The kinetics of incongruent reduction between sapphire and Mg-Al melts

Abstract

The kinetics of incongruent reduction between sapphire and oxygen-controlled Mg-Al melts was studied by measuring spinel-layer thickness, sample-weight change and sample-thickness change as a function of time at various temperatures. To eliminate the crucible contamination caused by impurities in commercial MgO crucibles, self-made high-purity MgO crucibles were achieved by gelcasting method, which is an attractive ceramic-forming technique for making high-purity ceramic parts. The oxygen-controlled alloys were obtained by the three-phase-equilibrium experiments at various temperatures. To avoid MgO formation, the oxygen-controlled alloys prepared at relatively lower temperatures were used for incongruent reaction at relatively higher temperatures. That is to say, the oxygen-controlled alloys prepared at 900°C, 1000°C, and 1100°C were used for spinel formation at 1000°C, 1100°C, and 1200°C, respectively. The experiments were conducted in a vertical furnace, and sapphire wafers were hung vertically in high-purity MgO crucibles so that the natural convection induced by the density change in the melt could be investigated. Experimental results obtained at 1000°C, 1100°C, and 1200°C showed that the spinel layer thickness on two kinds of sapphire wafers, namely {0001} and , followed orientation-independent parabolic kinetics, indicating the diffusion in spinel was one of the rate-limiting steps. In addition, the spinel layer thickness was not a function of position. The results of sample-thickness- change measurements also indicated that the effect of natural convection could be neglected. XPS, XRD, and TEM were also employed to characterize some samples in this study. Based on a simple model where the diffusion in spinel was the only rate-limiting step, the governing partial differential equations for diffusion and fluid dynamics were solved by the finite element method. The calculated theoretical parabolic constants at various temperatures were compared with these experimental results, and a good agreement was obtained. Some preliminary studies were also made on the morphologies of spinel particles at the nucleation stage. It was found that the triangular {111} faces of spinel particles were parallel to the surface of {0001} sapphire substrate. The product shape was consistent with the tetrahedron composed of {111} faces. The morphology of spinel particles on a sapphire substrate was more complicated in that the triangular {111} faces of spinel had to be inclined at a certain angle to the substrate in order to maintain the orientation relationship.