Intermetallics 19 (2011) 1455e1460

Contents lists available at ScienceDirect

Intermetallics
journal homepage: www.elsevier.com/locate/intermet

Effect of silicon on the formation of intermetallic phases in aluminide

coating on mild steel
Wei-Jen Cheng*, Chaur-Jeng Wang
Department of Mechanical Engineering, National Taiwan University of Science and Technology, No. 43, Sector 4, Keelung Road, Taipei 10607, Taiwan, ROC

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

Article history: Mild steel was coated by hot-dipping into molten baths containing pure aluminum, Ale0.5Si, Ale2.5Si,
Received 27 December 2010 Ale5Si and Ale10Si (wt.%) at 700
C for 180 s. Silicons effect on the formation of the intermetallic phase
Received in revised form in the aluminide layer was investigated by using a combination of scanning electron microscope (SEM),
17 May 2011
energy dispersive X-ray spectroscopy (EDS) and electron backscatter diffraction (EBSD). The micrograph
Accepted 18 May 2011
observation showed that the aluminide layer resulting from hot-dipping in pure aluminum possesses
Available online 12 June 2011
the thickest intermetallic layer and a rough interface between intermetallic layer and steel substrate. As
the silicon content in the molten bath increased, the thickness of the intermetallic layer decreased
Keywords:
A. Aluminides, miscellaneous
substantially and the interface between the intermetallic layer and the steel substrate became at. On
A. Multiphase intermetallics the other hand, EDS and EBSD observation revealed the aluminide layer resulting from hot-dipping in Al
B. Phase identication e2.5Si not only possessed FeAl3 and Fe2Al5, but also formed cubic s5(C)-Al7(Fe,M)2Si (M Mn, Cr or Cu)
C. Coatings, intermetallic and otherwise above the FeAl3 and scattered s1-(Al,Si)5Fe3 in the Fe2Al5. However, as the content of silicon in the
molten aluminum bath increased, s5(C)-Al7(Fe,M)2Si began to be replaced by hexagonal s5(H)-Al7Fe2Si and
s6-Al4FeSi.
2011 Elsevier Ltd. All rights reserved.

1. Introduction expansion coefcient (TEC) mismatch between the Al-rich inter-

Hot-dip aluminizing has been proven as one of the effective
coating techniques to plate an aluminide layer on steels in order to
improve the oxidation resistance of steels [1,2]. During the hot-dip
aluminizing process, steels are immersed into a molten aluminum
bath for a period of time to form an intermetallic layer over the
surface of steels by atomic inter-diffusion between the dipped steels
and the molten aluminum bath. Then the residual aluminum liquid
on the steels will form an aluminum topcoat with the same
composition as the aluminum bath after removal from the bath.
According to the composition of the molten aluminum bath, hot-dip
aluminizing can be classied as hot-dipping in pure aluminum or in
aluminumesilicon [3]. In the aluminide layer of mild steel hot-
dipped in pure aluminum, the intermetallic layer is composed of
a thick, brittle Al-rich intermetallic phase. This is, in practical terms,
unformable. It renders deformation of the aluminide steel by deep
drawing, bending or edging impossible [4]. Several studies [5e7],
have reported that the failure of the aluminide layer can be attrib-
uted to the formation of cracks in the layer. When the aluminide
steel undergoes thermal shock or thermal cycling, the thermal
* Corresponding author. Tel.: 886 2 2733 3141x7309; fax: 886 2 2737 6460.
E-mail address: d9603505@mail.ntust.edu.tw (W.-J. Cheng).
metallic layer and the steel substrate can result in cracking in the
layer. On the other hand, an irregular interface between the inter-
metallic layer and the steel substrate can be observed in the alu-
minide layer of mild steel hot-dipped in pure aluminum. This
irregular interface acts as a stress concentrator within the aluminide
layer. This may cause an aluminide layer with a rough intermetallic
layer/steel substrate interface to crack more easily than a at
intermetallic layer/steel substrate interface when external loads are
applied to the aluminide steel during assembly procedures at room
temperature [4]. Since good workability of aluminide steel is an
important condition for a wide number of applications, silicon is
often added into the aluminum bath in order to diminish the
thickness of the intermetallic layer and atten the interface
between the intermetallic layer and the steel substrate [3,4,8].
Studies [3,9] concerning the microstructure of mild steel hot-
dipped in aluminumesilicon indicate that the thickness of the
intermetallic layer when mild steel is hot-dipped in alumi-
nume2.5 wt.% silicon decreases to approximately half the thickness
of the intermetallic layer when mild steel is hot-dipped in pure
aluminum. Although the thickness of the intermetallic layer keeps
reducing as the silicon content in the aluminum bath increases, the
tendency to diminish the thickness of the intermetallic layer will
slow down when the hot-dip aluminum bath contains more than
10 wt.% silicon. Therefore, aluminum containing 10 wt.% silicon is

0966-9795/$ e see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.intermet.2011.05.013
1456 W.-J. Cheng, C.-J. Wang / Intermetallics 19 (2011) 1455e1460

also the most common composition of molten aluminum bath for are shown in Fig. 1. All of the aluminide layers were composed of an
hot-dipping aluminumesilicon. However, the formation of outer aluminum or aluminumesilicon topcoat and an inner
FeeAleSi ternary intermetallic phases in the aluminide layer of continuous intermetallic layer, and possessed several intermetallic
mild steel hot-dipped in an aluminum bath with 10 wt.% silicon phases with different morphologies scattered in the aluminum or
causes complicated phase transformations, leading to multiple aluminumesilicon topcoat. As the silicon content in the aluminum
voids and cracks forming in the aluminide layer during use in high- bath increased and reached 10 wt.%, the thickness of the interme-
temperature situations, after completion of hot-dipping. This leads tallic layer decreased from 130 mm when hot-dipped in pure
to reduction of the useful lifetime of aluminide steel [2,10]. Based aluminum to 3.5 mm when hot-dipped in Ale10Si. A typical tongue-
on the above characterization about hot-dip aluminide steel, it can like morphology at the intermetallic layer/steel substrate interface
be concluded that the phase constitution of the aluminide layer can be found in the aluminide layer of hot-dip pure aluminum, but
inuences the layers ability to resist high-temperature oxidation. this transforms into a at morphology as the silicon content in the
Unfortunately, the complex crystal structures and narrow range aluminum bath increases to more than 2.5 wt.%.
of composition of the Al-rich FeeAleSi ternary phases make phase Fig. 2 reveals the top-view OM micrographs of the aluminum or
identication difcult [11]. Electron backscatter diffraction (EBSD) aluminumesilicon topcoats of mild steel hot-dipped in aluminum
is a technique for crystallographic analysis of crystalline materials baths containing various silicon additions. The scattered interme-
in a scanning electron microscope. It provides crystallographic tallic phases possess the same needle-like morphology in both the
information regardless of the content of materials by analyzing aluminum and aluminumesilicon topcoats when hot-dipped in
Kikuchi patterns or electron backscattered diffraction patterns pure aluminum and in Ale0.5Si, and granular and Chinese script
(EBSPs). EBSPs are constructed by an extensive network of Kikuchi morphologies in the aluminumesilicon topcoat when hot-dipped
lines that join together at various zone axes. Each Kikuchi line and in Ale2.5Si as shown in Fig. 2(a) and (b). In the alumi-
zone axis represent a specic crystallographic plane and direction numesilicon topcoat, when hot-dipped in Ale5Si, the scattered
within the crystal, respectively. Thus, EBSD has been widely used intermetallic phases formed not only polyhedral particles, but also
for phase identication in many multiphase materials. In this study, plate-shaped morphologies, as shown in Fig. 2(c). Fig. 2(d) shows
the EBSD technique was employed to analyze the effect of silicon the top-view OM micrograph of the aluminumesilicon topcoat
addition in the aluminum baths on the phase constitution of alu- when hot-dipped in Ale10Si. The scattered intermetallic phases
minide layers on specimens of hot-dipped mild steel. possess the primary polyhedral particle morphology and a small
amount of plate-shaped morphology.
2. Experimental procedures
3.2. Phase identication of intermetallic phase in aluminide layers
A commercial AISI 1005 steel was used as the substrate material
in this study. The chemical composition of the adopted steel is
The cross-sectional BSE micrographs of the intermetallic layers
Fee0.05Ce0.24Mne0.01Pe0.01S (wt.%). The specimens for hot-
between the topcoats and steel substrates of mild steel hot-dipped
dipping were immersed in the pure aluminum, Ale0.5Si, Ale2.5Si,
Ale5Si and Ale10Si (wt.%) molten baths at 700
C for 180 s and then
cooled down to room temperature in static air. Each bath also con-
tained trace amounts of manganese, chromium and copper totaling
to about 1 wt.%. Details of the preparation of the hot-dipped spec-
imen have been described in our previous study [12]. Cross-sectional
aluminide layers were prepared for metallographic examination
using standard grinding and polishing procedures. Specimens were
examined using an optical microscope (OM) and a eld emission
gun-scanning electron microscope (FEG-SEM) in backscattered
electron mode (BSE) to reveal atomic number contrast images to
distinguish phases by their chemical composition difference. The
chemical composition of the phases observed from SEM/BSE
micrographs was revealed by energy-dispersive spectrometry (EDS)
in the FEG-SEM system. Specimens were analyzed using EBSD for
a further verication of the crystallographic structure of the phases
that formed in the aluminide layers. For EBSD analysis, the FEG-SEM,
operating at 20 kV, attached to an OXFORD EBSD acquisition system
with INCA Crystal software, was used to record the EBSPs. The
experimental EBSPs were further indexed by INCA Crystal software
through comparison with the simulated EBSPs which were created
according to the crystallographic structures from the Inorganic
Crystal Structure Database (ICSD). 6 Kikuchi lines and 1.5
angular
tolerance were employed to index the EBSPs to decrease misiden-
tication. Also, the mapping function in EBSD was used to expose the
phase distribution in the aluminide layers.

3. Results

3.1. Microstructure of aluminide layers

Fig. 1. Cross-sectional OM micrographs of mild steel after hot-dipping in (a) pure
The cross-sectional OM micrographs of aluminide layers on mild aluminum, (b) Ale0.5Si, (c) Ale2.5Si, (d) Ale5Si and (e) Ale10Si molten baths at 700
C
steel hot-dipped in aluminum baths with various silicon additions for 180 s.
 W.-J. Cheng, C.-J. Wang / Intermetallics 19 (2011) 1455e1460 1457

Fig. 2. Top-view OM micrographs of intermetallic phases with different morphologies

in outer aluminum or aluminumesilicon topcoat of mild steel after hot-dipping in
(aeb) Ale2.5Si, (c) Ale5Si and (d) Ale10Si molten baths at 700
C for 180 s. Matrix,
gray phase and black phase are aluminum, intermetallic phase and silicon, respec-
tively; G, H, P and L represent granular, Chinese script, polyhedral and plate-shaped
intermetallic phases, respectively.

in the aluminum baths with various silicon additions and the cor-
responding chemical compositional results determined by EDS
revealed that the intermetallic layers in the all of the aluminide
layers were composed of four phases with different compositions
(AeD phases) as shown in Fig. 3 and Table 1. Fig. 4(aec) is the
experimental EBSPs and their indexed results of the A, B and C
phases in the intermetallic layers. It reveals that the crystallo-
graphic structures of the A, B and C phases are monoclinic FeAl3
(space group C2/M, a 1.549, b 0.808 and c 1.247 nm, b 108
)
Fig. 3. Cross-sectional BEI micrographs of intermetallic layers between topcoats and
steel substrates of mild steel after hot-dipping in (a) pure aluminum, (b) Ale0.5Si, (c)
Ale2.5Si, (d) Ale5Si and (e) Ale10Si molten baths at 700
C for 180 s. Micrographs
were taken from entire intermetallic layer except for those hot-dipped in pure
aluminum and Ale0.5Si which were taken on topcoat/intermetallic layer interface. A,
B, C and D represent different intermetallic phases according to the atomic number
contrast and EDS compositional results.

Table 1
Phase identication results of intermetallic phases with different morphologies examined by EDS and EBSD.

Types of aluminum bath Morphologies of intermetallic phases EDS identication (at.%) EBSPs identication

Al Fe Si
Pure aluminum Needle-like 84.3 15.7 e FeAl3
Continuous IMC layer A 76.1 23.9 e FeAl3
Continuous IMC layer B 72.4 27.6 e Fe2Al5

Ale0.5Si Needle-like 84.8 13.6 1.6 FeAl3

Continuous IMC layer A 76.2 22.8 1.0 FeAl3
Continuous IMC layer B 71.7 27.4 0.9 Fe2Al5

Ale2.5Si Granular 74.7 15.9 9.4 s5(C)-Al7(Fe,M)2Si

Chinese script 73.3 16.9 9.8 s5(C)-Al7(Fe,M)2Si
Continuous IMC layer A 74.2 23.3 2.5 FeAl3
Continuous IMC layer B 70.4 26.5 3.1 Fe2Al5
Continuous IMC layer C 47.3 32.4 20.3 s1-(Al,Si)5Fe3
Continuous IMC layer D 74.7 17.2 8.1 s5(C)-Al7(Fe,M)2Si
Ale5Si Polyhedral 74.8 16.9 8.3 s5(C)-Al7(Fe,M)2Si
Plate-shaped 69.9 14.9 15.2 s6-Al4FeSi
Continuous IMC layer A 73.6 23.3 3.1 FeAl3
Continuous IMC layer B 69.1 27.8 3.1 Fe2Al5
Continuous IMC layer C 46.7 33.3 20.0 s1-(Al,Si)5Fe3
Continuous IMC layer D 73.5 18.2 8.3 s5(C)-Al7(Fe,M)2Si and
s5(H)-Al7Fe2Si
Ale10Si Polyhedral 68.4 20.3 11.3 s5(H)-Al7Fe2Si
Plate-shaped 68.8 16.3 14.9 s6-Al4FeSi
Continuous IMC layer A 67.7 25.1 7.2 FeAl3
Continuous IMC layer B 66.7 28.6 4.7 Fe2Al5
Continuous IMC layer C 44.1 32.3 23.6 s1-(Al,Si)5Fe3
Continuous IMC layer D 68.2 20.6 11.2 s5(H)-Al7Fe2Si
1458 W.-J. Cheng, C.-J. Wang / Intermetallics 19 (2011) 1455e1460

Fig. 4. Indexed EBSPs of (a) FeAl3, (b) Fe2Al5, (c) s1-(Al,Si)5Fe3, (d) s5(C)-Al7(Fe,M)2Si, (e) s5(H)-Al7Fe2Si and (f) s6-Al4FeSi. In the simulated EBSPs, the yellow, purple and red lines
represent that the intensity of Kikuchi line are >0.6, >0.25 and 0.25, respectively. (For interpretation of the references to colour in this gure legend, the reader is referred to the
web version of this article.)

[13], orthorhombic Fe2Al5 (space group CMCM, a 0.768, b 0.640 identied as s5(H)-Al7Fe2Si phase. Also, the plate-shaped interme-
and c 0.420 nm) [14] and triclinic s1-(Al,Si)5Fe3 (space group P-1, tallic phase in specimens hot-dipped in Ale5Si and in Ale10Si was
a 0.465, b 0.633 and c 0.750 nm, a 101
, b 106
and identied as monoclinic s6-Al4FeSi (space group C2/C, a 0.618,
g 101
) [15], respectively. However, D phase in the intermetallic b 0.617 and c 2.081 nm, b 91
) [18] as shown in Fig. 4(f).
layers when hot-dipped in Ale2.5Si and in Ale10Si were identied
as cubic s5(C)-Al7(Fe,M)2Si (M Mn, Cr or Cu; space group PM-3,
a 1.256) [16] and hexagonal s5(H)-Al7Fe2Si (space group P63/MMC,
a 1.240 and c 2.623 nm) [17], respectively as shown in Fig. 4(d)
and (e). However, D phase in the intermetallic layer, when hot-
dipped in Ale5Si, was composed of both s5(C)-Al7(Fe,M)2Si and
s5(H)-Al7Fe2Si phases. In order to fully understand the phase
distribution of s5(C)-Al7(Fe,M)2Si and s5(H)-Al7Fe2Si phases in the
intermetallic layer when hot-dipped in Ale5Si, the mapping func-
tion in EBSD was used to expose the crystallographic information in
the intermetallic layer. It can be discovered that the D phase in the
intermetallic layer when hot-dipped in Ale5Si comprised not only
the primary s5(C)-Al7(Fe,M)2Si phase, but also a small amount of
s5(H)-Al7Fe2Si phase in the inner part of the D phase as shown in
Fig. 5. Although the compositions of s5(C)-Al7(Fe,M)2Si and s5(H)-
Al7Fe2Si phases are similar, s5(C)-Al7(Fe,M)2Si possesses 0.5e1.3 at.%
of manganese, chromium and copper.
In the aluminum and aluminumesilicon topcoats of mild steel
hot-dipped in pure aluminum and Ale0.5Si, although the EDS
composition of the needle-like intermetallic phase does not match
with any FeeAl or FeeAleSi intermetallic phase, EBSD analysis still
can reveal that the needle-like intermetallic phase in these two
topcoats is FeAl3. The reason that EDS cannot expose the correct
composition of the needle-like intermetallic phase is that the small
phase area of the needle-like intermetallic phase caused the elec-
tron beam of FE-SEM to hit both the needle-like intermetallic phase
and the matrix of the topcoat during EDS analysis. On the other
hand, EDS and EBSD analyses of the scattered intermetallic phases
in the aluminum and aluminumesilicon topcoats conrmed that
the granular and Chinese script intermetallic phases in specimen
hot-dipped in Ale2.5Si and the polyhedral intermetallic phase in
specimen hot-dipped in Ale5Si are all the same s5(C)-Al7(Fe,M)2Si
Fig. 5. (a) Cross-sectional BSE micrograph and (b) corresponding EBSD phase distri-
phase. However, the polyhedral intermetallic phase in the alumi- bution map of intermetallic layer on mild steel after hot-dipping in Ale5Si molten bath
numesilicon topcoat of specimen hot-dipped in Ale10Si was at 700
C for 180 s.
 W.-J. Cheng, C.-J. Wang / Intermetallics 19 (2011) 1455e1460
Fig. 6 shows the comparison of the intermetallic layer thickness
of mild steel hot-dipped in aluminum baths with various silicon
additions. As the silicon content in the aluminum bath increased to
5 wt.%, the thickness of the intermetallic layer substantially
decreased, by about 85% from that of hot-dipping in pure
aluminum. The intermetallic layers are composed mainly of FeeAl
intermetallic layers while the silicon contents in the aluminum
baths are 2.5 and 5 wt.%, and the amounts of FeeAleSi intermetallic
layers become greater than the FeeAl intermetallic layers when the
silicon content in the aluminum bath is increased to 10 wt.%.
4. Discussion
In summary, from the characterization of microstructure and
phase constitution in the aluminide layers on mild steel hot-dipped
in aluminum baths with various silicon additions as shown in
Table 1, it can be concluded that the intermetallic layers, when hot-
dipped in aluminum baths containing less than 0.5 wt.% silicon,
comprise an outer minor FeAl3 layer and an inner major Fe2Al5 layer.
Also, FeAl3 and Fe2Al5 layers still can be observed co-existing with
FeeAleSi intermetallic phases when the silicon content in the
aluminum baths exceeds 2.5 wt.%. The FeeAleSi intermetallic
phases identied in this study, ranked by aluminum content, were
s5(C)-Al7(Fe,M)2Si, s6-Al4FeSi, s5(H)-Al7Fe2Si and s1-(Al,Si)5Fe3 pha-
ses. Among the FeeAleSi ternary intermetallic phases, the hexag-
onal structure of the s5(H)-Al7Fe2Si phase was rst reported in 1953
by Robson and Black [19]. On the other hand, several studies [20]
have reported that s5(H)-Al7Fe2Si phase would transform into
a cubic structure of s5(C)-Al7(Fe,M)2Si phase when trace amounts
(about 0.3 wt. %) of dissolved transition metals, such as manganese,
chromium and copper, are added into the aluminumeironesilicon
alloy. In this study, the total amount of these elements in the
aluminum baths with various silicon additions is about 1 wt.%,
which leads to the formation of cubic s5(C)-Al7(Fe,M)2Si phase.
Although the s5(C)-Al7(Fe,M)2Si and s5(H)-Al7Fe2Si phases are two
different phases, many studies have proposed that the reaction and
formation mechanisms for these two phases are the same [21e23].
Moreover, the formation of the intermetallic phases in the alumi-
nide layers is controlled by the inter-diffusion between molten
aluminum baths and mild steel substrate, in which aluminum and
silicon diffused inward to the steel substrate and iron migrated
outward to the molten baths. As a result, the formation of the s5(C)-
Al7(Fe,M)2Si and s5(H)-Al7Fe2Si phases located above the FeAl3 phase
Fig. 6. Comparison of thickness of intermetallic layers after mild steel is hot-dipped in
aluminum baths with various silicon additions at 700
C for 180 s.
1459
in the intermetallic layer may be attributed to the monovariant
peritectic reaction Liquid FeAl3 4 s5(C)-Al7(Fe,M)2Si/s5(H)-Al7Fe2Si
or the quasi-peritectic reaction U10 (Liquid FeAl3 4 (Al) s5(C)-
Al7(Fe,M)2Si/s5(H)-Al7Fe2Si) at 620
C while cooling from the hot-dip
temperature [21]. The s5(C)-Al7(Fe,M)2Si and s5(H)-Al7Fe2Si phases
scattered in the aluminumesilicon topcoats could form by the
eutectic reaction Liquid 4 (Al) s5(C)-Al7(Fe,M)2Si/s5(H)-Al7Fe2Si
while cooling from the diffusion temperature [22,23]. On the other
hand, it can be found that the s5(C)-Al7(Fe,M)2Si phase transforms
into a s5(H)-Al7Fe2Si phase when the silicon content in the aluminum
baths increases from 5 to 10 wt.%. Many studies concerning the
formation of cubic s5(C)-Al7(Fe,M)2Si and hexagonal s5(H)-Al7Fe2Si
phases [22] have indicated that the s5(C)-Al7(Fe,M)2Si phase is
a metastable phase, which is only formed during fast solidication.
On the contrary, the s5(H)-Al7Fe2Si phase formed preferentially at
a relatively slower solidication rate. In this study, the silicon
additions in the aluminum bath are 0.5, 2.5, 5 and 10 wt.%. As the
silicon content in the aluminum bath increased and drew close to
the eutectic point of aluminum and silicon (about 13 wt.% silicon),
the liquidus line of the molten aluminum baths decreased from
660
C for pure aluminum to 600
C for Ale10Si. This decrease of
the liquidus line of the molten aluminum baths with more silicon
added into the bath implies that the molten aluminum bath con-
taining more silicon would possess a relatively slower solidication
rate than a bath containing less silicon while these molten
aluminum baths were cooled from the same hot-dip temperature
of 700
C to room temperature in static air. Consequently, the s5(C)-
Al7(Fe,M)2Si phase formed in the aluminide layers by the traces of
manganese, chromium and copper in the aluminum baths tended
to be replaced by the s5(H)-Al7Fe2Si phase because the solidication
rate of residual aluminumesilicon liquid on the surface of the steel
was slowed down as the silicon content in the aluminum baths
increased. On the other hand, the s1-(Al,Si)5Fe3 phases observed in
this study all performed as precipitates in the Fe2Al5 phase of the
intermetallic layers or at the FeAl3/Fe2Al5 interface. In all of the
FeeAleSi intermetallic phases, the s1-(Al,Si)5Fe3 phase possesses
the highest iron content and a very high silicon content (about
30 at.% iron and 20 at.% silicon in this study), and the lower silicon
content in the Fe2Al5 phase shows that silicon is less soluble in the
Fe2Al5 phase [24]. Therefore, when the amount of solid-solute
silicon in the Fe2Al5 layers increased (from 0.9 to 4.7 at.%) as the
silicon content in the aluminum baths increased, more
s1-(Al,Si)5Fe3 would be forced to precipitate in the Fe2Al5 phase or
at the FeAl3/Fe2Al5 interface.
Considering both microstructure and phase constitution of the
aluminide layers of mild steel hot-dipped in aluminum baths with
various silicon additions, it can be found that the intermetallic layer
of steel hot-dipped in pure aluminum not only composed of an
outer minor FeAl3 layer and an inner major Fe2Al5 layer, but also
possessed a tongue-like morphology at the Fe2Al5/steel substrate
interface. A wealth of research [3,4,25] has claimed that the
formation mechanism of this tongue-like Fe2Al5 layer is due to the
30% vacancy rate in the c-axis of the crystal structure of Fe2Al5
causing aluminum atoms to diffuse much more rapidly inward.
Thus, Fe2Al5 tends to be orientated by the xed c-axis of the crystal
structure, and grows rapidly along the diffusion direction during
hot-dipping. On the other hand, it can be observed that the thick-
ness of the Fe2Al5 layer decreased substantially, but the thickness of
the FeAl3 layer reduced slightly, as the silicon addition in the
aluminum baths increased. Also, the Fe2Al5/steel substrate inter-
face transformed from the tongue-like morphology into a at
morphology as the silicon content in the aluminum baths has
increased to more than 2.5 wt.%. The explanation of these effects is
attributed to the silicon in the aluminum baths being incorporated
into the intermetallic layer and then reducing the diffusion rate of
1460 W.-J. Cheng, C.-J. Wang / Intermetallics 19 (2011) 1455e1460
aluminum atoms in Fe2Al5, by occupying the vacancies in the c-axis
of the crystal structure of Fe2Al5 [26].
Previous studies about modications to hot-dipped aluminide
steel, by adding silicon in the molten aluminum bath [3,9], have
proposed that the addition of 10 wt.% silicon can effectively
decrease the thickness of the intermetallic layer and atten the
intermetallic layer/steel substrate interface. Due to the fact that the
thinner intermetallic layer is much more deformable and the at
intermetallic layer/steel substrate interface has the ability to avoid
the accumulation of stress during the assembly processes, this
microstructure provides the aluminide layer on steel with better
mechanical properties [4]. However, the fact that the FeeAleSi
phase is the major intermetallic phase in this aluminide layer
caused complicated phase transformations and was accompanied
by several voids and the formation of cracks in the aluminide layer
during use in high-temperature situations after completion of hot-
dipping, resulting in the reduction of the useful lifetime of alumi-
nide steel [2,10]. Considering both mechanical properties and
useful lifetime of the hot-dipped aluminide steel, the optimal alu-
minide layer should possess a thin intermetallic layer and a at
intermetallic layer/steel substrate interface, but little or no forma-
tion of FeeAleSi phases. In the comparisons of the microstructures
and phase constitutions of the ve aluminide layers on mild steel
resulting from hot-dipping in aluminum baths with various silicon
contents in this study, it can be noted that the thickness of the
intermetallic layer decreased signicantly from 130 mm when steel
was hot-dipped in pure aluminum to 17 mm after hot-dipping in
a bath with 5 wt.% silicon. The tongue-like intermetallic layer/steel
substrate interfaces were eliminated also, when the silicon addition
in the aluminum bath increased to 5 wt.%. Also, the intermetallic
phase in the aluminide layer when hot-dipped in Ale5Si is still
dominated by the FeeAl phase. The useful lifetime of the ve alu-
minide steels in the present study, however, needs further inves-
tigations or tests with respect to their oxidation behaviors over
extended periods, which we will undertake in the near future.
5. Conclusions
EBSD provides a rapid and accurate phase identication of FeeAl
and FeeAleSi intermetallic phases in the aluminide layers on mild
steel hot-dipped in aluminum baths with various silicon additions.
Silicon addition in the aluminum bath not only decreased the
thickness of the intermetallic layer and eliminated the rough inter-
metallic layer/steel substrate interface, but also altered the phase
constitution of the aluminide layers. FeeAleSi intermetallic phases,
s5(C)-Al7(Fe,M)2Si, s5(H)-Al7Fe2Si, s6-Al4FeSi and s1-(Al,Si)5Fe3, were
found when the silicon addition in the aluminum baths exceeded
2.5 wt.%. The formation of the s5(C)-Al7(Fe,M)2Si phase could be
attributed to the traces of manganese, chromium and copper in the
aluminum baths, which stabilized cubic symmetry, at the expense
of the hexagonal structure of the s5(H)-Al7Fe2Si phase. However,
The s5(C)-Al7(Fe,M)2Si phase tended to be replaced by the
s5(H)-Al7Fe2Si phase because the solidication rate of residual
aluminumesilicon liquid on the surface of the steel was slowed
down as the silicon content in the aluminum baths increased.
Among the ve types of aluminide layers, the intermetallic layer
resulting from hot-dipping in Ale5Si is the thinnest layer still
dominated by the FeeAl phase. Ale10Si, on the other hand, is
dominated by FeeAleSi phase.
Acknowledgment
The authors are very grateful to the National Science Council of
the Republic of China for funding support under Grant No. NSC 98-
2221-E-011-038.
References
[1] Chang YY, Tsaur CC, Rock JC. Microstructure studies of an aluminide coating
on 9Cre1Mo steel during high temperature oxidation. Surf Coat Technol
2006;200:6588e93.
[2] Wang CJ, Chen SM. The high-temperature oxidation behavior of hot-dipping
AleSi coating on low carbon steel. Surf Coat Technol 2006;200:6601e5.
[3] Richards RW, Jones RD, Clements PD, Clarke H. Metallurgy of continuous hot
dip aluminizing. Int Mater Rev 1994;39:191e212.
[4] Bahadur A, Mohanty ON. Structural studies of hot dip aluminized coatings on
mild steel. Mater Trans JIM 1991;32:1053e61.
[5] Pint BA, Zhang Y, Tortorelli PF, Haynes JA, Wright IG. Evaluation of iron-
aluminide CVD coatings for high temperature corrosion protection. Mater
High Temp 2001;18:185e92.
[6] Zhang Y, Pint BA, Garner GW, Cooley KM, Haynes JA. Effect of cycle length on
the oxidation performance of iron aluminide coatings. Surf Coat Technol 2004;
188e189:35e40.
[7] Agero A, Muelas R, Gutirrez M, Van Vulpen R, Osgerby S, Banks JP. Cyclic
oxidation and mechanical behaviour of slurry aluminide coatings for steam
turbine components. Surf Coat Technol 2007;201:6253e60.
[8] Eggeler G, Auer W, Kaesche H. On the inuence of silicon on the growth
of the alloy layer during hot dip aluminizing. J Mater Sci 1986;21:
3348e50.
[9] Robert FM. Metals handbook. 9th ed., vol. 5. American Society of Metals; 1983.
[10] Cheng WJ, Wang CJ. Observation of high-temperature phase transformation in
the Si-modied aluminide coating on mild steel using EBSD. Mater Charact
2010;61:467e73.
[11] Gupta SP. Intermetallic compound formation in FeeAleSi ternary system:
part I. Mater Charact 2003;49:269e91.
[12] Cheng WJ, Chang YY, Wang CJ. Observation of high-temperature phase
transformation in the aluminide CreMo steel using EBSD. Surf Coat Technol
2008;203:401e6.
[13] Grin Y, Burkhardt U, Ellner M, Peters K. Renement of the Fe4Al13 structure
and its relationship to the quasihomological homeotypical structures.
Z Kristallogr 1994;209:479e87.
[14] Burkhardt U, Grin Y, Ellner M, Peters K. Structure renement of the iron-
ealuminium phase with the approximate composition Fe2Al5. Acta Crystallogr
Sect B 1994;50:313e6.
[15] Yanson TI, Manyako MB, Bodak OI, German NV, Zarechnyuk OS, Cerny R, et al.
Triclinic Fe3Al2Si3 and orthorhombic Fe3Al2Si4 with new structure types. Acta
Crystallogr Sect C 1996;52:2964e7.
[16] Cooper M. The crystal structure of the ternary alloy a(AlFeSi). Acta Crystallogr
1967;23:1106e7.
[17] Corby RN, Black PJ. The structure of a-(AlFeSi) by anomalous-dispersion
methods. Acta Crystallogr Sect B 1977;33:3468e75.
[18] Hansen V, Hauback BC, Sundberg M, Romming C, Gjonnes J. b-Al4.5FeSi:
a combined synchrotron powder diffraction, electron diffraction, high-
resolution electron microscopy and single-crystal X-ray diffraction study of
a faulted structure. Acta Crystallogr Sect B 1998;54:351e7.
[19] Robson K, Black PJ. An X-ray examination of a-(AlFeSi) ternary compounds.
Philos Mag 1953;44:1392e7.
[20] Shabestari G. The effect of iron and manganese on the formation of inter-
metallic compounds in aluminumesilicon alloys. Mater Sci Eng A 2004;383:
289e98.
[21] Takeda S, Mutuzaki K. The equilibrium diagram of the FeeAleSi system.
Tetsu-to-Hagane 1940;26:335e61.
[22] Tanihata H, Sugawara T, Matsuda K, Ikeno S. Effect of casting and homoge-
nizing treatment conditions on the formation of AleFeeSi intermetallic
compounds in 6063 AleMgeSi alloys. J Mater Sci 1999;34:1205e10.
[23] Sha G, OReilly KAQ, Cantor B, Titchmarsh JM, Hamerton RG. Quasi-peritectic
solidication reactions in 6xxx series wrought Al alloys. Acta Mater 2003;51:
1883e97.
[24] Bosselet F, Pontevichi D, Sacerdote-Peronnet M, Viala JC. Measurement of the.
isothermal section at 1000 K of AleFeeSi. J Phys IV France 2004;122:41e6.
[25] Deqing W, Ziyuan S, Longjiang Z. A liquid aluminum corrosion resistance
surface on steel substrate. Appl Surf Sci 2003;214:304e11.
[26] Heumann T, Dittrich S. ber die Kinetik der Reaktion von festem und ssi-
gem Aluminium mit Eisen. Z Metallkd 1959;50:617e25.