A Model for Transitions in Oxidation Regimes of ZrB2
A mechanistic model that interprets the transition in oxidation behavior of zirconium diboride as the temperature is varied from 600°C to 2500°C is presented. Available thermodynamic data and literature data for vapor pressures, oxygen permeability in boria, and viscosity of boria were used to evaluate the model. Three regimes and the temperatures of transition between them were identified. In the intermediate temperature regime, viz., 1000°C to 1800°C, good correspondence was obtained between theory and experiments for weight gain, recession, and scale thickness as functions of temperature and oxygen partial pressure. In this regime, the rate-limiting step is the diffusion of dissolved oxygen through a film of liquid boria in capillaries at the base of the oxidation product. At lower temperatures, an external boria scale forms, but it was not found to contribute significantly to oxidation resistance. Comparison with literature data on recession is very good, but weight gain is predicted to be higher than experimentally observed unless flow of viscous boria is included. At higher temperatures, the boria is lost by evaporation, and the oxidation rate is limited by diffusion of molecular oxygen through the capillaries between nearly columnar blocks of the oxide MO2.; this regime is soon followed by a rapid acceleration of recession due to vaporization of the oxide MO2 itself.
Pierre Steinmetz, Ian G. Wright, Alain Galerie, Daniel Monceau and Stéphane Mathieu
T.A. Parthasarathy et al., "A Model for Transitions in Oxidation Regimes of ZrB2", Materials Science Forum, Vols. 595-598, pp. 823-832, 2008