Surface & Coatings Technology 205 (2010) 1220–1224

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Surface & Coatings Technology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / s u r f c o a t

Microstructure and high temperature oxidation behavior of hot-dip aluminized

coating on high silicon ductile iron
Meng-Bin Lin ⁎, Chaur-Jeng Wang
Department of Mechanical Engineering, National Taiwan University of Science and Technology, Taipei, Taiwan

a r t i c l e i n f o a b s t r a c t

Available online 18 August 2010 High silicon ductile iron was coated by hot-dipping into an Al molten bath. The oxidation behavior of the
aluminized alloy and the bare substrate was studied in air at 750 °C. The results showed that the coating
Keywords: layers consisted of three layers, in the sequence of Al, Fe–Al intermetallic and Si pile-up layers from the
High silicon ductile iron external topcoat to the substrate. The intermetallic layer was composed of outer FeAl3 and inner Fe2Al5. The
Hot-dipping Al outer rod-shaped FeAl3 dispersed in the aluminum topcoat, while the inner tongue-like Fe2Al5 formed in the
High temperature oxidation
metallic layer becoming the major phase in the aluminide coating layer. Those three layers of aluminum,
Fe2Al5 and silicon pile-up layer exhibited hardness of HV 50, HV 1100 and HV 450, respectively. In this study,
when the as-coated specimens were examined, Fe–Al–Si compounds could not be found. But the silicon pile-
up at the interface between the substrate and the Fe–Al intermetallic layer could be seen in all the as-coated
specimens. The graphite nodules were noticed in the substrate. The presence of graphite nodules in the
substrate might be markers of hot-dipping. After hot-dipping in Al all the specimens contained graphite
nodules in the aluminide layer.
The oxidized graphite nodules resulted in cracks propagating in aluminide coating. Even though graphite
nodules meant the existence of crack in the aluminide coating, the high temperature oxidation experiments
indicated that the aluminide coating could prevent the oxidation of substrate effectively even at 750 °C.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction manufacturers to raise the top combustion temperature and therefore

High silicon ductile iron (HSI) is currently used in numerous high
temperature applications such as furnace parts, exhaust manifolds and
turbocharger housings which require both mechanical strength and
oxidation resistance [1]. The general oxidation of high silicon ductile
iron in air is nowadays well understood. The oxide layer consists of
Fe2O3 at the gas/oxide interface, then Fe3O4 and silicon oxides [2–4].
The porous iron oxide allows fast diffusion of oxygen and thus internal
oxidation of the alloy. Thus the oxidation resistance of untreated high
silicon ductile iron is dependent on the formation of a continuous layer
of amorphous SiO2 at the oxide/alloy interface which acts as a diffusion
barrier to further transport of metal ions into the Fe3O4 layers [5,6]. The
effective use of SiO2 layers forming in alloys at a high temperature is
restricted due to the fact that protective silica may form but may also
transform into Fe2SiO4 in the presence of FeO. The formation of
particles of Fe2SiO4 at the oxide/alloy interface will result in oxygen
diffusing into the alloy and thus oxidized alloy specimens will gain
weight at a temperature higher than about 700 °C [7].
In recent years, an increased engine efficiency, together with a
decrease in exhaust gas pollutant emissions, has pushed automobile
the exhaust gas temperature in engines. As a result, the corrosive
effect of the exhaust gas is enhanced and severe oxidation may occur
more easily. In order to improve the oxidation resistance of high
silicon cast iron at a high temperature and make it suitable for
applications in more challenging environments, the use of surface
coatings has been explored [8]. Taking into account the factors of
environmental protection, economy, convenience for mass produc-
tion, and superior corrosion resistance, hot-dip aluminizing is one of
the most practical processes to modify high silicon cast iron [9–11].
Much effort has been spent to evaluate the microstructure and high
temperature oxidation behavior of aluminized low carbon steel
[12,13]. However, currently, there is little information available
concerning high silicon cast iron hot-dipped in an Al bath.
The present work's object was to characterize the microstructure
of hot-dip aluminized coating on HSI. Oxidation tests were
conducted to evaluate the performance of the aluminized coating
and bare substrate. The microstructure of the coating and the bare
substrate after oxidation tests was also examined, and the oxidation
behavior is discussed.
2. Experimental procedures

⁎ Corresponding author. Tel.: +886 2 27376441; fax: +886 2 27376460. A commercial, fully-annealed, high silicon ductile iron was used as
E-mail address: d9603506@mail.ntust.edu.tw (M.-B. Lin). the experimental material in this study. The chemical composition of

0257-8972/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2010.08.047
 M.-B. Lin, C.-J. Wang / Surface & Coatings Technology 205 (2010) 1220–1224
the high silicon ductile iron was Fe–2.74C–4.71Si–0.14Mn–0.05Mg
(wt.%). The specimens were 15 × 10 × 2 mm platelets. They were
polished with grit paper up to 800 grade. Then they were degreased in
an acetone bath, finally cleaned ultrasonically in an ethanol bath, and
dried in air before hot-dip aluminizing. The pure aluminum bulks
(Al N 99 wt.%) were 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 18 cm/min. After
120 s of immersion, they were pulled out and air-cooled to room
temperature. 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. The microhardness of the coating layers of
aluminized specimens was measured using a Vickers microhardness
tester (Akashi MVK-H1). The hardness tests were performed under an
indentation load of 0.245 N for 15 s.
A thermo gravimetric analyzer (PYRIS 6 TGA) was used to conduct
the high temperature oxidation tests at 750 °C for 72 h. Specimens
were placed in the furnace at 30 °C and the temperature was raised,
over 5 min, to 750 °C in oxygen (flow rate of oxygen 20 ml/min) and
held for 72 h isothermally. The weight changes of the specimens with
time were recorded every 10 s. The phase constitutions in the
aluminide layers of all specimens were investigated by means of
metallographical examination in a scanning electron microscope
(SEM) equipped with energy-dispersive X-ray spectrometer (EDS)
and X-ray diffractometry (XRD).
3. Results and discussions
3.1. Microstructure and phase constitution of the aluminide layer
A cross-sectional morphology of hot-dipping Al on high silicon
ductile iron is shown in Fig. 1(a). The hot-dipping aluminide coating
on HSI consisted of three layers, in the sequence of Al, Fe–Al
intermetallic and Si pile-up layers from the external topcoat to the
(a) Aluminum topcoated
Substrate
(c) Si
Fig. 1. The BEI cross-section micrograph and EDS element maps of specimens of hot-dipping for 120 s at 700 °C. (a) As-coated specimen, (b) microhardness profile of aluminide
coating, (c) EDS element mapping of Si and (d) EDS line profiles of elements Al, Fe and Si distributions across the coating layer.
1221
substrate, and the aluminide coating layer showed good adhesion to
the substrate. The XRD and EDS identified intermetallic layer
composed of outer FeAl3 and inner Fe2Al5. Rod-shaped FeAl3
dispersed in the aluminum topcoat, while the tongue-like Fe2Al5
formed in the intermetallic layer, becoming the major phase in the
aluminide coating layer. These three layers of Al, Fe2Al5 and silicon
pile-up layer exhibited hardnesses HV 50, HV 1100 and HV 450,
respectively. The hardness of ferrite substrate was HV 200 as shown in
Fig. 1(b). It also can be seen in Fig. 1(a) that the tongue-like Fe2Al5
grew in a normal direction to the substrate. The thickness of the Fe2Al5
layer was approximately 60 μm measured in the micrographs and its
hardness profiles shown in Fig. 1(a) and (b). As the same
experimental conditions, the thickness of Fe2Al5 layers on aluminized
mild steel was approximately 120 μm. Thus the Fe2Al5 layer of
aluminized HSI was significantly thinner than found on aluminized
mild steel.
In the hot-dipping process, Fe showed a faster solid diffusion rate
than silicon during inter-diffusion reactions between substrate and Al
melt [13,14]. In other words, that means it was difficult for Si in the
substrate to react with Al to form any Al–Si compounds after hot-
dipping in Al. Therefore, many Fe–Al compounds were formed, but
not Al–Si compounds. In this study all the as-coated specimens had
been examined. No Al–Si or Fe–Al–Si compounds were found. But the
silicon pile-up at the interface between the substrate and Fe–Al
intermetallic layer could be seen in all the as-coated specimens as
shown in Fig. 1(c). The silicon pile-up results from the growth of an
Fe–Al intermetallic layer, in which the solubility of Si was very low
(less than 2.0 at.%) [15], then iron continued to diffuse outward
quickly, which led to a silicon concentration around the interface
which got higher and higher like an Si pile-up layer as shown in Fig. 1
(d). In this study, the silicon content in the Si pile-up layer was about
20 at.%. As mentioned above, the Fe2Al5 layer of aluminized HSI was
significantly thinner than that found on aluminized mild steel.
Comparing the compositions of HSI and mild steel, the presence of
Si in HSI is probably the major cause. The Si contained in the substrate
(b)
(d)
1222 M.-B. Lin, C.-J. Wang / Surface & Coatings Technology 205 (2010) 1220–1224
Fig. 2. Weight gain curves of the aluminide coating and bare substrate specimens
oxidized in oxygen (150 ml/min) at 750 °C for 72 h measured by a thermogravimetric
apparatus.
would reduce the growth rate of Fe2Al5. It was noticed that graphite
nodules in the substrate could be deemed markers indicating hot-
dipping in Al melt. While hot-dipping HSI into Al, the faster iron
diffusion rate also led to graphite nodules being trapped in the
aluminide layers as shown in Fig. 1(a). It was confirmed that after hot-
dipping in Al all the specimens contained graphite nodules in the
aluminide layer as well as in the substrate.
3.2. High temperature oxidation kinetics
The specific weight changes of the bare substrate and aluminide
coated specimens vs. duration time at 750 °C are plotted in Fig. 2. It
can be seen that the aluminide coated specimens showed much less
weight gain than bare substrate specimens after 750 °C oxidation for
72 h. The high temperature oxidation experiment indicated that the
aluminide coating after hot-dipping in Al could resist the oxidation of
the substrate effectively, even at 750 °C.
3.3. Microstructures and phases of oxidized specimens
3.3.1. High silicon ductile iron substrate
Visual inspections of the bare substrate after 72 h of oxidation test
at 750 °C indicated that the appearance of the scale was reddish
brown and not dense. XRD and EDS analysis showed that the oxide
layers consist of Fe2O3, Fe3O4 and Fe2SiO4 as shown in Fig. 3. Most of
the graphite nodules contained in the iron oxide layer and beneath
the oxide layer were oxidized. Even though decarburization would
reduce the weight gains of the specimens, specimens oxidized in
(a)
Fe2SiO4
Fe3O4 Fe2O3
Oxidized
Graphite
Fig. 3. The cross-sectional micrographs of the high silicon ductile iron after the 750 °C oxidation for 72 h, (a) iron oxide layers formed on the substrate after oxidation test at 750 °C
for 72 h, (b) Fe2SiO4 particles formed next to the metal (no SiO2 layers were found).
severe conditions showed much more weight gain; the overall
thickness of the oxide layers (Fe2O3, Fe3O4, and Fe2SiO4) was about
220 μm after the oxidation experiment. In this study, no SiO2 layer
could be found at the oxide/alloy interface, but the Fe2SiO4 particles
grew at the interface. Therefore, there was no effective diffusion
barrier to resist the oxidation of the substrate.
3.3.2. Aluminide coating on HSI
Fig. 4(a)–(d) reveals that graphite nodules trapped in the
aluminide coating at a high temperature oxidize rapidly, then they
facilitate cracking in the aluminide coating. There were two causes
leading to the rapid oxidation of trapped graphite nodules. One was
that carbon easily reacted with oxygen, then decarburizes [16]. The
other was that the Al2O3 scale did not grow densely and completely on
the aluminized specimens in the early oxidation period as shown in
Fig. 4(d). Subsequently, the oxygen was able to diffuse to the graphite
nodules in the aluminide coating leading to decarburization. The
cracks in the aluminide coating left by the oxidized graphite caused
the aluminide coating to partially fail which provided oxygen a
diffusion path as shown in Fig. 4(c). After exposure for 72 h, some
regions of the substrate were oxidized. The Fe2O3 oxide nodules grew
and broke through the aluminide coating following the cracks as
shown in Fig. 4(e) and (f). It can also be seen that Fe2SiO4 particles
grew beneath the iron oxide (Fig. 4(e)). Even though some regions of
the substrate were oxidized due to the cracks left by oxidized graphite
nodules, the aluminide coated specimens still showed much less
weight gain and much less oxidation microstructure than the bare
substrate after 750 °C oxidation for 72 h. The high temperature
oxidation experiment indicated that the aluminide coating after hot-
dipping could prevent the oxidation of the substrate effectively even
at 750 °C.
4. Conclusions
The hot-dipping aluminide coating on HSI consisted of three
layers, in the sequence of Al, Fe–Al intermetallic and Si pile-up layers
from the external topcoat to the substrate. The intermetallic layer was
composed of outer FeAl3 and inner Fe2Al5. Rod-shaped FeAl3
dispersed in the aluminum topcoat, while the tongue-like Fe2Al5
formed in the metallic layer becoming the major phase in the
aluminide coating layer. Those three layers of aluminum, Fe2Al5 and
silicon pile-up layer exhibited hardnesses of HV 50, HV 1100 and HV
450, respectively. No Fe–Al–Si or Al–Si compounds were found in any
of the examined specimens in this study. Silicon pile-up at the
interface between the substrate and the Fe–Al intermetallic layer
could be seen in all the as-coated specimens. It was noticed that
(b)
Fe2SiO4 particles Fe3O4
 (a) 5min,750 °C (b) Top-view,5min,750 °C
Aluminide coating

Graphite
Trapped graphite

Substrate

M.-B. Lin, C.-J. Wang / Surface & Coatings Technology 205 (2010) 1220–1224
100µm

(c) 15min,750 °C (d) Top-view,15min,750 °C

Aluminide coating
Oxidized graphite

Oxidized graphite
Substrate
100µm

(e) 72h,750 °C Fe2O3 nodule (f) Top-view,72h,750 °C

Aluminide coating Al2O3

Fe2SiO4 Fe2O3 nodule

Substrate
100µm

Fig. 4. Cross-sectional and top-view micrographs of the aluminide layer for various oxidation times at 750 °C. That oxidation of graphite nodules trapped in the aluminide coating facilitating cracks in the aluminide coating was observed, (a)
the aluminide layer contained graphite nodules, (b) graphite nodules trapped in the aluminide layer were observed in top-view, (c) graphite nodules were oxidized and left cracks in the aluminide layer, (d) cracks were observed in top-view,
(e) iron oxides grew and broke through the aluminide layer following the cracks, and (f) iron oxides nodules were observed in top-view.

1223
1224 M.-B. Lin, C.-J. Wang / Surface & Coatings Technology 205 (2010) 1220–1224
graphite nodules in the substrate could be deemed as markers
showing hot-dipping in the Al melt. After hot-dipping in Al all the
specimens also contained graphite nodules in the aluminide layer as
well as the substrate.
Even though the oxidized graphite nodules resulted in cracks
propagating in the aluminide coating, the high temperature oxidation
experiment indicated that the aluminide coating could prevent the
oxidation of the substrate effectively even at 750 °C.
Acknowledgement
The authors are very grateful to the National Science Council of
Republic of China for funding support under Grant No. NSC 97-2221-
E-011-008.
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