Structural variation in Ca(Ti_xSi_1-x)O₃ perovskites (1>x>0.65) and the ordered phase Ca₂TiSiO₆

High pressure perovskites in the system CaTiO₃-CaSiO₃ in the composition range from 0 to 50% CaSiO₃ have been re-examined using powder x-ray diffraction, Raman spectroscopy, and transmission electron microscopy. In runs performed at 9 GPa and 1200 °C, a solid solution is obtained with compositions ranging from CaTiO₃ to near Ca(Ti_0.65Si.,_0.35)O₃, and with the orthorhombic distortion in the CaTiO₃ end-member diminishing to pseudocubic for Ca(Ti_0.65Si_0.35)O₃. Raman spectra show intensity changes and band broadening which are attributed to the reduction of orthorhombic character, but still indicate lower than cubic symmetry for the entire solid solution range. An ordered intermediate, Ca₂TiSiO₆, has been recovered from a run at 14 GPa at 1200 °C. The space group is Fm3m, with a=7.410(2) Å, and the compound has the double perovskite structure. In this structure, Si-rich octahedral sites and Ti-rich octahedral sites alternate along the three principal axes. Transmission electron microscopy confirms the presence of the Fm 3m ordered structure, and also documents the presence of lesser amounts of at least three other ordered perovskite structures which are not resolved in the x-ray data. These may account for extra features observed in the Raman spectrum which are inconsistent with mode assignments for the Fm3m phase. Non face-centered ordering schemes for these regions are suggested based on modeling of the HRTEM patterns.