Zirconolite matrices for the immobilization of REE–actinide wastes

The structural and chemical properties of zirconolite (ideally CaZrTi2O7) as a host phase for separated REE–actinide-rich wastes are considered. Detailed analysis of both natural and synthetic zirconolite-structured phases confirms that a selection of zirconolite polytype structures may be obtained, determined by the provenance, crystal chemistry, and/or synthesis route. The production of zirconolite ceramic and glass–ceramic composites at an industrial scale appears most feasible by cold pressing and sintering (CPS), pressure-assisted sintering techniques such as hot isostatic pressing (HIP), or a melt crystallization route. Moreover, we discuss the synthesis of zirconolite glass ceramics by the crystallization of B–Si–Ca–Zr–Ti glasses containing actinides in conditions of increased temperatures relevant to deep borehole disposal (DBD)

APPLICATION OF MECHANICAL ACTIVATION TO PRODUCTION OF PYROCHLORE CERAMIC CONTAINING SIMULATED RARE-EARTH ACTINIDE FRACTION OF HLW

Samples of zirconate pyrochlore ceramic (REE)2(Zr,U)2O7 (REE = La-Gd) containing simulated REE-An fraction of HLW were synthesized by two routes: (1) conventional cold compaction of oxide mixtures in pellets under pressure of 200 MPa and sintering of the pellets at 1550 C for 24 hours; and (2) using preliminary mechanical activation of oxide powders in a linear inductive rotator (LIV-0.5E) and a planetary mill - activator with hydrostatic yokes (AGO-2U) for 5 or 10 min. All the samples sintered at 1550 C were monolithic and dense with high mechanical integrity. As follows from X-ray diffraction (XRD) data, the ceramic sample produced without mechanical activation is composed of pyrochlore as major phase but contains also minor unreacted oxides. The samples prepared from pre-activated mixtures are composed of the pyrochlore structure phase only. Scanning electron microscopy (SEM) data also show higher structural and compositional homogeneity of the samples prepared from mechanically activated batches. The samples produced from oxide mixtures mechanically activated in the LIV for 10 min were slightly contaminated with iron resulting in formation of minor perovskite structure phase not detected by XRD but seen on SEM-images of the samples. Comparison of the samples prepared from non-activated and activated batches showed higher density, lower open porosity, water uptake, and elemental leaching for the samples fabricated from mechanically activated oxide mixtures

The effect of irradiation on hydrodynamic properties of extraction mixtures based on diamides of N-heterocyclic dicarboxylic acids in heavy fluorinated diluents

Hydrodynamic properties have been investigated for promising extraction systems: 0.05 mol L−1 solutions of di(N-ethyl-4-ethylanilide) of 2,2′-bipyridine-6,6′-dicarboxylic acid, di(N-ethyl-4-fluoroanilide) of 2,6-pyridinedicarboxylic acid and di(N-ethyl-4-hexylanilide) of 2,2′-bipyridine-6,6′-dicarboxylic acid in meta-nitrobenzotrifluoride (F-3) or trifluoromethylphenyl sulfone (FS-13) diluents. To evaluate the perspectives for their use as extraction mixtures at the final stage of the nuclear fuel cycle, the change in density, viscosity, surface tension, and phase separation rate under irradiation with accelerated electrons was studied. The concentrations of extractants in the irradiated mixtures have been determined and the radiation-chemical yields have been calculated. Irradiation significantly decreases the phase separation rate at the stages of extraction and back extraction for all the studied systems. The viscosity of the DYP-7 solution in FS-13 increase above the values suitable for its use in extraction processes. Keywords: Diamides of dicarboxylic acids, Meta-nitrobenzotrifluoride, Trifluoromethylphenyl sulfone, Irradiation, Hydrodynamic stabilit