New data on microstructure of 16 years old (La, Pu)PO4 monazite ceramics doped with 8.1 wt% of 238Pu are presented. It is shown that the sample consists from at least two phases differing in La/Pu ratio and small precipitates of Pu-phosphate. Possible mechanisms of the compositional heterogeneity are discussed. Formation of Pu-containing rhabdophane after sample storage in air is observed. This phenomenon together with gradual mechanical destruction of the ceramic pellet formation of submicron particles will likely increase rate of radionuclides loss from the monazite-based waste form. X-ray emission lines produced by recoil uranium ions from Pu decay are analysed. It is suggested that careful examination of their relative intensities may provide important information about behaviour of "hot" recoils in nuclear waste forms.

The oxide films formed on spent fuel claddings are regarded as a potential source of the instantaneous release of radionuclides, such as 14C, after waste disposal. We investigated the instant release fraction using the irradiated oxide exfoliated from a Zircaloy-2 water rod, whose bundle burnup was 53.0 GWd/MTU. We performed a rapid leaching test in a dilute NaOH solution (pH of 12.5) for 10 min in an ultrasonic bath to ensure the release of radionuclides. The activity ratios of the leached amount to the total amount for 14C, 60Co, and 125Sb were extremely low at approximately 10-4 to 10-3, among which the maximum value was 2.65 × 10-3 for 125Sb. These ratios were higher than that predicted from the thermodynamic solubility of ZrO2, i.e., less than 10-6. However, given the low ratios, it is too conservative to regard the inventory of all radionuclides in the Zircaloy oxide as instantaneous release. A small part of the released 14C was found as volatile species.

Millimetre UO2 single crystals were cut and oriented at JRC Karlsruhe. The orientation of each face of the parallelepiped single crystals was determined with Laue diffraction and the corresponding surface area by geometric measurements. Then, the (111), (100), (110) faces of each single crystal were polished to optical grade and characterized by XRD in order to confirm the surface orientation. The dissolution of the three single crystals was achieved in nitric acid media under dynamic conditions, at room temperature. Two dissolution regimes were observed for all samples. The normalized dissolution rate measured in the first step was not influenced by the crystallographic orientation of the faces. However, during the second step, (110) oriented faces were found to dissolve 4 times faster than the (100) faces. One explanation could involve the atomic composition of each oriented surface in the fluorite-type structure

X-ray Absorption Spectroscopy is a technique of fundamental importance in nuclear waste management, as an element specific probe of speciation, which governs radionuclide solubility, immobilisation and migration. Here, we exploit recent developments in laboratory instrumentation for X-ray Absorption Spectroscopy, based on a Rowland circle geometry with a spherically bent crystal analyser, to demonstrate speciation in prototype ceramic and glass-ceramic waste forms. Laboratory and synchrotron XANES data acquired from the same materials, at the Ce and U L3 edges, were found to be in excellent quantitative agreement. We establish that analysable laboratory XANES data may be acquired, and interpreted for speciation, even from quite dilute absorber concentrations of a few mol%, albeit with data acquisition times of several hours. For materials with suitable absorber concentrations, this approach will enable routine element specific speciation studies to support rapid optimisation of radioactive waste forms and analysis of radiological materials in a purpose designed laboratory, without the risk associated with transport and manipulation at a synchrotron radiation facility.

A zirconolite glass-ceramic material is a candidate wasteform for immobilisation of chlorine contaminated plutonium residues, in which plutonium and chlorine are partitioned to the zirconolite and aluminosilicate glass phase, respectively. A preliminary investigation of chlorine speciation was undertaken by analysis of Cl K-edge X-ray Absorption Near Edge Spectroscopy (XANES), to understand the incorporation mechanism. Cl was found to be speciated as the Cl- anion within the glass phase, according to the characteristic chemical shift of the X-ray absorption edge. By comparison with Cl K-edge XANES data acquired from reference compounds, the local environment of the Cl- anion is most closely approximated by the mineral marialite, in which Cl is co-ordinate to 4 x Na and/or Ca atoms.

The addition of Cr2O3 to modern UO2 fuel modifies the microstructure so that, through the generation of larger grains during fission, a higher proportion of fission gases can be accommodated. This reduces the pellet-cladding mechanical interaction of the fuel rods, allowing the fuels to be “burned” for longer than traditional UO2 fuel, thus maximising the energy obtained. We here describe the preparation of UO2 and Cr-doped UO2 using Hot Isostatic Pressing (HIP), as a potential method for fuel fabrication, and for development of analogue materials for spent nuclear fuel research. Characterization of the synthesised materials confirmed that high density UO2 was successfully formed, and that Cr was present as particles at grain boundaries and also within the UO2 matrix, possibly in a reduced form due to the processing conditions. In contrast to studies of Cr-doped UO2 synthesised by other methods, no significant changes to the grain size were observed in the presence of Cr.

Improved budgeting of heat loads arising from radiogenic heating in high level wastes (HLW) could allow enhanced usage of geological disposal facility space. Separation of high heat generating nuclides from HLW, such as Cs, would simplify management of heat loads. A potential host matrix for Cs-disposal is hollandite. The incorporation of Cs into the hollandite phase is aided by substitution of cations on the B-site of the structure; these ions may include Ni and Zn. Two series of hollandites, Ni-substituted and Zn-substituted, were synthesised via an alkoxide-nitrate route and consolidated by cold uniaxial pressing and sintering or by hot isostatic pressing. Characterisation of the resultant material by X-ray diffraction and scanning electron microscopy found that hollandite was formed for all levels of substitution. Materials produced via HIP were found to be denser indicating lower Cs loss. HIPed Ni hollandites were found to contain fewer secondary phases and it was concluded that they were the most suitable candidates

Nuclear fuel debris generated at the Fukushima Daiichi nuclear power plant during the loss of coolant accident in 2011, still resides within the reactor units, constantly cooled by water. Until it is retrieved, the fuel debris will corrode, releasing radioactive elements into the coolant water and the ground surrounding the reactors. To predict the corrosion behaviour of these materials, and to establish parameters for experiments with U-containing and real fuel debris, the corrosion of two surrogate fuel debris materials, with a composition of Ce(1-x)ZrxO2 (x = 0.2 and 0.4), was investigated. Materials were synthesised by a wet chemistry route and pellets were sintered at 1700°C in air atmosphere. Due to the slow corrosion kinetics, aggressive conditions were applied, and corrosion experiments were performed in 9 mol.L-1 HNO3 under static conditions. The incorporation of Zr into the structure of Ce reduced the normalised dissolution rate; from (3.75 ± 0.15) × 10-6 g.m-2.d-1 to (4.96 ± 0.28) × 10-6 g.m-2.d-1 for RL(Ce) of Ce0.8Zr0.2O2 and Ce0.6Zr0.4O2, respectively.

A range of stoichiometric and mixed A-site cation brannerite glass-ceramics have been synthesised and characterised. The formation of UTi2O6 in glass is reliant on ensuring all uranium remains tetravalent by processing in an inert atmosphere. ThTi2O6 forms in glass under both inert and oxidising atmospheres due to the lack of other easily available oxidation states. CeTi2O6 could not be made to form within this glass system. The formation of A0.5B0.5Ti2O6 phases depends strongly on the oxidation states of the A and B cations available in the process atmosphere, with the most successful compositions having an average final oxidation state of (A,B)4+. Mixed cation brannerite compositions that formed in argon include U0.75Th0.25Ti2O6 and U0.71Ce0.29Ti2O6. Those forming in air include U0.23Th0.77Ti2O6, Th0.37Ce0.63Ti2O6, and U0.41Ce0.59Ti2O6.

The large-scale cold crucible induction melter (CCIM) with productivity of 12 kg/h was created for melting borosilicate glass containing 20 mass. % of high-level liquid wastes (HLLW) simulators. Tests were carried out to study the effect on the CCIM operating parameters during sedimentation of metallic silver, at the content of 3.8 mass. % Ag2O in glass. Post-test analyses of the glass shows the sedimentation of silver in the bottom layers of the molten pool. Experiments have confirmed that the presence of noble metals in the form of undissolved sediments in the bottom layers of furnace leads to a changes in the properties of the melt, the aggravation of its drain conditions, an increase in the thermal conductivity of the skull and heat losses during melting.

Immobilisation of Pu in a zirconolite matrix (CaZrTi2O7) is a viable pathway to disposition. A-site substitution, in which Pu4+ is accommodated into the Ca2+ site in zirconolite, coupled with sufficient trivalent M3+/Ti4+ substitution (where M3+ = Fe, Al, Cr), has been systematically evaluated using Ce4+ as a structural analogue for Pu4+. A broadly similar phase assemblage of zirconolite-2M and minor perovskite was observed when targeting low levels of Ce incorporation. As the targeted Ce fraction was elevated, secondary phase formation was influenced by choice of M3+ species. Co-incorporation of Ce/Fe resulted in the stabilisation of a minor Ce-containing perovskite phase at high wasteloading, whereas considerable phase segregation was observed for Cr3+ incorporation. The most favourable substitution approach appeared to be achieved with the use of Al3+, as no perovskite or free CeO2 was observed. However, high temperature treatments of Al containing specimens resulted in the formation of a secondary Ce-containing hibonite phase.