Synthesis of Coffinite, USiO^sub 4^, and Structural Investigations of U^sub x^ Th^sub (1-x)^SiO^sub 4^ Solid Solutions

The miscibility behavior of the USiO^sub 4-^ThSiO^sub 4^ system was investigated. The end members and 10 solid solutions U^sub x^Th^sub (1-x)^SiO^sub 4^ with x = 0.12-0.92 were successfully synthesized, without formation of other secondary uranium or thorium phases. Lattice parameters of the solid solutions evidently follow Vegard's Law. Investigation of the local structure with EXAFS reveals small differences between the U and Th environment attributed to different atomic radii of the metal atoms but no implications for a miscibility gap. The data provided confirm complete miscibility for the system USiO^sub 4-^ThSiO^sub 4^. The structure of the end members was studied in detail with XRD and discussed with special regard to the oxygen positions and the often neglected Si-O bond length. USiO^sub 4^ could be obtained without UO^sub 2^ impurities and the lattice parameters derived from Rietveld refinement as c = 6.2606(3) A and α = 6.9841(3) A. The Si-O distance in USiO^sub 4^ appears to be 1.64 A, which is more reasonable than earlier reported values. [PUBLICATION ABSTRACT]