Hydrothermal method of preparation of actinide(IV) phosphate hydrogen phosphate hydrates and study of their conversion into actinide(IV) phosphate diphosphate solid solutions

Several compositions of Th2-x/2Anx/2IV(PO4)2(HPO4).H2O (An = U, Np, Pu) were prepared through hydrothermal precipitation from a mixture of nitric solutions containing cations and concentrated phosphoric acid. All the samples were fully characterized by X-ray diffraction, UV-vis, and infrared spectroscopies to check for the existence of thorium-actinide(IV) phosphate hydrogen-phosphate hydrates solid solutions. Such compounds were obtained as single phases, up to x = 4 for uranium, x = 2 for neptunium, and x ≤ 4 for plutonium, the cations being fully maintained in the tetravalent oxidation state. In a second step, the samples obtained after heating crystallized precursors at high temperature (1100 degrees C) were characterized. Single-phase thorium-actinide(IV) phosphate-diphosphate solid solutions were obtained up to x = 0.8 for Np(IV) and x = 1.6 for Pu(IV). For higher substitution rates, poly-phase systems composed by β-TAnPD, An2O(PO4)2, and/or α-AnP2O7 were formed. Finally, this hydrothermal route of preparation was applied successfully to the synthesis of an original phosphate-based compound incorporating simultaneously tetravalent uranium, neptunium and plutonium