Transformation kinetics for mullite in kaolin–Al2O3 ceramics

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Yung-Feng Chen
Department of Materials Science and Engineering, National Cheng Kung University,
1 Ta-Hsueh Road, Tainan 70101, Taiwan
Moo-Chin Wang
Department of Mechanical Engineering, National Kaohsiung University of Applied Sciences,
415 Chien-Kung Road, Kaohsiung 80782, Taiwan
Min-Hsiung Hon
Department of Materials Science and Engineering, National Cheng Kung University,
1 Ta-Hsueh Road, Tainan 70101, Taiwan

(Received 9 December 2002; accepted 4 March 2003)

Transformation kinetics of mullite formation in kaolin–Al2O3 ceramics was studied

by x-ray diffraction, transmission electron microscopy, and energy dispersion
spectrometry. The mullitization process of kaolin–Al2O3 ceramics is described by two
stages; one is the primary mullite transformation at 1273 to 1573 K, and the other is the
secondary mullite formation at 1573 to 1873 K. The activation energy of 1164.6 kJ mol−1
obtained for the secondary mullite formation is lower than 1356.9 kJ mol−1 for the
primary mullite transformation by the general form of the Johnson–Mehl–Avrami
equation. The lower value of growth morphology parameter strongly supports that
in the secondary mullite formation the added alumina is dissolved into glassy phase
and the mullite is then precipitated.

I. INTRODUCTION that is the rate-limited factor, is consistent with those

In recent years, mullite (3Al2O3 · 2SiO2) has been
considered as a potentially important ceramic due to its
low thermal expansion, excellent creep resistance, good
chemical and thermal stabilities, very low dielectric con-
stant, and good optical properties. A variety of prepara-
tion methods are used to synthesize mullite, such as
conventional mixing, precipitation, hydrolysis, hydro-
thermal synthesis, spray pyrolysis, and chemical vapor
deposition, in which various starting materials such as
alumina–silica minerals, hydroxides, sols, silicon alkox-
ide, aluminum alkoxide, etc., are used.1,2
A number of factors affect the chemical reaction for
mullite formation, such as particle size and the crystalline
form of the precursors, Al/Si ratio, degree of mixing, and
impurities.3 However, the diffusion for species plays
an important role on the mullite phase transformation for
nucleation and grain growth. Most of the crystallization
kinetics for mullite formation shows a multiple stage of
nucleation, nucleation–growth, and coalescence.4–6
A possible mechanism proposed for mullite formation
from raw materials is dominated by the diffusion of the
different cations, Al3+ and Si4+.7 During the Al2O3 and
SiO2 solid reaction, the counterdiffusion of Al3+ and Si4+
ions through the mullite interlayer determines the reac-
tion rate. The average diffusion coefficient value of Si4+,
calculated using Aksay’s diffusion coefficient equa-
tion.7,8 The rate of the mullite formation is determined by
the average diffusion coefficient of the slower cation Si4+
rather than the faster cation Al3+.
For the reactants homogeneously distributed with a
shorter diffusion path, the mullite formation is nucleation
rate-controlled from the monophasic gels with appar-
ent activation energy around 300 kJ mol−1.6,9,10 For the
diffusion-limited powders7,8 and diphasic gels, a mass
transport of alumina and silica along the mullite grain
interface11–13 or via nucleation and growth mechanism
was proposed with a higher activation energy.14,15
The activation energies of mullite formation corre-
sponding to different crystallization routes from solid
reaction, diphasic gel, and monophasic gel were exam-
ined using the conventional isothermal3–7,9,12,15,16 or
nonisothermal method.11,12,14 The activation energy of
mullite formation in solid reaction or diphasic gel is around
1000 kJ mol−1, which is higher than that in the mono-
phasic gel system, namely 362 kJ mol−1.4,6,7–10,12,14–16
However, the phase-transformation kinetics of kaolin–
Al2O3 ceramics has not been studied in detail.
In this study, the phase transformation kinetics of
kaolin–Al2O3 ceramics was investigated using x-ray
diffraction (XRD), transmission electron microscopy

J. Mater. Res., Vol. 18, No. 6, Jun 2003 © 2003 Materials Research Society 1355
 Y-F. Chen et al.: Transformation kinetics for mullite in kaolin–Al2O3 ceramics
(TEM), and energy dispersion spectrometry (EDS). The
objective of this study is to determine the phases evolu-
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tion, the kinetics of phase transformation, and the micro-
structure in kaolin–Al2O3 ceramics.
II. EXPERIMENTAL
A. Preparation
The raw material powders of kaolin and Al2O3 were
supplied by Akima Co. (Berhad, Malaysia) (Ipoh, Ma-
laysia, AKIMA-25, average size 1.3 ␮m) and Sumitomo
Chemical (Tokyo, Japan, AM-21, average size 4 ␮m),
respectively, with their chemical compositions and prop-
erties listed in Table I. In this study, the kaolin–Al2O3
ceramics contained 60 wt.% kaolin and 40 wt.%
Al2O3 powders added with 28.3 wt.% multiple-organics
solution as binder, which consisted of 20.3 wt.% PEG-
10k, 5.1 wt.% glycerin, 30.4 wt.% selosol 920, and
5.1 wt.% Celuna D-305 dissolved in 39.1 wt.% deionized
water. A batch (1.0 kg) of admixed raw materials added
with multiple-organics solution was mixed by using a
double Z-blade at 298 K for 30 min; subsequently, the
resulting feedstock was extrusion molded under a pres-
sure of 18 MPa by a single-screw extruder at a tempera-
ture of 298 K to obtain a pipe sample with radius, wall
thickness, and length of 3, 0.5, and 10 cm, respectively.
In the process of thermal debinding, the water was
preferentially extracted at 383 K for 30 min, and glyc-
erin, selosol 920, and celuna D-305 were extracted at
about 443 K for 60 min. The samples were then heated to
748 K at a heating rate of 1 K min−1 and held for 30 min
for PEG-10k debinding. Finally, the debinded samples
were sintered at 1273 to 1873 K for various periods of
time at a heating rate of 5 K min−1.
B. Characterization
The phases in sintered kaolin–Al2O3 samples were
identified by XRD with Cu K␣ radiation and a Ni fil-
ter, operated at 30 kV, 20 mA, and a scanning rate of
0.25° min−1 (model XD-D1, Shimadzu, Kyoto, Japan).
TABLE I. Chemical compositions of kaolin and Al2O3 powders.
Chemical composition (wt.%) Kaolin
SiO2 54.0
Al2O3 32.0
Fe2O3 0.98
Na2O 0.25
TiO2 0.45
CaO 0.06
K2O 1.65
MgO 0.30
LOIa 10.31
Average particle size (␮m) 1.3
a
LOI, loss on ignition.
1356 J. Mater. Res., Vol. 18, No. 6, Jun 2003
The integrated intensity of the (121) reflection (2␪
from 40.5 to 41.5°) of the commercial mullite powder
(Mullite, 98%, Alfa Aesar, Johnson Matthey Catalog
Co., Inc., MA), which was leached with 20 wt.% hydro-
fluoric (HF) acid at room temperature for 12 h to remove
the impurities and calcined at 1873 K for 24 h, was used
as the standard for determining the relative phase content
of mullite. The integrated intensity of the reflection (113)
(2␪ from 43° to 44°) of the ␣–Al2O3 powder was used as
the standard for evaluating the relative phase content of
␣–Al2O3 in the sintered ceramics.
The morphology of the sintered samples and the
chemical compositions of glassy phase were observed
and analyzed with TEM (Hitachi model HF-2000 field
emission transmission electron microscope, Hitachi Ltd.,
Tokyo, Japan, operated at 200 kV) and EDS (Noran
model Voyager1000, Noran Ltd., WI). The foils for
TEM were prepared by slicing to a thickness of about
30 ␮m mechanically and ion-beam thinning to electron
transparency.
III. RESULTS AND DISCUSSION
A. Phases in sintered ceramics
The XRD pattern of the kaolin–Al2O3 samples sin-
tered at 1573 K for 30 min is shown in Fig. 1(a). It was
found that the sintered kaolin–Al2O3 ceramics contain
␣–Al2O3 and mullite as the major phases and cristobalite
as the minor phase. Mullite and cristobalite, liberated as
a result of decomposition of kaolin, are converted above
1373 and 1473 K, respectively.17–19 Since the reaction
between kaolin and the added Al2O3 powder is limited at
Al2O3
0.02
99.9
0.02
0.1
4
FIG. 1. XRD patterns of kaolin–Al2O3 ceramics sintered for 30 min at
(a) 1573 K and (b) 1873 K (s, cristobalite; a, ␣–Al2O3; m, mullite).
 Y-F. Chen et al.: Transformation kinetics for mullite in kaolin–Al2O3 ceramics

a low temperature of 1573 K, the XRD pattern shows the of the mullite phase is reasonably sharp without anoma-
unreacted ␣–Al2O3 phase. Figure 1(b) shows the XRD lous intensity change for the XRD reflection peak (121).
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pattern of the kaolin–Al2O3 sample sintered at 1873 K The relative amount of mullite present in the sintered
for 30 min. It indicates that the XRD reflection intensity kaolin–Al2O3 sample was determined by comparing the
of mullite increases but the ␣–Al2O3 decreases by the integral intensity of the reflection (121) of the mullite
formation of mullite and dissolution of Al2O3 powder at with the standard.
the sintering temperature. Besides, the cristobalite phase Figure 2 shows the relative content of mullite in the
disappears, dissolves into an amorphous glassy phase, sintered kaolin–Al2O3 samples. It indicates that the rela-
and improves the mullite formation at 1873 K. tive content of mullite increased as the sintering tempera-
The transformation of kaolinite to mullite and glassy ture increased from 1273 to 1873 K. Besides, when the
phase has been reported by Brindly and Nakahira.17–19 sintering was conducted at a fixed temperature in this
When sintering temperature is at 1273 K, the transfor- range, the mullite content increased as the sintering time
mation from kaolin to mullite occurs according to the increased. When the samples were sintered at 1873 K for
following reactions: 5 h, about 88 wt.% of mullite was obtained. However,
673–773 K
when the sintering was conducted at 1273 K for 30 min,
Al2O3 ⭈ 2SiO2 ⭈ 2H2O (kaolinite) → there was only a small amount of mullite in sintered
Al2O3 ⭈ 2SiO2 (metakaolinite) + 2H2O , (1) samples due to the low sintering temperature.17–19,21,22
Figure 2 also indicates the formation behavior of mul-
∼1253 K
2(Al2O3 ⭈ 2SiO2) (metakaolinite) → lite. The amounts of mullite in the sintered ceramics in-
Si3Al4O12 (spinel) + SiO2 (amorphous) , (2) creased slightly when sintering temperature increased
from 1473 to 1573 K due to the nearly complete trans-
>1273 K formation of kaolin. As the samples were sintered at
3Si3Al4O12 (spinel) → 2(3Al2O3 ⭈ 2SiO2) 1673 and 1773 K for various periods of time, the mullite
(mullite) + 5SiO2 (amorphous) , (3) content in sintered ceramics suddenly increased by the
>1473 K dissolution of added Al2O3 into the glassy phase and
SiO2 (amorphous) → SiO2 (cristobalite) . (4) the secondary mullite precipitated.
The dissolution of added ␣–Al2O3, at different sinter-
The phase transformation and growth of mullite in kaolin
ing temperatures and for different lengths of time, in
ceramics by the nonisothermal method and TEM analysis
kaolin–Al2O3 ceramics is shown in Fig. 3. It reveals that
also were reported by Chen et al.20 The bulk nucleation
the amount of ␣–Al2O3 content decreased from 39.9 to
is dominant in mullite crystallization and the crystal
36.8 wt.% when the samples were sintered at 1573 K for
growth is controlled by diffusion in kaolin. Chen et al.21
15 to 300 min. However, the ␣–Al2O3 content decreased
also have pointed out that, in the kaolin–Al2O3 ceramics,
when the sintering temperature was greater than 1573 K.
the secondary mullite formed by solution–precipitation is
As the samples were sintered at 1873 K for greater than
mainly surrounded by the glassy phase and shows a
platelike morphology when the sintered temperature is
greater then 1573 K. The Al2O3 content in the secondary
mullite crystals increased from 59.69 to 70.41 wt.%
when the grain width increased from 15 to 40 nm, but the
lattice parameters in the orthorhombic structure of the a,
b, and c axes decreased from 8.653, 8.770, and 3.167 to
7.958, 8.064, and 2.926 Å, respectively.
In the kaolin–Al2O3–SiO2 system, Chen et al.22
pointed out that the glassy phase and SiO2 content de-
creased when sintering temperature was above 1573 K. A
similar result was obtained in this study. The mullite in
the orthorhombic structure was obtained, as indicated by
the splitting of (120) and (210) reflections at 2␪ ⳱ 25.97
and 26.27°, respectively, in Fig. 1(b), which was also
demonstrated by Li et al.23

B. Quantitative phase analysis

The commercial mullite powder was leached in
20 wt.% HF acid at room temperature for 12 h and cal- FIG. 2. Relative content of mullite in kaolin–Al2O3 ceramics as a
cined at 1873 K for longer than 24 h. The XRD pattern function of sintering temperature and time.

J. Mater. Res., Vol. 18, No. 6, Jun 2003 1357

 Y-F. Chen et al.: Transformation kinetics for mullite in kaolin–Al2O3 ceramics

30 min, the ␣–Al2O3 content was below 4.4 wt.%, at

which temperature the added Al2O3 powder dissolved k = A exp − 冉 冊 Ea
, (6)
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almost completely into the glassy phase. According to
Figs. 2 and 3, it indicates that the reaction between kaolin
and the added Al2O3 powders is limited as the samples
were sintered at 1273 to 1573 K and leads to only the
primary mullite formation.21,22,24–26
RT
where Ea is the activation energy, R is the gas constant,
T is the absolute temperature, and A is a constant.
The integrated form of Eq. (5) can be expressed by the
Johnson–Mehl–Avrami (JMA) equation28,29

冉 冊
According to the above discussion, the transformation
of kaolin–Al2O3 ceramics can be described by two 1
ln = 共kt兲n . (7)
stages; (i) the primary mullite transformation at 1273 to 1−x
1573 K, and (ii) the secondary mullite formation at tem-
peratures from 1573 to 1873 K. Equation (8) is obtained by taking the logarithms for both
sides of Eq. (7)
C. Kinetics of phase transformation in
kaolin–Al2O3 ceramics
Figure 4 shows the relationship between relative con-
冋 冉 冊册
ln ln
1
1−x
= n ln k + n ln t . (8)

tent of mullite and sintering time for the kaolin–Al2O3

ceramics by isothermal treatment at various tempera-
tures. It reveals that the mullite content in the sintered
ceramics increased with the sintering temperature in-
creasing from 1273 to 1873 K. When kaolin–Al2O3
samples were sintered at 1573 K for 7 h, the mullite
content in the sintered samples was only 36.1 wt.%. This
value was smaller than 50 wt.% for kaolin sintered at
1573 K for 30 min20 due to the hindrance caused by the
added Al2O3 powder.
To obtain the kinetics of phase transformation of
kaolin–Al2O3 ceramics, the following rate equation is
assumed:27
dx
= kntn−1 共1 − x兲 .
dt
Here x is the mullite phase fraction at sintering time t, n
is the growth morphology parameter, and k is the rate
constant related to an Arrhenius-type equation:
When the left side of Eq. (8) ln{ln[1/(1 − x)]} is plotted
against ln t, as shown in Fig. 5, the straight line slope n
indicates the growth morphology parameter of the trans-
forming phase. By Eq. (8) and Fig. 5, the growth mor-
phology parameter n for kaolin–Al2O3 ceramics is
obtained and listed in Table II. Figure 5 also provides the
kinetic constant data k by the interception of the straight
line with the axis of ln{ln[1/(1 − x)]}.
Equation (9) is obtained by taking the logarithms for
both sides of Eq. (6)
Ea
ln k = ln A − . (9)
RT
(5) When the left side of ln k in Eq. (9) is plotted against the
reciprocal of sintering temperature, as shown in Fig. 6, a

FIG. 3. Relative content of the ␣–Al2O3 in kaolin–Al2O3 ceramics as FIG. 4. Relative content of mullite in kaolin–Al2O3 ceramics as a
a function of sintering temperature and time. function of sintering time and temperature.

1358 J. Mater. Res., Vol. 18, No. 6, Jun 2003

 Y-F. Chen et al.: Transformation kinetics for mullite in kaolin–Al2O3 ceramics

straight line is obtained, and then the apparent activation obtained from Eq. (11) by taking the double logarithm of
energy can be calculated from the slope, as is listed in both sides and rearranging the terms of the equation:
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Table III.
The general form of the JMA equation can be as-
sumed by30,31
ln t =
EI + nEG 1
+
1
共n + 1兲R T n + 1
ln 冋
共n + 1兲 ln共1 − xt兲
gIoGon
册 . (12)

冋兰 册
Figure 7 shows the relationship between the logarithm
t=t
xt = 1 − exp − gIGn 共t − t⬘兲n dt⬘ , (10) of time required to reach 20 and 45 wt.% conversion of
t=0
mullite and the reciprocal of sintering temperature for the
kaolin–Al2O3 ceramics, respectively. If the nucleation
where xt is the degree of conversion for a given sintering
and growth of crystal begin at the time when the crys-
time, g is a geometrical factor, I denotes the rate of
tal is first detected by XRD,31 then xt ⳱ 0 at this time.
nucleation, G is the growth rate, and n is an integer which
There is an error involved in making this assumption
depends on the dimensionality of the growth mechanism.
since the diffractometer cannot accurately detect frac-
If the nucleation and growth rates depend on the tem-
tion of phase below approximately 3 wt.%. The slopes
perature but the growth rate is assumed to be independent
(EI + nEG)/[(n + 1)R] of the lines are obtained from
of time, Eq. (10) can be expressed as29,32
Fig. 7, and the activation energy is determined by general
1
1 − xt
= exp
1
冋
g I G n t n+1 e−共EI+EG兲 Ⲑ RT
n+1 o o 册 , (11)
form of the JMA equation, as listed in Table III. These
values are greater than 531 kJ mol−1 as obtained by
Gualtieri et al.33
where EI and EG are the activation energies for nuclea- In Table III, it is found that the activation energy for
tion and crystal growth, respectively. Equation (12) is the primary mullite formation is higher than that for the
secondary mullite formation. The formation of mullite
from various raw materials directly depends on the de-
gree of mixing of Al3+, Si4+, and O2− components in
the raw materials7,8 (i.e., the chemical homogeneity
of the raw materials plays a key role in the mullite

FIG. 5. Relationship between ln{ln[1/(1 − x)]} and ln t of kaolin–

Al2O3 ceramics.

TABLE II. Values of the growth morphology parameter for kaolin–

Al2O3 ceramic sintered at various temperatures. FIG. 6. Plots of ln k versus 1/T for kaolin–Al2O3 ceramics.

Sintering temp. Growth morphology Average growth

(K) parameter, n morphology parameter
TABLE III. Activation energies (kJ mol−1) at various stages of mullite
1373
1473
1573
2.1
1.9
1.7
冎 1.9
(Primary mullite)
formation in kaolin–Al2O3 ceramics.

General form of JMA equation

1673
1773
1873
1.5
1.4
1.2
冎 1.4
(Secondary mullite)
JMA equation
609.6
Primary
1356.9
Secondary
1164.6

J. Mater. Res., Vol. 18, No. 6, Jun 2003 1359

 Y-F. Chen et al.: Transformation kinetics for mullite in kaolin–Al2O3 ceramics
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FIG. 7. Apparent activation energy for mullite transformation in
kaolin–Al2O3 ceramics.
formation). The natural minerals, such as kaolinite, ky-
anite, sillimanite, and topaz, etc., have a high degree of
mixing, a three-dimensional random network with infi-
nite mixing of Al2O3 and SiO2 at the atomic level of
Al3+, Si4+, and O2− components.33 On the other hand, the
mechanical mixtures of solid particles exhibit a very low
degree of homogeneity. So the unreacted Al2O3 powder
dispersed in the kaolin–Al2O3 ceramics reduces the ho-
mogeneity; as a result, the activation energy for the pri-
mary mullite formation is higher than the one for the
secondary mullite formation. In this study, the activation
energy of mullite formation obtained by general form of
the JMA equation is also higher than that for the kaolin
ceramics.20 Figure 3 shows ␣–Al2O3 content decreased
as the samples are sintered at secondary mullite forma-
tion stage; that will increase the source of Al3+ ion in
glass for the mullite formation. Since the diffusion coef-
ficient of Al3+ is greater than that of Si4+ in the glassy
phase,6,15 the activation energy of secondary mullite for-
mation is lower than the primary one.
D. Glassy phase formation and microstructure in
kaolin–Al2O3 ceramics
The TEM micrograph of kaolin–Al2O3 ceramic sin-
tered at 1673 K for 30 min is shown in Fig. 8. It is found
that these platelike mullite crystals have a broad size
distribution of 80–100 nm in length and 50–60 nm in
width. Sainz et al.26 have pointed out that the secondary
mullite formation took place when sintering temperature
was greater than 1673 K and the average grain size dis-
tribution and the aspect ratio were a function of tempera-
ture. The grain growth for both primary and secondary
mullites shows a broad size distribution of platelike
1360 J. Mater. Res., Vol. 18, No. 6, Jun 2003
FIG. 8. TEM morphology of kaolin–Al2O3 ceramics during sintering
at 1673 K for 30 min.
crystal in liquid-phase sintering. In this study, the growth
morphology parameter n is close to two, indicating the
platelike precipitation. The growth morphology param-
eter decreasing to 1.2 indicates that needlelike precipita-
tion occurred as sintering temperature was increased.
This result indicates that the mullite crystal grows to a
high aspect ratio in kaolin transformation or liquid-phase
sintering.17–19 The diffusion is necessary for grain
growth of the nuclei that the diffusion coefficient of ions
in liquid-phase sintering will be the important factor in
mullite formation. Gualtieri et al.33 have pointed out that,
in kaolin–mullite reaction sequence, the growth morphol-
ogy parameter decreased with the increasing sintering
temperature and that the lower value of n indicates that
the chemical diffusion plays a non-negligible role in mul-
lite crystallization. This result can also be related to a
change in the rate limiting mechanism of the reaction as
a function of temperature. The secondary mullite forma-
tion shows a value of n lower than two, which can be
related to a different crystallization mechanism.
Figure 9 shows the TEM microstructure and EDS
analysis of the kaolin–Al2O3 samples sintered at 1573
and 1673 K for 30 min. From Fig. 9(a), it can be found
that the interface between Al2O3 particle and glassy
phase is still smooth and distinct because the added
Al2O3 at 1573 K does not dissolve into the glassy phase.
Figure 9(b) shows that the added Al2O3 has already dis-
solved into the glassy phase at 1673 K, causing the
blurred interface to appear. The dissolution of Al2O3 into
the glassy phase is similar to the Al2O3–SiO2 powder
mixture system,34 in which the curved surfaces of alu-
mina grains start to develop low-energy facets, indicating
the dissolution of Al2O3 into the siliceous phase.
In Fig. 9, location a is the Al2O3 grain, locations b and
c are on the interface, and locations d and e are in the
glassy phase region. The Al and Si contents in Fig. 9(a),
 Y-F. Chen et al.: Transformation kinetics for mullite in kaolin–Al2O3 ceramics

at different locations, are listed in Table IV. It indicates

that the Al cation content suddenly decreases from 97.5
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to 51.3 at.% as location b switches to location c. How-

ever, when the location varies from d to e, the Al cation
content maintains at 59.5 to 52.7 at.%. This result reveals
that the added Al2O3 still does not react with the kaolin
at the interface.
Figure 9(b) shows that the interface between Al2O3
and glassy phase is not distinct. The Al cations content in
Fig. 9(b) remains at about 88.4 to 90.3 at.% when the
location varies from b to c, as listed in Table IV. How-
ever, when the location varies from d to e in Fig. 9(b), the
Al cation content decreases from 83.2 to 48.1 at.%. This
indicates the interaction of added Al2O3 with the glassy
phase at the interface. Besides melting, the primary mul-
lite rearrangement is aided by dissolution of the Al2O3 in
glassy phase. The preferential dissolution in glassy phase
of Al2O3 powders at the contact leads to the simultaneous
diffusion of the Al3+ and Si4+ ions.
The average chemical compositions of glassy phase
for kaolin–Al 2 O 3 ceramics sintered at 1573 and
1673 K for 30 min are listed in Table V. The mullite
formation will consume the Al3+ component more than
Si4+ when the temperature increases. According to
Figs. 2 and 3, the mullite increases 3.2 wt.% as sintering
temperature increases from 1573 to 1673 K for 30 min.
Although the Al2O3 content decreases 2.3 wt.% in
theory, it decreases 12.7 wt.% when sintering tempera-
ture increases from 1573 to 1673 K. It indicates that the
Al2O3 component does dissolve into the glassy phase.
Therefore, the Al at.% in glassy phase for kaolin–Al2O3
ceramics sintered at 1673 K for 30 min is higher than the
FIG. 9. TEM microstructure and EDS analysis of the kaolin–Al2O3 Al at.% sintered at 1573 K. The transitory liquid phase
samples sintered for 30 min at (a) 1573 K and (b) 1673 K. for secondary mullite formation may result either from
the presence of impurities in the kaolin raw materials
such as K2O or from a metastable eutectic composition
TABLE IV. Al and Si contents in the kaolin–Al2O3 ceramics at the for silica–alumina–alkali metal oxides (or transitory
different analysis locations in Fig. 9. metal oxide).35 In this study, there is about 1.65 wt.%
Locations and content (at.%) K2O in the raw materials of kaolin (Table I), and from
Sintering
the TEM–EDS analysis the glassy phase contents are
temp. (K) Element a b c d e
about 0.3 to 0.4 wt.%, as shown in Table IV. The tran-
Al 99.3 97.5 51.3 59.5 52.7 sitory metal oxide forms the liquid phase to promote
1573 Si 0.7 2.5 48.7 40.5 47.3
the mullite formation during the sintering process, and the
Al 100 88.4 90.3 83.2 48.1
1673 Si 0 11.6 9.7 16.8 51.9 mullite crystal grows from the platelike to needlelike
precipitation.

IV. CONCLUSION
TABLE V. Average chemical compositions of glassy phase for Transformation kinetics of mullite formation in
kaolin–Al2O3 ceramics as sintered at 1573 and 1673 K for 30 min.
kaolin–Al2O3 ceramics were studied using XRD, TEM,
Sintering
Chemical composition (at.%) and EDS. The mullitization process of kaolin–Al2O3 ce-
temp. (K) Aluminum Silicon Potassium ramics could be described by two stages; the primary
mullite transforms at temperatures from 1273 to 1573 K,
1573 33.5 66.1 0.4
1673 51.3 48.2 0.5
and the secondary mullite forms at temperatures from
1573 to 1873 K. The unreacted Al2O3 powder dispersed

J. Mater. Res., Vol. 18, No. 6, Jun 2003 1361

 Y-F. Chen et al.: Transformation kinetics for mullite in kaolin–Al2O3 ceramics
in the kaolin–Al2O3 ceramics reduces the homogeneity
and increases the activation energy of the first stage. The
Downloaded from https://www.cambridge.org/core. University of Arizona, on 02 Apr 2020 at 19:02:27, subject to the Cambridge Core terms of use, available at https://www.cambridge.org/core/terms. https://doi.org/10.1557/JMR.2003.0186
lower value of growth morphology parameter for sec-
ondary mullite formation strongly supports that the
added alumina dissolved into glassy phase and precipi-
tated the mullite. The activation energy of the secondary
mullite formation (1164.6 kJ mol−1) is lower than that of
the primary mullite formation (1356.9 kJ mol−1), by the
general form of the JMA equation.
ACKNOWLEDGMENTS
The financial support from the National Science Coun-
cil of Taiwan, Republic of China, as Grant No. 89-2216-
E-006-072 is appreciated. The authors sincerely thank
Mr. H.Y. Yao for the assistance with the TEM–EDS
analysis.
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