Abstract:
The rate of spinel (MgAl2O4) growth at the interface between MgO and Al2O3 was investigated systematically at temperatures of 1200° to ∼2000°C and pressures between 1.0 and 4.0 GPa with a solid-media, piston-cylinder apparatus. As reported in previous 1-atm studies, the thickness (ΔX) of the spinel layer increases linearly with the square root of time for experiments differing only in duration, irrespective of pressure–temperature (P-T) conditions. The reaction rate constant (k = ΔX2/2t) is log-linear in 1/T and also in pressure. The apparent activation energy of 410 kJ/mol is independent of pressure; the apparent activation volume increases systematically with increasing temperature. Electron microprobe traverses across the spinel layer reveal a significant Al excess and charge-compensating Mg deficit near the spinel/corundum interface. This nonstoichiometry is promoted by high temperatures (>1500°C), suppressed by high pressures and varies linearly across the spinel to a near-stoichiometric composition at the interface with periclase. The Al and Mg composition gradients can be used to extract interdiffusion coefficients for Al ↔ Mg exchange through the spinel, which are described by D̃=2.5×10−6 exp(−28200/T) m2sThese diffusivities differ substantially from the reaction rate constant k, reflecting the fact that k is a combination of the diffusivity and the reaction potential as indicated by the difference in spinel composition across the spinel layer (i.e., coexisting with corundum vs. coexisting with periclase). A simple model can be used to separate the two effects and show that the reaction potential (i.e., the MgO-Al2O3 phase diagram) is sensitive to changes in both temperature and pressure, whereas the governing diffusivity depends only on temperature.
