Determination of the high-pressure crystal structure of BaWO4 and PbWO4

We report the results of both angle-dispersive x-ray diffraction and x-ray absorption near-edge structure studies in BaWO4 and PbWO4 at pressures of up to 56 GPa and 24 GPa, respectively. BaWO4 is found to undergo a pressure-driven phase transition at 7.1 GPa from the tetragonal scheelite structure (which is stable under normal conditions) to the monoclinic fergusonite structure whereas the same transition takes place in PbWO4 at 9 GPa. We observe a second transition to another monoclinic structure which we identify as that of the isostructural phases BaWO4-II and PbWO4-III (space group P21/n). We have also performed ab initio total energy calculations which support the stability of this structure at high pressures in both compounds. The theoretical calculations further find that upon increase of pressure the scheelite phases become locally unstable and transform displacively into the fergusonite structure. The fergusonite structure is however metastable and can only occur if the transition to the P21/n phases were kinetically inhibited. Our experiments in BaWO4 indicate that it becomes amorphous beyond 47 GPa.Comment: 46 pages, 11 figures, 3 table

Angular and energy dependence of ion bombardment of Mo/Si multilayers

The process of ion bombardment is investigated for the fabrication of Mo/Si multilayer x-ray mirrors using e-beam evaporation. The ion treatment is applied immediately after deposition of each of the Si layers to smoothen the layers by removing an additional thickness of the Si layer. In this study the parameters of Kr+ ion bombardment have been optimized within the energy range 300 eV-2 keV and an angular range between 20 degrees and 50 degrees. The optical performance of the Mo/Si multilayers is determined by absolute measurements of the near-normal-incidence reflectivity at 14.4 nm wavelength. The multilayer structures are analyzed further with small-angle reflectivity measurements using both specular reflectivity and diffuse x-ray scattering. The optimal smoothening parameters are obtained by determining the effect of ion bombardment on the interface roughness of the Si layer. The optimal conditions are found to be 2 keV at 50 degrees angle of incidence with respect to the surface. These settings result in 47% reflectivity at 85 degrees (lambda = 14.4 nm) for a 16-period Mo/Si multilayer mirror, corresponding to an interface roughness of 0.21 nm rms. Analysis shows that the interface roughness is determined by ion induced viscous flow, an effect which increases with ion energy as well as angle of incidence. In order to determine the effect of intermixing of the Si and Mo atoms, the penetration depth of the Kr+ ions is calculated as a function of ion energy and angle of incidence. Furthermore, the angular dependence of the etch yield, obtained from the in situ reflectivity measurements, is investigated in order o determine the optimal ion beam parameters for the production of multilayer mirrors on curved substrates. (C) 1997 American Institute of Physics

Incorporation of uranium into hematite during crystallization from ferrihydrite

Ferrihydrite was exposed to U(VI)-containing cement leachate (pH 10.5) and aged to induce crystallization of hematite. A combination of chemical extractions, TEM, and XAS techniques provided the first evidence that adsorbed U(VI) (≈3000 ppm) was incorporated into hematite during ferrihydrite aggregation and the early stages of crystallization, with continued uptake occurring during hematite ripening. Analysis of EXAFS and XANES data indicated that the U(VI) was incorporated into a distorted, octahedrally coordinated site replacing Fe(III). Fitting of the EXAFS showed the uranyl bonds lengthened from 1.81 to 1.87 Å, in contrast to previous studies that have suggested that the uranyl bond is lost altogether upon incorporation into hematite the results of this study both provide a new mechanistic understanding of uranium incorporation into hematite and define the nature of the bonding environment of uranium within the mineral structure. Immobilization of U(VI) by incorporation into hematite has clear and important implications for limiting uranium migration in natural and engineered environments. © 2014 American Chemical Society

Formation of stable uranium(VI) colloidal nanoparticles in conditions relevant to radioactive waste disposal

The favored pathway for disposal of higher activity radioactive wastes is via deep geological disposal. Many geological disposal facility designs include cement in their engineering design. Over the long term, interaction of groundwater with the cement and waste will form a plume of a hyperalkaline leachate (pH 10-13), and the behavior of radionuclides needs to be constrained under these extreme conditions to minimize the environmental hazard from the wastes. For uranium, a key component of many radioactive wastes, thermodynamic modeling predicts that, at high pH, U(VI) solubility will be very low (nM or lower) and controlled by equilibrium with solid phase alkali and alkaline-earth uranates. However, the formation of U(VI) colloids could potentially enhance the mobility of U(VI) under these conditions, and characterizing the potential for formation and medium-term stability of U(VI) colloids is important in underpinning our understanding of U behavior in waste disposal. Reflecting this, we applied conventional geochemical and microscopy techniques combined with synchrotron based in situ and ex situ X-ray techniques (small-angle X-ray scattering and X-ray adsorption spectroscopy (XAS)) to characterize colloidal U(VI) nanoparticles in a synthetic cement leachate (pH > 13) containing 4.2-252 μM U(VI). The results show that in cement leachates with 42 μM U(VI), colloids formed within hours and remained stable for several years. The colloids consisted of 1.5-1.8 nm nanoparticles with a proportion forming 20-60 nm aggregates. Using XAS and electron microscopy, we were able to determine that the colloidal nanoparticles had a clarkeite (sodium-uranate)-type crystallographic structure. The presented results have clear and hitherto unrecognized implications for the mobility of U(VI) in cementitious environments, in particular those associated with the geological disposal of nuclear waste

ALLIAGES DE TERRES RARES ET DE MÉTAUX DE TRANSITIONMAGNETIC STRUCTURE OF PrCo5D4

PrCo5 D4-x(x= 0-,l à 0,3) a été étudié par diffraction de neutrons sur poudres, et par mesures d'aimantation sur des échantillons de poudres alignées. La courbe σ|| en fonction de T présente un maximum à 50 °K . Au-dessus de 50 °K l'aimantation dépend faiblement du champ ; au-dessous, la dépendance est forte. En accord avec ce qui précède, la structure à 292 et 77 °Kest ferromagnétique, les moments étant dirigés le long de l'axe c. A 4,2 °K , on trouve que les moments réduits sont dirigés selon z, ce qui indique que les moments ont une composante non nulle dans le plan (x, y).PrCo5 D4-x(x= 0-,l à 0,3) haz been studied by neutron powder diffraction and by magnetization measurements on aligned powder specimens. The σ|| vs T curve shows a maximum at 50 °K. Above 50 °K the field dependence of the magnetization is small, below 50 °K it is large. In accordance with this, the magnetic structure at 292 °K and 77 °K is ferromagnetic with the moments pointing along the c-axis. At 4.2 °K reduced moments are found in the z-direction indicating that the moments have components in the x-y plane