Effect of the sintering additive content on the protective passive oxidation behaviour of pressureless liquid-phase-sintered SiC

The long-term oxidation behaviour in air of pressureless liquid-phase-sintered SiC was investigated as a function of the sintering-additive content (a mixture of Y₂O₃ and Al₂O₃ in the 3:5 molar ratio) at oxidizing temperatures in the interval 1100–1300 °C. It is shown that oxidation under these mild conditions is always passive, and with formation of protective oxide scales. However, the oxidation kinetics cannot be described appropriately by the parabolic-rate law. Instead, due to the gradual crystallization of the oxide scales during oxidation, it is more complex, exhibiting two different stretches given respectively by the arctan- and parabolic-rate laws. Furthermore, it was found that the rate-limiting mechanism of the initial arctan oxidation is the outward diffusion of metal cations from the secondary intergranular phase into the oxide scale, with the activation energy of the oxidation being very high and decreasing from 545 to 432 kJ/mol with increasing sintering-additive content from 5 to 20 wt%. The rate-limiting mechanism of the subsequent parabolic oxidation is however the inward diffusion of oxygen through the multicomponent oxide scale, with the activation energy being lower than before and also decreasing from 345 to 205 kJ/mol as the sintering-additive content increases from 5 to 20 wt%. It is also shown that the oxidation resistance decreases with increasing sintering-additive content, but that while the decrease is moderate up to 10 wt%, it is very marked for greater contents.