5 Structural oxides I: Al,O3 and mullite 5.1 INTRODUCTION TO ALUMINA, Some useful properties of alumina are its high melting temperature, ‘chemical resistance, electrical resistance and hardness (Gitzen, 1970), Alumina is to the ceramic industry what steel is to the metallurgical industry and is the most widely used ceramic. Alumina powder is produced cheaply in massive quantities. A diverse range of types of alumina ceramic exist with a concomitant range of properties. The major markets for alumina-based materials on a weight basis are refractories (50%), abrasives (20%), whitewares and spark plugs (15%), and engineering ceramics (10%). Aluminas are used in a variety of applications ranging from the calcined bauxite anti-skid road dressin Jumps in some refractory and building applications to m-sized ci aluminate cements used in monolithic refractories down to the sub- micron aluminas produced, for example by sol-gel routes. Figure 5.1 shows the diversity of products formed from aluminas. Included in the igure are 5.2 ALUMINA POWDER PRODUCTION 5.2.1 Mineral sources ‘Alumina occurs abundantly ‘which are the essential cons Bauxite is an impure mixture o ture, most often as impure hydroxides ‘of bauxite ores (Gitzen, 1970) ibbsite AI(OH), = «-Al,05,3H,0,256 LAL100% a-AlzO5 whereas crystallite size, may also lly y. This may cause dit The Bayer process produces highh-aggregated powders which mi be milled 1 release theultimate particles and so enable high ps ensies and reduced porosity in the gren formed sate Te evel of powder morphology can be controlled. during, pred Calation so that the fetes can be wsed to facta breakup. introduce substantial amounts of contamination from the milling media. ‘areful control of the Bayer process and caleination/milling conditions iminas of up to 99.99% purity indicates typical chemical analyses of the main forms tain about SSwt% Na,O which degrades many proper ‘causing deterioration ja alumina, Table 5.2 indica 1 of calcined Bayer alumina powders (Maczura et ., 1992). ‘Low soda alumina is produced by using: low soda gibbsite prepared by adjusting the Bayer process precipi ion condi Spark plugs2. washing alumi followed by fui 3. adding chiorine, may give low green density and poor sintering. Reactive powders require low soda but high surface area. Table 5.3 (Southern, 1991) illustrates the effect of these variables on sintered density for several alumina powders, powder 3 being the most reactive, Reactive alumina powders are used in those applications requiring the best high- temperature mechanical behaviour such as in ZTA (section 9.3.2) and SiC-reinforced alumina CMCs (section 9.3.3). 5.2.3 Fused and tabular refractory grades to large shaped crystals occurs. The recrystallized alumina is in the massive state and tabular alumina crystals are hard and dense with good thermal conductivity and high crushing strength. A wide range of (0 >2004m), hexagonal, elongated tablet- Alumina Powder Production 263, ‘Table 5.4 Properties of tabular and fused akamina Tabular Fused White Brown >9 29 955 o.1-0.02 o.01-0.05 12 0-03 003-015 01s. 0.02-0.36 002-05 ° TiO, o.ot-0.02 26 MgO 045 Bulk density 3.56 3.86 32 3 3 1 2050 2000 6 6 85 8S particle sizes (25jzm to 6mm) are made by crushing and grading the tabular alumina. Table 5.4 lists useful properties of tabular and fused alumina, Tabular aluminas are used extensively in alumina~graphite refractories (Chapter 8), and in low-cement and ultra low cement castable mixes ist produced in 1909 as an abrasive. In the ich is mixed, charged and melted in an electric arc furnace using graphite electrodes with a removable, water-cooled, stee! shell, The fused refractory grain is massive and requires crushing and milling to obtain the desired siz alumina is produced in two forms: white and brown (Table 5.4). White fused alumina (WFA) is ‘made from calcined Bayer alumina and different grades are avai based on differences in alkali contents. The grain and, as an abrasive, superior removal of impurities as ferrosilicon. The impurities ‘melting temperature by about than WEA and has superior wear resistank00 eructuras Urades I: AlO3 and 5.3 ALUMINA POLYMORPHS AND CRYSTAL STRUCTURES 5.3.1 Transition aluminas Many proceses such a the oxidation of aluminium metal andthe for mation of alumina by heating gost or vapour deposited aera ous akumina thin fs involve the formation of ntermedate metocheg alumina phases, These tansiion. phases are denoted ae ye tt, 5, @ and x and ate of parcalar importance ‘teva their use as catalysts or catalyst supports. The sequence of annie! aluminas that form is strongly dependent onthe sang maternl aon as formed. For example i the starting materia fs bookie ) formed from solution or amorphous lumina then the me probable sequence sy -» 8» 8a. However, the stare na I ghbsite, wAIOHy then the soquence may incde te et = 0 — even though Boehmite fo formed prior f0 7, Digpor another polymorph of AIO(OH) transforms dell 1 ALOe Re tion of the transiton aluminas from hydrted compounds soc ied by development of a highly porous powder micrstnseer {Wilson 1979) ‘The transition aluminas have pasty disordered crystal structures ll based on a close-packed oxygen subatice with Varying testa aluminium configurations. As equim i approached the stacey become more ordered forming. hexagonal cxygen sublatice ont Sable walumina i formed. Table 5.5 Ists coptllogaphi inter mation forthe tansition aluminas bu since few ofthese inernedice aluminas have been subjected to sngle-aystal XRD examination the fable incomplete The rst structures ofthe transition alumina are characterized by the maintenance of an approximately fc anion sublatice 197) While isted a8 cuble in Table 53 ‘alumina hes tecagonally-distorted defect spinel stuctre (about O95, hed ton varying with heat uestmend Balumina has tttagonal seper structure with one unit cell parameter tripled with the ation vaca thought te ordered on the vtahedal ste o monocinc with space group Adi but’ and often twinned, Eta cube apne! 5.3.2 @-Alumina Unlike the transition aluminas the crystal structure of «alumina (termed corundum in mineral form and sapphire as the single crystal) is well known. (Sapphire is a misnomer since sapphire is «Al containing Ti** conferring, the characteristic blue colour. Ruby is a \ Table 5.5 Crystallographic data for transition aluminas Delta (8) ‘Theta (@) Kappa te) deta) Epson Ce) Chi) Eta) Gamma) Hexagonal Péame 55 9.028 5.62 2.906 179 Monoclinic Orthorhombic Adm 103.74 Tetragonal 7.983 8 i i ae Bie : pos HuLik 26-31 16-394 37-1462 4978s 4875344900 10-425 JCPDS* card no, powder XRD peak positions and intensities for most known mated suchas space groups, densily and reactive indices. ion Standards, Ist the *JCPDS, the Joint Committe on Powder Dirac ‘The cards also list much other useful information|and Mullite for ALO, Crystal Space group Lattice pr ycpps ster @ bc aard No, Rhomb. RB «4.7559 — 12991 10-173 ontaining CP* impurity responsible forthe red colour.) Crystal the hexagonal structural 1¢ close-packed directions lie alo collated useful crystallographic an¢ Microstructures and Prop ior) led circles are Al, open circles are ices (after Kronberg, 1957) 54 ALUMINA CERAMIC FABRICATION ROUTES, MICROSTRUCTURES AND PROPERTIES High density, high-alumina ceramics can be categorized as (a) those densified wit the aid of aliquid by viscous flow there is essentially no liquid phase and sintering In the following sections we will cover ge id the resulting properties. Solid ly pure (>99,7 wt % AlO3) requiring careful processing. They are used in requiring good mechanical properties very pure starting powders the most demanding applic