Metallic carbides

The mechanism of the Fischer-Tropsch reactions has been the object of much study (note Eqs. XVI11-55-XV111-57) and the subject of much controversy. Fischer and Tropsch proposed one whose essential feature was that of a metal carbide—patents have been issued on this basis. It is currently believed that a particular form of active adsorbed carbon atoms is involved, which is then methanated through a series of steps such as... 

Metal-carbide clusters are relevant to the fonnation of both endohedral fullerenes and carbon nanotubes [1351. There also exists a class of apparently stable metal-carbide cluster ions, = Ti, V, Cr, Zr and Hf), called... 

Duncan M A 1997 Synthesis and characterization of metal-carbide clusters in the gas phase J. duster Soi. 8 239... 

Hafnium dioxide is formed by ignition of hafnium metal, carbide, tetrachloride, sulfide, boride, nitride, or hydrous oxide. Commercial hafnium oxide, the product of the separation process for zirconium and hafnium, contains 97—99% hafnium oxide. Purer forms, up to 99.99%, are available. 

The reaction of finely ground ores and an excess of carbon at high temperatures produces a mixture of metal carbides. The reaction of pyrochlore and carbon starts at 950°C and proceeds vigorously. After being heated to 1800—2000°C, the cooled friable mixture is acid-leached leaving an insoluble residue of carbides of niobium, tantalum, and titanium. These may be dissolved in HF or may be chlorinated or burned to oxides for further processing. 

Niobium carbide is used as a component of hard metals, eg, mixtures of metal carbides that are cemented with cobalt, iron, and nickel. Along with tantalum carbide, niobium carbide is added to impart toughness and shock and erosion resistance. The spiraling rise in the price of tantalum has spurred the development of a hafnium carbide—niobium carbide substitute for tantalum carbide (68). These cemented carbides are used for tool bits, drill bits, shovel teeth, and other wear-resistant components turbine blades and as dies in high pressure apparatus (see Carbides). 

L. E. Toth, Transition Metal Carbides andlSHtrides, Academic Press, New York, 1971. 

As previously stated, uranium carbides are used as nuclear fuel (145). Two of the typical reactors fueled by uranium and mixed metal carbides are thermionic, which are continually being developed for space power and propulsion systems, and high temperature gas-cooled reactors (83,146,147). In order to be used as nuclear fuel, carbide microspheres are required. These microspheres have been fabricated by a carbothermic reduction of UO and elemental carbon to form UC (148,149). In addition to these uses, the carbides are also precursors for uranium nitride based fuels. 

Zirconium carbide is inert to most reagents but is dissolved by hydrofluoric acid solutions which also contain nitrate or peroxide ions, and by hot concentrated sulfuric acid. Zirconium carbide reacts exothermically with halogens above 250°C to form zirconium tetrahaHdes, and with oxidizers to zirconium dioxide in ak above 700°C. Zirconium carbide forms soHd solutions with other transition-metal carbides and most of the transition-metal... 

Metallic Carbides. This class of compounds comprises the interstitial carbides of the transition metals of Groups 4—6 (see Industrial,... 

Easily decomposed, volatile metal carbonyls have been used in metal deposition reactions where heating forms the metal and carbon monoxide. Other products such as metal carbides and carbon may also form, depending on the conditions. The commercially important Mond process depends on the thermal decomposition of Ni(CO)4 to form high purity nickel. In a typical vapor deposition process, a purified inert carrier gas is passed over a metal carbonyl containing the metal to be deposited. The carbonyl is volatilized, with or without heat, and carried over a heated substrate. The carbonyl is decomposed and the metal deposited on the substrate. A number of papers have appeared concerning vapor deposition techniques and uses (170—179). 

A similar case is the preparation of metal carbides from metal and carbon,... 

Carbides may also be prepared, either by dhect carburizing, as in the case of steel, in which a surface carbide film dissolves into the subsuate steel, or by refractoty metal carbide formation as in die cases when one of the refractory metal halides is mixed with methane in the plasma gas. 

When tire metal/carbide boundaiy moves away from tire free surface of the sample by an increment d, the flux balance at tlris interface reads... 

It is also important to point out that pure cobalt oxide, alone or finely dispersed in Si02 (i.e. Co-Si02, Co-Si02-l and Co-Si02-2 in Table 1), zeolite HY, fullerene (i.e. C q/C-,0 80/20) is at least as effective as the reduced oxides for the production of nanotubules in our experimental conditions. In fact, the catalysts studied in this work are also active if the hydrogenation step is not performed. This important point, is presently being investigated in our laboratory in order to elucidate the nature of the active catalyst (probably a metal carbide) for the production of nanotubules. 

Alkali-metal graphites are extremely reactive in air and may explode with water. In general, reactivity decreases with ease of ionization of M in the sequence Li > Na > K > Rb > Cs. Under controlled conditions H2O or ROH produce only H2, MOH and graphite, unlike the alkali-metal carbides M2C2 (p. 297) which produce hydrocarbons such as acetylene. In an important new reaction CgK has been found to react smoothly with transition metal salts in tetrahydrofuran at room temperature to give the corresponding transition metal lamellar compounds ... 

Carbon forms binary compounds with most elements those with metals are considered in this section whilst those with H, the halogens, O, and the chalcogens are discussed in subsequent sections. Alkali metal fullerides and encapsulated (endohedral) metallafullerenes have already been considered (pp. 285, 288 respectively) and met-allacarbohedrenes (metcars) will be dealt with later in this section (p. 300). Silicon carbide is discussed on p. 334. General methods of preparation of metal carbides are ... 

H. H. Johansen, Survey of Progress in Chemistry 8, 57-81 (1977). See also A. Cottrell, Chemical Bonding in Transition Metal Carbides, Inst, of Materials, London, 1995, 99 pp. 

---