Crystal chemical design, synthesis and characterisation of U(IV)-dominant betafite phases for actinide immobilisation.

Crystal chemical design principles were applied to synthesise novel U4+ dominant and titanium excess betafite phases Ca1.15(5)U0.56(4)Zr0.17(2)Ti2.19(2)O7 and Ca1.10(4)U0.68(4)Zr0.15(3)Ti2.12(2)O7, in high yield (85-95 wt%), and ceramic density reaching 99% of theoretical. Substitution of Ti on the A-site of the pyrochlore structure, in excess of full B-site occupancy, enabled the radius ratio (rA/rB = 1.69) to be tuned into the pyrochlore stability field, approximately 1.48 ≲ rA/rB ≲ 1.78, in contrast to the archetype composition CaUTi2O7 (rA/rB = 1.75). U L3-edge XANES and U 4f7/2 and U 4f5/2 XPS data evidenced U4+ as the dominant speciation, consistent with the determined chemical compositions. The new betafite phases, and further analysis reported herein, point to a wider family of actinide betafite pyrochlores that could be stabilised by application of the underlying crystal chemical principle applied here.

Correction: Mixed H2O/H2 plasma-induced redox reactions of thin uranium oxide films under UHV conditions.

Correction for 'Mixed H2O/H2 plasma-induced redox reactions of thin uranium oxide films under UHV conditions' by Ghada El Jamal et al., Dalton Trans., 2021, DOI: 10.1039/d1dt01020d.

Mixed H2O/H2 plasma-induced redox reactions of thin uranium oxide films under UHV conditions.

X-ray photoelectron spectroscopy (XPS) has been used to study the effect of mixed H2O/H2 gas plasma on the surfaces of UO2, U2O5 and UO3 thin films at 400 °C. The experiments were performed in situ under ultra-high vacuum conditions. Deconvolution of the U4f7/2 peaks into U(IV), U(V) and U(VI) components revealed the surface composition of the films after 10 min plasma exposure as a function of H2 concentration in the feed gas of the plasma. Some selected films (unexposed and exposed) were also analysed using grazing-incidence X-ray diffraction (GIXRD). The XPS results show that U(V) is formed as a major product upon 10 minutes exposure of UO3 by a mixed H2O/H2 plasma in a fairly wide H2 concentration range. When starting with U(V) (U2O5), rather high H2 concentrations are needed to reduce U(V) to U(IV) in 10 minutes. In the plasma induced oxidation of UO2, U(V) is never observed as a major product after 10 minutes and it would seem that once U(V) is formed in the oxidation of UO2 it is rapidly oxidized further to U(VI). The grazing incidence X-ray diffraction analysis shows that there is a considerable impact of the plasma and heating conditions on the crystal structure of the films in line with the change of the oxidation state. This structural difference is proposed to be the main kinetic barrier for plasma induced transfer between U(IV) and U(V) in both directions.

Time-dependent surface modification of uranium oxides exposed to water plasma.

Thin UO2 films exposed to water plasma under UHV conditions have been shown to be interesting models for radiation induced oxidative dissolution of spent nuclear fuel. This is partly attributed to the fact that several of the reactive oxidizing and reducing species in a water plasma are also identified as products of radiolysis of water. Exposure of UO2 films to water plasma has previously been shown to lead to oxidation from U(iv) to U(v) and (vi). In this work we have studied the dynamics of water plasma induced redox changes in UO2 films by monitoring UO2 films using X-Ray photoelectron Photoemission (XPS) and Ultra-Violet Photoemission (UPS) spectroscopy as a function of exposure time. The surface composition in terms of oxidation states obtained from U4f7/2 peak deconvolution could be retraced along the exposure time, and compared to the valence band. The spectral analysis showed that U(iv) is initially oxidized to U(v) which is subsequently oxidized to U(vi). For extended exposure times it was shown that U(vi) is slowly reduced back to U(v). UPS data show that, unlike the U(v) formed on the surface upon oxidation of U(iv), the U(v) formed upon reduction of U(vi) is localized in the bulk of the film. It also displays a different reactivity than the initially formed U(v). The experiments can be reproduced using a simple kinetic model describing the redox processes involved.

X-Ray and ultraviolet photoelectron spectroscopy studies of Uranium(IV),(V) and(VI) exposed to H2O-plasma under UHV conditions.

Thin films of UO2, U2O5, and UO3 were prepared in situ and exposed to reactive gas plasmas of O2, H2 and H2O vapour produced with an ECR plasma source (electron cyclotron resonance) under UHV conditions. The plasma constituents were analysed using a residual gas analyser mass spectrometer. For comparison, the thin films were also exposed to the plasma precursor gases under comparable conditions. Surface analysis was conducted using X-Ray and ultraviolet photoelectron spectroscopy before and after exposure, by measuring the U 4f, O 1s core levels and the valence band region. The evolution of the peaks was monitored as a function of temperature and time of exposure. After interacting with water plasma at 400 °C, the surface of UO2 was oxidized to a higher oxidation state compared to when starting with U2O5 while the UO3 film displayed weak surface reduction. When exposed to water plasma at ambient temperature, the outermost surface layer is composed of hexavalent uranium in all three cases.

An Atomic-Scale Understanding of UO2 Surface Evolution during Anoxic Dissolution.

Our present understanding of surface dissolution of nuclear fuels such as uranium dioxide (UO2) is limited by the use of nonlocal characterization techniques. Here we discuss the use of state-of-the-art scanning transmission electron microscopy (STEM) to reveal atomic-scale changes occurring to a UO2 thin film subjected to anoxic dissolution in deionized water. No amorphization of the UO2 film surface during dissolution is observed, and dissolution occurs preferentially at surface reactive sites that present as surface pits which increase in size as the dissolution proceeds. Using a combination of STEM imaging modes, energy-dispersive X-ray spectroscopy (STEM-EDS), and electron energy loss spectroscopy (STEM-EELS), we investigate structural defects and oxygen passivation of the surface that originates from the filling of the octahedral interstitial site in the center of the unit cells and its associated lattice contraction. Taken together, our results reveal complex pathways for both the dissolution and infiltration of solutions into UO2 surfaces.

Size Dependence of Lattice Parameter and Electronic Structure in CeO2 Nanoparticles.

Intrinsic properties of a compound (e.g., electronic structure, crystallographic structure, optical and magnetic properties) define notably its chemical and physical behavior. In the case of nanomaterials, these fundamental properties depend on the occurrence of quantum mechanical size effects and on the considerable increase of the surface to bulk ratio. Here, we explore the size dependence of both crystal and electronic properties of CeO2 nanoparticles (NPs) with different sizes by state-of-the art spectroscopic techniques. X-ray diffraction, X-ray photoelectron spectroscopy, and high-energy resolution fluorescence-detection hard X-ray absorption near-edge structure (HERFD-XANES) spectroscopy demonstrate that the as-synthesized NPs crystallize in the fluorite structure and they are predominantly composed of CeIV ions. The strong dependence of the lattice parameter with the NPs size was attributed to the presence of adsorbed species at the NPs surface thanks to Fourier transform infrared spectroscopy and thermogravimetric analysis measurements. In addition, the size dependence of the t2g states in the Ce LIII XANES spectra was experimentally observed by HERFD-XANES and confirmed by theoretical calculations.

U2O5 Film Preparation via UO2 Deposition by Direct Current Sputtering and Successive Oxidation and Reduction with Atomic Oxygen and Atomic Hydrogen.

We describe a method to produce U2O5 films in situ using the Labstation, a modular machine developed at JRC Karlsruhe. The Labstation, an essential part of the Properties of Actinides under Extreme Conditions laboratory (PAMEC), allows the preparation of films and studies of sample surfaces using surface analytical techniques such as X-ray and ultra-violet photoemission spectroscopy (XPS and UPS, respectively). All studies are made in situ, and the films, transferred under ultra-high vacuum from their preparation to an analyses chamber, are never in contact with the atmosphere. Initially, a film of UO2 is prepared by direct current (DC) sputter deposition on a gold (Au) foil then oxidized by atomic oxygen to produce a UO3 film. This latter is then reduced with atomic hydrogen to U2O5. Analyses are performed after each step involving oxidation and reduction, using high-resolution photoelectron spectroscopy to examine the oxidation state of uranium. Indeed, the oxidation and reduction times and corresponding temperature of the substrate during this process have severe effects on the resulting oxidation state of the uranium. Stopping the reduction of UO3 to U2O5 with single U(V) is quite challenging; first, uranium-oxygen systems exist in numerous intermediate phases. Second, differentiation of the oxidation states of uranium is mainly based on satellite peaks, whose intensity peaks are weak. Also, experimenters should be aware that X-ray spectroscopy (XPS) is a technique with an atomic sensitivity of 1% to 5%. Thus, it is important to obtain a complete picture of the uranium oxidation state with the entire spectra obtained on U4f, O1s, and the valence band (VB). Programs used in the Labstation include a linear transfer program developed by an outside company (see Table of Materials) as well as data acquisition and sputter source programs, both developed in-house.

Crystal Structure and Magnetic Properties of Uranium Hydride UH2 Stabilized as a Thin Film.

A new type of uranium binary hydride, UH2, with the CaF2 crystal structure, was synthesized in a thin-film form using reactive sputter deposition at low temperatures. The material has a grain size of 50-100 nm. The lattice parameter a = (535.98 ± 0.14 pm) is close to that in known Np (534.3 pm) and Pu (535.9 pm) iso-types. UH2 is a metallic ferromagnet with the Curie temperature TC ≈ 120 K. A very wide hysteresis loop indicates strong magnetocrystalline anisotropy. X-ray photoelectron spectroscopy reveals similarities with electronic structure of UH3, which is also ferromagnet with higher TC = 165 K.

Controlled synthesis of thorium and uranium oxide nanocrystals.

Very little is known about the size and shape effects on the properties of actinide compounds. As a consequence, the controlled synthesis of well-defined actinide-based nanocrystals constitutes a fundamental step before studying their corresponding properties. In this paper, we report on the non-aqueous surfactant-assisted synthesis of thorium and uranium oxide nanocrystals. The final characteristics of thorium and uranium oxide nanocrystals can be easily tuned by controlling a few experimental parameters such as the nature of the actinide precursor and the composition of the organic system (e.g., the chemical nature of the surfactants and their relative concentrations). Additionally, the influence of these parameters on the outcome of the synthesis is highly dependent on the nature of the actinide element (thorium versus uranium). By using optimised experimental conditions, monodisperse isotropic uranium oxide nanocrystals with different sizes (4.5 and 10.7 nm) as well as branched nanocrystals (overall size ca. 5 nm), nanodots (ca. 4 nm) and nanorods (with ultra-small diameters of 1 nm) of thorium oxide were synthesised.

Reducing uncertainties affecting the assessment of the long-term corrosion behavior of spent nuclear fuel.

Reducing the uncertainties associated with extrapolation to very long term of corrosion data obtainable from laboratory tests on a relatively young spent nuclear fuel is a formidable challenge. In a geologic repository, spent nuclear fuel may come in contact with water tens or hundreds of thousands of years after repository closure. The corrosion behavior will depend on the fuel properties and on the conditions characterizing the near field surrounding the spent fuel at the time of water contact. This paper summarizes the main conclusions drawn from multiyear experimental campaigns performed at JRC-ITU to study corrosion behavior and radionuclide release from spent light water reactor fuel. The radionuclide release from the central region of a fuel pellet is higher than that from the radial periphery, in spite of the higher burnup and the corresponding structural modifications occurring at the pellet rim during irradiation. Studies on the extent and time boundaries of the radiolytic enhancement of the spent fuel corrosion rate indicate that after tens or hundreds of thousands of years have elapsed, very small or no contribution to the enhanced corrosion rate has to be expected from α radiolysis. A beneficial effect inhibiting spent fuel corrosion due to the hydrogen overpressure generated in the near field by iron corrosion is confirmed. The results obtained so far point toward a benign picture describing spent fuel corrosion in a deep geologic repository. More work is ongoing to further reduce uncertainties and to obtain a full description of the expected corrosion behavior of spent fuel.

Cross-sections of the reaction 232Th(p,3n)230Pa for production of 230U for targeted alpha therapy.

(230)U/(226)Th is a promising novel alpha-emitter system for application in targeted alpha therapy of cancer. The therapeutic nuclides can be produced by proton irradiation of natural (232)Th according to the reaction (232)Th(p,3n)(230)Pa, followed by subsequent beta decay of (230)Pa to (230)U. In this study, the experimental excitation function for the (232)Th(p,3n)(230)Pa reaction up to 34 MeV proton energy has been measured using the stacked-foil technique. The proton energies in the various foils were calculated with the SRIM 2003 code and gamma-ray spectrometry was used to measure the activities of the various radioisotopes produced. The measured cross-sections are in good agreement with selected literature values and with model calculations using the EMPIRE II code. The reaction (232)Th(p,3n)(230)Pa allows the production of carrier-free (230)U in clinically relevant levels.