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International audience; Although uranium–cerium dioxides are frequently used as a surrogate material for (U,Pu)O2−δ nuclear fuels, there is currently no reliable data regarding the oxygen stoichiometry and redox speciation of the cations in such samples. In order to fill this gap, this manuscript details a synchrotron study of highly homogeneous (U,Ce)O2±δ sintered samples prepared by a wet-chemistry route. HERFD-XANES spectroscopy led to determining accurately the O/M ratios (with M = U + Ce). Under a reducing atmosphere (pO2 ≈ 6 × 10–29 atm at 650 °C), the oxides were found to be close to O/M = 2.00, while the O/M ratio varied with the sintering conditions under argon (pO2 ≈ 3 × 10–6 atm at 650 °C). They globally appeared to be hyperstoichiometric (i.e., O/M > 2.00) with the departure from the dioxide stoichiometry decreasing with both the cerium content in the sample and the sintering temperature. Nevertheless, such a deviation from the ideal O/M = 2.00 ratio was found to generate only moderate structural disorder from EXAFS data at the U-L3 edge as all the samples retained the fluorite-type structure of the UO2 and CeO2 parent compounds. The determination of accurate lattice parameters owing to S-PXRD measurements led to complementing the data reported in the literature by various authors. These data were consistent with an empirical relation linking the unit cell parameter, the chemical composition, and the O/M stoichiometry, showing that the latter can be evaluated simply within a ± 0.02 uncertainty

Microbial U(VI) reduction influences the uranium mobility in contaminated subsurface environments and can affect the disposal of high-level radioactive waste by transform-ing the water-soluble U(VI) to less mobile U(IV). The reduction of U(VI) by the sulfate-reducing bacterium Desulfosporosinus hippei DSM 8344T, a close phylogenetic relative to naturally occurring microorganism present in clay rock and bentonite, was investigat-ed. D. hippei DSM 8344T showed a relatively fast removal of uranium from the superna-tants in artificial Opalinus Clay pore water. Combined speciation calculations and lumi-nescence spectroscopic investigations showed the dependence of U(VI) reduction on the initial U(VI) species. Scanning transmission electron microscopy coupled with ener-gy-dispersive X-ray spectroscopy showed uranium-containing aggregates on the cell surface and the formation of membrane vesicles. By combining different spectroscopic techniques, including UV/Vis spectroscopy, as well as uranium M4-edge X-ray absorp-tion near-edge structure (XANES) recorded in high-energy-resolution fluorescence-detection (HERFD) mode and extended X-ray absorption fine structure (EXAFS) analy-sis, the partial reduction of U(VI) could be verified, whereby the formed U(IV) product has an unknown structure. Furthermore, the U M4 HERFD-XANES showed the presence of U(V) during the process, suggesting a single-electron transfer mechanism for the microbial U(VI) reduction by sulfate reducers. These findings offer new insights into the U(VI) reduction by sulfate-reducing bacteria and contribute to a comprehensive safety concept for a repository for high-level radioactive waste.

In situ XANES is a powerful method to collect new experimental data in the U–O phase diagram., The U–O phase diagram is of paramount interest for nuclear-related applications and has therefore been extensively studied. Experimental data have been gathered to feed the thermodynamic calculations and achieve an optimization of the U–O system modelling. Although considered as well established, a critical assessment of this large body of experimental data is necessary, especially in light of the recent development of new techniques applicable to actinide materials. Here we show how in situ X-ray absorption near-edge structure (XANES) is suitable and relevant for phase diagram determination. New experimental data points have been collected using this method and discussed in regard to the available data. Comparing our experimental data with thermodynamic calculations, we observe that the current version of the U–O phase diagram misses some experimental data in specific domains. This lack of experimental data generates inaccuracy in the model, which can be overcome using in situ XANES. Indeed, as shown in the paper, this method is suitable for collecting experimental data in non-ambient conditions and for multiphasic systems.

In view of safe management of the nuclear wastes, a sound knowledge of the atomic-scale properties of U1-xMxO2+y nanoparticles is essential. In particular, their cation valences and oxygen stoichiometries are of great interest as these properties drive their diffusion and migration behaviors into the environment. Here, we present an in-depth study of U1-xCexO2+y, over the full compositional domain, by combining X-ray diffraction and high-energy resolution fluorescence detection X-ray absorption near-edge structure. We show, on one hand, the coexistence of UIV, UV, and UVI and, on the other hand, that the fluorite structure is maintained despite this charge distribution.

International audience; The mobility of 79Se, a fission product of 235U and long-lived radioisotope, is an important parameter in the safety assessment of radioactive nuclear waste disposal systems. Nonradioactive selenium is also an important contaminant of drainage waters from black shale mountains and coal mines. Highly mobile and soluble in its high oxidation states, selenate (Se(VI)O42–) and selenite (Se(IV)O32–) oxyanions can interact with magnetite, a mineral present in anoxic natural environments and in steel corrosion products, thereby being reduced and consequently immobilized by forming low-solubility solids. Here, we investigated the sorption and reduction capacity of synthetic nanomagnetite toward Se(VI) at neutral and acidic pH, under reducing, oxygen-free conditions. The additional presence of Fe(II)aq, released during magnetite dissolution at pH 5, has an effect on the reduction kinetics. X-ray absorption spectroscopy analyses revealed that, at pH 5, trigonal gray Se(0) formed and that sorbed Se(IV) complexes remained on the nanoparticle surface during longer reaction times. The Se(0) nanowires grew during the reaction, which points to a complex transport mechanism of reduced species or to active reduction sites at the tip of the Se(0) nanowires. The concomitant uptake of aqueous Fe(II) and Se(VI) ions is interpreted as a consequence of small pH oscillations that result from the Se(VI) reduction, leading to a re-adsorption of aqueous Fe(II) onto the magnetite, renewing its reducing capacity. This effect is not observed at pH 7, where we observed only the formation of Se(0) with slow kinetics due to the formation of an oxidized maghemite layer. This indicates that the presence of aqueous Fe(II) may be an important factor to be considered when examining the environmental reactivity of magnetite.

For the first time, the structural investigation of a Pb-exchanged zeolite (Pb13.4(OH)10Al17.4Si54.6O144 ∙38H2O) with STI framework type, revealed a highly unusual and intriguing sudden volume increase under continuous heating. Understanding the fundamental mechanisms leading to such an unusual behaviour is essential for technological applications and interpretation of chemical bonding in zeolites. The dehydration was tracked in situ from 25 to 450 °C by single crystal X-ray diffraction, infrared and X-ray absorption spectroscopy. Further interpretation of the experimental observations was supported by ab initio molecular dynamics simulations. Initially, Pb-STI unit-cell volume contracts (ΔV = -3.5%) from 25 to 100°C. This agrees with the trend observed in STI zeolites. Surprisingly, at 125°C, the framework expanded (ΔV = +2%), adopting a configuration, which resembles that of the room temperature structure. Upon heating, the structure loses H2O but no de-hydroxylation occurred. The key mechanism leading to the sudden volume increase was found to be the formation of Pbx(OH)y clusters, which prevent the shrinking of the channels, rupture of the tetrahedral bonds and occlusion of the pores. This zeolite has therefore an increased thermal stability with respect to other STI metal-exchanged zeolites, with important consequences on its applications.

For the first time, the structural investigation of a Pb-exchanged zeolite (Pb

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., Comment: Inorganic Chemistry (2020)

Clay rock represents a suitable host rock for the long-term storage of high-level radioactive waste with bentonite as backfill material. In the event of a worst-case scenario, water can enter the repository. It is possible that naturally occurring microorganisms can interact with the radionuclides and thereby change the chemical speciation or induce redox reactions. Among different sulfate-reducing bacteria, Desulfosporosinus species represent important members of the microbial communities in both clay rock and bentonite.[1,2] Desulfosporosinus hippei DSM 8344T is a close phylogenetic relative to an isolated bacterium from bentonite.[3] Therefore, this strain was selected to get a more profound insight into the uranium(VI) interactions with naturally occurring microorganisms from deep geological layers. Time-dependent experiments in artificial Opalinus Clay pore water[4] (100 µM uranium(VI), pH 5,5) showed a high removal of uranium from the supernatants within a short time range. UV/Vis studies of the dissolved cell pellets provided clear proof of a partial reduction of uranium(VI) to uranium(IV) in the samples, although bands of uranium(VI) were still observable. These findings propose a combined association-reduction process as an explanation for the ongoing interaction mechanism. Uranium aggregates formed on the cell surface were visible in TEM images. Furthermore, cells released membrane vesicles as a possible defense mechanism against cell encrustation. In addition, HERFD-XANES measurements confirmed the reduction of uranium(VI). But with these measurements also the presence of uranium(V) in the cell pellets could be demonstrated. This provides first evidence of the involvement of uranium(V) in uranium(VI) reduction by sulfate-reducing microorganisms. With the help of EXAFS measurements, different cell-related uranium species were detected. This study helps to better understand the complexity of redox processes in the environment and contribute to a safety concept for a nuclear repository in clay rock. Moreover, new insights into the uranium(VI) reduction mechanisms of sulfate-reducing bacteria were presented. References: [1] Bagnoud et al. (2016) Nat. Commun 7, 1–10. [2] Matschiavelli et al. (2019) Environ. Sci. Technol. 53, 10514–10524. [3] Vatsurina et al. (2008) Int. J. Syst. Evol. Microbiol. 58, 1228–1232. [4] Wersin et al. (2011) Appl. Geochemistry 26, 931–953.

In view of safe management of the nuclear wastes, a sound knowledge of the atomic-scale properties of U

Three different Spark Plasma Sintering (SPS) treatments were applied to highly sinteractive, near-stoichiometric UO2.04 nanocrystalline (5 nm) powders produced by U(IV) oxalate hydrothermal decomposition at 170 °C. The sintering conditions for reaching 95 % Theoretical Density (TD) in regular SPS, high pressure SPS (HP-SPS), and, for the first time, two-step SPS (2S-SPS), were found. Densification to 95 % TD was achieved at 1000 °C in regular SPS (70 MPa applied pressure), 660 °C in HP-SPS (500 MPa), and 650-550 °C in 2S-SPS (70 MPa). With the goal of minimising the grain growth during densification, the sintering treatments were optimised to favour densification over coarsening, and the final microstructures thus obtained are compared. Otherwise identical, stochiometric UO2 samples of different grain sizes, ranging from 3.08 μm to 163 nm, were produced. Room-temperature oxidation of the powders could not be avoided due to their nanometric dimensions, and a final annealing treatment was designed to reduce hyper stoichiometric samples to UO2.00.

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 CeO

This study combines bulk structural and spectroscopic investigations of Eu3+- or Y3+/Eu3+ co-doped tetragonal and cubic zirconia polymorphs to gain an in-depth understanding of the solid solution formation process. Our bulk structural characterizations show that the dopant is homogenously distributed in the ZrO2 host structure resulting in an increase of the bulk symmetry with increasing dopant substitution (from 8 to 26 mol%). The local site symmetry around the Eu3+ dopant, however, determined with luminescence spectroscopy (TRLFS), remains low in all samples. Results obtained with X-ray pair distribution function and X-ray absorption spectroscopy show that the average coordination environment in the stabilized zirconia structures remains practically unchanged. Despite this very constant average dopant environment, site-selective TRLFS data show the presence of three nonequivalent Eu3+ environments in the ZrO2 solid structures. These Eu3+ environments are assumed to arise from Eu3+ incorporation at superficial sites, which increase in abundance as the size of the crystallites decrease, and incorporation on two bulk sites differing in the location of the oxygen vacancies with respect to the dopant cation.

In the context of a comprehensive campaign for the characterisation of transmutation fuels for next generation nuclear reactors, the melting behaviour of mixed uranium-americium dioxides has been experimentally studied for the first time by laser heating, for Am concentrations up to 70 mol. % under different types of atmospheres. Extensive post-melting material characterisations were then performed by X-ray absorption spectroscopy and electron microscopy. The melting temperatures observed for the various compositions follow a markedly different trend depending on the experimental atmosphere. Uranium-rich samples melt at temperatures significantly lower (around 2700 K) when they are laser-heated in a strongly oxidizing atmosphere compressed air at (0.300 ± 0.005) MPa, compared to the melting points (beyond 3000 K) registered for the same compositions in an inert environment (pressurised Ar). This behaviour has been interpreted on the basis of the strong oxidation of such samples in air, leading to lower-melting temperatures. Thus, the melting temperature trend observed in air is characterized, in the purely pseudo-binary dioxide plane, by an apparent maximum melting temperature around 2850 K for 0.3 < x(AmO2) < 0.5. The melting points measured under inert atmosphere uniformly decrease with increasing americium content, displaying an approximately ideal solution behaviour if a melting point around 2386 K is assumed for pure AmO2. In reality, it will be shown that the (U, Am)-oxide system can only be rigorously described in the ternary U-Am-O phase diagram, rather than the UO2-AmO2 pseudo-binary, due to the aforementioned over-oxidation effect in air. Indeed, general departures from the oxygen stoichiometry (Oxygen/Metal ratios ≠ 2.0) have been highlighted by the X-ray Absorption Spectroscopy (XAS). Finally, to help interpret the experimental results, thermodynamic computations based on the CALPHAD method will be presented.

Most materials expand with temperature because of the anharmonicity of lattice vibration, and only a few shrink with increasing temperature. UO2, whose thermal properties are of significant importance for the safe use of nuclear energy, was considered for a long time to belong to the first group. This view was challenged by recent in situ synchrotron X-ray diffraction measurements, showing an unusual thermal decrease of the U–O distances. This thermal shrinkage was interpreted as a consequence of the splitting of the U–O distances due to a change in the U local order from Fm3m to Pa3. In contrast to these previous investigations and using an element-specific synchrotron-based spectroscopic method, we show here that the U sublattice remains locally of the fluorite type from 50 to 1265 K, and that the decrease of the first U–O bond lengths is associated with an increase of the disorder.

For nuclear fuel related applications, the oxygen stoichiometry of mixed oxides U1-yMyO2±x is an essential property as it affects fuel properties and may endanger the safe operation of nuclear reactors. A careful review of the open literature indicates that this parameter is difficult to assess properly and that the nature of the defects, i.e., oxygen vacancies or UV, in aliovalent cation-doped UO2 is still subject to controversy. To confirm the formation of UV, we have investigated the room-temperature stable U1-yLayO2±x phase using several experimental methods (e.g., XRD, XANES, and NMR) confirmed by theoretical calculations. This paper presents the experimental proof of UV and its effect we identified in both electronic and local structure. We observe that UV is formed in quasi-equimolar proportion as LaIII in U1-yLayO2±x (y = 0.06, 0.11, and 0.22) solid solutions. The fluorite structure is maintained despite the cationic substitution, but the local structure is affected as variations of the interatomic distances are found. Therefore, we provide here the definitive proof that the substitution of UIV with LaIII is not accommodated by the creation of O vacancies as has often been assumed. The UO2 fluorite structure compensates the incorporation of an aliovalent cation by the formation of UV in quasi-equimolar proportions.

Actinide research at the nanoscale is gaining fundamental interest due to environmental and industrial issues. The knowledge of the local structure and speciation of actinide nanoparticles, which possibly exhibit specific physico-chemical properties in comparison to bulk materials, would help in a better and reliable description of their behaviour and reactivity. Herein, the synthesis and relevant characterization of PuO

International audience; The preparation and structural characterization of an original Th peroxo sulfate dihydrate, crystallizing at room temperature in the form of stable 1D polymeric microfibres is described. A combination of laboratory and synchrotron techniques allowed solution of the structure of the Th(O2)(SO4)(H2O)2 compound, which crystallizes in a new structure type in the space group Pna21 of the orthorhombic crystal system. Particularly, the peroxide ligand coordinates to the Th cations in an unusual μ3‐η2:η2:η2 bridging mode, forming an infinite 1D chain decorated with sulfato ligands exhibiting simultaneously monodentate and bidentate coordination modes.

International audience; Actinide research at the nanoscale is gaining fundamental interest due to environmental and industrial issues. The knowledge of the local structure and speciation of actinide nanoparticles, which possibly exhibit specific physico-chemical properties in comparison to bulk materials, would help in a better and reliable description of their behaviour and reactivity. Herein, the synthesis and relevant characterization of PuO2 and ThO2 nanoparticles displayed as dispersed colloids, nanopowders or nanostructured oxide powders, allow to establish a clear relationship between the size of the nanocrystals composing these oxides and their corresponding An(IV) local structure investigated by EXAFS spectroscopy. Particularly, the probed An(IV) first oxygen shell evidences an analogous behaviour for both Pu and Th oxides. This observation suggests that the often observed and controversial splitting of the Pu-O shell on the Fourier transformed EXAFS signal of PuO2 samples is attributed to a local structural disorder driven by a nanoparticle surface effect rather than to the presence of PuO2+x species.

To assure the safety of oxide-fuel based nuclear reactors, the knowledge of the atomic-scale properties of U1−yMyO2±x materials is essential. These compounds show complex chemical properties, originating from the fact that actinides and rare earths may occur with different oxidation states. In these mostly ionic materials, aliovalent cationic configurations can induce changes in the oxygen stoichiometry, with dramatic effects on the properties of the fuel. First studies on U1−yAmyO2±x indicated that these materials exhibit particularly complex electronic and local-structure configurations. Here we present an in-depth study of these compounds, over a wide compositional domain, by combining XRD, XAS and Raman spectroscopy. We provide evidences of the co-existence of four different cations (U4+, U5+, Am3+, Am4+) in U1−yMyO2±x compounds, which nevertheless maintain the fluorite structure. Indeed, we show that the cationic sublattice is basically unaffected by the extreme multi-valence states, whereas complex defects are present in the oxygen sublattice.

The charge distributions in α-Na2UO4, Na3NpO4, α-Na2NpO4, Na4NpO5, Na5NpO6, Na2PuO3, Na4PuO5, and Na5PuO6 are investigated in this work using X-ray absorption near-edge structure (XANES) spectroscopy at the U-L3, Np-L3, and Pu-L3 edges. In addition, a Rietveld refinement of monoclinic Na2PuO3, in space group C2/c, is reported for the first time, and the existence of the isostructural Na2NpO3 phase is revealed. In contrast to measurements in solution, the number of published XANES data for neptunium and plutonium solid phases with a valence state higher than IV is very limited. The present results cover a wide range of oxidation states, namely, IV to VII, and can serve as reference for future investigations. The sodium actinide series show a variety of local coordination geometries, and correlations between the shape of the XANES spectra and the local structural environments are discussed herein.

Most materials expand with temperature because of the anharmonicity of lattice vibration, and only a few shrink with increasing temperature. UO

Americium 241 is a potential alternative to plutonium 238 as an energy source for missions into deep space or to the dark side of planetary bodies. In order to use the 241Am isotope for radioisotope thermoelectric generator or radioisotope heating unit (RHU) production, americium materials need to be developed. This study focuses on the stabilization of a cubic americium oxide phase using uranium as the dopant. After optimization of the material preparation, (Am0.80U0.12Np0.06Pu0.02)O1.8 has been successfully synthesized to prepare a 2.96 g pellet containing 2.13 g of 241Am for fabrication of a small scale RHU prototype. Compared to the use of pure americium oxide, the use of uranium-doped americium oxide leads to a number of improvements from a material properties and safety point of view, such as good behavior under sintering conditions or under alpha self-irradiation. The mixed oxide is a good host for neptunium (i.e., the 241Am daughter element), and it has improved safety against radioactive material dispersion in the case of accidental conditions.

For nuclear fuel related applications, the oxygen stoichiometry of mixed oxides U

PuPO4 was prepared by a solid state reaction method and its crystal structure at room temperature was solved by powder X-ray diffraction combined with Rietveld refinement. High resolution XANES measurements confirm the +III valence state of plutonium, in agreement with valence bond derivation. The presence of the americium (as β− decay product of plutonium) in the +III oxidation state was determined based on XANES spectroscopy. High resolution solid state 31P NMR agrees with the XANES results and the presence of a solid-solution.

The melting behaviour in the pseudo-binary system (UO2 + NpO2) has been studied experimentally for the “rst time in this work with the help of laser heating under controlled atmosphere. It has been observed that the solidus and liquidus lines of this system follow an ideal solution behaviour (negligible mixing enthalpy) between the well-established solid/liquid transition temperatures of pure UO2 (3130 K) and that recently assessed for NpO2 (T = 3070 K). Pre- and post-melting material characterizations performed with the help of X-ray diffraction and Raman spectroscopy are also consistent with ideal mixing of the two end members. Such behaviour follows the similar structure and bonding properties of tetravalent uranium and neptunium and the similar melting points of the two oxides. The interest of this investigation is twofold. From a technological viewpoint, it indicates that the incorporation of NpO2 in UO2 fuel or transmutation targets is a viable option to recycle neptunium without inducing any relevant change in the chemical or thermal stability of the uranium dioxide matrix, even up to the melting point. From a more fundamental perspective, it con“rms that actinide dioxides, and particularly UO 2, tend to mix in a way closer to ideal, the closer are the atomic numbers, 5-f electron shell “lling, atomic radii and oxygen potentials of the metals forming the pure dioxides. � 2015 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://

The thermal properties of Np- and Am-MOX solid solution materials were investigated. Their linear thermal expansion, determined using high temperature X-ray diffraction from room temperature to 1973 K showed no significant difference between the Np and the Am doped MOX. The thermal conductivity of the Am-MOX is about 10% higher than that of Np-MOX. The melting temperatures of Np-MOX and Am-MOX, measured using a laser heating self crucible arrangement were 3020 ± 30 K and 3005 ± 30 K, respectively.

Solid/liquid equilibria in the system UO2–ZrO2 are revisited in this work by laser heating coupled with fast optical thermometry. Phase transition points newly measured under inert gas are in fair agreement with the early measurements performed by Wisnyi et al., in 1957, the only study available in the literature on the whole pseudo-binary system. In addition, a minimum melting point is identified here for compositions near (U0.6Zr0.4)O2+y, around 2800 K. The solidus line is rather flat on a broad range of compositions around the minimum. It increases for compositions closer to the pure end members, up to the melting point of pure UO2 (3130 K) on one side and pure ZrO2 (2970 K) on the other. Solid state phase transitions (cubic-tetragonal-monoclinic) have also been observed in the ZrO2-rich compositions X-ray diffraction. Investigations under 0.3 MPa air (0.063 MPa O2) revealed a significant decrease in the melting points down to 2500 K–2600 K for increasing uranium content (x(UO2)> 0.2). This was found to be related to further oxidation of uranium dioxide, confirmed by X-ray absorption spectroscopy. For example, a typical oxidised corium composition U0.6Zr0.4O2.13 was observed to solidify at a temperature as low as 2493 K. The current results are important for assessing the thermal stability of the system fuel – cladding in an oxide based nuclear reactor, and for simulating the system behaviour during a hypothetical severe accident.

The effect of La doping on the electronic structure of U in UO2 was studied using an advanced technique, namely, X-ray absorption spectroscopy (XAS) in the high-energy-resolution fluorescence-detection (HERFD) mode, at the U 3d3/2 (M4) edge. Thanks to a significant reduction of the core–hole lifetime broadening and distinct chemical shifts of the HERFD-XAS lines, the U(V) formation as a result of La doping was identified. The isolated contribution of U(V) in the M4 HERFD-XAS spectrum reveals the so-called charge-transfer satellites due to the U 5f–O 2p hybridization. The analysis of the experimental data within the framework of the Anderson impurity model (AIM) indicates a significant change in the characteristics and degree of covalency for the chemical bonding in the U(V) subsystem of UO2 as compared to undoped UO2, which is a Mott–Hubbard system. The results are also supported by AIM calculations of X-ray photoelectron and optical absorption data.

The electric field has a large effect on the stoichiometry and grain growth of UO2+x during Spark Plasma Sintering. UO2+x is gradually reduced to UO2.00 as a function of sintering temperature and time. A gradient in the oxidation state within the pellets is observed in intermediate conditions. The shape of the gradient depends unequivocally on the direction of the electrical field. The positive surface of the pellet shows a higher oxidation state compared to the negative one. An area with larger grain size is found close to the positive electrode, but not in contact with it. We interpret these findings with the redistribution of defects under an electric field, which affect the stoichiometry of UO2+x and thus the cation diffusivity. The results bear implications for understanding the electric field assisted sintering of UO2 and non-stoichiometric oxides in general.

Uranium–neptunium mixed dioxides are considered as fuels and targets for the transmutation of the minor actinides in fast neutron reactors. Hereafter, a local and atomic scale structural analysis was performed on a series of U1–xNpxO2 (x = 0.01; 0.05; 0.20; 0.50; 0.75; 0.85) synthesized by the sol–gel external gelation method, for which longer range structural analysis indicates that the process yields solid solutions. The oxidation state of IV for uranium and neptunium cations was confirmed using U LIII and Np LIII edge X-ray absorption near edge structure (XANES). The atomic scale structure was probed with 17O magic angle spinning nuclear magnetic resonance (MAS NMR) for the anion. Structural distortions due to the substitution of U by the smaller Np cation were detected by 17O MAS NMR.

Understanding of the behaviour of nuclear material in extreme conditions is essential for the analyses of the operation limits of nuclear fuels, and prediction of possible nuclear reaction accidents. In this context, the high temperature behaviour of uranium nitride and mixed uranium–plutonium nitrides has been studied in the present work by laser heating under controlled atmosphere coupled with fast multi-wavelength pyrometry. Such an approach has allowed performing a thermal arrest analysis and establishing the solid–liquid phase boundaries in the investigated compositions, whereby non-congruent vaporisation was avoided by setting a suitable nitrogen overpressure. In addition, the normal spectral emissivities of the current samples were determined by radiance spectroscopy. Besides revealing a slightly more metallic optical behaviour in plutonium-containing compositions, this latter characterisation led to the determination of the real melting/solidification temperatures of the investigated nitrides. It is confirmed that UN melts congruently at (3120 ± 30) K in a nitrogen pressure of 0.25 MPa (2.5 bar). The melting/solidification temperatures decrease in plutonium containing samples, reaching (3045 ± 25) K for x(PuN) = 0.2, a composition of interest for potential applications of this material as a nuclear fuel. Besides their fundamental importance, the current results are useful for a deeper understanding of the nitride fuel behaviour under accidental conditions, whereby uncontrolled thermal excursions might occur in the nuclear reactor core.

The mixed oxide Th0.60Am0.40O2−x has been synthesized and characterized after reductive and oxidative thermal treatments. Both materials are monophasic solid solutions. The determination of O/M ratio was achieved combining XRD, XANES and TGA, showing the consistence between the three methods. This study represents a further step in our investigation of the Th–Am–O system and improves it comprehension.

Studying self-irradiated materials is an ideal means to investigate the effect of the damage on material structure and to better understand the behavior of irradiated nuclear fuels. In this context, X-ray diffraction, X-ray absorption spectroscopy and transmission electron microscopy have been used to investigate self-irradiation damaged AmO2. Combining these techniques allows studying the microstructure and the variation of the fluorite structure at both short-range and long-range order. Thus, the increase of both interatomic distances and lattice parameter was shown, as well as the presence of nanometer sized He bubbles and dislocation loops. As confirmed by the observed high-level of crystallinity, the fluorite structure exhibits a high radiation tolerance, which is confirmed by the low increase of the lattice parameter. This could be explained by a self-annealing mechanism of the created defects at room temperature.

During in-pile, irradiation-induced damage occurs in nuclear fuel and results in a deterioration of its properties, which can affect the margin to melt of the fuel. Damage also occurs in fresh fuel through the self-irradiation process, and thus provides a convenient means to investigate changes in the material. A uranium–plutonium mixed nitride fuel made over 25 years ago, and stored in the ITU archives has been retrieved. Coupling EXAFS and TEM has shown that this material was still well-crystallized. However, an increase of 0.3% of the lattice parameter was found. As shown by the EXAFS, the U–N and Pu–N as well as the metal–metal distances are similarly affected. However, no significant modification of both anion and cation sublattice was found. Although no defect clustering was found by EXAFS, the presence of nanometric helium bubbles was demonstrated by TEM as well as nanometric disordered domains.

The thermal recovery of self-irradiated and damaged U 0.80 Am 0.20 O 2− x solid solution has been studied in situ using high-temperature x-ray diffraction between 25 °C and 1300 °C. The cumulative α decay dose of the damaged material was equal to 2.2 displacements per atom, leading to a lattice expansion of 0.31%. This value is close to the saturated lattice expansion of self-irradiated polycrystalline UO 2 and AmO 2 . The thermal recovery process is characterized by three stages, as revealed by the temperature derivative of the lattice parameter showing two maxima at 600 °C and 1000 °C. The thermal recovery is completed at about 1200 °C. These data are compared with existing studies on other oxide fuels. In addition, the lattice expansion of the damaged U 0.80 Am 0.20 O 2− x sample is also discussed and compared to that of defect free UO 2 , NpO 2 and AmO 2 materials. The thermal energy necessary to initiate the annealing of the defects is reached at about 400 °C, whilst at 1100 °C, a defect free U 0.80 Am 0.20 O 2− x sample is obtained.

X-ray Diffraction and X-ray Absorption Spectroscopy have shown that a material composed of two (Pu,Am)O2-x substoichiometric fluorite-type structures is obtained by sintering in moisturized Ar-H2. The Pu oxidation state is, surprisingly, strictly (+IV) while Am exhibits a (+III/+IV) mixed valence. Thus, the Am-O system and particularly the Am oxidation state play a major role in the sintering behavior of the Pu-Am-O system. The heating of this compound in air leads to the formation of a fluorite Pu0.80Am0.20O1.98 solid solution. The transition from one phase to two phase structure takes place in a temperature inferior to 800°C. The results were compared with previous studies on Am bearing UO2 and ThO2 which have evidenced different behaviors., JRC.E.4-Nuclear fuels

The effect of La doping on the electronic structure of U in UO

Cubic fluorite-type phases have been reported in the U(IV)O2-Bi2O3 system for the entire compositional range, but an unusual non-linear variation of the lattice parameter with uranium substitution has been observed. In the current extensive investigation of the uranium(iv) oxide-bismuth(iii) oxide system, this behaviour of the lattice parameter evolution with composition has been confirmed and its origin identified. Even under inert atmosphere at 800 °C, U(IV) oxidises to U(V)/U(VI) as a function of the substitution degree. Thus, using a combination of three methods (XRD, XANES and Raman) we have identified the formation of the BiU(V)O4 and Bi2U(VI)O6 compounds, within this series. Moreover, we present here the Rietveld refinement of BiU(V)O4 at room temperature and we report the thermal expansion of both BiU(V)O4 and Bi2U(VI)O6 compounds.

In the frame of a potential contact of MOX fuels with the Na coolant in fast breeder reactors, the chemistry and charge distributions in α-Na2UO4, Na3NpO4, α-Na2NpO4, Na4NpO5, Na5NpO6, Na2PuO3, Na4PuO5, and Na5PuO6 are investigated by XANES spectroscopy at the U-L3, Np-L3, and Pu-L3 edges.

Florent LEBRETON, Denis HORLAIT, Damien PRIEUR, Philippe MARTIN, Jean-Yves COLLE, Arne JANSSEN, Thierry WISS, Andreas SCHEINOST, Thibaud DELAHAYE CEA-DEN-DTEC, Service d’Etudes des Combustibles et materiaux a base d’Actinides, SECA, (Marcoule, France) CEA-DEN-DTEC, Service de Developpement des Technologies du Cycle, SDTC, (Marcoule, France) European Commission, Joint Research Centre, Institute for Transuranium Elements (Karlsruhe, Germany) Helmholtz Zentrum Dresden Rossendorf (HZDR), Institute of Resource Ecology (Dresden, Germany) CEA-DEN-DRCP, Service d’Etude du Recyclage des combustibles et d’Analyses, SERA, (Marcoule, France) Am isotopes are amongst the largest contributors to the radiotoxicity and heat load of spent nuclear fuels, especially in scenarios including plutonium recycling in MOX fuels. Transmutation in heterogeneous mode is a promising option to lower Am inventory in the ultimate nuclear waste, thus decreasing the ecological impact of deep-geological repository sites. It consists in the irradiation Ambearing blankets (AmBB, i.e., U1-xAmxO2±δ with x values close to 10-15 at.%) in the periphery of a fast neutron reactor core. In this context, studies are being performed to assess the feasibility and safety of AmBB transmutation, notably focusing on innovative fabrication processes [1–3], AmBB behavior under irradiation [4] and U1-xAmxO2±δ properties [5]. Am being a strong α emitter (activity of 130 MBq), U1-xAmxO2±δ behavior under α self-irradiation is also monitored [6–8].

Uranium-americium mixed oxides are promising fuels for achieving an efficient Am recycling. Previous studies on U{sub 0.85}Am{sub 0.15}O{sub 2{+-}x} materials showed that the high {alpha} activity of {sup 241}Am induces pellet swelling which is a major issue for cladding materials design. In this context, X-ray Diffraction and X-ray Absorption Spectroscopy measurements were used to study self-irradiation effects on U{sub 0.85}Am{sub 0.15}O{sub 2{+-}x} local structure and to correlate these results with those obtained at the macroscopic scale. For a cumulative {alpha} decay dose equal to 0.28 dpa, it was shown that non-defective fluorite solid solutions were achieved and therefore, that the fluorite structure is stable for the studied doses. In addition, both interatomic distance and lattice parameter expansions were observed, which only partially explains the macroscopic swelling. As expected, an increase of the structural disorder with self-irradiation was also observed. - Graphical abstract: X-ray Diffraction and X-ray Absorption Spectroscopy measurements were performed on U{sub 0.85}Am{sub 0.15}O{sub 2{+-}x}, exhibiting various cumulative {alpha} decay doses, in order to study self-irradiation effects on local structure and to correlate these results with those obtained at the macroscopic scale. Thus, it was shown that the fluorite structure is stable for the studied doses. In addition, bothmore » interatomic distance and lattice parameter expansions were observed, explaining partially the macroscopic swelling. Highlights: Black-Right-Pointing-Pointer Non-defective fluorite U{sub 0.85}Am{sub 0.15}O{sub 2{+-}x} solid solutions were achieved. Black-Right-Pointing-Pointer The fluorite structure is stable for the studied doses. Black-Right-Pointing-Pointer A lattice parameter increase was observed, which partially explains the macroscopic swelling. Black-Right-Pointing-Pointer The increase of the structural disorder can be understood from the ballistic effect associated to the Am high alpha activity.« less

The effect of oxygen potential on the sintering behaviour of U 1− y AmyO 2− x ( y = 0.15) has been studied. Sintering tests were performed in an Ar–4% H 2 atmosphere with various partial pressures of oxygen. It has been shown that the density is significantly affected by the sintering atmosphere. A density higher than 93 ± 0.5% has been achieved at −390 kJ mol −1 . Pore morphology varies from an open to a closed type as the oxygen potential increases.

International audience; The CEA is currently assessing minor actinides (MA) recycling in nuclear fuels in fast neutrons reactors (FNR). Two routes are investigated: homogeneous recycling, where MA are added up to several percents in UPu-type fuel to be used in the whole core, and heterogeneous recycling, which consists in higher amounts of MA in uranium oxide fuel used in the periphery of the core. The studies include various subject areas: neutronics, thermo-physical properties, coolant type (sodium, lead, bismuth, helium), etc..., and experimental work concerning the fabrication of minor actinides compounds. The first part of this work consisted in the structural study by XRD of AmO2. We studied the lattice parameter change versus time due to α self-irradiation. In this context, AmO2 powder was prepared in the ATALANTE facility in the CEA Marcoule. It is a first approach of swelling phenomenon at the structural scale which has been extended at the macroscopic scale in the second part of the work with the study of the geometrical stability in time of UO2 sintered pellets containing 30% Am. Pellets were fabricated by conventional powder metallurgy process in hot cell at the laboratory scale. Swelling behaviour has been studied by accurate diameter measurements performed along the pellets and correlated to the cumulative α decay dose. Up to 2.1 × 1017 α decay in the sample, no evidence of pellet macroscopic swelling was observed.

International audience; Uranium-plutonium mixed oxide containing 30 per cent of plutonium is a candidate fuel for several fast neutron and accelerator driven reactor systems. In this work, a detailed structural investigation on sol-gel synthesized stoichiometric U0.7Pu0.3O2.00 and substoichiometric U0.7Pu0.3O2-x, using X-ray diffraction (XRD), oxygen 17 magic angle spinning nuclear magnetic resonance ((17)O MAS NMR) and X-ray absorption spectroscopy is described. As observed by XRD, the stoichiometric U0.7Pu0.3O2.00 is monophasic with a lattice parameter in good agreement with Vegard's law, while the substoichiometric U0.7Pu0.3O2-x material is biphasic. Solid solution ideality in terms of a random distribution of metal atoms is proven for U0.7Pu0.3O2.00 with (17)O MAS NMR. X-ray absorption near-edge structure (XANES) spectroscopy shows the presence of plutonium(III) in U0.7Pu0.3O2-x. Extended X-ray absorption fine-structure (EXAFS) spectroscopy indicates a similar local structure around both cations, and comparison with XRD indicates a close similarity between uranium and plutonium local structures and the long-range ordering.

Uranium-americium mixed oxides are potential compounds to reduce americium inventory in nuclear waste via a partitioning and transmutation strategy. A thorough assessment of the oxygen-to-metal ratio is paramount in such materials as it determines the important underlying electronic structure and phase relations, affecting both thermal conductivity of the material and its interaction with the cladding and coolant. In 2011, various XAS experiments on U1(-x)Am(x)O(2 +/-delta) a samples prepared by different synthesis methods have reported contradictory results on the charge distribution of U and Am. This work alleviates this discrepancy. The XAS results confirm that, independently of the synthesis process, the reductive sintering of U1-xAmxO2 +/-delta leads to the formation of similar fluorite solid solution indicating the presence of Am+III and U+V in equimolar proportions.

Heating in air at 625 °C a Th0.80Am0.20O2−x sample leads to its full oxidation to stoichiometric oxide. The O/M ratio of a Th0.80Am0.20O2−x sintered in moisturized Ar–H2 is equal to 1.90. More importantly, an excellent agreement was observed between the values obtained by thermogravimetry, by conventional gravimetric analysis and by X-ray Absorption Near Edge Structure (XANES).