Influence of Sintering Conditions on the Structure and Redox Speciation of Homogeneous (U,Ce)O2+δ Ceramics: A Synchrotron Study.

Although uranium-cerium dioxides are frequently used as a surrogate material for (U,Pu)O2-δ nuclear fuels, there is currently no reliable data regarding the oxygen stoichiometry and redox speciation of the cations in such samples. In order to fill this gap, this manuscript details a synchrotron study of highly homogeneous (U,Ce)O2±Î´ sintered samples prepared by a wet-chemistry route. HERFD-XANES spectroscopy led to determining accurately the O/M ratios (with M = U + Ce). Under a reducing atmosphere (pO2 ≈ 6 × 10-29 atm at 650 °C), the oxides were found to be close to O/M = 2.00, while the O/M ratio varied with the sintering conditions under argon (pO2 ≈ 3 × 10-6 atm at 650 °C). They globally appeared to be hyperstoichiometric (i.e., O/M > 2.00) with the departure from the dioxide stoichiometry decreasing with both the cerium content in the sample and the sintering temperature. Nevertheless, such a deviation from the ideal O/M = 2.00 ratio was found to generate only moderate structural disorder from EXAFS data at the U-L3 edge as all the samples retained the fluorite-type structure of the UO2 and CeO2 parent compounds. The determination of accurate lattice parameters owing to S-PXRD measurements led to complementing the data reported in the literature by various authors. These data were consistent with an empirical relation linking the unit cell parameter, the chemical composition, and the O/M stoichiometry, showing that the latter can be evaluated simply within a ± 0.02 uncertainty.

Uranium removal from mining water using Cu substituted hydroxyapatite.

In this study, synthetic copper substituted hydroxyapatite (Cu-Hap), CuxCa10-x(PO4)6(OH)2 were prepared by co-precipitation method and were used as reactive materials in batch experiments to immobilize uranyl. The limit of incorporation of Cu into a single-phased Cu-Hap reached xCu ≤1.59. The synthetic Cu-Hap samples obtained with various Cu contents were contacted with synthetic uranyl doped solutions and with real mining waters showing various pH and chemical compositions. A fast and strong decrease of the uranium concentration was observed, followed by the establishment of an equilibrium after 1-4 days of contact with the solutions. Examination of the solid phase after uranium uptake was performed using a combination of techniques. Depending on the composition of the solution and the copper content of the Cu-Hap, various mechanisms of uranium removal were observed. Based on the experimental results and geochemical simulations, it appeared that the main interest for using Cu-Hap is to enlarge the domain of water compositions for which the precipitation of meta-torbernite, (H3O)0.4Cu0.8(UO2)2(PO4)2·7.6 H2O is the predominant mechanism associated to the uranium removal, especially for pH > 6.7 where carbonate uranium species are predominant.