Titanium, Zirconium and Hafnium Carbides

Zirconium carbide also is a refractory compound [10]. The material has a melting point of 3450°C and is used as a coating for nuclear fuel particles such as Th02 and UO2 [10, 189, 190]. The compound is obtained by the CVD of a mixture of either ZrCU [189, 191] or ZrBr4 [190, 192] and methane (or propane) in the presence of hydrogen at 1000-1500 °C. 

Hafnium carbide has a melting point of 3890°C and exhibits extreme hardness and good electrical conductivity. It is used as an oxidation-resistant coating for composites and as a coating for superalloys [10]. The material is prepared by the CVD of a mixture of hafnium tetrachloride, methane and hydrogen [193, 194]. 

Vanadium carbide is employed as a wear- and corrosion-resistant coating.[10] It can be prepared by the CVD of a mixture of VCI4, methane and hydrogen at temperatures 

Niobium carbide is used as a protective coating for niobium metal.[10] It can be prepared by the reaction of elemental niobium metal with methane or by reacting NbCIs with CCI4 and H2. It also has been obtained from the arene complex Nb(CH3-C(,H, i)2 (21) by LPCVD [198] and from (MeCp)iNb(allyl) at 300 °C and ambient pressure [199]. 

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Carbides of Group IV Titanium, Zirconium, and Hafnium Carbides... 

The transition metal carbides and nitrides have often been called interstitial compounds [70] however, this is somewhat misleading. The small boron, carbon, or nitrogen atoms certainly occupy octahedral or trigonal prismatic voids of the metal sublattice, but the arrangement of the metal atoms themselves is different from that of the element. In the monocarbides the transition metal atoms show cubic close packing. However, titanium, zirconium, and hafnium are packed hexagonally and vanadium, niobium, and tantalum are body centered cubic [1]. Thus, these monocarbides are inorganic compounds with their individual crystal structures and they should not be considered as an interstitial compound of a transition metal host lattice. 

Kohl, F.L, Stearns, C.A. (1974) Vaporization and dissociation energies of the molecular carbides of titanium, zirconium, and hafnium. High Temperature Science, 6, 284-302. 

The nitrides and carbides of titanium and zirconium and the carbide of hafnium are extremely hard substances, resembling metals both in appearance and in electrical conductivity. Their formulae approach AxBh but some departure from stoichiometry is possible. Each of these refractory substances has the sodium chloride structure, described alternately (p. 190) as cubic close-packed arrays of metal atoms with the small nonmetal atoms in the octahedral holes. Note, however, that the parent metals themselves do not have cubic close-packed structures. Thus, the older view of such nitrides and carbides as lattices of the parent metals that are expanded to accommodate nitrogen or carbon atoms in the holes (interstices) is not admissible. The nature of the bonding in such refractory nitrides and carbides appears to be linked to the nature of bonding in metals in general, an important and interesting topic, but best pursued in more advanced works. 

Zirconium carbide, ZrC, and hafnium carbide, HfC, can be manufactured in a similar way to titanium carbide. They are not very important in cemented carbide technology. The recent strong reduction in the price of HfC has enabled its application as a substitute for the dearer tantalum carbide. 

The first carbonitride alloys based on Ti(C,N)—Ni—Mo were iatroduced ia 1970 foUowed by (Ti, Mo)(C,N)-based compositions having fine microstmctures that provided a balance of wear resistance and toughness (4). Continued research on the titanium carbonitride alloys, often called TiC—TiN cermets, ia the 1980s led to the developmeat of complex cermets having a variety of additives such as molybdeaum carbide(2 l) [12069-89-5] M02C, TaC, NbC, zirconium carbide [12020-14-3], ZrC, hafnium carbide [12069-85-1], HfC, WC, vanadium carbide [12070-10-9], VC, chromium carbide (3 2)... 

Other compounds have been deposited by fluidized-bed CVD including zirconium carbide (from ZrCl4 and a hydrocarbon), hafnium carbide (from HfC and methane or propylene), and titanium carbide (from TiCl3 and propylene). 

Of a series of powdered refractory compounds examined, only lanthanum hexa-boride, hafnium carbide, titanium carbide, zirconium carbide, magnesium nitride, zirconium nitride and tin(II) sulfide were dust explosion hazardous, the 2 latter being comparable with metal dusts. Individual entries are ... 

In this paper we review the results of our systematic work on the catalytic and adsorptive properties of transition metal carbides (titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, and iron). We focus our attention on the oxidation of hydrogen, carbon monoxide, ammonia, and the oxidative coupling of methane. The first two reactions are examples of complete (non-selective) oxidation, while the oxidation of ammonia simulates a selective oxidation process. The reaction of oxidative coupling of methane is being intensively explored at present as a means to produce higher hydrocarbons.5 10... 

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