Transition metal nitrides binary compounds

Kumta and co-workers [20] have used a three-step sol-gel-based procedure to prepare ternary transition metal nitrides involving heat treatment under ammonia of a metal organic hydroxide precursor. This route consists in the hydrolysis of a polymeric liquid precursor to form a metal-organic hydroxide. Thermochemical decomposition of the metal-organic hydroxide precursor under ammonia leads to ternary nitrides such as NijMOjN, FeWN and Ti AIN. DiSalvo and co-workers incorporated alkaU metal ions to increase the stability of the nitrides compared to binary compounds. They used a sol-gel-based route to prepare ternary alkali and alkaline-earth metal nitrides such as NaTaN, KTaN and NaNbN [21, 22]. 

We note that the valence orbitals of metal atoms order in energy as AE>Ln>M. The d-levels of transition elements (M) range the lowest, and are therefore most sensitive for reduction, or to form a stable binary metal nitride. This may also explain the virtual absence of d-element compounds with 16 (valence) electron species, such as [N=N=N] , [N=C=N] , [N=B=N] T [C=C=CfT or [C=B=C] T at least through high-temperature syntheses. 

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. 

Hydrides of variable composition are not only formed with pure metals as solvents. A large number of the binary metal hydrides are non-stoichiometric compounds. Non-stoichiometric compounds are in general common for d,f and some p block metals in combination with soft anions such as sulfur, selenium and hydrogen, and also for somewhat harder anions like oxygen. Hard anions such as the halides, sulfates and nitrides form few non-stoichiometric compounds. Two factors are important the crystal structures must allow changes in composition, and the transition metal must have accessible oxidation states. These factors are partly related. FeO,... 

Because intermetallic systems undoubtedly display certain special features that follow from their metallic binding forces, considerable importance attached to the growing evidence that the chalcogenides, the essentially ionic oxides, the nitrides, and other representative binary compounds of the transition metals were, not infrequently, both variable and irrational in composition. Schenck and Ding-mann s equilibrium study of the iron-oxygen system (39) was notable in this connection They showed that stoichiometric ferrous oxide, FeOi 000, the oxide of an important and typical valence state, did not exist. It lay outside the broad existence field of a nonstoichiometric phase. It is, perhaps, still not certain... 

Ternary phases with structures different from those of the phases of the binary boundary systems are more the exception than the rule. Such phases have been reported in the systems Nb-Mo-N, Ta-Mo-N, Nb-Ta-N, Zr-V-N, Nb-Cr-N, and Ta-Cr-N. Information about ternary transition metal-nitrogen systems is often available for specific temperatmes only. This is even more the case for quaternary nitride systems, which play a role in the production of carbonitride cermets where quaternary compounds of the types (Ti,Mo)(C,N) and (Ti,W)(C,N) are of interest (see Carbides Transition Metal Solid-state Chemistry), as well as in layer technology where titanium nitride-based coatings of the type Ti(C,B,N) are prepared by magnetron sputtering. Layers consisting of ternary compounds of the type (Ti,Al)N and (Ti,V)N also have favorable properties with respect to abrasion resistance. 

The phenomenon of superconductivity is common in several particular types of compounds. Thus more than two dozen binary compounds with the fee sodium chloride (NaCl) stracture are superconducting. The carbides AC and nitrides AN, such as NbN with Tc = 17 K, have the highest transition temperatures of this group, and the metallic A atoms with values above 10 K were Nb, Mo, Ta, W, and Zr. The NaCl-type superconductors are compositionally stoichiometric but not structurally so. hi other words, these compounds have a small to moderate concentration of vacancies in the lattice. For example, YS has 10% vacancies, which means that its chemical formula should properly be written 0,980.9. Nonstoichiometric NaCl-type compounds such as Tai.oCo.ye also exist. Ordinarily the vacancies are random, but sometimes they are ordered. 

We comment elsewhere on the inadequacy of current bonding theory to account for the complexity of some binary systems in which solid phases appear with unexpected formulae and/or properties-for example, the oxides of caesium and the nitrides of calcium. Certain transition metals, notably Ti, V, Nb, Mo, and W, have a suprisingly complex oxide chemistry, and although it may be difficult to appreciate all the features of their structures from diagrams, these compounds are sufficiently important to justify mention here. 

By far the largest class of ternary lithium nitrides are those with the antifluorite structure, prepared largely by Juza, and reviewed by him [42], The ternaries are more thermally stable than the binaries which would seem to indicate a relaxation of the internal strain (both cation- cation and anion-anion repulsions) of binary nitrides. Many of these compounds are in fact ordered superstructures of antifluorite and it is remarkable that most of the transition metals are observed in high oxidation states--much higher than those in the binaries (e.g. Li7Mn + N4 vs Mn5 + N2). They are Li+ conductors at elevated... 

While most of the binary carbides and nitrides considered above form unlimited homogeneous solid solutions, some other 5 and p elements (B, Be, Al, Mg, etc.) have only a low solubility in these phases. As their content in carbides and nitrides increases, ternary compounds with very specific crystal structures are formed which were reviewed by Alyamovsky et al (1981) and Goldschmidt (1967). It is well known (see Samsonov, Serebryakov and Neronov (1975)) that B or transition metal borides do not form unlimited solid solutions, when interacting with MX phases (X = C, N) and single-phase TiNjBj, compounds exist over a narrow composition range for example, when z + y = 0.62-0.94, y < 0.03 (see Alyamovsky, Zainulin and Shveikin (1976)). As the B/N ratio increases. 

The large class of complex carbides and nitrides includes compounds of the A,By(C,N)j type, where A is a transition metal and B denotes a nontransition metal (Al, Ge, Mg, Zn, etc.). Interatomic interactions in these systems differ from those in the binary and multicomponent carbide and nitride alloys, which have been discussed above. This is reflected, first of all, in their crystallochemical properties, revealing the formation of a great number of individual phases (jt, x. 1, H, parivskite-like, and some other carbides and nitrides, see reviews of Goldschmidt (1967) and Jardin Table (1983)). 

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