Alumino-silicate refractories

Abstract
The steel and the glass industry are two main users of alumino‐silicate based refractories. Among the alumino‐
silicates mullite is widely used as a refractory material. Here we present a brief review of these materials
highlighting their properties, methods of production and use.
Introduction
“Mullite” has been part of our vocabulary in a geological and mineralogical context for many years. Its
derivation is from a rock composed of lath‐like crystals found on the isle of Mull ( off the North West coast of
Scotland).The natural type of this material is most unusual if not unique. In spite of the abundance of the
elements aluminium, silicon and oxygen in the earth’s crust, the isle of Mull is probably one of the only places
on earth where a combination of these elements to form the alumino‐silicate known as mullite exists.

Mullite, in contrast to other alumino‐silicates shown, is favored by low pressure and high temperatures. While
high temperatures certainly prevailed at the various times of geological formation of alumino‐silicates, this was
normally accompanied by high pressure leading to the formation of Andalusite, Sillimanite, Kyanite, etc. At
atmospheric pressures therefore and with increasing temperature, it is to be expected that aluminosilicate will
reach a state of equilibrium known as mullite. Clearly this is the reason that Andalusite, etc. is employed in the
refractories industry, i.e. in situ formation of mullite. However, naturally occurring minerals such as Andalusite,
etc. are normally accompanied by various impurities which have deleterious effects on refractory properties.
Complete formation of theoretical mullite composition is not feasible as stoichiometry infers a higher alumina
content than is available in Andalusite.

Examination of the phase diagram for the alumino‐silicates

demonstrates that mullite is the only a stable compound of the
alumino‐
silicate system at atmospheric pressure. On heating to a liquid or
near liquid‐phase, all alumino‐silicates produce mullites with free
silica or free alumina. Pure mullite with a melting point of 1850°C
exhibits excellent refractory properties. An excess of silica would
present phase changes and inferred phase reversions would be
unacceptable to a refractory producer while excess alumina
would increase thermal expansion and hence reduce thermal
shock resistance. An interest has therefore been established for a
pure synthetic mullite free from other phases which reduces its
all‐round refractory performance.
Mullite production – Sintered
In terms of commercial production there are in the world today
two predominant methods for production for synthetic mullite.
These are:
1Sintered mullite
2Electrofused mullite

Synthetic Sintered Mullite is produced commercially by two distinct routes:

1Tunnel kiln
2Rotary kiln

In both cases formulations are based on the reaction of the pure kandite mineral (kaolinite, halloysite, etc.) with
alumina (as the oxide or hydrate). Both materials are available in highly refined or beneficiated forms and thus
the stoichiometry may be controlled. Reference to the phase diagram, however, shows that the addition of
alumina to kandite mineral is necessary for complete mullitisation (3Al2O3, 2SiO2) to occur. Comparison of
these two methods of heat input to raw mullite formations indicates differences which are significant in terms
of the final reacted product. Rotary calcination is utilized to achieve high outputs with high temperatures and
consequently low dwell times. Tunnel kiln firing on the other hand is used to control time and temperature to
ensure, as far as possible, that complete mullitisation has occurred with control of the soak time at peak
temperatures. The two different processes also involve two distinct processes of fabrication of the raw mullite
mix to the firing zone. Rotary calcination consists of the firing of extruded or pressed bricquettes or pellets to
the rotary kiln. A tunnel kiln requires, out of sheer practicality, that pieces (bricks or dobies) are stacked into a
kiln car before entering the kiln. This feature is also exploited for quality control purposes after firing. Clearly it
is much easier to handle and inspect a brick of fired mullite than a handful of pellets. The mullite can therefore
be examined visually and physically by quality control personnel to ensure that control parameters are adhered
to.
Microscopic examination of Sintered Mullite formed by the routes demonstrates that the method of heat
treatment determines the size of mullite crystals formed. By thermally recycling various grades of mullite it has
been shown that rotary calcined mullites incur further size reductions (and hence stress in a finished refractory)
than is the case with tunnel kiln heat treatment.
All sintered mullite is produced by whatever route must be crushed and graded into discrete sizes to achieve
maximum theoretical packing in a finished refractory. Sizing is now available to closely controlled parameters
from 10 mm through to 5 micron and below. In this manner maximum density in association with minimum
stress may be achieved.
Mullite Production – Electrofused
In contrast with sintered mullite, electrofused mullite is formed by fusing the oxides of silicon and aluminium.
Even greater degree of purity are thus obtainable than in the case with sintered mullite. Massive crystals of
mullite are grown principally in the cooling process with crystal centimeters long and millimeters wide. (In
comparison the sintered process the sintered process an average size of 60 microns is achieved). Electrofusion
takes place in a water cooled arc furnace with melting temperatures in excess of 2000°C. Control of fusion
techniques enables mullites with properties of high density (low porosity) and also with a very white colour
(higher porosity to be produced. Not only is a technique of importance here but also control of inter‐electrode
and fusion pot geometry.
Comparison of refractory properties of bricks made from Sintered and Electrofused Mullite

In both cases bricks have been fabricated from sintered or fused Mullite using a clay bond. The
most salient points arising from this comparison are:
1The mechanical properties of both types of Mullite are excellent.
Properties
2High refractoriness of both types, i.e. comfortably in excess of the working temperatures of steel and glass.
3The hot Modulus of rupture of sintered Mullite is significantly Fused
higher than that of fused. This is attributable to
the interlocking network of small but well developed crystallitesSintered
in sintered mullites.
4The excellent value of creep resistance shown by fused mullite Bulk density
is due to primarily to the stability of its
massive crystals. 2.75 g/cc
2.6 g/cc
Crystallite size of mullite has therefore a pronounced effect upon Apparent porosity
its physical and chemical properties.
14%exciting prospects of chemistry modification
It is, perhaps, the flexibility of electrofusion which offers the most
to vary the physical properties of the fused or co‐fused material. 15% Perhaps the most significant of these co‐
fusions has been the development of fused Zirconia Mullite. Variations
Reversibleof chemistry has enabledtothe
thermal expansion selection
1400?C
of 36% zirconia content Fused Zirconia Mullite to optimize such properties
0.49% as chemical/corrosion resistance with
thermal shock resistance/thermal expansion. Microscopic analysis of Fused Zirconia Mullite shows zirconia
0.53%
precipitated in the mullite in regular patterns even in the very small size range. This appears to be indicative of
Thermal Conductivity W/m K 1300?C
the dendritic structure of zirconia. It is the interlock of the dendrites of the zirconia with the massive lath
2.0 most likely reason for this corrosion
crystallites of mullite which confers the properties of interest. The
resistance improvement is that the dendritic structure increases 2.2the diffusion path of matrix reactants.
The variation of the alumina/silica ratio still further enables theCreep % Subsidence
production 1700?C
of a 40% silica 2hours at 2kg/cm2
“mullite”.
This particular species of mullite is developed for its needle‐like0.5%
structure, particularly for areas of high thermal
2.0%
shock, crucibles, precision casting stuccos, etc. The effect of increased but combined silica on thermal
expansion has a pronounced effect increasing thermal shock resistance.
Hot Modulus of rupture MN/m2
The tendency of the steel industry worldwide as a consequence 3.0of costs and economic studies has been to
reduce the ratio of refractories used to produce the unit of steel.7.0Refractory usage in steel manufacture has
fallen from 30kg to, in some cases, less than 10kg of refractories per tonne of steel.
Summary
Although mullite occurs in nature, its availability is spasmodic and subject to impurity as a naturally occurring
material. Mullite derived from naturally occurring alumino‐silicates is also a subject to these impurity
contaminations.
Synthetic mullite enables control of chemistry to ensure predictable and non‐variable refractory properties. The
two methods of production of sintered mullite have been examined and properties derived from crystallite size
discussed. The formation and more importantly the stability of mullite formed is dependent upon the heat input
on the mullite reaction leading to greater stability of refractories derived from synthetic mullite.
It is perhaps the flexibility of mullite and the positive variation that can be achieved by its cofusion or co‐
sintering which will sustain interest well into the future.