Étude du système U-Sr-O par diffraction X à haute température

Abstract

High-temperature X-ray diffraction (293 [Formula: see text] T(K) [Formula: see text] 1773) is used to investigate the reaction between strontium monoxide and uranium dioxide under controlled atmosphere (105[Formula: see text] [Formula: see text] (Pa) [Formula: see text] 10-24), with lattice parameter measurements and composition estimates of the different uranates obtained. Thus, with a Sr/U = 1 sample, we successively observe the phases: (a) orthorhombic α-"SrUO4", whose reduction (3.67 [Formula: see text] O/U [Formula: see text] 3.62) is shown by a constant volume of the cell (V = 0.367 nm3) between 1173 et 1373 K; (b) rhombohedral β-"SrUO4", which shows a large composition variation between the metastable oxidized form (β-SrUO3.60) below 1108 K and the stable conjugate reduced form (β'-SrUO3.11) at whatever temperature; (c) "SrUO3" of constant composition (O/U [Formula: see text] 3) between 293 and 1533 K, then variable (O/U < 3) above 1533 K, with a probable second-order transformation (α-Pnma, β-Imma) for this distorted perovskite near 1073 K; (d) fluorite type U1-δSrδO2-δsolid solution for which a maximal account in SrO (δ [Formula: see text] 0.25) induces a 0.5 % thermal expansion parameter in comparison with UO2.00. A pseudo-binary "SrUO3"-"SrUO4" phase diagram is propounded. With a sample compound of Sr/U = 3, the monoclinic "Sr3UO6" perovskite is stable under [Formula: see text] [Formula: see text] 105Pa up to 1373 K. On the other hand, in reducing atmosphere ([Formula: see text] [Formula: see text] 10-19Pa), it becomes orthorhombic "Sr3UO5" with much greater lattice constants at every temperature.Key words: high-temperature X-ray diffraction, reactivity in metallic oxides, U-Sr-O system, nuclear fuels.