JRP CALL information
Supported By

European Commission

Short description of the work
During this stay, the work done at HZDR-IRE was dedicated to the synthesis and the characterization of new neptunium-based coordination polymers, involving new neptunium crystal chemistry. The synthesis with 4,4’-biphenyldicaboxilic acid (H2-bpdc) in dimethylformamide (DMF) leaded to the crystallization of very nice octahedral crystals. Crystal data were collected and analyzed during this stay at HZDR-IRE. The corresponding structure revealed for the first time the isolation of the hexanuclear cluster An6O8 with neptunium in a solid state. During this stay, the same inorganic building unit was also stabilized with other carboxylate-based ligands (terephthalate and 2,6-naphtalendicarboxylate). The structural determination of these two solids is still in progress. We also analyzed the stabilization of new neptunium based clusters, from oxygen-free aqueous solutions with phthalic and mellitic acids as organic ligand precursors. We isolated two new compounds, showing also new neptunium crystal chemistries (infinite chains and layers). Based on the obtained data, several publications are expected and the manuscript will be prepared by early 2016.


Short description of the work
The samples described in the proposal could not have been measured in the framework of this call as an unexpected problem preventing the sample preparation occurred 2 weeks before the beamtime. For this reason, we measured several compounds in the Bi-U-O ternary system in the frame of the safety assessment of lead bismuth eutectic (LBE) cooled fast reactors.
Cubic fluorite-type phases have been reported in the UIVO2-Bi2O3 system for the entire compositional range, but a non-linear evolution of the lattice parameter with uranium substitution has been observed. In the current extensive investigation of the uranium(IV) oxide – bismuth (III) oxide system, the unusual behaviour of the lattice parameter evolution with composition has been confirmed and its origin identified. Even under inert atmosphere at 800 °C, UIV oxidises to UV/UVI 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 BiUVO4 and Bi2UVIO6 compounds, within this series..


Short description of the work
The speciation of uranium (VI) in aqueous media in presence of sulfates is complex with the coexistence of various species according to the sulfate concentration and the pH of the medium. In acidic conditions, UO2(SO4)(aq), UO2(SO4)22- and UO2(SO4)34- may co-exist. At pH > 3, the speciation is even more complex as oligomeric species or ternary species may form as a consequence of the uranium hydrolysis. Therefore, it is a challenge to perform an accurate characterization of the speciation in view to determine not only the stoichiometry of the species in solution, but also their structure. Sulfate ions have the ability to bind uranium (VI) in two ways, as monodentate or as bidentate fashion, and some contradictory results were obtained, especially at low sulfate ratio. According to authors, a monodentate or a bidentate coordination is evidenced for the 1:1 complex. In this context, we would like to use the specific properties of ionic liquids (IL) to investigate the coordination of sulfate ions with uranium (VI). In this kind of solvent constituted only by ions and easy to dry, we can get rid of the uranium (VI) hydrolysis. Also, we can choose the dissolved uranyl and sulfate salts so that their counter-ions are identical to the ions constituting the IL. In that way, we avoid any interferences due to counter-ions, the studied system being composed only by uranyl, sulfate and the cation and anion of the IL.
We used this experiment at the uranium L3 edge to identify the stoechiometry and configuration of sulfato-complexes of uranium(VI) in ionic liquids, as a function of the sulfate/uranium ratio in solution. We show in particular the formation of a solid compound which corresponds to the 1:1 complex where the sulfate group is bound to uranium in a bidentate fashion.


Short description of the work
In the framework of the partitioning and transmutation, the Am recycling is one of the milestones requiring notably a full understanding of the Am electronical properties. Different XANES studies at LIII edges have shown different charge distribution in uranium-americium mixed oxides. U(IV) and Am(III/IV) were found in sol-gel synthesized materials while U(IV/V) and Am(III) were observed in powder metallurgy prepared compounds. In order to understand this discrepancy, the U and Am oxidations states in uranium-americium oxides have been studied using high resolution XANES (HRXANES) at M4 edge. Compared to L3 XANES, M4 HR XANES allows a significant improvement of the spectrum resolution by overcoming the core-hole lifetime broadening ffects leading then to sharper spectral features. In this context, the M4 XANES spectra of U reference compounds (UO2, U3O8, UO3), Am reference compounds (AmO2) and uranium-americium mixed oxides have been collected. Comparing these latter spectra with the U and Am reference samples, it has been established that Am is purely trivalent in uranium-americium mixed oxides while U is tetra- and pentavalent.


Short description of the work
X-ray fluorescence (XRF), X-ray diffraction (XRD) and X-ray absorption spectroscopic (XAS) measurements have been performed on single and agglomerates of micrometer sized uranium particles at the MicroXAS beamline (PSI, Villigen, Switzerland) in order to determine the physio chemical properties.
Monodisperse microspheres were produced at Forschungszentrum Juelich GmbH by spray pyrolysis with sintering temperatures ranging from 400 °C to 593 °C using uranyl nitrate and uranyl acetate precursor solutions. These microspheres are intended to be used as (certified) reference materials with respect to the isotopic composition and uranium content. As the stability of these property values is of high importance, structural information about the microspheres is required. The different microspheres have been investigated to determine the optimal production route to obtain stable microspheres.
XRF measurements confirmed the presence of uranium and provided auxiliary assurance that the particles do not contain significant impurities. XRD measurements showed for all these microspheres an orthorhombic phase similar to U3O8 and XANES measurements confirmed the presence of U3O8. It can be derived that the microsphere production using an uranyl nitrate precursor solution and sintered at 500 °C yielded in results with consistent and desired quality, although an unexpected behavior compared to literature data for bulk materials was observed.


Short description of the work
Radiation stability of extractants (CyMe4-BTBP and CyMe4-BTPhen) and the influence of solvent irradiation on its extraction properties are an important factors for use in a processes, such as European SANEX and/or Ganex proces.
The solutions of CyMe4-BTBP or CyMe4-BTPhen ligands were dissolved in various alkylated cyclohexanone derivatives or FS-13 (phenyl trifluoromethyl sulfone) and were irradiated by gamma source with the dose from 20 kGy to 1000 kGy to study the radiation stability of CyMe4-BTBP and CyMe4-BTPhen in various diluents. The selected cyclohexanone-based diluents were cyclohexanone, 3 methylcyclohexanone and 2,6-dimethylcyclohexanone. Some of the samples were irradiated also in the presence of the nitric acid solutions.
The irradiated samples were transported to CTU in Prague and the extraction properties of the irradiated solvents were compared with the extraction properties of non-irradiated solvents to estimate the influence of the degradation products in the organic phase.
The irradiated samples are still analysed for the degree of extractant degradation.


Short description of the work

In the framework of the proposed study, batch incubations of depleted uranium (DU) corrosion product with five different soils were performed with artificial rain events during several weeks. The resulting DU-contaminated soils were collected in function of depth and characterized for mineralogy and chemistry. The goal of the bulk and micro-XAS and micro-XRD experiments conducted at SLS was: (1) identify the bulk DU speciation in various soils that were in contact with DU corrosion product; (2) characterize mineralogical changes in the corrosion products at the microscale under various geochemical conditions.
The results obtained for bulk XANES indicate that U(VI) is the dominant oxidation state in the soils. Additionally, micro-XANES data show that U(VI) is distributed diffusely in the soils while there are mixed U(IV)-U(VI) hotspots in both StSul soil (agricultural soil) and Ins soil (organic-rich low pH). Moreover, U-Ca correlation seems observable at the U hotpsots of the Ins soil, while U and Fe seem not correlated.

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