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Polyultraphosphates, the corresponding branched and crosslinked analogs, ae obtained by having phosphoric acid present in the reaction mixture. Chalcogenide glasses are crosslinked polymers formed by the fusion of a chalcogen (S, Se, Te) with one or more of various polyvalent elements (e.g., As, Cd, Ge, P, Si, Sn). Some of these polymers are useful as infrared transparent windows in applications such as infrared detectors and for encapsulating photosensitive transistors.
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Ceramic materials have higher heat resistance than do their corresponding glass compositions. The traditional ceramics, such as brick, pottery, and porcelain, are aluminosilicates derived from clay as the main raw material [Jastrzebski, 1976; Thornton and Colangelo, 1985]. These are heterogeneous materials in which microcrystals are embedded in a glass matrix. Clays are produced by the weathering of the mineral feldspar, an aluminosilicate containing sodium and potassium ions. Weathering of feldspar produces kaolinite, empirical formula Al2Si2O5(OH)4, in the form of small thin platelets. Clays are mixtures of kaolinite with small amounts of feldspar, sand, and other minerals. Most clays are reddish because of the presence of iron(III) oxide as an impurity. Ceramic ojects are made by working a mixture of clay with water. Other silicate materials are often added depending on the desired properties in the nal product. The presence of water renders the mixture pliable as kaolinite platelets can slide over one another. Firing (heating) of the shaped object results in a complex set of reaction. Water is lost during the process, and the kaolinite platelets can no longer slip past one another. In addition, an aluminosilicate glassy network with its associated cations is formed. The resulting ceramic consists of kaolinite platelets distributed in a glassy aluminosilicate matrix. The partially crystalline nature of these ceramics results in denser materials with higher strength, heat conduction, and heat resistance compared to glasses. Traditional ceramics nd a range of applications: pottery, construction bricks, whitewares (porcelain coatings on various household items, and spark plugs, ovenware), and refractory (furnace bricks, mortar, liners, coatings). Most of these applications require the heat-resistant properties inherent in the ceramic materials. However, the strength requirements are not very high in such applications. A second group of ceramic materials, often referred to as new ceramics or high-performance ceramics, have been developed in more recent years [Baldus and Jansen, 1997; Corriu, 2000; Segal, 1991]. These include various pure and mixed oxides, carbides, nitrides, borides, and silicides, (e.g., BeO, ZrO, a-Al2O3, a-SiC, B4C, TiC, BN, AlN, Si3N4, ZrB2, TaB2; empirical formulas). The new ceramics are used in applications requiring high strength at high temperature, such as parts for gas and jet engines, nuclear plants, hightemperature chemical plants and abrasives, cutting tools, and dies for high-speed machining of metals. Silicon carbide is used for the heat-resistant tiles that protect the space shuttle during reentry into the earth s atmosphere. Many of the new ceramics are close to being completely crystalline materials. Others consist of crystalline material embedded in a glassy matrix, but the amount of crystalline phase is typically greater than that for the traditional ceramics. Synthesis of the various materials used for the newer ceramics typically requires high-temperature processes; for instance, SiC is produced by the reaction of silica and
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anthracite coal or coke in an electric resistance furnace. The production of objects from the newer ceramics follows in the same manner as the traditional ceramics but with higher ring temperatures (800 1800 C). The ring process at these higher temperatures is referred to as sintering. The formation of objects from glass and ceramic (especially the new ceramic) materials is achieved only at very high temperatures where there are considerable limitations on the manipulative techniques available to form desired shapes and forms. Two new methods hold considerable promise for producing glass and ceramic objects more easily and at much more moderate temperatures. The key to both methods is the use of very different chemical reactions, based on organic derivatives of the inorganic element, to form the glass or ceramic compound(s). The preceramic polymer method is described in Sec. 2-15b-3. The sol-gel method involves the in situ generation of silica by the base- or acid-catalyzed hydrolysis of tetramethoxy- or tetraethoxysilane in an alcohol water mixture (Eq. 2-233) [Brinker et al., 1984; Celzard and Mareche, 2002; Corriu, 2000; Corriu and Leclercq, 1996; Hench and West, 1990]. The polymerization conditions (temperature, reactant and catalyst concentrations) may be varied to yield reaction times from minutes to hours or days for completion. Polymerization generally involves initial reaction at ambient temperature followed by an aging process at 50 80 C to develop a controlled network structure. The acid-catalyzed process is slower and easier to control compared to the base-catalyzed process. Tetraacetoxysilanes have also been used as the silica precursor.
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