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Ceramics and single crystals of LaPO4 monazite doped with Eu(III) were irradiated with 14 MeV Au5+ ions at three different fluences. Changes to crystallinity, local coordination environments, and topography were probed using grazing-incidence X-ray diffraction (GIXRD), vertical scanning interferometry (VSI), scanning electron microscopy (SEM), Raman, and luminescence spectroscopy. GIXRD data of the ceramics revealed fluence dependent amorphization. A similar level of amorphization was detected for samples irradiated with 5 × 1013 ions/cm2 and 1 × 1014 ions/cm2, whereas the sample irradiated with the highest fluence of 1 × 1015 ions/cm2 appeared slightly less amorphous. VSI showed clear swelling of entire grains at the highest ion fluence, while more localized damage to grain boundaries was detected for ceramic samples irradiated at the lowest fluence. Single crystal specimens showed no pronounced topography changes following irradiation. SEM images of the ceramic irradiated at the highest fluence showed topological features indicative of grain surface melting. Raman and luminescence data showed a different degree of disorder in polycrystalline vs. single crystal samples. While changes to PO4 vibrational modes were observed in the ceramics, changes were more subtle or not present in the single crystals. The opposite was observed when probing the local Ln-O environment using Eu(III) luminescence, where the larger changes in terms of an elongation of the Eu-O (or La-O) bond and an increasing relative disorder with increasing fluence were observed only for the single crystals. The dissimilar trends observed in irradiated single crystals and ceramics indicate that grain boundary chemistry likely plays a significant role in the radiation response. [ABSTRACT FROM AUTHOR]

Cr-doped UO2 is a leading accident tolerant nuclear fuel where the complexity of Cr chemical states in the bulk material has prevented acquisition of an unequivocal understanding of the redox chemistry and mechanism for incorporation of Cr in the UO2 matrix. To resolve this, we have used electron paramagnetic resonance, high energy resolution fluorescence detection X-ray absorption near energy structure and extended X-ray absorption fine structure spectroscopic measurements to examine Cr-doped UO2 single crystal grains and bulk material. Ambient condition measurements of the single crystal grains, which have been mechanically extracted from bulk material, indicated Cr is incorporated substitutionally for U+4 in the fluorite lattice as Cr+3 with formation of additional oxygen vacancies. Bulk material measurements reveal the complexity of Cr states, where metallic Cr (Cr0) and oxide related Cr+2 and Cr+32O3 were identified and attributed to grain boundary species and precipitates, with concurrent (Cr+3xU+41-x)O2-0.5x lattice matrix incorporation. The deconvolution of chemical states via crystal vs. powder measurements enables the understanding of discrepancies in literature whilst providing valuable direction for safe continued use of Cr-doped UO2 fuels for nuclear energy generation. Additive based UO2 nuclear fuels, which incorporate small amounts of metal oxides such as chromia (Cr2O3), are an important class of accident tolerant fuels. Here authors determine the structural-redox mechanism for Cr lattice incorporation into UO2 nuclear fuels. [ABSTRACT FROM AUTHOR]

We report a comprehensive study on lanthanide monouranate–based glass–ceramic (GC) composites as potential waste forms for the immobilization of the lanthanide actinide fraction waste arising from the reprocessing of spent nuclear fuel (SNF). Although the crystalline LnUO4 precursor prepared via a nitrate route can be well stabilized in a sodium aluminoborosilicate glass, the in situ crystallization of EuUO4 in glass from oxide precursors (Eu2O3 and U3O8) is rather robust with regards to various processing conditions such as waste loadings, ceramic‐to‐glass ratios, and cooling rates. Scanning electron microscopy and transmission electron microscopy investigations revealed the detailed microstructures, where ∼1–5‐μm spheres for NdUO4 and EuUO4, and ∼1–5‐μm rectangular crystals for DyUO4 and HoUO4 were observed in residual glasses. As designed, the pentavalent uranium has been confirmed by diffuse reflectance spectroscopy. Overall, LnUO4‐based GC composite waste forms are chemically durable, offering flexible processing options with wide operating windows for SNF and process waste stream management. [ABSTRACT FROM AUTHOR]

A novel polymorph of ThB2O5, denoted as β-ThB2O5, was synthesised under high-temperature high-pressure (HT/HP) conditions. Via single crystal X-ray diffraction measurements, β-ThB2O5 was found to form a three-dimensional (3D) framework structure where thorium atoms are ten-fold oxygen coordinated forming tetra-capped trigonal prisms. The only other known polymorph of ThB2O5, denoted α, synthesised herein using a known borax, B2O3–Na2B4O7, high temperature solid method, was found to transform to the β polymorph when exposed to conditions of 4 GPa and ∼900 °C. Compared to the α polymorph, β-ThB2O5 has smaller molar volume by approximately 12%. Exposing a mixture of the α and β polymorphs to HT/HP conditions ex situ further demonstrated the preferred higher-pressure phase being β, with no α phase material being observed via Rietveld refinements against laboratory X-ray powder diffraction (PXRD) measurements. In situ heating PXRD measurements on α-ThB2O5 from RT to 1030 °C indicated that α-ThB2O5 transforms to the β variant at approximately 900 °C via a 1st order mechanism. β-ThB2O5 was found to exist only over a narrow temperature range, decomposing above 1050 °C. Ab initio calculations using density functional theory (DFT) with the Hubbard U parameter indicated, consistent with experimental observations, that β is both the preferred phase at higher temperatures and high pressures. Interestingly, it was found by switching from B2O3–Na2B4O7 to H3BO3–Li2CO3 flux using consistent high temperature solid state conditions for the synthesis of the α variant, β-ThB2O5 could be generated. Comparison of their single crystal measurements showed this was identical to that obtained from HT/HP conditions. [ABSTRACT FROM AUTHOR]

A novel polymorph of ThB2O5, denoted as β-ThB2O5, was synthesised under high-temperature high-pressure (HT/HP) conditions. Via single crystal X-ray diffraction measurements, β-ThB2O5 was found to form a three-dimensional (3D) framework structure where thorium atoms are ten-fold oxygen coordinated forming tetra-capped trigonal prisms. The only other known polymorph of ThB2O5, denoted α, synthesised herein using a known borax, B2O3–Na2B4O7, high temperature solid method, was found to transform to the β polymorph when exposed to conditions of 4 GPa and ∼900 °C. Compared to the α polymorph, β-ThB2O5 has smaller molar volume by approximately 12%. Exposing a mixture of the α and β polymorphs to HT/HP conditions ex situ further demonstrated the preferred higher-pressure phase being β, with no α phase material being observed via Rietveld refinements against laboratory X-ray powder diffraction (PXRD) measurements. In situ heating PXRD measurements on α-ThB2O5 from RT to 1030 °C indicated that α-ThB2O5 transforms to the β variant at approximately 900 °C via a 1st order mechanism. β-ThB2O5 was found to exist only over a narrow temperature range, decomposing above 1050 °C. Ab initio calculations using density functional theory (DFT) with the Hubbard U parameter indicated, consistent with experimental observations, that β is both the preferred phase at higher temperatures and high pressures. Interestingly, it was found by switching from B2O3–Na2B4O7 to H3BO3–Li2CO3 flux using consistent high temperature solid state conditions for the synthesis of the α variant, β-ThB2O5 could be generated. Comparison of their single crystal measurements showed this was identical to that obtained from HT/HP conditions. [ABSTRACT FROM AUTHOR]

Cr-doped UO2 as a modern nuclear fuel type has been demonstrated to increase the in-reactor fuel performance compared to conventional nuclear fuels. Little is known about the long-term stability of spent Cr-doped UO2 nuclear fuels in a deep geological disposal facility. The investigation of suitable model materials in a step wise bottom-up approach can provide insights into the corrosion behavior of spent Cr-doped nuclear fuels. Here, we present new wet chemical approaches providing the basis for such model systems, namely co-precipitation and wet coating. Both were successfully tested and optimized, based on detailed analyses of all synthesis steps and parameters: Cr-doping method, thermal treatment, reduction of U3O8 to UO2, green body production, and pellet sintering. Both methods enable the production of suitable model systems with a similar microstructure and density as a reference sample from AREVA. In comparison with results from the classical powder route, similar trends upon grain size and lattice parameter were determined. The results of this investigation highlight the significance of subtly different synthesis routes on the properties of Cr-doped UO2 ceramics. They enable a reproducible tailor-made well-defined microstructure, a homogeneous doping, for example, with lanthanides or alpha sources, the introduction of metallic particles, and a dust-free preparation. [ABSTRACT FROM AUTHOR]

The long- and short-range structural chemistry of the C-type bixbyite compounds Th 0.40 Nd 0.48 Ce 0.12 O 1.76 , Th 0.47 Nd 0.43 Ce 0.10 O 1.785 , and Th 0.45 Nd 0.37 Ce 0.18 O 1.815 is systematically examined using synchrotron X-ray powder diffraction (S-PXRD), high-energy resolution fluorescence detection X-ray absorption near edge (HERFD-XANES), and extended X-ray absorption fine structure spectroscopy (EXAFS) measurements supported by electronic structure calculations. S-PXRD measurements revealed that the title compounds all form classical C-type bixbyite structures in space group Ia 3̅ that have disordered cationic crystallographic sites with further observation of characteristic superlattice reflections corresponding to oxygen vacancies. Despite the occurrence of oxygen vacancies, HERFD-XANES measurements on the Ce L 3 -edge revealed that Ce incorporates as Ce 4+ into the structures but involves local distortion that resembles cluster behavior and loss of nearest-neighbors. In comparison, HERFD-XANES measurements on the Nd L 3 -edge supported by electronic structure calculations reveal that Nd 3+ adopts a local coordination environment similar to the long-range C-type structure while providing charge balancing for the formation of oxygen defects. Th L 3 -edge EXAFS analysis reveals shorter average Th-O distances in the title compounds in comparison to pristine ThO 2 in addition to shorter Th-O and Th-Ce distances compared to Th-Th or Ce-Ce in the corresponding F-type binary oxides (ThO 2 and CeO 2 ). These distances are further found to decrease with the increased Nd content of the structures despite simultaneous observation of the overall lattice structure progressively expanding. Linear combination calculations of the M-O bond lengths are used to help explain these observations, where the role of oxygen defects, via Nd 3+ incorporation, induces local bond contraction and enhanced Th cation valence, leading to the observed increased lattice expansion with progressive Nd 3+ incorporation. Overall, the investigation points to the significance of dissimilar cations exhibiting variable short-range chemical behavior and how it can affect the long-range structural chemistry of complex oxides., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

In situ synchrotron powder X-ray diffraction measurements have demonstrated that SrUO 4 undergoes a reversible phase transformation under reducing conditions at high temperatures, associated with the ordering of oxygen defects resulting in a lowering of crystallographic symmetry. When substoichiometric rhombohedral α-SrUO 4- x , in space group R3̅ m with disordered in-plane oxygen defects, is heated above 200 °C in a hydrogen atmosphere it undergoes a first order phase transformation to a (disordered) triclinic polymorph, δ-SrUO 4- x , in space group P1̅. Continued heating to above 450 °C results in the appearance of superlattice reflections, due to oxygen-vacancy ordering forming an ordered structure δ-SrUO 4- x . Cooling δ-SrUO 4- x toward room temperature results in the reformation of the rhombohedral phase α-SrUO 4- x with disordered defects, confirming the reversibility of the transformation. This suggests that the transformation, resulting from oxygen vacancy ordering, is not a consequence of sample reduction or decomposition, but rather represents a change in the energetics of the system. A strong reducing atmosphere is required to generate a critical amount of oxygen defects in α-SrUO 4- x to enable the transformation to δ-SrUO 4- x but once formed the transformation between these two phases can be induced by thermal cycling. The structure of δ-SrUO 4- x at 1000 °C was determined using symmetry representation analysis, with the additional reflections indexed to a commensurate distortion vector k = ⟨1/4 1/4 3/4⟩. The ordered 2D layered triclinic structure of δ-SrUO 4- x can be considered a structural distortion of the disordered 2D layered rhombohedral α-SrUO 4- x structure through the preferential rearrangement of the in-plane oxygen vacancies. Ab initio calculations using density functional theory with self-consistently derived Hubbard U parameter support the assigned ordered defect superstructure model. Entropy changes associated with the temperature dependent short-range ordering of the reduced U species are believed to be important and these are discussed with respect to the results of the ab initio calculations.