Phase transformations in hypereutectic MgO-Y2O3 nanocomposites at 5.5 GPa.

Hypereutectic 0.8MgO-0.2Y2O3 nanocomposites were studied using high pressure and high temperature in situ synchrotron energy dispersive x-ray diffractometry at 5.5 GPa and 1273 K. Polymorphic transformations in the Y2O3 phase, which resulted in a quadruple phase equilibria among cubic, hexagonal, and monoclinic phases with cubic MgO, were observed at 298 K under 5.5 GPa-a pressure much smaller than the pressures at which polymorphic transitions in macroscopic Y2O3. Time-resolved diffractometry at (1273 K, 5.5 GPa, 120 min) revealed a 0.87% expansive volumetric lattice strain in MgO, and is attributed to solid solution formation with Y2O3 which is otherwise absent at ambient conditions. The residual MgO unit cell volume expansion is 0.69% at 298 K, which is indicative that yttrium remained in solid solution. The macroscopic shrinkage due to densification at (1273 K, 5.5 GPa, 120 min) is 3.45% by volume. The partial molar volume of Y3+ in the solid solution is smaller than its molar volume in the pure state per thermodynamic considerations. The importance of repulsion among O2- ions in the immediate vicinity of a Mg2+ vacancy as well as misfit strain due to differences in ionic radii upon Y3+ substitution on Mg2+ sites is presented. A self-consistent model and explanation for the observed concomitant occurrence of cubic → monoclinic and cubic → hexagonal polymorphic transitions in Y2O3 and their stabilization at room temperature is proposed. [ABSTRACT FROM AUTHOR]