Solid state synthesis and X-ray diffraction characterization of Pu 3+(1-2x)Pu4+xCa2+xPO4

In the framework of the 1991 French law concerning nuclear waste management, several studies have been carried out in order to elaborate crystalline matrices for specific immobilization of the radionuclides. In the case of high level and long-lived minor actinides (Np, Am and Cm), which are high level and long-lived radioactive elements, monazite, a light rare earth (Re) orthophosphate with general formula Re3+PO4 (with Re = La to Gd), has been proposed as a host matrix, thanks to its high resistance to self irradiation and its low solubility. Monazite crystallizes in the monoclinic space group P21/n. In this structure, trivalent cations (Re3+) could be substituted by an equivalent amount of bivalent (A2+) and tetravalent (B4+) cations, allowing the simultaneous incorporation of Am3+, Cm3+ and Np4+. According to Podor's work1, the limit of a tetravalent element incorporation in monazite is related to its size in the ninefold coordination (RIX)

Solid-State Synthesis of Monazite-type Compounds Containing Tetravalent Elements

International audienceOn the basis of optimized grinding/heating cycles developed for several phosphate-based ceramics, the preparation of brabantite and then monazite/brabantite solid solutions loaded with tetravalent thorium, uranium, and cerium (as a plutonium surrogate) was examined versus the heating temperature. The chemical reactions and transformations occurring when heating the initial mixtures of AnO2/CeO2, CaHPO4·2H2O (or CaO), and NH4H2PO4 were identified through X-ray diffraction (XRD) and thermogravimetric/differential thermal analysis experiments. The incorporation of thorium, which presents only one stabilized oxidation state, occurs at 1100 °C. At this temperature, all the thorium−brabantite samples appear to be pure and single phase as suggested by XRD, electron probe microanalyses, and μ-Raman spectroscopy. By the same method, tetravalent uranium can be also stabilized in uranium−brabantite, i.e., Ca0.5U0.5PO4, after heating at 1200 °C. Both brabantites, Ca0.5Th0.5PO4 and Ca0.5U0.5PO4, begin to decompose when increasing the temperature to 1400 and 1300 °C, respectively, leading to a mixture of CaO and AnO2 by the volatilization of P4O10. In contrast to the cases of thorium and uranium, cerium(IV) is not stabilized during the heating treatment at high temperature. Indeed, the formation of Ca0.5Ce0.5PO4 appears impossible, due to the partial reduction of cerium(IV) into cerium(III) above 840 °C. Consequently, the systems always appear polyphase, with compositions of CeIII1-2xCeIVxCaxPO4 and Ca2P2O7. The same conclusion can be also given when discussing the incorporation of cerium(IV) into La1-2xCeIIIx-yCeIVyCay(PO4)1-x+y. This incomplete incorporation of cerium(IV) confirms the results obtained when trying to stabilize tetravalent plutonium in Ca0.5PuIV0.5PO4 samples