Process Development of Zirconolite Ceramics for Pu Disposition: Use of a CuO Sintering Aid

Abstract

Zirconolite-structured ceramics are candidate wasteform materials for the immobilisation of separated Pu. Due to the refractory properties of zirconolite and other titanates, removing residual porosity remains challenging in the final wasteform product when utilising a conventional solid state sintering route. Herein, we demonstrate that the addition of CuO as a sintering aid increases densification and promotes grain growth. Moreover, zirconolite phase formation was enhanced at lower process temperatures than typically required (≥1350 °C). CuO addition allowed an equivalent density to be reached using process temperatures of 250 °C lower than the undoped composition. At 150 °C lower than the undoped zirconolite, the addition of CuO resulted in a favourable microstructure and phase assemblage, as confirmed via X-ray diffraction and scanning electron microscopy. Secondary phases of CaTiO3 and Ca0.25Cu0.75TiO3 were observed at some processing temperatures, which may prove deleterious to wasteform performance. The use of a CuO sintering aid provides an avenue for the further development of the thermal processing of ceramic wasteform materials.