Binary Oxide Ceramics: Al2O3, ZrO2, Structure and Properties of

The structure of a material can, of course, be dened at multiple length scales ranging from subatomic to macroscopic. However, when considering what is usually meant by the term material properties, two levels of structure are of central interestcrystal H ) and microstructure (1100 m). In structure (110 A addition, for oxide materials characterized by ionic interatomic bonding, defect structure (i.e., concentration and type of point defects) also frequently plays an important role. When used in the engineering sense, alumina and zirconia really refer to nonmetallic alloys. Alumina is sometimes used as a single-phase pure material but zirconia never is, due to an inherent phase instability that takes place between normal processing and service temperatures. In both material systems, engineering control over structure is routinely accomplished through the introduction of intentional impurities. Furthermore, in most situations, the material is not allowed to adopt a fully equilibrated structure, but is used in a metastable, but kinetically persistent state. The consequence is that at the conclusion of processing, the material often reects some of the characteristics of the raw material. Some specic examples are discussed in the following. As a result of this exibility, both alumina and zirconia can be engineered to exhibit a wide range of properties. Lastly, materials such as alumina and zirconia can be used as dense monolithic materials or a loose granular material. Often, but not always, in the latter situation, the material is treated as a consumable. 1. Aluminum Oxide Alumina is the most widely utilized oxide ceramic. It is the only oxide ceramic widely used in single crystal form. Single crystal alumina, often incorrectly referred to as sapphire rather than corundum, is used for both its structural and optical properties. The only other signicant uses of bulk single crystal oxides are articial gemstones and laser hosts. The overwhelming majority of alumina products, however, use the polycrystalline form. The major markets for aluminabased materials on a weight basis are refractories (50%), abrasives (20%), whitewares and spark plugs (15%), and engineering ceramics (10%). There is only one thermodynamically stable phase of aluminum oxide, a-alumina, which has the corundum structure, see Fig. 1. The crystal structure is often described as having O# anions in an approximately hexagonal close packed arrangement with Al$+ cations occupying two-thirds of the octahedral interstices. Although this idealized model of the crystal structure correctly predicts many of the properties, such as anisotropy of optical and elastic constants, it

has been pointed out recently that the crystal structure deviates from this ideal, due primarily to electrostatic repulsion between aluminum ions, and that this loss of symmetry restricts plastic deformation at high temperature in important ways. The engineering properties of single-crystal a-alumina are given in Table 1. Of particular note are: the high possible use temperatures; the high values for hardness, stiness, and strength; the moderate thermal expansion and density relative to structural metals; the low optical absorption of visible light; and the excellent electrical resistivity and corrosion resistance. 1.1 Single Crystal Alumina Bulk single crystal alumina is exploited in a number of commercial applications. Historically, the rst commercial uses of synthetic sapphires and rubies (a solid solution of chromium oxide in alumina) were as jewelry, abrasion resistant thread guides, components in the clockwork mechanism in watches, and draw plates for wire drawing (Belyaev 1980). In such applications the high hardness and excellent wear resistance, both at room and elevated temperatures, are the key properties. Optical properties dominate in another, perhaps more familiar, application of chromium-doped single-crystal alumina: as the active optical element for an important class of solid-state lasers. The crystal structure of the alumina host modies the electron energy levels of the partially lled d-shell electrons in the chromium, which gives rise to the characteristic red color in contrast to the green color normally associated chromium ions. The most exible process for producing single crystal alumina from a melt is a modied Czochralski method, termed edge-dened lm-fed growth (EFG), developed by LaBelle (1980). In this process the melt is shaped by extraction through a refractory metal tool as solidication takes place. Variants of the EFG process have led to the exploitation of the unique combination of properties oered by single crystal alumina in diverse applications. These include: substrates for silicon-on-sapphire integrated circuits, arc tubes for lighting applications, hollow bers as optical waveguides for medical applications of lasers, and (one of the most important commercial applications) as abrasion resistant windows for supermarket laser scanners. 1.2 Alumina Ceramics and their Application The vast majority of aluminum oxide is used as a polycrystalline solid. High density, high-alumina ceramics can be categorized as: (i) those densied with the aid of a liquid by viscous ow; and (ii) those where there is essentially no liquid phase and sintering is via the solid state. 1