Carbon alloy crystal chemistry

Remarks on the alloy crystal chemistry of the 14th group elements. Carbides. Among the elements of the 14th group, the chemical behaviour of carbon is peculiar. It may be useful to dedicate a few particular comments to its combinations with the metals. 

In this entry, the principal chemical features of defect populations (defect chemistry) will be described from the restricted viewpoint of crystalline inorganic solids. The influence of defects upon mechanical properties will be excluded and defects that may have greatest relevance to physical properties will be treated from the point of view of chemical importance. Defects in molecular crystals and amorphous and glassy solids will be omitted see Noncrystalline Solids), as will the important areas of alloys see Alloys), thin films see Thin Film Synthesis of Solids), and carbon nanotubes and related nanoparticles see Carbon Fullerenes). References to the literature before 1994 are to be found in the corresponding article in the first edition of this Encyclopedia. ... 

Although the silicon atom has the same outer electronic structure as carbon its chemistry shows very little resemblance to that of carbon. It is true that elementary silicon has the same crystal structure as one of the forms of carbon (diamond) and that some of its simpler compounds have formulae like those of carbon compounds, but there is seldom much similarity in chemical or physical properties. Since it is more electro-positive than carbon it forms compounds with many metals which have typical alloy structures (see the silicides, p. 789) and some of these have the same structures as the corresponding borides. In fact, silicon in many ways resembles boron more closely than carbon, though the formulae of the compounds are usually quite different. Some of these resemblances are mentioned at the beginning of the next chapter. Silicides have few properties in common with carbides but many with borides, for example, the formation of extended networks of linked Si (B) atoms, though on the other hand few silicides are actually isostructural with borides because Si is appreciably larger than B and does not form some of the polyhedral complexes which are peculiar to boron and are one of the least understood features of boron chemistry. 

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