Surface & Coatings Technology 200 (2006) 6601 – 6605

www.elsevier.com/locate/surfcoat

The high-temperature oxidation behavior of hot-dipping Al–Si

coating on low carbon steel
Chaur-Jeng Wang ⁎, Shih-Ming Chen
Department of Mechanical Engineering, National Taiwan University of Science and Technology, 43 Keelung Road, Section 4, Taipei, 106, Taiwan
Available online 15 December 2005

Abstract

Low carbon steel was coated by hot-dipping into a molten bath containing Al–10 wt.% Si. The high-temperature oxidation behavior of the
specimen was tested at 750, 850 and 950 °C for 72 h in air using a thermobalance. The element distribution, phase composition, and morphology
of the aluminide layer and the oxide scale were characterized by OM, XRD and SEM/EDX. After hot-dip treatment, the coating layers consisted of
three phases, where Al, FeAl3, and Fe2Al5 were detected from external topcoat to the aluminide/steel substrate. The result of high-temperature
oxidation test showed oxidation kinetics basically followed the parabolic rate law at all temperatures. The Fe2Al5 formed during the immersion
process completely transformed to FeAl2, FeAl and α-Fe(Al) phases because of the composition gradient and the chemical diffusion by oxidation.
In the present study, Kirkendall voids were found to form at the coating/substrate interface due to the rapid inter-diffusion of iron and aluminum
during oxidation and, therefore, the adherence of the coatings should be compromised. Afterwards, loss of protective behavior of coating layer
occurred only by iron oxide nodules formed on the coating specimen exposed at 850 °C for 24 h.
© 2005 Elsevier B.V. All rights reserved.

Keywords: Low carbon steel; Hot-dip; Si; Aluminide; Fe2Al5; Voids; Nodules

1. Introduction cases, and the intermetallic layer mainly consisted of Fe2Al5. It

Low carbon steel plays an important role in structural
applications due to the lower cost than high alloy steels [1].
With the lack of compact-scale formation on the steel surface, it
cannot be used for oxidation resistance application, especially in
oxidizing environment at elevated temperatures [2]. For
improving high-temperature oxidation resistance of low carbon
steel, alloying element addition or surface treatment was chosen
[3,4]. Among the various surface coating techniques, the hot-
dipping process is an effective and inexpensive method to
modify the surface of low carbon steel [5,6]. This technique has
been used to form an Al-rich layer on steel surface. The coating
treatment is expected to form a continuous, protective Al2O3
layer on the steel surface after exposure at elevated temperatures
[7]. Aluminizing is usually carried out by the hot-dip process in
which the component to be coated is treated in an aluminum
molten bath. The interface between the substrate and the
intermetallic layer appeared tongue-like morphology in most
⁎ Corresponding author. Tel.: +886 2 27376441; fax: +886 2 27376460.
E-mail address: cjwang@mail.ntust.edu.tw (C.-J. Wang).
0257-8972/$ - see front matter © 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2005.11.031
is generally recognized that the thickness of the intermetallic
layer decreases with the increase of the silicon content in the
melt [8,9]. The effect of Si in reducing the alloy layer thickness
has been attributed to the fact that Si reduces the rate of solid
state diffusion of aluminum in steel [10]. Silicon could be
incorporated into the alloy layer and inhibited Fe2Al5 growth.
However, the high-temperature oxidation behavior of Fe–Al–
Si-aluminized layers on low carbon steel is not yet understood
well. Thus, the present research was to characterize the high-
temperature oxidation behavior of low carbon steel with hot-dip
aluminizing coating and to examine the defects of composition
and microstructure on coating response and substrate protection
in oxidizing environment.
2. Experimental procedures
The chemical composition of the steel and Al–10 wt.% Si
alloy used in this study are shown in Table 1. The thermal
mechanical treatments of the steel prior to tests were cold-rolling
and annealing. Rectangular specimens were cut to the dimen-
sions of 15 × 12 × 2 mm3 by a water-cooled cutting machine.
6602 C.-J. Wang, S.-M. Chen / Surface & Coatings Technology 200 (2006) 6601–6605
Table 1
Chemical composition of alloys employed (wt.%)
Alloy Si Mn Cr Ni C Fe
Low carbon steel 0.28 0.97 0.02 0.11 0.20 Bal.
Al–10 wt.% Si 10.00 0.50 0.40 – – 0.70
Bal. = balance compositions of alloy.
After machining the samples were degreased in acetone bath and
finally cleaned ultrasonically in ethanol bath, and dried in air
before hot-dip aluminizing. The Al–10 wt.% Si aluminum alloy
was melted in an alumina crucible and maintained at 700 °C.
Specimens for further hot-dip aluminizing treatment were hung
by stainless steel wires and coated with a uniform welding flux.
The up/down speed of the specimen elevator was 15 cm/min.
After 16 s of exposure, they were pulled out and air-cooled to
room temperature. Platinum wire (25 μm diameter) was used as
a marker by spot-welding on the surface of some specimens. The
marker specimens were carried out by hot-dipping process under
the same conditions. The hot-dipped specimens were cleaned by
a mixed aqueous solution of nitric acid, phosphoric acid, and
water in a 1:1:1 volume ratio at 25 °C. After hot-dip aluminizing,
metallographical examination was carried out to study the
developing mechanism and the thickness of the intermetallic
layers. The aluminized samples were placed in a furnace heated
in static air at temperatures of 750, 850 and 950 °C for 10 min to
56 h. The oxidation kinetics were evaluated by thermogravi-
metric analysis (TGA). After oxidation tests, the phase
constitutions in the intermetallic layers of all samples were
investigated by means of metallographical examination, scan-
ning electron microscopy (SEM) with energy-dispersive X-ray
facility analysis (EDX) and X-ray diffraction (XRD) using Cu-
Kα radiation.
Fig. 1. (a–l) Optical cross-sectional micrographs of coated specimens oxidized for various time at 750, 850 and 950 °C in air.
3. Results and discussion
Al 3.1. Microstructure and phase constitution
–
Bal. A typical cross-section morphology of an as-coated steel is
shown in Fig. 1(a), where three layers are presented: topcoat
aluminum (dissolved Si), intermetallics and the steel substrate.
XRD analysis showed that the coating layers consisted of three
phases, where Al, FeAl3, and Fe2Al5 were detected from the
external topcoat to the aluminide/steel substrate. Typically, the
thickness of the coating layers was about 25 μm and the coating
layers showed good adhesion to the steel substrate. The surface
morphology of the as-coated specimen is shown in Fig. 2(a),
where eutectic Si particle formed on the coating surface. For
determining the formation mechanism of the aluminide layer
during the hot-dip process, some specimens with platinum
markers were performed. An optical micrograph of the coated
specimen with platinum marker is shown in Fig. 1(b). The
platinum marker was located at the interface between the
aluminum topcoat and aluminide layer. This suggested that the
formation of the aluminide layer was mainly due to the outward
diffusion of iron, while the inward diffusion of Al contributed to
the growth of the aluminide layer.
In order to understand the oxidation behavior and the phase
formation in the aluminide layer, oxidation tests were carried
out at 750, 850 and 950 °C in air for various durations of time.
For 10-min oxidation at 750 and 850 °C as shown in Fig. 1,
the aluminum topcoat could still be observed in the coating
layers. After oxidation for 20 min at both temperatures, the
aluminum topcoat disappeared and an aluminide layer formed
owing to the outward diffusion of iron from the matrix and to
the inward diffusion of aluminum. The aluminide layers being
 C.-J. Wang, S.-M. Chen / Surface & Coatings Technology 200 (2006) 6601–6605 6603

approximately 75 μm thick consisted of a thin α-Al2O3 layer

on the surface, followed by a thicker layer of Fe2Al5 + FeAl2
on the steel substrate side. As the oxidation time increased to 1
h at 850 °C, some cracks generated in the aluminide layer due
to the thermal expansion mismatch at the interface between
the brittle Fe2Al5 + FeAl2 layer and the steel substrate [11].
The thickness of aluminide layer was kept almost the same for
all testing periods. However, the dominating Fe2Al5 + FeAl2 in
the aluminide layer transformed to FeAl gradually with
increasing time owing to the aluminum dilution. The Al
consumption in the aluminide layer was mainly by two ways:
one is the outward diffusion of Al to form Al2O3 scale, and
the other is Al inward diffusion toward the steel substrate [12].
Thus, FeAl was formed beneath the oxide scale and at the
interface between Fe2A5 + FeAl2 phases and the steel substrate
as shown in Fig. 3.
For oxidation at 850 °C for 2 h, some voids formed at the
interface between the aluminide layer and the steel substrate as a
result of Kirkendall effect [13]. Vacancies were generated at the
interface and might then condense into voids due to the rapid
inter-diffusion of ferrite and aluminum during the oxidation or
heat treatment processes [14], as indicated in the black area
between the steel and the aluminide layer as shown in Fig. 1.
The accumulation of voids might generate cracks and further
lead to the degradation of the aluminide layer. The black area in
the aluminide layer was likely to be oxides formed from the
specimen surface by high-temperature oxidation. For specimens
oxidized at 750 °C for 8 and 56 h, the phases present in the
aluminide layer and cross-sectional morphologies were similar
to that of specimen oxidized at 850 °C for 3 h. A cross-sectional
micrograph of coated specimen oxidized at 750 °C for 56 h and Fig. 3. (a) Cross-sectional micrograph of coated specimen oxidized at 750 °C for
its corresponding EDX line profiles of elements Fe, Al and Si 56 h and (b) its corresponding EDX line profiles of elements Fe, Al and Si
distributions across the coating layer on the steel substrate were distributions across the coating layer on the steel substrate.

Fig. 2. Surface morphologies of (a) as-coated specimen, (b) coated specimen after being oxidized at 750 °C for 56 h, (c) coated specimen after oxidized at 850 °C for 24
h, and (d) enlarged view of panel (c).
6604 C.-J. Wang, S.-M. Chen / Surface & Coatings Technology 200 (2006) 6601–6605

depicted in Fig. 3. Three distinct phases present in the aluminide

layer consisted of FeAl, Fe2Al5 + FeAl2 and FeAl, starting from
the outer aluminide layer/steel substrate. Silicon was enriched in
FeAl area due to the fact that the solubility of Si ranged from 15
to 17 at.% when FeAl was in equilibrium with the Fe2Al5 and
FeAl2 [15]. The SEM micrograph in Fig. 2(b) revealed the oxide
morphology of the aluminized steel specimen after oxidation at
750 °C for 56 h; the surface morphology of the oxide scale
revealed dense character, which consisted of Al2O3. More voids
and pores were observed in the aluminide layers and at the
interface between the aluminide layer and the steel substrate
after oxidation at 850 °C for 4 h.
As mentioned above, it can be observed that a crack was
generated across the interface between the aluminide layer and
the steel substrate after oxidation at 850 °C for 8 h. Crack at the
interface between the aluminide layer and the steel substrate Fig. 5. SEI fractograph of aluminide layer formed on the coated specimen after
might promote exfoliation of the aluminide layer. Consequently, oxidation at 750 °C for 24 h.
the microcracks became short-circuit diffusion paths for oxygen
penetration when mechanical failure of the aluminide layer took
place, leading to the nucleation and growth of oxide nodules on occurred after oxidation at 850 °C for 24 h as shown in Fig. 1
the coating surface. During high-temperature oxidation, a sign (h). Meanwhile, through the top view investigation of scanning
of failure as the formation of spore-like oxidation nodules of electron micrograph, it was clearly observed that the oxide
dark color formed on the surface of the aluminide layer. nodules formed on the coated specimen, as shown in Fig. 2(c)
Protrusion of iron oxide on the surface of coated specimen and (d). The degradation might cause the voids formation
between the aluminide layer and the steel substrate. The
phenomenon would be more pronounced when the aluminide
layer lost its protective ability. The cross-sectional micrograph
of the aluminide layer with protrusion of iron oxide and its
corresponding EDX quantitative analysis were depicted in Fig.
4. It can be seen clearly that the steel substrate was oxidized
directly by oxygen penetration through the cracks. The iron
oxides were formed at the surface of the aluminide layer and in
the internal-oxidation layer. The brittle Fe2Al5 + FeAl2 phases
formed during the hot-dip aluminizing process transformed
completely to FeAl phase after oxidation at 850 °C for 56 h. It
also can be observed that voids formed in the aluminide layer
after oxidation at 950 °C for 8 h due to fast inter-diffusion rates
of Fe/Al in the coating layer. Thus, the Fe–Al intermetallic in

Fig. 4. (a) Cross-sectional micrograph of coated specimen oxidized at 850 °C for

24 h and (b) its corresponding EDX quantitative analysis results showing the Fig. 6. Plot of oxidation kinetics of coated specimens after oxidation at 750, 850
concentration variations of Al, Fe, Si, O and Mn elements. and 950 °C for 72 h.
 C.-J. Wang, S.-M. Chen / Surface & Coatings Technology 200 (2006) 6601–6605
the coating layer totally transformed to α-Fe(Al), and oxidation
behavior would be similar to that of the steel substrate.
The mechanism of the internal voids formation was
attributed to the Kirkendall effect. The different diffusion
rates between Fe and Al caused a net flux of vacancies to form
voids at the interface between the aluminide layer and the steel
substrate. Fig. 5 shows the surface morphology and fractured
section of the aluminide layer after oxidation at 750 °C for 24 h.
It can be seen that some voids formed at the interface between
the aluminide layer and the steel substrate.
3.2. Oxidation resistance
The oxidation kinetics of the coated specimens were studied
at 750, 850 and 950 °C for 72 h. Fig. 6 shows changes in weight
gain per unit surface area versus time, revealing that the kinetics
curves approximately obeyed the parabolic rate law, regardless
of temperature. In addition, it can be seen that the weight gain of
specimens increases with increasing temperature. It was due to
the fact that voids condensed to form cracks extensively at the
interface between the aluminide layer and steel substrate and
provide more substrate surface area for oxidation, leading to
faster weight-gain kinetics at 850 °C. On the other hand, the Fe–
Al intermetallic transformed completely to α-Fe(Al) after
oxidation at 950 °C for a short period of time. The coating
layer fully lost its efficacy and, afterwards, oxidation could
almost match the direct oxidation of the substrate steel. As
mentioned above, severe cracking and internal oxidation would
occur in the coated specimen after high-temperature oxidation.
Thus, these limitations degrade the use of aluminized coatings
in high-temperature oxidation environments.
4. Conclusions
The high-temperature oxidation behavior of low carbon steel
with hot-dip aluminizing coating was investigated in the
temperature range from 750 to 950 °C in air for various
durations of time. The results may be summarized as follows:
1. The thickness of aluminide layer kept almost the same for all
testing durations of time. However, the Fe2Al5 + FeAl2
6605
dominated aluminide layer transformed to FeAl gradually
with increasing time owing to the aluminum dilution.
2. The accumulation of voids at the interface between the
aluminide layer and the steel substrate might produce
cracks and result in the degradation of the aluminide layer.
Therefore, protrusion of iron oxide nodules on the surface
of coated specimen occurred after oxidation at 850 °C for
24 h.
3. The oxidation kinetics of the coated specimens followed the
parabolic rate law at all three temperatures. Furthermore,
severe cracking and internal oxidation occur in the coated
specimen after high-temperature oxidation. Thus, these
limitations degraded the use of aluminized coatings in
high-temperature oxidation environments.
Acknowledgements
The authors are very grateful to the National Science Council
of Republic of China for funding support under Grant No. NSC
93-2216-E-011-023.
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