Silicon carbide formation

Insertion of SiH2 into H—C and H—Si bonds of CH4 and SiH4, respectively, and H-abstraction are among the model reactions for silicon carbide formation that were... 

Gern, F.H. and Kochendoerfer, R., Liquid silicon infiltration description of infiltration dynamics and silicon carbide formation. Composites, 28A, 355-364, 1997. 

Allendore MD, Osterheld TH (1995) Modeling the gas-phase chemistry of silicon carbide formation. In Gallois BM, Lee WY, Pickering MA (eds) Chemical vapour deposition of refractory metals and ceramics III. Materials Research Society, Pittsburgh, PA, pp39 14... 

Sujirote K, Leangsuwan P (2003) Silicon carbide formation from pretreated rice husks. J Mater Sci 38 4739 744... 

The formation of silicon carbide, SiC (carborundum), is prevented by the addition of a little iron as much of the silicon is added to steel to increase its resistance to attack by acids, the presence of a trace of iron does not matter. (Addition of silicon to bronze is found to increase both the strength and the hardness of the bronze.) Silicon is also manufactured by the reaction between silicon tetrachloride and zinc at 1300 K and by the reduction of trichlorosilane with hydrogen. 

Metal dusting usually occurs in high carbon activity environments combined with a low oxygen partial pressure where carburisation and graphi-tisation occur. Usually pits develop which contain a mixture of carbon, carbides, oxide and metal (Fig. 7.52). Hochmann" proposed that dusting occurs as the result of metastable carbide formation in the high carbon activity gas mixture which subsequently breaks down into metal plus free carbon. The dependence of the corrosion resistance of these nickel alloys on the protective oxide him has been described accelerated or internal oxidation occurs only under conditions that either prevent the formation, or lead to the disruption, of this him. In many petrochemical applications the pO is too low to permit chromia formation (ethylene furnaces for example) so that additions of silicon" or aluminium are commonly made to alloys to improve carburisation resistance (Fig. 7.53). 

A trivalent hard chromium bath has recently been described . The bath contains potassium formate as a complexing agent, and thicknesses in excess of 20 m can be deposited. Hardnesses of up to l650Hy can be obtained by heat treatment at 700°C. The deposits contain 1.6-4.8% carbon, and the bath is suitable for the deposition of composite deposits containing diamond or silicon carbide powder. 

Soluble polysilane polymers can also be used as precursors to silicon carbide. The first such application, using (PhMeSi)n-(Me2Si)m copolymers ("Polysilastyrene"), was to strengthen silicon nitride ceramics. The Si3N4 ceramic body was soaked in polysilane and refired, leading to the formation of silicon carbide whiskers in the pore spaces and a consequent increase in strength. (U)... 

As these experiments indicate, polysilanes can in some cases be converted to silicon carbide directly, without the necessity for formation of polycarbosilane, fractionation, or oxidation. For example, polysilastyrene copolymers can be formed into films or fibers and then crosslinked by irradiation with UV light. The crosslinked polysilane forms silicon carbide when heated to 1100°C in vacuum. (1U This method can be used in a "printing" mode, if a film of polysilane is cast onto a ceramic or metal substrate, then... 

Alumina spheres polluted by carbon residues have been also reactivated by use of microwaves [33]. Their regeneration has been performed in a stream of air and in the presence of silicon carbide as an auxiliary microwave absorber. Microwave heat treatment led to full recovery of the catalyst in times varying from a half to a quarter of the conventional treatments. Regeneration of a commercial Ni catalyst (Ni/Al203) deactivated, presumably, by coke formation, by means of a flow of hydrogen or oxygen and water vapor under the action of microwave irradiation was, however, unsuccessful [34]. 

Apart from the reactions described above for the formation of thin films of metals and compounds by the use of a solid source of the material, a very important industrial application of vapour phase transport involves the preparation of gas mixtures at room temperature which are then submitted to thermal decomposition in a high temperature furnace to produce a thin film at this temperature. Many of the molecular species and reactions which were considered earlier are used in this procedure, and so the conclusions which were drawn regarding choice and optimal performance apply again. For example, instead of using a solid source to prepare refractory compounds, as in the case of silicon carbide discussed above, a similar reaction has been used to prepare titanium boride coatings on silicon carbide and hafnium diboride coatings on carbon by means of a gaseous input to the deposition furnace (Choy and Derby, 1993) (Shinavski and Diefendorf, 1993). 

Pyrolysis analogous to polymer carbon formation has also been applied to methylchlorodisilane. This is converted to beta silicon carbide fibers of high tenacity. 

Hoppe P, Ott U (1997) Mainstream silicon carbide grains from meteorites. In Astrophysical Implications of the Laboratory Study of Presolar Materials. Bematowicz TJ, Zinner E (eds) AlP, New York, p 27-59 Hsu W, Wasserburg GJ, Huss GR (2000) High time resolution by use of the Al chronometer in the multistage formation of CAL Earth Planet Sci Lett 182 15-29... 

As noted above, the range of fibers employed does not precisely overlap with those employed for organic composites. Because the formation of the MMCs generally requires melting of the metal-matrix, the fibers need to have some stability to relatively high temperatures. Such fibers include graphite, silicon carbide, boron, alumina-silica, and alumina fibers. Most of these are available as continuous and discontinuous fibers. It also includes a number of thin metal wires made from tungsten, titanium, molybdenum, and beryllium. 

A review article on the CVD processes used to form SiC and Si3N4 by one of the pioneers in this area, Erich Fitzer [Fitzer, E., and D. Hegen, Chemical vapor deposition of silicon carbide and silicon nitride—Chemistry s contribution to modem silicon ceramics, Angew. Chem. Int. Ed. Engl, 18, 295 (1979)], describes the reaction kinetics of the gas-phase formation of these two technical ceramics in various reactor arrangements (hot wall, cold... 

Silica is reduced to silicon at 1300—1400°C by hydrogen, carbon, and a variety of metallic elements. Gaseous silicon monoxide is also formed. At pressures of >40 MPa (400 atm), in the presence of aluminum and aluminum halides, silica can be converted to silane in high yields by reaction with hydrogen (15). Silicon itself is not hydrogenated under these conditions. The formation of silicon by reduction of silica with carbon is important in the technical preparation of the element and its alloys and in the preparation of silicon carbide in the electric furnace. Reduction with lithium and sodium occurs at 200—250°C, with the formation of metal oxide and silicate. At 800—900°C, silica is reduced by calcium, magnesium, and aluminum. Other metals reported to reduce silica to the element include manganese, iron, niobium, uranium, lanthanum, cerium, and neodymium (16). 

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