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Synroc, a candidate nuclear wasteform and Synroc technology, a waste treatment solution utilizing hot‐isostatic pressing (HIPing) have significant potential for the immobilisation of challenging nuclear wastes from both current and innovative reactors and fuel cycles. Hot isostatic press (HIP) consolidation is undertaken within sealed metal HIP canisters, where metal buffers (e.g., Ti, Fe and Ni) can be incorporated to control the redox environment within the canister. This study, for the first time, reports the effect of varying Ti‐metal addition (0, 2, 4, and 8 wt.%) on phase formation, microstructural characteristics, and wasteform performance for HIP consolidated Synroc‐C containing 20 wt.% simulated PUREX type (PW‐4b) high level waste. Quantitative X‐ray diffraction analysis, scanning electron microscopy‐energy dispersive X‐ray spectroscopy (EDS) and transmission electron microscopy‐EDS analyses were undertaken for analytical investigations. The chemical durability of the samples was assessed using ASTM C1220‐21 standard test. Hot‐isostatically pressed (HIPed) samples with 0 and 8 wt.% Ti added for redox control produced unfavourable phase formation. However, the HIPed samples with Ti additions of 2 and 4 wt.% as a redox buffer showed the desired phase formation of Synroc‐C without any significant change to the partitioning of waste elements among the phases along with compatible durability results, when compared to previous literature for hot uniaxial pressing (HUPed) or sintered materials. [ABSTRACT FROM AUTHOR]

Two new mixed-valence uranium oxide hydrate frameworks (UOFs), incorporating either Er3+ or Y3+ ions, were successfully synthesised under hydrothermal conditions and characterised with single-crystal X-ray diffraction and a variety of other structural and spectroscopic techniques. Both frameworks are isostructural and crystallise in the triclinic P1¯ space group, consisting of β-U3O8 type layers pillared by additional uranyl centres, with the Er3+/Y3+ ions lying in the channels of the framework. SEM-EDS analysis found that both materials existed in plate-like morphologies, with a U:Er/Y ratio of 5.5. Bond valence sum analysis revealed the possible existence of pentavalent uranium centres, which was confirmed with diffuse reflectance spectroscopy. Being the first reported UOFs in this space group, this work highlights the complex and flexible nature of these materials, and the broader uranium oxide hydrate systems which exist in the surrounds of spent nuclear fuel disposal in the underground repository. [ABSTRACT FROM AUTHOR]

The previously unattained fabrication of single phase Ln2ZrO5 (Ln = Sm, Eu, Gd, and Tb) compounds via relatively low sintering temperature (1400°C) is achieved in this study using a coprecipitation method. The crystal structures have been investigated by neutron, synchrotron X‐ray powder diffraction, and electron diffraction techniques. While the general long‐range structure may be well described by the defect‐fluorite type structure with Fm3¯$\bar{3}$m symmetry, electron diffraction has highlighted a complex underlying modulated structure that varies between each compound. These compounds have been tested for ion‐irradiation response using in situ 1 MeV krypton ions and transmission electron microscopy characterization. None of the compounds undergo a crystalline to amorphous transition, even holding at 50 K. Both the underlying fluorite and modulated superstructures are little affected by the irradiation. However, some atomic rearrangements are observed in the postirradiated electron diffraction patterns for the Sm2ZrO5 specimen. [ABSTRACT FROM AUTHOR]

In the search for novel ceramics for use within nuclear fuel–related applications and nuclear waste-form matrices, a major focus has been on the development of radiation-tolerant materials. Of particular interest in this field have been numerous compounds with either pyrochlore or the related fluorite-type structures. In this study, we look to expand the family of compounds with defect fluorite–type structure. We have fabricated three new compounds; Yb2Sn1.125O5.25, Yb2Sn1.25O5.5, and Yb2Sn1.375O5.75. The compound Yb2Sn1.125O5.25 was determined, via x-ray diffraction, to have the long-range defect fluorite structure, Fm-3 m symmetry, with cell parameter a = 5.17233(1). Further to this, Sm2ZrO5 and Yb2TiO5 compounds were also fabricated and crystal structures characterised. The use of transmission electron microscopy has revealed a much more complex crystal structure than that of the relatively high symmetry fluorite, with the presence of structural modulations being detected. The ion-irradiation response of these compounds was tested via bulk specimen irradiation using 15-MeV gold ions with grazing incidence x-ray diffraction characterisation. The results show that both Sm2ZrO5 and Yb2Sn1.25O5.5 are highly tolerant to ion-irradiation exposure whilst Yb2TiO5 is susceptible to amorphisation. [ABSTRACT FROM AUTHOR]

A comprehensive study on the development of sodium zirconium phosphate (NZP)‐based glass‐ceramic composites as potential wasteforms for the immobilization of nuclear wastes is reported. Two complementary waste treatment routes, the ex situ and in situ crystallisation of NZP with a sodium aluminoborosilicate glass, were investigated with various processing conditions including sintering temperature, cooling rate and NZP to glass ratios. While the ex situ route with mixing of pre‐made NZP and glass is a robust and reliable means of producing the glass‐ceramic composites, the in situ crystallisation of NZP from an amorphous NZP precursor is a more realistic processing route. The formation of ZrO2 as a minor phase was observed especially for high NZP to glass ratios due to the solubility difference between Zr and P oxides in glass. The addition of extra phosphate can overcome this and yield glass‐ceramic composites with appropriate NZP stoichiometry. Overall, the NZP glass‐ceramic system is versatile offering multiple processing options for nuclear waste management. [ABSTRACT FROM AUTHOR]

As part of a broader study of ceramic nuclear waste‐forms, four different lanthanide titanates were fabricated; La0.1Sm0.1Gd0.1Tb0.1Dy0.3Ho0.1Er0.2YbTiO5, Sm0.3Gd0.3Dy0.3Yb1.1TiO5, Sm0.1Gd0.4Dy0.4Yb1.1TiO5, and Sm0.2Gd0.2Dy0.2Yb1.4TiO5. The aim was to produce single‐phase novel materials with cubic symmetry, capable of incorporating a wide variety of cations and with acceptable radiation tolerance. The chemistry flexibility and radiation tolerance are some of the major desirable properties for nuclear waste‐form materials. By using multiple lanthanides the average lanthanide radius can be controlled and consequently the structure, along with properties such as radiation tolerance. The radiation tolerance was assessed using in situ 1 MeV krypton irradiation and transmission electron microscopy characterization. Those materials for which cubic symmetry was achieved displayed better radiation tolerance; a greater critical fluence of ions (Fc) was required for the crystalline to amorphous transition, and a lower temperature was required to maintain crystallinity (Tc) during irradiation. [ABSTRACT FROM AUTHOR]

The effects of irradiation on CaWO4, SrWO4, BaWO4, YVO4, LaVO4, YNbO4, and LaNbO4 were investigated on thin crystals using 1.0 MeV Kr ions at 50‐1000 K. All of the ABO4 compounds can be amorphized with calculated damage cross sections (σa = 1/Fc0) in the range of ~0.30‐1.09 × 10‐14 cm2 ion−1 at zero Kelvin. The analysis of fluence‐temperature data returned critical temperatures for amorphization (Tc) of 311 ± 1, 358 ± 90, 325 ± 19, 415 ± 17, 541 ± 6, 636 ± 26, and 1012 ± 1 K, respectively, for the compounds listed above. Compared with previous in situ irradiation of ABO4 orthophosphate samples using 0.8 MeV Kr ions, the Tc values of LaVO4 and YVO4 are higher than those of LaPO4 and YPO4 by 82 K and 124 K, respectively. The Tc values of the three scheelite structures, CaWO4, SrWO4, and BaWO4, indicate that they are the most radiation tolerant compounds under these conditions. The A‐B cation anti‐site energies, EfAB, determined by DFT range from 2.48 to 10.58 eV and are highly correlated with the A‐B cation ionic radius ratio, rA/rB, but are not correlated with Tc across the different structure types, suggesting that the formation and migration energies of Frenkel defects play a more important role in damage recovery in these compounds. We also discuss the role of cation and anion charge/iconicity as determined by DFT. ABO4 compounds with the zircon structure and B = P or V have a distinct advantage over those with B = Si as the damaged regions do not appear to be significantly affected by polymerization of (PO4)3− or (VO4)3− groups which might stabilize the amorphous fraction and ultimately lead to phase separation as observed in zircon (ZrSiO4). [ABSTRACT FROM AUTHOR]

New microsphere sorbents are reported, which could find application in demanding radiation environments and especially as targets for the production of nuclear medicines by neutron irradiation. An easily-synthesized Zr anionic complex was introduced into quaternary amine-functionalised polystyrene-divinylbenzene-based anion-exchange resins by batch adsorption. Upon carbothermal reduction, the precursors were converted to porous carbon matrices containing particles of ZrC and ZrO2 polymorphs. The most phase-pure material, ZrAX-1, possessed high surface area, multi-scale porosity and high mechanical strength. Adsorption of Re and W was investigated and its possible deployment as a reusable host for the production of 188W/188Re is discussed. [ABSTRACT FROM AUTHOR]

Ln2Ti2O7 (Ln=Y and Gd) pyrochlore glass-ceramics have been fabricated successfully via internal crystallization. Subsequently, the phase evolution from Ln2Ti2O7 pyrochlores to Ln0.5U0.5Ti2O6 brannerites in glass with uranium (U) substitutions on the Ln-site of Ln2Ti2O7 has been investigated using X-ray diffraction, scanning electron microscope-electron dispersive spectroscopy, transmission electron microscopy, Raman and diffuse reflectance spectroscopy. Combined characterization by XRD, SEM- EDS and TEM SAED confirms the structures and phase evolution while Raman spectroscopy reveals characteristic vibration modes for both pyrochlore and brannerite. In addition, DRS of the U5+ ion has been used to probe the phase evolution, with the corresponding f- f transition band of 2 F7/2 energy level significantly shifting to longer wavenumbers due to the local coordination environment changing from eightfold coordination in pyrochlore to sixfold coordination in brannerite. [ABSTRACT FROM AUTHOR]

Abstract: A series of single phase compounds with nominal stoichiometry Sm(x)Yb(2−x)TiO5 (x=2, 1.4, 1, 0.6, and 0) have been successfully fabricated to generate a range of crystal structures covering the most common polymorphs previously discovered in the Ln 2TiO5 series (Ln=lanthanides and yttrium). Four of the five samples have not been previously fabricated in bulk, single phase form so their crystal structures are refined and detailed using powder synchrotron and single crystal x-ray diffraction, neutron diffraction and transmission electron microscopy. Based on the phase information from diffraction data, there are four crystal structure types in this series; orthorhombic Pnma, hexagonal P63 /mmc, cubic (pyrochlore-like) Fd-3m and cubic (fluorite-like) Fm-3m. The cubic materials show modulated structures with variation between long and short range ordering and the variety of diffraction techniques were used to describe these complex crystal structure types. [Copyright &y& Elsevier]

Abstract: Thin crystals of La2O3, LaAlO3, La2/3TiO3, La2TiO5, and La2Ti2O7 have been irradiated in situ using 1MeV Kr2+ ions at the Intermediate Voltage Electron Microscope-Tandem User Facility (IVEM-Tandem), Argonne National Laboratory (ANL). We observed that La2O3 remained crystalline to a fluence greater than 3.1×1016 ionscm−2 at a temperature of 50K. The four binary oxide compounds in the two systems were observed through the crystalline–amorphous transition as a function of ion fluence and temperature. Results from the ion irradiations give critical temperatures for amorphisation (T c ) of 647K for LaAlO3, 840K for La2Ti2O7, 865K for La2/3TiO3, and 1027K for La2TiO5. The T c values observed in this study, together with previous data for Al2O3 and TiO2, are discussed with reference to the melting points for the La2O3–Al2O3 and La2O3–TiO2 systems and the different local environments within the four crystal structures. Results suggest that there is an observable inverse correlation between T c and melting temperature (T m ) in the two systems. More complex relationships exist between T c and crystal structure, with the stoichiometric perovskite LaAlO3 being the most resistant to amorphisation. [ABSTRACT FROM AUTHOR]

Two new mixed-valence uranium oxide hydrate frameworks (UOFs), incorporating either Er 3+ or Y 3+ ions, were successfully synthesised under hydrothermal conditions and characterised with single-crystal X-ray diffraction and a variety of other structural and spectroscopic techniques. Both frameworks are isostructural and crystallise in the triclinic P 1̄ space group, consisting of β-U 3 O 8 type layers pillared by additional uranyl centres, with the Er 3+ /Y 3+ ions lying in the channels of the framework. SEM-EDS analysis found that both materials existed in plate-like morphologies, with a U:Er/Y ratio of 5.5. Bond valence sum analysis revealed the possible existence of pentavalent uranium centres, which was confirmed with diffuse reflectance spectroscopy. Being the first reported UOFs in this space group, this work highlights the complex and flexible nature of these materials, and the broader uranium oxide hydrate systems which exist in the surrounds of spent nuclear fuel disposal in the underground repository.