Nitridation, direct

Yoo C S, Akella J, Nicol M and Cynn H 1997 Direct elementary synthesis of hexagonal and cubic boron nitrides at high pressures and temperatures Phys. Rev. B 56 140... 

Lithium Nitride. Lithium nitride [26134-62-3], Li N, is prepared from the strongly exothermic direct reaction of lithium and nitrogen. The reaction proceeds to completion even when the temperature is kept below the melting point of lithium metal. The lithium ion is extremely mobile in the hexagonal lattice resulting in one of the highest known soHd ionic conductivities. Lithium nitride in combination with other compounds is used as a catalyst for the conversion of hexagonal boron nitride to the cubic form. The properties of lithium nitride have been extensively reviewed (66). 

Tantalum Nitrides. Tantalum nitride [12033-62-4] TaN, is produced by direct synthesis of the elements at 1100°C. Very pure TaN has been produced by spontaneous reaction of lithium amide, L1NH2, and TaCl ( )- The compound is often added to cermets in 3—18 wt %. Ta N [12033-94-2] is used as a red pigment in plastics and paints (78). 

Plasmas can be used in CVD reactors to activate and partially decompose the precursor species and perhaps form new chemical species. This allows deposition at a temperature lower than thermal CVD. The process is called plasma-enhanced CVD (PECVD) (12). The plasmas are generated by direct-current, radio-frequency (r-f), or electron-cyclotron-resonance (ECR) techniques. Eigure 15 shows a parallel-plate CVD reactor that uses r-f power to generate the plasma. This type of PECVD reactor is in common use in the semiconductor industry to deposit siUcon nitride, Si N and glass (PSG) encapsulating layers a few micrometers-thick at deposition rates of 5—100 nm /min. 

Derivatives such as borides, carbides, nitrides, and hydrides are best prepared by direct reaction between the elements. These metaHoid-type compounds, which often show variable composition, are colored and sometimes semiconducting. 

Industrial uses make up most of the market for cyanamide. Calcium cyanamide is used directly for steel nitridation (34) and to some extent for desulfurization (36) (see Steel). Cyanamide is used to produce cationic starch (36) and calcium cyanide. Cyanamide is, of course, the raw material for dicyandiamide and melamine. New uses include intermediates for pesticides, detergents (37), medicines such as antihistamines, hypertension, sedatives, contraceptives, etc (38), the photography industry (39), as an additive for fuels and lubricants, as a paper preservative, and as a cement additive. 

Deuterioammonia (about 5 ml) is generated by adding deuterium oxide (14 ml) to a stirred suspension of magnesium nitride (20 g) in mineral oil (30 ml). Tlie deuterioammonia is collected directly in the reaction flask (equipped with a dry ice condenser) at —79° after passing through a trap which is kept at 0°. 

The heavier alkaline earth metals Ca, Sr, Ba (and Ra) react even more readily with non-metals, and again the direct formation of nitrides M3N2 is notable. Other products are similar though the hydrides are more stable (p. 65) and the carbides less stable than for Be and Mg. There is also a tendency, previously noted for the alkali metals (p. 84), to form peroxides MO2 of increasing stability in addition to the normal oxides MO. Calcium, Sr and Ba dissolve in liquid NH3 to give deep blue-black solutions from which lustrous, coppery, ammoniates M(NH3)g can be recovered on evaporation these ammoniates gradually decompose to the corresponding amides, especially in the presence of catalysts ... 

The most important nitride of Si is Si3N4 this is formed by direct reaction of the elements above 1300 or more economically by heating Si02 and coke in a stream of N2/H2 at 1500". The compound is of considerable interest as an engineering material since it is almost completely inert chemically, and retains its strength, shape and resistance to corrosion and wear even above 1000°. ° Its great hardness (Mohs 9), high... 

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. ... 

Industrial use of HCl gas for the manufacture of inorganic chemicals includes the preparation of anhydrous NH4CI by direct reaction with NH3 and the synthesis of anhydrous metal chlorides by reaction with appropriate carbides, nitrides, oxides or even the free metals themselves, e,g, ... 

There have been few satisfactory demonstrations that decompositions of hydrides, carbides and nitrides proceed by interface reactions, i.e. either nucleation and growth or contracting volume mechanisms. Kinetic studies have not usually been supplemented by microscopic observations and this approach is not easily applied to carbides, where the product is not volatile. The existence of a sigmoid a—time relation is not, by itself, a proof of the occurrence of a nucleation and growth process since an initial slow, or very slow, process may represent the generation of an active surface, e.g. poison removal, or the production of an equilibrium concentration of adsorbed intermediate. The reactions included below are, therefore, tentative classifications based on kinetic indications of interface-type processes, though in most instances this mechanistic interpretation would benefit from more direct experimental support. 

All alkali metals react directly with almost all nonmetals except the noble gases. However, only lithium reacts with nitrogen, which it reduces to the nitride ion ... 

FIGURE 14.27 (a) The structure of hexagonal boron nitride, BN, resembles that of graphite, consisting of flat planes of hexagons of alternating B and N atoms (in place of C atoms but, as shown for two adjacent layers in part (b), the planes are stacked differently, with each B atom directly over an N atom and vice-versa (compare with Fig. 14.29). Note that (to make them distinguishable) the B atoms in the top layer are red and the N atoms blue. 

In Fig. 14.27 we see that the planes in hexagonal boron nitride take positions in which the B atoms are located directly over N atoms, whereas in graphite (Fig. 14.29 ), the carbon atoms are offset. Explain this difference in structure between the two substances. 

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