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The solid solubility of CaTiOGeO 4  with CaZrOGeO 4  and the structural phase transitions occurring in this solid solution as a function of temperature and composition were examined using in situ high temperature X-ray powder diffraction. Structural phase transitions were identified based on the determination of spontaneous strain. The transition P2 1 /a-A2/a, which is typical for titanite and CaTiOGeO 4 , was observed in samples with Zr concentrations up to 10%. The addition of Zr destabilizes the ordered P2 1 /a phase and T c  decreases accordingly. The aristotype structure of titanite in space group symmetry A2/a was observed for intermediate compounds. Compounds with high Zr contents exhibit a triclinically distorted titanite structure. Their structure was modeled in space group A1̄. The triclinic structure appears at Zr contents of about 70% with Tc close to ambient temperature. Further increase of the Zr content stabilizes the triclinic structure and leads to an increase of T c  up to T c  = 488 K in CaZrOGeO 4 .

Temperature and composition dependence of structural phase transitions in Ca(Ti x Zr 1-x )OGeO 4