Transformations of the stuffed cristobalites, K2MSiO4, M=Mg, Zn, Co, Cd, with temperature and composition

The effects of composition and of temperature on the orthorhombic, Pca2 ₁ to cubic, F4ˉ3m transition of the stuffed cristobalite structure are reported. A distorton index which measures the departure of the orthorhombic unit cell from a metrically cubic cell shows that at room temperature, distortion increases in the progression K₂CdSiO₄ <K₂MgSiO₄ <K₂ZnSiO₄≈K₂CoSiO₄. High temperature X-ray powder measurements document an apparently discontinuous transition to a structure of F4ˉ3m symmetry. Differential scanning calorimetry shows a sharp, reversible, first order transition to the high temperature phase at about 500–600 °C for these compounds. Measured transformation enthalpies in the range of 7 to 16 J/g correlate roughly with the distortion index. The transformation involves tetrahedral rotation to an orientationally disordered cubic structure which retains an ordered M²⁺/Si distribution. Received: 8 November 1996 / Revised, accepted: 14 October 1997