Metal carbides oxidation

Motojima, S., Asakura, S., Kasemura, T., Takeuchi, S. and Iwanaga, H., Catalytic effects of metal carbides oxides and Ni single crystal on the vapor growth of micro-coiled carbon fibers, Carbon, 1996,34, (3), 289 296. 

The chemical properties of the residual solid products from metal carboxylate decomposition are largely controlled by the reactant cation present and may include one or more of the following metal, carbide, oxide or oxides, carbonate. 

Hafnium dioxide is formed by ignition of hafnium metal, carbide, tetrachloride, sulfide, boride, nitride, or hydrous oxide. Commercial hafnium oxide, the product of the separation process for zirconium and hafnium, contains 97—99% hafnium oxide. Purer forms, up to 99.99%, are available. 

Metal-Matrix Composites. A metal-matrix composite (MMC) is comprised of a metal ahoy, less than 50% by volume that is reinforced by one or more constituents with a significantly higher elastic modulus. Reinforcement materials include carbides, oxides, graphite, borides, intermetahics or even polymeric products. These materials can be used in the form of whiskers, continuous or discontinuous fibers, or particles. Matrices can be made from metal ahoys of Mg, Al, Ti, Cu, Ni or Fe. In addition, intermetahic compounds such as titanium and nickel aluminides, Ti Al and Ni Al, respectively, are also used as a matrix material (58,59). P/M MMC can be formed by a variety of full-density hot consolidation processes, including hot pressing, hot isostatic pressing, extmsion, or forging. 

The reaction of finely ground ores and an excess of carbon at high temperatures produces a mixture of metal carbides. The reaction of pyrochlore and carbon starts at 950°C and proceeds vigorously. After being heated to 1800—2000°C, the cooled friable mixture is acid-leached leaving an insoluble residue of carbides of niobium, tantalum, and titanium. These may be dissolved in HF or may be chlorinated or burned to oxides for further processing. 

Zirconium carbide is inert to most reagents but is dissolved by hydrofluoric acid solutions which also contain nitrate or peroxide ions, and by hot concentrated sulfuric acid. Zirconium carbide reacts exothermically with halogens above 250°C to form zirconium tetrahaHdes, and with oxidizers to zirconium dioxide in ak above 700°C. Zirconium carbide forms soHd solutions with other transition-metal carbides and most of the transition-metal... 

It is also important to point out that pure cobalt oxide, alone or finely dispersed in Si02 (i.e. Co-Si02, Co-Si02-l and Co-Si02-2 in Table 1), zeolite HY, fullerene (i.e. C q/C-,0 80/20) is at least as effective as the reduced oxides for the production of nanotubules in our experimental conditions. In fact, the catalysts studied in this work are also active if the hydrogenation step is not performed. This important point, is presently being investigated in our laboratory in order to elucidate the nature of the active catalyst (probably a metal carbide) for the production of nanotubules. 

Viable methods of producing the metals from oxide ores have to siumount two problems. In the first place, reduction with carbon is not possible because of the formation of intractable carbides (p. 299), and even reduction with Na, Ca or Mg is unlikely to remove all the oxygen. In addition, the metals are extremely reactive at high temperatures and, unless prepared in the absence of air, will certainly be contaminated with oxygen and nitrogen. 

Metal dusting usually occurs in high carbon activity environments combined with a low oxygen partial pressure where carburisation and graphi-tisation occur. Usually pits develop which contain a mixture of carbon, carbides, oxide and metal (Fig. 7.52). Hochmann" proposed that dusting occurs as the result of metastable carbide formation in the high carbon activity gas mixture which subsequently breaks down into metal plus free carbon. The dependence of the corrosion resistance of these nickel alloys on the protective oxide him has been described accelerated or internal oxidation occurs only under conditions that either prevent the formation, or lead to the disruption, of this him. In many petrochemical applications the pO is too low to permit chromia formation (ethylene furnaces for example) so that additions of silicon" or aluminium are commonly made to alloys to improve carburisation resistance (Fig. 7.53). 

Increased hardness and wear resistance may also be achieved by incorporating approximately 25-50% by volume of small non-metallic particles. These may be carbides, oxides, borides or nitrides, and hardness values up to 560 Hy have been reported. ... 

Chromium carbide has three phases Cr23Cg, Cr7C3, Cr3C2 (major). The latter phase is the one reviewed here. Chromium carbideis an important material because of its excellent resistance to corrosion. It is the most oxidation resistant of all metal carbides. Its characteristics and properties are summarized in Table 9.3. 

The number of oxides is large since most metallic elements form stable compounds with oxygen, either as single or mixed oxides. However, the CVD of many of these materials has yet to be investigated and generally this area of CVD has lagged behind the CVD of other ceramic materials, such as metals, carbides, or nitrides. The CVD of oxides has been slower to develop than other thin-film processes, particularly in optical applications where evaporation. 

Carbides oxidize readily although less rapidly than the nitrides but more so than the borides. Oxidation becomes more rapid going from the Group IV carbides (TiC, ZrC, HfC) to those of Group VI (Cr3C7, MoC, WC). In some cases, a protective film of the metal oxide is formed. Such is the case with SiC, as reviewed in Sec. 5.7 below. 

The application of ly transition metal carbides as effective substitutes for the more expensive noble metals in a variety of reactions has hem demonstrated in several studies [ 1 -2]. Conventional pr aration route via high temperature (>1200K) oxide carburization using methane is, however, poorly understood. This study deals with the synthesis of supported tungsten carbide nanoparticles via the relatively low-tempoatine propane carburization of the precursor metal sulphide, hi order to optimize the carbide catalyst propertira at the molecular level, we have undertaken a detailed examination of hotii solid-state carburization conditions and gas phase kinetics so as to understand the connectivity between plmse kinetic parametera and catalytically-important intrinsic attributes of the nanoparticle catalyst system. 

Perspectives for fabrication of improved oxygen electrodes at a low cost have been offered by non-noble, transition metal catalysts, although their intrinsic catalytic activity and stability are lower in comparison with those of Pt and Pt-alloys. The vast majority of these materials comprise (1) macrocyclic metal transition complexes of the N4-type having Fe or Co as the central metal ion, i.e., porphyrins, phthalocyanines, and tetraazaannulenes [6-8] (2) transition metal carbides, nitrides, and oxides (e.g., FeCjc, TaOjcNy, MnOx) and (3) transition metal chalcogenide cluster compounds based on Chevrel phases, and Ru-based cluster/amorphous systems that contain chalcogen elements, mostly selenium. 

It is now worthwhile to focus attention on the carbide-oxide reactions which may be identified as the specific variant of the carbothermy under pyrovacuum conditions for some metals. Such reactions can be represented as ... 

Metal oxides, metal sulfides, metal nitrides, metal carbides, metal borides, metal alloys, metallic glasses, molecular sieves, salts, acids... 

Leclercq, L., Almazouari, A., Dufour, M., and Leclercq, G. 1996. Carbide-oxide interactions in bulk and supported tungsten carbide catalysts for alcohol synthesis. In Chemistry of transition metal carbides and nitrides, ed. S. T. Oyama, 345-61. Glasgow Blackie. 

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