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Phase Transformation and Sintering Behaviour

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Article in Advances in Applied Ceramics April 2011

DOI: 10.1179/1743676111Y.0000000004

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Phase transformation and sintering behaviour
of mullite and mullitezirconia composite
materials
F. Sahnoune1, H. Belhouchet1, N. Saheb*2, M. Heraiz1, M. Chegaar3 and
P. Goeuriot4
Mullite is one of the most promising engineering materials for applications at elevated
temperatures, but has poor mechanical properties at ambient temperature; therefore, it is usually
reinforced with particles, fibres or whiskers to improve its properties. Among particles added to
mullite are ZrO2 particles which improve its fracture toughness through the well known process of
phase transformation from tetragonal to monoclinic in zirconia particles. The aim of the present
work is to explore the utilisation of Algerian kaolin, a-Al2O3 and ZrO2 to synthesise mulliteZrO2
composites through reaction sintering and investigate phase transformation and sintering
behaviour of the composites. The raw materials were mixed through planetary ball milling followed
by attrition milling. Compacted samples were sintered at temperatures between 1100 and 1600uC
for 2 h. The bulk density was measured by the water immersion method. X-ray diffraction (Rietveld
method) was used to characterise phases present in the sintered samples. It was found that the
zirconia phase retained its tetragonal structure with the addition of up to 16% zirconia. The
formation of primary mullite in all samples was complete at 1250uC. The cristobalite started to form
at 1150uC, and disappeared at 1300uC in the samples of mullite, and at 1250uC when ZrO2 was
added. The zircon compound ZrSiO4 started to form at 1250uC and completely disappeared at
1400uC. The increase in ZrO2 ratio promoted the formation of grains with spherical shape.
Keywords: Phase transformation, Mullite, Alumina, Kaolin, Reaction sintering

Introduction are often necessary to sinter stoichiometric mullite.

Because of its high melting point, low thermal expan-
sion, good chemical stability, excellent creep resistance
and high strength at high temperature, dense mullite
(3Al2O32SiO2) is recognised as one of the most
promising engineering materials for applications at
elevated temperature.1,2 One of the methods used for
preparation of mullite is reaction sintering of alumina
silica, kaolinalumina mixtures or solid state sintering of
fine crystalline mullite powders. Fine crystalline mullite
powder compacts require high temperatures (.1600uC)
to sinter to high density.3,4 From the other side, to
maximise properties, a close compositional and micro-
structural control is necessary.36 Pressure assisted
sintering such as hot pressing and hot isostatic pressing
1
Department of Physics, Mohamed Boudiaf University, 28000 Msila,
Algeria
2
Department of Mechanical Engineering, King Fahd University of
Petroleum and Minerals (KFUPM), Dhahran 31261, Saudi Arabia
3
Department of Physics, Ferhat Abbas University, 19000 Setif, Algeria
4
Department of Special Ceramics, ENSM, 158, cours Fauriel, 42023
Saint-Etienne cedex 2, France
*Corresponding author, email nouari@kfupm.edu.sa
Applications of mullite were limited because of its poor
properties at ambient temperature. As a result, it is
usually reinforced with particles or fibres (whiskers) to
produce composites with superior properties.1,712
A well known process to improve fracture toughness1,2,1316
is phase transformation, under applied pressure, from
tetragonal to monoclinic in zirconia particles. This stress
induced phase transformation is accompanied by a
volume expansion (y4%) and shear deformation
(y6%).2,17 MulliteZrO2 composites have been prepared
though many routes2,18,19 including sintering of mixed
mullite and ZrO2 powders, reaction sintering of mixtures
of ZrO2 and mullite precursors, reaction sintering of
zircon (ZrSiO4) and Al2O3, and crystallisation of rapidly
quenched melts in the system Al2O3ZrO2SiO2 with
subsequent sintering. However, the reaction sintering
method remained the most commonly used because of its
low cost. In previous works, we synthesised mullite from
reaction sintering Algerian kaolin and pure alumina20
and reported the effect of MgO addition and sintering
parameters on mullite formation.21 Also, the authors
investigated the kinetics of mullite formation and
evaluated the temperature of formation, activation
energies and growth morphology parameters.22 The

2011 Institute of Materials, Minerals and Mining

Published by Maney on behalf of the Institute
Received 7 November 2008; accepted 15 January 2011
DOI 10.1179/1743676111Y.0000000004 Advances in Applied Ceramics 2011 VOL 110 NO 3 175
Sahnoune et al. Phase transformation and sintering behaviour of mullite
1 Micrographs (SEM) of a kaolin powder, b kaolinalumina powder after 5 h of wet milling and c kaolinalumina powder
after 5 h of wet milling and 1 h attrition milling
aim of the present work is to synthesis mullitezirconia
composites through reaction sintering Algerian kaolin, a-
Al2O3 and ZrO2 with three different ratios and investi-
gate phase transformation and sintering behaviour of the
composites.
Materials and experimental procedure
Algerian raw kaolin (from Djabal Debagh) was used in
this investigation. It was calcined at 700uC for 2 h to
yield meta-kaolin. The chemical composition of the
calcined kaolin as determined by X-ray fluorescence is
shown in Table 1. a-Al2O3 powder (MARTOX TD
MDS-6, 6 m2 g21, high purity) and zirconia containing
3 mol.-%Y2O3 (3Y-TZP CRICERAM, 18 m2 g21, high
purity).
The powder mixtures were prepared to obtain 100/00
(wt-%), 84/16 and 68/32 mullite/ZrO2 composites, and
they are named KA00Z, KA16Z and KA32Z respec-
tively. The powders were charged into cylindrical
zirconia vials (250 mL in volume) together with 15
zirconia balls (10 mm in diameter). Water was added to
the mixture at a ratio of 2 : 1. The ball milling
experiments were performed in a high energy planetary
ball mill (Fritsch P6) and were carried out at room
temperature at a rotation speed of 250 rev min21. The
mixture was ball milled for 5 h followed by attrition for
1 h using ZrO2 balls (diameter of 1?2 mm) at a speed of
1250 rev min21. The addition of 1 wt-% of ammonium
polymethacylate dispersant (Darvan C) and ammoniac
was used to adjust the pH of the suspension with y10?5.
The slurry was dried at 110uC, powdered and sieved
through a 163 mm mesh, then compacted at a pressure of
75 MPa using a cold uniaxial press. Cylindrical speci-
mens of 8 mm diameter were produced. Dynamic
sintering studies of kaolinalumina and kaolinalu-
minaxzirconia were performed using a SETARAM
Labsys thermal analyser; kaolin/Al2O3/ZrO2 composi-
tions with the following molar proportion were studied
Al2 O3 :2SiO2 :2H2 Oz2Al2 O3 zx(ZrO2 )
Table 1 Chemical composition of calcined
determined by X-ray uorescence
Component Al2O3 SiO2 MnO P2O5 SO3
Content/wt-% 44.40 53.05 1.54 0.03 0.02
Component Co3O4 NiO ZnO As2O3 CaO
Content/wt-% 0.13 0.09 0.08 0.37 0.17
176 Advances in Applied Ceramics 2011 VOL 110
where x is a variable. These compositions are located on
the straight line defined by the equation
Al2 O3 :2SiO2 :2H2 Oz2Al2 O3 zx (ZrO2 )
?Al6 Si2 O13 zxZrO2 z2H2 O
The shrinkage versus temperature was measured at a
constant heating rate of 10uC min21. Particles morphol-
ogy and the microstructure of the sintered samples were
characterised using a JEOL scanning electron micro-
scope (model JSM 5600). The compacted samples were
heated from room temperature to different temperatures
(11001600uC) at heating rates of 10uC min21 for 2 h.
Phases present and their transformations were charac-
terised using a Bruker X-ray diffractometer model D8
(with Ni-filtered Cu Ka radiation) operated at 40 kV,
and 40 mA with a scanning speed 0?3u min21 and 0?05
of step. Phase compositions of the reaction sintered
samples were quantitatively determined by the Rietveld
method using the software package XPert Highscore
Plus. The retained tetragonal fraction of ZrO2 was
obtained from the ratio of intensity of the (111)
tetragonal peak to the sum of the intensities of the
(111) and (111) monoclinic and (111) tetragonal peaks.23
The density of sintered samples was measured using a
densimeter model KERN ARS 220-4 and quantified
according to the Archimedes principle.
Results and discussion
Figure 1 shows scanning electron micrographs of
kaolin powder before milling (Fig. 1a), kaolin and
alumina mixture ball milled for 5 h (Fig. 1b), and
kaolin and alumina after milling for 5 h and attrition
milling for 1 h (Fig. 1c). It can be clearly seen that
particles of kaolin before milling have irregular shapes
and large particle size distribution. Ball milling for 5 h
reduced particle size. However, the particle size
distribution remained broad because of the agglomera-
tion of small particles to form large particles. This is
due to the fact that ball milling involves repeated
welding, fracturing and rewelding of powder particles.
Attrition milling for 1 h reduced the particle size as a
kaolin as result of the breakdown of agglomerates formed during
milling. Also, after attrition particles have more regular
K2O shape (close to spherical). These characteristics have an
important role in the compaction and sintering
0.02 behaviour of kaolin when it is used as raw material to
Fe2O3 synthesise ceramic materials because of the reduction of
0.06
sintering time and temperature.
NO 3
 Sahnoune et al. Phase transformation and sintering behaviour of mullite

2 Dilatometric studies on unred kaolinalumina and kaolinaluminazirconia samples a shrinkage curves; b rst deriva-
tives of shrinkage curves

Figure 2 shows the linear shrinkage DL/L0 (%) curves
at a constant heating rate of 10uC min21, and its
derivatives as a function of temperatures for samples
KA00Z, KA16Z and KA32Z. A sample of a-Al2O3 with
the same dimensions was used as a reference. Phase
transformations that may take place at specific tem-
peratures are presented in Table 2. It can be noticed that
the linear shrinkage curves for the three samples have
five common stages and one uncommon stage. The
expansion of around 0?4% and 0?2% with increasing
ZrO2 for temperature less than 180uC is due to the
dehydration of kaolin and its transformation to
kaolinite. The relative shrinkages of around 1?4 and
1% which start at 500uC and end at 670uC, with a
maximum speed at 600uC, are a result of the loose of
water when kaolinite transforms to metakaolinite. The
shrinkages of around 3?6% and 2?9% between 890 and
1040uC with decreasing ZrO2 content with a maximum
rate at 970uC are a result of phase transformations that
take place in metakaolinite to give spinel (SiAl) and
amorphous SiO2.22,2429 The relative shrinkage due to
the transformation of spinel to amorphous SiO2 and
primary mullite starts just after the end of the previous
step and ends at 1340uC; this relative shrinkage is
maximum for the sample with higher ZrO2 and reaches
14% (DL/L0). This shows the role of ZrO2 in the increase
in sintering (pore elimination), while this ratio does not
exceed 12% for KA00Z sample. At this stage, the SiO2
undergoes different transformations which end with its
transformation to cristobalite.
Secondary mullite (which results from the reaction of
the added Al2O3 with SiO2 remaining from the forma-
tion of primary mullite) starts to form at 1400uC and
ends at 1540uC with a maximum rate at 1500uC
(Fig. 2b).30,31 This is accompanied with a linear expan-
sion that results from many factors such as impurities
present in kaolin like Fe2O3 which transforms at this
temperature to Fe3O4. This will lead to an increase in the
volume. The bulk density of the constituents which gives
mullite (theoretically it is 3?31 g cm23) is less than
(3?16 g cm23). This decrease in the density is accom-
panied with an expansion DV/V of y4?7%. After this
stage, sintering reaches the last step which is the
elimination of internal porosity and formation of regular
grains, which will be accompanied with a relative
contraction of not more that 2%. In samples containing
ZrO2, there is a six-stage shrinkage that starts at 1340uC
and ends at 1480uC; the shrinkage will be maximum at
1475uC with a maximum rate at 1430uC (for sample,
KA32Z). This shrinkage is due to the formation of
ZrSiO4 (which will dissolve at a later stage) from ZrO2
and SiO2 as it will de explained below.30
Figure 3 shows the XRD patterns of the three samples
after performing the thermal expansion experiment. It is

Table 2 Phenomena observed during dynamic sintering of samples with different additions of ZrO2

Description 00Z 16Z 32Z Attribution

First expansion peak in 603 602 594 2Al2O3zC.ZrO2zAl2O3.2SiO2.2H2O(Kaolinite)R

shrinkage rate curve/uC 2Al2O3zC.ZrO2zAl2O3.2SiO2 (metakaolinite)z2H2O (vapour)
Second expansion peak in 966 962 969 2[2Al2O3zC.ZrO2zAl2O3.2SiO2 (metakaolinite)]R
shrinkage rate curve/uC Si3Al4O12(AlSi spinel)zSiO2 (amorphous)z2(2Al2O3zC.ZrO2)
Third expansion peak in 1193 1181 1168 3[Si3Al4O12(AlSi spinel)zSiO2 (amorphous)z2(2Al2O3zC.ZrO2)]R
shrinkage rate curve/uC 2(3Al2O3.2SiO2) (mullite)z8SiO2 (amorphous)z6(2Al2O3zC.ZrO2)
Fourth expansion peak in No 1447 1428 2(3Al2O3.2SiO2) (mullite)z8SiO2 (cristobalite)z6(2Al2O3zC.ZrO2)R
shrinkage rate curve/uC 6C.ZrSiO4z(86.C)SiO2 (if 8.6C)z12.Al2O3z2(3Al2O3.2SiO2)
Five expansion peak in 1492 1517 1507 6C.ZrSiO4z(86.C)SiO2 (if 8.6C)z12.Al2O3z2(3Al2O3.2SiO2)R
shrinkage rate curve/uC 6C.ZrO2z6(3Al2O3.2SiO2)
Observation of 16.2 18 21.1
maximum shrinkage/%

Advances in Applied Ceramics 2011 VOL 110 NO 3 177

Sahnoune et al. Phase transformation and sintering behaviour of mullite
3 XRD patterns of KA00Z, KA16Z and KA32Z samples
after sintering at 1500uC for 2 h: M, mullite; ZS, zircon;
Zm, monoclinic zirconia; Zt, tetragonal zirconia; A,
a-alumina
clear that the reaction between Al2O3 and SiO2 has
almost finished because all clear XRD peaks are of
mullite and ZrO2 with its two phases (tetragonal and
monoclinic). Alumina was last detected in all samples
because this temperature is lower than 1600uC and the
short time is not sufficient to form mullite. Figure 4
shows XRD spectra of two samples (KA00Z and
KA32Z) sintered at various temperatures (1100
1500uC) for 2 h. It is clear that mullite started to form
4 XRD patterns of a KA00Z and b KA32Z samples treated at shown temperatures for 2 h: M, mullite; ZS, zircon; Zm,
monoclinic zirconia; Zt, tetragonal zirconia; A, a-alumina; C, cristobalite
178 Advances in Applied Ceramics 2011 VOL 110 NO
at 1100uC (primary mullite that forms from spinel). On
the other hand, the cristobalite started to form from
amorphous SiO2 at 1150uC, and disappeared at 1300uC in
the sample of KA00Z. While for the KA32Z samples, the
cristobalite disappeared at 1250uC. Zircon (ZrSiO4) starts
to appear at 1250uC (sample KA32Z) and dissolves to
give ZrO2 and SiO2 after 1350uC. It has been reported
that zircon forms from the reaction of zirconia with silica
at 1300 and 1400uC.30 Also, it is known that pure zircon
usually dissociates at higher temperature (over 1675uC),
whereas in the presence of impurities, zircon dissociates at
temperature below 1675uC.31 Monoclinic ZrO2 starts to
appear at 1450uC, and ZrO2 stabilisation in the amor-
phous matrix is lost, giving rise to m-ZrO2 formation with
increasing sintering temperature.
Figure 5 shows the weight fraction of mullite formed
relative to mullite and Al2O3, and it also shows the weight
fraction of tetragonal ZrO2 relative to the total ZrO2
(tetragonal and monoclinic). The results were obtained
using the Rietveld method for three samples sintered at
different temperatures ranging from 1100 to 1600uC for
2 h. The fraction of primary mullite formed in the three
samples sintered at 1100uC is more than 30%. This
confirms that all metakaolinite has been transformed to
primary mullite and amorphous SiO2. The three samples
were prepared by mixing of 1 mol of kaolin and 2 mol of
Al2O3, which will theoretically give 33% mullite after the
transformation of the whole kaolin.
The amount of primary mullite increases with
increasing sintering temperature. At 1250uC, the total
fraction of mullite exceeds 45% in all the samples. In the
ZA32Z sample, the amount of mullite decreases until it
reaches 25% at 1300uC. This is due to the formation of
ZrSiO4. The rate of mullite formation in sample KA00Z
is higher compared with those of the other samples. This
is due to the role of ZrO2 which prevents diffusion of Al
3

5 Zirconia and mullite formation versus sintering tempera-
ture after 2 h heating: Czm and Czt are concentra-
tions of monoclinic and tetragonal zirconia respectively;
Cm and CA are concentration of mullite and alumina
respectively
and Si to form mullite, and the time of soaking (2 h) is
not sufficient for the complete formation of mullite. In
the sample KA16Z, the retention of t-ZrO2 transformed
to m-ZrO2 is relatively smaller, and it does not exceed
18%. This fraction has an important role in determining
the mechanical properties. While for sample KA32Z, the
retention of t-ZrO2 transformed to m-ZrO2 is relatively
higher (up to 75%), which leads to the appearance of
cracks in the sample when used.
SEM images of the fractured surface of sample
KA00Z (Fig. 6a) and KA32Z (Fig. 6b) sintered at
1600uC for 2 h are shown in Fig. 6. The increase in
ZrO2 ratio promoted the formation of grains with
spherical shape.
The ratio between the bulk density and theoretical
density for the three samples (AK00Z, AK16Z and
AK32Z) sintered at different temperatures (1100
1600uC) for 2 h is presented in Fig. 7. The theoretical
density was calculated from all phases present at each
temperature through quantitative XRD analysis using
the Rietveld method taking into account the added
Al2O3. It can be seen that the density increases after
1250uC with increasing ZrO2 content. Also, it is clear
that the relative density reaches 95% at 1500uC and
remains almost constant after this temperature.
6 Micrographs (SEM) of fractured surface of sample sintered at 1600uC for 2 h: a KA00Z; b KA32Z
Sahnoune et al. Phase transformation and sintering behaviour of mullite
7 Density of samples AK00Z, AK16Z and AK32Z samples
held for 2 h at different temperatures
Conclusion
The utilisation of Algerian kaolin was found suitable for
the synthesis of mulliteZrO2 composites through its
reaction with a-Al2O3 and ZrO2. Phase transformation
and sintering behaviour of the developed composites
were investigated. It was found that the zirconia phase
retained its tetragonal structure with the addition of up
to 16% zirconia. The formation of primary mullite in all
samples was complete at 1250uC. The cristobalite started
to form at 1150uC, and disappeared at 1300uC in the
samples of mullite, and at 1250uC when ZrO2 was
added. The zircon compound ZrSiO4 started to form at
1250uC and completely disappeared at 1400uC in the
sample of KA32Z. The increase in ZrO2 ratio promoted
the formation of grains with spherical shape.
Acknowledgements
The first author is grateful to the technical support from
Laboratoire de Physique et Chimie des Materiaux,
Universite de Msila, Algeria, and the Department of
Special Ceramics, ENSM, France. Also, the correspond-
ing author (Dr N. Saheb) would like to acknowledge the
support from King Fahd University of Petroleum and
Minerals, Saudi Arabia.
Advances in Applied Ceramics 2011 VOL 110 NO 3 179
Sahnoune et al. Phase transformation and sintering behaviour of mullite
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