Microchemical and crystallographic characterisation of fluorite-based ceramic wasteforms

A number of possible options have been proposed for the encapsulation and immobilisation of long lived actinide (Act) fractions in nuclear waste. Ceramics offer superior durability against chemical migration and the ability to be tailored to accommodate a variety of different waste streams. Research on the fabrication of dense, durable crystalline matrices for the safe disposal of fissile plutonium is ongoing and this study reports quantitative chemical, structural and spectroscopic analysis on fluorite based host phases. Ceramics based on the fluorite structure are known to be able to incorporate a variety of actinides and in this work two candidate ceramic matrices were investigated: a pyrochlore, Gd2Zr1.60Ce0.20Hf0.20O7; and a zirconolite, (Ca0.90Gd0.10)(Zr0.50Ce0.20Hf0.20Gd0.10)Ti2O7. The chemical compositions of the two major phases observed in the 'zirconolite' sample were consistent with the 2M and 4M zirconolite polytypes and the presence of the 4M structure was confirmed by Electron Diffraction (ED). The major phase in the 'pyrochlore' ceramic was confirmed by ED to have the pyrochlore structure. Electron Energy Loss Spectroscopy (EELS) data indicated the presence of both Ce3+ and Ce4+ in all the samples. (author)