Carbide decompositions

Carbide decompositions yield no volatile product and, therefore, many of the more convenient experimental techniques based on gas evolution or mass change cannot be applied. This is a probable reason for the relative lack of information about the kinetics of reaction of these and other compounds which are correctly classifed under this heading, such as borides, silicides, etc. 

Few detailed studies of the kinetics and mechanisms of carbide decompositions have been reported. The absence of a volatile product increases the experimental difficulties. 

From the above comparisons it is evident that both structure and composition of the anion may influence the mechanism of decomposition of nickel carboxylates. The crystal structure of the reactant can probably be discounted as a rate controlling parameter because dehydration usually yields amorphous materials. Depending on temperature, carbon deposited on the surface of a germ metallic nucleus may effectively prevent or inhibit growth, it may be accommodated in the structure to yield carbide, or be deposited elsewhere (by carbide decomposition). These mechanistic interpretations are based on the relative reactivities of the nickel salt and of nickel carbide, for which the temperature of decomposition is known, 570 K [150]. 

HAZARD RISK Flammable reaction with water forms explosive acetylene gas fire risk with moisture or combined with calcium carbide decomposition emits toxic fumes of NOx and CN NFPA code not available. 

HAZARD RISK Ignites on contact with fluorine, hexalithium disilicide, metal acety-lides and carbides decomposition emits toxic vapors of chlorine gas attacks many metals to form toxic fumes NFPA Code H 3 F 0 R 1. 

Sht2] Shtansky, D.V., Inden, G., Phase Transformation in Fe-Mo-C and Fe-W-C Steels. II. Eutec-toid Reaction of M23C6 Carbide Decomposition during Austenization , Acta Mater, 45(7), 2879-2895 (1997) (Crys. Stracture, Morphology, Phase Relations, Thermodyn., Caleula-tion. Experimental, Transport Phenomena, 26)... 

Does not show a clear boiling point. Starts carbide decomposition at 150°C. 

Ucon HTF-500. Union Carbide Corp. manufactures Ucon HTE-500, a polyalkylene glycol suitable for Hquid-phase heat transfer. The fluid exhibits good thermal stabHity in the recommended temperature range and is inhibited against oxidation. The products of decomposition are soluble and viscosity increases as decomposition proceeds. The vapor pressure of the fluid is negligible and it is not feasible to recover the used fluid by distiHation. Also, because the degradation products are soluble in the fluid, it is not possible to remove them by filtration any spent fluid usuaHy must be burned as fuel or discarded. The fluid is soluble in water. 

H. G. Pisher and D. D. Goetz, Determination of S elf Accelerating Decomposition Temperatures (SADTSJ Using the Accelerating Bute Calorimeter (ABC), AlChE Meeting, Nov. 11—16, Urdon Carbide Chemicals and Plastics Co., Inc., S. Charleston, W. Va., 1990 M. W. Whitmore and J. K. 

Newer high velocity thermal spray coating processes produce coatings in compression rather than tension because of the shot peening effect of the supersonic particles on impact. This has permitted coating as thick as 12,500 p.m without delamination as compared to older processes limited to 1,250 p.m. The reduced residence time of particles at temperature minimises decomposition of carbides present in conventional d-c plasma. This improves wear and hardness (qv) properties. 

Beryllium Nitride. BeryUium nitride [1304-54-7], Be N2, is prepared by the reaction of metaUic beryUium and ammonia gas at 1100°C. It is a white crystalline material melting at 2200°C with decomposition. The sublimation rate becomes appreciable in a vacuum at 2000°C. Be2N2 is rapidly oxidized by air at 600°C and like the carbide is hydrolyzed by moisture. The oxide forms on beryllium metal in air at elevated temperatures, but in the absence of oxygen, beryllium reacts with nitrogen to form the nitride. When hot pressing mixtures of beryUium nitride and sUicon nitride, Si N, at 1700°C, beryllium sUicon nitride [12265-44-0], BeSiN2, is obtained. BeSiN2 may have appHcation as a ceramic material. 

Boron carbide is resistant to most acids but is rapidly attacked by molten alkalies. It may be melted without decomposition in an atmosphere of carbon monoxide, but is slowly etched by hydrogen at 1200°C. It withstands metallic sodium fairly well at 500°C and steam at 300°C (8). 

Easily decomposed, volatile metal carbonyls have been used in metal deposition reactions where heating forms the metal and carbon monoxide. Other products such as metal carbides and carbon may also form, depending on the conditions. The commercially important Mond process depends on the thermal decomposition of Ni(CO)4 to form high purity nickel. In a typical vapor deposition process, a purified inert carrier gas is passed over a metal carbonyl containing the metal to be deposited. The carbonyl is volatilized, with or without heat, and carried over a heated substrate. The carbonyl is decomposed and the metal deposited on the substrate. A number of papers have appeared concerning vapor deposition techniques and uses (170—179). 

Vapor-Phase Techniques. Vapor-phase powder synthesis teclmiques, including vapor condensation, vapor decomposition, and vapor—vapor, vapor—Hquid, and vapor—soHd reactions, employ reactive vapors or gases to produce high purity, ultrafine, reactive ceramic powders. Many nonoxide powders, eg, nitrides and carbides, for advanced ceramics are prepared by vapor-phase synthesis. 

Vapor decomposition (14,15) iavolves dryiag, decomposiag, and vaporising a spray of salt precursor solution ia a plasma, and subsequentiy nucleating and growing ceramic particles ia the vapor. Silicon carbide [12504-67-5] SiC, powder is produced by this method. 

Commercial interest in poly(vinyl chloride) was revealed in a number of patents independently filed in 1928 by the Carbide and Carbon Chemical Corporaration, Du Pont and IG Farben. In each case the patents dealt with vinyl chloride-vinyl acetate copolymers. This was because the homopolymer could only be processed in the melt state at temperatures where high decomposition rates occurred. In comparison the copolymers, which could be processed at much lower temperatures, were less affected by processing operations. 

---