J O U R N A L O F M A T E R I A L S S C I E N C E L E T T E R S 2 0, 2 0 0 1, 1089 – 1091

Mullite ceramics derived from coal fly ash

J. S. JUNG, H. C. PARK
Division of Materials Science and Engineering, Pusan National University, Pusan 609-735, South Korea
E-mail: hcpark1@hyowon.pusan.ac.kr

R. STEVENS
Department of Applied Science and Engineering, Bath University, Bath BA2 9JT, UK

The stable intermediate compound mullite, which is Sumitomo Chemicals, Japan) was added to the coal
formed in a narrow composition range of the Al2 O3 - fly ash in order to increase a deficient alumina com-
SiO2 system [1] is a potential candidate material for position to stoichiometric mullite (71.8 wt% Al2 O3 ,
advanced structural applications because it has a high 28.2 wt% SiO2 ). The average particle size and spe-
melting point, low thermal expansion, creep resistance, cific surface area of the alumina powder were 0.6 µm
good chemical stability and high strength at high tem- and 8.23 g/m2 , respectively. The batch powders were
perature [2]. The important processing routes of mullite mixed and homogenised by ball milling in ethanol for
ceramics are: 24 h. After drying using a rotary vacuum evaporator,
the mixed powders were crushed in an agate mortar and
(i) sintering of mullite powder compacts [3–6];
passed through a 140 mesh sieve. The 3Y-PSZ pow-
(ii) reaction sintering of Al2 O3 - and SiO2 -
der, (20 wt%), was added to some batches. Rectangular
containing materials [7–10];
(10 mm × 10 mm × 50 mm) compacts were prepared
(iii) reaction bonding of mullite [11–13];
by die pressing at 20 MPa, and then cold isostatic press-
(iv) reaction sintering of chemically produced mul-
ing at 200 MPa. Reaction sintering was carried out at
lite precursors [3, 6, 14];
temperatures up to 1600 ◦ C for a given time after pre-
(v) transient viscous sintering of composite powders
liminary heating at 1400 ◦ C for 2 h in air with a heating
[15, 16].
rate of 4 ◦ C/min, using a super kanthal furnace. The
Crystalline mullite powder is not readily sinterable, crystalline phases of the reaction product were exam-
due to the low diffusion rates of the aluminum and sil- ined by XRD (D/max-IIA, Rigaku) with operating con-
icon species [7, 8, 17], consequently a high sintering ditions: Ni-filtered Cu Kα, 40 kV-20 mA and scanning
temperature (>1700 ◦ C) is required to reach full den- speed 8 ◦ /min. The sintered bulk density was measured
sity. The activation enthalpy for the densification and by the water immersion method. The sintered, polished,
grain growth of mullite is very high (700 kJ/mol−1 ) and thermally etched surfaces were examined using an
[18, 19]. An appropriate way to avoid such problems is SEM (JSM500, Jeol). Four point bending strength was
by reaction sintering of Al2 O3 and SiO2 mixtures; this measured at room temperature using a universal testing
allows a high degree of densification prior to mullitiza- machine (KSU-5M, Kyung Sung Testing Machine Co.)
tion. It also has the further advantage of low fabrication with a cross head speed of 0.5 mm/min, a supporting
costs [20, 21]. The temperatures and rates of mullite for- span of 30 mm, and a loading span of 10 mm.
mation depend on the properties of the Al2 O3 and SiO2 The morphology and characteristics of the coal fly
starting materials [7–9, 21]. The objective of this publi- ash are shown in Fig. 1 and Table I, respectively. The
cation is to report on the fabrication of mullite ceramics coal fly ash contained 56.77 SiO2 and 17.31 wt% Al2 O3 ,
using a fly ash precursor, formed as the combustion by-
product of coal fuel and to determine the properties of
resulting material. The effect of 3Y-PSZ addition on
the microstructural development and strength of sin-
tered mullite has been briefly investigated.
The coal fly ash yielded by combustion in a thermo-
electric power plant, Samchunpo, Korea, was used as
a starting raw material. The coal fly ash was examined
by means of XRD and XRF to determine the nature of
the crystalline phases and their constituent components,
respectively. The particle morphology was observed
using SEM. The specific surface area and particle size
distributions were measured using nitrogen adsorption,
BET [22], and a standard X-ray sedimentation tech-
nique. The coal fly ash was calcined at 600 ◦ C for 2 h
in air to remove residual carbon. On the basis on the
results of the XRF analysis, Al2 O3 powder (AES11-C, Figure 1 Scanning electron micrograph of coal fly ash.

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C 2001 Kluwer Academic Publishers 1089
T A B L E I Characteristics of coal fly ash
Chemical component
(wt%) Crystalline phase
SiO2 (56.77) Al2 O3 (17.31) Fe2 O3 (8.27) mullite, sillimanite,
K2 O(1.22) Na2 O(0.42) P2 O5 (0.27) quartz
MnO(0.13) CaO(3.57) MgO(0.91)
TiO2 (0.80), Ig. Loss(10.33)
and consisted of mainly silicate minerals being a mix-
ture of flake-like and nearly spherically-shaped parti-
cles with a specific surface area of 4.53 m2 /g and an
agglomerate size of 29.9 µm (<100%). With increas-
ing firing temperature to 1200 ◦ C, the quartz compo-
nent of the coal fly ash disappeared while newly formed
cristobalite was detected (Fig. 2). At 1300 ◦ C, the peak
intensities of cristobalite and α-Al2 O3 decreased, and
the mullite peak intensities increased. At ∼1400 ◦ C,
only the mullite crystalline phase was identified (Fig. 3).
With increasing firing temperature up to 1600 ◦ C, the
mullite peak intensities increased due to crystal growth.
From the XRD results, the mullitization process of coal
fly ash with an addition of alumina powder is presumed
as follows:
(i) one of the major mineral phases, quartz, trans-
forms to cristobalite at around 1200 ◦ C;
(ii) at ∼1300 ◦ C, mullitization starts by the reaction
of cristobalite and α-Al2 O3 , and with increasing tem-
perature, mullite production is increased,
(iii) the mullitization reaction was practically com-
pleted at 1400 ◦ C and mullite crystallinity increased
with further increasing firing temperature.
A study [23] of the temperature dependence of mul-
lite formation using various SiO2 crystalline phases and
α-Al2 O3 as starting materials, reported that the forma-
tion reaction of mullite in the SiO2 glass and α-Al2 O3
couple occurred by the solid state reaction of cristo-
balite and α-Al2 O3 at ∼1550 ◦ C, after crystallization
of almost all the SiO2 glass into cristobalite prior to
mullitization. With increasing firing temperature, from
1400 ◦ C to 1600 ◦ C, the bulk density (2.04 g/cm3 ),
porosity (2.1%) and water absorption (2.0%) decreased,
Figure 2 XRD patterns of mixed powder compact of coal fly ash and
α-Al2 O3 after firing at 1200 ◦ C for 1 h in air.
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Agglomerate size
distribution (µm)
SBET
(m2 /g) <30% <50% <100%
4.53 4.0 25.0 29.9
according to the increase of shrinkage (10.2%). This
infers that an increased volume fraction of liquid forms
with increasing temperature and the densification of
powder compacts still continues after completion of
mullitization.
The sintered microstructures are shown in Fig. 4.
At 1500 ◦ C, relatively small equiaxed (<2 µ) and elon-
gated mullite grains (aspect ratio >6) coexisted. After a
further increase in sintering temperature (1600 ◦ C), the
volume fraction of equiaxed mullite grains decreased
and the increased development of interlinked elongated
grains resulted in large voids being generated. In the
later stage of reaction sintering ( >1200 ◦ C), the liquid
phase sintering of low-Al2 O3 compositions produces
relatively large prismatic mullite crystals embedded in
a fine-grained matrix whilst for the high-Al2 O3 compo-
sitions, an equiaxed mullite microstructure formed by
solid state sintering [24]. In this study, the exaggerated
grain growth of mullite was probably due to the par-
tial liquid phase sintering at temperatures >1400 ◦ C
because of the considerable iron oxide content
(8.3 wt%). Minor impurities containing alkali compo-
nents, which help form low melting point liquids during
firing, were also contained in coal fly ash (Table I).
The 3Y-PSZ particles (globular-shaped) somewhat
inhibited the grain growth of the mullite phase and
enhanced the densification (Fig. 4c and d). The aver-
age bending strength values for each of the five speci-
mens sintered at 1400, 1500 and 1600 ◦ C for 2 h were
80, 169 and 115 MPa, respectively. The decrease of
strength in the 1600 ◦ C-sintered specimens compared
with the 1500 ◦ C-sintered is considered to be due to the
exaggerated grain growth of mullite, resulting in large
voids. The existence of 3Y-PSZ particles increased the
Figure 3 XRD patterns of mixed powder compact of coal fly ash and
α-Al2 O3 after firing at 1400 ◦ C for 2 h in air. All peaks correspond to
those of mullite.
Figure 4 SEM micrographs of polished and etched surfaces of mullite ceramics without (a, b) and with 20 wt% 3Y-PSZ (c, d) sintered at (a, c)
1500 ◦ C and (b, d) 1600 ◦ C for 2 h.
fracture strength of the mullite which had been sin-
tered at 1500 ◦ C (395 MPa) and 1600 ◦ C (215 MPa) for
2 h.
In conclusion, low density (63% of theoretical) mul-
lite ceramics with low porosity can be fabricated by
the reaction sintering at ∼1500 ◦ C, of appropriate mix-
tures of coal fly ash and Al2 O3 powders. The fracture
strength of mullite materials appears to be controlled
by the mullite grain shape and size, and the void size.
An addition of 3Y-PSZ powders inhibits grain growth
of the mullite and enhances the fracture strength.
Acknowledgments
This study was supported financially by the Pusan
Metropolitan City Government through the Institute for
Environmental Technology and Institute (IETI), Pusan
National University, Korea (Project number: 99-10-12-
99-B-1).
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Received 28 December 2000
and accepted 30 March 2001
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