Covalent diamond

Diamondlike Carbides. SiUcon and boron carbides form diamondlike carbides beryllium carbide, having a high degree of hardness, can also be iacluded. These materials have electrical resistivity ia the range of semiconductors (qv), and the bonding is largely covalent. Diamond itself may be considered a carbide of carbon because of its chemical stmeture, although its conductivity is low. 

Nitrogen forms binary compounds with almost all elements of the periodic table and for many elements several stoichiometries are observed, e.g. MnN, Mn Ns, Mn3N2, MniN, Mn4N and Mn tN (9.2 < jc < 25.3). Nitrides are frequently classified into 4 groups salt-like , covalent, diamond-like and metallic (or interstitial ). The remarks on p. 64 concerning the limitations of such classifications are relevant here. The two main methods of preparation are by direct reaction of the metal with Ni or NH3 (often at high temperatures) and the thermal decomposition of metal amides, e.g. ... 

Silicon and germanium as elemental substances are found only in the diamond-type form. The reluctance of Si and Ge to enter into pre-p bonding prohibits a graphite-type structure as a plausible allotrope. These are rather more reactive than diamond the weaker Si-Si and Ge-Ge bonds make disruption of the lattice kinetically easier. Tin occurs in both a metallic form (white tin) and a covalent (diamond-type) form the latter is slightly more stable at low temperatures. Lead forms only a metallic elemental substance. 

From this tabulation, it is obvious, that the (111) surface has the lowest surface free energy because it exhibits the smallest number of dangling bonds per unit area. This simple bond counting picture indicates correctly that the minimum energy surface of a covalent diamond structure crystal is the (111) surface and also the natural shape of a diamond crystal. The (111) plane is also the cleavage plane for C, Si, and Ge because the number of broken bonds is minimal as shown in Table 9.4. The dependence of the surface free energy with crystal orientation has... 

The wave function T i oo ( = 11 / = 0, w = 0) corresponds to a spherical electronic distribution around the nucleus and is an example of an s orbital. Solutions of other wave functions may be described in terms of p and d orbitals, atomic radii Half the closest distance of approach of atoms in the structure of the elements. This is easily defined for regular structures, e.g. close-packed metals, but is less easy to define in elements with irregular structures, e.g. As. The values may differ between allo-tropes (e.g. C-C 1 -54 A in diamond and 1 -42 A in planes of graphite). Atomic radii are very different from ionic and covalent radii. 

The group IV semiconductor materials are fourfold coordinated covalent solids from elements in column IV of tire periodic table. The elemental semiconductors are diamond, silicon and gennanium. They crystallize in tire diamond lattice. 

Boron nitride is chemically unreactive, and can be melted at 3000 K by heating under pressure. It is a covalent compound, but the lack of volatility is due to the formation of giant molecules as in graphite or diamond (p. 163). The bond B—N is isoelectronic with C—C. 

Pure carbon occurs naturally in two modifications, diamond and graphite. In both these forms the carbon atoms are linked by covalent bonds to give giant molecules (Figure S.2). 

The covalent compounds of graphite differ markedly from the crystal compounds. They are white or lightly colored electrical insulators, have Hi-defined formulas and occur in but one form, unlike the series typical of the crystal compounds. In the covalent compounds, the carbon network is deformed and the carbon atoms rearrange tetrahedraHy as in diamond. Often they are formed with explosive violence. 

Covalent bonding appears in its pure form in diamond, silicon and germanium - all materials with large moduli (that of diamond is the highest known). It is the dominant... 

Many of the most floppy polymers have half-melted in this way at room temperature. The temperature at which this happens is called the glass temperature, Tq, for the polymer. Some polymers, which have no cross-links, melt completely at temperatures above T, becoming viscous liquids. Others, containing cross-links, become leathery (like PVC) or rubbery (as polystyrene butadiene does). Some typical values for Tg are polymethylmethacrylate (PMMA, or perspex), 100°C polystyrene (PS), 90°C polyethylene (low-density form), -20°C natural rubber, -40°C. To summarise, above Tc. the polymer is leathery, rubbery or molten below, it is a true solid with a modulus of at least 2GNm . This behaviour is shown in Fig. 6.2 which also shows how the stiffness of polymers increases as the covalent cross-link density increases, towards the value for diamond (which is simply a polymer with 100% of its bonds cross-linked. Fig. 4.7). Stiff polymers, then, are possible the stiffest now available have moduli comparable with that of aluminium. 

The ultimate covalent ceramic is diamond, widely used where wear resistance or very great strength are needed the diamond stylus of a pick-up, or the diamond anvils of an ultra-high pressure press. Its structure, shown in Fig. 16.3(a), shows the 4 coordinated arrangement of the atoms within the cubic unit cell each atom is at the centre of a tetrahedron with its four bonds directed to the four corners of the tetrahedron. It is not a close-packed structure (atoms in close-packed structures have 12, not four, neighbours) so its density is low. 

Fig. 16.3. Covalent ceramics, (a) The diamond-cubic structure each atom bonds to four neighbours.

If the polymer is completely cross-linked (/= 1) then the modulus (Ej) is known it is that of diamond, 10 GPa. If it has no covalent bonds at all, then the modulus (E2) is that of a simple hydrocarbon like paraffin wax, and that, too, is known it is 1 GPa. 

The single-bond covalent radius of C can be taken as half the interatomic distance in diamond, i.e. r(C) = 77.2pm. The corresponding values for doubly-bonded and triply-bonded carbon atoms are usually taken to be 66.7 and 60.3 pm respectively though variations occur, depending on details of the bonding and the nature of the attached atom (see also p. 292). Despite these smaller perturbations the underlying trend is clear the covalent radius of the carbon atom becomes smaller the lower the coordination number and the higher the formal bond order. 

Several nonmetallic elements and metalloids have a network covalent structure. The most important of these is carbon, which has two different crystalline forms of the network covalent type. Both graphite and diamond have high melting points, above 3500°C. However, the bonding patterns in the two solids are quite different... 

In diamond, each carbon atom forms single bonds with four other carbon atoms arranged tetrahedrally around it The hybridization in diamond is sp3. The three-dimensional covalent bonding contributes to diamond s unusual hardness. Diamond is one of the hardest substances known it is used in cutting tools and quality grindstones (Figure 9.12). 

Solids with different structures, (a) Diamond, a network covalent solid, (b) Potassium dichromate. K2 2O7, an ionic solid, (c) Manganese, a metallic solid. 

Even though silicon is metallic in appearance, it is not generally classified as a metal. The electrical conductivity of silicon is so much less than that of ordinary metals it is called a semiconductor. Silicon is an example of a network solid (see Figure 20-1)—it has the same atomic arrangement that occurs in diamond. Each silicon atom is surrounded by, and covalently bonded to, four other silicon atoms. Thus, the silicon crystal can be regarded as one giant molecule. 

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