Ignition of nickel in environments containing oxygen and chlorine

The mixed oxidation of nickel in gases containing both oxygen and chlorine has been investigated using the techniques of thermogravimetric analysis and examination of the corrosion products by scanning electron microscopy. Two regimes of corrosion behavior have been detected: one in which a protective oxide film is present and the rate of corrosion is controlled by the transport of the volatile products of the reaction between the gas phase and the oxide, and one in which the protective film is penetrated and corrosion occurs rapidly enough to result in the ignition of the specimen. The oxide corrosion products on the specimens after corrosion have characteristic morphologies, with the products of volatilization type corrosion consisting of large grains and the products of ignition type attack consisting of fine spherical particles. Ignition is a serious hazard in environments containing 0.25 pct or more Cl₂ and 4 pct or more O₂ by volume at temperatures between 1000 K and 1100 K, but is not produced by exposures at higher temperatures. A model based on the stability of the protective film in steady state corrosion is presented which can be used to predict the transition from volatilization to ignition type attack.     

Friction and wear of single-crystal silicon at elevated temperatures

Single-crystal silicon wafers ((1 1 1) and (1 0 0)p-type) were abraded at room temperature 300 °C, and 600 °C by a polycrystalline partially stabilized zirconia ball in a ball-on reciprocating flat geometry. The sliding direction was 1 1 0. The friction coefficient was recorded as a function of reciprocating strokes and the deformation mode of the silicon. The friction coefficient at room temperature decreased with the number of strokes, and this variation was less affected by the number of strokes at the higher temperatures. The wear track width and depth were measured at the three temperatures. Wear increases as the temperature is raised to 300 and 600 °C. Optical and scanning electron microscopy of the subsurface damage reveals that cracks are generated at RT and 300 °C and dislocations are produced at 600 °C. The change in deformation mode with temperature from brittle fracture to plastic deformation accounts for the differences in wear.     

Oxidation of Si-based ceramics in the presence of alkali halide vapors

Nonoxide silicon-based ceramics owe their oxidation resistance to the formation of a thin silica film that separates the ceramic from oxidizing environments. This silica film can be fluxed by alkali oxides to form low-melting alkali silicate corrosion products that do not provide protection. Alkali chlorides and other halides have sufficiently high vapor pressures that silica fluxing can occur without the formation of a condensed halide salt. The rates of oxidation of Si, SiC, and Si₃N₄ are influenced by the composition of gas mixtures containing these species.     

Active Corrosion of Sintered α-Silicon Carbide in Oxygen–Chlorine Gases at Elevated Temperatures

The active corrosion of sintered α-silicon carbide from heat exchanger tubes in the temperature range 900° to 1100°C in gas mixtures containing 2% Cl₂ by volume with additions of O₂ or H₂ has been investigated by thermogravimetric analysis and subsequent examination of the corrosion products. The presence of a small amount of oxygen accelerated rapid active corrosion in chlorine-containing gas mixtures, but the corrosion was suppressed by an active-to-passive transition when the concentration of oxygen in the gas mixture was too high. Low rates of attack were observed in the environments containing H₂ even when the chlorine potential was high. The concentration of oxygen necessary to produce the active-to-passive transition was found to vary from one material to another and may be related to the amount of excess carbon in the sintered silicon carbide.     

Kinetics of deoxidation of liquid copper by graphite particles during submerged injection

Liquid copper can be deoxidized by submerged injection of inert gas in the presence of graphite particles. This paper describes the results of experiments in which approximately 20 kg copper melts were deoxidized by injection of N₂, CO₂, and air in the presence of low sulfur graphite particles. The apparent kinetics of the deoxidation process are first order with respect to the concentration of dissolved oxygen, and the concentration of oxygen in the melt could be reduced to less than 10 ppm by weight after less than 30 minutes of injection. The kinetics are consistent with mixed rate control with both mass transfer and chemical reaction rate affecting the rate of deoxidation. In these experiments, the rate of deoxidation under a graphite covering was slower when particles were injected with the gas stream than when gas was injected alone, although this result may have been influenced by the small size of the melt. Y. W. Chang, formerly Graduate Student with the Department of Civil Engineering, Mechanics, and Metallurgy, University of Illinois at Chicago This paper is based on a presentation made in the T.B. King Memorial Symposium on “Physical Chemistry in Metals Processing” presented at the Annual Meeting of The Metallurgical Society, Denver, CO, February, 1987, under the auspices of the Physical Chemistry Committee and the PTD/ISS.     

Morphology of corrosion products formed on cobalt and nickel in argon-oxygen-chlorine mixtures at 1000 K

The morphology of corrosion products formed on cobalt and nickel in argonoxygen-chlorine mixtures at 1000 K have been examined using optical microscopy, scanning electron microscopy, and X-ray diffraction. The corrosion products formed under conditions where the oxides are thermodynamically stable consist of porous oxides containing little or no chlorine. This morphology is consistent with a corrosion mechanism involving vapor phase transport of volatile metal chlorides.     

Endothermic Reactions between Mullite and Silicon Carbide in an Argon Plasma Environment

Reactions between SiC and mullite in an Ar plasma were investigated using a model composite in which a free-standing CVD SiC coupon was imbedded in mullite cement. After treatment in a radio frequency (RF) plasma, the Si content of the mullite in contact with SiC was found to be less than that in the starting material, and deposits were found on the walls of the plasma chamber due to the reaction of mullite with SiC as follows: Al₆Si₂O₁₃( s )+ SiC( s )= 3Al₂O₃( s )+ 3SiO( g )+ CO( g ). This reaction, which is endothermic (1405 kJ/mol at 1500 K), absorbs thermal energy and consequently prevents the rapid sintering which is observed for single-phase mullite in similar environments. As a consequence, it is suggested that RF plasma sintering probably cannot be used to densify SiC-reinforced mullite-matrix composites because of the resulting energy consumption and damage to the SiC phase.     

Mass spectrometric observations of metal oxychlorides produced by oxidation-chlorination reactions

formerly Graduate Student, University of Illinois at Chicago, is with the Research Institute for Industrial Science and Technology, P.O. Box 135, Pohang, Korea.     

Surface tension of binary metal—surface active solute systems under conditions relevant to welding metallurgy

Since the fluid flow, heat transfer, and the resulting weld properties are significantly affected by interfacial tension driven flow, the variation of interfacial tension in dilute binary solutions is studied as a function of both composition and temperature. Entropy and enthalpy of adsorption of surface active components such as oxygen, sulfur, selenium, and tellurium in Fe-O, Fe-S, Fe-Se, Cu-O, Cu-S, Cu-Se, Cu-Te, Ag-O, and Sn-Te systems were calculated from the analysis of the published data on interfacial tension of these systems. For these calculations, a formalism based on the combination of Gibbs and Langmuir adsorption isotherms was used. Interfacial tensions in Cr-O, Co-S, and Ni-S systems, where the data are scarce, were predicted by using certain approximations. The computed values were found to be in reasonable agreement with the data available in the literature. Temperature coefficients of interfacial tensions were calculated for several binary systems. It was demonstrated that in dilute solutions, the temperature coefficient of interfacial tension is strongly influenced by the heat of adsorption which, in turn, is influenced by the difference in electronegativity between the solute and solvent ions.