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Refractories of Alumina-Silica System

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Refractories of Alumina-Silica System

a a a a
Kausik Dana , Somnath Sinhamahapatra , Himansu Sekhar Tripathi & Arup Ghosh
a
Refractory Division, CSIR-Central Glass & Ceramic Research Institute, 196, Raja S. C.
Mullick Road, Kolkata – 700 032, India
Published online: 01 Apr 2014.

To cite this article: Kausik Dana, Somnath Sinhamahapatra, Himansu Sekhar Tripathi & Arup Ghosh (2014) Refractories of
Alumina-Silica System, Transactions of the Indian Ceramic Society, 73:1, 1-13, DOI: 10.1080/0371750X.2014.905265

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 Topical Reviews Trans. Ind. Ceram. Soc., vol. 73, no. 1, pp. 1-13 (2014).
© 2014 The Indian Ceramic Society
ISSN 0371-750X (Print), ISSN 2165-5456 (Online)
http://dx.doi.org/10.1080/0371750X.2014.905265

Refractories of Alumina-Silica System

Kausik Dana, Somnath Sinhamahapatra, Himansu Sekhar Tripathi and Arup Ghosh*
Refractory Division, CSIR-Central Glass & Ceramic Research Institute
196, Raja S. C. Mullick Road, Kolkata – 700 032, India
[MS received March 07, 2014; Accepted March 20, 2014]

The inorganic phases belonging to the binary alumina-silica system exhibit a plethora of excellent high temperature
properties that make them useful for refractory applications. Synthesized from abundant aluminosilicate minerals,
these refractories are ubiquitous in high temperature industrial applications. The refractories of alumina-silica
system can be engineered to generate a range of high temperature properties by varying the Al 2O3/SiO2 ratio,
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presence of other oxides and texture. This versatility is unique to this system and is reflected in widely varied
fields of applications of these refractories. Composed predominantly of mullite and corundum phases, the non
crystalline phases also play important role in determining the property and end use of these refractories. This
review covers different theoretical and practical aspects of refractories of aluminosilicate system spanning
30-100% alumina. Important role of microstructure in aluminosilicate refractory has been discussed in light of
phase diagram, raw materials and thermo-chemical reactions. The applications of these refractories in different
areas have been discussed in detail with structure-property correlation.
[Keywords: Refractory, Aluminosilicate, Mullite, Corundum, Application]

Introduction raw materials. World War II (after 1940) largely influenced

The progress of human civilization is made specially
based on the design and development of materials like
metals, ceramics and polymers. Interestingly, the historical
development of metals and ceramics are strongly
interdependent as high temperature metallurgical
processes necessitated development of suitable
‘refractory’ containers of molten metals. These ‘refractories’
are non-metallic materials possessing desirable physical
and chemical properties that make them suitable for
structural, or as components of systems, which are
exposed to temperature above 1000oF (811 K; 538oC).1
These materials significantly retain its properties even at
an elevated temperature of sustain operation.
Refractories can be classified in accordance with the
physicochemical nature of the raw materials used for
manufacturing, e.g. silica, aluminosilicate, magnesia, etc,
or with the nature of the manufacturing process (shaped/
unshaped), or with the application temperature, or with
their chemical nature (basic, acidic or neutral) etc. The
use of refractories in furnace began with the natural stones
of brick shape, which was followed by combination of clay
and sand. Eventually it was found that some natural stones
and clay rendered better thermal resistance property than
others. This heat resistant clay was termed as fireclay.
Depletion of natural stones triggered the development of
hand moulded clay refractories. Use of mechanical press
and downdraft kiln for fabrication and firing of refractories
respectively started in the late 1800s. At that point,
scientific principles guided the development of fireclay
brick rather than trial and error with different sources of
*Corresponding author; e-mail: arup@cgcri.res.in
the development of aluminosilicate refractories which was
closely associated with the development of bauxite based
refractories in North America due to unavailability of basic
refractories from Europe. A new line of ‘high alumina’
refractories started with the development of Bayer process
for alumina production from bauxite. World War II set an
impetus on the process technology of the refractory
production. With the development of refractory concrete
or castable refractories in the 1970s the consumption of
aluminosilicate refractories reached its peak, however, in
the late 80s it showed a negative trend in the consumption
pattern. Continuous development both in the raw materials
as well as processing technology in the refractory field
has regulated consumption of overall use of refractories.
Aluminosilicate is no exception to this and its production
and consumption steadily decreased. In today’s world,
aluminosilicate refractories are being produced in the
developing countries mainly and are imported to the
developed countries.
Aluminosilicate refractories can be classified according
to the alumina content (Table I). W hile the principal
mineralogical phases are mullite and corundum, minor
amount of glass phase in the grain boundary plays
important role in determining the refractory properties at
elevated temperatures. The temperature withstanding
properties of the aluminosilicate refractories largely
depend on the alumina content of the system and
accordingly the application areas are decided.
Aluminosilicate refractories are among the oldest and
most widely used refractories in the world. The use of
aluminosilicate refractories with lower alumina content
plummeted due to the stringent requirement of high
temperature processing industries. However, this leads

VOL. 73 (1) JANUARY – MARCH 2014 1

 Table I : Classification of aluminosilicate refractories

Al2O3 range Common terminology Mineralogical phases Raw materials

50% Fireclay refractory Mullite and glass Fireclay, china clay

50 to 60% Sillimanite, kyanite or Major - mullite, Minor - glass Sillimanite group minerals and
andalusite refractory clay, or bauxite and clay

70% Mullite refractory Major - mullite, Minor - corundum, glass Calcined bauxite and clay
80 to 85% Bauxite refractory Major - corundum, Minor - mullite, glass Calcined bauxite
90% Alumina refractory Major - corundum, Minor - mullite, glass Tabular or fused alumina

to greater demand of higher alumina containing 2200

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aluminosilicate refractories. Also, aluminosilicate

2100
refractories are ubiquitous in several application areas, like
blast furnace stack, torpedo ladle, backup lining in steel 2000

TEMPERATURE (oC)
LIQUID
LIQUID +
ladle, reheating furnace in ferrous metallurgy, lime kiln, CORUNDUM
1900
melting and holding furnace, pot furnace, anode baking 1853±10 1843±10
furnace in aluminium metallurgy and many other areas 1800 SiO2 + LIQUID
where use of these refractories is unavoidable. This review 1726±5

describes various aspects of alumina-silicate refractory 1700 MULLITE (ss) + LIQUID

system starting from raw materials to applications.
Phase Diagram of Al2O3-SiO2 System
The thermo-mechanical properties of refractory are
governed by the identity and quantity of phases present
in the system at the operating temperature. Phase diagram
is a graphical representation of equilibrium situation of
different phases against temperature and an invaluable
tool to characterize the composite ceramic system. This
gives a clear idea about the composition of phases present,
their relative abundance and the number of phases present
at equilibrium. It is immensely useful to know desired
compositions, thermal effect on crystallization and
behaviour of a specific composition.
Various thermo-mechanical properties of entire cohort
of aluminosilicate refractory system can be correlated with
the Al2O3-SiO2 phase diagram; the rationale behind this is
that specific composition will impart certain qualities of
refractories. The phase diagram of Al2O3-SiO2 system 2
depicting the composition in mole against temperature is
shown in Fig. 1. Although there are modifications in the
diagram, the basic facts remain unchanged. The salient
features of this phase diagram are the following.
Mullite (3Al2O3.2SiO2) is the most stable phase formed
during heating a mixture of alumina and silica with
theoretical composition 71.6% Al2O3 and 28.4% SiO2 (on
weight basis). It has a melting point of 1850oC. Refractory
properties of a material improve with increasing mullite
content. From 0% alumina (100% silica) to 72% alumina,
solid phases (viz. cristobalite or mullite and glass) exist
below the eutectic temperature 1595oC. A refractory in this
range is not suitable above this eutectic temperature.
Solidus line exists at 1840oC for composition with above
72 wt% alumina. This solidus line indicates a composition
range of just above 72% alumina to just below 100 wt%
alumina and it shows no melting up to 1840 oC. With
CORUNDUM +
1600 1597±10 MULLITE (ss)
–SiO2
-SiO 2
1500 SILICA + MULLITE (ss) MULLITE (ss)
1400
0 10 20 30 40 50 60 70 80 90 100
Al2O3 (mol%)
Fig. 1 – Phase diagram of Al2O3-SiO2
increasing alumina content the refractory properties
improve. Pure alumina (corundum, -alumina) has a melting
point of about 2050oC.
The properties of the aluminosilicate refractories
depend on the two major crystalline phases, mullite and
corundum, and the associated glassy phase, as revealed
by the phase diagram. Apart from the above well accepted
predictions from the phase diagram, there are several
points of ambiguity and could be debated as attested by
some remarkable research works.
Various aspects of Al2O3-SiO2 phase equilibrium have
been studied by several investigators2–8 and the major
focus was on the melting behaviour and the solid solution
range of mullite. Even after extensive investigations on
Al2O3-SiO2 system, the controversy still persists on the
exact location in the immiscibility region. The first published
work on Al2O3-SiO2 binary phase diagram was reported
by Shepherd et al.9 in 1909 and sillimanite (Al2O3.SiO2)
was reported as the most stable binary compound. Bowen
and Greig,4 in 1924, suggested that the only stable phase
at room temperature of the Al2O3-SiO2 binary system is
3:2 (Al2O3:SiO2) instead of 1:1 (Al2O3:SiO2) and this has
incongruent melting behaviour at 1828oC. They coined the
term “mullite” for this phase, from its natural occurrence
at island of Mull. However, few other researchers2, 10

2 TRANSACTIONS OF THE INDIAN CERAMIC SOCIETY

 contradicted the incongruent melting behaviour of mullite
and opined that it melts congruently.
Aramaki and Roy2 proposed a revised phase diagram
(Fig. 1) on the basis of their experimental findings from
quenching furnace data. They have reported that mullite
melts congruently at 1850oC with eutectic formation at
1840oC with 67 mol% of alumina. They have also reported
that the solid solution of mullite ranges from 60 mol% to
about 63 mol% (71.8 to 73.4 wt%) of alumina at equilibrium.
This solid solution range increases up to 67 mol% alumina
(77.3 wt%) under disordered metastable condition. Davis
and Pask5 determined the solid solution range of mullite
as 71 to 74 wt% of alumina. Aksay and Pask3 extended
this study to above 1800oC by using a diffusion couple of
sapphire and fused silica. In contradiction to the findings
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(x = 0.809) and -alumina at 700oC has been reported.
Maximum alumina inclusion of 92.1 mol% has been
observed at 1000oC; above this temperature alumina
content in mullite decreases and at 1650oC, the phase
comprising 34 mol% mullite with x = 0.32 and 66%
corundum is formed as the final product.
Structure of the Major Crystalline Phases
Mullite has orthorhombic crystal structure with unit cell
dimensions a = 0.7540 nm, b = 0.7680 nm and c = 0.2885
nm for the stoichiometric composition. 12–15 Mullite is
intermediate in composition between alumina (Al2O3) and
sillimanite (Al2SiO5). It can be seen from Fig. 2 that mullite
consists of chains of AlO6 octahedra at the edges and the
centre of the unit cell.16 These chains are joined by Al2SiO4

of Aramaki and Roy, they have agreed with the incongruent tetrahedra.
melting theory of mullite originally suggested by Bowen
and Greig. Under stable equilibrium condition, metastable Al (1) O (3)
mullite melted incongruently at 1828 o±10 oC with a O*
peritectic at 52.3 wt% of alumina. The stable solid solution O (2)
T*
range of mullite was 70.5 to 74.0 wt% alumina below
1753oC and 71.6 to 74 wt% at 1813oC. It has been further T
O (1)
suggested that under metastable condition, ordered mullite
exhibits congruent melting behaviour at 1880oC and the
solid solution range extends up to ~77 wt% alumina,
whereas for disordered mullite it is ~1900oC and the solid
solution range increases up to ~83 wt% alumina. Klug
et al.6 have studied the Al2O3-SiO2 phase relations and
concluded that the mullite solid solution boundaries b
changes with change in temperature and at 77.15 wt% (7.7 Å)

alumina composition it joined at 1890 oC and shows a (7.6 Å)

incongruent melting. The peritectic composition has an
alumina content of 76.5 to 77.0 wt%. The system was
further examined for melt-grown mullite of the composition
OXYGEN ALUMINIUM SILICON / ALUMINIUM
range 65 to 87.5 wt% alumina under equilibrium
condition.7 A continuous solid solution range exists up to Fig. 2 – Atom positions in unit cell of mullite
83.6±0.6 wt% or 75 mol% of Al2O3 having a nominal
formula of 3Al2O3.2SiO2. Beyond this limit exsolution of
The crystal structure of mullite can be seen as a defect
oriented -Al2O3 occurs as primary phase.
structure of sillimanite – a chain of slightly distorted Al-O
Difference in opinion on the high alumina region of the
octahedra linked by discontinuous double chains of Al-O
phase diagram has been reported repetitively and
and Si-O tetrahedra with randomly distributed aluminium
contradictions have been raised. Pask8 has studied the
and silicon atoms. The movement of aluminium and silicon
phase diagram and correlated them with the starting raw
ions into vacant tetrahedral positions are considered to
materials. According to Pask, the nature of phase diagram,
create such discontinuity. The oxygen atoms are forced
i.e. stable or metastable equilibrium in the Al2O3-SiO2
to occupy slightly different locations from their original
system, is guided by the presence or absence of -Al2O3
locations by these new sites. This defect structure helps
in the system during the reaction. The zone between the
to accommodate non-stoichiometry and the average
higher temperature -Al 2 O 3 liquidus, w hich is in
composition for mullite may range from 3Al2O3.2SiO2 (3:2
thermodynamic equilibrium but not saturated with -Al2O3,
mullite) to 2Al2O3.SiO2 (2:1). The substitution of Si4+ and
and the low temperature liquidus, which is saturated with
removal of O ion from the (Al, Si)O4 tetrahedra creates an
-Al 2 O 3 , represents -Al 2 O 3 -supersaturated liquid
oxygen vacancy and positional shift in partially occupied
structure. On cooling, -Al2O3 precipitates out from the
sites. The overall change can be summarized as
liquids after attaining saturation with -Al2O3. Another
interesting work in the alumina rich zone has been carried 2Si4+ + O2–  2Al3+ + oxygen vacancies
out by Fischer et al.11 On studying the formation of alumina
rich mullite (Al4+2xSi2-2xO10-x, where x2/3) from amorphous The number of oxygen vacancies corresponds to the ‘x’
powder in the temperature range of 700o to 1650oC, value of the mullite mixed structure (AlVI2(AlIV2+2xSi2-2x))O10–x,
simultaneous formation of 88 mol% Al2O3 containing mullite where, IV and VI represent coordination of aluminium

VOL. 73 (1) JANUARY – MARCH 2014 3

 cations and ‘x’ denotes the number of missing oxygen per Table II : Typical properties of the major crystalline
average unit cell. The value of ‘x’ can vary from 0.17 to phases in aluminosilicate system
0.59, so mullite can exist with a wide range of compositions
with different Al:Si ratios.17 When x = 0, it will be of three Properties Mullite Corundum
polymorphic forms, i.e. sillimanite, andalusite and kyanite
(Al2SiO5), and when ‘x’ is unity it represents the chemical Cell dimensions (Å) a = 7.5785, a = 4.7587,
b = 7.6817, c = 12.9929, Z = 6
composition of -Al2O3 phase. Theoretically mullite c = 2.8864, Z = 1
structure can be fitted anywhere between a disordered
Crystal system Orthorhombic- Trigonal
sillimanite and -Al2O3.13 Dipyramidal
The crystal structure of corundum (Fig. 3) can be
X-ray diffraction By intensity (I/Io): By Intensity (I/Io):
described as a hexagonal close packing of O2– ions with
(major peaks; Å) 3.39 (1), 2.55085 (0.9),
Al3+ ions in 2/3 part of the octahedral voids. In the closest 3.428 (0.95), 1.60156 (0.8),
packing, there are two tetrahedral voids and one 2.206 (0.6) 2.08532 (1)
octahedral void per atom/ion. Ions that can fit into the Density (g.cm–3) 3.15 3.96
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tetrahedral and octahedral voids are 0.225r and 0.414r,

RT fracture toughness 1.5-3 ~4.5
where ‘r’ is the radius of the anion. In Al2O3, the Al3+ having
KIc (MPam1/2)
radii <0.414r can occupy only the octahedral void. To
maintain the electrical neutrality, only 2/3 fraction of the Bend strength (MPa) 150-500 500
octahedral voids are filled up by Al 3+ ions. Due to o
Melting point ( C) ~1830 2050
multivalent ions, the bond strength in Al2O3 is very high, Linear thermal ~4.5 8
resulting in its hard crystal structure with high melting point. expansion coefficient
(x10–6 oC–1); 20o-1400oC

Thermal conductivity
(kcal.m–1h–1o C –1)
at room temp 6 26
O Al at 1400oC 3 4

mechanical properties. Mullite, the major crystalline phase

c
b
a
Fig. 3 – Atom positions in unit cell of corundum
Properties of Major Crystalline Phases
The properties of aluminosilicate refractories largely
depend on the abundance of two crystalline phases, namely
mullite and corundum, and the glassy phase. Mullite, owing
to its various advantageous properties like high thermal
stability, low thermal expansion and inertness at high
temperature, very good creep resistance, high corrosion
resistance, adequate strength and fracture toughness, has
found wide applications as a refractory material. In the
absence of grain boundary glassy phase, polycrystalline
mullite can retain >90% of its room temperature strength
at 1500oC. The typical properties of the major phases of
Al2O3-SiO2 system18–22 are shown in Table II.
Development of Aluminosilicate Refractory
The development of aluminosilicate refractories can
be construed as development of mullite and corundum
phases using suitable raw materials in order to achieve
required phase assemblage and consequently, the thermo-
in aluminosilicate refractories, is either developed in situ
or added as synthetic mullite aggregate. Mullites are
classified into three distinct categories depending on their
preparation techniques: (i) sintered mullite (ii) fused mullite
and (iii) chemical mullite. Sintered and fused mullites are
mainly used for refractory applications.
(i) Sintered mullite: In this process different raw materials
are mixed in powdered form and then sintered at an
optimum temperature after compaction. Oxides,
hydroxides, salts and silicates are used as starting
materials. Mullitization takes place by solid-solid or
transient liquid phase reactions of the starting materials
by aluminium, silicon and oxygen atom inter-diffusion.
(ii) Fused mullite: Fused mullites are commercially
produced by melting the starting materials above
2000oC, casting the aluminium silicate melt into the
ingot moulds and cooling it to room temperature. Raw
materials with low impurity levels, e.g. Bayers alumina,
quartz sand and fused silica are used. For lower quality
mullite, bauxite and mixture of alumina and kaolinite
have also been used.
(iii) Chemical mullite: Mullite prepared by advanced
processing techniques, such as sol-gel, hydrolysis,
precipitation, spray pyrolysis, chemical vapour
deposition, etc is termed as chemical mullite. Main
advantage of these methods is the production of high
purity mullite at lower temperature.

4 TRANSACTIONS OF THE INDIAN CERAMIC SOCIETY

 Any inorganic source containing high amount of alumina cell parameters and volume of mullite at different
and/or silica, like clay, sillimanite group of minerals and temperatures by employing X-ray technique. It was
bauxite, can be utilized for the development of aluminosilicate observed that the increasing temperature decreased the
refractories. The chemistry and mineralogical properties ‘a’ parameter. Brown and co-workers24 confirmed the
of the starting materials are summarized in Table III. findings by measuring the parameters through X-ray
techniques. This was further substantiated by Okada
Table III : Chemistry and mineralogy of et al.25 They extensively studied the transformation of
different starting materials kaolinite group of minerals and observed similar trend for
allophone, halloysite, kaolinite and dickite. Transformation
of kaolinite was a two-step process. This simultaneous
Properties China clay/ Sillimanite group of
fire clay minerals (sillimanite, two-step theory of formation of mullite from kaolinite was
andalusite, kyanite) also suggested by Chakraborty et al.26 after studying the
effect of heat on English china clay using standard X-ray
Chemical formula Al2O 3.2SiO 2.2H 2O Al2O3.SiO 2 technique. According to them kaolinite to mullite
transformation was a three-step process. At around 600oC,
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Chemical
constituents (%) amorphous metakaolinite was formed as a result of loss
(theoretical) of structural water followed by rapid decomposition at
Al2O 3 39.5 63
around 1000oC and formation of weakly crystalline spinel
phase and a very poorly crystalline mullite. The final step
SiO 2 46.5 37
was formation of 3:2 mullite from the spinel phase and
LOI 13.9 – poorly crystalline mullite phase. Two growth steps were
Major impurities TiO2, Fe2O3 TiO2, Fe2O3 reported – one from 1050o to 1150oC and another from
Mineralogy Kaolinite Sillimanite, 1250o to 1350oC. Mullite peak intensity increased with
Andalusite, Kyanite increase in temperature up to 1550 oC. These two
simultaneous paths of mullite formation rather than a single
solid state reaction process was further confirmed by them
Clay Based Refractory after studying a preheated Rajmahal china clay in the
mullite formation region using DTA technique.27 Different
China clay and fire clay, which are rich in alumina, have
steps of kaolinite to mullite transformation are schematically
been extensively used for the production of alumina-
silicate refractory and mullite aggregates through solid depicted in Fig. 4.
state sintering. It is known that kaolinite undergoes a series
of transformation reactions during the early stage of
heating. Phase transformation, mullitization temperature, 100 KAOLINITE
CRYSTALLINE PHASE (wt%)

METAKAOLIN
nature of the starting materials and effect of mineralizers
have been studied extensively. The reaction sequence of 80
Si-Al SPINEL
kaolinite during heat treatment has been studied by various
researchers 23–28 and the reaction/transformation 60
sequence29 is depicted below.
40
>550oC
2Al2(OH)4[Si2O5] 2Al2Si2O7 + 4H2O MULLITE
20
0.375Si8[Al10.675.33]O32 + SiO2 (i)
980°C
0
400 600 800 1000 1200 1400 1600
0.188Al8 [Al13.332.66]O32 + 4SiO2 (ii) TEMPERATURE (oC)
(spinel phase) (amorphous
silica) Fig. 4 – Schematic of kaolinite to mullite transformation
1000°C
0.67(3Al2O3.2SiO2) + 2.67SiO2
(mullite) (amorphous The debate in the reaction series is centered around
silica) the nature of the metakaolin and the identity of the cubic
phase, i.e. whether it is simple -Al2O3 (Al-spinel) or -Al2O3
where  is vacancy and (i), (ii) are alternate spinel phase. containing Si atoms (Al-Si spinel) or mullite phase
The formation of mullite from clay was studied corresponding to ~980oC exotherm. Initially it was thought
extensively by various researchers. Brindley and that this cubic phase is -Al2O3, which was supported by
Nakahira23 studied the transformation of kaolinite single Percival et al.28 by analysing the octahedral and tetrahedral
crystal to mullite on heat treatment and measured the unit Al in kaolinite heated above 980 o C using infrared

VOL. 73 (1) JANUARY – MARCH 2014 5

 measurements. The radial electron density distribution
(RED) and X-ray spectroscopy measurement of
dehydroxylation phases of kaolinite indicated the presence
of alumina spinel phase rather than Al-Si spinel at 900oC.30
However, Brindley and Nakahira23 showed that the unit
cell size of the cubic phase differed from that of -Al2O3
formed by decomposition of Al2O3.3H2O and proposed that
this was an Al-Si spinel rather than -alumina. Roy et al.31
identified the cubic phase in kaolinite and halloysite heated
for long periods and concluded that exothermic peak was
associated with the formation of mullite. However,
Sonuparlak et al.32 categorically denied this and opined
that 980oC exotherm in the kaolinite-to-mullite reaction
series was due to spinel phase formation and not due to
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formation of spinel and mullite.
Chen and co-workers33 studied the kinetics of mullite
formation from kaolinite and found the non-isothermal
activation energy for mullite formation to be 1182.3 kJ.mol–1,
where mullitization was dominated by bulk nucleation and
crystal growth was controlled by diffusion. Chen et al.34
used kaolin for mullite synthesis. They studied micro-
structural evolution of mullite from kaolin compacts and
reported that anisotropic shrinkage took place after firing.
China clay (kaolinite) alone cannot yield high alumina
refractory and hence, reaction sintering of kaolinite and
various alumina-rich materials is important for synthesis
of this type of materials. In the reaction sintering of
kaolinite-alumina system, kaolinite is first dehydroxylated
to metakaolin in the temperature range of 500o-600oC.
Below 1300oC, alumina is largely inert and the dominant
reactions are the kaolinite reaction series to form primary
mullite/spinel, amorphous silica. At temperatures above
1400oC, secondary mullite formation takes place from the
intermittent liquid phase followed by precipitation. The rate
of formation is very slow at 1555oC due to eutectic liquid
formation at 1595oC; the rate is much faster at 1600oC.
Comeforo et al.35 studied the mullite formation from high
grade kaolin of Georgia, which was slowly heated to
1450oC in order to establish the mechanism of mullite
formation from kaolinite. Viswabaskaran et al.36 studied
the mullitization behaviour of three south Indian clays
(Neyveli, Panruti and Udayarpalayam clays) and three
different alumina sources (reactive alumina, gibbsite and
boehmite) to produce sintered mullite commercially. The
raw materials were wet milled in a planetary mill, uniaxially
pressed to make bars and then sintered at 1600oC for 3 h
under normal atmospheric conditions. Mullite was formed
by reaction sintering of the clay-alumina mixture. It was
reported that Neyveli clay and reactive alumina showed
better result in terms of mullitization, whereas addition of
boehmite exhibited poor physical and mechanical
properties. The effect of sintering additives (MgO and Y2O3,
1-5 wt%) on reaction sintering of Neyveli clay and reactive
alumina was studied by them. 37 It was observed that
3 wt% MgO addition improved the density as well as
strength whereas yttria addition, in spite of favouring the
equiaxed mullite formation, did not help to improve the
6 TRANSACTIONS OF THE INDIAN CERAMIC SOCIETY
properties. It was further reported by Viswabaskaran
et al.38 that the calcined clay derived samples showed
better strength and density than the uncalcined clay
samples and the microstructure also showed higher aspect
ratio of mullite crystals. In another work,39 mullitization
behaviour of clay from West Bengal, India was studied in
relation with the bauxite addition in the temperature range
of 1400o-1500oC. It was reported that 50% bauxite addition
maximized the bulk density (2·89 g.cm–3) and minimized
the apparent porosity (0·58%) of the samples. Presence
of two types of mullite (elongated and equiaxed mullite)
was confirmed through electron microscopy.
Sanhoune et al.40 synthesized mullite through reaction
sintering of Algerian kaolinite and high purity alumina. They
studied mullite formation using XRD, and found that the
process completed at 1550oC and 94% relative density
(of the theoretical density) was achieved at 1600oC in 4 h.
Algerian refractory clays were also utilized for the
development of refractory products based on a mixture of
halloysite from Djebel Debbagh and kaolin from Tamazert.
Thermo-mechanical behaviour was extensively studied.
The evolution of the material rheological behaviour from
quasi-brittle, between ambient condition and 900oC, to
viscous at higher temperatures was shown by both bending
and compression tests.41 The thermo-mechanical study of
a mullitic refractory made of Algerian kaolin showed a linear
increase in bending strength up to 900oC. It became visco-
plastic at 1000oC. The maximum strength of 33 MPa was
reached at 900oC and the maximum elastic modulus of
8.21 GPa was measured at 700oC.42
Castelein et al.43 studied the thermal behaviour and
mullite formation of well crystallized bio-kaolin with
muscovite mineral content as a function of temperature.
In bio-kaolin, mullite was formed directly without any spinel
intermediate. The amount of mullite formed increased with
heating rate and it was higher than pure kaolinite.
Pilipchatin44 showed that sintering of fire clay kaolin was
intensified by replacing plastic clays with high melting clay.
Emphasis was given on the method of preparation and
also the developed technology was tested under industrial
conditions. Djangang et al. 45 investigated the clay-
chamotte refractory bricks. Kaolinitic refractory clays,
mined in Cameroon, and two calcined clays (chamottes)
were sintered at 1200o-1350oC. Investigation showed the
formation of cristobalite and mullite. Porosity increased
with the chamotte content and the mechanical strength
was controlled by the matrix behaviour. In another study
they mixed chamotte with sand-poor Mayouom and sandy
Mvan clays to prepare refractory ceramic bricks with
30-50 wt% and 10-30 wt% of chamotte and observed that
a minimum of 40 wt% and a maximum of 20 wt% of
chamotte must be added to Mayouom and Mvan clays,
respectively, for attaining an open porosity of 31-44% and
a flexural strength of 2-4 MPa.46 Andrews et al.47, 48 utilized
lithomargic clay underlying bauxite deposits to produce
fireclay refractory materials by adding a suitable clay binder
and analysed the physical properties, like apparent
porosity, linear firing shrinkage, bulk density and cold
 crushing strength. It was reported that cold crushing
strength increased up to a temperature of 1400oC and
with the increase in binder content. This was due to
formation of high refractory phases, like mullite, and
densification of the bricks. Recently, they have reported
that the gibbsite addition to lithomargic clay increases the
mullite and corundum formation and suppresses the free
silica phase formation. Up to 40 wt% gibbsite addition has
been reported to be advantageous for bulk density,
apparent porosity and cold crushing strength. 49 Khalil
et al.50 studied the formation of mullite-alumina containing
refractory ceramics using clay from four different places
of South Libya with addition of aluminium oxide and found
that the thermo-mechanical as well as refractory properties
were improved with increase in alumina content.
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Sillimanite Based Refractory
Sillimanite group of minerals (Al 2 O 3.SiO 2 ), viz.
sillimanite, andalusite and kyanite, on heat treatment
transform to 3:2 mullite and silica at high temperature under
oxidizing condition according to the equation
3Al2SiO5 3Al2O3.2SiO2 + SiO2
sillimanite, andalusite 3/2 mullite amorphous silica
kyanite cristobalite
Sillimanite and andalusite produce amorphous silica,
whereas, kyanite produces cristobalite. The thermal
transformation of sillimanite to mullite is a multi-step
reaction with a high degree of orientation.51 Heat treatment
of sillimanite just below the transformation temperature to
mullite yields slightly expanded lattice. These structural
changes were explained by Hariya et al.52 as continuous
change of composition from sillimanite to 3/2 mullite. Guse
et al.53 suggested this as an increase in aluminium silicon
disorder in sillimanite at constant composition. Durovic54
concluded that a continuous isomorphous series can be
expected between sillimanite and 2/1 mullite. W ith
increase in the SiO 2 content the mullite resembled
sillimanite more closely, and the Al/Si ratio in tetrahedral
coordination decreased to 1. Simultaneously, the lattice
constant decreased and the refractive indices and the
specific gravity increased. The formation of individual
member of this series depended on the temperature and
pressure conditions used. At 1 atm. pressure the members
between 3/2 and 2/1 mullite were stable.
Various authors studied the thermal decomposition of
sillimanite group of minerals. Pannhorst and Schneider,55
Hulsmans et al.56 studied the thermal decomposition
reaction of andalusite to 3/2 mullite by scanning and
tunnelling electron microscopy. It was reported that no
glassy or crystalline transition phase occured at andalusite/
mullite phase boundary. Hulsmans et al. suggested a
topotactical transformation, which was evident by lack of
heavy lattice distortion across the phase boundary. The
octahedral chain of AlO6 continued without any distortion
during the transition from andalusite to mullite. The double
chains consisting of SiO4 tetrahedra and AlO5 bipyramids
VOL. 73 (1) JANUARY – MARCH 2014
(connecting the octahedral chains) decomposed and was
reconstructed during the transformation process. The rate
of transformation was dependent on diffusion process
required for reconstruction. The silica liquid, which was
formed during the transformation, exsolved in the small
channels present between newly formed elongated mullite
crystallites. Exsolution of silica did not have any retarding
effect on mullite formation.
Gypesova and Durovic57 studied the thermal transfor-
mation of sillimanite single crystal. They carried out heat
treatment of sillimanite single crystal up to 1650oC and
observed that sillimanite structure was retained up to
1600oC and no 3/2-mullite plus silica was found as reaction
products. Above 1500oC, formation of -Al2O3 together
with silica rich melt was found. They interpreted these
phases as metastable intermediate reaction products.
Similar decomposition process of kyanite led to the
conclusion that furnace atmospheres, especially the
presence of alkali metals, was responsible for this type of
disproportion reaction.58
Shock induced transformation of sillimanite, andalusite
and kyanite powders (40 m) was studied by Schneider
and Maj dic, 59 and Schneider and Hornemann. 60, 61
Exposure of the material to high dynamic pressure revealed
characteristic phase transformation. In case of sillimanite,
XRD pattern indicated the formation of a small amount of
corundum, and IR study indicated the formation of a long
range disordered Al2O3 and SiO2. Mullite was not formed
from sillimanite upon shock. The transformation process
was favoured by high shock temperature. Andalusite
powder underwent partial transformation into X-ray-
amorphous Al2O3+SiO2 and mullite. While the formation of
mullite must be associated with high (shock) temperature,
the formation of Al2O3+SiO2 mixture may be a (shock)
pressure effect. Neither X-ray pattern nor IR spectra of
shocked kyanite yielded any evidence of possible high
pressure and high temperature reaction.62 Absence of high
pressure transformation in kyanite was due to its dense
structure which was more resistant to shock waves.
Sintering behaviour of sillimanite beach sand was
studied by various researchers.63–67 Tripathi and Banerjee65
studied the effect of chemical composition on sintering and
properties of Al2O3-SiO2 system derived from sillimanite
beach sand and alumina. It was reported that the use of
submicron size powder enhanced the sintering process.
The densification behaviour was dependent on the
Al2O 3:SiO 2 ratio. Mullite developed from silica rich
composition was acicular in nature, whereas it was non-
acicular for alumina rich composition. Tripathi et al.67 studied
the thermal shock resistance behaviour of high alumina
aggregates developed from sillimanite sand; the aggregates
with higher alumina content exhibited better thermal shock
resistance than that of sillimanite composition. Mullite and
other high alumina aggregates were developed from
sillimanite sand and alumina for refractory applications.68
Refractory castables based on mullite, derived from
sillimanite, exhibited good modulus of rupture, refractoriness
and excellent creep resistance at 1400oC.
7
 ZrO2 slightly retards the densification of mullite alumina
composites without much change in the thermo-
mechanical properties of the sintered ZrO2. However, they
always exhibit better thermal shock resistance than that
of ZrO2 free samples. It was observed that ZrO2 occupies
both intergranular and intragranular position within the
mullite matrix. Mullite grains are mostly equiaxed in
nature.63, 69 Sintering behaviour of sillimanite sand in
presence of titania, zirconia and combination of the two
was studied by Sen and Aggarwal.63 It was found that in
case of mullite-titania, densification might occur in
presence of a liquid phase and the formation of fine
needles of mullite was observed. Relatively large amount
of liquid phase formation during sintering was responsible
for the acicular nature of mullite. In sillimanite-zirconia and
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sillimanite-zirconia-titania system, the amount of liquid
phase is negligible and the mullite grains are plate like in
nature. Flexural strength of sintered sillimanite varied from
45.2 to 93.5 MPa.
Effect of gaseous atmosphere on the mullitization of
sillimanite group of minerals was studied by Lysak and
Drizheruk.70 They observed that reducing atmosphere,
especially CO, had a favouring influence on the thermal
transformation of sillimanite and kyanite and possibly
andalusite. The influence was stronger in sillimanite. The
structural defects, generated due to the reaction of CO with
the surface of aluminosilicate, reduce the activation energy
of phase transition. Reducing atmosphere also favoured
oxygen diffusion, thereby increasing the transformation
velocity. Kinetics study of high temperature transformation
of sillimanite group of minerals to mullite was carried out
by many researchers.59, 71, 72 The onset temperature of
transformation and temperature range were different within
the groups. Typical data are shown in Table IV.
Table IV : Data for high temperature transformation of
sillimanite groups to mullite
Properties Kyanite71 Andalusite59 Sillimanite72
Onset of 1150 1250 1300
transformation ( oC)
Transformation 1150-1300 1250-1500 1300-1700
temperature range (oC) 6
Width of transformation 150 250 400
interval (oC)
The rates of mullite formation from sillimanite group of
minerals over a range of temperature were investigated
by Wilson.73 No mullite formation from sillimanite was
observed below 1450 oC in 24 h. The rate of mullite
formation was not appreciable up to 1550oC. Andalusite
decomposed noticeably at 1300oC and the rate was higher
at 1400oC. Kyanite started to transform to mullite at
1250oC, the rate was considerably higher at 1350oC. High
temperature transformation of sillimanite to mullite was
8 TRANSACTIONS OF THE INDIAN CERAMIC SOCIETY
studied by different characterization techniques, like
dilatometry, XRD, FTIR and SEM. It was observed that
complete transformation of sillimanite to mullite occurred
in the temperature range of 1550 o-1600 oC. A rapid
nucleation occurred above 1550oC and the grain growth of
elongated mullite crystals took place almost simultaneously
with the nucleation stage.
Ganesh and Ferreira 74 prepared dense mullite
aggregates with 47-70% alumina content by conventional
dry powder pressing technique using different types of clay,
beach sand, sillimanite and a high purity aluminium
hydroxide. Beach sand sillimanite produced equiaxed
mullite, whereas clay generated elongated grain. The
properties of final product were strongly influenced by the
pre-mullitization step of the precursors and less by the
type and impurity content of the raw materials. Double
stage sintering produced better sintered properties, like
bulk density, apparent porosity and higher mullite content,
than those of single stage firing.
Goski and Caley75 produced mullite by casting a green
body from an aqueous submicron alumina-kyanite
suspension and then sintering. Naturally occurring kyanite
thermally decomposed above 1400oC to form mullite and
free silica. By sintering the mineral in an alumina-rich matrix
the silica subsequently reacted to form additional mullite,
thereby forming an alumina-mullite composite.
Sainz et al.76 studied the microstructural evolution of
mullite during thermal transformation of kyanite in the
temperature range of 1200o-1600oC. SEM-EDS analysis
of the grains showed that the total transformation took
place between 1350o and 1400oC. Below 1350oC, needle-
shaped mullite was reported and at higher temperature,
the structures had rounded and platelet morphology.
Namiranian and Kalantar,77 working on kyanite concentrate,
observed total transformation of kyanite to mullite to take
place in the temperature range 1500 o-1550oC. They
reported that mullite grains were needle-like below 1500oC
and at higher temperatures the mullite grains had rounded
and platelet morphology. The kinetics of the solid state
high temperature transformation of kyanite (Al2O3.SiO2)
powders (40 m) to 3:2-mullite (3Al2O3.2SiO2) and silica
(SiO2) were  investigated  by  means  of  quantitative  X-ray
diffraction techniques. The entire transformation was found
to occur between 1150o and 1350oC. Addition of Fe2O3 and
TiO2 to the starting material decreased the transformation
temperature. Performance of TiO2 was found to be better
than that of Fe2O3.71
The kinetics of high temperature transformation of
andalusite (40 m) was investigated by X-ray techniques.
The transformation interval was determined to lie in the
temperature range 1250o-1500oC. Below 1380oC, mullite
(+SiO2) formation was essentially restricted to an initial
rapid period of transformation, because nucleation and
product growth occur only at energetically favoured lattice
sites (e.g. grain boundaries). Above 1380oC, nucleation
and growth of mullite and SiO2 might take place throughout
the volume of the low temperature phase (andalusite) over
the whole range investigated.59
 Yugeswaran et al.78 utilized bauxite and coal ash from
thermal power plant unit to develop mullite by using
transferred arc plasma processing (TAP) technique. They
observed that the bauxite addition greatly influenced
mullite phase formation during the processes.
Wei et al.79 studied the hot MOR and deformation of
corundum-mullite refractories by three-point bending
method using different high alumina aggregates, like
andalusite, tabular alumina and fused mullite. The results
were interpreted in terms of microstructure. W hen
andalusite aggregates were used and fired at 1450oC, the
microstructure consisted of corundum bonded by
amorphous mullite without glass phase. When tabular
alumina was used, the microstructure consisted of granular
corundum with a small amount of mullite and trace quantity
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of glass phase. Refractories exhibited highest hot MOR
at 1000o, 800o and 800oC for andalusite, tabular alumina
and fused mullite respectively.
Tripathi et al.80 developed dense mullite aggregates
with 72% Al2O3 by reaction sintering of Indian bauxite and
silica sol. They used inferior grade Indian bauxite with
considerable amount of impurities, such as Fe2O3, TiO2,
CaO. Grain morphology of sintered mullite, developed from
bauxite with lower impurities, was mostly equiaxed,
whereas higher impurity content, particularly CaO,
favoured needle-shaped mullite. They reported that CaO
in bauxite was more harmful than TiO 2 and Fe 2O 3 .
Considerable amounts of TiO2 and Fe2O3 entered into the
mullite structure.
Aluminosilicate based refractory with different alumina
contents can be developed from different raw materials
and with wide range of low end to high end applications.
Application of Aluminosilicate Refractory
Earliest refractories were aluminosilicate bricks with
30-40% Al2O3 content, used widely for various applications.
However, with the advancement of modern technology, the
specific requirements by the consumers of aluminosilicate
refractories have been changed. In recent times, alumino-
silicate refractories starting from 30 to 98% Al2O3 content
are used. Refractories having 30-45% Al2O3 are termed as
fire clay refractory whereas those having more than 45%
Al2O3 are termed as high alumina refractory.
Fireclay refractory are further subdivided into different
classes starting from super heat duty, high heat duty,
medium and low heat duty. These classes cover 25-44%
Al2O3 range. High and super heat duty bricks consist of
blended clays. Kaolin contributes for high refractoriness,
calcined clay controls shrinkage due to firing, and plastic
clay develops bond strength. Super heat duty is a volume
stable brick with Al2O3 content up to 44%. High temperature
firing controls volume stability, resistance to corrosion and
shows inertness against carbon monoxide disintegration.
High duty bricks, because of their thermal shock
resistance, are commonly used in furnaces operated at
moderate temperature for long duration. Medium heat duty,
within their temperature ranges, are resistant to abrasion
and low heat duty is suitable for backup lining of furnaces.
VOL. 73 (1) JANUARY – MARCH 2014
The detailed application of aluminosilicate refractory with
controlled alumina content is described in subsequent steps.
30% Al2O3 Refractory
This category of bricks is widely used in the back-up
lining of pot furnace in aluminium industry. It contains
mainly mullite phase embedded in silica-rich glassy matrix.
They have excellent resistance towards sodium and
fluorine-bearing electrolytic bath present in the pot furnace.
Excess silica present in the matrix also resists crack
formation in the bricks by preventing the formation of
expansive phases like nepheline (NaAlSiO4).
35-40% Al2O3 Refractory
35-40% Al2O3-containing dense quality fire clay bricks,
because of their dense structure and high abrasion
resistance, find application in inlet and outlet zones of lime
calcination kiln. They can protect the lining from abrading
action of incoming raw materials and outgoing products.
In cement kilns generic aluminosilicate refractory is
sufficient for application in majority areas, except for upper
and lower transition zones as well as burning zone. 81
These refractories are always used in upper cyclones as
this area is not vulnerable to abrasion and alkali attack.
42-45% Al2O3 Refractory
42% Al2O3-containing dense quality fire clay bricks are
extensively used in the stack areas of blast furnaces. They
are characterized by their resistance to CO disintegration
and alkali attack. Generally they are manufactured from
high quality fire clay grog having low iron oxide content,
which can minimize CO disintegration.
50% Al2O3 Refractory
The base raw material used in the 50% Al 2 O 3 -
containing bricks is andalusite. Andalusite is used to
develop some high temperature properties, like
refractoriness under load (RUL), resistance to creep in
the bricks. Andalusite also leads to faster rate of mullite
formation. In spite of initial high silica glass content, and
as a result of trapping of the main part of the glass in the
capillary network of the mullite composite crystal, mullitized
andalusite leads to excellent corrosion resistance, which
matches with that of monocrystalline fused mullite.82 These
bricks are used in head wall and flue wall of anode baking
furnaces with an operating temperature 1280 o C.
Andalusite based refractories are the choicest material
due to their low cost, low creep under compression, high
resistance to thermal cycle, CO disintegration and alkali
attack in anode baking furnace application.83 Anode baking
furnace produces new and fresh anodes from coal tar pitch
and petroleum coke. These anodes are used in the pot
furnace containing electrolytic bath of cryolite, where
production of molten aluminium takes place. The spent
anodes from the pot furnace are also used for the
production of fresh anodes in anode baking furnace (ABF).
So, used anodes, when taken along with coke and pitch,
as a starting material for manufacture of anodes, has
9
 damaging effects on the refractory of the anode baking
furnace.84 The refractories in ABF flue wall and head wall
are subjected to many destructive forces, like stresses
caused by thermal expansion, reactions from intruded
aluminium and sodium fluoride, stresses resulting from
thermal cycling, mechanical damage during loading and
unloading of anodes, deformation due to prolonged
exposure to high temperature, etc. Alumina containing
refractories with small amount of iron oxide, controlled
particle size, distribution and formation of mullite and
corundum during firing may be an effective solution for
flue wall and head wall problem.85 The refractory used in
the anode baking furnace should have certain critical
properties, as given in Table V.
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Table V : Typical properties of bricks used
in anode baking furnace
Properties Values
Al2O3 (wt%) 54.51
Fe2O3 (wt%) 1.1
TiO2 (wt%) 1.8
Na2O (wt%) 0.26
K2O (wt%) 0.32
Apparent porosity (%) 14.9
–3
Bulk density (g.cm ) 2.36
–2
Cold crushing strength (kg.cm ) 870
Spalling (air quenching) 15+
RUL, ta ( oC) 1650
Creep at 1350oC (%), 20-50 h 0.035
MOR (kg.cm–2) 147
The properties of aluminosilicate brick developed from
andalusite and mullitized andalusite were compared86 and
found that mullitized andalusite provided better alkali
resistance than andalusite, high alumina chamotte and
bauxite. In fired bricks, mullitized andalusite shows a
similar behaviour to sintered mullite. Andalusite-based
refractory has the advantages of high resistance to
abrasion and slag corrosion, excellent thermal shock and
alkali resistance, good dimensional stability (creep
resistance), and the capacity to be directly used without
calcinations.87 Andalusite is mainly used as the raw material
for refractory shapes in blast and electric arc furnace
linings. It is also used as monolithic for ladles, sleeves
and casting pits, mortars, cements and ramming mixes.
Other andalusite consuming industries comprise non-
ferrous metals, glass, ceramics and cement. Andalusite
boasts an international market of over 300,000 mt/yr and
is used in many industrialized, steel and aluminium
producing countries of the world.
10
Chlorinator is another vessel where good quality
aluminosilicate refractory is in demand. It is a vertical
fluidized bed reactor used for making TiO2 by chloride
process. Chlorine gas is blown from the bottom into the
bed of a suitable blend of ore and carbon. The operating
temperature is around 1000 o C. In chlorinator, the
refractories are subjected to infiltration and corrosion by
acidic chlorides and gaseous chlorine. The reactions
occurring here, being exothermic, also leads to some
thermal load along with fluctuation of temperature. The
refractories used in chlorinator must be chemically inert
towards acidic chlorides and chlorine gas. They should
also have very low porosity and permeability to avoid
infiltration of corrosive gases. So, the brick should be
designed in such a way so as to maximize mullite phase
and to fill up the open pores by a high melting glassy phase
of suitable composition. Table VI shows typical properties
of a brick used in the chlorinator.88
Table VI : Typical properties of chlorinator bricks
Properties Values
Al2O3 (wt%) 53
Fe2O3 (wt%) 1.3
Apparent porosity (%) 18-20
Bulk density (g.cm–3) 2.50-2.55
–2
Cold crushing strength (kg.cm ) 550-600
o
RUL, ta ( C) 1600-1620
o
PLC at 1500 C, 2 h ±0.3
o
Creep at 1300 C (%), 0-50 h 0.37
60-65% Al2O3 Refractory
The 60-62% Al2O3-containing bricks have very good
refractoriness, excellent resistance to creep, hot strength
and volume stability at high temperature. Some products
are also developed from calcined bauxite and pure clay
to provide low level of impurities. They are also used in
glass tank furnace application.
The blast furnace stove provides preheated air inside
the blast furnace. The process of delivering hot air from
the stoves is critical since the system operates in a periodic
manner where it gets reversed by delivering hot air and
accepting cold air. The temperature of the hot blast
increases from 600o to 1300oC for optimizing the coke
consumption in the blast furnace. To meet the demand of
the operating conditions, high alumina bricks are preferred
for stove application due to their high refractoriness under
load (RUL), low creep tendency and superior thermal
shock resistance. Andalusite is the most suitable raw
material for blast furnace stove refractory due to its high
temperature properties like high RUL, low creep, good
resistance to thermal shock and good volume stability at
elevated temperature. The base raw material used is
TRANSACTIONS OF THE INDIAN CERAMIC SOCIETY
 andalusite group of minerals. They are used in the hot
blast stove of blast furnace as solid bricks as well as
checker bricks to withstand hot blast temperature of
1200oC and dome temperature as high as 1450oC. The
properties89 of the bricks for this particular application are
given in Table VII.
of torpedo ladle, hearth of reheating furnace, etc. High
abrasion resistance of these bricks makes them suitable
to be used in the hearth of reheating furnace. In addition
to that, they have very good corrosion and erosion
resistance towards molten metal and slag, so they can be
effectively used in the torpedo ladle application.

Table VII : Property requirements of the bricks

Bauxite based High Alumina Refractory
for hot blast stove of blast furnace Another important category of aluminosilicate refractory
is bauxite based bricks. They are characterized by the
expansive property at the application temperature, hence,
Properties Values
can be used to construct jointless structure without any
Al2O3 (wt%) 62-65
mortar. The Al2O3 content in these refractory varies from
60 to 80%. They also possess very good thermal shock
Fe2O3 (wt%) 1.5-2.0
resistance and high refractoriness, and can successfully
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Apparent porosity (%) 3.8 be used in cement rotary kiln, steel teeming ladle, roof of
–3
Bulk density (g.cm ) 2.52 electric arc furnaces, etc.
Cold crushing strength (kg.cm–2) 1160 90-95% Al2O3 Refractory
RUL, ta ( oC) 1550 Refractories with high concentration of Al2O3 are mainly
MOR (kg.cm–2) 275 corundum based bricks having very high abrasion
resistance and thermo-mechanical properties. The main
raw materials used are different synthetic aluminas like
70-80% Al2O3 Refractory BFA, WFA (white fused alumina) and WTA (white tabular
The raw material used in the manufacture of 70% Al2O3 alumina), depending on the operating parameters of the
containing bricks are combination of synthetic mullite and application areas. In order to improve the bond matrix for
synthetic alumina like brown fused alumina (BFA). The corundum bricks, addition of calcined alumina and clay is
main constituent phases in these bricks are mullite and necessary to form a mullite bond. These bricks contain
corundum with co-existing glassy phase. They are majority of alumina with minor amount of silica. They are
extensively used in tap hole area of blast furnace and glass widely used in hearth of reheating furnace, submerged
tank furnace regenerator due to their high resistance to arc furnace, carbon black reactor, fertilizer industry and
creep and thermal shock.90 70% Al2O3 bricks are also used petrochemical industry because of their resistance to
in cement and lime rotary kilns. Typical properties of this corrosive fuel impurities and also their wear resistance by
brick, developed and used in the tap hole area, with proven moving abrasive materials.
performance is given in Table VIII. Refractories for steel ladle side walls should be resistant
to slag attack. In case of Al-kilned steel, CaO:Al2O3 ratio is
1. Silica containing high alumina refractories, such as
Table VIII : Typical properties of bricks developed
and used in the tap hole area
andalusite or bauxite, show high rate of wear in low melting
calcium aluminate slag.91 SiO2, on the other hand, gets
Properties Values
reduced in contact with ‘Al’ of liquid steel and degrades
the steel cleanliness. Therefore, high purity alumina and
Apparent porosity (%) 16 spinel refractories replace andalusite and bauxite
–3
refractories in the steel ladle. Additionally, alumina based
Bulk density (g.cm ) 2.50
refractories, when compared with MgO-C refractories for
–2
Cold crushing strength (kg.cm ) 1000 ladle side walls, have two advantages. Carbon pick up for
RUL, ta ( oC) 1700 alumina refractories is very nominal and they possess low
o thermal conductivity to minimize heat dissipation.
Compressive creep at 1300 C (%) 0.005
The RUL and creep properties of different high alumina
Al2O3 (wt%) 72 refractory blocks developed from corundum, mullite,
Fe2O3 (wt%) 0.8 bauxite and andalusite have been reported.92 It showed
that corundum blocks possessed the lowest creep rate
and the highest RUL, followed by the values for andalusite,
The main raw material used in 80% Al2O3 containing mullite and bauxite.
bricks is BFA. They are highly dense bricks having
corundum as the main phase. They have good thermo- Conclusions
mechanical strength, high RUL and high hot MOR. The Aluminosilicate refractories with low Al2O3 content
main application areas of these bricks are melting and (30%) were historically being used in kilns and furnaces.
holding furnace of aluminium industry, non-impact zone With the development in metallurgical engineering, other

VOL. 73 (1) JANUARY – MARCH 2014 11

 high temperature processing industries and subsequent
discovery of Al2O3-SiO2 phase diagram, this refractory with
varying Al2O3 contents (40-90%) was utilized depending
on the requirement of vessels, e.g. thermo-mechanical
load, corrosion properties, volume stability, etc. In 50-60%
Al2O3 containing refractory range, sillimanite group of
refractory, particularly andalusite based mineral, is
beneficial. Andalusite is a volume stable material and
possesses excellent creep and thermal shock properties
after corundum. Mullite (72%) is also an excellent refractory
with good corrosion resistance and thermal shock
resistance due to its low thermal expansion coefficient. In
the present days, requirement of clean steel production is
increasing. This requires more stringent operating
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conditions of vessels with minimum inclusion from
refractories. For Al-killed steel, Si inclusion from refractory
will be detrimental. High Al2O3 refractory with low level of
SiO2 will be a good choice for high grade steel production.
As a futuristic refractory in this group, high Al2O 3
refractory with 55% Al2O3 content will be more demanding.
Al2O3-SiO2 castable based refractories, with varying Al2O3
content, are also gaining importance in ferrous and non-
ferrous metallurgical industries. This area is not covered
in this review and may be reported in future.
Acknowledgements: The authors are thankful to the Director, CSIR-
CGCRI for giving permission to publish this review paper. They are
also thankful to Ajita Chakraborty and Mithun Nath for providing
some references in the application of alumina-silicate refractories.
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