Handbook of SiC properties for fuel performance modeling

The processes of passive oxidation, deposit-induced corrosion, active oxidation, scale/substance interactions, and scale volatility are presently studied in the case of high-purity SiC and Si3N4 in pure oxygen, giving attention to such secondary elements in the ceramics as water and CO2 oxidants, combustion environment impurities, and thermal cycling. Deposit-induced corrosion is discussed for the cases of NaSO4 as well as vanadate and oxide-slag deposits; issues associated with the active-to-passive oxidation transition are noted.

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Corrosion of Silicon-Based Ceramics in Combustion Environments

The oxidation kinetics of CVD SiC were monitored by thermogravimetric analysis (TGA) in a 50% H2O/50% O2 gas mixture flowing at 4.4 cm/s for temperatures between 1200 and 1400 C. Paralinear weight change kinetics were observed as the water vapor oxidized the SiC and simultaneously volatilized the silica scale. The long-term degradation rate of SiC is determined by the volatility of the silica scale. Rapid SiC surface recession rates were estimated from these data for actual aircraft engine combustor conditions.

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Paralinear Oxidation of CVD SiC in Water Vapor

Fiber-reinforced ceramic composites achieve high toughness through distributed damage mechanisms. These mechanisms are dependent on matrix cracks deflecting into fiber/matrix interfacial debonding cracks. Oxidation resistance of the fiber coatings often used to enable crack deflection is an important limitation for long-term use in many applications. Research on alternative, mostly oxide, coatings for oxide and non-oxide composites is reviewed. Processing issues, such as fiber coatings and fiber strength degradation, are discussed. Mechanics work related to design of crack deflecting coatings is also reviewed, and implications on the design of coatings and of composite systems using alternative coatings are discussed. Potential topics for further research are identified.

Interface Design for Oxidation‐Resistant Ceramic Composites

A modified Deal Grove model for the oxidation of 4H-SiC is presented, which includes the removal of the carbon species. The model is applied to data on the oxidation rates for the (0001) Si, (0001) C, and (1120) a faces, which are performed in 1 atm dry oxygen and in the temperature range 950–1150 °C. Analysis within the model provides a physical explanation for the large crystal-face dependent oxidation rates observed.

Modified Deal Grove model for the thermal oxidation of silicon carbide

The oxidation kinetics of several single-crystal and polvcrystalline silicon carbide materials and single-crystal silicon in dry oxygen over the temperature range 1200° to 1500°C were fitted to the linear-parabolic model of Deal and Grove. The lower oxidation rates of silicon carbide compared to silicon can be rationalized by additional consumption of oxidant in oxidizing carbon to carbon dioxide. The (000J) Si face of the silicon carbide platelets exhibited lower parabolic oxidation rates than the (0001) C face, by a factor of 10 at 1200°C. Apparent activation energies increased from a value of ∼120 kJ/mol below 1400°C to a value of ∼300 kJ/mol above this temperature. The (0001) Si face exhibited this high activation energy over the entire temperature range. The controlled nucleation thermally deposited material exhibited the highest oxidation rates of the polycrystalline materials followed by the hot-pressed and sintered α-silicon carbides. In general, the oxidation rates of the polycrystalline materials were bracketed by the oxidation rates of the basal planes of the single-crystal materials. Higher impurity concentrations and higher density of nucleation sites led to a greater susceptibility to crystallization of the scale which significantly complicated the oxidation behaviors observed. When crystallization of the oxide scale occurred in the form of a layer of spherulitic cristobalite crystals, a retardation of the oxidation rates was observed. An accelerated oxidation behavior was found when this coherent layer was superseded by the formation of fine mullite crystals.

John A. Costello

Papers

Oxidation Kinetics of Silicon Carbide Crystals and Ceramics: I, In Dry Oxygen