Stacking silicon carbides

On silicon carbide, it is easier to see and measure step heights than in crystals like beryl, because SiC has polytypes, first discovered by the German crystallog-rapher Baumhauer (1912). The crystal structure is built up of a succession of close-packed layers of identical structure, but stacked on top of each other in alternative ways (Figure 3.24). The simplest kind of SiC simply repeats steps ABCABC, etc., and the step height corresponds to three layers only. Many other stacking sequences... 

Flameholder - Flameholders are necessary to prevent the flame from "riding" up to the top of the stack. They provide a surface at which burning can take place and also promote better mixing of air and gas by the additional turbulence which they cause above the jets. Construction is simply a solid, 25 mm diameter rod of refractory material (silicon carbide) supported horizontally above each burner line. The bottom of the rod should be 13 mm above the tips of the jets. 

Other stacking sequences than these are also possible, for example AaBpAaCy... or statistical sequences without periodic order. More than 70 stacking varieties are known for silicon carbide, and together they are called a-SiC. Structures that can be considered as stacking variants are called polytypes. We deal with them further in the context of closest-sphere packings (Chapter 14). 

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. 

Subsequent preliminary comparative studies of the behavior of an SiC based layer on Ta, Mo, Ti and steel substrates showed that better mechanical stability was obtained with a coating deposited on tantalum. This element was consequently considered to make PFCVD deposit/interlayer/steel stacks. Tantalum can be produced by physical vapor deposition (PVD), at variable thickness, with reproducible morphology. Note that preparation by chemical vapor deposition with or without plasma assistance (CVD or PECVD) is possible at low temperature but would require an optimization study in order to be compatible with the deposition conditions of the silicon carbide layer, the aim being to increase the mechanical stability. 

Silicon carbide is remarkable for its unusually large variety of different morphologies, which differ in their stacking sequences of hexagonal and rhombohedral layers. All hexagonal and rhombohedral forms are often simply described as a-SiC. The commercially available SiC produced by the Acheson process is a-SiC. 

The sphere arrangements described are only two of an infinite number of ways for spheres to be stacked. It is surprising, for example, that the sequence ABAC is not commonly encountered in metal structures, although this is the structure of the metal lanthanum (La). In addition, a number of more complex arrangements have been found, especially in the compounds silicon carbide (SiC) and zinc sulphide (ZnS). 

The layer sequences can repeat themselves in the cycles ABC, ABC. .. (zinc blende, type 3C) or AB, AB. .. (wurtzite, type 2H), according to cubic or hexagonal close packing. In addition, numerous others stack sequences are formed in the case of silicon carbide, resulting in many similar polytypes. 

Silicon carbide is known to crystallize in several crystallographic modifications, all having the same a parameters (3.078 A) but different c parameters, known as polytypes. The structural reason for this phenomenon is a low stacking fault energy and the possibility to form different modes of stacking of two-dimensional, structural, compatible units along a definite direction. Some 200 polytypes of SiC are known to exist, but the most common are 3C,... 

Figurf 16.15. Making a silicon carbide laminate, (a) Silicon carbide powder, (b) twin roll mflled into poiyrmer. solution, (c) printed with graphite ink, (d) stacked and fired.

Carbon-carbon composites can be produced with a multitude of structures. The simplest have two-dimensional order and consist of stacked plies of carbon fabric held together by a carbon matrix. The fabric fibers may be any of those described previously, prepared from the pyrolysis of polyacrylonitrile and the like. The matrix could be derived from petroleum pitch or be infiltrated pyrolytic carbon or even silicon carbide. The latter are generally referred to as SiC/C composites. From two-dimensional, the next progression in structure is three-dimensional on to n-dimensional. This terminology refers to fiber orientation within the matrix. 

Silicon carbide exists in two crystallographically distinct modifications (i) hexagonal a-SiC, with a wurtzite-type lattice and a huge number of polytypic variants, depending on the stacking order of the Si-C lattice planes and (ii) cubic 3-SiC, with a zincblende-type lattice (a = 0.437nm). 

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