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

In this manner maximum density in association with minimum stress may be achieved. Sizing is now available to closely controlled parameters from 10 mm through to 5 micron and below. 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. 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. .treatment determines the size of mullite crystals formed.

0 fallen from 30kg to. 2.5% This particular species of mullite is developed for its needle‐like structure. etc. the flexibility of electrofusion which offers the most exciting prospects of chemistry modification 14% to vary the physical properties of the fused or co‐fused material.0 crystallites of mullite which confers the properties of interest.49% thermal shock resistance/thermal expansion. It is. comfortably in excess of the working temperatures of steel and glass. Electrofusion takes place in a water cooled arc furnace with melting temperatures in excess of 2000°C. Variations of chemistry expansion to 1400?C Reversible thermal has enabled the selection of 36% zirconia content Fused Zirconia Mullite to optimize such properties as chemical/corrosion resistance with 0. particularly for areas of high thermal shock. Perhaps the most significant of these co‐ 15% fusions has been the development of fused Zirconia Mullite. in some cases. The effect of increased but combined silica on thermal 2. precision casting stuccos. Even greater degree of purity are thus obtainable than in the case with sintered 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.0 reduce the ratio of refractories used to produce the unit of steel. Massive crystals of mullite are grown principally in the cooling process with crystal centimeters long and millimeters wide. The two methods of production of sintered mullite have been examined and properties derived from crystallite size discussed. 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. Properties 2High refractoriness of both types. Not only is a technique of importance here but also control of inter‐electrode and fusion pot geometry.53% precipitated in the mullite in regular patterns even in the very small size range.0% expansion has a pronounced effect increasing thermal shock resistance. Summary Although mullite occurs in nature.Mullite Production – Electrofused In contrast with sintered mullite.e.75 g/cc massive crystals. . perhaps. less than 10kg of refractories per tonne of steel. Hot Modulus of rupture MN/m2 The tendency of the steel industry worldwide as a consequence of costs and economic studies has been to 3. 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. Refractory usage in steel manufacture has 7. This is attributable to higher Sintered the interlocking network of small but well developed crystallites in sintered mullites. Bulk density 4The excellent value of creep resistance shown by fused mullite is due to primarily to the stability of its 2. Synthetic mullite enables control of chemistry to ensure predictable and non‐variable refractory properties.6 g/cc Apparent porosity Crystallite size of mullite has therefore a pronounced effect upon its physical and chemical properties. The most salient points arising from this comparison are: 1The mechanical properties of both types of Mullite are excellent. Creep % Subsidence 1700?C 2hours at 2kg/cm2 The variation of the alumina/silica ratio still further enables the production of a 40% silica “mullite”. 0. The most likely reason for this corrosion 2. It is the interlock of the dendrites of the zirconia with the massive lath 2. i. its availability is spasmodic and subject to impurity as a naturally occurring material. electrofused mullite is formed by fusing the oxides of silicon and aluminium. 3The hot Modulus of rupture of sintered Mullite is significantly Fusedthan that of fused.2 resistance improvement is that the dendritic structure increases the diffusion path of matrix reactants. This appears to be indicative of Thermal Conductivity W/m K 1300?C the dendritic structure of zirconia. Microscopic analysis of Fused Zirconia Mullite shows zirconia 0. Mullite derived from naturally occurring alumino‐silicates is also a subject to these impurity contaminations. (In comparison the sintered process the sintered process an average size of 60 microns is achieved). crucibles. 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.