Cerium

Abstract: On 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, ie, Ca05U05PO4, after heating at 1200 °C Both brabantites, Ca05Th05PO4 and Ca05U05PO4, 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 Ca05Ce05PO4 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 Ca05PuIV05PO4 samples