The CaO-TiO2-ZrO2 System at 1200 °C and the Solubilities of Hf and Gd in Zirconolite

Abstract

AbstractPhase equilibria are established in the CaO-TiO2-ZrO2 system at 1200 °C, using X-ray diffraction and electron probe microanalysis. The existence of two previously reported ternary phases, zirconolite (CaZrTi2O7) and calzirtite (Ca2Zr5Ti2O16), is confirmed. Each of these phases exhibits a significant range of homogeneity between TiO2 and ZrO2 while maintaining a nearly constant concentration of CaO. The ternary solubilities of the constituent binary phases are found to be negligible, with the exceptions of the perovskites, which display mutual solubility of at least 22 mol.% and may in fact form a series of continuous solid solutions. The solubilities of Hf and Gd in zirconolite are also investigated. While Hf-bearing samples did not reach thermodynamic equilibrium under the experimental conditions employed, the existence of a Hf analog to zirconolite, CaHfTi2O7, is conclusively demonstrated. The phase is stable at the stoichiometric composition, and its lattice parameters are very close to those reported in the literature for stoichiometric zirconolite. A Gd-bearing sample of the composition Ca0.88Zr0.88Gd0.24Ti2O7 is found to be essentially single phase zirconolite, in agreement with previous investigations at higher temperatures.