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The corrosion mechanisms and kinetics of a Mg-rich alkali aluminoborosilicate glass simulating UK high-level waste (CaZn28) were investigated upon dissolution in synthetic cement solutions. Dissolution varied as a function the different pH and alkali/alkaline earth content of each cement solution. High resolution microscopy and spectroscopy techniques ascertained the nature of the interface between the glass and the cement solutions. TEM-EDS revealed alkali- and alkaline earth-rich silica gels, into which K, Ca and Mg were incorporated. TEM-SAED, combined with synchrotron micro-focus XRD, identified the ubiquitous precipitation of the Mg-aluminate layered double hydroxide phase, meixnerite (Mg6Al2(OH)18·4H2O), in addition to goethite (FeOOH) and crystalline silica. The C-S-H phase, tobermorite (Ca5Si6O16(OH)2·4H2O), was identified in the most Ca-rich solution only. These data give insight to the role of alkali/alkaline earth-rich solutions in the dissolution or radioactive waste glasses, of importance to the final disposition in a geological disposal facility.

Zirconolite is considered to be a suitable wasteform material for the immobilization of Pu and other minor actinide species produced through advanced nuclear separations. Here, we present a comprehensive investigation of Dy3+ incorporation within the self-charge balancing zirconolite Ca1–xZr1–xDy2xTi2O7 solid solution, with the view to simulate trivalent minor actinide immobilization. Compositions in the substitution range 0.10 ≤ x ≤ 1.00 (Δx = 0.10) were fabricated by a conventional mixed oxide synthesis, with a two-step sintering regime at 1400 °C in air for 48 h. Three distinct coexisting phase fields were identified, with single-phase zirconolite-2M identified only for x = 0.10. A structural transformation from zirconolite-2M to zirconolite-4M occurred in the range 0.20 ≤ x ≤ 0.30, while a mixed-phase assemblage of zirconolite-4M and cubic pyrochlore was evident at Dy concentrations 0.40 ≤ x ≤ 0.50. Compositions for which x ≥ 0.60 were consistent with single-phase pyrochlore. The formation of zirconolite-4M and pyrochlore polytype phases, with increasing Dy content, was confirmed by high-resolution transmission electron microscopy, coupled with selected area electron diffraction. Analysis of the Dy L3-edge XANES region confirmed that Dy was present uniformly as Dy3+, remaining analogous to Am3+. Fitting of the EXAFS region was consistent with Dy3+ cations distributed across both Ca2+ and Zr4+ sites in both zirconolite-2M and 4M, in agreement with the targeted self-compensating substitution scheme, whereas Dy3+ was 8-fold coordinated in the pyrochlore structure. The observed phase fields were contextualized within the existing literature, demonstrating that phase transitions in CaZrTi2O7–REE3+Ti2O7 binary solid solutions are fundamentally controlled by the ratio of ionic radius of REE3+ cations.

Within the context of the UK's radioactive waste vitrification programme, which utilises a lithium-sodium borosilicate glass modified with CaO and ZnO to immobilise high level nuclear waste, an investigation was undertaken to evaluate the effects on the structure and chemical durability of altering the CaO to ZnO ratio. Using a 6-component simplified alkali aluminoborosilicate glass, replacement of CaO by ZnO, even in moderate amounts, had a marked effect on the glass structure. Zn K-edge EXAFS identified that Zn existed within two distinct environments, both containing Zn in tetrahedral coordination. At high CaO content, Zn was coordinated in a “hardystonite-like” (Ca2ZnSi2O7) environment, while higher ZnO content induced destabilization and nano-scale phase separation occurred, forming discrete tri-clusters of Si/Al–O–Zn in a “willemite-like” (Zn2SiO4) environment. The presence of these environments was corroborated by thermal analysis and 29Si MAS NMR data. Despite this phase separation, glasses with higher ZnO content were found to exhibit the lowest normalized dissolution rates under dilute conditions, as determined using the Single-Pass Flow-Through methodology. Chemical structure analysis indicates that such behaviour is a result of enhanced polymerization of the glass network in the presence of Zn, and a reduced propensity for Si–O–Zn bond hydrolysis in water, resolving a long-running literature debate on the role of Zn on the dissolution of glass in the forward rate. Evidence is presented that indicates the phase-separated regions dissolve at somewhat different rates. These results enhance understanding of CaO : ZnO-containing glass behaviour, important to assess the long-term safety of radioactive waste management and disposal strategies.

Reactive spark plasma sintering has been utilised as a high-throughput processing route for the synthesis of two simulant zirconolite wasteform materials, targeting Ca0.80Ce0.20ZrTi1.60M0.40O7 (M = Fe3+ and Al3+). Materials were processed under 15 MPa uniaxial pressure, with heating/cooling rates of 100 °C/min to 1320 °C, maintained under vacuum. Despite moderate yield (> 80 wt%) of zirconolite-2M, a considerable Ce-rich perovskite phase was formed in both formulations, attributed to complete reduction of the Ce inventory to Ce3+, as determined by Ce L3-edge XANES analysis. The composition charge balanced with Al3+ was favoured on the basis of lower accompanying perovskite fraction.

HERMES, a graphical user interface software tool, is presented, for pre-processing X-ray absorption spectroscopy (XAS) data from laboratory Rowland circle spectrometers, to meet the data handling needs of a growing community of practice. HERMES enables laboratory XAS data to be displayed for quality assessment, merging of data sets, polynomial fitting of smoothly varying data, and correction of data to the true energy scale and for dead-time and leakage effects. The software is written in Java 15 programming language, and runs on major computer operating systems, with graphics implementation using the JFreeChart toolkit. HERMES is freely available and distributed under an open source licence.

A series of zirconolite ceramics with stoichiometry Ca1-xCexZrTi2-2xAl2xO7 (x = 0–0.35), considered as a host phase for the immobilisation of separated plutonium, were prepared from a mixture of oxide precursors by sintering in air at 1450 °C. Ce was utilised as a structural surrogate for Pu, with Al added to provide charge compensation. XRD and electron diffraction analyses indicated crystallisation of the zirconolite-2M polytype for all compositions, accompanied by various secondary phases contingent on the doping level, consistent with microstructure observation. The relative yield of zirconolite phases remained above 94 wt.% for 0.05 < x < 0.20. It was determined that Ce was partially reduced to the Ce3+ oxidation state and Al occupied mainly octahedral Ti sites. The incorporation rate of CeO2 was calculated to be 9.27 wt.% in Ca0.80Ce0.20ZrTi1.60Al0.40O7 with a comparatively high yield of 94.7 wt.%, which is representative of a PuO2 incorporation rate of 14.86 wt.%.

Magnesium aluminosilicate and magnesium borosilicate glass formulations were developed and evaluated for the immobilisation of the radioactive waste known as Magnox sludge. Glass compositions were synthesised using two simplified bounding waste simulants, including corroded and metallic uranium and magnesium at waste loadings of up to 50 wt.%. The glasses immobilising corroded simulant waste formed heterogeneous and fully amorphous glasses, while those immobilising metallic wastes contained crystallites of UO2 and U3O8. Uranium speciation within the glass was investigated by micro-focus X-ray absorption near edge spectroscopy and it was shown that the borosilicate glass compositions were characterised by a slightly lower mean uranium oxidation state than the aluminosilicate counterparts. This had an impact upon the durability, and uranium within glasses of higher mean oxidation states was dissolved more readily. All material showed dissolution rates that were comparable to simulant high level radioactive waste glasses, while the borosilicate-based formulations melted at a temperature suitable for modern vitrification technologies used in radioactive waste applications. These data highlights the potential for vitrification of hazardous radioactive Magnox sludge waste in borosilicate or aluminosilicate glass formulations, with the potential to achieve >95 % reduction in conditioned waste volume over the current baseline plan.

Detailed chemical analysis of the solidified molten fuel still residing in the stricken Chernobyl reactor unit 4 are inferred using multi-modal micro-focus X-ray analysis of a low-radioactivity proxy. A fascinating mixture of molten UO2, nuclear fuel cladding, concrete, stainless steel and other nuclear reactor components, these materials behaved like lava, solidifying to form a complex, highly radioactive glass-ceramic. Using element-specific chemical probes (micro-X-ray fluorescence and X-ray absorption spectroscopy), coupled with micro-diffraction analysis, the crystalline phase assemblage of simulants of these heterogeneous materials was established, which included “chernobylite” and a range of compositions in the (U1−xZrx)O2 solid solution. Novel insight to nuclear accident fuel chemistry was obtained by establishing the oxidation state and local coordination of uranium not only in these crystalline phases, but uniquely in the amorphous fraction of the material, which varied depending on the history of the nuclear lava as it flowed through the reactor. This study demonstrates that micro-focus X-ray analysis of very small fractions of material can yield rich chemical information, which can be applied to nuclear-melt down materials to aid decommissioning and nuclear fuel management at nuclear accident sites.

SEM–EDX and Raman spectroscopy analysis of radioactive compounds is often restricted to dedicated instrumentation, within radiological working areas, to manage the hazard and risk of contamination. Here, we demonstrate application of WetSEM® capsules for containment of technetium powder materials, enabling routine multimodal characterisation with general user instrumentation, outside of a controlled radiological working area. The electron transparent membrane of WetSEM® capsules enables SEM imaging of submicron non-conducting technetium powders and acquisition of Tc Lα X-ray emission, using a low cost desktop SEM–EDX system, as well as acquisition of good quality μ-Raman spectra using a 532 nm laser.

A series of zirconolite ceramics with composition CaZr1‐xThxTi2O7 (Δx = 0.10) were reactively sintered at 1350 ˚C for 20 h, in air (0 ≤ x ≤ 0.60) and 5% H2/N2 (0 ≤ x ≤ 0.40). A sample with composition corresponding to x = 0.20 was also produced by hot isostatic pressing (HIP) at 1300 ˚C and 100 MPa for 4 h. Th4+ immobilisation was most readily achieved under oxidising conditions, with Th4+ preferentially incorporated within a pyrochlore‐structured phase in the range 0.10 ≤ x ≤ 0.50, yet formation of the zirconolite‐4M polytype was not observed. We report the novel synthesis of single phase pyrochlore with nominal composition CaZr0.40Th0.60Ti2O7 when targeting x = 0.60. Th4+ incorporation under reducing conditions produced a secondary Th‐bearing perovskite, comprising 24.2 ± 0.6 wt. % of the phase assemblage when targeting x = 0.40, alongside 8.8 ± 0.3 wt. % undigested ThO2. Under reducing conditions, powder XRD data were consistent with zirconolite adopting the 3T polytype structure. The sample produced by HIP presented a non‐equilibrium phase assemblage, yielding a major phase of zirconolite‐2M alongside accessory Th4+ bearing phases ThTi2O6, ThO2 and perovskite. These data highlight the efficacy of Th4+ as a Pu4+ surrogate, with implications for the formation of Zr‐stabilised Th‐pyrochlore phases as matrices for waste with elevated Th4+ content.

Refractory ‘stuffed’ pyrochlores such as Gd2TiO5 are of interest for nuclear applications, including as matrices for actinide disposition and as neutron absorbers in control rods. Here, we report the results of a preliminary comparative investigation of the synthesis of Gd2TiO5 by molten salt and conventional solid-state synthesis. We show that synthesis of Gd2TiO5 proceeds from the pyrochlore phase Gd2Ti2O7 which is first formed as a kinetic product. Molten salt synthesis afforded single phase Gd2TiO5 at 1300 °C in 2 h, via a template growth mechanism, and is effective for the synthesis of these refractory materials. This work demonstrates molten salt mediated synthesis of ‘stuffed’ pyrochlore for the first time.

A sample of zirconolite with nominal composition Ca0.80Ce0.20ZrTi1.60Cr0.40O7 was processed via Hot Isostatic Pressing (HIP), with a dwell temperature and pressure of 1320 °C/100 MPa maintained for 4 h. The produced wasteform was characterised by powder XRD, SEM–EDS, Ce L3 and Cr K-edge XANES. A significant portion of the Ce inventory did not fully partition within the zirconolite phase, instead remaining as CeO2 within the microstructure. Inspection of the stainless steel–ceramic interface detailed the presence of an interaction region dominated by a Cr-rich oxide layer. No significant Cr or Fe migration was observed, although a greater concentration of perovskite was observed at the periphery, relative to the bulk ceramic matrix. The X-ray absorption features of Cr remained analogous with Cr3+ accommodation within TiO6 octahedra in the zirconolite matrix. The absorption edge of Ce was comprised of contributions from zirconolite-2M and unincorporated CeO2, with an average oxidation state of Ce3.9+. As zirconolite-2M accounted for > 92 wt% of the overall phase assemblage, it is clear that the dominant oxidation state of Ce in this phase was Ce4+.

In this study, a multi-technique approach was utilised to determine the high temperature performance of magnesium potassium phosphate cement (MKPC) blended with fly ash (FA) or ground granulated blast furnace slag (GBFS) with respect to nuclear waste immobilisation applications. Conceptual fire conditions were employed (up to 1200 °C, 30 min) to simulate scenarios that could occur during interim storage, transportation or within a final geological disposal facility. After exposure up to 400 °C, the main crystalline phase, struvite-K (MgKPO4·6H2O), was dehydrated to poorly crystalline MgKPO4 (with corresponding volumetric and mass changes), with MgKPO4 recrystallisation achieved by 800 °C. XRD and SEM/EDX analysis revealed reaction occurred between the MgKPO4 and FA/GBFS components after exposure to 1000–1200 °C, with the formation of potassium aluminosilicate phases, leucite and kalsilite (KAlSi2O6 and KAlSiO4), commensurate with a reduced relative intensity (or complete elimination) of the dehydrated struvite-K phase, MgKPO4. This was further supported by solid-state NMR (27Al and 29Si MAS), where only residual features associated with the raw FA/GBFS components were observable at 1200 °C. The high temperature phase transformation of blended MKPC binders resulted in the development of a glass/ceramic matrix with all existing porosity infilled via sintering and the formation of a vitreous phase, whilst the physical integrity was retained (no cracking or spalling). This study demonstrates that, based on small-scaled specimens, blended MKPC binders should perform satisfactorily under fire performance parameters relevant to the operation of a geological disposal facility, up to at least 1200 °C.

Studtite is known to exist at the back-end of the nuclear fuel cycle as an intermediate phase formed in the reprocessing of spent nuclear fuel. In the thermal decomposition of studtite, an amorphous phase is obtained at calcination temperatures between 200 and 500 °C. This amorphous compound, referred to elsewhere in the literature as U2O7, has been characterised by analytical spectroscopic methods. The local structure of the amorphous compound has been found to contain uranyl bonding by X-ray absorption near edge (XANES), Fourier transform infrared and Raman spectroscopy. Changes in bond distances in the uranyl group are discussed with respect to studtite calcination temperature. The reaction of the amorphous compound with water to form metaschoepite is also discussed and compared with the structure of schoepite and metaschoepite by X-ray diffraction. A novel schematic reaction mechanism for the thermal decomposition of studtite is proposed.

Low-temperature soft chemical synthesis routes to transition-metal nitrides are of interest as an alternative to conventional high-temperature ammonolysis reactions involving large volumes of chemotoxic NH3 gas. One such method is the reaction between metal oxides and NaNH2 at ca. 200 °C to yield the counterpart nitrides; however, there remains uncertainty regarding the reaction mechanism and product phase assemblage (in particular, noncrystalline components). Here, we extend the chemical tool box and mechanistic understanding of such reactions, demonstrating the nitridation of Fe3O4 by reaction with NaNH2 at 170–190 °C, via a pseudomorphic reaction. The more reduced Fe3O4 precursor enabled nitride formation at lower temperatures than the previously reported equivalent reaction with Fe2O3. The product phase assemblage, characterized by X-ray diffraction, thermogravimetric analysis, and 57Fe Mössbauer spectroscopy, comprised 49–59 mol % ε-Fe2+xN, accompanied by 29–39 mol % FeO1–xNx and 8–14 mol % γ″-FeN. The oxynitride phase was apparently noncrystalline in the recovered product but could be crystallized by heating at 180 °C. Although synthesis of transition-metal nitrides is achieved by reaction of the counterpart oxide with NaNH2, it is evident from this investigation that the product phase assemblage may be complex, which could prove a limitation if the objective is to produce a single-phase product with well-defined electrical, magnetic, or other physical properties for applications. However, the significant yield of the FeO1–xNx oxynitride phase identified in this study opens the possibility for the synthesis of metastable oxynitride phases in high yield, by reaction of a metal oxide substrate with NaNH2, with either careful control of H2O concentration in the system or postsynthetic hydrolysis and crystallization.

Uranyl oxalate (UO2C2O4·xH2O) may exist at the back-end of the nuclear fuel cycle (NFC) as an intermediate in spent fuel reprocessing. The conditions used in aqueous reprocessing and thermal treatment can affect the physical and chemical properties of the material. Furthermore, trace impurities, such as Fe, may incorporate into the structure of these materials. In nuclear forensics, understanding relationships between processing variables aids in determination of provenance and processing history. In this study, the thermal decomposition of UO2C2O4·3H2O and phase analysis of its thermal products are examined. Their morphologies are discussed with respect to a matrix of solution processing conditions.

Materials from GeoMelt® In-Container Vitrification (ICV)™ of simulant UK nuclear wastes were characterised to understand the partitioning of elements, including inactive surrogates for radionuclide species of interest, within the heterogeneous products. Aqueous durability analysis was performed to assess the potential disposability of the resulting wasteforms. The vitrification trial aimed to immobilise a variety of simulant legacy waste streams representative of decommissioning operations in the UK, including plutonium contaminated material, Magnox sludges and ion-exchange materials, which were vitrified upon the addition of glass forming additives. Two trials with different wastes were characterised, with the resultant vitreous wasteforms comprising olivine and pyroxene crystalline minerals within glassy matrices. Plutonium surrogate elements were immobilised within the glassy fraction rather than partitioning into crystalline phases. All vitrified products exhibited comparable or improved durability to existing UK high level waste vitrified nuclear wasteforms over a 28 day period.

Brannerite glass-ceramic composites have been suggested as suitable wasteform materials for high-actinide content wastes, but the formation of glass-ceramic composites containing stoichiometric uranium brannerite (UTi2O6) has not been well-studied. Uranium brannerite glass-ceramic composites were synthesised at by a one-pot cold-press and sinter route from the component oxides. As a comparison, two further samples were produced using an alkoxide-nitrate route. A range of compositions with varying molar ratios of uranium and titanium oxides (from 1:2 to 1:3.20) were synthesised, with a range of different heat treatments (1200 °C for 12–48 h, and 1250 °C for 12 h). All compositions were analysed by X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectroscopy, and X-ray near-edge spectroscopy, and found to contain UTi2O6 as the majority crystalline phase forming within a glass matrix of nominal stoichiometry Na2AlBSi6O16. In compositions with UO2:TiO2 ratios of 1:2 and 1:2.28, particles of UO2 were observed in the glass matrix, likely due to dissolution of TiO2 in the glass phase; this was prevented by the addition of excess TiO2. This work demonstrates the suitability of this system to produce highly durable wasteforms with excellent actinide waste loading, even with a simple one-pot process. Some grains of brannerite consist of a UO2 particle encapsulated in a shell of UTi2O6, suggesting that brannerite crystallises around particles of UO2 until either the UO2 is fully depleted, or the kinetic barrier becomes too large for further diffusion to occur. We propose that the formation of brannerite within glass-ceramic composites at lower temperatures than that for pure ceramic brannerite is caused by an increase in the rate of diffusion of the reactants within the glass.

Molten salt mediated synthesis of zirconolite Ca0.9Zr0.9Ce0.2Ti2O7 was investigated, as a target ceramic matrix for the clean-up of waste molten salts from pyroprocessing of spent nuclear fuels and the immobilisation of separated plutonium. A systematic study of reaction variables, including, reaction temperature, time, atmosphere, reagents and composition, was made to optimise the yield of the target zirconolite phase. Zirconolite 2 M and 3T polytypes were formed as the major phase (with minor perovskite) between 1000 – 1400 °C, in air, with the relative proportion of 2 M polytype increasing with temperature. Synthesis under 5% H2/N2 or Ar increased the proportion of minor perovskite phase and reduced the yield of the zirconolite phase. The yield of zirconolite polytypes was maximised with the addition of 10 wt% TiO2 and 5 wt% TiO2, yielding 91.7 ± 2.0 wt% zirconolite, primarily as the 2 M polytype, after reaction at 1200 °C for 2 h, in air. The particle size and morphology of the zirconolite product bears a close resemblance to that of the TiO2 precursor, demonstrating a dominant template growth mechanism. Although the molten salt mediated synthesis of zirconolite is effective at lower reaction temperature and time, compared to reactive sintering, this investigation has demonstrated that the approach does not offer any clear advantage with over conventional reactive sintering for the envisaged application.

The structure of amorphous U2O7 has been examined by extended x-ray absorption near edge spectroscopy (EXAFS) and modelled using density functional theory (DFT) simulations. A hybridised metastudtite-UO3 structure is proposed, consisting of peroxide bonds (O-Operoxo), uranyl units (U=Oyl) and U-O bonding. Experimental and simulated X-ray diffraction (XRD) is used to confirm the proposed structure.

In this study, the effect of Ti4+ on the structure of nepheline glass (NaAlSiO4) is investigated as SiO2 is systematically replaced with TiO2. Traditionally, TiO2 is considered to be a nucleating agent for silicate crystallization but can also be incorporated into the glass network in relatively large amounts as either a network former or modifier depending on its coordination with oxygen. To determine the effect of Ti4+ on the structure of nepheline glass, X-ray and neutron pair distribution function (PDF) analysis paired with Empirical Potential Structure Refinement (EPSR) were conducted and are supplemented with Raman spectroscopy, electron probe microanalysis, and X-ray absorption spectroscopy (including Extended X-ray Absorption Fine Structure, EXAFS). Through these methods, it has been found that up to 15 mol% (16 wt%) TiO2 can incorporate into the glass network as a four-fold coordinated species, with a minor contribution of higher coordinated Ti. Between NaAlTi0.1Si0.9O4 and NaAlTi0.2Si0.8O4, EXAFS suggests a local structure change in the second coordination sphere of Ti, which changes from Ti-Ti to Ti-Al. Raman spectroscopy also suggests that as Ti content increases, the Na environment becomes more ordered. These results suggest that the Ti activity coefficient and its isotopic fractionation for magnetite and other Ti-bearing minerals should be fairly constant in polymerized melts, such as metaluminous and peraluminous rhyolites.

A series of Ca1-xCexZrTi2-2xCr2xO7 zirconolite ceramics (0 ≤ x ≤ 0.35) were reactively sintered in air at 1350 °C for 20 h. Single phase zirconolite-2M was formed for x ≤ 0.15, with Cr2O3 and an undesirable Ce-bearing perovskite phase present above x = 0.20. Electron diffraction analysis confirmed that the zirconolite-2M polytype was maintained over the solid solution. X-ray absorption near edge structure (XANES) data determined that between 10–20% Ce was speciated as Ce3+, and Cr was present uniformly as Cr3+ with near edge features consistent with occupation of octahedral sites within the zirconolite-2M structure. A sample corresponding to x = 0.20 was processed by reactive spark plasma sintering (RSPS), with a rapid processing time of less than 1 h. XANES data confirmed complete reduction to Ce3+ during RSPS, promoting the formation of a Ce-bearing perovskite, comprising 19.3 ± 0.4 wt. % of the phase assemblage.

The Dion-Jacobson (DJ) family of perovskite-related materials have recently attracted interest due to their polar structures and properties, resulting from hybrid-improper mechanisms for ferroelectricity in n = 2 systems and from proper mechanisms in n = 3 CsBi2Ti2NbO10. We report here a combined experimental and computational study on analogous n = 3 CsLn2Ti2NbO10 (Ln = La, Nd) materials. Density functional theory calculations reveal the shallow energy landscape in these systems and give an understanding of the competing structural models suggested by neutron and electron diffraction studies. The structural disorder resulting from the shallow energy landscape breaks inversion symmetry at a local level, consistent with the observed second-harmonic generation. This study reveals the potential to tune between proper and hybrid-improper mechanisms by composition in the DJ family. The disorder and shallow energy landscape have implications for designing functional materials with properties reliant on competing low-energy phases such as relaxors and antiferroelectrics.

The crystallization of iron-containing sodium silicate phases holds particular importance, both in the management of high-level nuclear wastes and in geosciences. Here, we study three as-quenched glasses and their heat-treated chemical analogs, NaFeSiO4, NaFeSi2O6, and NaFeSi3O8 (with nominal stoichiometries from feldspathoid, pyroxene, and feldspar mineral groups, i.e., Si/Fe = 1, 2, and 3, respectively) using various techniques. Phase analyses revealed that as-quenched NaFeSiO4 could not accommodate all Fe in the glass phase (some Fe crystallizes as Fe3O4), whereas as-quenched NaFeSi2O6 and NaFeSi3O8 form amorphous glasses. NaFeSi2O6 glass is the only composition that crystallizes into its respective isochemical crystalline polymorph, i.e., aegirine, upon isothermal heat-treatment. As revealed by Mössbauer spectroscopy, iron is predominantly present as fourfold-coordinated Fe3+ in all glasses, though it is present as sixfold-coordinated Fe3+ in the aegirine crystals (NaFeSi2O6), as expected from crystallography. Thus, Na-Fe silicate can form a crystalline phase in which it is octahedrally coordinated, even though it is mostly tetrahedrally coordinated in the parent glasses. Thermal behavior, magnetic properties, iron redox state (including Fe K-edge X-ray absorption), and vibrational properties (Raman spectra) of the above compositions are discussed.

The synthesis of a palladium-containing iodovanadinite derivative, hypothetically “PdPb9(VO4)6I2”, was attempted using PdI2 as a source of iodine in searching for a novel waste form for radioiodine. Stoichiometric amounts of Pb3(VO4)2 and PdI2 were batched and reacted at elevated temperatures in sealed vessels. Batched material was also subjected to high-energy ball-milling (HEBM) in order to reduce reaction time and the potential for iodine volatilization during subsequent reaction at 200–500 °C. The resulting products were characterized using X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray analysis, IR spectroscopy, thermal analysis and Pd K XANES. Results showed that PdI2 can function as a sacrificial iodine source for the formation of iodovanadinite, prototypically Pb10(VO4)6I2, however, the incorporation of Pd into this phase was not definitively observed. The sacrificial reaction mechanism involved the decomposition of PdI2 to Pd metal and nascent I2, with the latter incorporated into the iodovanadinite Pb10(VO4)6I2 phase. In comparison to processing using standard solid state reaction techniques, the use of HEBM prior to high temperature reaction generates a more homogeneous end-product with better iodine retention for this system. Overall, the key novelty and importance of this work is in demonstrating a method for direct immobilisation of undissolved PdI2 from nuclear fuel reprocessing, in a composite wasteform in which I-129 is immobilised within a durable iodovandinite ceramic, encapsulating Pd metal.

A series of zirconolite ceramics with nominal stoichiometry CaZr1-xCexTi2O7 (0.0 ≤ x ≤ 0.4) were synthesised under oxidizing, inert and reducing conditions, by a conventional solid-state cold press and sinter method. The evolution of phase assemblage and microstructure were characterized by XRD, SEM-EDS, Ce-L3 XANES and Raman spectroscopy techniques. It was determined that the relative yield of zirconolite-2M and zirconolite-4M polytypes, alongside secondary perovskite phases, was influenced by processing environment via the control of Ce3+/4+ speciation. Oxidizing conditions produced a mixture of zirconolite-2M and zirconolite-4M polytypes due to the formation of Ce4+. Inert and reducing conditions yielded predominantly zirconolite-2M and a Ce-bearing perovskite phase through favouring Ce3+ speciation.

An environmentally aged radioactive particle of UFeO4 recovered from soil contaminated with munitions depleted uranium (DU) was characterised by microbeam synchrotron X-ray analysis. Imaging of uranium speciation by spatially resolved X-ray diffraction (μ-XRD) and X-ray absorption spectroscopy (μ-XAS) was used to localise UFeO4 in the particle, which was coincident with a distribution of U(V). The U oxidation state was confirmed using X-ray Absorption Near Edge Structure (μ-XANES) spectroscopy as +4.9 ± 0.15. Le-Bail fitting of the particle powder XRD pattern confirmed the presence of UFeO4 and a minor alteration product identified as chernikovite (H3O)(UO2)(PO4)·3H2O. Refined unit cell parameters for UFeO4 were in good agreement with previously published values. Uranium–oxygen interatomic distances in the first co-ordination sphere were determined by fitting of Extended X-ray Absorption Fine Structure (μ-EXAFS) spectroscopy. The average first shell U–O distance was 2.148 ± 0.012 Å, corresponding to a U valence of +4.96 ± 0.13 using bond valence sum analysis. Using bond distances from the published structure of UFeO4, U and Fe bond valence sums were calculated as +5.00 and +2.83 respectively, supporting the spectroscopic analysis and confirming the presence of a U(V)/Fe(III) pair. Overall this investigation provides important evidence for the stability of U(V) ternary oxides, in oxic, variably moist surface environment conditions for at least 25 years.

X-ray absorption spectroscopy was applied to understand the speciation of elements relevant to the immobilisation and disposal of radioactive plutonium bearing wastes, utilizing Ce as a Pu surrogate. Ce L3 XANES (X-ray Absorption Near Edge Structure) characterisation of a crystallised glass material produced by cold crucible plasma vitrification, at demonstration scale, evidenced incorporation as Ce3+ within the glass phase, providing an important validation of laboratory scale studies. U and Ce L3 XANES investigation of brannerite ceramics, U0.9Ce0.1Ti2O6, synthesized under oxidizing, neutral and reducing conditions, established the charge compensation mechanism as incorporation of Ce3+ through formation of U5+ and/or U6+ In each of these examples, X-ray Absorption Spectroscopy has provided a pivotal understanding of element speciation in relation to the mechanism of incorporation within the host wasteform intended for geological disposal.

To study radiation stability of iron phosphate glasses, cerium is used as surrogate of actinides. Cerium doped iron phosphate glasses have been synthesised. Heavy gold ion irradiations have been performed on pure and cerium doped iron phosphate glasses to mimic ballistic damage due to cascade of recoil atoms. Pure and cerium doped glasses are irradiated with gold ions of energy 750 keV at fluence of 2 × 1015 ions/cm2. In this paper, ion irradiation effects on glass network modification and change in speciation of network former have been discussed. Significant changes in glass network structure and speciation of network former is observed.

Understanding the physical and chemical properties of materials arising from nuclear meltdowns, such as the Chernobyl and Fukushima accidents, is critical to supporting decommissioning operations and reducing the hazard to personnel and the environment surrounding the stricken reactors. Relatively few samples of meltdown materials are available for study, and their analysis is made challenging due to the radiation hazard associated with handling them. In this study, small-scale batches of low radioactivity (i.e., containing depleted uranium only) simulants for Chernobyl lava-like fuel-containing materials (LFCMs) have been prepared, and were found to closely approximate the microstructure and mineralogy of real LFCM. The addition of excess of ZrO2 to the composition resulted in the first successful synthesis of high uranium–zircon (chernobylite) by crystallisation from a glass melt. Use of these simulant materials allowed further analysis of the thermal characteristics of LFCM and the corrosion kinetics, giving results that are in good agreement with the limited available literature on real samples. It should, therefore, be possible to use these new simulant materials to support decommissioning operations of nuclear reactors post-accident.