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Acta Materialia 52 (2004) 2173–2184
www.actamat-journals.com
Aluminization of high purity iron and stainless steelby powder liquid coating
Koji Murakami a,*, Norihide Nishida a, Kozo Osamura b, Yo Tomota c, Tetsuya Suzuki c
a Department of Materials Engineering, Industrial Technology Center of Okayama Prefecture, 5301, Haga, Okayama 701-1296, Japanb Department of Materials Science and Engineering, Kyoto University, Sakyo-ku, Kyoto 606-8501, Japan
c Department of Materials Science, Faculty of Engineering, Ibaraki University, 4-12-1 Nakanarusawa, Hitachi, Ibaraki 316-8511, Japan
Received 1 December 2003; received in revised form 1 December 2003; accepted 8 January 2004
Abstract
Powder liquid coating is investigated metallographically as an aluminization technique for high-purity iron [Acta Mater., in
press] and stainless steel. In this process, Fe2Al5 forms initially during heat treatment, with c axis preferentially aligned with the
sample normal. In Fe–18mass%Cr alloy, Cr exhibits almost the same concentration profile as Fe except for the temporary formation
of a Cr5Al8 network in the early stage of heat treatment. Fe–25Cr–18Ni alloy forms a thinner aluminized layer compared to the
other substrates, and contains an Al–Ni-rich layer and spherical precipitates (ordered B2). The diffusion of Al and Ni in the system
(B2/bcc/fcc) is simulated using a new formulation of the diffusion equation for the ternary Fe–Al–Ni system taking the concen-
tration-dependent interdiffusion coefficient into account. The bcc layer is found to be predominantly in a steady state due to the
large interdiffusion coefficients, and characteristic uphill diffusion of Al in the B2 layer is attributed to the existence of Ni.
� 2004 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
Keywords: Powder processing; Aluminization; Steels; Texture; Kinetics
1. Introduction
The present authors recently presented a new methodfor aluminizing the surface of iron and steel [1], utilizing
a slurry of mixed Al and Ti (or Al and Al2O3) powder.
The method involves simply pasting the slurry onto the
substrate and a heating at close to the quenching or
solution temperature of the steels. The thickness and Al
concentration of the modified layer can be readily varied
at low cost by tuning the mixing ratio in the slurry
composition and/or heat treatment conditions. Theprocess can be applied to harden steel surfaces, as the
* Corresponding author. Tel.: +81-862-869-600; fax: +81-862-869-
630.
E-mail addresses: [email protected] (K. Mura-
kami), [email protected] (N. Nishida), osamura@
hightc.mtl.kyoto-u.ac.jp (K. Osamura), [email protected]
(Y. Tomota), [email protected] (T. Suzuki).
1359-6454/$30.00 � 2004 Acta Materialia Inc. Published by Elsevier Ltd. A
doi:10.1016/j.actamat.2004.01.009
subsequent nitridation creates hard nitrides and induces
internal stress in the modified layer [2,3]. The aluminized
and subsequently nitrided surfaces have high hardnessesof about HV1500, and also exhibit excellent resistivity
against erosion by molten Al. These properties make
long-run casting operations possible, where severe me-
chanical erosion and metallurgical reaction of steels with
molten Al cause deterioration in dies, pins, or other
construction materials in injection molding machines.
The corrosion resistance of stainless steels is also im-
proved by aluminization [4], with potential applicationsin environments involving of molten salt corrosion [5,6]
or vanadium attack. In this study, the process applied to
high-purity Fe was reexamined crystallographically,
followed by similar investigations of the aluminized
layers in ferritic and austenitic stainless steels. The dif-
fusion equation for the multi-component system is
treated numerically here using a new formulation that
takes the concentration-dependent interdiffusion coeffi-cient into consideration.
ll rights reserved.
2174 K. Murakami et al. / Acta Materialia 52 (2004) 2173–2184
2. Experimental
Disks of high-purity Fe (99.9%), Fe–Cr alloy (com-
mercial ferritic stainless steel, Fe–18mass%Cr), and Fe–
Cr–Ni alloy (austenitic, Fe–25Cr–18Ni) were used assubstrates. The surface of the substrate was polished
with abrasive paper to #600 and washed twice with
acetone in an ultrasonic cleaning bath for 0.3 ks each
time. A slurry was prepared by stirring a mixture of
atomized Al powder (under 3 lm in diameter), crushed
Ti (under 38 lm) and ethylene glycol (5.0� 103 mm3 for
mixed powders of 1.0� 10�2 kg) with an impeller at 50
revolutions per second for 0.6 ks. The slurry was pastedonto the disks at 0.65 mg/mm2, and the specimens were
heated in an oven at 473 K for 3.6 ks to remove ethylene
glycol. Each of the prepared disks was then heated in a
quartz cylinder by infrared radiation in a vacuum of
1.3� 10�3 Pa. In order to investigate the evolution of
the aluminized layer of the substrates, the heat treat-
ment conditions were varied as shown in Fig. 1. For
final heating, the temperature was raised at 1.33 K/s,after which the samples were cooled under N2 gas flow
(about )2 K/s) to room temperature. As shown in
Fig. 1, the heat treatment conditions are denoted here-
after in the form T 0 K–cooled or T K–t ks.X-ray diffraction (XRD) patterns of the aluminized
sample surface were measured in order to identify pha-
ses and textures. The microstructure of the modified
layer was observed by optical microscopy, electronprobe microanalysis (EPMA), and Auger electron
spectrometry (AES) with micro ion etching equipment.
Fe (Cr,Ni) and Al concentration profiles were quanti-
tatively measured by EPMA with ZAF matrix correc-
Fig. 1. Heat treatment pattern.
Fig. 2. Sample coordinates used in XRD and EBSD.
tion. Electron backscattering diffraction (EBSD) was
employed to collect local crystal orientations on sample
cross sections and to analyze the growth of the alumi-
nized region. Sample coordinates for XRD and EBSD
are depicted in Fig. 2.
3. Experimental results
3.1. Aluminized layer in high-purity Fe
As reported previously [1], the aluminized layer was
formed by heat treatment under conditions of 1173 K–cooled. Fig. 3(a) shows an XRD pattern obtained by 2h–h scan. According to reported diffraction data [7] for the
isotropic powder of Fe2Al5 (space group number 63,
orthorhombic, a ¼ 0:76559, b ¼ 0:64154, c ¼ 0:42184nm), the (2 2 1) diffraction intensity is largest and about
three times that of (0 0 2). Comparing the data with the
present diffraction pattern, it is apparent that the Fe2Al5layer is highly textured, and the pole figure of the Fe2Al5(0 0 2) plane (Fig. 3(b)) actually reveals a fibrous texture
with a sharp peak at the center and a second peak at 60�around the z axis. Fig. 4(a) shows a cross-sectional
Fig. 3. XRD patterns of surface of aluminized high-purity Fe: (a) 2h–hscan, (b) Fe2Al5 (0 0 2) pole figure.
Fig. 4. Cross-sectional microstructure of high-purity Fe aluminized
under conditions of 1173 K–cooled: (a) secondary electron image after
Ar ion etching, (c) histogram of crystal direction b in (b), (d) grain
boundary map of a-Fe.
Fig. 5. Ternary phase diagram for the Fe–Al–Cr system at 1273 K
(calculated using Thermo-Calc) and diffusion path (1273 K–3.6 ks).
Fig. 6. Cross-sectional microstructure of aluminized high-purity Fe:
(a) 1273 K–0.3 ks, (b) 1273 K–3.6 ks.
K. Murakami et al. / Acta Materialia 52 (2004) 2173–2184 2175
secondary electron image obtained by AES after Ar ion
etching. The image reveals Fe2Al5, the substrate (a-Fe),and columnar a-Fe at the interface. The orientation of
the c axis of Fe2Al5 grains is shown in Fig. 4(b). The
majority of grains are aligned with c axes subparallel
with the z axis. However, 90% of the oriented Fe2Al5grains had misorientation by more than 10� with eachother, and no characteristic orientational relationship
could be identified. The Fe2Al5 layer overlies the co-
lumnar a-Fe, as shown in Fig. 4(d), where misalignment
of adjacent grains is mostly within 10�. No clear FeAl2layer formed in the 1173 K–cooled sample, whereas a 10
lm-thick layer of FeAl2 was observed by EPMA in the
sample treated under conditions of 1273 K–cooled. This
1273 K–cooled sample exhibited a relatively smoothFe2Al5/FeAl2/a-Fe interface with textured Fe2Al5 (ckz).
In the 1273 K–0.3 ks sample, the Fe2Al5 and FeAl2compound layers were no longer apparent, and the en-
tire aluminized layer consisted of a-Fe. As shown in
Fig. 5, the solid solubility of Al in a-Fe is so broad that
all Al at the surface can be involved in the a-Fe phase.
The orientational relationship of a-Fe grains was ob-
served by EBSD analysis for samples treated underconditions of 1273 K–0.3/0.9/1.8/3.6/7.2 ks. Selected
grain boundary maps are shown in Fig. 6. The bound-
aries between the substrate and the diffusion layer were
preserved during the growth of the diffusion layer (a-Fe), and the misalignment is less than 1�. At treatment
above 1185 K, the substrate was c-Fe. Misalignment
between the additive and diffusion layers was observed
to become smaller as heat treatment was prolonged, asexpressed quantitatively in Fig. 7. Here, the misalign-
ment histograms were calculated from 1000 pairs of
adjacent points across the additive/diffusion layer in-
terface in 1 lm steps.
3.2. Aluminized layer in Fe–Cr alloy
Fig. 8(a) shows a cross-sectional compositional imageof the aluminized Fe–Cr alloy (1173 K–cooled). Two
intermetallic compound layers; Fe2Al5, and FeAl2 and
Fig. 8. Cross-sectional compositional image of aluminized Fe–Cr alloy:
(a) 1173 K–cooled, (b) 1273 K–cooled.
(a)
(c)
(b)
Fig. 9. Concentration profiles of: (a) Al, (b) Fe, and (c) Cr in Fe–Cr
alloy aluminized at 1273 K for 3.6 ks.
Fig. 10. Cross-sectional grain boundary maps of aluminized Fe–Cr
alloy: (a) 1273 K–3.6 ks (vertical arrow denotes the diffusion path in
Fig. 5), (b) 1173 K–3.6 ks.
Fig. 7. Histogram of misalignment between additive layer and diffusion
layer in high-purity Fe (1 lm step, 1000 points for each specimen).
2176 K. Murakami et al. / Acta Materialia 52 (2004) 2173–2184
a-Fe, formed on the substrate (a-Fe). In the FeAl2 layer,
a second phase Cr5Al8 is observed as a bright network in
the image. The Fe2Al5 layer has a fibrous texture (ckz),as determined by XRD (2h–h scan) and EBSD. The a-Feregion does not have a columnar structure in this case,
instead forming a flat a/FeAl2 interface. In the sample
prepared under conditions of 1273 K–cooled (Fig. 8(b)),
an intermetallic compound of FeAl2 and a-Fe phaseswere observed.
The concentration profiles of Al, Fe, and Cr in the a-Fe layer of the samples 1273 K–0.3, 0.9, 1.8, 3.6 ks are
shown in Fig. 9. Spikes in the profiles correspond to
AlN particles formed due to N originally present in the
substrate. The Al profiles weakened gradually and fi-
nally disappeared in the a-Fe(Cr) region, whereas there
was a concentration gap in high-purity Fe at the inter-
face between the diffusion layer and the substrate, con-
sistent with the previous report [1]. Cr coexistedpreferentially with Al at 1173 K as shown in Fig. 8(a),
but did not form intermetallic compounds at 1273 K–0.3
ks or above, and the Cr content decreased gradually
toward the surface.
Fig. 10(a) shows a grain boundary map of the alu-
minized Fe–Cr alloy (1273 K–3.6 ks). Misalignment
between adjacent grains across the additive/diffusion
layer interface was mostly within 5�, and the grain size inthe vicinity of the surface was similar to that in the
substrate. However, a diffusion layer began to grow in
the coarse columnar structure toward the substrate. In
the Fe–Cr alloy aluminized at 1173 K–3.6 ks, shown
in Fig. 10(b), grains close to the additive/diffusion layer
interface appear similar to those in the 1273 K–3.6 ks
case with almost the same orientation, differing only
in that the grain boundaries of the substrate werepreserved throughout the diffusion layer.
K. Murakami et al. / Acta Materialia 52 (2004) 2173–2184 2177
3.3. Aluminized layer in Fe–Cr–Ni alloy
In the aluminization of Fe–Cr–Ni alloy, unlike the
cases for high-purity Fe and Fe–Cr alloy, an FeAl3 layer
with no characteristic texture was detected by XRD forthe 1073 K–cooled sample. However, the sample had a
flat interface similar to that obtained in the case of Fe–
Cr alloy. The Fe2Al5 layer, confirmed by EPMA anal-
ysis in the 1173 K–cooled sample, was not present in the
1273 K–cooled sample.
Fig. 11. Cross-sectional microstructures in Fe–Cr–Ni alloy aluminized under c
map, (e) grain boundary map.
Fig. 12. Cross-sectional microstructures in Fe–Cr–Ni alloy aluminized under c
map.
In Fig. 11, three characteristic boundaries parallel to
the surface can be observed. Boundary (ii) corresponds
to the additive/diffusion interface, (iii) is the interface
between the diffusion layer and the substrate, and
boundary (i) in the additive layer separates two regionsof different grain size. The coarse-grain region in the
additive layer, between (i) and (ii) in Fig. 11(e), corre-
sponds to the Ni-rich layer in Fig. 11(b). The Ni con-
centration in the coarse-grain region was 10–20 at.%,
whereas that in the fine-grain region was 3–9 at.%.
onditions of 1273 K–cooled: (a) Al map, (b) Ni map, (c) Fe map, (d) Cr
onditions of 1273 K–3.6 ks: (a) Al map, (b) Ni map, (c) grain boundary
umnar,wav.:wavy,net.:network,fin.:fine,
coa.:coarse,
sph.:spherical,(a;c):phase
ofsubstrate
atroom
temperature)
Fe–Cr
Fe–Cr–Ni
3.6
ks
1173K–cooled
1273K–cooled
1173K–3.6
ks
1273K–0.3–3.6
ks
1073K–cooled
1273K–cooled
1273K–0.3–3.6
ks
Fe 2Al 5FeA
l 2Cr 5Al 8(net.)
FeA
l 2a-Fe
a-Fe
a-Fe
FeA
l 3B2(fin.)B2
(coa.)
B2(A
l–Ni-poor)
B2(A
l–Ni-rich)
–a-Fe
a-Fe
a-Fe
–a-Fe
a-FeB2(sph.)
aðaÞ
cðcÞ
Fig. 13. Concentration profiles for Al, Ni, Fe, and Cr in Fe–Cr–Ni
alloy aluminized under conditions of 1273 K–3.6 ks.
2178 K. Murakami et al. / Acta Materialia 52 (2004) 2173–2184
An Al–Ni-rich layer formed in the additive layer for
sample treated under heating conditions of 1273 K–
cooled or higher, and spherical Al–Ni-rich regionsbecame distributed separately in the diffusion layer in the
samples treated at above 1273 K–0.3 ks. These Al–Ni
regions evolved into the structure shown in Fig. 12(a)
and (b), where Al and Ni coexist preferetially in the same
area. In Fig. 12(c), there is no grain morphology by
which the Al–Ni-rich layer can be distinguished in the
additive layer, and the orientation of Al–Ni-rich particles
is consistent with that of the surrounding diffusion layermatrix. The Al, Ni, Fe, and Cr concentration profiles of
the 1273 K–3.6 ks sample are plotted in Fig. 13. Al and
Ni both exhibit similar a variation, whereas Fe and Cr
vary complementarily. The concentration varied gradu-
ally in the Al–Ni-poor layer of the additive layer and also
in the diffusion layer, whereas a concentration gap oc-
curred at the interface between the diffusion layer and the
substrate. Phase formation in the aluminized layers andthe substrate in high-purity Fe, Fe–Cr, and Fe–Cr–Ni
alloy is summarized in Table 1.
Table
1
Phase
form
ationin
aluminized
layer
andsubstrate.(col.:col
Substrate
Fe
Heat
treatm
ent
1173K–cooled
1273K–cooled
1273K–0.3–
Additive
layer
Fe 2Al 5
a-Fe(col.)
Fe 2Al 5FeA
l 2a-Fe(w
av.)
a-Fe
Diffusion
layer
–a-Fe
a-Fe
Substrate
aðaÞ
cðaÞ
4. Discussion4.1. Phase transformation and grain growth during
aluminization of high-purity Fe
From the thermochemical data [8], the free energy of
FeAl3 formation is the lowest among the solid phases.
However, Fe2Al5 has been reported to be the first phase
that appears in hot dipping processes [9,10]. The growth
rate of reaction layer when an Fe substrate is dipped
into molten Al is given by
d2 ¼ kt; ð1Þwhere d is the thickness of the reaction layer, t is the
holding time, and k is a constant. The reported value of
k is 2.2� 102 lm2/s for Fe2Al5 at 988 K [11], and
Fig. 14. Schematic illustration of decomposition of intermetallic compounds and growth of a-Fe on high-purity Fe substrate: (a) immediately after
contact with molten Al, (b) 1173 K–cooled, (c) 1273 K–cooled, (d) held at 1273 K.
K. Murakami et al. / Acta Materialia 52 (2004) 2173–2184 2179
2.1� 101 lm2/s for FeAl3 [12]. This large difference isrelated to the differing diffusion properties of Fe2Al5and FeAl3, which have interdiffusion coefficients at
1273 K of 4.74� 102 [13] and 1.00� 101 [14] lm2/s,
respectively. The unit cell of Fe2Al5 is characteristic in
having densely packed Al columns along the c axis,
which is the shortest of its axes. Therefore, movement
of vacancies has been suggested to fastest along the caxis in Fe2Al5, in comparison to other directions [11].From these reports, it can be said that the phase
transformation in the early stage of this process is al-
most the same as that for hot dipping. The development
of a strong fibrous texture by Fe2Al5 with c axis alignedparallel with the z direction is explained as due to the
minimization of surface energy between molten Al and
Fe2Al5, the (0 0 l) planes of which are thought to be the
most densely packed and smooth, giving the lowestsurface energy.
When the a-Fe phase nucleates at the interface be-
tween Fe2Al5 and a-Fe (Fig. 14(a)), the excess Al atoms
may diffuse into the substrate or the Fe2Al5 layer. As no
meaningful amount of Al was detected in the 1173 K–
cooled sample [1], the excess Al is thought to diffuse into
the Fe2Al5 layer initially due to the large interdiffusion
coefficient for the Fe2Al5 phase. The interface frontwould then proceed toward the Fe2Al5 phase, producing
the columnar a-Fe phase structure as shown in
Fig. 14(b). Growth of the a-Fe region is accelerated with
increasing temperature, accompanied by increased Al
diffusion into the substrate and the formation of FeAl2between Fe2Al5 and a-Fe (Fig. 14(c)). As columnar
grains of a-Fe phase are observed in high-purity Fesamples aluminized under conditions of 973 K–3.6 ks
[1], the nucleation sites of a-Fe are suggested to be
sparsely dispersed. The increase in nucleation frequency
and active diffusion lead to the less wavy Fe2Al5/FeAl2/
a-Fe interface with increasing temperature, and the
small a-Fe grains in the additive layer are gradually
grown over by the large adjacent grains in the diffusion
layer (Fig. 14(d)).
4.2. Effect of Cr and Ni in the aluminization of Fe–Cr and
Fe–Cr–Ni alloy
In the aluminized Fe–Cr alloy, the concentration gap
in the Al, Fe, and Cr profiles for the other substrates was
not observed (Fig. 9). This is because the substrate
composition falls outside of the c-loop at 1273 K asshown in Fig. 5, that is, the substrate remained as a-Fethroughout heat treatment. The diffusion path in the
1273 K–3.6 ks sample lies on the isothermal section of
the Fe–Al–Cr phase diagram (Fig. 5), however, the in-
terdiffusion coefficients for this system have not yet been
reported. In Fig. 10(a), the grain boundaries in the
substrate appear to have been preserved in the vicinity
of the additive/diffusion layer interface, as can also beobserved in the map in Fig. 10(b). The preservation of
grain boundaries is thought to be determined by the
aluminizing temperature; the diffusion layer forming in
the early stages of heating preserves the grain bound-
aries in the substrate, while subsequent heating above a
certain temperature (between 1173 and 1273 K) results
Fig. 15. Ternary phase diagram for the Fe–Al–Ni system at 1273 K [25]
and diffusion path in sample 1273 K–3.6 ks (Fe concentration is the
sum of the observed values of Fe and Cr).
2180 K. Murakami et al. / Acta Materialia 52 (2004) 2173–2184
in the formation of the columnar structure, overwriting
the original features.
In the aluminized Fe–Cr–Ni alloy (Fig. 11, 1273 K–
cooled), the diffusion layer (a-Fe) developed to a
thickness of about 3 lm into the substrate, seemingly
due to a lack of c-form Ni in the substrate rather than
due to the existence of a-form Al. The Al and Ni con-centration profiles were characteristic, indicating an
enriched layer in these two elements around the additive/
diffusion layer interface as well as precipitates in the
diffusion layer. According to the ternary phase diagram
for the Fe–Al–Ni system (Fig. 15), these spherical pre-
cipitates are thought to represent ordered B2 phase,
presumably formed during cooling through the en-
largement of the B2+bcc region with decreasing tem-perature as reported by [15,16].
The concentration gap in the elements at the interface
between the diffusion layer and the substrate, as shown
in Fig. 13, is observed for both aluminized high-purity
Fe [1] and aluminized Fe–Cr–Ni alloy. It should be
noted that the Al concentration gradient is very low in
the diffusion layer (Fig. 13) compared with the result for
the high-purity Fe [1]. This fact may explain the signif-icant difference in thickness of the aluminized layer for
these two substrates; about 110 lm for 1273 K–3.6 ks
high-purity Fe, and 30 lm for Fe–Cr–Ni alloy. As the
quaternary phase diagram for the Fe–Cr–Ni–Al system
has yet to be reported, the ternary Fe–Al–Ni phase di-
agram will be considered in the present discussion as-
suming that the diffusion of Cr is similar to that of Fe in
the a-Fe phase because Cr is a ferritic element with largebcc region in the Fe–Cr binary system. Although the
presence of Cr is expected to result in enlargement of the
a region and shrinkage of the c region in the phase di-
agram, this assumption of diffusion is also supported by
the very similar intrinsic diffusion coefficients of Fe and
Cr at 1273 K in an Fe-based bcc alloy (3.2� 10�3 and
2.7� 10�3 lm2/s, respectively [17]). Qualitatively, the
Al–Ni-rich layer, corresponding to the B2 phase in
Fig. 15, is thought to lower the diffusion rate, as the
diffusion of Al and Ni reduces the degree of order of the
B2 alloy. Fe has been reported to substitute into both Aland Ni sites [18]. Therefore, Al supply from the additive
layer into the diffusion layer is supported by the sub-
stitution of Fe from the substrate, avoiding a reduction
in the degree of order. However, Ni supply into the
additive layer leads to disorder in the B2 phase. The
numerical analyses below will provide a quantitative
description of this ternary diffusion system.
4.3. Numerical analysis of diffusion in the aluminization of
Fe–Cr–Ni alloy
4.3.1. Formulation and calculation procedure
The numerical analysis reported previously [1] is ex-
tended here to deal with a ternary system. Flux in the
system is expressed in terms of the concentration of two
solute elements as follows [19–21]:
~Jijðt; xÞ ¼ �~D3ij
ocjðt; xÞox
; ð2Þ
~Jiðt; xÞ ¼ ~Ji1ðt; xÞ þ ~Ji2ðt; xÞ: ð3Þ
Here i ¼ 1 (Al), 2 (Ni), and the superscript 3 to the right
of ~D indicates an dependent element (Fe). The conser-
vation of each solute element leads to the followingdiffusion equations for the ternary system.
ociðt; xÞot
¼ o
ox~D3i1ðxÞ
oc1ðt; xÞox
�þ ~D3
i2ðxÞoc2ðt; xÞ
ox
�06 x < 1;
06 t < 1:
�ð4Þ
The value of ci (in mol/mm3) is calculated using the
following equation:
ci ¼xi
xAlvAl þ xNivNi þ ð100� xAl � xNiÞvFe: ð5Þ
This equation takes the atomic percent xi and the
molar volume of each element vi (vAl ¼ 10:0� 103,
vNi ¼ 6:60� 103, vFe ¼ 7:10� 103 mm3/mol) for sim-
plicity. Each side of Eq. (4) is rewritten as follows:
l:h:s of ð4Þ ¼ ciðtþDt; xÞ � ciðt; xÞDt
� 1
2
o2ciot2
DtþOððDtÞ2Þ;
ð6Þ
r:h:s of ð4Þ
¼ 1
2ðDxÞ2~D3i1ðx
n�þ DxÞ½c1ðt; xþ DxÞ � c1ðt; xÞ�
þ ~D3i2ðxþ DxÞ½c2ðt; xþ DxÞ � c2ðt; xÞ�
� ~D3i1ðxÞ½c1ðt; xÞ � c1ðt; x� DxÞ�
oK. Murakami et al. / Acta Materialia 52 (2004) 2173–2184 2181
� ~D3i2ðxÞ½c2ðt;xÞ�c2ðt;x�DxÞ�
þ ~D3i1ðx
nþDxÞ½c1ðtþDt;xþDxÞ�c1ðtþDt;xÞ�
þ ~D3i2ðxþDxÞ½c2ðtþDt;xþDxÞ�c2ðtþDt;xÞ�
� ~D3i1ðxÞ½c1ðtþDt;xÞ�c1ðtþDt;x�DxÞ�
� ~D3i2ðxÞ½c2ðtþDt;xÞ�c2ðtþDt;x�DxÞ�
o��1
2
o
oxo~D3
i1
oxoc1ox
þo~D3
i2
oxoc2ox
!Dx
�1
2
o2ciot2
DtþOðDtDxÞ: ð7Þ
Substituting Eq. (6) and (7) into Eq. (4) gives the dif-
ference equation with a round-off error of OðDtDxÞ. InEq. (7), m and n represent time and position, respec-
tively, that is, t ¼ mDt (m ¼ 0; 1; . . . ;M � 1) and x ¼ nDx(n ¼ 0; 1; . . . ;N � 1). Using m and n, the difference
equation is given by
ci;mþ1;n � ci;m;n
¼ a2½~D3
i;1;nþ1ðc1;m;nþ1 � c1;m;nÞ þ ~D3i;2;nþ1ðc2;m;nþ1 � c2;m;nÞ
� ~D3i;1;nðc1;m;n � c1;m;n�1Þ � ~D3
i;2;nðc2;m;n � c2;m;n�1Þþ ~D3
i;1;nþ1ðc1;mþ1;nþ1 � c1;mþ1;nÞþ ~D3
i;2;nþ1ðc2;mþ1;nþ1 � c2;mþ1;nÞ� ~D3
i;1;nðc1;mþ1;n � c1;mþ1;n�1Þ� ~D3
i;2;nðc2;mþ1;n � c2;mþ1;n�1Þ�; ð8Þ
where
a ¼ Dt
ðDxÞ2: ð9Þ
Although there are 2N unknown values (ci;mþ1;0;ci;mþ1;1; . . . ; ci;mþ1;N�1 ði ¼ 1; 2Þ), the number of inde-
pendent equations generated from Eq. (8) is 2N � 4
(i ¼ 1; 2 and n ¼ 1; 2; . . . ;N � 2). Four additional
equations are derived from the following boundary
conditions as described in [1].
ci;mþ1;0 � ci;m;0
¼ a2
~D3i;1;0ðc1;m;2
hn� 2c1;m;1 þ c1;m;0Þ
þ ~D3i;2;0ðc2;m;2 � 2c2;m;1 þ c2;m;0Þ
iþ ~D3
i;1;0ðc1;mþ1;2
h� 2c1;mþ1;1 þ c1;mþ1;0Þ
þ ~D3i;2;0ðc2;mþ1;2 � 2c2;mþ1;1 þ c2;mþ1;0Þ
io; ð10Þ
ci;m;N�1 ¼ 0: ð11ÞTreatment of the B2/bcc and bcc/fcc interface is
handled in the same as in [1], i.e.,
DX ¼~J1;m;k � ~J1;m;kþ1
c1;m;k � c1;m;kþ1
Dt: ð12Þ
Here X is the position of the interface (kDx6X 6
ðk þ 1ÞDx), and DX is the movement of the interface in
Dt.The observed concentration profile (1273 K–0.3 ks)
was used for the initial condition. The values of the
observed concentration profile, which corresponds to
the bcc structure (circled area in Fig. 18(a)), were shifted
to the bcc region of the Fe–Al–Ni phase diagram (cir-
cled area in Fig. 18(b)). The time increment and spatialresolution were set at Dt ¼ 0:05 s and Dx ¼ 0:2 lm. In-
terdiffusion coefficients were taken from [22–25], as
plotted in Fig. 16. These interdiffusion coefficients indi-
cate that diffusion in the bcc region is much faster than
that in the B2 or fcc regions, that is, the Al–Ni-rich layer
(B2) at the additive/diffusion interface acts as a barrier
to the supply of Al from the additive layer into the
diffusion layer. Thus, it is qualitatively recognizedthat almost flat concentration profiles at the surface of
the additive layer and in the diffusion layer result
from the highly concentration-dependent interdiffusion
coefficients.
4.3.2. Calculation results
Figs. 17 and 18 show the observed and calculated
concentration profiles and diffusion paths for the alu-
minized Fe–Cr–Ni alloy. The calculated results repro-
duce the concentration profiles in the Al–Ni-poor and
Al–Ni-rich regions well, particularly in terms of the
gentle slope of the profile in the Al–Ni-poor layer. Theconcentration gap at the bcc/fcc interface was also
properly represented. These results are in qualitative
agreement with the observed data, except for the
thickness of the aluminized layer, which is overestimated
by a factor of two or more. In the Al–Ni-poor region of
the additive layer, the Al concentration decreased
monotonically with time, even though the partial de-
rivative of Al concentration with respect to x is positive(oc1=ox > 0).
This uphill diffusion phenomenon indicates that the
total flux of Al (Eq. (3)) is positive (~J1 > 0). This can be
explained based on the present calculations as follows.
The partial derivative of ci with respect to x was calcu-
lated by considering a cubic and its derivative at each
point by the Savitzky–Golay method (5-point-smooth-
ing). As a consequence of the sum of partial flux (~J11 < 0and ~J12 > 0), the total flux of Al (~J1 ¼ ~J11 þ ~J12) be-
comes positive in the Al–Ni-poor region (Fig. 19(a) and
(c)). The derivative of flux for the diffusion of Ni ~J2 withrespect to x changes sign at the Ni concentration peak.
This means that the Ni concentration increases in the
Al–Ni-poor region of the additive layer and decreases in
the region between the peak and the additive/diffusion
layer interface, leading to shrinkage of the B2 layer as
(a)
(c) (d)
(b)
Fig. 16. Interdiffusion coefficients for the Fe–Al–Ni system at 1273 K reported by [22–25]: (a) ~Dð3Þ1;1, (b)
~Dð3Þ1;2, (c)
~Dð3Þ2;1, (d)
~Dð3Þ2;2.
(a) (b)
(d)(c)
Fig. 17. Observed and calculated concentration profiles of the sample aluminized at 1273 K: (a) observed Al concentration, (b) calculated Al
concentration, (c) observed Ni concentration, (d) calculated Ni concentration.
2182 K. Murakami et al. / Acta Materialia 52 (2004) 2173–2184
(a) (b)
Fig. 18. Observed and calculated diffusion paths of the sample
aluminized at 1273 K: (a) observed, (b) calculated.
K. Murakami et al. / Acta Materialia 52 (2004) 2173–2184 2183
shown in Fig. 17(b). The entire aluminized layer is then
thought to consist solely of bcc phase.
The diffusion rate of Al and Ni was qualitatively
discussed in Section 4.2, which can be discussed basedon the difference observed in Fig. 19. Around the peak
position in the Al and Ni concentration profile, j~J1j islarger than j~J2j. This flux imbalance suggests that the
decrease in Al concentration is compensated not only by
the incoming Ni flux toward the surface, but also by the
flux of Fe, which can substitute into both Al and Ni sites
without decreasing the degree of order in B2 NiAl alloy
[18].In the diffusion layer, the variation in the concen-
tration profile is almost linear between the B2/bcc and
bcc/fcc interfaces. This can be explained in terms of the
(a) (b
(c)
Fig. 19. Calculated flux profiles: (a) J1 and J1j (ini.+0.6 ks), (b) J2 and J2j
interdiffusion coefficients in the bcc region, which are
much larger than those in other phases. In contrast to
the B2 and fcc regions, the bcc region is in a steady state
(oci=ot ’ 0), resulting in a linear compositional varia-
tion regardless of the changes in the position of the B2/bcc and bcc/fcc interfaces. The dominant term in the
numerator of Eq. (12) is ~J1;m;k at the bcc/fcc interface, asshown in Fig. 19. Therefore, the velocity of bcc/fcc
boundary movement DX=Dt can be discussed directly
based on the gradient of the Al concentration profile in
the bcc layer. As the calculated gradient of the Al con-
centration in the bcc layer is much larger than in the
observed data (Fig. 17(a) and (b)), a higher gradient isthought to result in the thicker aluminized layer. In
other words, the large discrepancy between the observed
and the calculated thickness of the aluminized layer is
attributable to the differences in B2/bcc and bcc/fcc in-
terface concentration.
As discussed above, the thickness of the diffusion
layer is suggested to be governed by the difference in
interdiffusion coefficients between phases and the dif-ference in the equilibrium concentration between the
two extremes of the bcc region in the phase diagram. It
is thought that the change in Al and Ni concentration
along the diffusion path in the bcc layer is limited by the
existence of Cr, which modifies the phase diagram of the
Fe–Al–Ni ternary system, shifting the B2/bcc phase
boundary toward the origin in Fig. 18. From this
viewpoint, an appropriate amount of Cr in the substrateis effective for suppressing any deterioration in oxidation
resistivity as a result of secondary diffusion in high-
temperature service.
)
(d)
(ini.+0.6 ks), (c) J1 and J1j (ini.+3.3 ks), (d) J2 and J2j (ini.+3.3 ks).
2184 K. Murakami et al. / Acta Materialia 52 (2004) 2173–2184
5. Conclusions
The main results obtained in this study can be sum-
marized as follows:
1. In the aluminization of high-purity Fe, Fe2Al5formed first, aligned with [0 0 1] direction parallel
with the z axis of the sample, followed by the decom-
position of the intermetallic compound layer to form
a-Fe. After complete conversion of the aluminized
layer to a-Fe, grains in the additive layer became
aligned with the diffusion layer.
2. The formation and decomposition process for the in-
termetallic compound layer in the aluminization ofFe–Cr alloy proceeded in almost the same as for
high-purity Fe. Both the aluminized layer and the
substrate formed a bcc structure during heat treat-
ment due to the presence of a-form Cr. In this case,
there was no clear interface between the diffusion
layer and the substrate in the concentration profile.
However, characteristic columnar grains correspond-
ing to the diffusion layer formed during heat treat-ment at 1273 K. At lower temperature, 1173 K,
the original grain boundaries in the substrate were
preserved.
3. In the aluminization of Fe–Cr–Ni alloy, an Al–Ni-
rich layer (ordered B2 phase) formed in the additive
layer in the early stage of heat treatment. Each ele-
ment diffused through the ordered layer, resulting in
the growth of the diffusion layer (bcc) as a columnarstructure with spherical Al–Ni-rich precipitates and a
flat interface with the substrate. The thickness of the
diffusion layer was 20 lm, in contrast to 70 and 100
lm for high-purity Fe and Fe–Cr alloy, respectively.
4. Numerical analysis of the Fe–Al–Ni ternary system
satisfactorily explained the uphill diffusion of Al in
the Al–Ni-poor region of the additive layer, where
oc1=ox > 0. This occurs because the flux of Al is de-fined not only by the concentration profile of Al,
but also by that of Ni, which contributes to makeeJ1 positive, resulting in the supply of Al from the ad-
ditive layer to the diffusion layer. The equilibrium
concentration at the B2/bcc and bcc/fcc interfaces
derived from the phase diagram and the diffusion
path is an important factor determining the growth
rate of the diffusion layer, as well as the interdiffusion
coefficients for each phase.
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