coatings

Article
Identification of Intermetallic Compounds and Its
Formation Mechanism in Boron Steel Hot-Dipped in
Al-7 wt.% Mn Alloy
Sung-Yun Kwak 1 , Jung-Gil Yun 2 , Jae-Hyeong Lee 1 , Dong-Ik Shin 1 and Chung-Yun Kang 1, *
1 Department of Material Science and Engineering, Pusan National University, Busan 46241, Korea;
kwaksy@pusan.ac.kr (S.-Y.K.); ljhjg896@pusan.ac.kr (J.-H.L.); sdi@posceramics.co.kr (D.-I.S.)
2 Department of Hybrid Materials & Machining Technology, Graduate School of Convergence Science,
Pusan National University, Busan 46241, Korea; clsky712@pusan.ac.kr
* Correspondence: kangcy@pusan.ac.kr; Tel.: +82-10-8329-8429

Academic Editor: Joaquim Carneiro

Received: 10 November 2017; Accepted: 1 December 2017; Published: 6 December 2017

Abstract: In laser welding and hot stamping Al-Si-coated boron steel, there is a problem that the
strength of the joint is lowered due to ferrite formation in the fusion zone. The purpose of this study
is to develop an Al-7 wt.% Mn hot-dip coating in which Mn, an austenite stabilizing element, replaces
the ferrite stabilizing element Si. The nucleation and formation mechanism of the reaction layer was
studied in detail by varying the dipping time between 0 and 120 s at 773 ◦ C. The microstructure
and phase constitution of the reaction layer were investigated by various observational methods.
Phase formation is discussed using a phase diagram calculated by Thermo-CalcTM . Under a 30 s
hot-dipping process, no reaction occurred due to the formation of a Fe3 O4 layer on the steel surface.
The Fe3 O4 layer decomposed by a reduction reaction with Al-Mn molten alloy, constituent elements
of steel dissolved into a liquid, and the reaction-layer nucleus was formed toward the liquid phase.
A coated layer consists of a solidified layer of Al and Al6 Mn and a reactive layer formed beneath
it. The reaction layer is formed mainly by inter-diffusion of Al and Fe in the solid state, which is
arranged on the steel in the order of Al11 Mn4 → FeAl3 (θ) → Fe2 Al5 (η) phases, and the Fe3 AlC (κ) in
several nm bands formed at the interface between the η-phase and steel.

Keywords: hot-dipped coating; Fe–Al–Mn phases; nucleation and growth; phase transformation;
diffusion; advanced high-strength steel

1. Introduction
In recent years, in the automobile industry, as the strength of the vehicle body has been increased
to attain light weight and strength, there has been a problem in that spring-back phenomenon occurs
due to insufficient ductility during the forming process [1,2]. In order to overcome this challenge using
Advanced High Strength Steel (AHSS), a hot stamping process has been developed that stabilizes
both the formation and strength of boron steel [3–5]. However, in this process, scale formation and
surface decarburization occur, caused by surface oxidation of the steel when heated in excess of 900 ◦ C.
In turn, to solve this issue, Al-Si hot-dipped coating is typically performed [4–7].
However, when an Al-Si–coated boron steel sheet for hot stamping is laser-welded, a coated layer
composed of the ferrite-forming elements is mixed into the fusion zone, and the δ-ferrite is formed in a
band shape at the fusion zone boundary. As a large amount of ferrite is formed, the strength of the
joint decreases, and fracture occurs in the segregation region [8–10].
To address these challenges, in this study, a coating layer was developed that suppresses
the formation of ferrite in the fusion zone during laser welding by adding Mn, which is an
austenite-forming element, to the Al-Si coating layer typically used.

Coatings 2017, 7, 222; doi:10.3390/coatings7120222 www.mdpi.com/journal/coatings

Coatings 2017, 7, 222 2 of 15

Previous studies on intermetallic compounds between solid Fe and liquid Al have reported the
formation of intermetallic compounds including Fe2 Al5 and FeAl3 [11–14]. In addition, many studies
have investigated the growth rate of Fe2 Al5 among such intermetallic compounds. [15–18]. Studies
using Al-Mn coatings have shown that Mn can be used to improve the corrosion resistance of the
coating layer, as studied by Xinmei Li et al. [19] and Debabrata Pradhan et al. [20]. Xinmei Li et al. [19]
performed a hot-dipping process for 10 min using pure Al, Al-2 wt.% Mn, Al-9 wt.% Mn, and
Al-13 wt.% Mn composites on low-carbon steel. After hot dipping, a scratch test was conducted
to characterize adhesion, showing that the coating layer containing Mn adhered well. Debabrata
Pradhan et al. [20] reported that steel sheets in hot dipping of Al-Mg-Mn alloys have about six times
better corrosion resistance than zinc coating. Studies have also been performed on the growth rate
of intermetallic compounds formed after the reaction of liquid Al and solid Fe and on the corrosion
resistance of Al-Mn-coated layers. However, few studies have attempted to identify the phases of
intermetallic compounds and the formation and growth mechanisms of each phase.
Therefore, in this study, in order to improve the mechanical properties of the fusion zone after
hot stamping, instead of using ferrite-forming element Si, the austenite-forming element Mn was
added to inhibit the formation of ferrite in the fusion zone, and an Al-7 wt.% Mn coating layer was
applied. The use of 7 wt.% Mn was selected as 7 wt.% in consideration of the inhibitory effect of
ferrite formation of Mn and the coating temperature (under 800 ◦ C). The purpose of this study was to
investigate the coating conditions to obtain a uniform coating layer on a 1.5 Ga grade boron steel sheet
for automobiles, and to study the formation process of the reaction phases formed in the coating layer
and its mechanism.

2. Materials and Methods

In this study, 1.2-mm-thick boron steel (SABC1470 grade) was used as the base material, with a
chemical composition of Fe-0.23 C-0.24 Si-1.19 Mn-0.002 B (wt.%) as shown in Table 1. The specimens
were cut to a size of 40 mm × 120 mm to clean the surface of the boron steel before hot-dipping,
washed with 20 mL HCl + 200 mL CH3 OH and a solution of 20 mL H2 SO4 + 20 mL distilled water for
5 min, and finally washed with CH3 OH.

Table 1. Chemical composition of Boron steel.

Chemical Composition (wt.%)

C S Mn Cr Nb Ti B P S Fe
0.229 0.238 1.189 0.183 0.004 0.036 0.002 0.002 0.002 Bal.

Al-7 wt.% Mn alloy was prepared by mixing 373.3 g of pure Al and 326.7 g of Al-15wt.% Mn
alloy. The specimens were pre-heated at 150 ◦ C for 20 s to remove moisture from the surface of the
Al-7Mn (wt.%) molten alloy. The temperature of the molten metal was maintained at 773 ◦ C, which is
the lowest possible coating temperature, for 0–120 s to perform hot dip process then air cooling.
The coated specimens were polished by using 1 mm Diamond + 0.04 mm Silica after arranging
the surfaces through several stages of SiC sand paper. After polishing, 50 mL CH4 OH + 2 mL HNO3
etching solution was used for the base material. 100 mL distilled water + 1 g NaOH solution, which is
the etching solution of the 3000 series Al alloy, was used for the coating layer [21].
To observe the microstructure of the coated layer after hot-dipping, the Olympus (Tokyo, Japan)
BX-51M optical microscopy and the Carl Zeiss (Oberkochen, Germany) SUPRA 45 field-emission
Scanning Electron Microscope (FE-SEM) were used. Phase identification of large areas of the oxide
layer was performed using the Rigaku (Tokyo, Japan) Ultima IV X-ray diffraction (XRD) at 1◦ /min.
EDAX (Mahwah, NJ, USA). Energy-dispersive spectroscopy (EDS) was performed to observe the
element distribution in the coating layer.
Coatings 2017, 7, 222 3 of 15

In order to analyze the chemical composition distribution, the JEOL (Tokyo, Japan) JXA-8530F
field-emission electron probe micro-analysis (FE-EPMA) was performed to analyze the area, with a
1Coatings
kV voltage, 100 nA current, and step sizes of 0.1–0.5 mm in a non-etching state. To analyze the phase
2017, 7, 222
of the reaction layer, specimens were deflected using the FEI (Hillsboro, OR, USA) Scios focused ion
beam (FIB), and their chemical composition and diffraction pattern were then obtained using the FEI
(Hillsboro, OR, USA) TALOS F200X field-emission transmission electron microscopy (FE-TEM). The
EDAX Hikari Electron backscatter diffraction (EBSD) was used to observe the phase distribution and
crystal orientation
orientation of the reaction layer during formation and growth, and the Media Cybernetics
(Rockville, MD,
(Rockville, MD,USA)USA)Image-plus
Image-plus pro
pro image
image analysis
analysis program
program was was
usedused for analyzing
for analyzing imagesimages to
to obtain
obtain parameters
parameters such assuch as the thickness
the thickness and of
and length length
eachof each phase.
phase.

3. Results

3.1. Formation
3.1. Formation of
of the
the Reaction
Reaction Layer
Layer at
at Initial
Initial Hot
Hot Dipping
Dipping
Boron steel
steel was
was hot-dipped
hot-dipped inin Al-7
Al-7 wt.%
wt.% MnMn molten
molten metal
metal at
at 773 ◦ C for various dipping times.
773 °C
Boron for various dipping times.
Figure 11 shows
Figure shows the the cross-sectional
cross-sectionaloptical
opticalmicrostructure
microstructureofofhothotdipped
dippedspecimens
specimens forfor
various times
various at
times
◦
773773C.°C.
In In
thethe
specimens hothot
dipped forfor
10 10
s and 2020
s, the reaction layer was notnot
formed. AsAs
shown in
at specimens dipped s and s, the reaction layer was formed. shown
Figure 1a, the localized reaction layer was formed on the surface of steel for
in Figure 1a, the localized reaction layer was formed on the surface of steel for 30 s. 30 s.

Figure 1. Cross-sectional optical microstructure of specimens hot dipped for various dipping times.
Figure 1. Cross-sectional optical microstructure of specimens hot dipped for various dipping times.
(a) 30 s; (b) 40 s; (c) 50 s; (d) 90 s; (e) 100 s; (f) 120 s.
(a) 30 s; (b) 40 s; (c) 50 s; (d) 90 s; (e) 100 s; (f) 120 s.

Figure 2 shows the results of the back-scattered electron (BSE) image in which the reaction phase
Figure(Figure
is present 2 shows 1a)the results
and the Feof and
the back-scattered
O componentselectron (BSE)
of Al, Mn, andimage
steel.inThe
which the line
white reaction
showsphase
the
is present
original (Figure
steel 1a) A
surface. and the structure
band Fe and Owithcomponents of Al, Mn, and
high concentrations of Festeel. The1d)
(Figure white
andline shows the
O (Figure 1e)
original steel surface. A band structure with high concentrations of Fe (Figure 1d)
was formed on the surface of the steel. From this result, this layer is considered to be a Fe-based oxide and O (Figure 1e)
was formed on the surface of the steel. From this result, this layer is considered to be
layer. On the other hand, the elliptical shape phase in the area indicated by γ on the surface coexisted a Fe-based oxide
layer.the
with On coating
the other hand, the elliptical
components Al and Fe,shape
butphase
Mn andin the
O area indicated
are not by γThus,
detected. on thethesurface
reactioncoexisted
phase
with the coating components Al and Fe, but Mn and O are not detected.
formed where the oxide layer broke, and the Al-Mn coating solution permeated, reacting with the Thus, the reaction phase
formed
steel wherethe
to form thereaction
oxide layer broke, and the Al-Mn coating solution permeated, reacting with the steel
layer.
to form the reaction layer.
Figure 3 includes an enlarged SEM microstructure and an EPMA surface analysis results of the
Figure 3 by
area denoted includes an enlarged
γ in Figure SEMspecimens
1b, where microstructure and an for
were dipped EPMA 40 s.surface analysis
A reaction layerresults
formed ofand
the
area denoted
increased by absence
in the γ in Figure 1b,oxide
of an where specimens
layer. were dipped
The reaction layer canfor be
40 classified
s. A reaction
intolayer
four formed and
phases—A,
increased in the absence of an oxide layer. The reaction layer can be classified
B, C, and D—from the comparison of the Al, Mn, and Fe concentrations with the formed positions, into four phases—A,
B, C, and
either at theD—from the comparison
steel surface of theThe
or coating layer. Al, AMn, andcontains
phase Fe concentrations with the formed
a high concentration of Al andpositions,
Fe but
either at no
contains theMn steel
andsurface or coating
was formed layer.
in the Thelayer
coating A phase contains
and the a high concentration
steel interior. The B phase formedof Al and Fe
in the
coating layer and was a high concentration of Al and Mn, but was characterized by a small amount
of Fe, which was connected to the A phase and the end. The C phase had a slightly higher in Mn
concentration than the B phase. Phase D consisted almost entirely of Al.
Coatings 2017, 7, 222 4 of 15

but contains no Mn and was formed in the coating layer and the steel interior. The B phase formed
in the coating layer and was a high concentration of Al and Mn, but was characterized by a small
amount of Fe, which was connected to the A phase and the end. The C phase had a slightly higher in
Mn concentration
Coatings 2017, 7, 222 than the B phase. Phase D consisted almost entirely of Al.
Coatings 2017, 7, 222

Figure 2. Electron probe micro-analysis (EPMA) area-analysis results of the coating layers hot dipped
Figure
Figure Electron probe
2. Electron
2. probe micro-analysis (EPMA)
(EPMA) area-analysis
area-analysis results
results of
of the
the coating
coating layers
layers hot dipped
at 773 °C
◦ C for 30 s. (a) BSE;micro-analysis
(b) Al; (c) Mn; (d) Fe; (e) O. hot dipped
at 773 for 30 s. (a) BSE; (b) Al; (c) Mn; (d) Fe; (e)
at 773 °C for 30 s. (a) BSE; (b) Al; (c) Mn; (d) Fe; (e) O.O.

Figure 3. EPMA area-analysis results of the coating layers hot dipped at 773 °C for 40 s. (a) BSE; (b)
Figure 3. EPMA area-analysis results of the coating layers hot dipped at 773 °C for 40 s. (a) BSE; (b)
Al; (c) Mn;
Figure (d) Fe;area-analysis
3. EPMA (e) O; (f) C. results of the coating layers hot dipped at 773 ◦ C for 40 s. (a) BSE; (b) Al;
Al; (c) Mn; (d) Fe; (e) O; (f) C.
(c) Mn; (d) Fe; (e) O; (f) C.
Figure 4 shows the results of the XRD of the steel surface after dipping for 5 s at 773 °C, confirming
Figure
that the oxide4 shows the results
layer was comprised of the
ofXRD
Fe3Oof the steel surface after dipping for 5 s at 773 °C, confirming
4. This oxide layer is the most thermodynamically stable Fe-
that Figure
the oxide4 shows
layer the
was results
comprised of the
of XRD
Fe of the steel surface after dipping for 5 s at 773 ◦ C, confirming
3O4. This oxide layer is the most thermodynamically stable Fe-
based oxide at temperatures below the dipping temperature. When the boron steel was heated in an
that
based the oxide
oxide atlayer was comprised the
temperatures of Fe3 O4 . This oxide layer is thethe most thermodynamically stable
electric furnace maintained atbelow 773 °C fordipping
10 s in temperature.
air, no oxide When
layer was boron
formed.steel was heated
However, when inthe
an
Fe-based
electric oxide
furnace at temperatures
maintained at below
773 °C the
for 10dipping
s in temperature.
air, no oxide When
layer was the boron
formed. steel was
However, heated
when in
the
boron steel was dipped into the Al-7◦wt.% Mn molten metal, an oxide layer formed. Thus, the Fe3O4
an electric
boron steelfurnace
was maintained
dipped at 773 wt.%
C for Mn10 s molten
in air, no oxideanlayer was formed. However, when Fethe
formed by the reaction ofinto
the the
steelAl-7
surface with oxygen in metal,
the moltenoxide layer
metal. formed. Thus, the 3O4

formed by the reaction of the steel surface with oxygen in the molten metal.
Figure 5 shows the formation rate which is defined as the ratio (%) of the formed reaction layer
to theFigure 5 shows the
measurement formation
length (10 mm) rate
fromwhich
the is defined as thestructure.
cross-sectional ratio (%) of the
The formedarea
reaction reaction layer
increased
to the measurement length (10 mm) from the cross-sectional structure. The reaction
with an increase in the dipping time, and the reaction layer formed over the entire surface at 100 s. area increased
with an increase
Moreover, in the dipping
the thickness time, and
(in the depth the reaction
direction) layer formed
distribution over thelayer
of the reaction entire surface
was at 100 s.
non-uniform,
Moreover,
as shown inthe thickness
Figure 1e, but(inthe
thespecimen
depth direction) distribution
after hot-dipping for of
120the reaction
s had layer reaction
a uniform was non-uniform,
layer.
Coatings 2017, 7, 222 5 of 15

boron steel was dipped into the Al-7 wt.% Mn molten metal, an oxide layer formed. Thus, the Fe3 O4
formed by the reaction of the steel surface with oxygen in the molten metal.
Figure 5 shows the formation rate which is defined as the ratio (%) of the formed reaction layer
to the measurement length (10 mm) from the cross-sectional structure. The reaction area increased
with an increase in the dipping time, and the reaction layer formed over the entire surface at 100 s.
Coatings 2017, the
Moreover, 7, 222
thickness (in the depth direction) distribution of the reaction layer was non-uniform, as
Coatings 2017,
shown 7, 222 1e, but the specimen after hot-dipping for 120 s had a uniform reaction layer.
in Figure

Figure
Figure 4. X-ray
4. X-ray diffraction
diffraction (XRD) (XRD)
analysisanalysis of thelayer
of the oxide oxide layer on
formed formed on surface
the steel the steel surface
upon upon
initial dipping.
Figure 4. X-ray
initial diffraction (XRD) analysis of the oxide layer formed on the steel surface upon initial dipping.
dipping.

Figure 5. Change in formation ratio of reaction layer on boron steel with dipping time (s).
Figure 5.
Figure 5. Change
Change in
in formation
formation ratio
ratio of
of reaction
reaction layer
layer on
on boron
boron steel
steel with
with dipping
dipping time
time (s).
(s).

3.2.
3.2.Evolution
Evolutionofof
ofMicrostructure
Microstructure in in the Coating
the Coating Layer
Coating Layer
Layer
3.2. Evolution Microstructure in the
The
Thereaction
reactionlayer
layer(Figure
(Figure 1a)
1a) of the
of the specimen
the specimen dipped for
specimen dipped
dipped for 30
30 ss was
was tootoosmall,
small,thetheoxide
oxidelayer
layerwas
was
The reaction layer (Figure 1a) of for 30 s was too small, the oxide layer was
nearby,
nearby,andand TEM
andTEM specimens
TEMspecimens
specimens could
could not be obtained by FIB. Among the reaction layers of the 40ss
nearby, could notnot be obtained
be obtained by Among
by FIB. FIB. Among the reaction
the reaction layers layers ofsthe
of the 40 40
dipped
dipped
dippedspecimens,
specimens, the
thesmallest,
smallest, corresponding
corresponding to
to the
the area in
in Figure 3a,3a, was
wasselected.
selected.TEMTEMspecimens
specimens
specimens, the smallest, corresponding to the area in area
Figure Figure
3a, was selected. TEM specimens were
were
were collected
collected by
by FIB
FIB (focused
(focused ion
ion beam)
beam) and
and observed
observed by
by STEM
STEM to
to identify
identify which
which phases
phases were
were
collected by FIB (focused ion beam) and observed by STEM to identify which phases were formed
formed
formed ininthe
thereaction
reaction layer.
layer.Figure
Figure 6a
6a shows
shows aa specimen
specimen cut in
cut in the depth
depthdirection
directionin in γarea
areaofofFigure
Figure3a,
3a,
in the reaction layer. Figure 6a shows a specimen cut in thethe
depth direction in γ γarea of Figure 3a,
allowing observation
allowing observation
observation of of the
of the phases
the phases
phases of of the
of the liquid
the liquid (area
liquid (area 1)
(area 1) and
1) and the
and the steel
the steel (area
steel (area
(area 2).2). Additionally,
2). Additionally, (c,d)
(c,d)
allowing Additionally, (c,d)
shows
shows the
the STEM—HAADF
STEM—HAADF (high-angle
(high-angle annular
annular dark-field)
dark-field) microstructureobserved
microstructure observedin inareas
areas11and
and2,2,
shows the STEM—HAADF (high-angle annular dark-field) microstructure observed in areas 1 and
respectively.
respectively.
2, respectively.
Figure 7 is the surface analysis by EDS for Al, Mn, Fe, and C in Figure 6c and Table 2 shows the
results of EDS point analysis of the phases 1–5 in Figure 6c. From the distributions of Mn and Fe, the
areas of 1, 2, and 3 had high Mn concentrations but low Fe concentration. Region 5 contains high Fe
and low Mn concentrations, and 4 region contains a high Fe concentration and negligible Mn.
specimens, the smallest, corresponding to the area in Figure 3a, was selected. TEM specimens
Coatings 2017, 7, 222
llected by FIB (focused ion beam) and observed by STEM to identify which phases were
n the reaction layer. Figure 6a shows a specimen cut in the depth direction in γ area of Figure 3a,
g observation of the phases of the liquid (area 1) and the steel (area 2). Additionally, (c,d)
he STEM—HAADF (high-angle annular dark-field) microstructure observed in areas 1 and 2,
Coatings 2017, 7, 222 6 of 15
vely.
Coatings 2017, 7, 222

Figure 6. (a) Back-scattered electron (BSE) structure enlarged of area denoted as γ in Figure 3a,b TEM specimen
took at area denoted as γ in (a) using FIB; (c,d) HAADF image of area 1 and area 2 in (b), respectively.

Figure 7 is the surface analysis by EDS for Al, Mn, Fe, and C in Figure 6c and Table 2 shows the
results ofFigure
EDS point Figure
analysis
Figure of6.the
6. Cont. (a) Back-scattered
phases electron
1–5structure
in Figure(BSE)6c.
structure
From enlarged of area denotedof
thedenoted
distributions as Mn
γ in Figure
and Fe, 3a,b the
TEM specimen
6. (a) Back-scattered electron (BSE) enlarged of area as γ in Figure 3a,b
areas of 1, 2, and 3 had took
high at area
Mndenoteddenoted as
concentrations γ in (a) using
but low FIB; (c,d) HAADF
Fe concentration.image of area 1 and area 2 in (b), respectively.
TEM specimen took at area as γ in (a) using FIB; (c,d) HAADF image ofRegion 5 contains
area 1 and area 2 in high Fe
and low (b),
Mnrespectively.
concentrations, and 4 region contains a high Fe concentration and negligible Mn.
5Figure 7 is the surface analysis by EDS for Al, Mn, Fe, and C in Figure 6c and Table 2 shows th
results of EDS point analysis of the phases 1–5 in Figure 6c. From the distributions of Mn and Fe, th
areas of 1, 2, and 3 had high Mn concentrations but low Fe concentration. Region 5 contains high F
and low Mn concentrations, and 4 region contains a high Fe concentration and negligible Mn.

Figure 7. Results
Figure of of
7. Results TEM-EDS
TEM-EDS(Transmission ElectronMicroscopy-Energy
(Transmission Electron Microscopy-Energy Dispersive
Dispersive Spectroscopy)
Spectroscopy)
analysis in Figure
analysis 6c.6c.
in Figure (a)(a)
Al;Al;(b)
(b)Mn;
Mn;(c)
(c)Fe;
Fe; (d) C.
(d) C.
Figure 7. Results of TEM-EDS (Transmission Electron Microscopy-Energy Dispersive Spectroscopy)
analysis in Figure 6c. (a) Al; (b) Mn; (c) Fe; (d) C.
Table
Table 2. EDS
2. EDS analysis
analysis results(at./wt.%)
results (at./wt.%)of
of phases
phases denoted
denotedasas1–5 1–5in in
Figure 6c, 6c,
Figure respectively.
respectively.

Al Table
Mn 2. EDS analysis
FeFe results (at./wt.%)
C C of phases denoted as 1–5 in Figure 6c, respectively.
Rem.Rem.
No. Al Mn Expected Phase
No. Expected Phase
at.%/wt.%
at.%/wt.%
at.%/wt.%
at.%/wt.% Alat.%/wt.%
at.%/wt.% Mnat.%/wt.%
at.%/wt.%Fe at.%/wt.% C
at.%/wt.% Rem.
No. Expected Phase
1 80.96/67.52 12.26/20.95 6.20/10.77
at.%/wt.% 0.32/0.12
at.%/wt.% at.%/wt.%Bal./Bal. Al6Mn
at.%/wt.% at.%/wt.%
1 80.96/67.52 12.26/20.95 6.20/10.77 0.32/0.12 Bal./Bal. Al6 Mn
2 2 76.11/61.17
76.11/61.17 15.06/24.69
15.06/24.69 8.24/13.73
1
8.24/13.73 0.36/0.13
80.96/67.52 12.26/20.95
0.36/0.13 Bal./Bal.
6.20/10.77 0.32/0.12 AlBal./Bal.
Bal./Bal. 11Mn4
Al11 Mn4
Al6Mn
3 3 74.01/58.37
74.01/58.37 2 76.11/61.17
16.16/26.01
16.16/26.01 15.06/24.69
8.33/15.26
8.33/15.26 8.24/13.73
0.36/0.13
0.36/0.13 0.36/0.13
Bal./Bal.
Bal./Bal. AlBal./Bal.
11 Mn
Al11 Mn4
4 Al 11Mn4

4 4 69.58/52.49
69.58/52.49 3
0.14/0.2274.01/58.37
0.14/0.22 16.16/26.01
29.98/47.01
29.98/47.01 8.33/15.26
0.23/0.08
0.23/0.08 0.36/0.13
Bal./Bal.
Bal./Bal. Bal./Bal.
Fe 2AlFe5 2 Al5 Al11Mn4
5 5 69.17/52.27
69.17/52.27 4
4.11/6.3269.58/52.49
4.11/6.32 26.4/41.020.14/0.22
26.4/41.02 29.98/47.01
0.32/0.11
0.32/0.11 0.23/0.08
Bal./Bal.
Bal./Bal. Bal./Bal.
FeAl FeAl
3 3 Fe2Al5
5 69.17/52.27 4.11/6.32 26.4/41.02 0.32/0.11 Bal./Bal. FeAl3

Figure 8 shows
Figure 8 showsthethe
results
resultsofofthe
thediffraction patternininthe
diffraction pattern thearea
area indicated
indicated by 1–5
by 1–5 in Figure
in Figure 6c and6c and
Figure 8 shows the results of the diffraction pattern in the area indicated by 1–5 in Figure 6c an
the diffraction pattern
the diffraction pattern analysis obtained the composition analysis result in Table 2. From the diffraction
theanalysis
diffractionobtained
pattern the composition
analysis obtained theanalysis result analysis
composition in Tableresult
2. From the 2. From th
in Table
pattern pattern
diffraction analysis,analysis,
Point 1 phase
Point is1Al 6 Mn (orthorhombic),
phase is Al 6Mn Point 2 and 3Point
(orthorhombic), phases2 are Al
and 3 Mn4 (triclinic)
phases
11 are Al 11 Mn 4 are Al11Mn
diffraction pattern analysis, Point 1 phase is Al6Mn (orthorhombic), Point 2 and 3 phases
phase, point 4 phase is Fe
(triclinic) phase, point(triclinic)Al (η,
4 phasephase,
2 5 orthorhombic)
is Fe2point
Al5 (η, phase, and
orthorhombic) point 5 phase
phase, is FeAl
and point
3 (θ, monoclinic)
5 phase phase.
is FeAl (θ, is FeAl3 (θ
4 phase is Fe2Al5 (η, orthorhombic) phase, and point 5 3phase
monoclinic) phase. monoclinic) phase.

6 6
Coatings 2017, 7, 222 7 of 15
Coatings 2017, 7, 222

Figure
Figure 8.8. Results
Resultsofofthe thediffraction
diffractionpattern
patternininthe
thearea indicated
area byby
indicated 1–51–5
in in
Figure 6c.6c.
Figure (a) Al
(a)6Mn, (b)
Al6 Mn,
Al 11 Mn 4 , (c) Fe 2 Al 5 (η), (d) FeAl 3 (θ).
(b) Al11 Mn4 , (c) Fe2 Al5 (η), (d) FeAl3 (θ).

Figure 9 shows the result of EDS analysis of the reaction zone Figure 6d in steel, and Table 3
Figure 9 shows the result of EDS analysis of the reaction zone Figure 6d in steel, and Table 3
shows the result of EDS analysis of the composition of each phase. The lower left part where Al was
shows the result of EDS analysis of the composition of each phase. The lower left part where Al was
not detected was steel. On the top of the steel, the reactive layer was much thinner than the other,
not detected was steel. On the top of the steel, the reactive layer was much thinner than the other, and
and as a result the intensity detected during the EDS was too low and not measured. In regions 6 and
as a result the intensity detected during the EDS was too low and not measured. In regions 6 and 7, the
7, the concentration of Al was high, but the concentrations of Mn, Fe, and C were low. Thus, it is a
concentration of Al was high, but the concentrations of Mn, Fe, and C were low. Thus, it is a reaction
reaction layer. In the band with a high concentration of C in Figure 9d as shown in Table 3, Al was
layer. In the band with a high concentration of C in Figure 9d as shown in Table 3, Al was detected
detected in addition to Fe, and this band was expected to be composed of Fe, Al, and C. However,
in addition to Fe, and this band was expected to be composed of Fe, Al, and C. However, the phases
the phases of regions 9 and 10 were expected to be steel structures because almost no Al was detected,
of regions 9 and 10 were expected to be steel structures because almost no Al was detected, yet the
yet the concentration of C was different.
concentration of C was different.
Figure 10 shows the results of the diffraction pattern analysis based on the diffraction pattern
obtained in the area indicated by 6–10 in Figure 9 and the composition analysis result (Table 3). The
phases of 6 and 7 are Fe2 Al5 (η, orthorhombic) phase in the same pattern. The phases 9 and 10 are α-Fe
(ferrite) and Fe3 C (cementite), which are steel structures. On the other hand, Fe3 AlC (κ, Cubic) formed
as a band-like phase at the interface between the steel and the reaction layer.

Table 3. Energy-dispersive spectroscopy (EDS) analysis results (at./wt.%) of phases denoted as 6–10 in
Figure 6d, respectively.

Al Mn Fe C Rem.
No. Expected Phase
at.%/wt.% at.%/wt.% at.%/wt.% at.%/wt.% at.%/wt.%
6 69.84/51.95 0.17/0.25 29.62/47.02 0.22/0.07 Bal./Bal. Fe2 Al5
7 68.67/51.60 0.15/0.23 30.9/48.06 0.26/0.09 Bal./Bal. Fe2 Al5
8 18.24/11.52 1.37/1.76 62.5/81.69 17.89/5.03 Bal./Bal. Fe3 AlC
9 0.09/0.04 1.14/1.13 97.16/98.01 1.01/0.22 Bal./Bal. Fe
10 0.03/0.02 7.07/8.15 74.37/87.16 18.53/4.67 Bal./Bal. Fe3 C

Figure 9. Results of TEM-EDS analysis of (d) in Figure 6. (a) Al; (b) Mn; (c) Fe; (d) C.

7
and as a result the intensity detected during the EDS was too low and not measured. In regions 6 and
7, the concentration of Al was high, but the concentrations of Mn, Fe, and C were low. Thus, it is a
reaction layer. In the band with a high concentration of C in Figure 9d as shown in Table 3, Al was
detected in addition to Fe, and this band was expected to be composed of Fe, Al, and C. However,
the phases
Coatings of7,regions
2017, 222 9 and 10 were expected to be steel structures because almost no Al was detected,
8 of 15
yet the concentration of C was different.

Coatings 2017, 7, 222

Table 3. Energy-dispersive spectroscopy (EDS) analysis results (at./wt.%) of phases denoted as 6–10
in Figure 6d, respectively.

Al Mn Fe C Rem.
No. Expected Phase
at.%/wt.% at.%/wt.% at.%/wt.% at.%/wt.% at.%/wt.%
6 69.84/51.95 0.17/0.25 29.62/47.02 0.22/0.07 Bal./Bal. Fe2Al5
7 68.67/51.60 0.15/0.23 30.9/48.06 0.26/0.09 Bal./Bal. Fe2Al5
8 18.24/11.52 1.37/1.76 62.5/81.69 17.89/5.03 Bal./Bal. Fe3AlC
9 0.09/0.04 1.14/1.13 97.16/98.01 1.01/0.22 Bal./Bal. Fe
10 0.03/0.02 7.07/8.15 74.37/87.16 18.53/4.67 Bal./Bal. Fe3C

Figure 10 shows the results of the diffraction pattern analysis based on the diffraction pattern
obtained in the area indicated by 6–10 in Figure 9 and the composition analysis result (Table 3). The
phases of 6 and 7 are Fe2Al5 (η, orthorhombic) phase in the same pattern. The phases 9 and 10 are
α-Fe (ferrite) and Fe3C (cementite), which are steel structures. On the other hand, Fe3AlC (κ, Cubic)
Figure 9.9.Results of TEM-EDS analysis of
of(d)
(d) in Figure 6. (a)
(a) Al; (b) Mn;
Mn; (c)
(c) Fe;
Fe; (d)
(d) C.
C.
band-likeResults
formed as a Figure phaseofatTEM-EDS analysis
the interface between in Figure
the steel6.and Al;
the(b)
reaction layer.

Figure 10.
10. Results
Results of
of the
the diffraction
diffraction pattern
pattern in
in the
the area
area indicated
indicated by
by 6–10
6–10 Figure
Figure6d.
6d. (a,b)
(a,b)Fe
Fe2Al
Al5 (η);
Figure 2 5 (η);
(c) Fe 3AlC (κ); (d) α-Fe; (e) Fe3C.
(c) Fe3 AlC (κ); (d) α-Fe; (e) Fe3 C.

The microstructure of the coating layer was classified into a reaction layer (reactive phase)
formed while maintaining the dipping temperature and a solidified structure formed during cooling
of the coating liquid. Figure 11 shows the microscopic optical structure of the Al-7 wt.% Mn cast alloy,
which consists of matrix Al and Al6Mn.
Coatings 2017, 7, 222 9 of 15

The microstructure of the coating layer was classified into a reaction layer (reactive phase) formed
while maintaining the dipping temperature and a solidified structure formed during cooling of the
coating liquid. Figure 11 shows the microscopic optical structure of the Al-7 wt.% Mn cast alloy, which
consists of matrix
Coatings 2017, 7, 222 Al and Al6 Mn.
Coatings 2017, 7, 222

Figure
Figure 11.
11. Microstructure of Al-7
Microstructure of Al-7 wt.%
wt.% Mn
Mn alloy
alloy (as
(as cast).
cast).
Figure 11. Microstructure of Al-7 wt.% Mn alloy (as cast).
Figure 12 shows the EBSD analysis of the reaction layer (also shown in Figures 1c, 4a, and 5a)
Figure
Figure 12
12shows the
theEBSD
showscoating EBSD analysis
analysis of thethe
reaction layer (also shown in Figures 1b and
1c, 6a) formed
formed at the initial process, 40 s.ofFigure reaction
12a is layer
an IQ(also shown
(image in Figures
quality) map; Figure 4a, 12b
andis5a)a
at the initial
formedmap;
at the coating
initial process,
coating 40 s. Figure 12a is an IQ (image quality) map; Figure 12b is a phase
phase and Figure 12c isprocess, 40 s. Figure
an IPF (inverse pole12a is an The
figure). IQ (image
phasesquality)
present map;
in theFigure
EBSD 12b is a
are the
map;
phaseand Figure
map; and 12c is an IPF
Figure is (inverse pole figure). The phases present
phases in the EBSD areEBSD
the same as
same as identified in the12c
TEM an IPF (inverse
observation; pole figure).
Figure 12d is aThe schematic present
diagram inofthe
a reaction are the
layer
identified
same ason in the TEM
identified in observation;
thebased
TEM on Figure 12dFigure
observation; is a schematic
12dTEMis adiagram
schematicof adiagram
reactionoflayer formed layer
a reaction on a
formed a steel surface the above described and EBSD analysis results.
steel surface based on the above described TEM and EBSD analysis
formed on a steel surface based on the above described TEM and EBSD analysis results.results.

Figure 12. Results of EBSD analysis hot—dipping for 40 s. (a) Image Quality (IQ) map; (b) Phase map;
Figure
(c) 12. Results
Inversed of EBSD
Pole Figure analysis
(IPF) hot—dipping
map and for 40 s. diagram
(d) the schematic (a) Imageof
Quality (IQ) map;
the reaction (b) Phase map;
layer
Figure 12. Results of EBSD analysis hot—dipping for 40 s. (a) Image Quality (IQ) map; (b)nucleated in
Phase map;
(c) Inversed
the liquid (40Pole
s). Figure (IPF) map and (d) the schematic diagram of the reaction layer nucleated in
(c) Inversed Pole Figure (IPF) map and (d) the schematic diagram of the reaction layer nucleated in the
the liquid (40 s).
liquid (40 s).
The microstructure arrangement from the coating layer toward the steel is, in order, Al + Al6Mn
(coated Thealloy
microstructure
structure) → arrangement
Al11Mn4 → FeAl from3the(θ) coating
→ Fe2Allayer 5 (η) → toward
Fe3AlC the(κ)
steel
→ αFeis, in(steel).
order,In Aladdition,
+ Al6Mn
Thealloy
microstructure arrangement
→ from the
4 → FeAl
coating layer toward the steel→is, in (steel).
order, AlIn + Al6 Mn
a(coated
Fe3O4 oxide structure)
layer formed Al Mnsurface
on11the the →
of3 (θ) Fe2Al
steel, Al 2→
but5 (η) O3 Fe 3AlC (κ)
formed around αFe the reaction addition,
layer.
(coated alloy structure) → Al Mn → FeAl
11 the4 surface of (θ) → Fe Al (η) → Fe AlC (κ) → αFe (steel). In addition,
a Fe3Compared
O4 oxide layer withformed on
the sample maintained3 for the120 s 2the
steel, but5 Al 2O3 formed
reaction layer 3 around
formed thethe
over reaction
entirelayer.
surface
a Fe3 O 4 oxide layer formed on the surface of the steel, but Al 2 O 3 formed around the reaction
entirelayer.
with Compared
an initially withformed thereaction
sample maintained
layer appearing for 120 s the
after 40reaction
s. Figurelayer formed
13 shows theover
SEM the surface
microstructure
Compared
withEPMA
an initially with
formed the sample maintained for 120after
s the40reaction layershows
formedthe over themicrostructure
entire surface
and analysis of thereaction layer appearing
area denoted as γ in Figure s. Figure
1f, which was13hot-dipped SEM
for 120 s. (a–e) show
with an initially
andsolidification
EPMA analysisformed reactiondenoted
of the layer appearing after 1f,40 which
s. Figure 13 shows the SEM microstructure
the layer neararea
the liquid phase as γ inandFigure
reaction layer,was andhot-dipped
(f–k) showfor the120 s. (a–e)of
analysis show
the
and EPMA analysis
the solidification of the area denoted as γ in Figure 1f, which was hot-dipped for 120 s. (a–e) show
reaction layer nearlayer nearmaterial.
the base the liquid phase
Table and reaction
4 shows the results layer,
of theandEDS(f–k)point
showanalysis
the analysis of the
for areas 1–
the solidification
reaction layer near layer
the near material.
base the liquidTable phase 4 and reaction
shows the layer,
results of and
the (f–k)point
EDS showanalysis
the analysis
for of the
areas 1–
8 in Figure 13a,f. Figure 14 shows the EBSD analysis of this area. Compared with the solidification
reaction
8 in layer
Figure nearFigure
13a,f. the base 14 material.
shows Table
the EBSD 4 shows
analysis theof results
this of theCompared
area. EDS pointwith analysisthe for areas 1–8
solidification
layer that formed on the surface of the steel, the reaction layer after 120 s (Figures 13 and 14) and at
in Figure
layer that13a,f.
formed Figureon the14 shows
surface the EBSD analysis of this area. Compared with the solidification layer
the initial 40 s (Figures 3 and 10),ofthethe steel,
shape the distribution
and reaction layer areafter 120 sFrom
similar. (Figures 13 and
the EDS, 14) and
EPMA, andat
that
the formed
initial 40ons the
(Figures surface
3 of
and the
10), steel,
the the
shape reaction
and layer
distribution afterare 120 s (Figures
similar. From 13
theandEDS,14) and
EPMA, at the
and
EBSD analysis results, the solidification layer consisted of Al (1) and Al 6Mn (2) on the surface of the
initial
EBSDthe 40 s (Figures
analysis 3 and 10),
results, the shape and distribution are similar. From the EDS, EPMA, and EBSD
steel, reaction layerthewassolidification
composed oflayer Al 11Mnconsisted
4 (3) below of Al Al(1)
6Mn and AlFeAl
(2). 6Mn3(2)(θ)on the surface
phase of the
(4) is formed
analysis
steel, results, thelayer solidification layer consisted of Al (1) and Al Al66Mn
Mn (2).(2) on the3 (θ)
surface of (4) the steel, the
on thethe
Al11reaction
Mn4 (3) and Fewas 2Al5composed
(5) interfaces.of AlThe
11Mn Fe42(3)
Al5below
(η) phase (5, 6) grewFeAl on thephase inside ofis theformed
steel,
on the
and Fe3Al
AlC11Mn (3) and at
(7)4 formed Fe2the
Al5interface
(5) interfaces.
between ThetheFe2Alsteel5 (η)(8)phase
and the (5, 6) grew on the inside of the steel,
η (6).
and Fe3AlC (7) formed at the interface between the steel (8) and the η (6).
 Coatings 2017, 7, 222 10 of 15

reaction layer was composed of Al11 Mn4 (3) below Al6 Mn (2). FeAl3 (θ) phase (4) is formed on the
CoatingsAl2017, 7, 222
11 Mn4 (3) and Fe2 Al5 (5) interfaces. The Fe2 Al5 (η) phase (5, 6) grew on the inside of the steel, and
Fe 3 AlC2017,
Coatings (7) formed
7, 222 at the interface between the steel (8) and the η (6).

Figure
FigureFigure 13. Scanning
13. Scanning electron
electron microscopy(SEM)
microscopy (SEM) microstructure and EPMA areaarea
results of the coating
13. Scanning electron microscopy (SEM) microstructure
microstructure and and EPMA
EPMA results
area results of theofcoating
the coating
layers hot dipped for 120 s. (a,f) SEM microstructure; (b,g) Al; (c,h) Mn; (d,i) Fe; (e,j) C.
layerslayers hot dipped
hot dipped for 120
for 120 s. (a,f)
s. (a,f) SEMSEM microstructure; (b,g)
microstructure; (b,g)Al;
Al;(c,h) Mn;
(c,h) (d,i)
Mn; Fe; (e,j)
(d,i) C. C.
Fe; (e,j)

Figure 14. EBSD results of the reaction layer (120 s). (a) Image Quality (IQ) map; (b) Phase map;
(c) Inversed Pole Figure (IPF) map.

FigureFigure
14. EBSD results
14. EBSD of the
results reaction
of the reactionlayer
layer (120 s). (a)
(120 s). ImageQuality
(a) Image Quality (IQ)
(IQ) map;
map; (b) Phase
(b) Phase map; map;
Table 4. Chemical composition (at.%) of phases denoted as 1–8 by EDS analysis.
(c) Inversed PolePole
(c) Inversed Figure (IPF)
Figure map.
(IPF) map.
No. Al Mn Fe C Rem. Expected Phase
Table 4. Chemical composition (at.%) of phasesBal.
Table 4. 1
Chemical98.30 0.21
composition 0.17
(at.%) of1.01
phases denoted
denoted 1–8Al
as as by EDS
1–8 analysis.
by EDS analysis.
2 82.21 11.34 5.72 0.37 Bal. Al6Mn
No. No. 3AlAl74.61 Mn 19.12 Fe
Mn 4.93
Fe 0.14
C C Bal.
Rem.Rem. Al11Mn
Expected 4 PhasePhase
Expected
4 98.30
1 98.30 69.17 0.21
4.94 0.17
25.01 1.010.27 Bal. FeAlAl
3
1 0.21 0.17 1.01 Bal. Bal. Al
2 5
82.21 69.1411.34
0.16 29.74
5.72 0.10
0.37 Bal. Bal. Fe2Al5 Al Mn
2 82.21 11.34 5.72 0.37 Bal. Al6Mn 6
3 6 68.73 0.19 30.10 0.21
0.14 Bal. Bal. Fe2Al5 Al11 Mn4
3 74.61 74.61 19.12
19.12 4.93 4.93
0.14 Bal. Al11Mn4
4 7
69.17 17.31 4.94
1.03 25.01
62.88 17.87 0.27 Bal. Bal. Fe3AlC FeAl3
5 4 69.14
8 69.17 4.94
1.21 25.01
0.02 0.16 95.94 0.27
29.74 1.81 Bal. Bal.
0.10 Bal. FeAl3Fe Al
Fe 2 5
6 5 68.73 69.14 0.190.16 29.74
30.10 0.10 0.21 Bal. Bal. Fe2Al5Fe2 Al5
7
Consequently, 6the 17.31 1.03
68.73microstructure
same 62.88
0.19 30.10 17.87 Bal.
0.21
arrangement Bal. initially
formed Fe2Al5Fe
(403 AlC
s). The arrangement
8 7 0.02 1.21 95.94
17.31 1.03 62.88 17.87 1.81 Bal. Bal. Fe3AlC Fe
from the coating layer toward the steel was, in order, Al + Al6Mn (coated alloy structure) → Al11Mn4
→ FeAl3 (θ) → Fe2Al 8 5 (η) 0.02
→ Fe3AlC1.21(κ) →
95.94 1.81 The
αFe (steel). Bal.η phase dippedFe for 40 s (see Figure 11)
mainly grew toward the liquid phase, whereas the specimen dipped for 120(40
Consequently, the same microstructure arrangement formed initially s). The14)
s (Figure arrangement
grew very
from the coating
Consequently, layer toward
theinterior.
deep into the steel the steel
same microstructure was, in
The growth direction order, Al
arrangement + Al Mn
formed
6
of the η phase (coated
was the alloy
initially structure)
same in(40thes). →
The
[001] Al 11 Mn4
arrangement
direction.
→ FeAl3 (θ) → Fe2 Al5 (η) → Fe3 AlC (κ) → αFe (steel). The η phase dipped for 40 s (see Figure 11)
from the coating layer toward the steel was, in order, Al + Al6Mn (coated alloy structure) → Al11Mn4
mainly grew toward the liquid phase, whereas the specimen dipped for 120 s (Figure 14) grew very
4. Discussion
→ FeAl 3 (θ) → Fe2Al5 (η) → Fe3AlC (κ) → αFe (steel). The η phase dipped for 40 s (see Figure 11)
deep into the steel interior. The growth direction of the η phase was the same in the [001] direction.
mainly grew Analyzing
towardthe reaction
the liquidlayer
phase,microstructure
whereas the formed during
specimen initial hot
dipped fordipping (within 14)
120 s (Figure 40 s), the very
grew
formation mechanism of the reaction layer its phase are as follows. The Fe 3O4 oxide layer is formed
deep into the steel interior. The growth direction of the η phase was the same in the [001] direction.
on the surface of the steel when the steel sheet is dipped in the Al-7 wt.% Mn molten alloy. However,
the Fe3O4 oxide layer is formed on the surface of the steel, but since Al 2O3 is formed around the
4. Discussion
reaction layer, Fe3O4 is destroyed as it reacts with Al-7 wt.% Mn molten alloy and is substituted with
Coatings 2017, 7, 222 11 of 15

4. Discussion
Analyzing the reaction layer microstructure formed during initial hot dipping (within 40 s), the
formation mechanism of the reaction layer its phase are as follows. The Fe3 O4 oxide layer is formed
on the surface of the steel when the steel sheet is dipped in the Al-7 wt.% Mn molten alloy. However,
the Fe3 O4 oxide layer is formed on the surface of the steel, but since Al2 O3 is formed around the
reaction layer, Fe3 O4 is destroyed as it reacts with Al-7 wt.% Mn molten alloy and is substituted with
Al2 O3 . It is well known that Al2 O3 is a more stable oxide than Fe3 O4 , and therefore a substitution
reaction occurred. When the Fe3 O4 was destroyed by the substitution reaction, the melt flowed into
the solid, reacting with the steel to form a reaction layer. The reaction layer formed mainly in the
liquid phase, with a thickness of about 1 µm or less inside the steel. The microstructure of the coating
layer formed at the initial stage (40 s) of the coating process as shown in Figure 12 was in the order of
Al + Al6 Mn (coated alloy structure) → Al11 Mn4 → FeAl3 (θ) → Fe2 Al5 (η) → Fe3 AlC → αFe(steel).
The microstructure of the coated layer can be classified into a solidification structure in which Al-7
wt.% Mn melts are formed during cooling and a reaction layer is formed while holding. As shown in
Figure 11, the solidification structure of Al-7 wt.% Mn is composed of Al with Al6 Mn as the matrix.
Therefore, Al and Al6 Mn were solidified structures and the remaining Al11 Mn4 , FeAl3 (θ), Fe2 Al5 (η)
are the reaction phases formed during the coating process.
Reaction layers or reaction phases have been studied for a long time in the diffusion reaction or
coating process of Fe and pure Al [22–24], Fe and Al alloys [25,26], steel and pure Al [27–31], and steel
and Al alloys [32,33]. The reaction layers formed in these studies were classified into the following
three types: (1) Al/FeAl3 (θ)/Fe2 Al5 (η)/Fe [22–24,33] where the intermetallic layer is composed
of an outer minor FeAl3 (θ) layer and an inner major Fe2 Al5 (η) layer; (2) Al/Fe4 Al13 (θ)/Fe2 Al5
(η)/Fe [31,32] where the intermetallic layer is composed of an outer minor Fe4 Al13 layer and an inner
major Fe2 Al5 layer; and (3) Al/Fe2 Al5 /Fe [33–35] where the only reaction product was Fe2 Al5 . Most
studies have reported that θ phase (Fe4 Al13 or FeAl3 ) is formed on Al side and η phase is formed on
Fe side or steel side. There is no study on the reaction of Al-Mn coated layer in these studies. In the
Al-Mn coating process of this study, Al11 Mn4 is formed before θ phase formation.
As seen in Figure 12b, all reaction phases except for Fe3 AlC (κ) phase formed on the liquid
side of the steel surface, the elements such as Fe dissolved and formed in the Al-7 wt.% Mn molten
alloy. Thus, an (Al-7 wt.% Mn)-Fe quasi-binary phase diagram was calculated using Thermo-CalcTM
(Ver.6.0, Stockholm, Sweden) to analyze phase transformation during and while maintaining the
dipping temperature. Figure 15 shows the phase diagram. When Fe is added into the melts at a
dipping temperature of 773 ◦ C at 0.6 wt.% or more, solid Al11 Mn4 (A) formed within the liquid
phase. However, the phase in the coating layer composed of Al and Mn had two phases, Al11 Mn4
and Al6 Mn (B). In the phase diagram, Al6 Mn does not exist at the dipping temperature, but does exist
below temperatures of 725 ◦ C. In particular, Al6 Mn can form on Al11 Mn4 or can form in the coating
layer. With this distribution, the Al11 Mn4 formed as the Fe concentration in the melts increased while
maintaining the dipping temperature. And Al6 Mn can crystallize in liquid phase during cooling or
form on Al11 Mn4 which is nucleation site during cooling. Therefore, Al11 Mn4 and Al6 Mn may be
connected to each other. The reaction layer, except for the coating structure (Al + Al6 Mn), was formed
as Al11 Mn4 → FeAl3 (θ) → Fe2 Al5 (η) → Fe3 AlC (κ) in the coating process, maintaining the dipping
temperature. Al11 Mn4 formed by reacting with the liquid phase, but the remaining FeAl3 (θ), Fe2 Al5
(η), and Fe3 AlC (κ) did not react directly with the liquid phase but instead would be formed by a
solid-phase diffusion mechanism between Al11 Mn4 and steel.
Figure 16 is a schematic diagram of the processes formed by inter-diffusion in the order of phases.
At interface Al11 Mn4 /liquid phase (L) formed first, and when Fe diffused toward the liquid phase and
Al diffused toward the solid phase Al11 Mn4 , the Al11 Mn4 phase grew. At the Al11 Mn4 phase/steel
interface, Al diffused toward the steel, and when Fe diffused into the A phase, the Al concentration
decreased in the region close to the steel. On the other hand, since the Fe concentration increased,
maintaining the dipping temperature. And Al6Mn can crystallize in liquid phase during cooling or
form on Al11Mn4 which is nucleation site during cooling. Therefore, Al11Mn4 and Al6Mn may be
connected to each other. The reaction layer, except for the coating structure (Al + Al6Mn), was formed
as Al11Mn4 → FeAl3 (θ) → Fe2Al5 (η) → Fe3AlC (κ) in the coating process, maintaining the dipping
Coatings 2017, 7, 222 12 of 15
temperature. Al11Mn4 formed by reacting with the liquid phase, but the remaining FeAl3 (θ), Fe2Al5
(η), and Fe3AlC (κ) did not react directly with the liquid phase but instead would be formed by a
the Fe-rich phase formed. The θ phase (FeAl3 ) formed when the Fe concentration increased from 0 to
solid-phase4diffusion
wt.% or more mechanism between
in the (Al-7 wt.% Al 11Fe
Mn)-x wt.% Mn 4 and steel.
quasi-binary diagram in Figure 15.

Coatings 2017, 7, 222

Figure 16 is a schematic diagram of the processes formed by inter-diffusion in the order of phases.
At interface Al11Mn4/liquid phase (L) formed first, and when Fe diffused toward the liquid phase and
Al diffused toward the solid phase Al11Mn4, the Al11Mn4 phase grew. At the Al11Mn4 phase/steel
interface, Al diffused toward the steel, and when Fe diffused into the A phase, the Al concentration
decreased in the region close to the steel. On the other hand, since the Fe concentration increased,
TM . TM
the
Figure 15. (Al-7
Fe-rich wt.%
Figure
phase Mn)-xFe
15.
formed. quasi-binary
(Al-7 wt.%
The θ phase (FeAl3) diagram calculated
Mn)-xFe quasi-binary diagram
formed when
calculatedby
by using Thermo-Calc
increased from .0 to 4
using Thermo-Calc
the Fe concentration
wt.% or more in the (Al-7 wt.% Mn)-x wt.% Fe quasi-binary diagram in Figure 15.
11

Figure 16.
Figure 16. Formation
Formation mechanism
mechanism of the reaction
of the reaction layer
layer formed
formed byby the
the dissolution
dissolution and and inter-diffusion
inter-diffusion
reactions at initial hot-dipping process. (a) Al11 Mn4 ; (b) FeAl3 (θ); (c) Fe2 Al5 (η); (d) κ (Fe3AlC).
reactions at initial hot-dipping process. (a) Al 11 Mn4 ; (b) FeAl 3 (θ); (c) Fe 2 Al 5 (η); (d) κ (Fe 3 AlC).

However, in Tables 2 and 3, the actual Mn concentrations of the θ and η phases are lower than
However, in Tables 2 and 3, the actual Mn concentrations of the θ and η phases are lower than
7 wt.%. That is, the amounts of Mn of θ and η phases were 6.32 wt.% and 0.22 wt.%, respectively, and
7 wt.%. That is, the amounts of Mn of θ and η phases were 6.32 wt.% and 0.22 wt.%, respectively, and
the Mn content of η was much lower than the Mn concentration in 1.13 wt.% of steel. Therefore, phase
the Mn content of η was much lower than the Mn concentration in 1.13 wt.% of steel. Therefore, phase
transformation by inter-diffusion while considering Mn content can be interpreted as Al-Mn-Fe
transformation by inter-diffusion while considering Mn content can be interpreted as Al-Mn-Fe ternary
ternary phase diagram. Figure 17 shows the Al-Mn-Fe ternary phase diagram calculated by Thermo-
phase diagram. Figure 17 shows the Al-Mn-Fe ternary phase diagram calculated by Thermo-CalcTM .
CalcTM. In the phase diagram, when the amount of Mn is 5% or less, Al 11Mn4 did not form and instead
In the phase diagram, when the amount of Mn is 5% or less, Al11 Mn4 did not form and instead the
the θ phase formed. Also, as Fe increased, it transformed from FeAl3 (θ) to Fe2Al5 (η). As a result, the
θ phase formed. Also, as Fe increased, it transformed from FeAl3 (θ) to Fe2 Al5 (η). As a result, the
amount of Fe increased by diffusion at the A11Mn4 phase/steel interface, and when the amount of Al
amount of Fe increased by diffusion at the A11 Mn4 phase/steel interface, and when the amount of Al
decreased, θ would form. At the θ phase/steel interface (c), when the amount of Al decreased and
decreased, θ would form. At the θ phase/steel interface (c), when the amount of Al decreased and the
the amount of Fe further increased, η (Fe2Al5) would form as shown in the phase diagram. As shown
amount of Fe further increased, η (Fe2 Al5 ) would form as shown in the phase diagram. As shown in
in Figure 14c, large columnar η grains grow along the c-axis of the phase. Morphology of the η phase
Figure 14c, large columnar η grains grow along the c-axis of the phase. Morphology of the η phase has
has been studied and explained as a result of the 30% vacancy rate in the c-axis of the crystal structure,
been studied and explained as a result of the 30% vacancy rate in the c-axis of the crystal structure,
which can be as a rapid diffusion tunnel. It causes η phase to be oriented by the fixed c-axis of the
which can be as a rapid diffusion tunnel. It causes η phase to be oriented by the fixed c-axis of the
crystal structure, and grows preferentially along the diffusion direction during hot-dipping.
crystal structure, and grows preferentially along the diffusion direction during hot-dipping.
in Figure 14c, large columnar η grains grow along the c-axis of the phase. Morphology of the η phase
has been studied and explained as a result of the 30% vacancy rate in the c-axis of the crystal structure,
which can be as a rapid diffusion tunnel. It causes η phase to be oriented by the fixed c-axis of the
Coatings 2017, 7, 222 13 of 15
crystal structure, and grows preferentially along the diffusion direction during hot-dipping.

17. Al-Mn-Fe ternary phase diagram at ◦ TM

Figure 17.Figure
Al-Mn-Fe ternary phase diagram at773
773C°C
calculated by using
calculated byThermo-Calc .
using Thermo-CalcTM.

The formation mechanism of the κ (Fe AlC) phase at the interface between the steel and the η
3
The formation mechanism of the κ (Fe3AlC) phase at the interface between the steel and the η
phase is as follows. As shown in Figure 3f, the concentration of C in the region transformed from α
phase is as Fe
follows.
(Steel) toAs shown
η phase in Figure
is lower than that3f, thesteel.
of the concentration of Ccoincides
This phenomenon in the region
with the transformed
maximum from α
TM
Fe (Steel) tosolubility
η phase is lower
of 0.07 wt.% ofthan
η phasethat
(seeof the5)steel.
Table Thisbyphenomenon
calculating using Thermo-Calccoincides
, and thewith the maximum
solubility
is very low. Therefore, C in the region transformed to η phase will be diffused and discharged toward
solubility of 0.07 wt.% of η phase (see Table 5) calculating by using Thermo-CalcTM, and the solubility
the steel that can be soluted by increasing the concentration of Al and C in the steel interface. The
is very low.content
Therefore,
of C in CtheinFethe region transformed to η phase will be diffused and discharged toward
3 AlC (κ) is 5.05 wt.%, and the average concentration of steel is 0.23 wt.%. Since
the amount of C for forming this phase is absolutely insufficient, the thickness is formed in nm.
12
Table 5. Equilibrium composition (wt.%) at 773 ◦ C calculated using Thermo-CalcTM .

Phase Al Mn Fe C
Al11 Mn4 57.40 35.89 6.62 0.09
FeAl3 (θ) 57.05 7.67 35.14 0.14
Fe2 Al5 (η) 54.71 0.32 44.9 0.07

5. Conclusions
Nucleation and growth of the reaction layer formed on boron steel hot-dipped in an Al-7 wt.%
Mn molten alloy at 773 ◦ C for various times was investigated.

1. The layer formed on the surface of the steel was classified into a reaction layer formed at the
coating temperature and a solidification layer in which the liquid phase solidified during cooling.
The solidification layer was composed of Al and Al6 Mn phases, and the reaction layer was
composed of Al11 Mn4 , FeAl3 (θ) and Fe2 Al5 (η) phases. In particular, the η phase grew long
inside the steel. The Fe3 AlC (κ) phase was formed at the interface between the η phase and the
steel in a very thin band of several nanometers.
2. The solid phase Al11 Mn4 was eluted when Fe was dissolved in Al-Mn molten alloy at 773 ◦ C at
0.6 wt.% or more from the (Al-7 wt.% Mn)-x wt.% Fe quasi phase diagram (Thermo-CalcTM ). At
the interface between Al11 Mn4 phase and the steel, as Fe diffused toward the Al11 Mn4 and Al
diffused toward the steel, at the interface, θ phase was formed as the Fe concentration increased
and the Al concentration decreased. In addition, η phase was formed due to inter-diffusion of Fe,
Al between the θ phase and the steel. In other words, Al11 Mn4 → θ → η was formed in which
the Fe content was higher toward the steel by inter-diffusion in the solid phase state.
3. The η phase formed by the reaction with the liquid phase initially had a fine polygonal structure.
However, it formed inside the steel, growing to the order of Al11 Mn4 → θ → η in the liquid phase,
Coatings 2017, 7, 222 14 of 15

and grew in a long columnar form because the Al diffusion was along the c-axis and the <100>
direction was fast, as already known.
4. Fe3 AlC (κ) phase was formed as the concentration of Al and C is increasing at the steel interface
because the η phase diffused C toward steel due to the fact that η hardly contains C.

Acknowledgments: This work was supported by a 2-Year Research Grant of Pusan National University.
Author Contributions: Sung-Yun Kwak and Chung-Yun Kang conceived and designed the experiments;
Sung-Yun Kwak, Jae-Hyeong Lee, Jung-Gil Yun, and Dong-Ik Shin performed the experiments; Sung-Yun Kwak
and Chung-Yun Kang analyzed the data; Sung-Yun Kwak wrote the manuscript.
Conflicts of Interest: The funding sponsors had no role in the design of the study; in the collection, analyses, or
interpretation of data; in the writing of the manuscript, and in the decision to publish the results.

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