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⁺³_xU⁺⁴_1-x)O_2-0.5x 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.

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.

The synthesis of the first actinide polyiodate, K ₄ [(UO ₂ ) ₂ (IO ₃ ) ₆ (I ₄ O ₁₁ )]·(HIO ₃ ) ₄ (H ₂ O) ₆ ( UP-1 ), is described and its X-ray luminescent and proton conductivity properties are examined.

Crystalline materials such as monazite have been considered for the storage of radionuclides due to their favorable radiation stability. Understanding their structural chemical response to radiation damage as solid solutions is a key component of determining their suitability for radionuclide immobilization. Herein, high-resolution structural studies were performed on ceramics of the monazite solid solution La_1-xCe_xPO₄ (x = 0.25, 0.5, 0.75, 1) in order to understand the role of structural chemistry on irradiation stability. Ceramic samples were irradiated with 14 MeV Au ions with 10¹⁴ ions/cm² and 10¹⁵ ions/cm² to simulate the recoil of daughter nuclei from the alpha decay of actinide radionuclides. The extent of radiation damage was analyzed in detail using scanning electron microscopy (SEM), Raman spectroscopy, grazing incidence X-ray diffraction (GI-XRD), and high-energy-resolution fluorescence detection extended X-ray absorption fine structure (HERFD-EXAFS) spectroscopy. SEM and Raman spectroscopy revealed extensive structural damage as well as the importance of grain boundary regions, which appear to impede the propagation of defects. Both radiation-induced amorphization and recrystallization were studied by GI-XRD, highlighting the ability of monazite to remain crystalline at high fluences throughout the solid solution. Both, diffraction and HERFD-EXAFS experiments show that while atomic disorder is increased in irradiated samples compared to pristine ceramics, the short-range order was found to be largely preserved, facilitating recrystallization. However, the extent of recrystallization was found to be dependent on the solid solution composition. Particularly, the samples with uneven ratios of solute cations, La_0.75Ce_0.25PO₄ and La_0.25Ce_0.75PO₄ were observed to exhibit the least apparent radiation damage resistance. The findings of this work are discussed in the context of the monazite solid solution chemistry and their appropriateness for radionuclide immobilization.

This perspective article discusses the developments over the last decade, state-of-the-art and future directions of examining actinide chemistry arising fromex situhigh pressure and high temperature conditions.