The structures of plutonium(IV) and uranium(VI) ions with a series of N,N-dialkyl amides ligands with linear and branched alkyl chains were elucidated from single-crystal X-ray diffraction (XRD), extended X-ray absorption fine structure (EXAFS), and theoretical calculations. In the field of nuclear fuel reprocessing, N,N-dialkyl amides are alternative organic ligands to achieve the separation of uranium(VI) and plutonium(IV) from highly concentrated nitric acid solution. EXAFS analysis combined with XRD shows that the coordination structure of U(VI) is identical in the solution and in the solid state and is independent of the alkyl chain: two amide ligands and four bidentate nitrate ions coordinate the uranyl ion. With linear alkyl chain amides, Pu(IV) also adopt identical structures in the solid state and in solution with two amides and four bidentate nitrate ions. With branched alkyl chain amides, the coordination structure of Pu(IV) was more difficult to establish unambiguously from EXAFS. Density functional theory (DFT) calculations were consequently performed on a series of structures with different coordination modes. Structural parameters and Debye-Waller factors derived from the DFT calculations were used to compute EXAFS spectra without using fitting parameters. By using this methodology, it was possible to show that the branched alkyl chain amides form partly outer-sphere complexes with protonated ligands hydrogen bonded to nitrate ions.

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The preparation of Th1-xYxO2-x/2 ceramics, to be used as electrolyte in oxygen sensors for sodium-cooled nuclear reactors, was successfully undertaken from oxalate precursors. Such method was found to provide quantitative precipitation of the cations into Th1-xYx(C2O4)2.2H2O solid solutions up to x = 0.15 while a polyphase system was obtained for x = 0.22. The corresponding oxides were obtained through heat treatment in air at 500°C and characterized by the means of PXRD, SEM and statistical X-EDS measurements. The conditions for the densification of Th1-xYxO2-x/2 ceramics were further determined by dilatometry (T = 1575°C, t = 8 hours) resulting in densification rates up to 99%. Finally, a first estimation of the electric properties of the solids was undertaken by impedance spectroscopy. Electrical conductivity was found to increase linearly with the incorporation of Y 3+ content while the associated values of activation energy decreased, with a minimum value of 1.1 eV for Th0.85Y0.15O1.925.

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Highly reactive and nanosized Th1‐xYxO2‐x/2 or Ce0.8Ln0.2O1.9 mixed oxides were prepared through the initial precipitation of hydroxide precursors which were further dried under vacuum. Whatever the chemical system investigated, the characterization of the powdered samples evidenced a rapid aging process leading to hydrated oxides. The thermal behavior of these samples was further investigated and first showed a two‐step dehydration process, with the successive departure of adsorbed and constitutive water, both yielding a drastic drop of the powders’ reactivity (i.e. decrease of the specific surface area). Sintering experiments were then undertaken by starting directly from raw powders and revealed very rapid densification kinetics. Highly densified pellets (above 95 %TD) with a fine grain microstructure were obtained after only 1 hour of heat treatment at 1600 °C. This easy and versatile process of precipitation, that can be followed by direct densification of the powders, then appears as a promising option for the elaboration of homogenous ceramic electrolytes.

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