Phases Formation and Elements Partitioning in the CaO-Gd 2 O 3 (UO 2 )-MnO-TiO 2 System: Application to Rare Earth - Act
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Phases Formation and Elements Partitioning in the CaO-Gd2O3(UO2)-MnO-TiO2 System: Application to Rare Earth - Actinide Waste Immobilization 1 2
Olga I. Kirjanova,1 Sergey V. Stefanovsky,1 Sergey V. Yudintsev2 SIA Radon, 7 Rostovskii per. 2/14, Moscow 119121 RUSSIA IGEM RAS, Staromonetnii per. 35, Moscow 109017 RUSSIA th
ABSTRACT Ceramics within the compositional series Ca4-xGdxMn2Ti7O20+x/2 (х = 0, 1, 2, 3, 4) and a sample with Ca2U2Ti7O20 formulation were studied as promising matrices for immobilization of rare earth (RE) and actinide (An) constituents of high level waste (HLW). The samples were prepared by cold pressing of oxide mixtures in pellets at 200 MPa followed by their sintering at 1400 0C or melting at 1500 0C and examined with X-ray diffraction, scanning and transmission electron microscopy. At x=0 and x=1 a perovskite – pyrophanite assemblage occurred. The sample with x=2 consisted of murataite and perovskite. Murataite was a major phase in the sample with x=3 (pyrochlore and perovskite were minor phases) and the only phase in the sample with x=4 prepared under oxidizing conditions (in air). The latter was composed of two murataite varieties with seven- and five-fold fluorite unit cells. The sample with the same formulation but synthesized under reducing conditions contained pyrochlore as an extra phase. Coupled substitution 2 Gd3+ = Ca2+ + U4+ resulted in formation of pyrochlore as the major phase. Murataite and perovskite are considered as the host phases for rare earths and actinides mainly trivalent, including Pu(III), Am(III), and Cm(III), and corrosion products (Mn, Fe, Al) whereas pyrochlore is the host phase for rare earths and tetravalent actinides (U(IV), Np(IV), Pu(IV)). This makes the system of calcium, gadolinium, manganese, and titanium oxides prospective for immobilization of RE – An fraction of HLW containing minor corrosion products (iron group elements). INTRODUCTION Actinides are the most dangerous components of radioactive waste due to the longest half-lives and high radiation and chemical toxicity. Currently great volume of An-containing high level waste (HLW) is stored. Such waste must be transformed into stable solid form preferably crystalline ceramic because glass is thermodynamically unstable and not able to survive for millions of years required to actinide decay. The most promising host phases for actinides and associate REs are synthetic phases with fluorite-related structure such as pyrochlore, murataite, and zirconolite [1]. Crystal chemical formulae of pyrochlore and zirconolite are known well, whereas murataite formula is under discussion now. Formulae of natural samples are as follows: from Colorado, USA, (Na,Y,Er)4Zn2(Ti,Nb,Fe)7O18 (F,OH)4 [2] or (Y,Na)6(Zn,Fe)5Ti12O29(O,F)10F4 [3]; from Pribaikalie (near Lake Baikal), Russia, Na1.15Ca1.07Y0.66Fe0.29Zn1.79Ti6.03O16.92 (in our recalculation) or (Na,Ca,Y)3(Fe,Zn)2Ti6O17 (simplified). For synthetic murataite found in the ceramics for Savannah River Plant (SRP) waste immobilization formulae Zr(Ca,Mn)2(Fe,Al)4Ti3
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