PRESSURE-INDUCED PHASE-TRANSITION AND PRESSURE-DEPENDENCE OF CRYSTAL-STRUCTURE IN LOW (ALPHA) AND CA/AL-DOPED CRISTOBALITE

The phase stability and atomic-level compression mechanisms for both SiO2 cristobalite, and for cristobalite partially stabilized by Ca/Al doping (Ca-x/2 Si2-xAlxO4), have been investigated. A phase transition to a lower symmetry phase, observed with in situ high-pressure energy-dispersive x-ray diffraction, occurs at about 1.2 GPa. Structure models of the low-pressure phase were obtained by Rietveld analysis of neutron powder-diffraction data from powdered samples contained in a gas pressure apparatus. These data were collected at pressures up to 0.6 GPa and at 298 and 60 K. The results suggest collapse of the corner-connected framework from rotations of the rigid SiO4 tetrahedra at high pressures and low temperatures as the dominant mechanism for the densification of both materials. Compared to pure SiO2 cristobalite at the same pressure and temperature, the Ca/Al-doped material has a larger unit-cell volume. It also has a larger Si-O-Si bending angle and a more expanded framework as evidenced by the smaller rotations of the rigid SiO4 tetrahedra. The rate of change of these parameters as a function of pressure and temperature is the same for both pure and Ca/Al-doped cristobalite. These observations are consistent with Ca occupying positions within the cavities formed by the (Si, Al)-O framework and bracing it against collapse.