Grain Boundary Engineering of Alumina Ceramics

Abstract

Oxygen permeability through alumina wafers was evaluated at high temperatures up to 1923 K to elucidate the mass-transfer mechanisms of polycrystalline alumina and serve as a model for protective alumina film formed on heat-resistant alloys. Oxygen permeation proceeded via grain boundary (GB) diffusion of oxygen from the higher oxygen partial pressure (P O2 ) surface side to the lower P O2 surface side, along with the simultaneous GB diffusion of aluminum in the opposite direction to maintain the Gibbs-Duhem relationship. Oxygen GB diffusion coefficients in the vicinity of the P O2 (hi) surface were lower than those of oxygen GB self-diffusion without an oxygen potential gradient (dµ O ). When dµ O was applied to the wafer, the oxygen and aluminum fluxes at the outflow side of the wafer were significantly larger than those at the inflow side. Ln (Y and Lu) and Hf segregation at the GBs selectively reduced the diffusivity of oxygen and aluminum, respectively. Thus, the mesoscopic arrangements of segregating dopants, which were selected by taking into consideration the behavior of the diffusion species and the role of dopants, enabled the alumina film to have enhanced oxygen shielding capability and structural stability at high temperatures. Furthermore, the GB diffusion data derived from the oxygen permeation experiments were compared to those for alumina scale formed by the so-called two-stage oxidation of alumina-forming alloys.