Borides from metal oxides

Preparative routes to metal borides are varied, as are their structures. Some may be made by direct combination of the elements at high temperatures, and others from metal oxides (e.g. reactions 13.74 and 13.75). 

Metal-Matrix Composites. A metal-matrix composite (MMC) is comprised of a metal ahoy, less than 50% by volume that is reinforced by one or more constituents with a significantly higher elastic modulus. Reinforcement materials include carbides, oxides, graphite, borides, intermetahics or even polymeric products. These materials can be used in the form of whiskers, continuous or discontinuous fibers, or particles. Matrices can be made from metal ahoys of Mg, Al, Ti, Cu, Ni or Fe. In addition, intermetahic compounds such as titanium and nickel aluminides, Ti Al and Ni Al, respectively, are also used as a matrix material (58,59). P/M MMC can be formed by a variety of full-density hot consolidation processes, including hot pressing, hot isostatic pressing, extmsion, or forging. 

Carbides oxidize readily although less rapidly than the nitrides but more so than the borides. Oxidation becomes more rapid going from the Group IV carbides (TiC, ZrC, HfC) to those of Group VI (Cr3C7, MoC, WC). In some cases, a protective film of the metal oxide is formed. Such is the case with SiC, as reviewed in Sec. 5.7 below. 

Compounds isotypic with the k phases arc found among intcrmetallics, borides, carbides and oxides and also with silicides, germanides, arsenides, sulfides and sclcnides no nitrides, however, are found. The mode of filling the various voids in the metal host lattice of the k phases follows the schemein Ref. 4 and is presented in Table 1 for all those compounds for which the atom distribution is well known from x-ray or neutron diffraction. Accordingly, B atoms in tc-borides, Zr, Mo, W, Re)4B and Hfy(Mo, W, Re, Os)4B , occupy the trigonal prismatic interstices within the parent metal framework of a Mn, Aln,-type structure (see Table 1 see also ref. 48). Extended solid solutions are found for (Hf, Al)[Pg.140]

The halide is not the only metal compound used as source of metal. Metal oxides and sulfides are employed to prepare vanadium, chromium, iron and nickel borides in this way from sulfides at lower reaction T than those required by reaction sintering of the elements . 

Borides of Nb and Ta have been reviewed67 and a method for their preparation from boron and metal oxide has been reported.68... 

Numerous ceramics are deposited via chemical vapor deposition. Oxide, carbide, nitride, and boride films can all be produced from gas phase precursors. This section gives details on the production-scale reactions for materials that are widely produced. In addition, a survey of the latest research including novel precursors and chemical reactions is provided. The discussion begins with the mature technologies of silicon dioxide, aluminum oxide, and silicon nitride CVD. Then the focus turns to the deposition of thin films having characteristics that are attractive for future applications in microelectronics, micromachinery, and hard coatings for tools and parts. These materials include aluminum nitride, boron nitride, titanium nitride, titanium dioxide, silicon carbide, and mixed-metal oxides such as those of the perovskite structure and those used as high To superconductors. 

In the fifteen years since publication of the first edition of Comprehensive Coordination Chemistry (CCC, 1987), group 5 chemistry has been part of the intensive development of ceramic, optical, and magnetic materials based upon metal borides, nitrides, phosphides, oxides, and sulfides. A major impetus came from the discovery of the high-temperature superconducting oxides. In addition, the search for new routes to these materials via sol-gel or chemical vapor deposition techniques has spurred growth in metal amido, oxo, alkoxo, thio, and carboxylato chemistry. 

Other complications for oxidation of transition metal borides at high temperatures, where boria no longer offers protection, result from the properties of transition metal oxides. The monoclinic to tetragonal phase transition for zirconia and hafnia is accompanied by a volume changes which... 

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