Main group element nitrides

IV. POLYMERIC ROUTES TO MAIN GROUP ELEMENT NITRIDES... 

Another main group element nitride with considerable hardness is aluminum nitride, AIN. It is important as a ceramic insulator with high thermal conductivity. It has the hexagonal wurtzite type structure (h-ZnS) [111]. In contrast to the high-pressure compound c-BN, it is prepared by various methods at ambient pressure [22,112]. 

Main-group elements X such as monovalent F, divalent O, and trivalent N are expected to form families of transition-metal compounds MX (M—F fluorides, M=0 oxides, M=N nitrides) that are analogous to the corresponding p-block compounds. In this section we wish to compare the geometries and NBO descriptors of transition-metal halides, oxides, and nitrides briefly with the isovalent hydrocarbon species (that is, we compare fluorides with hydrides or alkyls, oxides with alkylidenes, and nitrides with alkylidynes). However, these substitutions also bring in other important electronic variations whose effects will now be considered. 

For carbides and nitrides containing more than one transition metal, or a transition metal and another element, the compositions and structures are more varied and complex. Plate 1.3 shows examples where the secondary component is a metal or main group element. Figure 1.2 shows examples where one of the secondary components is an alkali or alkaline earth... 

Main group element analysis was carried out with a Perkin-Elmer CHN elemental analyzer, while molybdenum analysis was performed using atomic absorption spectroscopy. The content of Mo and O on the surface of the catalysts was obtained by X-ray photoelectron spectroscopy (XPS) using a Shimazu ESCA-850 spectrometer with monochromatic MgKa. Since Mo 3p3/2 spectra overlapped with the N Is spectra for the nitrided catalysts, the degree of nitriding (N IsfMo 3d ratio) had to be obtained from a combination of elemental analysis and XPS. 

The crystal structures adopted by the binary carbides and nitrides are similar to those found in noble metals. The resemblance is not coincidental, and has been explained using Engel-Brewer valence bond theory [5]. Briefly, the main group elements C and N increase the metal s effective s-p electron count, so that structures and chemical properties of the early transition metals resemble those of the Group 8 metals. This idea was first introduced by Levy and Boudart [6] who noted that tungsten carbide had platinum-like properties. 

Until now, polymeric routes to transition metal nitrides or carbides have not been as numerously reported in the literature as those of the main group elements. They have been developed in most cases to produce thin coatings on various substrates or fibers. 

All precursors are amorphous up to calcination temperatures of around 600°C. At higher temperatures, in most cases powders with extremely small crystallite sizes of around 20-40 nm are formed (Fig. 7). A further increase in calcination temperature promotes crystal growth. With aluminum nitride, a white powder with a low oxygen and carbon content is obtained [97]. Other main group element precursors exhibit fairly different behaviors Mg and Ca precursors yield metal cyanamide [99]. Calcination of the transition element precursors (Fig. 8) results in the formation of nitrides, carbonitrides, or carbides. For the titanium-containing precursors, TiN/TiC solid solutions can be obtained [96] the quantity of carbon strongly depends on the calcination atmosphere applied (argon, 31 wt% ammonia, 5.1 wt%). 

In both metal lattices and closo polyhedral metal clusters there are cavities present, whose dimensions are a function of the number of vertices, the shape of the polyhedral moiety, and the interatomic separation. Partial occupation of these sites within the metal lattice by main group elements results in the formation of interstitial alloys such as, for example, metal hydrides, carbides, and nitrides. Occupation of the cavity within a molecular metal cluster gives rise to interstitial clusters. Although close topological relationships are sometimes found between interstitial alloys and interstitial clusters, the greater degree of freedom of a molecular assembly of metals, in comparison to a three dimensional infinite array of metals, increases the possible number of interstitially lodged elements... 

Silicon-containing ceramics include the oxide materials, silica and the silicates the binary compounds of silicon with non-metals, principally silicon carbide and silicon nitride silicon oxynitride and the sialons main group and transition metal silicides, and, finally, elemental silicon itself. There is a vigorous research activity throughout the world on the preparation of all of these classes of solid silicon compounds by the newer preparative techniques. In this report, we will focus on silicon carbide and silicon nitride. 

Ternary nitrides have recently been extensively studied, because they may display a wider variety of useful properties compared to the binary nitrides. The majority of reported ternary nitrides contain an electropositive element along with a transition metal or main-group metal [245]. The electropositive element (e.g., Ca, Sr, Ba, Mg) is included to increase the stabUity of the nitride, via the inductive effect [246]. 

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