The dynamics of the gas release at thermal oxidation of the two-phase systems of 30% solution of tri-n-butyl phosphate (TBP) in isoparaffinic diluent Isopar M – aqueous solution of 4.3, 8.2 and 12 mol/L of HNO3 has been investigated within the temperature range from 70°C to 110°C. The effect of pre-irradiation of the system TBP–Isopar-M–HNO3 on the kinetics of its thermolysis has been determined. All of the samples were irradiated with an electron accelerator at a dose rate of 10 kGy/h up to integrated doses of 0.5, 1 and 2 MGy. The parameters of heat and gas emission during thermolysis of the tested extraction system in an open apparatus have been determined experimentally. It has been demonstrated, that there are no conditions for extension of autocatalytic oxidation under heat treatment of two-phase extraction systems in open vessels.

Slow cooling of phosphate melt at liquid nuclear waste solidification yields glass-crystalline material. Partial crystallization during melt solidification results in elemental partitioning among crystalline phase and glass: Al, Cr, Fe are concentrated in the crystalline phosphate phase while Ca, Ni, La, U enter predominantly in the residual glass. Glass dissolution rate and leach rate of La and U as rare earth and actinide surrogates depends strongly on the glass composition, for example reduction of Al2O3 content in the glass to ∼10-12 wt.% increases leachability by three orders of magnitude as compared to the glass with specified composition (∼18-22 wt.% Al2O3).

Two Mo-bearing glasses considered as candidate forms for high level waste (HLW) a uranium-graphite reactor spent nuclear fuel (SNF) reprocessing were characterized. Incorporation of Mo in sodium aluminophosphate (SAP) glass increases its tendency to devitrification with segregation of orthophosphate phases. Valence state and local environment of Mo in the materials containing ∼2 wt.% MoO3 were determined by X-ray absorption fine structure (XAFS) spectroscopy. In the quenched samples composed of major vitreous and minor AlPO4 nearly all Mo is located in the vitreous phase as [Mo6+О6] units whereas in the annealed samples Mo is partitioned among vitreous and one or two orthophosphate crystalline phases in favor of the vitreous phase. Mo predominantly exists in a hexavalent state in distorted octahedral environment. Four oxygen ions are positioned at a distance of ∼1.71-1.73 Å and two - at a distance of 2.02-2.04 Å. Minor Mo(V) is also present as indicated by a response in EPR spectra with g ≈ 1.911-1.915.

Copper valence and environment in two sodium aluminophosphate glasses suggested for immobilization of HLW from reprocessing of spent fuel of uranium-graphite channel reactor (Russian AMB) were studied by XRD, SEM/EDX, XAFS and EPR. Target glass formulations contained ∼2.4-2.5 mol.% CuO. The quenched samples were predominantly amorphous. The annealed MgO free sample had higher degree of crystallinity than the annealed MgO-bearing sample but both them contained orthophosphate phases. Cu in the materials was partitioned in favor of the vitreous phase. In all the samples copper is present as major Cu2+ and minor Cu+ ions. Cu2+ ions form planar square complexes (CN=4) with a Cu2+-O distance of 1.93-1.95 Å. Two more ions are positioned at a distance of 2.76-2.86 Å from Cu2+ ions. So the Cu2+ environment looks like a strongly elongated octahedron as it also follows from the absence of the pre-edge peak due to 1s→3d transition in Cu K edge XANES spectra of the materials. Cu+ ions form two collinear bonds at Cu+-O distances of 1.80-1.85 Å. Thus average Cu coordination number (CN) in the first shell was found to be 2.7-3.0.

Examples of uranium-oxide-based nanostructures are considered, including 2D organic-inorganic nanocomposites and nanotubules. In nanocomposites, interfacial interactions between organic and inorganic substructures can be studied by charge-density matching principle. Application of this principle to uranyl compounds requires special attention since surface area of uranyl-based 2D units is higher than that of other inorganic oxysalts units (i.e. metal phosphates). The charge-density matching principle is, however, observed either through tail interdigitation (for long-chain monoamines) or incorporation of acid-water interlayers into organic substructure (for long-chain diamines). In some compounds, protonated amine molecules form cylindrical micelles that involves self-assembly governed by competing hydrophobic/hydrophillic interactions. The flexible inorganic complexes present in the reaction mixture could then form around cylindrical micelles to produce highly undulated 2D sheets or nanotubules.