Silicon carbide amorphization

A typical 20-MW, a-c furnace is fitted with three 45-in. (114.3-cm) prebaked amorphous carbon electrodes equdateraHy spaced, operating on a three-phase delta connection. The spacing of the electrodes is designed to provide a single reaction zone between the three electrodes. The furnace is rotated to give one revolution in two to four days or it may be oscillated only. Rotation of the furnace relative to the electrodes minimizes silicon carbide buildup in the furnace. 

Benzene, ethylene and acetylene were the predominate observed volatiles at 550 °C whilst methane was evolved from 650 °C to 875 °C. An amorphous SiCO material was obtained at 1200 °C and bond redistribution and carbothermic reduction occurred up to 1800 °C to give a ceramic material composed of substantial amounts of crystalline fi-silicon carbide. The preparation of bulk ceramic components from materials in the system... 

In some instances, subtle changes in the precursor architecture can change the composition and microstructure of the final pyrolysis product. For example, pyrolysis of —[MeHSiNH] — leads to amorphous, silicon carbide nitride (SiCN) solid solutions at >1000°C (see SiCN section). At ca 1500 °C, these material transform to SisN SiC nanocomposites, of interest because they undergo superplastic deformation20. In contrast, chemically identical but isostructural — [F SiNMe] — transforms to Si3N4/carbon nanocomposites on heating, as discussed in more detail below21. 

The product is a partially crystalline, partially amorphous mixture of SiC, C and Si02. The silicon carbide content was shown to be highest for gels with the lowest relative oxygen content.19... 

Some of the chondritic meteorites contain grains (including crystalline and amorphous silicates, diamonds, silicon carbide, graphite, metal oxides, and metal nitrides) that have been identified as presolar based on non-solar isotopic ratios (Zinner 1988 Anders Zinner 1993 Bematowicz et al. 2006), particularly for... 

The last quarter of the twentieth century saw tremendous advances in the processing of continuous, fine diameter ceramic fibers. Figure 6.4 provides a summary of some of the important synthetic ceramic fibers that are available commercially. We have included in Fig. 6.4 two elemental fibers, carbon and boron, while we have excluded the amorphous, silica-based glasses. Two main categories of synthetic ceramic fibers are oxide and nonoxides. A prime example of oxide fibers is alumina while that of nonoxide fibers is silicon carbide. An important subclass of oxide fibers are silica-based glass fibers and we devote a separate chapter to them because of their commercial importance (see chapter 7). There are also some borderline ceramic fibers such as the elemental boron and carbon fibers. Boron fiber is described in this chapter while carbon fiber is described separately, because of its commercial importance, in Chapter 8. 

Local vibrational modes between 2800 and 3150 cm (see Fig. 1) have been observed in a number of semiconductors such as amorphous silicon carbide, GaAs, ° and GaN. In these materials the vibrational modes are assigned to symmetric and antisymmetric stretching modes of CHx complexes with x = 1, 2, 3. Therefore, the vibrational modes located at 2854 cm-i, 2890 cm-i, 2918 cm-i, 2948 cm-i, and 2988 cm-i should be due to the... 

A completely amorphous structure was found by X-ray diffraction on fibers which were pyrolysed at temperatures up to 1300 °C. A crystallization starts around 1400 °C and nanocrystalline silicon carbide is formed with a crystallite size of about 2 nm. Compared to an uncured sample the crystallization is retarded. A significant crystallite growth occurs around 1500 °C connected with a decreasing of the fiber properties. The oxygen content of these SiC fibers is less than 1 wt. % found by neutron activation... 

The preparation, manufacture, and reactions of SiC have been discussed in detail in Gmelin, as have the electrical, mechanical, and other properties of both crystalline and amorphous of SiC. Silicon carbide results from the pyrolysis of a wide range of materials containing both silicon and carbon but it is manufactured on a large scale by the reduction of quartz in the presence of an excess of carbon (in the form of anthracite or coke), (Scheme 60), and more recently by the pyrolysis of polysilanes or polycarbosUanes (for a review, see Reference 291). Although it has a simple empirical formula, silicon carbide exists in at least 70 different crystalline forms based on either the hexagonal wurtzite (ZnS) structme a-SiC, or the cubic diamond (zinc blende) structme /3-SiC. The structmes differ in the way that the layers of atoms are stacked, with Si being fom-coordinate in all cases. 

Salinger (44) reported the successful conversion of methyltrichloro-silanes to silicon carbide in a 50-kW RF plasma torch. The liquid methyltrichlorosilanes were fed to the tail flame of various plasmas and the solid products were recovered in an acid-resistant bag filter. Up to 85% recovery of theoretical solid product was reported, which was subsequently heated at 500°C to remove elemental carbon. Under the best condition (20-25% vol. hydrogen in argon plasma at 36 kW), up to 70%o conversion to j3-SiC was obtained with ca. 10% conversion to amorphous SiC. Salinger suggested that the good crystallinity of the )3-SiC so obtained meant that the reaction occurred in a gas temperature range in which )3-SiC was the stable crystalline form (i.e., < 2300°C). 

Tris transaminates readily with ammonia or primary amines when catalyzed by carbon dioxide or strong organic acids. The polysilazane products range from discrete solid disilazanes, to liquid distillable oligomers, and to highly cross-linked infusible polymers. Some of these polysilazanes can be pyro-lyzed to amorphous silicon nitride or mixtures of silicon nitride and silicon carbide below 1550 or to crystalline ceramics above that temperature. 

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