the coating
ance. During hot stamping the melting of Al can result in surface. The formation of Fe–Al intermetallic phase
the adhesion of Al to the furnace rollers. decreases the contact resistance for RSW, but their for-
In the hot stamped GI and GA coatings, the surface mation may increase the brittleness of the coating. The Mg
oxide effectively protects the coating from oxidation and particles provide the cathodic corrosion resistance. It is
suppresses the Zn evaporation at high temperature. The estimated that the wet coating application process and the
oxide layer is thicker and wavy due to the formation of subsequent drying stage may increase the process cost. In
loose ZnO. This oxide layer increases the contact resistance addition, the use of a TiO2 thin film coating on the Mg
for RSW. This oxide layer should be removed or the for- particles present in the hybrid coating may result in even
mation of oxide should be minimized by adjusting the higher process costs. The melting of Al and Mg may be also
heating conditions. The presence of liquid Zn in the coat- lead to furnace roller damage.

Aluminized coating Galvanized coating Galvannealed coating Zn-Ni alloy coating Hybrid coating
Al Hybrid matrix
Si
η-Zn Fe-Zn γ Zn21Ni5 Mg+TiO2 Al
Prior to Fe2SiAl7
hot stamping Fe2Al5 , FeAl3 Fe2 Al5 Fe2Al5

steel steel steel steel steel

Al2 O3 Al2O3 Al2 O3 + ZnO Al2O3 + ZnO ZnO + MnO Al2 O3

Fe2 Al5 /FeAl2 Fe-Zn Mg, MgO, TiO2
Fe2 SiAl2 Ni rich γ Fe-Al
voids voids
Fe2Al5 /FeAl2 α-Fe(Zn) Fe rich γ
Post to Fe2 SiAl2 FeAl+Fe3Al / Fe3Al α-Fe(Zn)
α-Fe(Zn)
hot stamping Diffusion layer Martensite

steel steel steel steel steel steel

Good oxidation resistance Good formability Higher melting temperature

No LMIE
Advantages Good barrier corrosion resistance Good oxidation resistance Cathodic corrosion resistance No LMIE Cathodic corrosion resistance
Cathodic corrosion resistance
No need for phosphating Good barrier corrosion resistance Cathodic corrosion resistance

LMIE Formation of bittle Fe-Al

Coating brittleness
Liquid Al adhesion Liquid Zn adhesion intermetallics
Challenges Liquid Al adhesion Brittleness of coating Higher cost
No cathodic corrosion protection Oxides removal Melting of Al and Mg
No cathodic corrosion protection
Brittleness of coating Higher cost

Drillet
and Grigorieva et al. [11, 15]
Dosdat et al.[31]
Takagi et al. [12]
Yoshikawa
Suehiro and Maki et al. [16] Fleischanderl
and Imai et al.[40, 41]
Maki et al. [17] and Faderl et al. [30]
Main Kim and Cho et al. [33, 34] Lee and Fan et al. [46] Kondratiuk
Im et al. [18] Dosdat et al. [31] Goedicke et al.[61-64]
references Fan et al. [36] Genderen et al.[49] and Kuhn et al.[54, 59]
Fan et al. [19] Faderl et al. [43, 45]
Akioka and Imai et al.[50]
Jener et al. [20] Lee and Fan et al. [46]
Kojima and Imai et al.[53]
Dessain et al. [25]
Drillet and Grigorieva et al.[56]
Allely et al. [28]
Dosdat et al. [31]

Figure 16. Comparison of the different coating systems for hot stamping application.

430 steel research int. 83 (2012) No. 5 ß 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.steel-research.de
For the Al–Zn alloy coating, the Zn–Al dual layer coating,
and the Zn–Al–Mg alloying coating, there are a few detailed
reports related to their application properties. In general,
the Al addition can protect steel from severe oxidation and
Zn evaporation. The Zn addition provides good corrosion
resistance. Complex intermetallic phases are formed in the
coatings.
The alternative Zn–Al–Mg coating post-process appli-
cation is carried out after the hot stamping process. This
approach does not avoid the problems associated with the
oxidation of the bare hot stamping steel during heating
stage.
9. Conclusions
The optimal coating for hot stamped steels should provide
a sufficient oxidation resistance, adequate formability
at high temperature and at room temperature, good
corrosion protection by barrier action and cathodic
dissolution, sufficient paint adhesion and weldability.
Additionally, the manufacture and application of this coat-
ing on hot stamped steels should be easy to implement and
cost effective.
Most coatings on hot stamped steels are currently
metal-based. Al, Zn, Ni, and Mg have a lower electro-
chemical potential than steel. Except for Ni, these metals
and their alloys used as coatings in hot stamping have a
lower melting temperature and a higher chemical reactiv-
ity than steel. Alloy coatings melt during the heating stage
of the hot stamping process. The formation of surface
oxide is essential since it can retard the further oxidation
of the coating. In the case of Zn-based coatings the oxi-
dation can suppress Zn evaporation. The oxide layer also
acts as a corrosion barrier. The surface oxide increases the
contact resistance in RSW, and the heating cycle should be
optimized to reduce the formation of the surface oxide
thickness, or the oxide should be removed before welding.
The diffusion processes occurring between the coating
and the steel are essential as well. The diffusion leads to
a gradual Fe enrichment of the coating and solid interme-
tallic phases are formed at higher temperatures. The coat-
ing properties are often determined by these intermetallic
phases. The intermetallic phases act as shield coating, but
there is still insufficient data about their physical proper-
ties to clearly evaluate and compare each type of hot
stamping coating. In addition, a solid solution of alloying
elements in the a-Fe phase is formed at the coating–steel
interface. The formation of this phase can eliminate the
problems related to the formation of liquid phases such as
LMIE. This phase is less brittle and the alloying usually
gives it a good corrosion resistance.
The corrosion resistance of hot stamped steel parts for
automotive vehicles is one of their essential properties. In
coatings on hot stamped steel, the metals are present as
intermetallic phases or in solid solution in a-Fe. Mg
particles are protected by TiO2 thin films in the hybrid
ß 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
REVIEW
coating. The content of the alloying elements in the coating
determines the corrosion properties of the coating after hot
stamping. In all studies analyzed for the present review, the
corrosion resistance of the hot stamped coatings was eval-
uated by means of accelerated corrosion tests, such as the
salt spray test, cyclic corrosion tests, and electro-chemical
tests. Most of these standardized tests were designed for
the evaluation of conventional coatings. The use of coated
hot stamped steel in automotive vehicles is very recent,
and there have hitherto been no reports on the coating
corrosion performance in actual in-service conditions. The
current corrosion performance evaluation of hot stamped
coatings should therefore be used with the necessary
precautions.
Acknowledgments
The authors gratefully acknowledge the support of POSCO
Technical Research Laboratories and POSCO C&C. The
authors sincerely acknowledge Dr. J. Kondratiuk, Dr. S.
Goedicke, Dr. Y. R. Cho, and Dr. H. G. Kim for granting
permission to use their Figures.
Received: November 23, 2011;
Published online: March 16, 2012
Keywords: hot stamping; coating; aluminized;
galvanized; intermetallics
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