Up to 0.15 formula unit (f.u.) of U4+ incorporated in the Zr site of zirconolite by firing CaUxZr(1−x)Ti2O7 compositions in argon at 1400°C allows retention of the 2M polytype. Further U4+ substitution for Zr, up to 0.4 f.u., produces the 4M polytype (containing ∼0.4 f.u. of U) plus the 2M polytype containing 0.15 f.u. of U. The pyrochlore structure (containing 0.6 f.u. of U) forms in conjunction with the 4M polytype at U contents of 0.4 f.u. up to 0.7 f.u. Higher U contents give the pyrochlore structure, but the solid‐state reactivity of even alkoxide‐based preparations becomes increasingly poor for x > ∼0.7 and hot pressing in graphite dies at ∼1250°C is necessary to achieve near single‐phase pyrochlore structures for x= 1. When samples of CaUxZr1−xTi2O7 stoichiometry (x= 0.1 and 0.2) are oxidized at 1400°C in air, diffuse reflectance spectroscopy (DRS) shows evidence for U5+ formation at the expense of U4+ via enhanced absorption bands, ∼50 nm in half‐width, near 970 and 1500 nm and correspondingly weakened absorption at 1150 and 1660 nm. Weight gains consistent with complete oxidation of U4+ to U5+ are observed when finely powdered argon‐fired samples with x= 0.1 and 0.4 are heated in air to 1200°C. Evidence for U valence states higher than +4 in both argon‐ and air‐heated materials containing charge compensators to encourage U5+ or U6+ formation was also derived from DRS (showing U5+ in particular), and XANES. DRS shows weak absorption bands attributable to U4+ in zirconolites containing ∼0.2 f.u. of U incorporated in the Ca site via Mg or Al substitutions in the Ti sites, with the spectrum being closely but not exactly similar to that attributed to U4+ in the Zr site. Zirconolite and pyrochlore compositions which are melted at 1500° or 1550°C in argon and furnace‐cooled yield broadly similar phase assemblages to the corresponding sintered materials, but there is evidence of incongruent melting in all materials.
Brannerite, UTi 2 O 6 , can be formed only under low oxygen pressures by dry ceramic processing techniques, but the substitution of ϳ0.2 and 0.3 formula units (fu) of Ca or Gd, respectively, for U allows the stabilization of the phase in air. The Ca/Gd in brannerite provides charge compensation for some U to exist in valence states >؉4, as found by X-ray absorption spectroscopy of the U L III -edge. The maximum solubilities of Ca and trivalent rare earths in the air-fired samples, 0.3 and 0.5 fu, respectively, correspond to U having an average valence of ؉5. Ca and Gd had maximum solubilities of 0.2 and 0.45 fu, respectively, in argon-fired samples. An absorption band at 1448 nm in both air-and Ar-fired U-brannerite doped with Ca and Gd was observed using diffuse-reflectance spectroscopy and attributed to an electronic transition of U 5؉ . A similar band was observed in an annealed natural brannerite, which contained Ca, rare earths, and Th, although the band was present at ϳ1520 nm in the unannealed, X-ray amorphous sample. In synthetic ThTi 2 O 6 (thorutite, having the brannerite structure), the solubility of Ca was undetectable and that of rare earths <0.1 fu. Other ionic substitutions in synthetic brannerites involved Hf, Pu, La, and Y for U, (Gd ؉ Nb) for U ؉ Ti, and Fe in the Ti site.
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