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Sample records for fluorite baf2 structure

  1. Structural properties of Bi2Te3 topological insulator thin films grown by molecular beam epitaxy on (111) BaF2 substrates

    NASA Astrophysics Data System (ADS)

    Fornari, Celso I.; Rappl, Paulo H. O.; Morelhão, Sérgio L.; Abramof, Eduardo

    2016-04-01

    Structural properties of topological insulator bismuth telluride films grown epitaxially on (111) BaF2 with a fixed Bi2Te3 beam flux were systematically investigated as a function of substrate temperature and additional Te flux. A layer-by-layer growth mode is observed since the early stages of epitaxy and remains throughout the whole deposition. Composition of the epitaxial films produced here stays between Bi2Te3 and Bi4Te5, as determined from the comparison of the measured x-ray diffraction curves with calculations. The substrate temperature region, where the growth rate remains constant, is found to be the most appropriate to obtain ordered Bi2Te3 films. Line width of the L = 18 Bi2Te3 diffraction peaks as low as 140 arcsec was obtained, indicating high crystalline quality. Twinning domains density rises with increasing growth temperature and reducing Te extra flux. X-ray reflectivity curves of pure Bi2Te3 films with thickness from 165 to 8 nm exhibited well defined interference fringes, evidencing homogeneous layers with smooth surface. Our results demonstrate that Bi2Te3 films with very well controlled structural parameters can be obtained. High structural quality Bi2Te3 films as thin as only eight quintuple layers grown here are promising candidates for intrinsic topological insulator.

  2. Glass structure and NIR emission of Er3+ at 1.5 μm in oxyfluoride BaF2-Al2O3-B2O3 glasses

    NASA Astrophysics Data System (ADS)

    Shinozaki, Kenji; Pisarski, Wojciech; Affatigato, Mario; Honma, Tsuyoshi; Komatsu, Takayuki

    2015-12-01

    The glass structure, photoluminescence properties of Eu3+, Judd-Ofelt analysis, and near infrared emissions of Er3+ at 1.5 μm in the oxyfluoride glasses and glass-ceramics of 1Eu2O3- or 1Er2O3-doped 50BaF2-xAl2O3-(50 - x)B2O3 (x = 0-25 mol%) were investigated. It was clarified on the ground of Raman scattering spectroscopy and F1s and O1s XPS measurements that the glass with no Al2O3 (1Er2O3-50BaF2-50B2O3) is composed of BO3, BO2F and BO3F units with F-Ba bonds. The glasses with 25Al2O3 (1Er2O3-50BaF2-25Al2O3-25B2O3) is mainly composed of BO3- and Al(O,F)x units. Existence of non-bridging oxygen was not detected by O1s-XPS spectra. It was proposed that these structures are largely affected on crystallization behavior, e.g., the glass with no Al2O3 forms BaF2 and β-BaB2O4 due to Ba-F bonds and the glass with 25Al2O3 forms BaAlBO3F2 because the glass structure composed of BO3 and Al(O,F) units is similar to the BaAlBO3F2 crystal structure. Judd-Ofelt parameters of Er3+ and Eu3+ in the glasses showed almost the same values in Ω4 and Ω6 for each glass, on the other hand Ω2 decreased with addition of Al2O3. The emission spectra of Er3+ at 1.5 μm in the glasses and glass-ceramics with BaAlBO3F2 crystals showed broad peaks. It is proposed that oxyfluoride glasses and glass-ceramics based on the BaF2-Al2O3-B2O3 system have a high potential for optical device applications such as broadband optical amplifiers.

  3. Giant Mechanocaloric Effects in Fluorite-Structured Superionic Materials.

    PubMed

    Cazorla, Claudio; Errandonea, Daniel

    2016-05-11

    Mechanocaloric materials experience a change in temperature when a mechanical stress is applied on them adiabatically. Thus, far, only ferroelectrics and superelastic metallic alloys have been considered as potential mechanocaloric compounds to be exploited in solid-state cooling applications. Here we show that giant mechanocaloric effects occur in hitherto overlooked fast ion conductors (FIC), a class of multicomponent materials in which above a critical temperature, Ts, a constituent ionic species undergoes a sudden increase in mobility. Using first-principles and molecular dynamics simulations, we found that the superionic transition in fluorite-structured FIC, which is characterized by a large entropy increase of the order of 10(2) JK(-1) kg(-1), can be externally tuned with hydrostatic, biaxial, or uniaxial stresses. In particular, Ts can be reduced several hundreds of degrees through the application of moderate tensile stresses due to the concomitant drop in the formation energy of Frenkel pair defects. We predict that the adiabatic temperature change in CaF2 and PbF2, two archetypal fluorite-structured FIC, close to their critical points are of the order of 10(2) and 10(1) K, respectively. This work advocates that FIC constitute a new family of mechanocaloric materials showing great promise for prospective solid-state refrigeration applications. PMID:27070506

  4. Thermodynamics of solid electrolytes and related oxide ceramics based on the fluorite structure

    SciTech Connect

    Navrotsky, Alexandra

    2010-01-01

    Oxides based on the fluorite structure are important as electrolytes in solid oxide fuel cells, thermal barrier coatings, gate dielectrics, catalysts, and nuclear materials. Though the parent fluorite structure is simple, the substitution of trivalent for tetravalent cations, coupled with the presence of charge-balancing oxygen vacancies, leads to a wealth of short-range and long-range ordered structures and complex thermodynamic properties. The location of vacancies and the nature of clusters affect the energetics of mixing in rare earth doped zirconia, hafnia, ceria, urania, and thoria, with systematic trends in energetics as a function of cation radius. High temperature oxide melt solution calorimetry has provided direct measurement of formation enthalpies of these refractory materials. Surface and interfacial energies have also been measured in yttria stabilized zirconia (YSZ) nanomaterials. Other ionic conductors having perovskite, apatite, and mellilite structures are discussed briefly.

  5. High-pressure U3O8 with the fluorite-type structure

    NASA Astrophysics Data System (ADS)

    Zhang, F. X.; Lang, M.; Wang, J. W.; Li, W. X.; Sun, K.; Prakapenka, V.; Ewing, R. C.

    2014-05-01

    A new high-pressure phase of U3O8, which has a fluorite-type structure, forms at pressures greater than ~8.1 GPa that was confirmed by in situ x-ray diffraction (XRD) measurements. The fluorite-type U3O8 is stable at pressures at least up to ~40 GPa and temperatures to 1700 K, and quenchable to ambient conditions. Based on the XRD analysis, there is a huge volume collapse (>20%) for U3O8 during the phase transition and the quenched high-pressure phase is 28% denser than the initial orthorhombic phase at ambient conditions. The high-pressure phase has a very low compressibility comparing with the starting orthorhombic phase.

  6. Fast ion conductivity in strained defect-fluorite structure created by ion tracks in Gd2Ti2O7

    DOE PAGESBeta

    Aidhy, Dilpuneet S.; Sachan, Ritesh; Zarkadoula, Eva; Pakarinen, Olli; Chisholm, Matthew F.; Zhang, Yanwen; Weber, William J.

    2015-11-10

    The structure and ion-conducting properties of the defect-fluorite ring structure formed around amorphous ion-tracks by swift heavy ion irradiation of Gd2Ti2O7 pyrochlore are investigated. High angle annular dark field imaging complemented with ion-track molecular dynamics simulations show that the atoms in the ring structure are disordered, and have relatively larger cation-cation interspacing than in the bulk pyrochlore, illustrating the presence of tensile strain in the ring region. Density functional theory calculations show that the non-equilibrium defect-fluorite structure can be stabilized by tensile strain. The pyrochlore to defect-fluorite structure transformation in the ring region is predicted to be induced by recrystallizationmore » during a melt-quench process and stabilized by tensile strain. Static pair-potential calculations show that planar tensile strain lowers oxygen vacancy migration barriers in pyrochlores, in agreement with recent studies on fluorite and perovskite materials. Lastly, in view of these results, it is suggested that strain engineering could be simultaneously used to stabilize the defect-fluorite structure and gain control over its high ion-conducting properties.« less

  7. Fast ion conductivity in strained defect-fluorite structure created by ion tracks in Gd2Ti2O7

    PubMed Central

    Aidhy, Dilpuneet S.; Sachan, Ritesh; Zarkadoula, Eva; Pakarinen, Olli; Chisholm, Matthew F.; Zhang, Yanwen; Weber, William J.

    2015-01-01

    The structure and ion-conducting properties of the defect-fluorite ring structure formed around amorphous ion-tracks by swift heavy ion irradiation of Gd2Ti2O7 pyrochlore are investigated. High angle annular dark field imaging complemented with ion-track molecular dynamics simulations show that the atoms in the ring structure are disordered, and have relatively larger cation-cation interspacing than in the bulk pyrochlore, illustrating the presence of tensile strain in the ring region. Density functional theory calculations show that the non-equilibrium defect-fluorite structure can be stabilized by tensile strain. The pyrochlore to defect-fluorite structure transformation in the ring region is predicted to be induced by recrystallization during a melt-quench process and stabilized by tensile strain. Static pair-potential calculations show that planar tensile strain lowers oxygen vacancy migration barriers in pyrochlores, in agreement with recent studies on fluorite and perovskite materials. In view of these results, it is suggested that strain engineering could be simultaneously used to stabilize the defect-fluorite structure and gain control over its high ion-conducting properties. PMID:26555848

  8. High-pressure U{sub 3}O{sub 8} with the fluorite-type structure

    SciTech Connect

    Zhang, F.X.; Lang, M.; Wang, J.W.; Li, W.X.; Sun, K.; Prakapenka, V.; Ewing, R.C.

    2014-05-01

    A new high-pressure phase of U{sub 3}O{sub 8}, which has a fluorite-type structure, forms at pressures greater than ∼8.1 GPa that was confirmed by in situ x-ray diffraction (XRD) measurements. The fluorite-type U{sub 3}O{sub 8} is stable at pressures at least up to ∼40 GPa and temperatures to 1700 K, and quenchable to ambient conditions. Based on the XRD analysis, there is a huge volume collapse (>20%) for U{sub 3}O{sub 8} during the phase transition and the quenched high-pressure phase is 28% denser than the initial orthorhombic phase at ambient conditions. The high-pressure phase has a very low compressibility comparing with the starting orthorhombic phase. - Graphical abstract: α-U{sub 3}O{sub 8} is in a layered structure with orthorhombic symmetry, at high pressures, it transformed to a fluorite-type cubic structure. There are a lot of defects in the cubic structure, and it is a new kind of hyperstoichiometric uranium oxide, which is stable at ambient conditions. - Highlights: • A new fluorite-type high-pressure phase was found in hyperstoichometric UO{sub 2}+x (x∼0.8). • The new high-pressure structure is quenchable to ambient conditions. • Pressure driven phase transition in orthorhombic U{sub 3}O{sub 8} was first found.

  9. Determination of solubility limit of Sn(4+) in fluorite structured terbia with simultaneous evaluation of photocatalytic function.

    PubMed

    Tripathi, Vikash Kumar; Nagarajan, Rajamani

    2016-07-01

    Although the fluorite structure is highly common among stoichiometric and non-stoichiometric terbia compositions, high pressures are necessary to stabilize SnO2 in the fluorite structure. With this objective, the extent of solubility of Sn(4+) in terbia possessing the fluorite structure has been determined by conducting its synthesis via an epoxide mediated sol-gel method. Up to 40% of Sn(4+) can be incorporated in terbia, which retains its fluorite structure, as concluded from PXRD, FTIR, Raman spectroscopy, FESEM, HR-TEM and SAED measurements. The cubic lattice constant decreases systematically, as inferred from successful Rietveld refinements of PXRD patterns. The stretching vibration of the Tb-O bond is manifested as broad band at 734 cm(-1) for the terbia, and moves to lower wavenumber for the tin substituted samples. The broad band at 611 cm(-1) in the Raman spectrum of terbia became even broader with the maxima shifting towards higher values, which indicated the strain of the lattice and generation of oxygen vacancies with progressive tin substitution. The band gap value increased from 1.78 eV for terbia to 2.05 eV for the 40% tin substituted sample. Emission in the blue region became intense upon tin substitution, which was indicative of increased oxygen vacancies and this has been constructively utilized for environmental remediation as a catalyst to degrade aqueous Rhodamine-6G and Methylene Blue dye solutions. PMID:27328282

  10. Low temperature epitaxy of Ge-Sb-Te films on BaF2 (111) by pulsed laser deposition

    NASA Astrophysics Data System (ADS)

    Thelander, E.; Gerlach, J. W.; Ross, U.; Lotnyk, A.; Rauschenbach, B.

    2014-12-01

    Pulsed laser deposition was employed to deposit epitaxial Ge2Sb2Te5-layers on the (111) plane of BaF2 single crystal substrates. X-ray diffraction measurements show a process temperature window for epitaxial growth between 85 °C and 295 °C. No crystalline growth is observed for lower temperatures, whereas higher temperatures lead to strong desorption of the film constituents. The films are of hexagonal structure with lattice parameters consistent with existing models. X-ray pole figure measurements reveal that the films grow with one single out-of-plane crystal orientation, but rotational twin domains are present. The out-of-plane epitaxial relationship is determined to be Ge2Sb2Te5(0001) || BaF2(111), whereas the in-plane relationship is characterized by two directions, i.e., Ge2Sb2Te5 [-12-10] || BaF2[1-10] and Ge2Sb2Te5[1-210] || BaF2[1-10]. Aberration-corrected high-resolution scanning transmission electron microscopy was used to resolve the local atomic structure and confirm the hexagonal structure of the films.

  11. Investigating the electronic structure of fluorite-structured oxide compounds: comparison of experimental EELS with first principles calculations

    SciTech Connect

    Aguiar, Jeff; Ramasse, Q. M.; Asta, Mark D.; Browning, Nigel D.

    2012-06-27

    Energy loss spectra from fluorite-structured ZrO2, CeO2, and UO2 compounds are compared with theoretical calculations based on density functional theory (DFT) and its extensions, including the use of Hubbard-U corrections (DFT + U) and hybrid functionals. Electron energy loss spectra (EELS) were obtained from each oxide using a scanning transmission electron microscope (STEM). The same spectra were computed within the framework of the full-potential linear augmented plane-wave (FLAPW) method. The theoretical and experimental EEL spectra are compared quantitatively using non-linear least squares peak fitting and a cross-correlation approach, with the best level of agreement between experiment and theory being obtained using the DFT + U and hybrid computational approaches.

  12. Monte Carlo Simulation of Gamma-Ray Response of BaF2 and CaF2

    SciTech Connect

    Gao, Fei; Xie, YuLong; Wang, Zhiguo; Kerisit, Sebastien N.; Wu, Dangxin; Campbell, Luke W.; Van Ginhoven, Renee M.; Prange, Micah P.

    2013-12-01

    We have employed a Monte Carlo (MC) method to study intrinsic properties of two alkaline-earth halides, namely BaF2 and CaF2, relevant to their use as radiation detector materials. The MC method follows the fate of individual electron-hole (e-h) pairs and thus allows for a detailed description of the microscopic structure of ionization tracks created by incident γ-ray radiation. The properties of interest include the mean energy required to create an e-h pair, W, Fano factor, F, the maximum theoretical light yield, and the spatial distribution of e-h pairs resulting from γ-ray excitation. Although W and F vary with incident photon energy at low energies, they tend to constant values at energies higher than 1 keV. W is determined to be 18.9 and 19.8 eV for BaF2 and CaF2, respectively, in agreement with published data. The e-h pair spatial distributions exhibit a linear distribution along the fast electron tracks with high e-h pair densities at the end of the tracks. Most e-h pairs are created by interband transition and plasmon excitation in both scintillators, but the e-h pairs along fast electron tracks in BaF2 are slightly clustered, forming nanoscale domains and resulting in the higher e-h pair densities than in CaF2. Combining the maximum theoretical light yields calculated for BaF2 and CaF2 with those obtained for CsI and NaI shows that the theoretical light yield decreases linearly with increasing band gap energy.

  13. Solid State Structure-Reactivity Studies on Bixbyites, Fluorites and Perovskites Belonging to the Vanadate, Titanate and Cerate Families

    NASA Astrophysics Data System (ADS)

    Shafi, Shahid P.

    This thesis primarily focuses on the systematic understanding of structure-reactivity relationships in two representative systems: bixbyite and related structures as well as indium doped CeO2. Topotactic reaction routes have gained significant attention over the past two decades due to their potential to access kinetically controlled metastable materials. This has contributed substantially to the understanding of solid state reaction pathways and provided first insights into mechanisms. Contrary to the widely used ex-situ methods, in-situ techniques including powder x-ray diffraction and thermogravimetric-differential thermal analysis have been employed extensively throughout this work in order to follow the reaction pathways in real time. Detailed analysis of the AVO3 (A = In, Sc) bixbyite reactivity under oxidative conditions has been carried out and a variety of novel metastable oxygen defect phases have been identified and characterized. The novel metastable materials have oxygen deficient fluorite structures and consequently are potential ion conductors. Structural aspects of the topotactic vs. reconstructive transformations are illustrated with this model system. The structure-reactivity study of AVO3 phases was extended to AVO3 perovskite family. Based on the research methodologies and results from AVO3 bixbyite reactivity studies a generalized mechanistic oxidation pathway has been established with a non-vanadium phase, ScTiO3 bixbyite. However, there is stark contrast in terms of structural stability and features beyond this stability limit during AVO3 and ScTiO3 bixbyite reaction pathways. A series of complex reaction sequences including phase separation and phase transitions were identified during the investigation of ScTiO3 reactivity. The two-step formation pathway for the fluorite-type oxide ion conductor Ce1-xInxO2-delta (0 ≤ x ≤ 0.3) is being reported. The formation of the BaCe1-xInxO 3-delta perovskites and the subsequent CO2-capture reaction

  14. Redetermination of the structure of ALa₂WO₇ (A=Ba, Sr) with fluorite-like metal ordering

    SciTech Connect

    Fu, W.T.; IJdo, D.J.W.; Bontenbal, A.

    2013-05-01

    The crystal structures of ALa₂WO₇ (A=Ba, and Sr) at room temperature were re-determined by the Rietveld method using the combined X-ray and neutron powder diffraction data. The compounds are confirmed to be isomorphic, crystallizing in the space group P112₁/b. In ALa₂WO₇ the ordering of metal atoms is fluorite-like, but it differs from that of the fluorite-defect compounds of the formula Ln₃MO₇ (Ln=lanthanide or Y, M=pentavalent metal). The structure of ALa₂WO₇ consists of isolated WO₆ octahedra, whereas in the normal Ln₃MO₇ the MO₆ octahedra share corners forming one-dimensional chains. Although ALa₂WO₇ has a centric space group, La ions are not situate at the centre of symmetry, which explains the ⁵D₀→⁷F₂ transition being dominant in emission spectrum of Eu-doped materials. - Graphical abstract: Schematic drawing of the crystal structures of ALa₂WO₇ (A=Ba, Sr) (left) and Ln₃MO₇ (right) showing the different arrangement of metal octahedra. Note that the example of Ln₃MO₇ is the structure of La₃TaO₇ with the space group Cmcm. Highlights: • The structural ambiguity of BaLa₂WO₇ has been resolved. • The details of the crystal structure of SrLa₂WO₇ are reported for the first time. • ALa₂WO₇ (A=Ba, Sr) closely resemble β-La₃RuO₇ and one of the La₃IrO₇ polymorph.

  15. Core-hole effect on XANES and electronic structure of minor actinide dioxides with fluorite structure

    NASA Astrophysics Data System (ADS)

    Suzuki, Chikashi; Nishi, Tsuyoshi; Nakada, Masami; Akabori, Mitsuo; Hirata, Masaru; Kaji, Yoshiyuki

    2012-02-01

    The authors investigated theoretically core-hole effects on X-ray absorption near-edge structures (XANES) of Np and Am LIII in neptunium dioxide (NpO2) and americium dioxide (AmO2) with CaF2-type crystal lattices using the all-electron full-potential linearized augmented plane-wave (FP-LAPW) method. The peak creation mechanism of XANES was shown by examining the electronic structures of these oxides, which indicated that core-hole screening was more marked for AmO2 than for NpO2 because of the difference in the charge transfer between these oxides. Furthermore, the results of charge density analysis suggested that the white line was assigned to the quasi-bound state composed of the localized Np d or Am d components and O components, and that the tail structure was created as a result of delocalized standing waves between the Np or Am atoms.

  16. Luminescence and scintillation properties of BaF2sbnd Ce transparent ceramic

    NASA Astrophysics Data System (ADS)

    Luo, Junming; Sahi, Sunil; Groza, Michael; Wang, Zhiqiang; Ma, Lun; Chen, Wei; Burger, Arnold; Kenarangui, Rasool; Sham, Tsun-Kong; Selim, Farida A.

    2016-08-01

    Cerium doped Barium Fluoride (BaF2sbnd Ce) transparent ceramic was fabricated and its luminescence and scintillation properties were studied. The photoluminescence shows the emission peaks at 310 nm and 323 nm and is related to the 5d-4f transitions in Ce3+ ion. Photo peak at 511 keV and 1274 keV were obtained with BaF2sbnd Ce transparent ceramic for Na-22 radioisotopes. Energy resolution of 13.5% at 662 keV is calculated for the BaF2sbnd Ce transparent ceramic. Light yield of 5100 photons/MeV was recorded for BaF2sbnd Ce(0.2%) ceramic and is comparable to its single crystal counterpart. Scintillation decay time measurements shows fast component of 58 ns and a relatively slow component of 434 ns under 662 keV gamma excitation. The slower component in BaF2sbnd Ce(0.2%) ceramic is about 200 ns faster than the STE emission in BaF2 host and is associated with the dipole-dipole energy transfer from the host matrix to Ce3+ luminescence center.

  17. Investigation on nanoscale processes on the BaF2(111) surface in various solutions by frequency modulation atomic force microscopy

    NASA Astrophysics Data System (ADS)

    Kobayashi, Naritaka; Kawamura, Ryuzo; Yoshikawa, Hiroshi Y.; Nakabayashi, Seiichiro

    2016-06-01

    In this study, we have directly observed nanoscale processes that occur on BaF2(111) surfaces in various solutions using liquid-environment frequency modulation atomic force microscopy (FM-AFM) with a true atomic resolution. In addition, to investigate atomic-scale mechanisms of crystal growth process of BaF2, we determined a suitable solution for atomic-resolution FM-AFM imaging of the BaF2(111) surface. For undersaturated solutions, the surface is roughened by barium hydroxo complexes in the case of high pH, whereas by dissolution and proton or water molecule adsorption throughout the surface in the case of low pH. On the other hand, for supersaturated solutions, the surface shows two-dimensional nucleation and growth (σ = 0.1) and three-dimensional crystal growth with tetrahedral structures (σ = 1), where σ is the degree of supersaturation. The atomic-resolution imaging of the BaF2(111) surface has been demonstrated in potassium fluoride (KF) and the supersaturated (σ = 0.1 and 1) solutions, wherein atomically flat terraces are shown at least for about 30 min.

  18. Effect of NiCr Clad BaF2·CaF2 Addition on Wear Performance of Plasma Sprayed Chromium Carbide-Nichrome Coating

    NASA Astrophysics Data System (ADS)

    Du, Lingzhong; Huang, Chuanbing; Zhang, Weigang; Zhang, Jingmin; Liu, Wei

    2010-03-01

    NiCr clad BaF2·CaF2 fluoride eutectic powders were added into chromium carbide-nichrome feedstock to improve the tribological properties of NiCr-Cr3C2 coating, and the structures, mechanical, and ball-on-disk sliding wear performance of the coating were characterized. The results show that NiCr cladding can effectively decrease the density and thermophysical difference between the feedstock components, while alleviate the decarburization and oxidization of the constituent phases, and form the coating with a uniform and dense microstructure. However, the addition of BaF2·CaF2 has a negative effect on mechanical properties of the coating. When the temperature reaches 500 °C, the BaF2·CaF2 eutectic is soften by the heat and smeared by the counterpart, thus the low shear stress lubricating film forms between the contact surface, that improves the tribological properties dramatically. At this temperature, the dominant wear mechanisms also change from splats spallation and abrasive wear at room temperature to plastic deformation and plawing by the counterpart. Within the temperature range from 600 to 800 °C, the friction coefficient, the wear rates of NiCr/Cr3C2-10% BaF2·CaF2 coating and its coupled Si3N4 ball are 20%, 40%, and 75% lower than those of the NiCr/Cr3C2 coating, respectively. The NiCr/Cr3C2-BaF2·CaF2 coating shows superior wear performance to the NiCr/Cr3C2 coating without lubricant additive.

  19. The fluorite related modulated structures of the Gd2(Zr2-xCex)O7 solid solution: An analogue for Pu disposition

    NASA Astrophysics Data System (ADS)

    Reid, D. P.; Stennett, M. C.; Hyatt, N. C.

    2012-07-01

    We present an overview of the Gd2(Zr2-xCex)O7 phase diagram, of interest as a model system for ceramic disposition of Pu (with Ce as a Pu surrogate). The fluorite related structures of this solid solution were determined using a modulated structure approach, to identify the underlying cation and vacancy ordering mechanisms from analysis of key satellite reflections in selected zone axis electron diffraction patterns. This revealed the formation of four structure types: pyrochlore for x<0.25, defect fluorite for 0.5structure for x=1.00, and a C-type structure for x>1.50. X-ray absorption (XAS) and electron energy loss (EELS) spectra confirmed the presence of Ce4+ as the dominant species in compositions across this system, remaining analogous to Pu4+.

  20. Formation, structure and magnetism of the metastable defect fluorite phases AVO{sub 3.5+x} (A=In, Sc)

    SciTech Connect

    Shafi, Shahid P.; Lundgren, Rylan J.; Cranswick, Lachlan M.D.; Bieringer, Mario

    2007-12-15

    We report the preparation and stability of ScVO{sub 3.5+x} and the novel phase InVO{sub 3.5+x}. AVO{sub 3.5+x} (A=Sc, In) defect fluorite structures are formed as metastable intermediates during the topotactic oxidation of AVO{sub 3} bixbyites. The oxidation pathway has been studied in detail by means of thermogravimetric/differential thermal analysis and in-situ powder X-ray diffraction. The oxidation of the bixbyite phase follows a topotactic pathway at temperatures between 300 and 400 deg. C in air/carbon dioxide. The range of accessible oxygen stoichiometries for the AVO{sub 3.5+x} structures following this pathway are 0.00{<=}x{<=}0.22. Rietveld refinements against powder X-ray and neutron data revealed that InVO{sub 3.54} and ScVO{sub 3.70} crystallize in the defect fluorite structure in space group Fm-3 m (227) with a=4.9863(5) and 4.9697(3)A, respectively with A{sup 3+}/V{sup 4+} disorder on the (4a) cation site. Powder neutron diffraction experiments indicate clustering of oxide defects in all samples. Bulk magnetic measurements showed the presence of V{sup 4+} and the absence of magnetic ordering at low temperatures. Powder neutron diffraction experiments confirmed the absence of a long range ordered magnetic ground state. - Graphical abstract: Topotactic oxidation of AVO{sub 3} bixbyite to AVO{sub 3.5} defect fluorite structure followed by in-situ powder X-ray diffraction. The upper structural diagram shows a six coordinated (A/V)-O{sub 6} fragment in bixbyite, the lower structure illustrates the same seven-fold coordinated (A/V)-O{sub 7} cubic environment in the defect fluorite structure.

  1. Phase formation in the BaB2O4-BaF2 system

    NASA Astrophysics Data System (ADS)

    Bekker, T. B.; Fedorov, P. P.; Kokh, A. E.

    2012-07-01

    It is shown that the BaB2O4-BaF2 system is quasi-binary with the following eutectics coordinates: 760°C, 59 mol % BaF2, 41 mol % BaB2O4. Due to the intense pyrohydrolysis during the growth of β-BaB2O4 crystals from the 55.6 mol % BaB2O4-44.4 mol % BaF2 composition, the Ba5B4O11 compound is formed in the system. This process leads to the cocrystallization of the β-BaB2O4 and Ba5B4O11 phases and impedes the formation of high-quality crystals.

  2. Luminescent and kinetic properties of the polystyrene composites based on BaF2 nanoparticles

    NASA Astrophysics Data System (ADS)

    Demkiv, T. M.; Halyatkin, O. O.; Vistovskyy, V. V.; Gektin, A. V.; Voloshinovskii, A. S.

    2016-02-01

    Luminescence-kinetic properties of polystyrene composites based on BaF2 nanoparticles were studied. The electron emission from the nanoparticles due to the photoelectric effect is the main luminescence excitation mechanism in the case of polystyrene composites loaded with small BaF2 nanoparticles (~20 nm). Scintillation pulse of polystyrene composites possesses only fast decay component with the time constant τ~2 ns, and its emission intensity considerably exceeds the one for pure polystyrene scintillator upon the X-ray excitations.

  3. Atomized BaF2-CaF7 for Better-Flowing Plasma-Spray Feedstock

    NASA Technical Reports Server (NTRS)

    DellaCorte, Christopher; Stanford, Malcolm K.

    2008-01-01

    Atomization of a molten mixture of BaF2 and CaF2 has been found to be superior to crushing of bulk solid BaF2- CaF2 as a means of producing eutectic BaF2-CaF2 powder for use as an ingredient of the powder feedstock of a high-temperature solid lubricant material known as PS304. Developed to reduce friction and wear in turbomachines that incorporate foil air bearings, PS304 is applied to metal substrates by plasma spraying. The constituents of PS304 are: a) An alloy of 80 weight percent Ni and 20 weight percent Cr, b) Cr2O3, c) Ag, and d) The BaF2-CaF2 eutectic, specifically, 62 weight percent BaF2 and 38 weight percent CaF2. The superiority of atomization as a means of producing the eutectic BaF2-CaF2 powder lies in (1) the shapes of the BaF2-CaF2 particles produced and (2) the resulting flow properties of the PS304 feedstock powder: The particles produced through crushing are angular, whereas those produced through atomization are more rounded. PS304 feedstock powder containing the more rounded BaF2-CaF2 particles flows more freely and more predictably, as is preferable for plasma spraying.

  4. Water orientation and hydrogen-bond structure at the fluorite/water interface.

    PubMed

    Khatib, Rémi; Backus, Ellen H G; Bonn, Mischa; Perez-Haro, María-José; Gaigeot, Marie-Pierre; Sulpizi, Marialore

    2016-01-01

    Water in contact with mineral interfaces is important for a variety of different processes. Here, we present a combined theoretical/experimental study which provides a quantitative, molecular-level understanding of the ubiquitous and important CaF2/water interface. Our results show that, at low pH, the surface is positively charged, causing a substantial degree of water ordering. The surface charge originates primarily from the dissolution of fluoride ions, rather than from adsorption of protons to the surface. At high pH we observe the presence of Ca-OH species pointing into the water. These OH groups interact remarkably weakly with the surrounding water, and are responsible for the "free OH" signature in the VSFG spectrum, which can be explained from local electronic structure effects. The quantification of the surface termination, near-surface ion distribution and water arrangement is enabled by a combination of advanced phase-resolved Vibrational Sum Frequency Generation spectra of CaF2/water interfaces and state-of-the-art ab initio molecular dynamics simulations which include electronic structure effects. PMID:27068326

  5. Water orientation and hydrogen-bond structure at the fluorite/water interface

    PubMed Central

    Khatib, Rémi; Backus, Ellen H. G.; Bonn, Mischa; Perez-Haro, María-José; Gaigeot, Marie-Pierre; Sulpizi, Marialore

    2016-01-01

    Water in contact with mineral interfaces is important for a variety of different processes. Here, we present a combined theoretical/experimental study which provides a quantitative, molecular-level understanding of the ubiquitous and important CaF2/water interface. Our results show that, at low pH, the surface is positively charged, causing a substantial degree of water ordering. The surface charge originates primarily from the dissolution of fluoride ions, rather than from adsorption of protons to the surface. At high pH we observe the presence of Ca-OH species pointing into the water. These OH groups interact remarkably weakly with the surrounding water, and are responsible for the “free OH” signature in the VSFG spectrum, which can be explained from local electronic structure effects. The quantification of the surface termination, near-surface ion distribution and water arrangement is enabled by a combination of advanced phase-resolved Vibrational Sum Frequency Generation spectra of CaF2/water interfaces and state-of-the-art ab initio molecular dynamics simulations which include electronic structure effects. PMID:27068326

  6. Water orientation and hydrogen-bond structure at the fluorite/water interface

    NASA Astrophysics Data System (ADS)

    Khatib, Rémi; Backus, Ellen H. G.; Bonn, Mischa; Perez-Haro, María-José; Gaigeot, Marie-Pierre; Sulpizi, Marialore

    2016-04-01

    Water in contact with mineral interfaces is important for a variety of different processes. Here, we present a combined theoretical/experimental study which provides a quantitative, molecular-level understanding of the ubiquitous and important CaF2/water interface. Our results show that, at low pH, the surface is positively charged, causing a substantial degree of water ordering. The surface charge originates primarily from the dissolution of fluoride ions, rather than from adsorption of protons to the surface. At high pH we observe the presence of Ca-OH species pointing into the water. These OH groups interact remarkably weakly with the surrounding water, and are responsible for the “free OH” signature in the VSFG spectrum, which can be explained from local electronic structure effects. The quantification of the surface termination, near-surface ion distribution and water arrangement is enabled by a combination of advanced phase-resolved Vibrational Sum Frequency Generation spectra of CaF2/water interfaces and state-of-the-art ab initio molecular dynamics simulations which include electronic structure effects.

  7. Structural determination of fluorite-type oxygen excess uranium oxides using EXAFS spectroscopy

    SciTech Connect

    Jones, D.J.; Roziere, J.; Allen, G.C.; Tempest, P.A.

    1986-06-01

    Extended x-ray absorption fine structure (EXAFS) spectroscopy has been carried out at 77 K at the uranium L/sub III/ edge for UO/sub 2/, ..beta..-U/sub 3/O/sub 7/, and U/sub 4/O/sub 9/ with the aim of determining the structure of these highly defective (oxygen excess) uranium oxide phases, which are of industrial importance. Use has been made of a difference Fourier technique for U/sub 3/O/sub 7/, in which the EXAFS of a perfect lattice model is subtracted. U--O bond lengths calculated from the remaining EXAFS signal, assumed to result only from interstitial oxygens, have been used to determine the atomic coordinates of these interstitials. The analysis of EXAFS data in terms of coordination number has allowed an insight into the defect aggregate arrangement of oxygens in U/sub 3/O/sub 7/ and U/sub 4/O/sub 9/. Furthermore, EXAFS data indicate that the uranium sublattice is perturbed by the incorporation of additional oxygen atoms.

  8. Investigating the Electronic Structure of Fluorite Oxides: Comparsion of EELS and First Principles Calculations

    SciTech Connect

    Aguiar, J; Asta, M; Gronbech-Jensen, N; Perlov, A; Milman, V; Gao, S; Pickard, C; Browning, N

    2009-06-05

    Energy loss spectra from a variety of cubic oxides are compared with ab-initio calculations based on the density functional plane wave method (CASTEP). In order to obtain agreement between experimental and theoretical spectra, unique material specific considerations were taken into account. The spectra were calculated using various approximations to describe core-hole effects and electronic correlations. All the calculations are based on the local spin density approximation to show qualitative agreement with the sensitive oxygen K-edge spectra in ceria, zirconia, and urania. Comparison of experimental and theoretical results let us characterize the main electronic interactions responsible for both the electronic structure and the resulting EEL spectra of the compounds in question.

  9. Relaxation and interaction of electronic excitations induced by intense ultra short light pulses in BaF2 scintillator

    NASA Astrophysics Data System (ADS)

    Kirm, M.; Nagirnyi, V.; Vielhauer, S.; Feldbach, E.

    2011-06-01

    Excitation density effects have a pronounced influence on relaxation processes in solids. They come into play in scintillating and dosimetric materials exposed to ionizing radiation or in laser materials operating in intense ultraviolet light fields. The scientific understanding of the underlying process is poor, mainly because most of the studies of light emitting materials under short wavelength excitation have been performed at weak and moderate excitation intensities due to limited availability of powerful light sources. Disembodied data on excitation density effects have been reported for wide-gap dielectrics studied by luminescence spectroscopy, by using such excitation sources as powerful ion beams,1,2pulsed electron beams,2,3 and wide-band hard X-ray synchrotron radiation.4 It is obvious that such non-selective excitation is a good tool for revealing density-related phenomena in these materials in general, but for investigating specific features of relaxation processes in insulators, light sources with well defined parameters are necessary. Since the shortwavelength free electron laser (FEL) technology has been devised by an international consortium at HASYLAB of DESY, resulting in the development of TESLA Test facility (TTF)5 and later in the construction of a dedicated FEL source FLASH in Hamburg,6 more advanced studies became possible. The range of interests towards this light source covers the fields from material science and various other branches of physics to structural biology. The pioneering luminescence study revealed excitation density effects in the decay of Ce3+ 5d-4f luminescence in Y3Al5O12 crystals and luminescence of BaF2 crystals in UV-visible range.7 These results motivated systematic investigations of excitation density effects in wide gap crystals using FEL8,9 and high-harmonic-generated VUV radiation,10 and, at lower energies, femtosecond laser pulses in the UV.11,12 The main goal of the present work is to analyze the same phenomenon

  10. Magnetic properties and structural transitions of fluorite-related rare earth osmates Ln{sub 3}OsO{sub 7} (Ln=Pr, Tb)

    SciTech Connect

    Hinatsu, Yukio; Doi, Yoshihiro

    2013-02-15

    Ternary rare-earth osmates Ln{sub 3}OsO{sub 7} (Ln=Pr, Tb) have been prepared. They crystallize in an ortho-rhombic superstructure of cubic fluorite with space group Cmcm. Both of these compounds undergo a structural phase transition at 130 K (Ln=Pr) and 580 K (Ln=Tb). These compounds show complex magnetic behavior at low temperatures. Pr{sub 3}OsO{sub 7} exhibits magnetic transitions at 8 and 73 K, and Tb{sub 3}OsO{sub 7} magnetically orders at 8 and 60 K. The Os moments become one-dimensionally ordered, and when the temperature is furthermore decreased, it provokes the ordering in the Ln{sup 3+} sublattice that simultaneously becomes three-dimensionally ordered with the Os sublattice. - Graphical abstract: Ternary rare-earth osmates Ln{sub 3}OsO{sub 7} (Ln=Pr, Tb) have been prepared. They crystallize in an orthorhombic superstructure of cubic fluorite with space group Cmcm. Both of these compounds undergo a structural phase transition at 130 K (Ln=Pr) and 580 K (Ln=Tb). These compounds show complex magnetic behavior at low temperatures. Pr{sub 3}OsO{sub 7} exhibits magnetic transitions at 8 and 73 K, and Tb{sub 3}OsO{sub 7} magnetically orders at 8 and 60 K. Highlights: Black-Right-Pointing-Pointer Ternary rare-earth osmates Ln{sub 3}OsO{sub 7} (Ln=Pr, Tb) with an ordered defect-fluorite structure have been prepared. Black-Right-Pointing-Pointer Both of these compounds undergo a structural phase transition at 130 K (Ln=Pr) and 580 K (Ln=Tb). Black-Right-Pointing-Pointer These compounds show complex magnetic behavior at low temperatures due to magnetic ordering of Ln and Os.

  11. Fast ion conductivity in strained defect-fluorite structure created by ion tracks in Gd2Ti2O7

    SciTech Connect

    Aidhy, Dilpuneet S.; Sachan, Ritesh; Zarkadoula, Eva; Pakarinen, Olli; Chisholm, Matthew F.; Zhang, Yanwen; Weber, William J.

    2015-11-10

    The structure and ion-conducting properties of the defect-fluorite ring structure formed around amorphous ion-tracks by swift heavy ion irradiation of Gd2Ti2O7 pyrochlore are investigated. High angle annular dark field imaging complemented with ion-track molecular dynamics simulations show that the atoms in the ring structure are disordered, and have relatively larger cation-cation interspacing than in the bulk pyrochlore, illustrating the presence of tensile strain in the ring region. Density functional theory calculations show that the non-equilibrium defect-fluorite structure can be stabilized by tensile strain. The pyrochlore to defect-fluorite structure transformation in the ring region is predicted to be induced by recrystallization during a melt-quench process and stabilized by tensile strain. Static pair-potential calculations show that planar tensile strain lowers oxygen vacancy migration barriers in pyrochlores, in agreement with recent studies on fluorite and perovskite materials. Lastly, in view of these results, it is suggested that strain engineering could be simultaneously used to stabilize the defect-fluorite structure and gain control over its high ion-conducting properties.

  12. Direct growth of nanocrystalline graphitic carbon films on BaF2 by alcohol CVD

    NASA Astrophysics Data System (ADS)

    Tan, Yan; Nakamura, Atsushi; Kubono, Atsushi

    2016-03-01

    Multilayered nanocrystalline graphitic carbon films were directly formed on BaF2 substrates by the alcohol chemical vapor deposition method using ethanol. Domain size was typically 46 nm as estimated from the peak intensity ratios of G- and D-band of the Raman spectra, which were higher than currently reported values for various dielectric substrates. Sheet resistance measured by the four-probe method was 900 Ω/sq. A possible formation mechanism of the graphitic carbon layer was discussed referring to the results of X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray spectroscopy (EDX) for a composition analysis. It was found that the graphitic carbon layers were formed on the BaO surface, which was produced by the oxidization of the BaF2 substrate by the ethanol source.

  13. Commissioning the DANTE array of BaF2 detectors at TRIUMF-ISAC using a fast-timing lifetime measurement

    NASA Astrophysics Data System (ADS)

    Cross, D. S.; Ball, G. C.; Garrett, P. E.; Triambak, S.; Williams, S. J.; Andreoiu, C.; Churchman, R.; Garnsworthy, A. B.; Hackman, G.; Leslie, J. R.; Orce, J. N.; Sumithrarachchi, C. S.; Svensson, C. E.

    2011-08-01

    The Di-pentagonal Array for Nuclear Timing Experiments (DANTE) is an array of ten BaF2 detectors used in conjunction with the 8π gamma-ray spectrometer at the TRIUMF-ISAC radioactive-ion beam facility. DANTE is used to conduct direct lifetime measurements of nuclear excited states in the picosecond - nanosecond range. This, in turn, will aid in probing the collective structures of deformed nuclei. The capability of DANTE to measure nanosecond-scale lifetimes is demonstrated by using a 152Eu source. The half-life of the Iπ = 21+ state of 152Sm is measured to be 1.426 ± 0.018 ns.

  14. Crystal structures and magnetic properties of fluorite-related oxides Ln{sub 3}NbO{sub 7} (Ln=lanthanides)

    SciTech Connect

    Doi, Yoshihiro; Harada, Yuka; Hinatsu, Yukio

    2009-04-15

    Crystal structures and magnetic properties of the ternary oxides Ln{sub 3}NbO{sub 7} (Ln=La, Pr, Nd, Sm-Lu) are reported. Their powder X-ray diffraction measurements and Rietveld analyzes show that they have the fluorite-related structures with space group Pnma (Ln=La, Pr, Nd), C222{sub 1} (Ln=Sm-Tb), or Fm-3m (Ln=Dy-Lu). Magnetic susceptibility measurements were carried out from 1.8 to 400 K. The Ln{sub 3}NbO{sub 7} compounds for Ln=Pr, Gd, Dy-Yb show Curie-Weiss paramagnetic behavior, and Sm{sub 3}NbO{sub 7} and Eu{sub 3}NbO{sub 7} show van Vleck paramagnetism. On the other hand, two magnetic anomalies were observed for both Nd{sub 3}NbO{sub 7} (0.6 and 2.7 K) and Tb{sub 3}NbO{sub 7} (2.0 and 3.2 K). From the results of specific heat measurements, it was found that these anomalies are due to the antiferromagnetic ordering of Ln ions in two different crystallographic sites (the 8-coordinated and 7-coordinated sites). - Ternary oxides Ln{sub 3}NbO{sub 7} (Ln=lanthanides) have the fluorite-related structures with space group Pnma (Ln=La, Pr, Nd), C222{sub 1} (Ln=Sm-Tb), or Fm-3m (Ln=Dy-Lu). In them, Nd{sub 3}NbO{sub 7} and Tb{sub 3}NbO{sub 7} show 'two-step' antiferromagnetic transitions due to the long-range antiferromagnetic ordering of Ln ions in different crystallographic sites.

  15. Magnetic properties and structural transitions of fluorite-related rare earth osmates Ln3OsO7 (Ln=Pr, Tb)

    NASA Astrophysics Data System (ADS)

    Hinatsu, Yukio; Doi, Yoshihiro

    2013-02-01

    Ternary rare-earth osmates Ln3OsO7 (Ln=Pr, Tb) have been prepared. They crystallize in an ortho-rhombic superstructure of cubic fluorite with space group Cmcm. Both of these compounds undergo a structural phase transition at 130 K (Ln=Pr) and 580 K (Ln=Tb). These compounds show complex magnetic behavior at low temperatures. Pr3OsO7 exhibits magnetic transitions at 8 and 73 K, and Tb3OsO7 magnetically orders at 8 and 60 K. The Os moments become one-dimensionally ordered, and when the temperature is furthermore decreased, it provokes the ordering in the Ln3+ sublattice that simultaneously becomes three-dimensionally ordered with the Os sublattice.

  16. Formation of defect-fluorite structured NdNiOxHy epitaxial thin films via a soft chemical route from NdNiO3 precursors.

    PubMed

    Onozuka, T; Chikamatsu, A; Katayama, T; Fukumura, T; Hasegawa, T

    2016-07-26

    A new phase of oxyhydride NdNiOxHy with a defect-fluorite structure was obtained by a soft chemical reaction of NdNiO3 epitaxial thin films on a substrate of SrTiO3 (100) with CaH2. The epitaxial relationship of this phase relative to SrTiO3 could be controlled by changing the reaction temperature. At 240 °C, NdNiOxHy grew with a [001] orientation, forming a thin layer of infinite-layer NdNiO2 at the interface between the NdNiOxHy and the substrate. Meanwhile, a high-temperature reaction at 400 °C formed [110]-oriented NdNiOxHy without NdNiO2. PMID:27396577

  17. Relationship between Oxide-Ion Conduction and Dielectric Properties of Gd2Zr2O7 Having a Fluorite-Type Structure

    NASA Astrophysics Data System (ADS)

    Yamamura, Hiroshi; Nishino, Hanako; Kakinuma, Katsuyoshi

    2008-07-01

    The relationship between electrical conduction and dielectric properties was investigated for the oxide-ion conductor Gd2Zr2O7 having a fluorite-type structure. Computer simulation clarified that the anomalously large dielectric constant (ɛr') was successfully explained by the superposition of the Debye-type polarization and the electrolyte-electrode interfacial polarization. Two Debye-type relaxations were observed at 673 K and above. The lower-frequency relaxation was ascribed to the dopant-vacancy associate, (GdCe'-VO••-GdCe'), and the higher one to the long range migration of oxide ions on the basis of the discussions of both the activation energies and the relaxation frequencies. The frequency dependences of both the ac conductivity (σac) and the loss tangent (tan δ) were also successfully explained using the dielectric parameters of the Debye-type dopant-vacancy associates.

  18. Hardness of CaF2 and BaF2 solid lubricants at 25 to 670 deg C

    NASA Technical Reports Server (NTRS)

    Deadmore, Daniel L.; Sliney, Harold E.

    1987-01-01

    Plastic deformation is a prominent factor in determining the lubricating value of solid lubricants. Little information is available and its direct measurement is difficult so hardness, which is an indirect measure of this property was determined for fluoride solid lubricant compositions. The Vickers hardness of BaF2 and CaF2 single crystals was measured up to 670 C in a vacuum. The orientation of the BaF2 was near the (013) plane and the CaF2 was about 16 degrees from the degrees from the (1'11) plane. The BaF2 has a hardness of 83 kg/sq mm at the 25 C and 9 at the 600 C. The CaF2 is 170 at 25 C and 13 at 670 C. The decrease in hardness in the temperature range of 25 to 100 C is very rapid and amounts to 40% for both materials. Melts of BaF2 and CaF2 were made in a platinum crucible in ambient air with compositions of 50 to 100 wt% BaF2. The Vickers hardness of these polycrystalline binary compositions at 25 C increased with increasing CaF2 reaching a maximum of 150 kn/sq mm near the eutectic. The polycrystalline CaF2 was 14% softer than that of the single crystal surface and BsF2 was 30% harder than the single crystal surface. It is estimated that the brittle to ductile transition temperature for CaF2 and BaF2 is less than 100 C for the conditions present in the hardness tester.

  19. Raman Scattering Study of PbSe Grown on (111) BaF2 Substrate

    NASA Astrophysics Data System (ADS)

    Yang, Ai-Ling; Wu, Hui-Zhen; Li, Zhi-Feng; Qiu, Dong-Jiang; Chang, Yong; Li, Jian-Feng; P, McCann J.; X, Fang M.

    2000-08-01

    PbSe films were grown on (111)-oriented BaF2 substrates by using molecular beam epitaxy. High resolution x-ray diffraction characterization showed good crystalline quality of PbSe films. Both longitudinal optical phonon at 135 cm-1 and transverse optical phonon at 47.6 cm-1 were observed by Raman scattering measurements. The Raman tensor calculation demonstrates that both transverse-optical and longitudinal-optical (LO) phonons in PbSe crystal are Raman active on (111)-oriented surface. Furthermore, 2LO phonon at about 270 cm-1 and polaron at about 800 cm-1 in PbSe, were also observed. The observed Raman frequencies are in good agreement with theoretical calculations using point ion model.

  20. Dislocations in YbF3 doped BaF2 crystals

    NASA Astrophysics Data System (ADS)

    Cirlan, Florina; Buse, Gabriel; Nicoara, Irina

    2014-11-01

    Three concentrations of YbF3 -doped BaF2 crystals were grown using the conventional Bridgman method. Transparent colorless crystals were obtained in graphite crucible in vacuum (˜10-1 Pa) using a shaped graphite furnace. The crystals have been cooled to room temperature using an established procedure. In order to study the etch pits morphology and the dislocations density the etching method have been used. This method consists in immersing the cleaved sample in 2N HCl at 60°C for 2 minutes. Small etch pits are developed at the emergence points of the dislocations. The etch pits have triangular or hexagonal shapes, depending on the dopant concentration. The dislocations density depends on the dopant concentration.

  1. Spectroscopic properties and energy transfer analysis of Tm3+-doped BaF2-Ga2O3-GeO2-La2O3 glass.

    PubMed

    Yu, Shenglei; Yang, Zhongmin; Xu, Shanhui

    2010-05-01

    This paper reports on the spectroscopic properties and energy transfer analysis of Tm(3+)-doped BaF(2)-Ga(2)O(3)-GeO(2)-La(2)O(3) glasses with different Tm(2)O(3) doping concentrations (0.2, 0.5, 2.0, 2.5, 3.0, 3.5, 3.5, 4.0 wt%). Mid-IR fluorescence intensities in the range of 1,300 nm-2,200 nm have been measured when excited under an 808 nm LD for all the samples with the same pump power. Energy level structure and Judd-Ofelt parameters have been calculated based on the absorption spectra of Tm(3+), cross-relaxation rates and multi-phonon relaxation rates have been estimated with different Tm(2)O(3) doping concentrations. The maximum fluorescence intensity at around 1.8 mum has been obtained in Tm(2)O(3)-3 wt% sample and the maximum value of calculated stimulated emission cross-section of Tm(3+) in this sample is about 0.48 x 10(-20) cm(2) at 1,793 nm, and there is not any crystallization peak in the DSC curve of this sample, which indicate the potential utility of Tm(3+)-doped BaF(2)-Ga(2)O(3)-GeO(2)- La(2)O(3) glass for 2.0-microm optical fiber laser. PMID:20204685

  2. From fluorite to pyrochlore: Characterisation of local and average structure of neodymium zirconate, Nd{sub 2}Zr{sub 2}O{sub 7}

    SciTech Connect

    Payne, Julia L.; Tucker, Matthew G.; Evans, Ivana Radosavljević

    2013-09-15

    The structural characterisation of Nd{sub 2}Zr{sub 2}O{sub 7} prepared via a precursor route was performed using a combination of local and average structure probes (neutron total scattering, X-ray and neutron diffraction). We present the first total scattering and reverse Monte Carlo (RMC) modelling study of Nd{sub 2}Zr{sub 2}O{sub 7}, which provides compelling evidence for the adoption of a disordered fluorite-type structure by Nd{sub 2}Zr{sub 2}O{sub 7} prepared by a low-temperature precursor route. Annealing the material at high temperatures leads to a transformation to a pyrochlore-type structure; however, Rietveld refinement using powder neutron diffraction data shows that the oxygen sublattice retains a degree of disorder. - Graphical abstract: Display Omitted - Highlights: • The first total scattering and RMC modelling study of Nd{sub 2}Zr{sub 2}O{sub 7}. • Demonstration that the synthetic route influences the crystal structure adopted. • Insight into the importance of total scattering in studies of complex superstructures, especially for nano-sized materials.

  3. Evaluation of minimum yields for planar channeling in CaF 2 and BaF 2

    NASA Astrophysics Data System (ADS)

    Saitoh, Kazuo; Kobayakawa, Mikio; Niwa, Hiroaki; Tanemura, Seita

    1980-04-01

    Minimum yields for planar channeling in CaF 2 and BaF 2 have been calculated using an average potential model. The use of the Lentz-Jensen ionic potential gives results consistent with the experimental data. The validity of the model and the dependence of the minimum yields on the potential are discussed.

  4. Structural mechanism of the formation of mineral Na-tveitite-a new type of phase with a fluorite-derivative structure-in the NaF-CaF{sub 2}-(Y,Ln)F{sub 3} natural system

    SciTech Connect

    Golubev, A. M. Otroshchenko, L. P.; Sobolev, B. P.

    2012-03-15

    Relationships between the chemical compositions and structures of the mineral tveitite from the southern Norway pegmatites (with the idealized formula Ca{sub 14}Y{sub 5}F{sub 43}) and Na-tveitite from the Rov mountain (Keivy, Kola Peninsula) Na{sub 2.5}Ca{sub 10}Ln{sub 1.5}Y{sub 5}F{sub 42} are considered. According to the structural mechanism of its formation, Na-tveitite is a nanocomposite crystal based on the crystalline matrix Ca{sub 14}Y{sub 5}F{sub 43} with the ordered arrangement of {l_brace}Ca{sub 8}[CaY{sub 5}]F{sub 69}{r_brace} clusters which contain anionic {l_brace}F{sub 13}{r_brace} cuboctahedra with F{sup 1-} at the center. When Na-tveitite is formed, 29% of these clusters are statistically replaced by Na-'Y' clusters {l_brace}[Na{sub 0.5}(Y,Ln){sub 0.5}]{sub 14}F{sub 64}{r_brace} with {l_brace}F{sub 8}{r_brace} cubes at the center (analogs of matrix fluorite groups {l_brace}Ca{sub 14}F{sub 64}{r_brace}). This replacement gives rise to composition-imperfect (Na, Ca, 'Y') cationic positions and occupancy-deficient F positions, which correspond to {l_brace}F{sub 13}{r_brace} cuboctahedra and the {l_brace}F{sub 8}{r_brace} cubes that replace them. The difference between Na-tveitite and fluorite phases M{sub 1-x}R{sub x}F{sub 2+x} is as follows: its matrix is the structure of the ordered phase (tveitite) into which Na-containing rare earth fragments of fluorite-type structure are incorporated instead of ordered-phase structural blocks (clusters).

  5. Investigation of rare nuclear decays with BaF2 crystal scintillator contaminated by radium

    NASA Astrophysics Data System (ADS)

    Belli, P.; Bernabei, R.; Cappella, F.; Caracciolo, V.; Cerulli, R.; Danevich, F. A.; Di Marco, A.; Incicchitti, A.; Poda, D. V.; Polischuk, O. G.; Tretyak, V. I.

    2014-09-01

    The radioactive contamination of a BaF2 scintillation crystal with mass of 1.714 kg was measured over 101 hours in the low-background DAMA/R&D set-up deep underground (3600 m w.e.) at the Gran Sasso National Laboratories of INFN (LNGS, Italy). The half-life of 212Po (present in the crystal scintillator due to contamination by radium) was measured as = 298.8±0.8( stat.)±1.4( syst.) ns by the analysis of the events' pulse profiles. The 222Rn nuclide is known as 100% decaying via the emission of the particle with T 1/2 = 3.82 d; however, its decay is also energetically allowed with keV. Search for decay chains of events with specific pulse shapes characteristic for or for signals and with known energies and time differences allowed us to set, for the first time, the limit on the branching ratio of 222Rn relatively to decay as % at 90% C.L. (equivalent to limit on partial half-life y). The half-life limits of 212Pb, 222Rn and 226Ra relatively to 2 decays are also improved in comparison with the earlier results.

  6. Neutron response of the LAMBDA spectrometer and neutron interaction length in BaF2

    NASA Astrophysics Data System (ADS)

    Dey, Balaram; Mondal, Debasish; Pandit, Deepak; Mukhopadhyay, S.; Pal, Surajit; Banerjee, K.; Bhattacharya, Srijit; De, A.; Banerjee, S. R.

    2013-11-01

    We report on the neutron response of the LAMBDA spectrometer developed earlier for high-energy γ-ray measurement. The energy dependent neutron detection efficiency of the spectrometer has been measured using the time-of-flight (TOF) technique and compared with that of an organic liquid scintillator based neutron detector (BC501A). The extracted efficiencies have also been compared with those obtained from Monte Carlo GEANT4 simulation. We have also measured the average interaction length of neutrons in the BaF2 crystal in a separate experiment, in order to determine the TOF energy resolution. Finally, the LAMBDA spectrometer has been tested in an in-beam-experiment by measuring neutron energy spectra in the 4He+93Nb reaction to extract nuclear level density parameters. Nuclear level density parameters obtained by the LAMBDA spectrometer were found to be consistent with those obtained by the BC501A neutron detector, indicating that the spectrometer can be efficiently used as a neutron detector to measure the nuclear level density parameter.

  7. Preparation and Properties of Ce3+:BaF2 Transparent Ceramics by Vacuum Sintering.

    PubMed

    Luo, Junming; Ye, Lifang; Xu, Jilin

    2016-04-01

    Ce0.001Ba0.999F2.001 powders were prepared by a chemical coprecipitation method using Ba(N03)2, KF.2H2O and Ce(NO3)3 6H20 as raw materials. Ce0.001Ba0.999F2.001 transparent ceramics were prepared by vacuum sintering. The results show that the Ce0.001Ba0.999F2.001 powders were blocky, and both powdered and sintered transparent ceramics were composed of BaF2 phases without the secondary phase. The maximum light transmittance of the Ce0.001Ba0.999F2.001 transparent ceramics reached 55%. The fracture morphology shows a cleavage fracture with a few micropores. The fluorescence spectra show that the Ce0.1Ba0.999F2.001 powders displayed emissions at 410 nm, 480 nm and 620 nm under 275 nm excitation. The Ce0.1Ba0.9F2.1 transparent ceramics displayed0emissions at 450 nm and 620 nm under 294 nm excitation. PMID:27451752

  8. Magnetic properties and structural transitions of orthorhombic fluorite-related compounds Ln3MO 7 ( Ln=rare earths, M=transition metals)

    NASA Astrophysics Data System (ADS)

    Wakeshima, Makoto; Hinatsu, Yukio

    2010-11-01

    Magnetic properties and structural transitions of ternary rare-earth transition-metal oxides Ln3MO 7 ( Ln=rare earths, M=transition metals) were investigated. In this study, we prepared a series of molybdates Ln3MoO 7 ( Ln=La-Gd). They crystallize in an orthorhombic superstructure of cubic fluorite with space group P2 12 12 1, in which Ln3+ ions occupy two different crystallographic sites (the 8-coordinated and 7-coordinated sites). All of these compounds show a phase transition from the space group P2 12 12 1 to Pnma in the temperature range between 370 and 710 K. Their magnetic properties were characterized by magnetic susceptibility measurements from 1.8 to 400 K and specific heat measurements from 0.4 to 400 K. Gd 3MoO 7 shows an antiferromagnetic transition at 1.9 K. Measurements of the specific heat for Sm 3MoO 7 and the analysis of the magnetic specific heat indicate a "two-step" antiferromagnetic transition due to the ordering of Sm magnetic moments in different crystallographic sites, i.e., with decreasing temperature, the antiferromagnetic ordering of the 7-coordinated Sm ions occur at 2.5 K, and then the 8-coordinated Sm ions order at 0.8 K. The results of Ln3MoO 7 were compared with the magnetic properties and structural transitions of Ln3MO 7 ( M=Nb, Ru, Sb, Ta, Re, Os, or Ir).

  9. Multiple-order resonant Raman scattering of the localized molecular rose center in BaF 2

    NASA Astrophysics Data System (ADS)

    Deyhimi, Farzad; Bill, Hans

    1983-11-01

    The rose center in BaF 2 is investigated by resonant Raman scattering. The spectra obtained at liquid-helium temperature show multiple order and combination bands of the internal local modes (up to the sixth order), and associated side bands of the lattice. The temperature dependence of the linewidth of the local-mode transitions has been investigated and is explained as being due to anharmonic coupling to the lattice.

  10. Time- and energy-resolution measurements of BaF2, BC-418, LYSO and CeBr3 scintillators

    NASA Astrophysics Data System (ADS)

    Ackermann, Ulrich; Egger, Werner; Sperr, Peter; Dollinger, Günther

    2015-06-01

    We have investigated the time and energy resolution (TTiming, ∆E/E) of four different scintillator materials BaF2, BC-418, LYSO and CeBr3 at a gamma energy of 511 keV in views of their possible usage for time, energy and position resolution for positron annihilation experiments. The shape of each scintillator was a cylinder with a diameter of 25 mm and a height of 10 mm readout by a Photonis XP2020/URQ photomultiplier tube. The best single time resolution was determined for each photomultiplier-scintillator setup in a three step optimization process. The optimized single time resolutions (FWHM) for BaF2, BC-418, LYSO and CeBr3 were 119 ps, 117 ps, 269 ps and 127 ps, respectively. We measured the energy resolution of the photomultiplier-scintillator setups which show a photopeak in the energy spectrum. The energy resolutions ∆E/E of BaF2, LYSO and CeBr3 were 9.8%, 9.7% and 5.4%, respectively. The overall most promising material for measuring simultaneously time, energy and position resolution for positron annihilation experiments seems to be CeBr3 due to its very good time and energy resolution characteristics.

  11. First-principles calculations of Mg2X (X = Si, Ge, Sn) semiconductors with the calcium fluorite structure

    NASA Astrophysics Data System (ADS)

    Sandong, Guo

    2015-05-01

    The electronic structures of Mg2X (X = Si, Ge, Sn) have been calculated by using generalized gradient approximation, various screened hybrid functionals, as well as Tran and Blaha's modified Becke and Johnson exchange potential. It was found that the Tran and Blaha's modified Becke and Johnson exchange potential provides a more realistic description of the electronic structures and the optical properties of Mg2X (X = Si, Ge, Sn) than else exchange-correlation potential, and the theoretical gaps and dielectric functions of Mg2X (X = Si, Ge, Sn) are quite compatible with the experimental data. The elastic properties of Mg2X (X = Si, Ge, Sn) have also been studied in detail with the generalized gradient approximation, including bulk modulus, shear modulus, Young's modulus, Poisson's ratio, sound velocities, and Debye temperature. The phonon dispersions of Mg2X (X = Si, Ge, Sn) have been calculated within the generalized gradient approximation, suggesting no structural instability, and the measurable phonon heat capacity as a function of the temperature has been also calculated. Project supported by the Fundamental Research Funds for the Central Universities (No. 2013QNA32) and the National Natural Science Foundation of China (No. 11404391).

  12. Magnetic properties and structural transitions of orthorhombic fluorite-related compounds Ln{sub 3}MO{sub 7} (Ln=rare earths, M=transition metals)

    SciTech Connect

    Wakeshima, Makoto; Hinatsu, Yukio

    2010-11-15

    Magnetic properties and structural transitions of ternary rare-earth transition-metal oxides Ln{sub 3}MO{sub 7} (Ln=rare earths, M=transition metals) were investigated. In this study, we prepared a series of molybdates Ln{sub 3}MoO{sub 7} (Ln=La-Gd). They crystallize in an orthorhombic superstructure of cubic fluorite with space group P2{sub 1}2{sub 1}2{sub 1}, in which Ln{sup 3+} ions occupy two different crystallographic sites (the 8-coordinated and 7-coordinated sites). All of these compounds show a phase transition from the space group P2{sub 1}2{sub 1}2{sub 1} to Pnma in the temperature range between 370 and 710 K. Their magnetic properties were characterized by magnetic susceptibility measurements from 1.8 to 400 K and specific heat measurements from 0.4 to 400 K. Gd{sub 3}MoO{sub 7} shows an antiferromagnetic transition at 1.9 K. Measurements of the specific heat for Sm{sub 3}MoO{sub 7} and the analysis of the magnetic specific heat indicate a 'two-step' antiferromagnetic transition due to the ordering of Sm magnetic moments in different crystallographic sites, i.e., with decreasing temperature, the antiferromagnetic ordering of the 7-coordinated Sm ions occur at 2.5 K, and then the 8-coordinated Sm ions order at 0.8 K. The results of Ln{sub 3}MoO{sub 7} were compared with the magnetic properties and structural transitions of Ln{sub 3}MO{sub 7} (M=Nb, Ru, Sb, Ta, Re, Os, or Ir). -- Graphical Abstract: Magnetic properties and structural transitions of ternary rare-earth transition-metal oxides Ln{sub 3}MO{sub 7} (Ln=rare earths, M=transition metals) were investigated. In this study, we prepared a series of molybdates Ln{sub 3}MoO{sub 7} (Ln=La{approx}Gd). These compounds show a phase transition from the space group P2{sub 1}2{sub 1}2{sub 1} to Pnma in the temperature range between 370 and 710 K. Their magnetic properties were characterized by magnetic susceptibility and specific heat measurements from 0.4 to 400 K. The results of Ln{sub 3}MoO{sub 7} were

  13. Influence of BaF2 and activator concentration on broadband near-infrared luminescence of Pr3+ ions in gallo-germanate glasses.

    PubMed

    Pisarska, Joanna; Kowal, Martyna; Kochanowicz, Marcin; Zmojda, Jacek; Dorosz, Jan; Dorosz, Dominik; Pisarski, Wojciech A

    2016-02-01

    Thermal stability and broadband NIR luminescence of Pr(3+) doped gallo-germanate glasses with BaF2 have been studied. The thermal factors are larger for glass samples with low BaF2 content exhibiting good thermal stability against devitrification. Luminescence due to (1)D2 → (1)G4 transition of Pr(3+) was measured under 450 nm excitation. The (1)D2 measured lifetimes depend critically on activator concentration, but remain nearly unchanged with BaF2 content. The emission linewidth, the emission cross-section, the figure of merit (FOM) and the σem x FWHM product are relatively large, suggesting that Pr(3+)-doped gallo-germanate glasses with presence of BaF2 are promising as gain media for broadband near-infrared amplifiers. PMID:26906818

  14. Neutron Scattering Studies of Fluorite Compounds

    NASA Astrophysics Data System (ADS)

    Goff, Jonathan Peter

    1992-01-01

    Available from UMI in association with The British Library. Requires signed TDF. The nature and mobility of defects in ionic materials with the fluorite structure have been studied using neutron scattering techniques. These systems model the behaviour of the fission fuel UO_2 at elevated temperature. A powder sample of beta -PbF_2 has been investigated using neutron diffraction, which gives the time-averaged occupation of sites in the unit cell. The temperature dependence of the lattice parameter, the concentration of Frenkel defects, and the thermal parameters of both fluorine and lead ions, have been determined at temperatures from ambient to well above the transition to the fast-ion phase. The defect structure of the anion-excess fluorite (Sr,Y)Cl_{2.03} has been studied using the coherent diffuse scattering from single -crystal samples. Excess chlorine ions are found to aggregate into cuboctahedral clusters whose ionic coordinates agree with those calculated from a simple hard sphere model. At elevated temperature the scattering exhibits quasielastic energy broadening, indicating the dynamic nature of the disorder. It is possible to account for the high temperature scattering in terms of 'snapshot' models of the diffusing anions and their associated relaxation fields, and to estimate the anion self diffusion coefficient from coherent scattering alone. Consistent and complementary information on the diffusion of chlorine ions in (Sr,Y)Cl_ {2.03} has been obtained from the quasielastic energy broadening of the single-crystal incoherent scattering measured at elevated temperature. Comparison with previous results from SrCl_2 shows that chlorine diffusion is faster in (Sr,Y)Cl_{2.03 }, and that the diffusional process in the anion-excess fluorite resembles that found when the level of thermally generated disorder is high in the pure compound. The coherent scatterer UO_{2 + delta} (delta = 0.13,0.14) transforms from a mixture of oxides at ambient temperature to a

  15. Light scattering and computer simulation studies of superionic pure and La-doped BaF2

    NASA Astrophysics Data System (ADS)

    Rammutla, K. E.; Comins, J. D.; Erasmus, R. M.; Netshisaulu, T. T.; Ngoepe, P. E.; Chadwick, A. V.

    2016-03-01

    A combination of both Raman and Brillouin scattering experiments as well as Molecular Dynamics (MD) was used to study the superionic behaviour of BaF2 doped with a wide range of LaF3 concentrations (0 ⩽ x ⩽ 50 mol%). Raman spectroscopy reveals that for undoped BaF2 and those doped with 5% and 10% LaF3, the room temperature spectra show the usual T2g symmetry mode at 241 cm-1 whereas for those doped with 20%, 30% and 50% LaF3, the dominant Raman mode is of the Eg symmetry situated at ∼263, 275 and 286 cm-1, respectively. The Raman linewidths show near linear increases with temperature followed by rapid increases above the characteristic transition temperatures (Tc), being at 1200, 850, 800, 975, 950 and 920 K for LaF3 concentrations of 0, 5, 10, 20, 30 and 50; respectively. The temperature dependence of the squares of the Brillouin frequencies (ΔωB)2 of the LA and TA acoustic modes respectively related to elastic constants C11 and C44 showed linear decreases followed by significant deviations around the same temperatures (Tc), at which the Raman linewidths start to show substantial increases. The complementary studies using MD simulations show that the diffusion coefficients increase markedly above the same temperatures observed experimentally. The extrinsic fluorine ion trajectories were also determined from the MD simulations to better understand the mechanisms of diffusion.

  16. Neutron Scattering Studies of Fluorite Compounds.

    NASA Astrophysics Data System (ADS)

    Hackett, Michael Andrew

    Available from UMI in association with The British Library. Requires signed TDF. The properties of some important compounds with the fluorite structure have been investigated using neutron scattering techniques. All of the compounds in this study have important technological applications, as well as being of intrinsic scientific interest. Inelastic neutron scattering and high temperature technology have been used to measure phonon energies in thorium dioxide at temperatures above 3000K. These phonon energies have been used to determine the elastic constants as a function of temperature. Thorium dioxide provides an interesting comparison with uranium dioxide which has been studied in order to try and establish the cause of the anomalously large enthalpy of this compound. Quasielastic neutron scattering has been used to demonstrate that the dynamic ionic-disorder which occurs in ThO_2 behaves in a similar way to that observed in UO _2 at high temperature. Whilst at only 12K, splittings have been measured in the crystal field excitations of UO_2 which have a significant effect on the theoretical analysis of its thermodynamic properties. This experiment was performed using neutrons scattered with a high energy transfer. Elastic and quasielastic diffuse scattering have both been used to investigate the vacancy-stabilised cubic structure of yttria doped zirconia. Computer modelling of the measured neutron scattering intensities has played a vital role in this part of the study. By the combination of neutron scattering measurements and computational techniques a three part model has been developed for the defect structure in yttria-stabilised zirconia which can explain the ionic conductivity in this compound. Ionic disorder has been observed in the anti-fluorite compounds lithium oxide and magnesium silicide at high temperature, using diffuse quasielastic neutron scattering. The full phonon energy dispersion relation and the elastic constants at high temperature have also

  17. Defect-induced wetting on BaF 2(111) and CaF 2(111) at ambient conditions

    NASA Astrophysics Data System (ADS)

    Cardellach, M.; Verdaguer, A.; Fraxedas, J.

    2011-12-01

    The interaction of water with freshly cleaved (111) surfaces of isostructural BaF2 and CaF2 single crystals at ambient conditions (room temperature and under controlled humidity) has been studied using scanning force microscopy in different operation modes and optical microscopy. Such surfaces exhibit contrasting behaviors for both materials: while on BaF2(111) two-dimensional water layers are formed after accumulation at step edges, CaF2(111) does not promote the formation of such layers. We attribute such opposed behavior to lattice match (mismatch) between hexagonal water ice and the hexagonal (111) surfaces of BaF2(CaF2). Optical microscope images reveal that this behavior also determines the way the surfaces become wetted at a macroscopic level.

  18. Progress in the development of a PET scanner based on BaF2 scintillator and photosensitive wire chambers.

    PubMed

    Tavernier, S; Bruyndonckx, P; Guerard, B; Zhang, S

    1991-01-01

    The work presented is part of a design study for a Positron Emission Tomograph (PET) scanner based on the use of BaF2 scintillator and photosensitive wire chambers. The detection efficiency for gamma radiation of 511 keV is found close to 100% for a sufficiently large crystal. For a matrix of small and elongated crystals as one would use in a PET scanner (5 x 5 x 50 mm3) we obtained 6 photoelectrons per 511 keV deposited. The following variants and alternatives were also studied: operation of the wire chamber at atmospheric pressure; double readout where the crystals are read on one side with a photomultiplier to give time and energy resolution, and on the other side with a wire chamber to localise the event; and Csl photocathodes. Encouraging results have been obtained for each of these, but particularly the Csl photocathodes look very promising. PMID:1839856

  19. Electronic structure of fluorides: general trends for ground and excited state properties

    NASA Astrophysics Data System (ADS)

    Cadelano, E.; Cappellini, G.

    2011-05-01

    The electronic structure of fluorite crystals are studied by means of density functional theory within the local density approximation for the exchange correlation energy. The ground-state electronic properties, which have been calculated for the cubic structures CaF2, SrF2, BaF2, CdF2, HgF2, β-PbF2, using a plane waves expansion of the wave functions, show good comparison with existing experimental data and previous theoretical results. The electronic density of states at the gap region for all the compounds and their energy-band structure have been calculated and compared with the existing data in the literature. General trends for the ground-state parameters, the electronic energy-bands and transition energies for all the fluorides considered are given and discussed in details. Moreover, for the first time results for HgF2 have been presented.

  20. Spectroscopic properties of Pr3+ and Er3+ ions in lead-free borate glasses modified by BaF2

    NASA Astrophysics Data System (ADS)

    Pisarska, Joanna; Pisarski, Wojciech A.; Dorosz, Dominik; Dorosz, Jan

    2015-09-01

    Lead-free oxyfluoride borate glasses singly doped with Pr3+ and Er3+ were prepared and next investigated using absorption and luminescence spectroscopy. In the studied glass system, barium oxide was substituted by BaF2. Two luminescence bands of Pr3+ located at visible spectral region are observed, which correspond to 3P0-3H4 (blue) and 1D2-3H4 (reddish orange) transitions, respectively. The luminescence bands due to 1D2-3H4 transition of Pr3+ are shifted to shorter wavelengths, when BaO was substituted by BaF2. Near-infrared luminescence spectra of Er3+ ions in lead-free borate glasses modified by BaF2 correspond to 4I13/2-4I15/2 transition. Their spectral linewidths increase with increasing BaF2 concentration. The changes in measured lifetimes of rare earth ions are well correlated with the bonding parameters calculated from the optical absorption spectra.

  1. Structures and magnetic properties of new fluorite-related quaternary rare earth oxides LnY2TaO7 and LaLn2RuO7 (Ln=rare earths)

    NASA Astrophysics Data System (ADS)

    Hinatsu, Yukio; Doi, Yoshihiro

    2016-01-01

    New fluorite-related quaternary rare earth oxides LnY2TaO7 (Ln=La-Dy) and LaLn2RuO7 (Ln=Eu-Tb) have been prepared. They crystallize in an orthorhombic superstructure of cubic fluorite with space groups C2221 and Cmcm, respectively. The results of the Rietveld analysis for LnY2TaO7 (Ln=La-Dy) indicate that there exists no structural ordering of the Ln and Y ions at the eight-coordinate 4b site and the seven-coordinate 8c site, but the larger Ln ions occupy the eight-coordinate 4b site rather than the seven-coordinate 8c site, with increasing the Ln ionic radius. On the other hand, the results of the Rietveld analysis for the X-ray diffraction profiles of LaTb2RuO7 showed that La and Tb atoms are almost situated at the eight-coordinated site (4a site) and seven-coordinated site (8g site), respectively, i.e., cation ordering occurs on the 4a and 8g sites. All compounds LnY2TaO7 (Ln=La-Dy) are paramagnetic down to 1.8 K. On the other hand, LaTb2RuO7 shows an antiferromagnetic transition at 17 K. In addition, another magnetic anomaly has been found at 10 K. Analysis of the magnetic specific heat for LaTb2RuO7 indicates that the magnetic transitions at 10 and 17 K are due to the magnetic ordering of Tb3+ and Ru5+ ions, respectively.

  2. Materials Data on BaF2 (SG:225) by Materials Project

    SciTech Connect

    Kristin Persson

    2014-11-02

    Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

  3. Variable helium diffusion characteristics in fluorite

    NASA Astrophysics Data System (ADS)

    Wolff, R.; Dunkl, I.; Kempe, U.; Stockli, D.; Wiedenbeck, M.; von Eynatten, H.

    2016-09-01

    Precise analysis of the diffusion characteristics of helium in fluorite is crucial for establishing the new fluorite (U-Th-Sm)/He thermochronometer (FHe), which potentially provides a powerful tool for dating ore deposits unsuitable for the application of conventional geochronometers. Incremental helium outgassing experiments performed on fluorites derived from a spectrum of geological environments suggest a thermally activated volume diffusion mechanism. The diffusion behaviour is highly variable and the parameters range between log D0/a2 = 0.30 ± 0.27-7.27 ± 0.46 s-1 and Ea = 96 ± 3.5-182 ± 3.8 kJ/mol. Despite the fact that the CaF2 content of natural fluorites in most cases exceeds 99 weight percent, the closure temperature (Tc) of the fluorite (U-Th-Sm)/He thermochronometer as calculated from these diffusion parameters varies between 46 ± 14 °C and 169 ± 9 °C, considering a 125 μm fragment size. Here we establish that minor substitutions of calcium by rare earth elements and yttrium (REE + Y) and related charge compensation by sodium, fluorine, oxygen and/or vacancies in the fluorite crystal lattice have a significant impact on the diffusivity of helium in the mineral. With increasing REE + Y concentrations F vacancies are reduced and key diffusion pathways are narrowed. Consequently, a higher closure temperature is to be expected. An empirical case study confirms this variability: two fluorite samples from the same deposit (Horni Krupka, Czech Republic) with ca. 170 °C and ca. 43 °C Tc yield highly different (U-Th-Sm)/He ages of 290 ± 10 Ma and 79 ± 10 Ma, respectively. Accordingly, the fluorite sample with the high Tc could have quantitatively retained helium since the formation of the fluorite-bearing ores in the Permian, despite subsequent Mesozoic burial and associated regional hydrothermal heating. In contrast, the fluorite with the low Tc yields a Late Cretaceous age close to the apatite fission track (AFT) and apatite (U-Th)/He ages (AHe

  4. Fractal and multifractal characteristics of swift heavy ion induced self-affine nanostructured BaF2 thin film surfaces.

    PubMed

    Yadav, R P; Kumar, Manvendra; Mittal, A K; Pandey, A C

    2015-08-01

    Fractal and multifractal characteristics of self-affine surfaces of BaF2 thin films, deposited on crystalline Si ⟨1 1 1⟩ substrate at room temperature, were studied. Self-affine surfaces were prepared by irradiation of 120 MeV Ag(9+) ions which modified the surface morphology at nanometer scale. The surface morphology of virgin thin film and those irradiated with different ion fluences are characterized by atomic force microscopy technique. The surface roughness (interface width) shows monotonic decrease with ion fluences, while the other parameters, such as lateral correlation length, roughness exponent, and fractal dimension, did not show either monotonic decrease or increase in nature. The self-affine nature of the films is further confirmed by autocorrelation function. The power spectral density of thin films surfaces exhibits inverse power law variation with spatial frequency, suggesting the existence of fractal component in surface morphology. The multifractal detrended fluctuation analysis based on the partition function approach is also performed on virgin and irradiated thin films. It is found that the partition function exhibits the power law behavior with the segment size. Moreover, it is also seen that the scaling exponents vary nonlinearly with the moment, thereby exhibiting the multifractal nature. PMID:26328566

  5. LAMBDA: Large Area Modular BaF2 Detector Array for the measurement of high energy γ rays

    NASA Astrophysics Data System (ADS)

    Mukhopadhyay, S.; Bhattacharya, Srijit; Pandit, Deepak; Ray, A.; Pal, Surajit; Banerjee, K.; Kundu, S.; Rana, T. K.; Bhattacharya, S.; Bhattacharya, C.; De, A.; Banerjee, S. R.

    2007-11-01

    A large BaF 2 detector array along with its dedicated CAMAC electronics and VME based data acquisition system has been designed, constructed and installed successfully at VECC, Kolkata for studying high energy γ rays ( >8 MeV). The array consists of 162 detector elements. The detectors were fabricated from bare barium fluoride crystals (each measuring 35 cm in length and having cross-sectional area of 3.5×3.5 cm2). The basic properties of the detectors (energy resolution, time resolution, efficiency, uniformity, fast to slow ratio, etc.) were studied exhaustively. Complete GEANT3 Monte Carlo simulations were performed to optimize the detector design and also to generate the response function. The detector system has been used successfully to measure high energy photons from 113Sb, formed by bombarding 145 and 160 MeV 20Ne beams on a 93Nb target. The measured experimental spectra are in good agreement with those from a modified version of the statistical model code CASCADE. In this paper, we present the complete description of this detector array along with its in-beam performance.

  6. NUCLEATION OF YBA(2)CU(3)O(7-D) IN THE BAF(2) PROCESS

    SciTech Connect

    WU,L.; SOLOVYOV,V.F.; WIESMANN,H.J.; ZHU,Y.; SUENAGA,M.

    2001-06-24

    The nucleation of the c-axis aligned and non-c-axis YBa{sub 2}Cu{sub 3}O{sub {approximately}6.1} (YBCO) from precursor films on [001]-cut SrTiO{sub 3} was investigated for the so-called BaF{sub 2} process. Specimens with different thickness were quenched from 735 C, then studied by transmission electron microscopy and x-ray diffraction techniques. Preceding the formation of YBCO nuclei, three intermediate phases of (Y,Ba) oxy-fluoride and a transition phase without F were found in the precursor films. These were structurally and chemically related to the nuclei of YBCO which was found to be deficient in Cu relative to its stoichiometric composition.

  7. High-temperature tribological properties of NiCoCrAlY-WSe2-BaF2·CaF2 solid lubricant coatings prepared by plasma spraying

    NASA Astrophysics Data System (ADS)

    Chen, X. H.; Yuan, X. J.; Xia, J.; Yu, Z. H.

    2015-12-01

    In this paper, NiCoCrAlY-WSe2-BaF2·CaF2 solid lubricant coatings were produced on a substrate by plasma spray and investigated at the high temperature, such as 500 °C and 800 °C. The structure of the coatings was characterized using XRD pattern and scanning electron microscopy. The TC1 (83wt% NiCoCrAlY) coating has a low friction coefficient at 500C, where the WSe2 is a good solid lubricant. The TC2 (65wt% NiCoCrAlY) coating has the low friction coefficient (0.279) at 800°C, due to the formation of BaCrO4 on the surfaces. As a result, the TC2 coating has the optimal tribological property in the wide temperature.

  8. BAF(2) POST-DEPOSITION REACTION PROCESS FOR THICK YBCO FILMS.

    SciTech Connect

    SUENAGA,M.; SOLOVYOV,V.F.; WU,L.; WIESMANN,H.J.; ZHU,Y.

    2001-07-12

    The basic processes of the so-called BaF{sub 2} process for the formation of YBa{sub 2}Cu{sub 3}O{sub 7}, YBCO, films as well as its advantages over the in situ formation processes are discussed in the previous chapter. The process and the properties of YBCO films by this process were also nicely described in earlier articles by R. Feenstra, et al. Here, we will discuss two pertinent subjects related to fabrication of technologically viable YBCO conductors using this process. These are (1) the growth of thick (>> 1 {micro}m) c-axis-oriented YBCO films and (2) their growth rates. Before the detail discussions of these subjects are given, we first briefly discuss what geometrical structure a YBCO-coated conductor should be. Then, we will provide examples of simple arguments for how thick the YBCO films and how fast their growth rates need to be. Then, the discussions in the following two sections are devoted to: (1) the present understanding of the nucleation and the growth process for YBCO, and why it is so difficult to grow thick c-axis-oriented films (> 3 {micro}m), and (2) our present understanding of the YBCO growth-limiting mechanism and methods to increase the growth rates. The values of critical-current densities J{sub c} in these films are of primary importance for the applications,. and the above two subjects are intimately related to the control of J{sub c} of the films. In general, the lower the temperatures of the YBCO formation are the higher the values of J{sub c} of the films. Thus, the present discussion is limited to those films which are reacted at {approx}735 C. This is the lowest temperature at which c-axis-oriented YBCO films (1-3 {micro}m thick) are comfortably grown. It is also well known that the non-c-axis oriented YBCO platelets are extremely detrimental to the values of J{sub c} such that their effects on J{sub c} dwarf essentially all of other microstructural effects which control J{sub c}. Hence, the discussion given below is mainly

  9. Optical characterization of Tm3+ doped Bi2O3-GeO2-Ga2O3 glasses in absence and presence of BaF2

    NASA Astrophysics Data System (ADS)

    Han, Kexuan; Zhang, Peng; Wang, Shunbin; Guo, Yanyan; Zhou, Dechun; Yu, Fengxia

    2016-08-01

    In this paper, Two new Bi2O3-GeO2-Ga2O3 glasses (one presence of BaF2) doped with 1mol% Tm2O3 were prepared by melt-quenching technique. Differential thermal analysis (DTA), the absorption, Raman, IR spectra and fluorescence spectra were measured. The Judd–Ofelt intensity parameters, emission cross section, absorption cross section, and gain coefficient of Tm3+ ions were comparatively investigated. After the BaF2 introduced, the glass showed a better thermal stability, lower phonon energy and weaker OH‑ absorption coefficient, meanwhile, a larger ~1.8 μm emission cross section σem (7.56 × 10‑21 cm2) and a longer fluorescence lifetime τmea (2.25 ms) corresponding to the Tm3+: 4F3 → 3H6 transition were obtained, which is due to the addition of fluoride in glass could reduce the quenching rate of hydroxyls and raise the cross-relaxation (3H6 + 3H4 → 3F4 + 3F4) rate. Our results suggest that the Tm3+ doped Bi2O3-GeO2-Ga2O3 glass with BaF2 might be potential to the application in efficient ~1.8 μm lasers system.

  10. Optical characterization of Tm(3+) doped Bi2O3-GeO2-Ga2O3 glasses in absence and presence of BaF2.

    PubMed

    Han, Kexuan; Zhang, Peng; Wang, Shunbin; Guo, Yanyan; Zhou, Dechun; Yu, Fengxia

    2016-01-01

    In this paper, Two new Bi2O3-GeO2-Ga2O3 glasses (one presence of BaF2) doped with 1mol% Tm2O3 were prepared by melt-quenching technique. Differential thermal analysis (DTA), the absorption, Raman, IR spectra and fluorescence spectra were measured. The Judd-Ofelt intensity parameters, emission cross section, absorption cross section, and gain coefficient of Tm(3+) ions were comparatively investigated. After the BaF2 introduced, the glass showed a better thermal stability, lower phonon energy and weaker OH(-) absorption coefficient, meanwhile, a larger ~1.8 μm emission cross section σem (7.56 × 10(-21) cm(2)) and a longer fluorescence lifetime τmea (2.25 ms) corresponding to the Tm(3+): (4)F3 → (3)H6 transition were obtained, which is due to the addition of fluoride in glass could reduce the quenching rate of hydroxyls and raise the cross-relaxation ((3)H6 + (3)H4 → (3)F4 + (3)F4) rate. Our results suggest that the Tm(3+) doped Bi2O3-GeO2-Ga2O3 glass with BaF2 might be potential to the application in efficient ~1.8 μm lasers system. PMID:27506152

  11. Enhanced 2.0 microm emission and gain coefficient of transparent glass ceramic containing BaF2: Ho3+,Tm3+ nanocrystals.

    PubMed

    Zhang, W J; Zhang, Q Y; Chen, Q J; Qian, Q; Yang, Z M; Qiu, J R; Huang, P; Wang, Y S

    2009-11-01

    Transparent glass ceramic containing BaF(2):Ho(3+),Tm(3+) nanocrystals has been prepared by melt quenching and subsequent thermal treatment. The precipitation of BaF(2) nanocrystals was confirmed by X-ray diffraction and high-resolution transmission electron microscopy. Intense 2.0 microm fluorescence originating from Ho(3+): (5)I(7) --> (5)I(8) transition was achieved upon excitation with 808 nm laser diode. A large ratio of forward Tm(3+) --> Ho(3+) energy transfer constant to that of backward process indicated high efficient energy transfer from Tm(3+)((3)F(4)) to Ho(3+)((5)I(7)), benefited from the reduced ionic distances of Tm(3+)-Tm(3+) and Tm(3+)-Ho(3+) pairs and low phonon energy environment with the incorporation of rare-earth ions into the precipitated BaF(2) nanocrystals. The results indicate that glass ceramic is a promising candidate material for 2.0 microm laser. PMID:19997333

  12. Optical characterization of Tm3+ doped Bi2O3-GeO2-Ga2O3 glasses in absence and presence of BaF2

    PubMed Central

    Han, Kexuan; Zhang, Peng; Wang, Shunbin; Guo, Yanyan; Zhou, Dechun; Yu, Fengxia

    2016-01-01

    In this paper, Two new Bi2O3-GeO2-Ga2O3 glasses (one presence of BaF2) doped with 1mol% Tm2O3 were prepared by melt-quenching technique. Differential thermal analysis (DTA), the absorption, Raman, IR spectra and fluorescence spectra were measured. The Judd–Ofelt intensity parameters, emission cross section, absorption cross section, and gain coefficient of Tm3+ ions were comparatively investigated. After the BaF2 introduced, the glass showed a better thermal stability, lower phonon energy and weaker OH− absorption coefficient, meanwhile, a larger ~1.8 μm emission cross section σem (7.56 × 10−21 cm2) and a longer fluorescence lifetime τmea (2.25 ms) corresponding to the Tm3+: 4F3 → 3H6 transition were obtained, which is due to the addition of fluoride in glass could reduce the quenching rate of hydroxyls and raise the cross-relaxation (3H6 + 3H4 → 3F4 + 3F4) rate. Our results suggest that the Tm3+ doped Bi2O3-GeO2-Ga2O3 glass with BaF2 might be potential to the application in efficient ~1.8 μm lasers system. PMID:27506152

  13. A DFT study of the structural, electronic and optical properties of transition metal doped fluorite oxides: Ce0.75M0.25O2 (M=Fe, Co, Ni)

    NASA Astrophysics Data System (ADS)

    Tian, Dong; Zeng, Chunhua; Fu, Yunchang; Wang, Hua; Luo, Hongchun; Xiang, Chao; Wei, Yonggang; Li, Kongzhai; Zhu, Xing

    2016-04-01

    The structural, electronic and optical properties of Ce1-xMxO2 (M=Fe, Co, Ni; x=0, 0.25) fluorite type oxides are studied by using the method of density functional theory (DFT) + U method. The calculated equilibrium lattice parameter, cell volume, bulk modulus and optical properties for CeO2 are in good agreement with the available experimental data and other theoretical results. The lattice parameter, cell volume, bulk modulus and bond length of Ce-O decreased after substituting Ce atom with Fe (or Co, Ni). Meanwhile, the band-gap (Eg) reduction is observed. It is interesting to find that doping of Fe (or Co, Ni) in CeO2 obviously decreases the O 2p-Ce 4f transition intensity and the covalent character of the Ce-O bond. On the contrary, the static dielectric constant ε0 and refractive index n0 for the doped system increased. Compared with the undoped CeO2, the doped system has steep absorption peaks ranging from 1.0 eV to 2.0 eV at lower energy, and it can be used for visible light absorption applications. The Ce0.75Co0.25O2 has a high refractive index and reflectivity, therefore it is suitable as a high-refractive index film material in single and multilayered optical coatings.

  14. Crystal structure of fluorite-related Ln{sub 3}SbO{sub 7} (Ln=La–Dy) ceramics studied by synchrotron X-ray diffraction and Raman scattering

    SciTech Connect

    Siqueira, K.P.F.; Borges, R.M.; Granado, E.; Malard, L.M.; Paula, A.M. de; Moreira, R.L.; Bittar, E.M.; Dias, A.

    2013-07-15

    Ln{sub 3}SbO{sub 7} (Ln=La, Pr, Nd, Sm, Eu, Gd, Tb and Dy) ceramics were synthesized by solid-state reaction in optimized conditions of temperature and time to yield single-phase ceramics. The crystal structures of the obtained ceramics were investigated by synchrotron X-ray diffraction, second harmonic generation (SHG) and Raman scattering. All samples exhibited fluorite-type orthorhombic structures with different oxygen arrangements as a function of the ionic radius of the lanthanide metal. For ceramics with the largest ionic radii (La–Nd), the ceramics crystallized into the Cmcm space group, while the ceramics with intermediate and smallest ionic radii (Sm–Dy) exhibited a different crystal structure belonging to the same space group, described under the Ccmm setting. The results from SHG and Raman scattering confirmed these settings and ruled out any possibility for the non-centrosymmetric C222{sub 1} space group describing the structure of the small ionic radii ceramics, solving a recent controversy in the literature. Besides, the Raman modes for all samples are reported for the first time, showing characteristic features for each group of samples. - Graphical abstract: Raman spectrum for La{sub 3}SbO{sub 7} ceramics showing their 22 phonon modes adjusted through Lorentzian lines. According to synchrotron X-ray diffraction and Raman scattering, this material belongs to the space group Cmcm. - Highlights: • Ln{sub 3}SbO{sub 7} ceramics belonging to the space groups Cmcm and Ccmm are synthesized. • SXRD, SHG and Raman scattering confirmed the orthorhombic structures. • Ccmm instead of C222{sub 1} is the correct one based on SHG and Raman data.

  15. Fluorite solubility equilibria in selected geothermal waters

    USGS Publications Warehouse

    Nordstrom, D.K.; Jenne, E.A.

    1977-01-01

    Calculation of chemical equilibria in 351 hot springs and surface waters from selected geothermal areas in the western United States indicate that the solubility of the mineral fluorite, CaF2, provides an equilibrium control on dissolved fluoride activity. Waters that are undersaturated have undergone dilution by non-thermal waters as shown by decreased conductivity and temperature values, and only 2% of the samples are supersaturated by more than the expected error. Calculations also demonstrate that simultaneous chemical equilibria between the thermal waters and calcite as well as fluorite minerals exist under a variety of conditions. Testing for fluorite solubility required a critical review of the thermodynamic data for fluorite. By applying multiple regression of a mathematical model to selected published data we have obtained revised estimates of the pK (10,96), ??Gof (-280.08 kcal/mole), ??Hof (-292.59 kcal/mole), S?? (16.39 cal/deg/mole) and CoP (16.16 cal/deg/mole) for CaF2 at 25??C and 1 atm. Association constants and reaction enthalpies for fluoride complexes with boron, calcium and iron are included in this review. The excellent agreement between the computer-based activity products and the revised pK suggests that the chemistry of geothermal waters may also be a guide to evaluating mineral solubility data where major discrepancies are evident. ?? 1977.

  16. Nanostructured crystals of the fluorite phases Sr{sub 1-x}R{sub x}F{sub 2+x}(R-rare-earth elements) and their ordering: II. Crystal structure of the ordered Sr{sub 4}Lu{sub 3}F{sub 17} phase

    SciTech Connect

    Sulyanova, E. A. Molchanov, V. N.; Verin, I. A.; Sulyanov, S. N.; Sobolev, B. P.

    2009-05-15

    The crystal structure of the ordered phase Sr{sub 4}Lu{sub 3}F{sub 17} prepared by directed crystallization of the melt has been investigated. The crystals have a trigonally distorted fluorite lattice (space group R3-bar, Z = 6, a = 10.615(2) A, c = 19.547(6) A). The Sr{sub 4}Lu{sub 3}F{sub 17} phase is isostructural to Ba{sub 4}R{sub 3}F{sub 17} (R = Y, Yb). The distortions of the fluorite cation sublattice manifest themselves in the splitting of the only mixed position (Sr, Lu) into three positions: Sr(1), Sr(2), and Lu. All Lu{sup 3+} atoms are displaced from the center of the [Sr{sub 8}{l_brace}Lu{sub 6}F{sub 36+1}{r_brace}F{sub 32}] octacubic cluster in the [001]{sub cub} direction, and the Sr(1) cations are displaced toward the center of the octacubic cluster in the [111]{sub cub} direction. The coordination numbers of the Lu, Sr(1), and Sr(2) cations are 8, 10, and 11, respectively. The distortions of the fluorite anion sublattice are caused by the incorporation of additional anions into both the center of the octacubic cluster and the {l_brace}F{sub 8}{r_brace} cubic holes outside the cluster.

  17. The Detector for Advanced Neutron Capture Experiments: A 4{pi} BaF2 Detector for Neutron Capture Measurements at LANSCE

    SciTech Connect

    Ullmann, J.L.; Esch, E.-I.; Haight, R.C.; Hunt, L.; O'Donnell, J.M.; Reifarth, R.; Agvaanluvsan, U.; Alpizar, A.; Hatarik, R.; Bond, E.M.; Bredeweg, T.A.; Kronenberg, A.; Rundberg, R.S.; Vieira, D.J.; Wilhelmy, J.B.; Folden, C.M.; Hoffman, D.C.; Greife, U.; Schwantes, J.M.; Strottman, D.D.

    2005-05-24

    The Detector for Advanced Neutron Capture Experiments (DANCE) is a 162-element 4{pi} BaF2 array designed to make neutron capture cross-section measurements on rare or radioactive targets with masses as little as one milligram. Accurate capture cross sections are needed in many research areas, including stellar nucleosynthesis, advanced nuclear fuel cycles, waste transmutation, and other applied programs. These cross sections are difficult to calculate accurately and must be measured. The design and initial performance results of DANCE is discussed.

  18. Fluorite-related one-dimensional units in natural bismuth oxysulfates: the crystal structures of Bi14O16(SO4)5 and Bi30O33(SO4)9(AsO4)2.

    PubMed

    Pinto, Daniela; Garavelli, Anna; Bindi, Luca

    2015-10-01

    The crystal structures of two new natural Bi oxysulfates with the formula Bi14O16(SO4)5 [labelled new phase I; monoclinic, space group C2, a = 21.658 (4), b = 5.6648 (9), c = 15.092 (3) Å, β = 119.433 (11)° and Z = 2] and Bi30O33(SO4)9(AsO4)2 [labelled new phase II; triclinic, space group P1, a = 5.670 (3), b = 13.9408 (9), c = 22.7908 (18) Å, α = 80.903 (5), β = 82.854 (14), γ = 78.27 (2)° and Z = 1] from the high-temperature fumarole deposit of the La Fossa crater at Vulcano (Aeolian Islands, Italy) are reported. The structures are built up by a combination of fluorite-related Bi-O units and isolated (SO4)(2-) tetrahedra (new phase I) or both (SO4)(2-) and (AsO4)(3-) tetrahedra (new phase II). Owing to the effect of stereoactive lone pairs of Bi(3+), Bi-O units in both the structures can be suitably described in terms of oxo-centered OBi4 tetrahedra. The structure of Bi14O16(SO4)5 is based upon one-dimensional [O16Bi14](10+) ribbons formed by six chains of edge-sharing OBi4 tetrahedra extending along [010]. In the structure of Bi30O33(SO4)9(AsO4)2 the same ribbon type coexists with another one-dimensional ribbon formed by seven chains of edge-sharing OBi4 tetrahedra and with the composition [O17Bi16](14+). Ribbons of the same type are joined by (SO4)(2-) and (AsO4)(3-) tetrahedra along [010] – if a reduced triclinic unit-cell setting is considered – so forming two different (001) slabs which alternate to each other along [001] and are joined by additional (SO4)(2-) tetrahedra. New phase I represents the natural analogues of synthetic Bi14O16(SO4)5, but with an ordered structure model. PMID:26428401

  19. Spectroscopy of laser properties of Nd(3+)-doped CaF2, SrF2, and BaF2

    NASA Astrophysics Data System (ADS)

    Payne, Stephen A.; Caird, John A.; Chase, L. L.; Smith, L. K.; Nielsen, N. D.; Krupke, William F.

    1990-03-01

    The optical properties of Nd(3+) in CaF2, SrF2, and BaF2 were investigated in order to determine if these materials are useful as laser-pumped amplifier media. The CaF2:Nd crystal was found to not be useful because the impurities tend to cluster at very low concentration, leading to the formation of nonluminescent centers. On the other hand, the Nd(3+) centers in BaF2 exhibit unacceptably low transition strengths. SrF2:Nd appears to have adequate absorption strength, and, in addition, to have a remarkably long emission lifetime of 1280 microns. A maximum doping of 0.20 atomic percent Nd(3+) can be tolerated in SrF2 without the occurrence of detrimental clustering. The peak emission cross section of SrF2:Nd is 1.7 x 10(exp -20) sq cm at 1036.5 nm. Direct measurement of the gain spectrum of SrF2:Nd(3+) reveals the presence of the F-4(sub 3/2) yields G-2(sub 9/2) excited state absorption lines, although the impact on the emission cross section is minor.

  20. Transient liquid assisted nucleation mechanism of YBa2Cu3O7-δ in coated conductor films derived by BaF2 process

    NASA Astrophysics Data System (ADS)

    Gu, Zhao-Hui; Yang, Wen-Tao; Bai, Chuan-Yi; Guo, Yan-Qun; Lu, Yu-Ming; Liu, Zhi-Yong; Lu, Qi; Shu, Gang-Qiang; Cai, Chuan-Bing

    2015-09-01

    It is significant for low-cost preparation of YBa2Cu3O7-δ (YBCO) coated conductors to make clear the mechanism of orientation, copper segregation, and nucleation density in BaF2-derived YBCO crystallization. In the present work, a distinct nucleation mechanism was proposed based on a transient liquid phase induced by the size effect as well as near-equilibrium assumption. With this scheme the nucleation of YBCO prepared by metal-organic deposition (MOD) or the physical vapor deposition BaF2 process was semi-quantitatively analyzed, revealing that the direct driving force for nucleation is YBCO supersaturation in the liquid phase. The theoretical analysis on the nucleation orientation portion is evidenced by the experimental result. Project supported by the Science and Technology Commission of Shanghai Municipality, China (Grant Nos. 13111102300 and 11dz1100302), the National Natural Science Foundation of China (Grant Nos. 11174193 and 51202141), the National Basic Research Program of China (Grant Nos. 2011CBA00105), and the Science and Technology Commission of Shanghai Municipality, China (Grant No. 14DZ2260700).

  1. Hyperstoichiometric Oxygen in Fluorite-type U3O8 Formed at Extreme Conditions

    NASA Astrophysics Data System (ADS)

    Zhang, Fuxiang; Lang, Maik; Ewing, Rod; Department of Earth and Environmental Sciences Team

    2014-03-01

    U3O8 was obtained by annealing UO3 in a reducing atmosphere at 200 °C. Powder sample of β-U3O8 was pressurized at room temperature up to 37.5 GPa and XRD patterns clearly indicated that a phase transition occurred between 3-11 GPa. The high-pressure phase is a fluorite-like structure. The high-pressure phase was then laser heated to over 1700 K in the diamond anvil cell at high pressure conditions. No phase transition was found at high pressure/ temperature conditions, and the fluorite-like structure of U3O8 is even fully quenchable. The lattice parameter of the fluorite-like high-pressure phase is 5.425 Å at ambient conditions, which is smaller than that of the stoichiometric UO2. Previous experiments have shown that the stoichiometric uranium dioxide (UO2) is not stable at high pressure conditions and starts to transform to a cotunnite structure at ~ 30 GPa. When heating the sample at high pressure, the critical transition pressure is greatly reduced. However, the fluorite-like high-pressure phase of U3O8 is very stable at high pressure/high temperature conditions. The enhanced phase stability is believed to be related to the presence of extra oxygen (or U vacancies) in the structure.

  2. Fluorine, fluorite, and fluorspar in central Colorado

    USGS Publications Warehouse

    Wallace, Alan R.

    2010-01-01

    Fluorine (F) is a widespread element that was deposited in a variety of rocks, minerals, and geologic environments in central Colorado. It occurs as a trace element, as a major component of the mineral fluorite (CaFs), and as a major economic source of fluorine in fluorspar deposits, which are massive concentrations of fluorite. This study has compiled available geochemical analyses of rocks, both unmineralized and mineralized, to determine the distribution of fluorine in specific age-lithologic categories, ranging from 1.8-giga-annum (Ga) metamorphic rocks to modern soils, throughout central Colorado. It also draws upon field studies of fluorine-rich mineral deposits, including fluorspar deposits, to decipher the nearly two-billion-year-long geologic history of fluorine in the study area, with implications for mineral-resource evaluations and exploration. The resulting compilation provides an important inventory of the naturally occurring levels and sources of fluorine that ultimately weather, erode, and become part of surface waters that are used for domestic water supplies in densely populated areas along the Colorado Front Range. Most commonly, fluorine is a trace element in virtually all rocks in the region. In the 3,798 unmineralized rocks that were analyzed for fluorine in the study area, the average fluorine content was 1,550 parts per million (ppm). The median was 640 ppm, nearly identical to the average crustal abundance of 650 ppm, and some high-fluorine rocks in the Pikes Peak area skewed the average to a value much greater than the median. Most unmineralized age-lithologic rock suites, including Proterozoic metamorphic rocks, 1.7- and 1.4-Ga granitic batholiths, Cambrian igneous rocks, Phanerozoic sedimentary rocks, and Laramide and Tertiary igneous rocks, had median fluorine values of 400 to 740 ppm fluorine. In all suites, however, a small number of analyzed samples contained more than 1 percent (10,000 ppm) fluorine. The 1.1-Ga plutonic rocks

  3. Nanostructured crystals of fluorite phases Sr{sub 1-x}R{sub x}F{sub 2+x} and their ordering: 7. A procedure for cluster modeling of Sr{sub 1-x}R{sub x}F{sub 2+x} Based on the Structure of an Ordered Phase (R = Lu)

    SciTech Connect

    Sul'yanova, E. A. Verin, I. A.; Sobolev, B. P.

    2012-01-15

    Single crystals of the Sr{sub 1-x}Lu{sub x}F{sub 2+x} nonstoichiometric phase (x = 0.095 and 0.189), which crystallizes in the CaF{sub 2} structure type (space group Fm3-barm), are studied by X-ray diffraction. A procedure for the cluster modeling of Sr{sub 1-x}Lu{sub x}F{sub 2+x} based on the fine structural features of the Sr{sub 4}Lu{sub 3}F{sub 17} stoichiometric compound with a fluorite derivative structure (one of the ordered phases in the SrF{sub 2}-LuF{sub 3} system) is proposed. The description of the structure of the Sr{sub 1-x}Lu{sub x}F{sub 2+x} solid solutions is based on the octacubic configuration of the {l_brace}M{sub 14-n}R{sub n}F{sub 64+n}{r_brace} defect cluster. Structural data on the displacements of cations and anions in the ordered Sr{sub 4}Lu{sub 3}F{sub 17} phase (in relation to the undistorted fluorite phase) allow one to identify the distortions of the crystal lattice of the disordered (nonstoichiometric) Sr{sub 1-x}Lu{sub x}F{sub 2+x} phase.

  4. Sm-Nd dating of fluorite from the worldclass Montroc fluorite deposit, southern Massif Central, France

    USGS Publications Warehouse

    Munoz, M.; Premo, W.R.; Courjault-Rade, P.

    2005-01-01

    A three-point Sm-Nd isotope isochron on fluorite from the very large Montroc fluorite vein deposit (southern Massif Central, France) defines an age of 111??13 Ma. Initial ??Nd of -8.6 and initial 87Sr/86Sr of ???0.71245 suggest an upper crustal source of the hydrothermal system, in agreement with earlier work on fluid inclusions which indicated a basinal brine origin. The mid-Cretaceous age of ???111 Ma suggests the Albian/Aptian transition as the most likely period for large-scale fluid circulation during a regional extensional tectonic event, related to the opening of the North Atlantic ocean. ?? Springer-Verlag 2004.

  5. Colloid formation and laser-induced bleaching in fluorite

    SciTech Connect

    LeBret, Joel B.; Cramer, Loren P.; Norton, M. Grant; Dickinson, J. T.

    2004-11-08

    Colloid formation and subsequent laser-induced bleaching in fluorite has been studied by transmission electron microscopy and electron diffraction. At high incident electron-beam (e-beam) energies, Ca colloids with diameter {approx}10 nm form a simple cubic superlattice with lattice parameter a{approx}18 nm. The colloids themselves are topotactic with the fluorite matrix forming low-energy interfaces close to a {sigma}=21 special grain boundary in cubic materials. Laser irradiation using {lambda}=532 nm has been shown to effectively bleach the e-beam-irradiated samples returning the fluorite to its monocrystalline state. The bleached samples appear more resistant to further colloid formation.

  6. Enhanced processability of ZrF4-BaF2-LaF3-AlF3-NaF glass in microgravity

    NASA Astrophysics Data System (ADS)

    Torres, Anthony; Ganley, Jeff; Maji, Arup; Tucker, Dennis; Starodubov, Dmitry

    2013-06-01

    Fluorozirconate glasses, such as ZBLAN (ZrF4-BaF2-LaF3-AlF3-NaF), have the potential for optical transmission from 0.3 μm in the UV to 7 μm in the IR region. However, crystallites formed during the fiber drawing process prevent this glass from achieving its desired transmission range. The temperature at which the glass can be drawn into a fiber is known as the working range, defined as (Tx - Tg), bounded by the glass transition temperature (Tg) and the crystallization temperature (Tx). In contrast to silica glasses, the working temperature range for ZBLAN glass is extremely narrow. Multiple ZBLAN samples were subject to a heating and quenching test apparatus on the parabolic aircraft, under a controlled 0-g and hyper-g environment and compared with 1-g ground tests. The microgravity duration on board Zero-G Corporation parabolic aircraft is approximately 20 seconds and the hyper-g intervals are approximately 56 seconds. Optical microscopy examination elucidates crystal growth in ZBLAN is suppressed when processed in a microgravity environment. The crystallization temperature, Tx, at which crystals form increased, therefore, significantly broadening the working temperature range for ZBLAN.

  7. The reasons for the color green fluorite Mehmandooye cover using UV spectroscopy and XRF results

    NASA Astrophysics Data System (ADS)

    Pirzadeh, Sara; Zahiri, Reza

    2016-04-01

    Fluorite mineral or fluorine with chemical formula CaF2 is most important mineralfluor in nature. This mineral crystallization to colors yellow, green, pink, blue, purple, colorless and sometimes black andin cubic system crystallized.assemi transparent and glass with polished.fluoritethe purity include 48/9% fluoreand 51/9% calcium. How the creation colors in minerals different greatly indebted to Kurt Nassau research from Bell Labs, Murray Hill, New Jersey.almostall the mechanisms that cause color in minerals, are the result of the interaction of light waves with the electrons The main factors affecting the color generation include the following: 1)the presence of a constructive element inherent (essential ingredient mineral composition) 2)The presence of a minor impurities (such a element as involved in latticesolid solution) 3) appearancedefects in the crystal structure 4) There are some physical boundaries with distances very small and delicate, like blades out of the solution (which may be the play of colors or Chatvyansy) 5) Mixing mechanical impurities dispersed in a host mineral Based on the results of the analysis, XRF and UV spectrum and also based on the results of ICP, because the color green fluorite examined, the focus color (F_center) and also the presence of some elementsintermediate (such as Y (yttrium). [1] Bill, H., Calas, G. Color centres associated rare earth ions and the origin of coloration in natural fluorites// PhysChem Min, (1978), v 3, pp. 117-131.

  8. Ba(OH)2 Equilibria in the System Ba-O-H-F, With Application to the Formation of Ba2YCu3O6.5 + x From BaF2-Precursors

    PubMed Central

    Cook, L. P.; Wong-Ng, W.; Feenstra, R.

    2005-01-01

    The ex situ process for fabricating Ba2YCu3O6.5 + x superconducting tapes from BaF2- based precursors involves a hydration/oxidation reaction at ≈730 °C to 750 °C generally written as: (2BaF2+Y+3Cu)(amorphous)+(2H2O+2.25O2)(g)→Ba2YCu3O6.5+x(s)+4HF(g). However, microscopic observations of partially processed films suggest the presence of a transient liquid phase during conversion. Alternatively, the conversion reaction can be rewritten as the sum of several intermediate steps, including the formation of a barium hydroxide liquid: (BaF2)(amorphous)+2H2O(g)→Ba(OH)2(liq)+2HF(g). To evaluate the possibility of a hydroxide liquid conversion step, thermodynamic calculations on the stability of Ba(OH)2(liq) have been completed from 500 °C to 900 °C at 0.1 MPa ptotal. Based on currently available data, the calculated phase diagrams suggest that a viable hydroxide reaction path exists in the higher part of this temperature range. The calculations indicate that Ba(OH)2(liq) may be stable at log pH2O (Pa) values from ≈4 to 5, provided log pHF (Pa) values can be maintained below 0 to −1. Limited experimental confirmation is provided by results of an experiment on BaF2(s) at 815 °C, 0.1 MPa pH2O, in which essentially all F at the surface was replaced by O. It is therefore possible that processing routes exist for producing Ba2YCu3O6.5 + x based on the presence of a Ba(OH)2 liquid, which might have an effect on conversion rates and texturing in the superconducting film. PMID:27308108

  9. Fluid inclusion study of some Sarrabus fluorite deposits, Sardinia, Italy.

    USGS Publications Warehouse

    Belkin, H.E.; de Vivo, B.; Valera, R.

    1984-01-01

    Fluid inclusions in six deposits of fluorite fracture fillings associated with Hercynian (Carboniferous) cycle magmatism were studied by microthermometric techniques. All the inclusions were liquid dominated, aqueous, and homogenized in the liquid phase. One-phase (liquid), two-phase (liquid + vapour) and three-phase (liquid, vapour, and solid NaCl daughter mineral) fluid inclusions were noted. This study indicates that five of the fluorite deposits formed from 95o-125oC fluids with approx 15 wt.% NaCl. One other deposit appears to have been formed by very dilute solutions at approx 125oC. It is suggested that the local fluorite-forming process was the formation of fracture-localized hydrothermal systems in which magmatic water interaction with some other fluid-connate, meteoric, or marine.-G.J.N.

  10. Effect of the introduction of oxide ion vacancies into cubic fluorite-type rare earth oxides on the NO decomposition catalysis

    SciTech Connect

    Masui, Toshiyuki; Nagai, Ryosuke; Imanaka, Nobuhito

    2014-12-15

    Cubic fluorite-type solid solutions based on Pr{sub 6}O{sub 11} and CeO{sub 2} were synthesized and oxide anion vacancies were intentionally introduced into the cubic fluorite-type lattice through the charge compensating mechanism by Mg{sup 2+} and/or Ca{sup 2+} doping into their lattices. The oxide anion vacancies bring about positive effect on NO decomposition catalysis. The reason for the increase in the catalytic activity was attributed to defect fluorite-type structures close to the C-type cubic one, because C-type cubic rare earth oxides, in which one-quarter of the oxygen atoms in the fluorite-type structure are removed, show high NO decomposition activity. In particular, the positive effect of the formation of oxide anion vacancies was significant for Pr{sub 6}O{sub 11} and its solid solutions, because the molar volume of Pr{sub 6}O{sub 11} is larger than that of CeO{sub 2}, and Pr{sub 6}O{sub 11} contains Pr{sup 3+} as well as Pr{sup 4+} and thereby a small amount of oxide anion vacancies exist inherently in the lattice. - Graphical abstract: Oxide anion vacancies intentionally introduced into the cubic fluorite-type lattice bring about positive effect on NO decomposition catalysis. - Highlights: • Cubic fluorite-type solid solutions were synthesized. • Oxide anion vacancies were intentionally introduced into the cubic fluorite-type lattice. • The oxide anion vacancies bring about positive effect on NO decomposition catalysis. • The activity was enhanced by making the structure close to the C-type cubic one.

  11. Transmission electron microscopic study of pyrochlore to defect-fluorite transition in rare-earth pyrohafnates

    SciTech Connect

    Karthik, Chinnathambi; Anderson, Thomas J.; Gout, Delphine; Ubic, Rick

    2012-10-15

    A structural transition in rare earth pyrohafnates, Ln{sub 2}Hf{sub 2}O{sub 7} (Ln=Y, La, Pr, Nd, Tb, Dy, Yb and Lu), has been identified. Neutron diffraction showed that the structure transforms from well-ordered pyrochloric to fully fluoritic through the lanthanide series from La to Lu with a corresponding increase in the position parameter x of the 48f (Fd3{sup Macron }m) oxygen site from 0.330 to 0.375. As evidenced by the selected area electron diffraction, La{sub 2}Hf{sub 2}O{sub 7}, Pr{sub 2}Hf{sub 2}O{sub 7} and Nd{sub 2}Hf{sub 2}O{sub 7} exhibited a well-ordered pyrocholoric structure with the presence of intense superlattice spots, which became weak and diffuse (in Dy{sub 2}Hf{sub 2}O{sub 7} and Tb{sub 2}Hf{sub 2}O{sub 7}) before disappearing completely as the series progressed towards the Lu end. High resolution electron microscopic studies showed the breakdown of the pyrochlore ordering in the form of antiphase domains resulting in diffused smoke-like superlattice spots in the case of Dy{sub 2}Hf{sub 2}O{sub 7} and Tb{sub 2}Hf{sub 2}O{sub 7}. - Graphical abstract: Transmission electron microscopic studies showed the ordered pyrochlore to defect fluorite transition in rare-earth pyrohafnates to occur via the formation of anti-phase domains to start with. Highlights: Black-Right-Pointing-Pointer Pyrochlore to fluorite structural transition in rare earth pyrohafnates. Black-Right-Pointing-Pointer La{sub 2}Hf{sub 2}O{sub 7}, Pr{sub 2}Hf{sub 2}O{sub 7} and Nd{sub 2}Hf{sub 2}O{sub 7} showed well ordered pyrochlore structure. Black-Right-Pointing-Pointer Short range ordering in Dy{sub 2}Hf{sub 2}O{sub 7} and Tb{sub 2}Hf{sub 2}O{sub 7}. Black-Right-Pointing-Pointer Break down of pyrochlore ordering due to antiphase boundaries. Black-Right-Pointing-Pointer Rest of the series showed fluoritic structure.

  12. Nature of the chemical bond and prediction of radiation tolerance in pyrochlore and defect fluorite compounds

    SciTech Connect

    Lumpkin, Gregory R. Pruneda, Miguel; Rios, Susana; Smith, Katherine L.; Trachenko, Kostya; Whittle, Karl R.; Zaluzec, Nestor J.

    2007-04-15

    The radiation tolerance of synthetic pyrochlore and defect fluorite compounds has been studied using ion irradiation. We show that the results can be quantified in terms of the critical temperature for amorphization, structural parameters, classical Pauling electronegativity difference, and disorder energies. Our results demonstrate that radiation tolerance is correlated with a change in the structure from pyrochlore to defect fluorite, a smaller unit cell dimension, and lower cation-anion disorder energy. Radiation tolerance is promoted by an increase in the Pauling cation-anion electronegativity difference or, in other words, an increase in the ionicity of the chemical bonds. A further analysis of the data indicates that, of the two possible cation sites in ideal pyrochlore, the smaller B-site cation appears to play the major role in bonding. This result is supported by ab initio calculations of the structure and bonding, showing a correlation between the Mulliken overlap populations of the B-site cation and the critical temperature. - Graphical abstract: Three-dimensional representation of the predicted critical amorphization temperature in pyrochlores.

  13. [Assessment of Soil Fluorine Pollution in Jinhua Fluorite Ore Areas].

    PubMed

    Ye, Qun-feng; Zhou, Xiao-ling

    2015-07-01

    The contents of. soil total fluorine (TF) and water-soluble fluorine (WF) were measured in fluorite ore areas located in Jinhua City. The single factor index, geoaccumulation index and health risk assessment were used to evaluate fluorine pollution in soil in four fluorite ore areas and one non-ore area, respectively. The results showed that the TF contents in soils were 28. 36-56 052. 39 mg.kg-1 with an arithmetic mean value of 8 325.90 mg.kg-1, a geometric mean of 1 555. 94 mg.kg-1, and a median of 812. 98 mg.kg-1. The variation coefficient of TF was 172. 07% . The soil WF contents ranged from 0. 83 to 74. 63 mg.kg-1 with an arithmetic mean value of 16. 94 mg.kg-1, a geometric mean of 10. 59 mg.kg-1, and a median of 10. 17 mg.kg-1. The variation coefficient of WF was 100. 10%. The soil TF and WF contents were far higher than the national average level of the local fluorine epidemic occurrence area. The fluoride pollution in soil was significantly affected by human factors. Soil fluorine pollution in Yangjia, Lengshuikeng and Huajie fluorite ore areas was the most serious, followed by Daren fluorite ore area, and in non-ore area there was almost no fluorine pollution. Oral ingestion of soils was the main exposure route. Sensitivity analysis of model parameters showed that children's weight exerted the largest influence over hazard quotient. Furthermore, a significant positive correlation was found among the three kinds of evaluation methods. PMID:26489337

  14. Thermal stability and thermal expansion studies of cubic fluorite-type MgF{sub 2} up to 135 GPa

    SciTech Connect

    Sun, X.W.; Song, T.; Wei, X.P.; Quan, W.L.; Liu, X.B.; Su, W.F.

    2014-04-01

    Highlights: • The thermal expansion of MgF{sub 2} with a fluorite-type structure has been investigated. • The quasi-harmonic Debye model is applied to take into account the thermal effect. • Particular attention is paid to the prediction of thermal expansion for the first time. - Abstract: The thermal expansion of MgF{sub 2} with a fluorite structure has been investigated at high pressures using plane-wave pseudopotential scheme within the local density approximation correction in the frame of density functional theory based on the analysis of thermal stability using classical molecular dynamics simulations up to 6500 K. To investigate the thermodynamic properties like as the P–V–T equation of state and volumetric thermal expansion coefficient α{sub V} of cubic fluorite-type MgF{sub 2} at extended pressure and temperature ranges, we apply the quasi-harmonic Debye model in which the phononic effects are considered. The P–V relationship and α{sub V} dependence of the pressure up to 135 GPa at different temperatures, and the V–T relationship and α{sub V} dependence of the temperature up to the melting temperature 1500 K at different pressures have been obtained.

  15. Methods of capturing and immobilizing radioactive nuclei with metal fluorite-based inorganic materials

    SciTech Connect

    Wang, Yifeng; Miller, Andy; Bryan, Charles R; Kruichar, Jessica Nicole

    2015-04-07

    Methods of capturing and immobilizing radioactive nuclei with metal fluorite-based inorganic materials are described. For example, a method of capturing and immobilizing radioactive nuclei includes flowing a gas stream through an exhaust apparatus. The exhaust apparatus includes a metal fluorite-based inorganic material. The gas stream includes a radioactive species. The radioactive species is removed from the gas stream by adsorbing the radioactive species to the metal fluorite-based inorganic material of the exhaust apparatus.

  16. Methods of capturing and immobilizing radioactive nuclei with metal fluorite-based inorganic materials

    DOEpatents

    Wang, Yifeng; Miller, Andy; Bryan, Charles R.; Kruichak, Jessica Nicole

    2015-11-17

    Methods of capturing and immobilizing radioactive nuclei with metal fluorite-based inorganic materials are described. For example, a method of capturing and immobilizing radioactive nuclei includes flowing a gas stream through an exhaust apparatus. The exhaust apparatus includes a metal fluorite-based inorganic material. The gas stream includes a radioactive species. The radioactive species is removed from the gas stream by adsorbing the radioactive species to the metal fluorite-based inorganic material of the exhaust apparatus.

  17. Origin of fluorite mineralizations in the Nuba Mountains, Sudan and their rare earth element geochemistry

    NASA Astrophysics Data System (ADS)

    Ismail, Ibrahim; Baioumy, Hassan; Ouyang, Hegen; Mossa, Hesham; Aly, Hisham Fouad

    2015-12-01

    Among other mineralizations in the basement complex of the Nuba Mountains, fluorite occurs as lenses and veins in a number of localities. The rare earth elements (REE) geochemistry in these fluorites along with their petrography and fluid inclusion was investigated in this study to discuss the origin the fluorites and shed the light on the economic importance of the REE. Fluorites in the Nuba Mountains are classified into four categories based on their petrography. Category I (F1) is characterized by pink color and free of inclusions. Category II (F2) is zoned of alternating pink and colorless zones with euhedral outline or anhedral patchy pink and colorless fluorite enclosing category I fluorite and is usually sieved with submicroscopic silicate minerals. Category III (F3) is colorless, euhedral to anhedral fluorite and associated with quartz and/or orthoclase. Category IV (F4) is colorless, either massive or dispersed, corroded grains associated with calcite and pertain to the late introduced carbonatites in Dumbeir area. Gangue minerals in the studied fluorites include quartz, calcite, orthoclase and muscovite. The ΣREE ranges between 541 and 10,430 ppm with an average of 3234 ppm. Chondrite-normalized REE patterns for fluorite from different localities exhibit LREE enrichment relative to HREE as shown by (La/Yb)N ratios that vary from 16 to 194 and significant positive Eu anomalies that are pronounced with Eu/Eu* from 1.1 to 2.5. The Tb/La and Tb/Ca ratios of fluorites in the present study indicate that they plot mainly in the pegmatitic or high-hydrothermal field with the characteristics of primary crystallization and remobilization trend. The clear heterogeneity of fluorite, abundance of growth zones, irregular shapes of grains, presence of fluorite inclusions in other minerals as well as the relatively high concentration of REE in the studied fluorites are supportive for this interpretation. The relatively high Tb/La (0.002-0.013) and low Tb/Ca (0

  18. Microstructural properties of (Ba,Sr)TiO3 films fabricated from BaF2/SrF2/TiO2 amorphous multilayers using the combinatorial precursor method

    SciTech Connect

    Takeuchi, I.; Chang, K.; Sharma, R.P.; Bendersky, L.A.; Chang, H.; Xiang, X.-D.; Stach, E.A.; Song, C.-Y.

    2001-01-12

    We have investigated the microstructure of (Ba,Sr)TiO3 films fabricated from BaF2/SrF2/TiO2 amorphous multilayers. Rutherford backscattering spectroscopy and x-ray diffraction studies show that a controlled thermal treatment can interdiffuse the multilayers so as to create predominantly single-phase epitaxial (Ba,Sr)TiO3 films. High resolution cross-sectional transmission electron microscopy investigation of the processed films shows that they consist of large epitaxial grains of (Ba,Sr)TiO3 with atomically sharp interfaces with the LaAlO3 substrates. In addition, we have identified regions where polycrystalline and amorphous phases exist in small pockets in the film matrix. The results here indicate that the combinatorial thin-film synthesis using precursors can produce (Ba,Sr)TiO3 films in combinatorial libraries which exhibit properties similar to those films made by conventional techniques.

  19. A new fluorite type compound Pb 5Bi 17X 5O 43: synchrotron and neutron structure determination (X=P) and conduction properties (X=P, V and As)

    NASA Astrophysics Data System (ADS)

    Roussel, Pascal; Giraud, Sophie; Suard, Emmanuelle; Wignacourt, Jean-Pierre; Steinfink, Hugo

    2002-09-01

    Recently, many new compounds have been discovered in the ternary system PbO-Bi 2O 3-P 2O 5: PbBi 6P 4O 20, nPbO-BiPO 4 (n=1, 2, 4), and Pb 5Bi 18P 4O 42. The structure of Pb 5Bi 18P 4O 42 was solved in a monoclinic I-centered cell, space group I2/ m. The structure of a new compound Pb 5Bi 17P 5O 43, monoclinic I-centered cell, is closely related and has been solved in the non centro symmetric Im space group from a joint refinement of X ray synchrotron single-crystal data and a powder neutron diffraction data; the cell parameters are a=11.341(2) Å, b=16.604(3) Å, c=11.432(2) Å, β=93.73(3)°. The atoms of lead, bismuth and phosphorus take the same positions as the bismuth atoms in the structure of δ-Bi 2O 3 with a distorted 3×3×3 superstructure of a tetragonal variety, as in Pb 5Bi 18P 4O 42. The homologous vanadate and arsenate phases are isostructural. Conductivity measurements were performed on the compounds of the series from 300°C to 800°C. The vanadate phase has the highest conductivity. An increase of the volume of the unit cell from the phosphate to the vanadate eases the ion migration through the structure.

  20. Luminescence emission of natural fluorite and synthetic CaF2:Mn (TLD-400)

    NASA Astrophysics Data System (ADS)

    Topaksu, Mustafa; Correcher, Virgilio; Garcia-Guinea, Javier

    2016-02-01

    The luminescence properties of natural white fluorite indicate that it could be employed as radiation dosimeter similarly to synthetic CaF2:Mn (TLD-400). The cathodoluminescence emission of the natural sample (two maxima) meanwhile TLD-400 (one peak) exhibits a different behaviour associated with the chemical composition. The mineral sample displays (i) a significant UV-blue emission associated with different structural defects (negligible in the synthetic sample) and (ii) a shift of the green emission to higher wavelengths respect to the TLD-400. The green induced TL emission also shows significant differences in intensity (higher in TLD-400) and sensitivity. Both samples display a complex induced green TL glow curve that could not be analysed assuming the model based on the discrete trap distribution. The Tm-Tstop method indicates the presence of close overlapping groups of components linked probably to a continuum in the trap distribution rather than a single trapping level.

  1. Symmetry-Guided Synthesis of Highly Porous Metal-Organic Frameworks with Fluorite Topology

    SciTech Connect

    Zhang, MW; Chen, YP; Bosch, M; Gentle, T; Wang, KC; Feng, DW; Wang, ZYU; Zhou, HC

    2013-11-11

    Two stable, non-interpenetrated MOFs, PCN-521 and PCN-523, were synthesized by a symmetry-guided strategy. Augmentation of the 4-connected nodes in the fluorite structure with a rigid tetrahedral ligand and substitution of the 8-connected nodes by the Zr/Hf clusters yielded MOFs with large octahedral interstitial cavities. They are the first examples of Zr/Hf MOFs with tetrahedral linkers. PCN-521 has the largest BET surface area (3411 m(2) g(-1)), pore size (20.5 x 20.5 x 37.4 angstrom) and void volume (78.5%) of MOFs formed from tetrahedral ligands. This work not only demonstrates a successful implementation of rational design of MOFs with desired topology, but also provides a systematic way of constructing non-interpenetrated MOFs with high porosity.

  2. Comparison of fluorite geochemistry from REE deposits in the Panxi region and Bayan Obo, China

    NASA Astrophysics Data System (ADS)

    Xu, Cheng; Taylor, Rex N.; Li, Wenbo; Kynicky, Jindrich; Chakhmouradian, Anton R.; Song, Wenlei

    2012-09-01

    Panxi region in west Sichuan province is one of the most economically significant REE mineralization belts in China, and includes the large Maoniuping and Daluxiang deposits and the minor Lizhuang deposit. The REE mineralization in these deposits is spatially and temporally associated with carbonatite-syenite complexes. Large proportional fluorites and REE minerals occurring as veins intrude Cretaceous granite and Oligocene syenite in Maoniuping, and Oligocene syenite and carbonatite in Lizhuang, and Miocene syenite in Daluxiang. Fluorite is also one of main gangue minerals in the world-class Bayan Obo REE deposit. We present a comparison of the trace element and isotopic compositions of fluorites from four REE deposits in the Panxi region and Bayan Obo. The fluorites from Maoniuping and Daluxiang are characterized by variable REE patterns, with either LREE enrichment or LREE depletion relative to MREE. Typically they have a larger range in La/Ho compared to Y/Ho ratios, and pronounced positive Y anomaly relative to chondrite-normalized REE patterns. Their REE distribution patterns are controlled by fluoride-complexes and the loss of separate LREE-rich minerals. Different Y/Ho (ca. 73 vs. 108) and initial Sr isotopic (ca. 0.7061 vs. 0.7077) ratios are observed between the fluorites from Maoniuping and Daluxiang, reflecting their different source compositions. This contrasts with the fluorites from Maoniuping and Lizhuang, which have similar initial Sr isotopes, and appear to be cogenetic. However, the Lizhuang fluorite shows a consistent depletion of LREE relative to MREE, as well as lower Y/Ho ratios and higher HREE content than that in Maoniuping. In this respect the Lizhuang fluorite may have precipitated from a late-stage fluid following abundant fluorite and REE mineral deposition in Maoniuping. Carbonate, more than fluoride complexing, appears to have a stronger control on REE fractionation in the Lizhuang fluorites. The fluorites from three deposits in Panxi

  3. Preparation and Electrochemical Characterization of Aluminium Liquid Battery Cells With Two Different Electrolytes (NaCl-BaCl2-AlF3-NaF and LiF-AlF3-BaF2).

    PubMed

    Napast, Viktor; Moškon, Jože; Homšak, Marko; Petek, Aljana; Gaberšček, Miran

    2015-01-01

    The possibility of preparation of operating rechargeable liquid battery cells based on aluminium and its alloys is systematically checked. In all cases we started from aluminium as the negative electrode whereas as the positive electrode three different metals were tested: Pb, Bi and Sn. Two types of electrolytes were selected: Na(3)AlF(6) -AlF(3) - BaCl(2) - NaCl and Li(3)AlF(3) - BaF(2). We show that some of these combinations allowed efficient separation of individual liquid layers. The cells exhibited expected voltages, relatively high current densities and could be charged and discharged several times. The capacities were relatively low (120 mAh in the case of Al-Pb system), mostly due to unoptimised cell construction. Improvements in various directions are possible, especially by hermetically sealing the cells thus preventing salt evaporation. Similarly, solubility of aluminium in alloys can be increased by optimising the composition of positive electrode. PMID:26680707

  4. Reel-to-reel x-ray diffraction and Raman microscopy analysis of differentially heat-treated Y BaF2 Cu precursor films on metre-length RABiTS

    NASA Astrophysics Data System (ADS)

    Venkataraman, K.; Lee, D. F.; Leonard, K.; Heatherly, L.; Cook, S.; Paranthaman, M.; Mika, M.; Maroni, V. A.

    2004-06-01

    Reel-to-reel x-ray diffraction (XRD) and Raman micro-spectroscopy are being evaluated as potential diagnostic tools for on-line feedback in the manufacturing of long-length coated conductors. To facilitate this evaluation, a procedure based on differentially heat-treated Y-BaF2-Cu precursors exposed to time-synchronized phase composition gradients has been developed. Two time-gradient-processed Y Ba2Cu3O7-x (YBCO) tapes of different thicknesses were fabricated using this procedure. The two techniques (used in combination) provided detailed phase and microstructure information as a function of temperature and heat treatment time and identified the same optimum processing time domain windows. More importantly, these deduced optimum times were found to be in close agreement with transport Jc measurements on replicate tapes. In addition, Raman data provided unambiguous identification of key intermediate phases such as BaF2, CuO, Y2Cu2O5, and barium cuprates. Using these results, a hypothetical Y-BaF2-Cu to YBCO reaction mechanism is proposed.

  5. Accommodation of multivalent cations in fluorite-type solid solutions: Case of Am-bearing UO2

    NASA Astrophysics Data System (ADS)

    Prieur, Damien; Martin, Philippe; Lebreton, Florent; Delahaye, Thibaud; Banerjee, Dipanjan; Scheinost, Andreas C.; Jankowiak, Aurélien

    2013-03-01

    The radiotoxicity of spent nuclear fuel is mainly due to the content of minor actinides, which could be substantially reduced by Partitioning and Transmutation. A possible transmutation method would be to employ americium-bearing uranium oxide materials as blanket fuels in fast neutron reactors. In order to maintain fuel performance and reactor safety, it is mandatory to control the structural homogeneity and oxygen stoichiometry during the sintering process. In this work, U0.85Am0.15O2-x materials, fabricated by a solid state chemistry process, were sintered at 2023 K under three oxygen potentials, i.e. -375, -350 and -325 kJ mol-1, thereby significantly extending the range of a previous study. By coupling X-ray diffraction and X-ray absorption spectroscopy measurements, it was shown that fluorite solid solutions are obtained whatever the sintering conditions. The presence of U(+V), pointed out in a previous work for oxygen potentials equal to -520 and -450 kJ mol-1, was confirmed. This result constitutes an experimental proof of the existence of U(+V) in An-doped UO2 fluorite-type structure materials. These experimental data are major results in view of the developing thermodynamical model of the U-Am-O system. Considering the now available extended range, the effect of the oxygen potential is discussed in terms of charge distribution and local structure.

  6. A new anion-deficient fluorite-related superstructure of Bi{sub 28}V{sub 8}O{sub 62}

    SciTech Connect

    Đorđević, T.; Karanović, Lj.

    2014-12-15

    New hydrothermally synthesized Bi{sub 28}V{sub 8}O{sub 62} was structurally characterized using single-crystal X-ray diffraction data. Bi{sub 28}V{sub 8}O{sub 62} crystallizes in the novel type of defect fluorite structure related to the face-centered cubic δ-Bi{sub 2}O{sub 3}. It is monoclinic, s. g. P2{sub 1}/c, and the relation to the fluorite subcell is given as a∼(3/2)a{sub F}+(3/2)c{sub F}; b∼ −b{sub F}; c∼2a{sub F} −4c{sub F} (F in subscript indicate the unit cell parameter of fluorite). Its structure is characterized by slabs of edge sharing OBi{sub 4} tetrahedra surrounded by the OBi{sub 3} triangles. As a part of these OBi{sub 3} triangles, two positionally disordered Bi{sup 3+} cations were observed in the marginal part of the slabs. The slabs are extending along b axis and are linked by inter-slab portion of the structure composed of VO{sub 4} tetrahedra and BiO{sub 6−x} coordination polyhedra, where x is a number of vacant oxygen sites. Raman spectra verified the coordination environment of vanadium atoms in the structure. - Graphical abstract: The [4{sup ¯}01] projection of two slabs and inter-slab part of the structure in one layer parallel to the (3{sup ¯}08)=(002{sup ¯}){sub F} plane (F in subscript indicate a fluorite type structure). The large green circles are Bi atoms. Small blue circles represent partly and fully occupied O sites, respectively. Pink (hatched black) are V1O{sub 4} and blue (hatched white) are V2O{sub 4} coordination tetrahedra. - Highlights: • Single crystals of Bi{sub 28}V{sub 8}O{sub 62} were grown using hydrothermal technique. • The crystal structure of Bi{sub 28}V{sub 8}O{sub 62} was solved using single-crystal XRD method. • Bi{sub 28}V{sub 8}O{sub 62} has an anion-deficient fluorite-related superstructure. • Raman spectrum confirmed the coordination environment of vanadium atoms. • Relation to the structurally related compound was discussed.

  7. Vacuum ultraviolet thin films. I - Optical constants of BaF2, CaF2, LaF3, MgF2, Al2O3, HfO2, and SiO2 thin films. II - Vacuum ultraviolet all-dielectric narrowband filters

    NASA Technical Reports Server (NTRS)

    Zukic, Muamer; Torr, Douglas G.; Spann, James F.; Torr, Marsha R.

    1990-01-01

    An iteration process matching calculated and measured reflectance and transmittance values in the 120-230 nm VUV region is presently used to ascertain the optical constants of bulk MgF2, as well as films of BaF2, CaF2, LaF3, MgF2, Al2O3, HfO2, and SiO2 deposited on MgF2 substrates. In the second part of this work, a design concept is demonstrated for two filters, employing rapidly changing extinction coefficients, centered at 135 nm for BaF2 and 141 nm for SiO2. These filters are shown to yield excellent narrowband spectral performance in combination with narrowband reflection filters.

  8. Metastable NaYF 4 fluorite at high pressures and high temperatures

    NASA Astrophysics Data System (ADS)

    Grzechnik, Andrzej; Bouvier, Pierre; Crichton, Wilson A.; Farina, Luca; Köhler, Jürgen

    2002-06-01

    High-pressure high-temperature behavior of metastable NaYF 4 fluorite (Fm 3¯m, Z=4), with the Na and Y atoms randomly distributed in the cationic sublattice, is studied with synchrotron angle-dispersive powder X-ray diffraction in diamond anvil (DAC) and large-volume Paris-Edinburgh cells and synthesis in a multi-anvil apparatus. The onset of a pressure-induced phase transition at room temperature takes place above 10 GPa as observed in DACs loaded with different hydrostatic and non-hydrostatic pressure media (nitrogen, paraffin oil, or ethanol:methanol media). In situ powder X-ray diffraction measurements in the Paris-Edinburgh cell and syntheses using the multi-anvil apparatus at high pressures and high temperatures show that the new polymorph is of the gagarinite-type (P6 3/m, Z=1) with partially ordered cations, the formula being Na 1.5Y 1.5F 6. This phase is structurally related to the Na 1.5Y 1.5F 6 modification (P 6¯, Z=1) stable at ambient conditions. At higher temperatures, the new pressure-induced hexagonal variant of NaYF 4 eventually decomposes into a non-stoichiometric gagarinite-like phase and yttrium fluoride YF 3 (Pnma, Z=4).

  9. Molecular dynamics simulation of ionic transport at coherent interfaces in fluorite heterostructures

    NASA Astrophysics Data System (ADS)

    Morgan, Benjamin J.; Madden, Paul A.

    2014-02-01

    The standard model of enhanced ionic conductivities in solid electrolyte heterostructures follows from a continuum mean-field description of defect distributions that makes no reference to crystalline structure. To examine ionic transport and defect distributions while explicitly accounting for ion-ion correlations and lattice effects, we have performed molecular dynamics simulations of a model coherent fluorite heterostructure without any extrinsic defects, with a difference in standard chemical potentials of mobile fluoride ions between phases induced by an external potential. Increasing the offset in fluoride ion standard chemical potentials across the internal interfaces decreases the activation energies for ionic conductivity and diffusion and strongly enhances fluoride ion mobilities and defect concentrations near the heterostructure interfaces. Non-charge-neutral "space-charge" regions, however, extend only a few atomic spacings from the interface, suggesting a continuum model may be inappropriate. Defect distributions are qualitatively inconsistent with the predictions of the continuum mean-field model, and indicate strong lattice-mediated defect-defect interactions. We identify an atomic-scale "Frenkel polarization" mechanism for the interfacial enhancement in ionic mobility, where preferentially oriented associated Frenkel pairs form at the interface and promote local ion mobility via concerted diffusion processes.

  10. Immiscible fluids (CO 2-brines) in optical fluorite, Nordvik-Taimyr, Russia

    NASA Astrophysics Data System (ADS)

    Prokof'ev, Vsevolod Y.; Baksheev, Ivan A.; Korytov, Feodor Y.; Touret, Jacques

    2006-07-01

    Fluid inclusion investigations in optical fluorite from the Nordvik salt dome caprock (Khatanga Gulf, Taimyr Peninsula, Russia) show that the fluorite has been formed at a temperature of about 300 °C, from CO 2-brine immiscible hydrothermal fluids. Unmixing occurred at a depth of several kilometres, resulting in the liberation of dense CO 2-rich fluids, which played a significant role in helping the diapir to reach its intrusive character. Compared to other optical fluorite deposits in Russia, the exceptional quality of the Nordvik occurrence is due to a relatively high formation temperature, as well as a high salinity (30-35 wt% NaCl eq.) of hydrothermal aqueous fluids. To cite this article: V.Y. Prokof'ev et al., C. R. Geoscience 338 (2006).

  11. Genesis of the Ordovician fluorite and its geological significance in central uplift of the Tarim basin, China

    NASA Astrophysics Data System (ADS)

    Wang, Zhenyu; Zhang, Yunfeng; Tao, Xiayan; Zhu, Bo; Luo, Chunshu

    2015-06-01

    Based on analysis of karst fractured-vuggy filling mineralogy and geochemical fluorite in the Hercynian, further research was carried out regarding the formation and significance of fluorite in the Central Uplift of the Tarim Basin. The Hercynian fractured-vuggy and filling succession of fracture-cave minerals were developed under a mixed background of low-temperature magmatic hydrothermal fluid and upper strata brine. An overlapping and associating relationship exists between the generation of fluorite and the buried dissolution or oil and gas migration. The fluorite volume decreased by 26.4 % after the calcite had been metasomatized by fluorite, resulting in plentiful intergranular spaces, which formed an appreciable reservoir space. At the same time, the hydrothermal fluid carried by fluorite eroded adjacent rock through fractures or fissures, forming an irregular fracture-cave system, accompanied by hydrocarbon migration. The hydrocarbon migration and accumulation occurring in the Late Hercynian-Indosinian are closely related to the sedimentation of fluorite and several hydrothermal minerals.

  12. Synthesis, properties and phase transitions of pyrochlore- and fluorite-like Ln{sub 2}RMO{sub 7} (Ln = Sm, Ho; R = Lu, Sc; M = Nb, Ta)

    SciTech Connect

    Shlyakhtina, A.V.; Belov, D.A.; Pigalskiy, K.S.; Shchegolikhin, A.N.; Kolbanev, I.V.; Karyagina, O.K.

    2014-01-01

    Graphical abstract: Temperature dependences of bulk conductivity for Sm{sub 2}ScTaO{sub 7} pyrochlore prepared at (1) 1400 °C, 20 h; and (2) 1200 °C, 40 h. - Highlights: • The phase formation of Ln{sub 2}RMO{sub 7} (Ln = Sm, Ho; R = Lu, Sc; M = Nb, Ta) at 1200–1600 °C. • The bulk conductivity and magnetic susceptibility were measured. • The bulk conductivity of Sm{sub 2}ScTaO{sub 7} has oxygen ion type at T ≥ 750 °C. • The first-order structural phase transition was observed in Sm{sub 2}ScTaO{sub 7} at ∼650–700 °C. • This phase transformation is not typical for defect fluorites. - Abstract: We have studied the new compounds with fluorite-like (Ho{sub 2}RNbO{sub 7} (R = Lu, Sc)) and pyrochlore-like (Sm{sub 2}ScTaO{sub 7}) structure as potential oxide ion conductors. The phase formation process (from 1200 to 1600 °C) and physical properties (electrical, thermo mechanical, and magnetic) for these compounds were investigated. Among the niobate materials the highest bulk conductivity is offered by the fluorite-like Ho{sub 2}ScNbO{sub 7} synthesized at 1600 °C: 3.8 × 10{sup −5} S/cm at 750 °C, whereas in Sm system the highest bulk conductivity, 7.3 × 10{sup −6} S/cm at 750 °C, is offered by the pyrochlore Sm{sub 2}ScTaO{sub 7} synthesized at 1400 °C. In Sm{sub 2}ScTaO{sub 7} pyrochlore we have observed the first-order phase transformation at ∼650–700 °C is related to rearrangement process in the oxygen sublattice of the pyrochlore structure containing B-site cations in different valence state and actually is absent in the defect fluorites. The two holmium niobates show Curie–Weiss paramagnetic behavior, with the prevalence of antiferromagnetic coupling. The magnetic susceptibility of Sm{sub 2}ScTaO{sub 7} is a weak function of temperature, corresponding to Van Vleck paramagnetism.

  13. Mineralogical, textural, geochemical and thermometric characteristics of Central Anatolian fluorites (Turkey): Tracing the origin of post-magmatic fluids

    NASA Astrophysics Data System (ADS)

    Cosanay, Pelin; Mutlu, Halim; Koc, Sükrü; Cevik, Nihal; Oztürk, Ceyda; Varol, Ece

    2016-04-01

    In this study, we investigate the spatial distribution of fluorite veins in Central Anatolia with emphasis on mineralogical, textural, geochemical and thermometric variations. The studied fluorite mineralizations (Kaman, Akçakent, Pöhrenk and Şefaatli mineralizations from west to east) are located on northern part of Kırşehir Massif which is a part of Central Anatolian Crystalline Complex that is bordered by the İzmir-Ankara-Erzincan Suture Zone. The Kaman, Akçakent and Şefaatli fluorite deposits are formed in association with magmatic rocks such as syenite and monzonite / monzodiorite in composition which are of Upper Cretaceous age. Fluorite in these deposits occurs as purple- and green-colored stockwork veins and/or disseminations along fault/fracture systems and is accompanied by quartz and rare pyrite. The Pöhrenk ore, however, is precipitated as space filling-breccia type within karstic voids of Eocene limestones and marl levels. The silicification/carbonatization and barite occurrences are found as the main alteration and secondary products of mineralization. Thickness of fluorite veins is between 2 and 30 cm. ΣREE contents of host rocks and fluorite veins are in the range of 2-806 ppm and 20-390 ppm, respectively. In element variation diagrams constructed for both host rocks and fluorite mineralizations, LREE concentrations are found to be greater than HREEs. REE contents of green-colored fluorites are about 10-fold higher than those of purple-colored ones. Negative Ce and Eu anomalies indicate high oxygen fugacity for the mineralizing fluids. Fluid inclusion studies indicated three different types of inclusions: 1) two-phase (liquid-vapor) primary and secondary inclusions, 2) single-phase (liquid) primary and secondary inclusions and 3) two-phase (liquid-vapor) and single-phase (liquid) pseudo-secondary inclusions. Results of homogenization temperatures from a number of about 200 measurements chiefly on fluorite and less often quartz and barite

  14. Thermal-Driven Fluorite-Pyrochlore-Fluorite Phase Transitions of Gd2Zr2O7 Ceramics Probed in Large Range of Sintering Temperature

    NASA Astrophysics Data System (ADS)

    Zhou, Li; Huang, Zhangyi; Qi, Jianqi; Feng, Zhao; Wu, Dengxue; Zhang, Wei; Yu, Xiaohe; Guan, Yongbing; Chen, Xingtao; Xie, Landong; Sun, Kai; Lu, Tiecheng

    2016-01-01

    Fluorite (F)-pyrochlore (P)-fluorite (F) phase transitions of Gd2Zr2O7 were investigated from 573 K to 1873 K (300 °C to 1600 °C), by means of X-ray diffraction, infrared spectra (IR), and Raman spectra. The low-temperature F phase can stably exist below 1523 K (1250 °C) and the F-P transition occurs at 1523 K to 1573 K (1250 °C to 1300 °C). The ordering process of P phase forms at 1573 K to 1773 K (1300 °C to 1500 °C) and the ordering degree increases with increasing sintering temperature and heat preservation period. High-temperature phase transition from P to F occurs between 1773 K and 1823 K (1300 °C and 1550 °C). IR spectra of samples with different ordering degrees show an interesting shift at 510 cm-1. Raman spectra show that only the A1 g mode displays a significant change between F and P phases. This ordering degree and phase transition temperature studies would allow a more targeted experimental optimization of Gd2Zr2O7 to use in nuclear waste host, thermal barrier coatings, and solid oxide fuel cells.

  15. Geochemical associations between fluorite mineralization and A-type shoshonitic magmatism in the Keban-Elazig area, East Anatolia, Turkey

    NASA Astrophysics Data System (ADS)

    Akgul, Bunyamin

    2015-11-01

    Keban fluorite mineralizations are closely related Coniacian-Campanian subvolcanics intruded into Permian-Triassic Keban metamorphites; this event caused pyrometasomatic, porphyry, and vein-type Pb-Zn-Ag, Cu, W, and Pb-Zn-Ag-Mo-F mineralizations. These rocks are syenitic and syenomonzonitic in composition and have high Al2O3, alkali (Na2O + K2O), FeO*/MgO, Zr, Nb, Ta, Ga, Rb, Y, and rare earth element (REE) contents. They are A-type, metaluminous, and all fall in the shoshonitic series field in K2O vs SiO2 and Th/Yb vs Ta/Yb diagrams. The trace element contents and discriminations indicate that the Keban syenitoids were derived from lithospheric mantle metasomatized by oceanic-crust/sediment fluids. The metal and halogen contents of the Keban mineralizations apparently originated from metasomatized mantle and were transported to the crust by syenitoid magmas. Clear resemblances in chondrite-normalized REE patterns, LREE-HREE partionation, and high LILE contents of the magmatics and fluorites indicate a close kinship between the syenitoids and fluorite mineralizations. The HFSE contents of the fluorites are lower than those of the magmatics, as HFSEs are not soluble in aqueous fluids. The fluorites are products of early-phase alkali magmatism (LREE > HREE). The high contents of Rb, Sr, and Ba of fluorites are inherited from the magma, which also has very high contents of these elements. In Sc-∑REE, (La/Yb)n-(Eu/Eu*)n and (Tb/La)n-(Tb/Ca)n diagrams, Keban fluorites fall into distinct areas from Akcakisla-Akdagmadeni and Celikhan-Adiyaman fluorites.

  16. Lead-barium fluoroborate glass ceramics doped with Nd3+ or Er3+

    NASA Astrophysics Data System (ADS)

    Petrova, O. B.; Sevostjanova, T. S.; Anurova, M. O.; Khomyakov, A. V.

    2016-02-01

    Lead-barium fluoroborate glasses in the PbF2-BaF2-B2O3, PbF2-BaO-B2O3, and PbO- BaF2-B2O3 systems doped with rare-earth ions (Nd3+ or Er3+) are synthesized and studied. It is shown that, based on these glasses, it is possible to produce transparent glass ceramics with fluoride crystalline phases, including ceramics with one crystalline phase of the fluorite structure. The spectral and luminescent properties of the doped glasses, glass ceramics, and polycrystalline complex fluorides containing Pb, Ba, and rare ions are studied.

  17. A kinetic study of the replacement of calcite marble by fluorite

    NASA Astrophysics Data System (ADS)

    Trindade Pedrosa, Elisabete; Boeck, Lena; Putnis, Christine V.; Putnis, Andrew

    2016-04-01

    Replacement reactions are relevant in any situation that involves the reequilibration between a solid and an aqueous fluid phase and are commonly controlled by an interface-coupled dissolution-precipitation mechanism (Putnis and Putnis, 2007). These reactions control many large-scale Earth processes whenever aqueous fluids are available, such as during metamorphism, metasomatism, and weathering. An important consequence of coupled dissolution-precipitation is the generation of porosity in the product phase that then allows the infiltration of the fluid within the mineral being replaced. Understanding the mechanism and kinetics of the replacement of carbonates by fluorite has application in earth sciences and engineering. Fluorite (CaF2) occurs in all kinds of rocks (igneous, sedimentary, and metamorphic) and its origin is commonly associated with hydrothermal fluids. Moreover, calcium carbonate has been suggested as a successful seed material for the sequestration of fluoride from contaminated waters (Waghmare and Arfin, 2015). The aim of the present work is to investigate aspects of the replacement of calcium carbonate by fluorite to better understand the mechanism and kinetics of this reaction. Small cubes (˜ 3 × 3 × 3 mm) of Carrara marble (CaCO3 > 99 %) were cut and reacted with a 4 M ammonium fluoride (NH4F) solution for different times (1 to 48 hours) and temperatures (60, 80, 100, and 140 ° C). The microstructure of the product phases was analysed using SEM. The kinetics of replacement was monitored from the Rietveld analysis of X-ray powder diffraction patterns of the products as a function of temperature and reaction time. After reaction, all samples preserved their size and external morphology (a pseudomorphic replacement) and the product phase (fluorite) was highly porous. The activation energy Ea (kJ/mol) of the replacement reaction was empirically determined by both model-fitting and model-free methods. The isoconversional method yielded an

  18. Hydrothermal uranium deposits containing molybdenum and fluorite in the Marysvale volcanic field, west-central Utah

    USGS Publications Warehouse

    Cunningham, C.G.; Rasmussen, J.D.; Steven, T.A.; Rye, R.O.; Rowley, P.D.; Romberger, S.B.; Selverstone, J.

    1998-01-01

    Uranium deposits containing molybdenum and fluorite occur in the Central Mining Area, near Marysvale, Utah, and formed in an epithermal vein system that is part of a volcanic/hypabyssal complex. They represent a known, but uncommon, type of deposit; relative to other commonly described volcanic-related uranium deposits, they are young, well-exposed and well-documented. Hydrothermal uranium-bearing quartz and fluorite veins are exposed over a 300 m vertical range in the mines. Molybdenum, as jordisite (amorphous MoS2, together with fluorite and pyrite, increase with depth, and uranium decreases with depth. The veins cut 23-Ma quartz monzonite, 20-Ma granite, and 19-Ma rhyolite ash-flow tuff. The veins formed at 19-18 Ma in a 1 km2 area, above a cupola of a composite, recurrent, magma chamber at least 24 ?? 5 km across that fed a sequence of 21- to 14-Ma hypabyssal granitic stocks, rhyolite lava flows, ash-flow tuffs, and volcanic domes. Formation of the Central Mining Area began when the intrusion of a rhyolite stock, and related molybdenite-bearing, uranium-rich, glassy rhyolite dikes, lifted the fractured roof above the stock. A breccia pipe formed and relieved magmatic pressures, and as blocks of the fractured roof began to settle back in place, flat-lying, concave-downward, 'pull-apart' fractures were formed. Uranium-bearing, quartz and fluorite veins were deposited by a shallow hydrothermal system in the disarticulated carapace. The veins, which filled open spaces along the high-angle fault zones and flat-lying fractures, were deposited within 115 m of the ground surface above the concealed rhyolite stock. Hydrothermal fluids with temperatures near 200??C, ??18OH2O ~ -1.5, ?? -1.5, ??DH2O ~ -130, log fO2 about -47 to -50, and pH about 6 to 7, permeated the fractured rocks; these fluids were rich in fluorine, molybdenum, potassium, and hydrogen sulfide, and contained uranium as fluoride complexes. The hydrothermal fluids reacted with the wallrock resulting in

  19. C-type related order in the defective fluorites La2Ce2O7 and Nd2Ce2O7 studied by neutron scattering and ab initio MD simulations.

    PubMed

    Kalland, Liv-Elisif; Norberg, Stefan T; Kyrklund, Jakob; Hull, Stephen; Eriksson, Sten G; Norby, Truls; Mohn, Chris E; Knee, Christopher S

    2016-09-14

    This work presents a structural investigation of La2-xNdxCe2O7 (x = 0.0, 0.5, 1.0, 1.5, 2.0) using X-ray powder diffraction and total scattering neutron powder diffraction, analysed using Rietveld and the reverse Monte Carlo method (RMC). Ab initio molecular dynamics (MD) modelling is also performed for further investigations of the local order. The main intensities in the neutron diffraction data for the La2-xNdxCe2O7 series correspond to the fluorite structure. However, additional C-type superlattice peaks are visible for x > 0 and increase in intensity with increasing x. The Nd-containing compositions (x > 0) are best fitted with Rietveld analysis by using a combination of oxygen deficient fluorite and oxygen excess C-type structures. No indications of cation order are found in the RMC or Rietveld analysis, and the absence of cation order is supported by the MD modelling. We argue that the superlattice peaks originate from oxygen vacancy ordering and associated shift in the cation position away from the ideal fluorite site similar to that in the C-type structure, which is seen from the Rietveld refinements and the observed ordering in the MD modelling. The vacancies favour alignments in the 〈110〉, 〈111〉 and especially the 〈210〉 direction. Moreover, we find that such ordering might also be found to a small extent in La2Ce2O7, explaining the discernible modulated background between the fluorite peaks. The observed overlap of the main Bragg peaks between the fluorite and C-type phase supports the co-existence of vacancy ordered and more disordered domains. This is further supported by the observed similarity of the radial distribution functions as modelled with MD. The increase in long range oxygen vacancy order with increasing Nd-content in La2-xNdxCe2O7 corresponds well with the lower oxide ion conductivity in Nd2Ce2O7 compared to La2Ce2O7 reported earlier. PMID:27526388

  20. Hydrocarbon-bearing fluid inclusions in fluorite associated with the Windy Knoll bitumen deposit, UK

    NASA Astrophysics Data System (ADS)

    Moser, M. R.; Rankin, A. H.; Milledge, H. J.

    1992-01-01

    Hydrocarbon-bearing fluid inclusions in fluorite, associated with an outcropping bitumen deposit at Windy Knoll, Derbyshire, have been analysed in situ using a combination of microthermometry, Fourier transform infrared (FTIR) microspectrometry, and ultraviolet (UV) microscopy. The inclusions in these samples can be considered as a series with two endmembers: aqueous inclusions containing a low-density vapour phase and inclusions containing liquid "oil" with no detectable aqueous phase. The majority of the inclusions are mixed types containing both aqueous and liquid hydrocarbon phases. Although microthermometry distinguishes at least two different aqueous fluids with varying homogenization temperatures and salinities, the oil fraction is cogenetic and trapped together with just one fluid, a low-salinity, low-calcium brine with an average homogenization temperature of 134°C. The majority of the liquid hydrocarbon-bearing inclusions fluoresce bright blue under UV illumination with peaks around 475 nm, characteristic of paraffinic oils. The FTIR spectra of these inclusions are dominated by peaks assigned to aliphatic C - H bonding. However, inclusions have also been found which display a fluorescence typical of the red-shift associated with less mature oils. The FTIR spectra display peaks assigned to CO, C - O, and O - CH 2 bonding. This study presents new data on the in-situ analysis of hydrocarbon-bearing fluid inclusions from this important area of natural petroleum seepage and ore mineralization. The results suggest a direct link between the fluid inclusion populations, the outcropping bitumens, and fluorite deposition.

  1. Genesis of rare-metal pegmatites and alkaline apatite-fluorite rocks of Burpala massi, Northern Baikal folded zone

    NASA Astrophysics Data System (ADS)

    Sotnikova, Irina; Vladykin, Nikolai

    2015-04-01

    Burpalinsky rare metal alkaline massif in the Northern Baikal folded zone in southern margin of Siberian Platform, is a of intrusion central type, created 287 Ma covering area of about 250 km2. It is composed of nepheline syenites and pulaskites grading to quartz syenites in the contacts. Veines and dykes are represented by shonkinites, sodalite syenite, leucocratic granophyres, alkali granites and numerous rare metal alkaline syenite pegmatites and two dykes of carbonatites. All rocks except for granites are cut by a large apatite-fluorite dyke rocks with mica and magnetite, which in turn is cut by alaskite granites dyke. The massif has been studied by A.M. Portnov, A.A. Ganzeev et al. (1992) Burpalinsky massif is highly enriched with trace elements, which are concentrated in pegmatite dykes. About 70 rare-metal minerals we found in massif. Zr-silicates: zircon, eudialyte, lovenite, Ti-lovenite, velerite, burpalite, seidozerite, Ca- seidozerite, Rosenbuschite, vlasovite, katapleite, Ca-katapleite, elpidite. Ti- minerals:- sphene, astrophyllite, ramsaite, Mn-neptunite bafertisite, chevkinite, Mn-ilmenite, pirofanite, Sr-perrerit, landauite, rutile, anatase, brookite; TR- minerals - loparite, metaloparite, britolite, rinkolite, melanocerite, bastnesite, parisite, ankilite, monazite, fluocerite, TR-apatite; Nb- minerals - pyrochlore, loparite. Other rare minerals leucophanite, hambergite, pyrochlore, betafite, torite, thorianite, tayniolite, brewsterite, cryolite and others. We have proposed a new scheme massif: shonkinites - nepheline syenites - alkaline syenite - quartz syenites - veined rocks: mariupolites, rare-metal pegmatites, apatite, fluorite rock alyaskite and alkaline granites and carbonatites (Sotnikova, 2009). Apatite-fluorite rocks are found in the central part of massif. This is a large vein body of 2 km length and a 20 m width cutting prevailing pulaskites. Previously, these rocks were regarded as hydrothermal low-temperature phase. New geological and

  2. Metastable extension of the fluorite phase field in Y2O3-ZrO3-ZrO2 and its effect on grain growth

    NASA Astrophysics Data System (ADS)

    Jayaram, V.; Degraef, M.; Levi, C. G.

    1994-06-01

    Pure Y2O3 and Y2O3-ZrO2 solid solutions have been prepared by melt atomization and by pyrolysis of nitrate solutions. Extended solubility is readily achieved in both techniques for the entire composition range investigated: melts with 0.30% ZrO2 and precursors with 0.50% ZrO2. However, solidification of under cooled droplets yields almost exclusively single phase powders with the structure of cubic yttria (D5(sub 3)). In contrast, the pyrolysis route leads to a sequence of metastable microstructures beginning with a nanocrystalline disordered fluorite-based (C1) solid solution. Further heating leads to the evolution of much larger (micron size) flake crystals with a (001) texture, concurrent with partial ordering of the oxygen ions to the sites occupied in the D5(sub 3) addition.

  3. New quenched-in fluorite-type materials in the Bi{sub 2}O{sub 3}-La{sub 2}O{sub 3}-PbO system: Synthesis and complex phase behaviour up to 750 {sup o}C

    SciTech Connect

    Webster, Nathan A.S.; Hartlieb, Karel J.; Saines, Paul J.; Ling, Chris D.; Lincoln, Frank J.

    2011-04-15

    Research highlights: {yields} New quenched-in fluorite-type materials synthesised by solid state reaction. {yields} Compositions (BiO{sub 1.5}){sub 0.94-x}(LaO{sub 1.5}){sub 0.06}(PbO){sub x}, x = 0.02, 0.03, 0.04 and 0.05. {yields} Variable-temperature X-ray diffraction data collected in the range of 400-750 {sup o}C. {yields} Fluorite-type structure transforms during heating, complex phase behaviour characterised. {yields} Tetragonal, monoclinic, rhombohedral and bcc phases identified. -- Abstract: New quenched-in fluorite-type materials with composition (BiO{sub 1.5}){sub 0.94-x}(LaO{sub 1.5}){sub 0.06}(PbO){sub x}, x = 0.02, 0.03, 0.04 and 0.05, were synthesised by solid state reaction. The new materials undergo a number of phase transformations during heating between room temperature and 750 {sup o}C, as indicated by differential thermal analysis. Variable temperature X-ray diffraction performed on the material (BiO{sub 1.5}){sub 0.92}(LaO{sub 1.5}){sub 0.06}(PbO){sub 0.02} revealed that the quenched-in fcc fluorite-type material first undergoes a transformation to a {beta}-Bi{sub 2}O{sub 3}-type tetragonal phase around 400 {sup o}C. In the range 450-700 {sup o}C, {alpha}-Bi{sub 2}O{sub 3}-type monoclinic, Bi{sub 12}PbO{sub 19}-type bcc and {beta}{sub 1}/{beta}{sub 2}-type rhombohedral phases, and what appeared to be a {epsilon}-type monoclinic phase, were observed, before a single-phase fluorite-type material was regained at 750 {sup o}C.

  4. Regional stratigraphy and distribution of epigenetic stratabound celestine, fluorite, barite and Pb-Zn deposits in the MVT province of northeastern Mexico

    NASA Astrophysics Data System (ADS)

    González-Sánchez, Francisco; Camprubí, Antoni; González-Partida, Eduardo; Puente-Solís, Rafael; Canet, Carles; Centeno-García, Elena; Atudorei, Viorel

    2009-04-01

    Northeastern Mexico hosts numerous epigenetic stratabound carbonate-hosted low-temperature hydrothermal deposits of celestine, fluorite, barite and zinc-lead, which formed by replacement of Mesozoic evaporites or carbonate rocks. Such deposits can be permissively catalogued as Mississippi Valley-type (MVT) deposits. The deposits studied in the state of Coahuila are associated with granitic and metasedimentary basement highs (horsts) marginal or central to the Mesozoic Sabinas Basin. These horsts controlled the stratigraphy of the Mesozoic basins and subsequently influenced the Laramide structural pattern. The Sabinas Basin consists of ~6,000-m-thick Jurassic to Cretaceous siliciclastic, carbonate and evaporitic series. The MVT deposits are mostly in Barremian and in Aptian-Albian to Cenomanian formations and likely formed from basinal brines that were mobilized during the Laramide orogeny, although earlier diagenetic replacement of evaporite layers (barite and celestine deposits) and lining of paleokarstic cavities in reef carbonates (Zn-Pb deposits) is observed. Fluid inclusion microthermometry and isotopic studies suggest ore formation due to mixing of basinal brines and meteoric water. Homogenization temperatures of fluid inclusions range from 45°C to 210°C; salinities range from 0 to 26 wt.% NaCl equiv., and some inclusions contain hydrocarbons or bitumen. Sulfur isotope data suggest that most of the sulfur in barite and celestine is derived from Barremian to Cenomanian evaporites. Regional geology and a compilation of metallogenic features define the new MVT province of northeastern Mexico, which comprises most of the state of Coahuila and portions of the neighboring states of Nuevo León, Durango and, perhaps extends into Zacatecas and southern Texas. This province exhibits a regional metal zonation, with celestine deposits to the south, fluorite deposits to the north and barite and Zn-Pb deposits mostly in the central part.

  5. Magnetic properties of orthorhombic fluorite-related oxides Ln{sub 3}SbO{sub 7} (Ln=rare earths)

    SciTech Connect

    Hinatsu, Yukio; Ebisawa, Haruka; Doi, Yoshihiro

    2009-07-15

    Ternary rare earth antimonates Ln{sub 3}SbO{sub 7} (Ln=rare earths) were prepared and their structures were determined by X-ray diffraction measurements. They crystallize in an orthorhombic superstructure of cubic fluorite (space group Cmcm for Ln=La, Pr, Nd; C222{sub 1} for Ln=Nd-Lu), in which Ln{sup 3+} ions occupy two different crystallographic sites (the 8-coordinated and 7-coordinated sites). Their magnetic properties were characterized by magnetic susceptibility and specific heat measurements from 1.8 to 400 K. The Ln{sub 3}SbO{sub 7} (Ln=Nd, Gd-Ho) compounds show an antiferromagnetic transition at 2.2-3.2 K. Sm{sub 3}SbO{sub 7} and Eu{sub 3}SbO{sub 7} show van Vleck paramagnetism. Measurements of the specific heat down to 0.4 K for Gd{sub 3}SbO{sub 7} and the analysis of the magnetic specific heat indicate that the antiferromagnetic ordering of the 8-coordinated Gd ions occur at 2.6 K, and the 7-coordinated Gd ions order at a furthermore low temperature. - Graphical Abstract: Ternary rare earth antimonates Ln{sub 3}SbO{sub 7} (Ln=rare earths) crystallize in an orthorhombic superstructure of cubic fluorite (space group Cmcm for Ln=La, Pr, Nd; C222{sub 1} for Ln=Nd-Lu), in which Ln{sup 3+} ions occupy two different crystallographic sites (the 8-coordinated and 7-coordinated sites). Any of these compounds Ln{sub 3}SbO{sub 7} (Ln=Nd, Gd-Ho) shows an antiferromagnetic transition at 2.2-3.2 K.

  6. Experimental replacement of calcium carbonates by fluorite: high volume changes and porosity generation

    NASA Astrophysics Data System (ADS)

    Trindade Pedrosa, Elisabete; Putnis, Andrew

    2015-04-01

    Pseudomorphic mineral replacement reactions are a common phenomena in nature, and often described as interface-coupled dissolution-reprecipitation processes. The generation of porosity is a key factor for its progression since it creates the pathway for fluid infiltration towards an ongoing reaction front. The generation of porosity depends on two key factors: the molar volume differences between parent and product phase, and the relative solubilities of the parent and product in the fluid at the mineral-fluid interface (Pollok et al., 2011). Jamtveit et al., (2009) demonstrated that the permeability of the parent rock may also be enhanced by the development of fractures as a response to stresses generated by local volume changes at the reaction interface, which in turn increases the reaction rate. The replacement of calcite (CaCO3) by fluorite (CaF2) involves a molar volume decrease of 33.5 %. If indeed high volume changes generate high local stresses, a fragmentation process is expected to be driven by this replacement reaction. To test this hypothesis, a number of hydrothermal experiments were performed. Small cubes of calcite rock (Carrara marble), and single crystals of calcite were used as parent materials. Two fluoride solutions (ammonium fluoride and sodium fluoride) were used as reactants. Samples were reacted at temperatures up to 200°C for various times and quenched to room temperature. After drying, samples were mounted in epoxy holders, cross sections through the centre of the samples were cut and polished, and analysed using scanning electron microscopy (SEM), X-ray diffraction (XRD), and electron microprobe analysis (EMP). The replacement end product of all experiments was confirmed to be fluorite. In every case the external shape of the samples was perfectly maintained. No reaction induced fracturing was visible in any of the samples (rock or single crystals) although the texture of the replaced material was quite complex, often with a 'V' shaped

  7. A late Triassic 40Ar/39Ar age for the El Hammam high-REE fluorite deposit (Morocco): mineralization related to the Central Atlantic Magmatic Province?

    NASA Astrophysics Data System (ADS)

    Cheilletz, Alain; Gasquet, Dominique; Filali, Fouad; Archibald, Douglas A.; Nespolo, Massimo

    2010-04-01

    El Hammam is the only fluorite mine in Morocco (production 100,000 t/year). The fluorite mineralization is in an array of fluorite-calcite veins and is characterized by unusually high REE content in carbonate minerals (1,400 ppm in calcite; up to 2,000 ppm in siderite) and in fluorite (about 600 ppm). Since the 1960s, the genesis of the deposit has been attributed to a mesothermal hydrothermal event connected with late-Variscan granitic intrusions. Precise 40Ar/39Ar dating of hydrothermal K-feldspar yields an age of formation of the El Hammam deposit at 205 ± 1 Ma. Its genesis is therefore associated in time and space with the development of the Triassic-Jurassic basins and the associated anorogenic continental flood basalts of the Moroccan Mesetian Middle Atlas. The source of the hydrothermal mineralization (magmatic and/or metamorphic) is discussed.

  8. Laser-excited fluorescence of rare earth elements in fluorite: Initial observations with a laser Raman microprobe

    USGS Publications Warehouse

    Burruss, R.C.; Ging, T.G.; Eppinger, R.G.; Samson, a.M.

    1992-01-01

    Fluorescence emission spectra of three samples of fluorite containing 226-867 ppm total rare earth elements (REE) were excited by visible and ultraviolet wavelength lines of an argon ion laser and recorded with a Raman microprobe spectrometer system. Narrow emission lines ( 0.9 for Eu2+ and 0.99 for Er3+. Detection limits for three micrometer spots are about 0.01 ppm Eu2+ and 0.07 ppm Er3+. These limits are less than chondrite abundance for Eu and Er, demonstrating the potential microprobe analytical applications of laser-excited fluorescence of REE in fluorite. However, application of this technique to common rock-forming minerals may be hampered by competition between fluorescence emission and radiationless energy transfer processes involving lattice phonons. ?? 1992.

  9. Geology, mineralogy and fluid inclusion data of the Kizilcaören fluorite barite REE deposit, Eskisehir, Turkey

    NASA Astrophysics Data System (ADS)

    Gültekin, Ali Haydar; Örgün, Yüksel; Suner, Fikret

    2003-01-01

    The Kizilcaören fluorite-barite-Rare Earth Element (REE) deposit occurs as epithermal veins and breccia fillings in altered Triassic metasandstones and Oligocene-Miocene pyroclastics adjacent to alkaline porphyritic trachyte and phonolite. This deposit is the only commercial source of REE and thorium in Turkey. Most of the fluorite-barite-REE mineralisation at Kizilcaören has been formed by hydrothermal solutions, which are thought to be genetically associated with alkaline volcanism. The occurrence of the ore minerals in vuggy cavities and veins of massive and vuggy silica indicate that the ore stage postdates hydrothermal alteration. The deposit contains evidence of at least three periods of hypogene mineralisation separated by two periods of faulting. The mineral assemblage includes fluorite, barite, quartz, calcite, bastnäsite, phlogopite, pyrolusite and hematite as well as minor amounts of plagioclase feldspar, pyrite, psilomelane, braunite, monazite, fluocerite, brockite, goethite, and rutile. Fluid inclusion microthermometry indicates that the barite formed from low salinity (0.4-9.2 equiv. wt% NaCl) fluids at low temperatures, between 105 and 230 °C, but fluorite formed from slightly higher salinity (<12.4 equiv. wt% NaCl) fluids at low and moderate temperatures, between 135-354 °C. The depositional temperature of bastnäsite is between 143-286 °C. The local coexistence of liquid- and vapour-rich inclusions suggests boiling conditions. Many relatively low-salinity (<10.0 equiv. wt% NaCl), low and moderate temperature (200-300 °C) inclusions might be the result of episodic mixing of deep-saline brines with low-salinity meteoric fluids. The narrow range of δ34S (pyrite and barite) values (2.89-6.92‰ CDT)suggests that the sulphur source of the hydrothermal fluids are the same and compatible with a volcanogenic sulphate field derived from a magmatic sulphur source.

  10. Wetting characteristics and stability of Langmuir-Blodgett carboxylate monolayers at the surfaces of calcite and fluorite

    SciTech Connect

    Jang, W.H.; Drelich, J.; Miller, J.D.

    1995-09-01

    Although surface chemistry fundamentals of semisoluble minerals have been studied by many researchers, detailed understanding of these systems is still incomplete. In situ Fourier transform infrared internal reflection spectroscopy (FT-IR/IRS) techniques have recently been used to successfully describe the adsorption of carboxylates at semisoluble mineral surfaces. The wetting characteristics of these adsorbed films, however, require further consideration. In this regard, the hydrophobicity and stability of transferred Langmuir-Blodgett (LB) monolayers of fatty acids at fluorite and calcite surfaces have been studied by contact angle measurements with water and diiodomethane. Generally, it was found that the transferred LB monolayers of fatty acids at a calcite surface are unstable whereas such monolayers transferred onto a fluorite surface are stable, as revealed from advancing and receding contact angle measurements. These results are believed to be due to incomplete reaction of the fatty acid monolayer at the calcite surface. In addition it was found that a closely packed well-ordered stearate monolayer similar to that of a transferred LB monolayer can be formed at fluorite surfaces by spontaneous adsorption and self-assembly from aqueous solutions. 41 refs., 13 figs., 1 tab.

  11. Assessment in situ of genotoxicity in tadpoles and adults of frog Hypsiboas cordobae (Barrio 1965) inhabiting aquatic ecosystems associated to fluorite mine.

    PubMed

    Pollo, Favio E; Grenat, Pablo R; Otero, Manuel A; Salas, Nancy E; Martino, Adolfo L

    2016-11-01

    Non-lethal biological techniques such as blood biomarkers have gained attention due to their value as early signals of anthropic effects of contamination representing significant tools to evaluate ecosystems health. We evaluate and characterize in situ genotoxicity of water samples collected from aquatic ecosystems around a fluorite mine using amphibian frogs Hypsiboas cordobae as bioindicator species complemented with 16 physicochemical parameters. Four stations associated with fluorite mine sampling were sampled: a stream running on granitic rock with natural high fluorite content; two streams both running on metamorphic rock with low fluorite content; and an artificial decantation pond containing sediments produced by fluorite flotation process with high variation in physicochemical parameters. We analyses the blood of tadpoles and adults of H. Cordobae, calculated frequencies of micronuclei, erythrocyte nuclear abnormalities, mitosis, immature and enucleated erythrocytes. Individuals were measured and weighed and body condition was calculated. The results of this study indicate that individuals of decantation pond are exposed to compounds or mixtures which are causing cell damage when compared to those that were collected of stream. Larval stage was more vulnerable than the adult phase and it could be related mainly to the higher exposure time to xenobiotics, which can penetrate easily by skin, mouth and gills; additionally this site offers a reduced availability of food than other sites. Therefore, chronic exposure to pollutants could derive in degenerative and neoplastic diseases in target organs. Moreover these individuals may experience reproductive and behavioral disturbances which could lead to population decline in the long term. PMID:27522316

  12. Studies of EPR spectra and defect structure for Er³⁺ ions in BaF₂ and SrF₂ crystals.

    PubMed

    Li, Hui; Kuang, Xiao-Yu; Mao, Ai-Jie; Li, Cheng-Gang

    2013-02-01

    The local lattice structure and electron paramagnetic resonance (EPR) spectra have been studied systematically by diagonalizing 364 × 364 complete energy matrices for a f(11) ion in a trigonal ligand-field. By simulating the calculated Stark levels and EPR parameters to the experimental results, the shift parameters are determined for Er(3+) ions in BaF(2) and SrF(2). The results show that the trigonal center is attributed to an interstitial F(-) ion located at the [111] axis of the cube, and the nearest ligand close to the charge compensator has a displacement towards central ion by 0.042Å for L center in BaF(2):Er(3+) and 0.026Å for J center in SrF(2):Er(3+), respectively. Moreover, the relationships between g-factors and shift parameter ΔZ as well as orbit reduction factor k' are discussed. PMID:23220532

  13. Stable isotope study of fluid inclusions in fluorite from Idaho: implications for continental climates during the Eocene

    USGS Publications Warehouse

    Seal, R.R., II; Rye, R.O.

    1993-01-01

    Isotopic studies of fluid inclusions from meteoric water-dominated epithermal ore deposits offer a unique opportunity to study paleoclimates because the fluids can provide direct samples of ancient waters. Fluorite-hosted fluid inclusions from the Eocene (51-50 Ma) epithermal deposits of the Bayhorse mining district, have low salinities and low to moderate homogenization temperatures indicating meteoric origins for the fluids. Oxygen and hydrogen isotope data on inclusion fluids are almost identical to those of modern meteoric waters in the area. The equivalence of the isotope composition of the Eocene inclusion fluids and modern meteoric waters indicates that the Eocene climatic conditions were similar to those today. -from Authors

  14. Evidence for an Early Cretaceous mineralizing event above the basement/sediment unconformity in the intracratonic Paris Basin: paragenetic sequence and Sm-Nd dating of the world-class Pierre-Perthuis stratabound fluorite deposit

    NASA Astrophysics Data System (ADS)

    Gigoux, Morgane; Delpech, Guillaume; Guerrot, Catherine; Pagel, Maurice; Augé, Thierry; Négrel, Philippe; Brigaud, Benjamin

    2015-04-01

    World-class stratabound fluorite deposits are spatially associated with the basement/sediment unconformity of the intracratonic Paris Basin and the Morvan Massif in Burgundy (France). The reserves are estimated to be about 5.5 Mt of fluorite within six fluorite deposits. In this study, we aim to determine the age of the major fluorite mineralization event of the Pierre-Perthuis deposit (1.4 Mt fluorite) by a combined study of the paragenetic mineral sequence and Sm-Nd dating on fluorite crystals. Fluorite occurs as isolated cubes or filling geodes in a Triassic, silicified, dolomitic formation. Three fluorite stages associated with sphalerite, pyrite, galena, barite, and quartz have been distinguished using optical, cathodoluminescence, and scanning electron microscopes. Seven crystals of the geodic fluorite stage were analyzed for their rare earth element (REE) contents and their 147Sm/144Nd and 143Nd/144Nd isotopic compositions. The normalized REE distribution displays homogeneous bell-shaped patterns for all the geodic fluorite samples with a Mid-REE enrichment over the Light-REE and Heavy-REE. The 147Sm/144Nd varies from 0.3108 to 0.5504 and the 143Nd/144Nd from 0.512313 to 0.512518. A six-point Sm-Nd isochron defines an age of 130 ± 15 Ma (initial 143Nd/144Nd = 0.512054, MSWD = 0.21). This Sm-Nd isochron provides the first age for the stratabound fluorite sediment-hosted deposit, related to an unconformity in the Paris Basin, and highlights a major Early Cretaceous fluid circulation event mainly above the basement/sediment unconformity during a flexural deformation of the Paris Basin, which relates to the rifting of the Bay of Biscay and the formation of the Ligurian Sea in the Western Europe domain.

  15. Stable isotope study of fluid inclusions in fluorite from Idaho: Implications for continental climates during the Eocene

    NASA Astrophysics Data System (ADS)

    Seal, Robert R., II; Rye, Robert O.

    1993-03-01

    Isotopic studies of fluid inclusions from meteoric water-dominated epithermal ore deposits offer a unique opportunity to study paleoclimates because the fluids can provide direct samples of ancient waters. The oxygen and hydrogen isotope compositions of meteoric waters vary because of changes in climatic variables such as mean annual temperature of precipitation, relative humidity, origin and history of air masses, and the isotope composition of the oceans. Inclusion fluids found in fluorite (CaF2) are especially useful because their host is devoid of oxygen or hydrogen, thus precluding postentrapment isotope exchange. Fluorite-hosted fluid inclusions from the Eocene (51-50 Ma) epithermal deposits of the Bayhorse mining district, northeastern Idaho, have low salinities, most less than 0.6 equivalent wt% NaCl, and low to moderate homogenization temperatures (98 to 146 °C), indicating meteoric origins for the fluids. Oxygen and hydrogen isotope data on inclusion fluids are almost identical to those of modern meteoric waters in the area. The equivalence of the isotope composition of the Eocene inclusion fluids and modern meteoric waters indicates that the Eocene climatic conditions were similar to those today. This conclusion supports the climate modeling of Sloan and Barron, who suggested that the climates of continental interiors do not reflect the magnitude of warming preserved by the deep-ocean paleoclimate record during the Eocene.

  16. Fluid evolution and mineralogy of Mn-Fe-barite-fluorite mineralizations at the contact of the Thuringian Basin, Thüringer Wald and Thüringer Schiefergebirge in Germany

    NASA Astrophysics Data System (ADS)

    Majzlan, Juraj; Brey-Funke, Maria; Malz, Alexander; Donndorf, Stefan; Milovský, Rastislav

    2016-02-01

    Numerous small deposits and occurrences of Mn-Fe-fluorite-barite mineralization have developed at the contact of the Thuringian Basin, Thüringer Wald and Thüringer Schiefergebirge in central Germany. The studied mineralizations comprise the assemblages siderite+ankerite-calcite-fluorite-barite and hematite-Mn oxides-calcite-barite, with the precipitation sequence in that order within each assemblage. A structural geological analysis places the origin of the barite veins between the Middle Jurassic and Early Cretaceous. Primary fluid inclusions contain water vapour and an aqueous phase with NaCl and CaCl2 as the main solutes, with salinities mostly between 24-27 mass. % CaCl2 eq. Th measurements range between 85 °C and 160 °C in barite, between 139 °C and 163 °C in siderite, and between 80 °C and 130 °C in fluorite and calcite. Stable isotopes (S, O) point to the evaporitic source of sulphur in the observed mineralizations. The S,C,O isotopic compositions suggest that barite and calcite could not have precipitated from the same fluid. The isotopic composition of the fluid that precipitated barite is close to the sea water in the entire Permo-Mesozoic time span whereas calcite is isotopically distinctly heavier, as if the fluids were affected by evaporation. The fluid evolution in the siliciclastic/volcanic Rotliegend sediments (as determined by a number of earlier petrological and geochemical studies) can be correlated with the deposition sequence of the ore minerals. In particular, the bleaching of the sediments by reduced Rotliegend fluids (basinal brines) could be the event that mobilized Fe and Mn. These elements were deposited as siderite+ankerite within the Zechstein carbonate rocks and as hematite+Mn oxides within the oxidizing environment of the Permian volcanic and volcanoclastic rocks. A Middle-Jurassic illitization event delivered Ca, Na, Ba, and Pb from the feldspars into the basinal brines. Of these elements, Ba was deposited as massive barite

  17. EFFECT OF LASER LIGHT ON MATTER. LASER PLASMAS: Optical strength of mirrors on fluorite substrates subjected to cw radiation from a chemical CO laser

    NASA Astrophysics Data System (ADS)

    Dudkin, V. A.; Rukhin, V. B.

    1994-02-01

    Optimisation of the energy characteristics of a chemical CO laser revealed damage to the optical resonator mirrors. Estimates indicated that when the power density of the incident cw laser radiation was 2-2.5 kW cm-2 the induced thermoelastic stresses could reach the damage threshold of mirrors on fluorite substrates.

  18. Transformation of proton-conducting Perovskite-type into fluorite-type fast oxide ion electrolytes using a CO2 capture technique and their electrical properties.

    PubMed

    Trobec, Francesca; Thangadurai, Venkataraman

    2008-10-01

    Fast oxide ion conducting Ce 1- x M x O 2-delta (M = In, Sm; x = 0.1, 0.2) and Ce 0.8Sm 0.05Ca 0.15O 1.825 were prepared from the corresponding perovskite-like structured materials with nominal chemical composition of BaCe 1- x M x O 3-delta and BaCe 0.8Sm 0.05Ca 0.15O 2.825, respectively, by reacting with CO 2 at 800 degrees C for 12 h. Powder X-ray diffraction (PXRD) analysis showed the formation of fluorite-type CeO 2 and BaCO 3 just after reaction with CO 2. The amount of CO 2 gained per ceramic gram was found to be consistent with the Ba content. The CO 2 reacted samples were washed with dilute HCl and water, and the resultant solid product was characterized structurally and electrically employing various solid-state characterization methods, including PXRD, and alternating current (ac) impedance spectroscopy. The lattice constant of presently prepared Ce 1- x M x O 2-delta and Ce 0.8Sm 0.05Ca 0. 15O 1.825 by a CO 2 capture technique follows the expected ionic radii trend. For example, In-doped Ce 0.9In 0.1O 1.95 (In (3+) (VIII) = 0.92 A) sample showed a fluorite-type cell constant of 5.398(1) A, which is lower than the parent CeO 2 (5.411 A, Ce (4+) (VIII) = 0.97 A). Our attempt to prepare single-phase In-doped CeO 2 samples at 800, 1000, and 1500 degrees C using the ceramic method was unsuccessful. However, we were able to prepare single-phase Ce 0.9In 0.1O 1.95 and Ce 0.8In 0.2O 1.9 by the CO 2 capture method from the corresponding barium perovskites. The PXRD studies showed that the In-doped samples are thermodynamically unstable above 800 degrees C. The ac electrical conductivity studies using Pt electrodes showed the presence of bulk, grain-boundary, and electrode contributions over the investigated temperature range in the frequency range of 10 (-2)-10 (7) Hz. The bulk ionic conductivity and activation energy for the electrical conductivity of presently prepared Sm- and (Sm + Ca)-doped CeO 2 samples shows conductivities similar to those of materials

  19. Accelerator-based analytical technique in the evaluation of some Nigeria’s natural minerals: Fluorite, tourmaline and topaz

    NASA Astrophysics Data System (ADS)

    Olabanji, S. O.; Ige, O. A.; Mazzoli, C.; Ceccato, D.; Akintunde, J. A.; De Poli, M.; Moschini, G.

    2005-10-01

    For the first time, the complementary accelerator-based analytical technique of PIXE and electron microprobe analysis (EMPA) were employed for the characterization of some Nigeria's natural minerals namely fluorite, tourmaline and topaz. These minerals occur in different areas in Nigeria. The minerals are mainly used as gemstones and for other scientific and technological applications and therefore are very important. There is need to characterize them to know the quality of these gemstones and update the geochemical data on them geared towards useful applications. PIXE analysis was carried out using the 1.8 MeV collimated proton beam from the 2.5 MV AN 2000 Van de Graaff accelerator at INFN, LNL, Legnaro, Padova, Italy. The novel results which show many elements at different concentrations in these minerals are presented and discussed.

  20. Single crystals of the fluorite nonstoichiometric phase Eu{sub 0.916}{sup 2+}Eu{sub 0.084}{sup 3+}F{sub 2.084} (conductivity, transmission, and hardness)

    SciTech Connect

    Sobolev, B. P. Turkina, T. M.; Sorokin, N. I.; Karimov, D. N.; Komar'kova, O. N.; Sulyanova, E. A.

    2010-07-15

    The nonstoichiometric phase EuF{sub 2+x} has been obtained via the partial reduction of EuF{sub 3} by elementary Si at 900-1100 deg. C. Eu{sub 0.916}{sup 2+}Eu{sub 0.084}{sup 3+}F{sub 2.084} (EuF{sub 2.084}) single crystals have been grown from melt by the Bridgman method in a fluorinating atmosphere. These crystals belong to the CaF{sub 2} structure type (sp. gr. Fm3-barm) with the cubic lattice parameter a = 5.8287(2) A, are transparent in the spectral range of 0.5-11.3 {mu}m, and have microhardness H{sub {mu}} = 3.12 {+-} 0.13 GPa and ionic conductivity {sigma} = 1.4 x 10{sup -5} S/cm at 400 deg. C with the ion transport activation energy E{sub a} = 1.10 {+-} 0.05 eV. The physicochemical characteristics of the fluorite phases in the EuF{sub 2} - EuF{sub 3} systems are similar to those of the phases in the SrF{sub 2} - EuF{sub 3} and SrF{sub 2} - GdF{sub 3} systems due to the similar lattice parameters of the EuF{sub 2} and SrF{sub 2} components. Europium difluoride supplements the list of fluorite components MF{sub 2} (M = Ca, Sr, Ba, Cd, Pb), which are crystal matrices for nonstoichiometric (nanostructured) fluoride materials M{sub 1-x}R{sub x}F{sub 2+x} (R are rare earth elements).

  1. Magnetic interactions in new fluorite-related rare earth oxides LnLn'2RuO7 (Ln, Ln'=rare earths)

    NASA Astrophysics Data System (ADS)

    Hinatsu, Yukio; Doi, Yoshihiro

    2016-07-01

    New fluorite-related quaternary rare earth oxides Pr2YRuO7 and La2TbRuO7 have been prepared. They crystallize in an orthorhombic superstructure of cubic fluorite with space group Cmcm. Through magnetic susceptibility and specific heat measurements, Pr2YRuO7 shows an antiferromagnetic transition at 27 K, which is considerably lowered compared with that for Pr3RuO7. Analysis of the magnetic specific heat indicates that the magnetic behavior observed at 27 K for Pr2YRuO7 is predominantly due to the magnetic interactions between Ru ions, and that the interactions between the Pr3+ and Ru5+ ions are also important. La2TbRuO7 shows magnetic ordering at 9.0 K, which is ascribed to the magnetic ordering between Ru5+ ions from the analysis of the magnetic specific heat data.

  2. Formation and properties of silicon/fluorite heterostructures. Final report, June 1, 1994--May 31, 1997

    SciTech Connect

    Olmstead, M.A.

    1997-10-01

    Our primary goal during the previous support periods was to determine the interrelationship among the structure of the CaF{sub 2}/Si interface, the growth kinetics, the structure and morphology of the overlying film, and the intrinsic dielectric properties of the interface itself. The experiments were designed (i) to determine the CaF{sub 2} overlayer structure and morphology as a function of kinetic conditions [Den93a, Den93b, Won93, Den95, Hes95], (ii) to develop and test models explaining the observed structures [Den95, Hes95], (iii) to investigate the stability of the interface structure [Les97] and (iv) to determine and interpret the photoelectron kinetic energy distributions as a function of the emitting atom location [Rot93, Rot94, Rot96]. As summarized below, we were successful in accomplishing these experiments and in largely fulfilling our original goal.

  3. Crystal structure and optical properties of oxynitride rare-earth tantalates RTa-(O, N) (R = Nd, Gd, Y)

    SciTech Connect

    Kikkawa, Shinichi Takeda, Takashi; Yoshiasa, Akira; Maillard, Pascal; Tessier, Franck

    2008-04-01

    X-ray absorption and photoluminescence were used to investigate the structure of rare-earth tantalum oxynitrides RTa-(O, N) (R = Nd, Gd, Y). Owing to the size of the rare-earth element, the crystal structure tends towards the pyrochlore or defect fluorite-type structure. EXAFS suggested neodymium and yttrium atoms are coordinated either by 6 + 2 or 6 oxygen/nitrogen atoms in the Nd or Y respective oxynitrides although the coordination number of tantalum is six in both compounds. Photoluminescence for 5 at.% doped europium showed the spectra compatible with the point symmetry C{sub 3v} lower than O{sub h} in fluorite and D{sub 3d} in pyrochlore structure type for both the Gd and Y tantalum oxynitrides. These measurements supported that their structure types were basically pyrochlore for Nd and Gd tantalum oxynitrides and defect fluorite for Y tantalum oxynitride but they are highly defective.

  4. Simple thermodynamic model for the specific heat of the fluorite crystals PbF2, CaF2, and SrCl2

    NASA Astrophysics Data System (ADS)

    Bouteiller, Yves

    1992-04-01

    The excess specific heat for SrCl2, PbF2, and CaF2 fluorite crystals has been computed by means of statistical mechanics using a model derived from the Welch and Dienes phenomenological model for phase transitions. The enthalpy is written in a form that partly takes the long-range interactions into consideration. It is shown that the transition temperature is always attained for low defect concentrations, as experimentally found by Schröter and Nöltig. The calculations are in quantitative agreement with available experimental data.

  5. Intervalence charge transfer luminescence: Interplay between anomalous and 5d − 4f emissions in Yb-doped fluorite-type crystals

    SciTech Connect

    Barandiarán, Zoila Seijo, Luis

    2014-12-21

    In this paper, we report the existence of intervalence charge transfer (IVCT) luminescence in Yb-doped fluorite-type crystals associated with Yb{sup 2+}–Yb{sup 3+} mixed valence pairs. By means of embedded cluster, wave function theory ab initio calculations, we show that the widely studied, very broad band, anomalous emission of Yb{sup 2+}-doped CaF{sub 2} and SrF{sub 2}, usually associated with impurity-trapped excitons, is, rather, an IVCT luminescence associated with Yb{sup 2+}–Yb{sup 3+} mixed valence pairs. The IVCT luminescence is very efficiently excited by a two-photon upconversion mechanism where each photon provokes the same strong 4f{sup 14}–1A{sub 1g}→ 4f{sup 13}({sup 2}F{sub 7/2})5de{sub g}–1T{sub 1u} absorption in the Yb{sup 2+} part of the pair: the first one, from the pair ground state; the second one, from an excited state of the pair whose Yb{sup 3+} moiety is in the higher 4f{sup 13}({sup 2}F{sub 5/2}) multiplet. The Yb{sup 2+}–Yb{sup 3+} → Yb{sup 3+}–Yb{sup 2+} IVCT emission consists of an Yb{sup 2+} 5de{sub g} → Yb{sup 3+} 4f{sub 7/2} charge transfer accompanied by a 4f{sub 7/2} → 4f{sub 5/2} deexcitation within the Yb{sup 2+} 4f{sup 13} subshell: [{sup 2}F{sub 5/2}5de{sub g},{sup 2}F{sub 7/2}] → [{sup 2}F{sub 7/2},4f{sup 14}]. The IVCT vertical transition leaves the oxidized and reduced moieties of the pair after electron transfer very far from their equilibrium structures; this explains the unexpectedly large band width of the emission band and its low peak energy, because the large reorganization energies are subtracted from the normal emission. The IVCT energy diagrams resulting from the quantum mechanical calculations explain the different luminescent properties of Yb-doped CaF{sub 2}, SrF{sub 2}, BaF{sub 2}, and SrCl{sub 2}: the presence of IVCT luminescence in Yb-doped CaF{sub 2} and SrF{sub 2}; its coexistence with regular 5d-4f emission in SrF{sub 2}; its absence in BaF{sub 2} and SrCl{sub 2}; the quenching of

  6. Determination of the {sup 22}Ne{sub nucl}/{sup 4}He{sub rad} ratio in natural uranium-rich fluorite by mass spectrometry

    SciTech Connect

    Sole, Jesus; Pi, Teresa

    2006-10-15

    A determination by noble gas mass spectrometry of {sup 22}Ne production through the combined reactions {sup 19}F({alpha},n){sup 22}Na({beta}{sup +}){sup 22}Ne and {sup 19}F({alpha},p){sup 22}Ne on natural calcium fluoride is made for the first time. Six samples of U-rich fluorite from a fluorspar deposit in Mexico were used to determine the {sup 22}Ne{sub nucl}/{sup 4}He{sub rad} ratio generated by the spontaneous decay of U during the last 32 Ma. The obtained ratio (1.33 {+-} 0.11) x10{sup -5} (95% confidence), is compared to other experimental data on natural uranium oxides and theoretical values.

  7. Partitioning of lanthanides and Y between immiscible silicate and fluoride melts, fluorite and cryolite and the origin of the lanthanide tetrad effect in igneous rocks

    NASA Astrophysics Data System (ADS)

    Veksler, Ilya V.; Dorfman, Alexander M.; Kamenetsky, Maya; Dulski, Peter; Dingwell, Donald B.

    2005-06-01

    Some F-rich granitic rocks show anomalous, nonchondritic ratios of Y/Ho, extreme negative Eu anomalies, and unusual, discontinuous, segmented chondrite-normalised plots of rare earth elements (REE). The effects of F-rich fluids have been proposed as one of the explanations for the geochemical anomalies in the evolved granitic systems, as the stability of nonsilicate complexes of individual rare earths may affect the fluid-melt element partitioning. The lanthanide tetrad effect, related to different configurations of 4f-electron subshells of the lanthanide elements, is one of the factors affecting such complexing behaviour. We present the first experimental demonstration of the decoupling of Y and Ho, and the tetrad effect in the partitioning of rare earths between immiscible silicate and fluoride melts. Two types of experiments were performed: dry runs at atmospheric pressure in a high-temperature centrifuge at 1100 to 1200°C, and experiments with the addition of H 2O at 700 to 800°C and 100 MPa in rapid-quench cold-seal pressure vessels. Run products were analysed by electron microprobe (major components), solution-based inductively coupled plasma mass spectrometry (ICP-MS) (REE in the centrifuged runs), and laser ablation ICP-MS (REE and Li in the products of rapid-quench runs). All the dry centrifuge runs were performed at super-liquidus, two-phase conditions. In the experiments with water-bearing mixtures, minor amounts of aqueous vapour were present in addition to the melts. We found that lanthanides and Y concentrated strongly in the fluoride liquids, with two-melt partition coefficients reaching values as high as 100-220 in water-bearing compositions. In all the experimental samples, two-melt partition coefficients of lanthanides show subtle periodicity consistent with the tetrad effect, and the partition coefficient of Y is greater than that of Ho. One of the mixtures also produced abundant fluorite (CaF 2) and cryolite (Na 3AlF 6) crystals, which enabled

  8. Taolin Zn-Pb-fluorite deposit, People's Republic of China: an example of some problems in fluid inclusion research on mineral deposits.

    USGS Publications Warehouse

    Roedder, E.; Howard, K.W.

    1988-01-01

    The ore in this large Zn-Pb-fluorite deposit in NE Hunan Province occurs as open space-filling in a major fault zone between granite and metasedimentary rocks. Following barren, pre-ore quartz, three stages of ore deposition are recognized. Studies on 400 fluid inclusions from all four stages show homogenization T of 120-200oC (av. approx 160o) and salinities of 0-14 wt.% equiv. NaCl (av. 7.7) . These results differ considerably from some previously published sulphur isotopic T (221-344oC), and data for five inclusions that are more saline (9.0-7.7 wt.% equiv. NaCl) and hotter (up to 345oC) (M.A. 85M/2835, 87M/0888).-R.A.H.

  9. High-temperature X-ray diffraction measurements of fluorite-related rare earth antimonates Ln{sub 3}SbO{sub 7} (Ln=Nd, Tb) and their magnetic properties

    SciTech Connect

    Hinatsu, Yukio Doi, Yoshihiro

    2014-09-15

    Ternary rare-earth antimonates Ln{sub 3}SbO{sub 7} (Ln=rare earths) were prepared, and their structures were determined by X-ray diffraction measurements. They crystallize in an orthorhombic superstructure of cubic fluorite (space group Cmcm for Ln=La, Pr; Ccmm for Ln=Sm–Dy), in which Ln{sup 3+} ions occupy two different crystallographic sites (the 8-coordinated and 7-coordinated). For Ln=Nd, two phases with the Cmcm and Ccmm space groups coexist at room temperature. When the temperature was increased, the Nd{sub 3}SbO{sub 7} compound transformed into a single phase with the space group Cmcm. Through magnetic susceptibility measurements, an antiferromagnetic transition was observed at 3.0 K (Ln=Nd) and 7.8 K (Ln=Tb). Analysis of the magnetic specific heat for Tb{sub 3}SbO{sub 7} indicates that the 8-coordinated Tb ions magnetically orders at 7.8 K, and with furthermore decreasing temperature, the 7-coordinated Tb ions shows antiferromagnetic ordering at 3.0 K. - Graphical abstract: Temperature dependence of the specific heat divided by temperature (C{sub p}/T) and the magnetic entropy (S{sub mag}) for Tb{sub 3}SbO{sub 7}. Two-step magnetic transition has been observed. - Highlights: • The phase transition of Nd{sub 3}SbO{sub 7} is from the Ccmm space group to the Cmcm one. • Nd{sub 3}SbO{sub 7} shows an antiferromagnetic transition at 3.0 K. • For Tb{sub 3}SbO{sub 7}, two-step magnetic transition has been observed at 7.8 and 3.0 K.

  10. Phase Transformation of U3O8 and Enhanced Structural Stability at Extreme Conditions

    NASA Astrophysics Data System (ADS)

    Zhang, Fuxiang; Lang, Maik; Ewing, Rodney

    2013-06-01

    A powder sample of β-U3O8 was pressurized at room temperature up to 37.5 GPa with a symmetric diamond anvil cell. XRD patterns clearly indicated that a phase transition occurred between 3-11 GPa. The high-pressure phase is a fluorite-like structure. The fluorite-like structure is stable up to 37.5 GPa. The high-pressure phase was then laser heated to over 1700 K in the diamond anvil cell at high pressure conditions. No phase transition was found at high pressure/ temperature conditions, and the fluorite-like structure of U3O8 is even fully quenchable. The lattice parameter of the fluorite-like high-pressure phase is 5.425 Å at ambient conditions, which is smaller than that of the stoichiometric UO2. Previous experiments have shown that the stoichiometric uranium dioxide (UO2) is not stable at high pressure conditions and starts to transform to a cotunnite structure at ~30 GPa. When heating the sample at high pressure, the critical transtion pressure is greatly reduced. However, the fluorite-like high-pressure phase of U3O8 is very stable at high pressure/high temperature conditions. The enhanced phase stability is believed to be related to the presence of extra oxygen (or U vacancies) in the structure. This work was supported by Materials Science of Actinides, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, under Award No. DE-SC0001089.

  11. Brine history indicated by argon, krypton, chlorine, bromine, and iodine analyses of fluid inclusions from the Mississippi Valley type lead-fluorite-barite deposits at Hansonburg, New Mexico

    USGS Publications Warehouse

    Böhlke, J.K.; Irwin, J.J.

    1992-01-01

    Argon, krypton, chlorine, bromine, and iodine were measured in a homogeneous population of high-salinity hydrothermal fluid inclusions from the Tertiary-age Mississippi Valley-type (MVT) lead-fluorite-barite deposits at Hansonburg, New Mexico to establish new types of evidence for the history of both the fluid and the major dissolved salts. Noble gases and halogens in fluid inclusions containing 10-10-10-9 L of brine (Cl = 3 molal) were analyzed by laser microprobe noble-gas mass spectrometry (lmngms) on neutron-irradiated samples. The concentrations of 36Ar (4.7 ?? 10-8 molal) and 84Kr 1.8 ?? 10-9 molal) in the fluid inclusions are equal to those of fresh surface waters in equilibrium with air at approximately 20 ?? 5??. The mole ratios of Br Cl (1.2 ?? 10-4) and I Cl (1-2 ?? 10-6) are among the lowest measured in any natural waters, similar to those of modern brines formed by dissolution of Permian NaCl-bearing evaporites in southeast New Mexico. 40Ar 36Ar ratios (600) are twice that of air, and indicate that the fluid inclusions had excess radiogenic 40Ar (1.4 ?? 10-5 molal) when trapped. The amount of excess 40Ar appears to be too large to have been acquired with Cl by congruent dissolution of halite-bearing evaporites, and possibly too small to have been acquired with Pb by congruent dissolution of granitic basement rocks with Proterozoic KAr ages. From the lmngms data, combined with published Pb and S isotope data, we infer the following sequence of events in the history of the Hansonburg MVT hydrothermal brine: (1) the brine originated as relatively dilute meteoric water, and it did not gain or lose atmospheric Ar or Kr after recharge; (2) the originally dilute fluid acquired the bulk of its Cl and sulfate in the subsurface after recharge by dissolving halite-bearing Permian? marine evaporites; (3) the high salinity brine then acquired most of its Pb and excess radiogenic 40Ar from interactions with aquifer rocks other than evaporites, possibly clastic

  12. An APD for the efficient detection of the fast scintillation component of BaF2

    NASA Astrophysics Data System (ADS)

    Hitlin, D. G.; Kim, J. H.; Trevor, J.; Hoenk, M.; Hennessy, J.; Jewell, A.; Farrell, R.; McClish, M.

    2016-07-01

    Barium fluoride crystals are the baseline choice for the calorimeter of the Mu2e experiment at Fermilab. By the fast (decay time 0.9 ns) 220 nm scintillation component and discriminating against the larger slow (decay time 630 ns) 300 nm component, it is possible to build a radiation-hard calorimeter with good energy and time resolution and high rate capability. This requires a solid state photosensor with high quantum efficiency at 220 nm, discrimination against the 300 nm component and good rise and decay times. Progress on the development of such a sensor is presented.

  13. New cubic structure compounds as actinide host phases

    NASA Astrophysics Data System (ADS)

    Stefanovsky, S. V.; Yudintsev, S. V.; Livshits, T. S.

    2010-03-01

    Various compounds with fluorite (cubic zirconia) and fluorite-derived (pyrochlore, zirconolite) structures are considered as promising actinide host phases at immobilization of actinide-bearing nuclear wastes. Recently some new cubic compounds — stannate and stannate-zirconate pyrochlores, murataite and related phases, and actinide-bearing garnet structure compounds were proposed as perspective matrices for complex actinide wastes. Zirconate pyrochlore (ideally Gd2Zr2O7) has excellent radiation resistance and high chemical durability but requires high temperatures (at least 1500 °C) to be produced by hot-pressing from sol-gel derived precursor. Partial Sn4+ substitution for Zr4+ reduces production temperature and the compounds REE2ZrSnO7 may be hot-pressed or cold pressed and sintered at ~1400 °C. Pyrochlore, A2B2O7-x (two-fold elementary fluorite unit cell), and murataite, A3B6C2O20-y (three-fold fluorite unit cell), are end-members of the polysomatic series consisting of the phases whose structures are built from alternating pyrochlore and murataite blocks (nano-sized modules) with seven- (2C/3C/2C), five- (2C/3C), eight- (3C/2C/3C) and three-fold (3C — murataite) fluorite unit cells. Actinide content in this series reduces in the row: 2C (pyrochlore) > 7C > 5C > 8C > 3C (murataite). Due to congruent melting murataite-based ceramics may be produced by melting and the firstly segregated phase at melt crystallization is that with the highest fraction of the pyrochlore modules in its structure. The melts containing up to 10 wt. % AnO2 (An = Th, U, Np, Pu) or REE/An fraction of HLW form at crystallization zoned grains composed sequentially of the 5C → 8C → 3C phases with the highest actinide concentration in the core and the lowest — in the rim of the grains. Radiation resistance of the "murataite" is comparable to titanate pyrochlores. One more promising actinide hosts are ferrites with garnet structure. The matrices containing sometime complex fluorite

  14. Fluorite-like phases in the BaF{sub 2}-BiF{sub 3}-Bi{sub 2}O{sub 3} system-synthesis, conductivity and defect clustering

    SciTech Connect

    Serov, T.V.; Dombrovski, E.N.; Ardashnikova, E.I. . E-mail: ard@inorg.chem.msu.ru; Dolgikh, V.A.; El Omari, Malika; El Omari, Mohamed; Abaouz, A.; Senegas, J.; Chaban, N.G.; Abakumov, A.M.; Van Tendeloo, G.

    2005-05-18

    A fluorite-like solid solution Ba{sub 1-x}Bi {sub x}O {sub z}F{sub 2+x-2z} on the basis of cubic BaF{sub 2} was synthesised in the BaF{sub 2}-Bi{sub 2}O{sub 3}-BiF{sub 3} system and the homogeneity range at 873 K was determined. The samples were studied by X-ray powder diffraction and electron diffraction, and their transport properties were measured by the complex impedance method at 300-623 K. Tendencies of variation of lattice parameters and transport properties were determined. These tendencies are discussed on the basis of a defect clustering hypothesis. Thermal treatment at 573 K of the solid solution, quenched from 873 K results in the formation of a new ordered tetragonal fluorite-like phase with lattice parameters a = 9.5355(4) A, c = 18.151(1) A.

  15. Effect of clustering on the space-charge relaxation phenomena in fluorite-type solid solutions Sr1-xDyxF2+x and Sr1-xErxF2+x

    NASA Astrophysics Data System (ADS)

    Meuldijk, J.; Kiers, G.; den Hartog, H. W.

    1983-11-01

    In this paper we present the results of ionic thermocurrent (ITC) and dielectric loss experiments on two systems of solid solutions: Sr1-xDyxF2+x and Sr1-xErxF2+x. The materials investigated have the fluorite structure, and the value of x has been varied in the range 0<=x<=0.4. In contrast with results published in earlier papers on solid solutions Sr1-xLaxF2+x, we find, for the above-mentioned materials, that clustering plays an important role. It appears that clustering becomes more and more important with decreasing ionic radius of the trivalent lanthanide. We have observed that for Yb-, Er-, and Dy-doped crystals the concentration of next-nearest-neighbor (NNN) dipoles decreases for RF3 concentrations higher than 0.4, 0.6, and 1.0 mol%, respectively. The ITC peak associated with space-charge relaxation shows a complicated behavior as a function of the RF3 concentration (R=Dy or Er). For low concentrations the space-charge relaxation peak shifts to lower temperatures with increasing concentration until a minimum value for the temperature is reached. For Sr1-xErxF2+x and Sr1-xDyxF2+x the concentrations for which this minimum occurs are 0.6 and 1.0 mol%, respectively; i.e., the same concentrations as those mentioned above, where the NNN dipole concentration has its maximum value. The position of the high-temperature (HT) band turns out to be related to the concentration of dipoles in the low-concentration range. In heavily doped materials the position of the HT band probably depends upon the number of clusters present. It will be concluded that clustering is very complex and that it is not possible to draw unambiguous conclusions from our experimental results concerning the defect structure of heavily doped materials. In spite of this we have presented a few possible descriptions which may be applicable.

  16. Nanostructured crystals of Sr{sub 1-x}R{sub x}F{sub 2+x} fluorite phases and their ordering: 6. Microindentation analysis of crystals

    SciTech Connect

    Gryaznov, M. Yu. Shotin, S. V.; Chuvil'deev, V. N.; Marychev, M. O.; Sul'yanova, E. A.; Sul'yanov, S. N.; Sobolev, B. P.

    2012-01-15

    Hardness, crack resistance, brittleness, and effective fracture energy have been studied for crystals of 24 fluorite phases Sr{sub 1-x}R{sub x}F{sub 2+x} (R are 14 rare earth elements (REEs); 0 < x {<=} 0.5) and SrF2 grown by the Bridgman method from a melt. These characteristics change nonlinearly with an increase in the REE content for Sr{sub 1-x}R{sub x}F{sub 2+x} (0 < x {<=} 0.5) with R = La, Nd, Sm, Gd, and Lu; it is maximum in the range x < 0.1 for all REEs. The changes in a number of REEs have been traced for an isoconcentration series of Sr{sub 0.90}R{sub 0.10}F{sub 2.10} crystals (R = La, Nd, Sm, Gd, Ho, Er-Lu, or Y) and crystals (similar in composition) with R = Tb and Dy. The hardness of Sr{sub 1-x}R{sub x}F{sub 2+x} crystals is higher by a factor of {approx}2-3 than that of SrF2. The effect of decrease in microstresses in SrF{sub 2} crystals is confirmed by the isomorphic introduction of R{sup 3+} ions into this crystalline matrix.

  17. Investigation of material property influenced stoichiometric deviations as evidenced during UV laser-assisted atom probe tomography in fluorite oxides

    NASA Astrophysics Data System (ADS)

    Valderrama, Billy; Henderson, Hunter B.; Yablinsky, Clarissa A.; Gan, Jian; Allen, Todd R.; Manuel, Michele V.

    2015-09-01

    Oxide materials are used in numerous applications such as thermal barrier coatings, nuclear fuels, and electrical conductors and sensors, all applications where nanometer-scale stoichiometric changes can affect functional properties. Atom probe tomography can be used to characterize the precise chemical distribution of individual species and spatially quantify the oxygen to metal ratio at the nanometer scale. However, atom probe analysis of oxides can be accompanied by measurement artifacts caused by laser-material interactions. In this investigation, two technologically relevant oxide materials with the same crystal structure and an anion to cation ratio of 2.00, pure cerium oxide (CeO2) and uranium oxide (UO2) are studied. It was determined that electronic structure, optical properties, heat transfer properties, and oxide stability strongly affect their evaporation behavior, thus altering their measured stoichiometry, with thermal conductance and thermodynamic stability being strong factors.

  18. Epitaxial crystals of Bi₂Pt₂O₇ pyrochlore through the transformation of δ–Bi₂O₃ fluorite

    SciTech Connect

    Gutiérrez–Llorente, Araceli; Joress, Howie; Woll, Arthur; Holtz, Megan E.; Ward, Matthew J.; Sullivan, Matthew C.; Muller, David A.; Brock, Joel D.

    2015-03-01

    Bi₂Pt₂O₇ pyrochlore is thought to be one of the most promising oxide catalysts for application in fuel cell technology. Unfortunately, direct film growth of Bi₂Pt₂O₇ has not yet been achieved, owing to the difficulty of oxidizing platinum metal in the precursor material to Pt⁴⁺. In this work, in order to induce oxidation of the platinum, we annealed pulsed laser deposited films consisting of epitaxial δ–Bi₂O₃ and co-deposited, comparatively disordered platinum. We present synchrotron x-ray diffraction results that show the nonuniform annealed films contain the first epitaxial crystals of Bi₂Pt₂O₇. We also visualized the pyrochlore structure by scanning transmission electron microscopy, and observed ordered cation vacancies in the epitaxial crystals formed in a bismuth-rich film but not in those formed in a platinum-rich film. The similarity between the δ–Bi₂O₃ and Bi₂Pt₂O₇ structures appears to facilitate the pyrochlore formation. These results provide the only route to date for the formation of epitaxial Bi₂Pt₂O₇.

  19. Epitaxial crystals of Bi₂Pt₂O₇ pyrochlore through the transformation of δ–Bi₂O₃ fluorite

    DOE PAGESBeta

    Gutiérrez–Llorente, Araceli; Joress, Howie; Woll, Arthur; Holtz, Megan E.; Ward, Matthew J.; Sullivan, Matthew C.; Muller, David A.; Brock, Joel D.

    2015-03-01

    Bi₂Pt₂O₇ pyrochlore is thought to be one of the most promising oxide catalysts for application in fuel cell technology. Unfortunately, direct film growth of Bi₂Pt₂O₇ has not yet been achieved, owing to the difficulty of oxidizing platinum metal in the precursor material to Pt⁴⁺. In this work, in order to induce oxidation of the platinum, we annealed pulsed laser deposited films consisting of epitaxial δ–Bi₂O₃ and co-deposited, comparatively disordered platinum. We present synchrotron x-ray diffraction results that show the nonuniform annealed films contain the first epitaxial crystals of Bi₂Pt₂O₇. We also visualized the pyrochlore structure by scanning transmission electron microscopy,more » and observed ordered cation vacancies in the epitaxial crystals formed in a bismuth-rich film but not in those formed in a platinum-rich film. The similarity between the δ–Bi₂O₃ and Bi₂Pt₂O₇ structures appears to facilitate the pyrochlore formation. These results provide the only route to date for the formation of epitaxial Bi₂Pt₂O₇.« less

  20. Some electronic and magnetic properties of Fluoride ion in Fluoride structure nanocrystals

    NASA Astrophysics Data System (ADS)

    Imtani, Ali Nasir

    2012-01-01

    We have investigated the effects of the environment potential around Fluoride ion on some important electronic and magnetic properties such as dipole polarisability, moment of oscillator strengths S(k) and magnetic susceptibility. The theoretical procedure is based on the variational-perturbation theory with two parameter trial functions incorporated in an ionic model. We estimate these properties in four cases for Fluoride ion; free ion, ion under different potentials, ion in the crystals and ion in nanocrystal, CdF2, CaF2, PbF2, SrF2 and BaF2. Our results indicate that these properties vary with ion environments and the free state of Fluoride ion has higher values and there is linearity behaviour of these properties with lattice constant. For Fluoride ion in nanocrystal, we have found that there is an extra parameter that can also affect the dipole polarisability, the number of ions in the structure.

  1. Structural investigation of self-irradiation damaged AmO2

    NASA Astrophysics Data System (ADS)

    Prieur, Damien; Vigier, Jean-François; Wiss, Thierry; Janssen, Arne; Rothe, Jörg; Cambriani, Andrea; Somers, Joseph

    2014-04-01

    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.

  2. The Li–Si–(O)–N system revisited: Structural characterization of Li{sub 21}Si{sub 3}N{sub 11} and Li{sub 7}SiN{sub 3}O

    SciTech Connect

    Casas-Cabanas, M.; Santner, H.; Palacín, M.R.

    2014-05-01

    A systematic study of the Li–Si–(O)–N system is presented. The synthetic conditions to prepare Li{sub 2}SiN{sub 2}, Li{sub 5}SiN{sub 3}, Li{sub 18}Si{sub 3}N{sub 10}, Li{sub 21}Si{sub 3}N{sub 11} and Li{sub 7}SiN{sub 3}O are described and the structure of the last two compounds has been solved for the first time. While Li{sub 21}Si{sub 3}N{sub 11} crystallizes as a superstructure of the anti-fluorite structure with Li and Si ordering, Li{sub 7}SiN{sub 3}O exhibits the anti-fluorite structure with both anion and cation disorder. - Graphical abstract: A systematic study of the Li–Si–(O)–N system is presented. Li{sub 21}Si{sub 3}N{sub 11} crystallizes as a superstructure of the anti-fluorite structure with Li and Si ordering, Li{sub 7}SiN{sub 3}O exhibits the anti-fluorite structure with both anion and cation disorder. - Highlights: • Li{sub 2}SiN{sub 2}, Li{sub 5}SiN{sub 3}, Li{sub 18}Si{sub 3}N{sub 10}, Li{sub 21}Si{sub 3}N{sub 11} and Li{sub 7}SiN{sub 3}O are prepared. • The structures of Li{sub 21}Si{sub 3}N{sub 11} and Li{sub 7}SiN{sub 3}O are presented. • Li{sub 21}Si{sub 3}N{sub 11} exhibits an anti-fluorite superstructure with Li and Si ordering.

  3. Generalized adsorption isotherms for molecular and dissociative adsorption of a polar molecular species on two polar surface geometries: Perovskite (100) (Pm-3m) and fluorite (111) (Fm-3m)

    DOE PAGESBeta

    Danielson, Thomas; Hin, Celine; Savara, Aditya

    2016-08-10

    Lattice based kinetic Monte Carlo (KMC) simulations have been used to determine a functional form for the second order adsorption isotherms on two commonly investigated crystal surfaces: the (111) fluorite surface and the (100) perovskite surface which has the same geometric symmetry as the NaCl (100) surface. The functional form is generalized to be applicable to all values of the equilibrium constant by a shift along the pressure axis. Functions have been determined for estimating the pressure at which a desired coverage would be achieved and for estimating the coverage at a certain pressure. The generalized form has been calculatedmore » by investigating the surface adsorbate coverage across a range of thermodynamic equilibrium constants that span the range 10-26 to 1013. Finally, the equations have been shown to be general for any value of the adsorption equilibrium constant.« less

  4. Generalized adsorption isotherms for molecular and dissociative adsorption of a polar molecular species on two polar surface geometries: Perovskite (100) (Pm-3m) and fluorite (111) (Fm-3m)

    NASA Astrophysics Data System (ADS)

    Danielson, Thomas; Hin, Celine; Savara, Aditya

    2016-08-01

    Lattice based kinetic Monte Carlo simulations have been used to determine a functional form for the second order adsorption isotherms on two commonly investigated crystal surfaces: the (111) fluorite surface and the (100) perovskite surface which has the same geometric symmetry as the NaCl (100) surface. The functional form is generalized to be applicable to all values of the equilibrium constant by a shift along the pressure axis. Functions have been determined for estimating the pressure at which a desired coverage would be achieved and, conversely, for estimating the coverage at a certain pressure. The generalized form has been calculated by investigating the surface adsorbate coverage across a range of thermodynamic equilibrium constants that span the range 10-26 to 1013. The equations have been shown to be general for any value of the adsorption equilibrium constant.

  5. An overview of DANCE: a 4II BaF[2] detector for neutron capture measurements at LANSCE.

    SciTech Connect

    Ullmann, J. L.

    2004-01-01

    The Detector for Advanced Neutron Capture experiments (DANCE) is a 162-element, 4{pi} BaF{sub 2} array designed to make neutron capture cross-section measurements on rare or radioactive targets with masses as little as 1 mg. Accurate capture cross sections are needed in many research areas, including stellar nucleosynthesis, advanced nuclear fuel cycles, waste transmutation, and other applied programs. These cross sections are difficult to calculate accurately and must be measured. Up to now, except for a few long-lived nuclides there are essentially no differential capture measurements on radioactive nuclei. The DANCE array is located at the Lujan Neutron Scattering Center at LANSCE, which is a continuous-spectrum neutron source with useable energies from below thermal to about 100 keV. Data acquisition is done with 320 fast waveform digitizers. The design and initial performance results, including background minimization, will be discussed.

  6. 10.1142/9789813109636_fmatter + BaF2 Reaction Studied by TALYS1.4 Toolkit

    NASA Astrophysics Data System (ADS)

    Lü, Cui-Juan; Ma, Chun-Wang

    The neutron induced reactions on the 138Ba and 19F nuclei are investigated by using the optical model implanted in the Talys1.4 toolkit. The results of the n + 138Ba and n + 19F reactions within the incident energy ranging from 1 keV to 30MeV are calculated and compared to the measured results.

  7. Crystal structure of the Fe-member of usovite.

    PubMed

    Weil, Matthias

    2015-06-01

    Crystals of the title compound, with the idealized composition Ba2CaFeAl2F14, dibarium calcium iron(II) dialuminium tetra-deca-fluoride, were obtained serendipitously by reacting a mixture of the binary fluorides BaF2, CaF2 and AlF3 in a leaky steel reactor. The compound crystallizes in the usovite structure type (Ba2CaMgAl2F14), with Fe(2+) cations replacing the Mg(2+) cations. The principal building units are distorted [CaF8] square-anti-prisms (point group symmetry 2), [FeF6] octa-hedra (point group symmetry -1) and [AlF6] octa-hedra that are condensed into undulating (2) ∞[CaFeAl2F14](4-) layers parallel (100). The Ba(2+) cations separate the layers and exhibit a coordination number of 12. Two crystal structure models with a different treatment of the disordered Fe site [mixed Fe/Ca occupation, model (I), versus underoccupation of Fe, model (II)], are discussed, leading to different refined formulae Ba2Ca1.310 (15)Fe0.690 (15)Al2F14 [model (I)] and Ba2CaFe0.90 (1)Al2F14 [model (II)]. PMID:26090139

  8. Crystal structure of the Fe-member of usovite

    PubMed Central

    Weil, Matthias

    2015-01-01

    Crystals of the title compound, with the idealized composition Ba2CaFeAl2F14, dibarium calcium iron(II) dialuminium tetra­deca­fluoride, were obtained serendipitously by reacting a mixture of the binary fluorides BaF2, CaF2 and AlF3 in a leaky steel reactor. The compound crystallizes in the usovite structure type (Ba2CaMgAl2F14), with Fe2+ cations replacing the Mg2+ cations. The principal building units are distorted [CaF8] square-anti­prisms (point group symmetry 2), [FeF6] octa­hedra (point group symmetry -1) and [AlF6] octa­hedra that are condensed into undulating 2 ∞[CaFeAl2F14]4− layers parallel (100). The Ba2+ cations separate the layers and exhibit a coordination number of 12. Two crystal structure models with a different treatment of the disordered Fe site [mixed Fe/Ca occupation, model (I), versus underoccupation of Fe, model (II)], are discussed, leading to different refined formulae Ba2Ca1.310 (15)Fe0.690 (15)Al2F14 [model (I)] and Ba2CaFe0.90 (1)Al2F14 [model (II)]. PMID:26090139

  9. Structural investigation of self-irradiation damaged AmO{sub 2}

    SciTech Connect

    Prieur, Damien; Vigier, Jean-François; Wiss, Thierry; Janssen, Arne; Rothe, Jörg; Cambriani, Andrea; Somers, Joseph

    2014-04-01

    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 AmO{sub 2}. 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. - Graphical abstract: The structure of damaged AmO2 (36 dpa) has been studied by XRD, XAS and TEM. Thus, the effects of the self-irradiation on the oxidation state, the lattice distances, the structural disorder, the radiation stability and the microstructure have been discussed. - Highlights: • The structure of highly self-irradiated AmO{sub 2} (36 dpa) was studied by XAS and TEM. • XRD, EXAFS and TEM confirm the high stability of the fluorite structure. • XRD and EXAFS show an increase of 0.3% of the structural distances. • XANES shows that Am is tetravalent as well as the Np recoil nucleus. • The presence of He bubbles was evidenced by TEM.

  10. High temperature crystal structures and superionic properties of SrCl{sub 2}, SrBr{sub 2}, BaCl{sub 2} and BaBr{sub 2}

    SciTech Connect

    Hull, Stephen; Norberg, Stefan T.; Ahmed, Istaq; Eriksson, Sten G.; Mohn, Chris E.

    2011-11-15

    The structural properties of the binary alkaline-earth halides SrCl{sub 2}, SrBr{sub 2}, BaCl{sub 2} and BaBr{sub 2} have been investigated from ambient temperature up to close to their melting points, using the neutron powder diffraction technique. Fluorite-structured SrCl{sub 2} undergoes a gradual transition to a superionic phase at 900-1100 K, characterised by an increasing concentration of anion Frenkel defects. At a temperature of 920(3) K, the tetragonal phase of SrBr{sub 2} undergoes a first-order transition to a cubic fluorite phase. This high temperature phase shows the presence of extensive disorder within the anion sublattice, which differs from that found in superionic SrCl{sub 2}. BaCl{sub 2} and BaBr{sub 2} both adopt the cotunnite crystal structure under ambient conditions. BaCl{sub 2} undergoes a first-order structural transition at 917(5) K to a disordered fluorite-structured phase. The relationship between the (disordered) crystal structures and the ionic conductivity behaviour is discussed and the influence of the size of the mobile anion on the superionic behaviour is explored. - Graphical abstract: Anomalous behaviour of the lattice expansion of SrCl{sub 2} at temperatures of {approx}1000 K is associated with the gradual transition to a superionic phase, whilst SrBr{sub 2} undergoes a first-order structural transition ({beta}{yields}{alpha}) to a fluorite-structured superionic phase at 920(3) K. Highlights: > Anomalous behaviour of the lattice expansion of SrCl{sub 2} occurs at temperatures {approx}1000 K. > Crystal structure of {beta}-SrBr{sub 2} is described in detail. > On heating, SrBr{sub 2} and BaCl{sub 2} transform to a fluorite-structured superionic phase. > Temperature dependence of the BaCl{sub 2} and BaBr{sub 2} structures is presented. > Nature of the superionic phases within the alkaline-earth halides is discussed.

  11. Interplay of structural, optical and magnetic properties in Gd doped CeO{sub 2}

    SciTech Connect

    Soni, S.; Dalela, S.; Kumar, Sudish; Meena, R. S.; Vats, V. S.

    2015-06-24

    In this research wok systematic investigation on the synthesis, characterization, optical and magnetic properties of Ce{sub 1-x}Gd{sub x}O{sub 2} (where x=0.02, 0.04, 0.06, and 0.10) synthesized using the Solid-state method. Structural, Optical and Magnetic properties of the samples were investigated by X-ray diffraction (XRD), UV-VIS-NIR spectroscopy and VSM. Fluorite structure is confirmed from the XRD measurement on Gd doped CeO{sub 2} samples. Magnetic studies showed that the Gd doped polycrystalline samples display room temperature ferromagnetism and the ferromagnetic ordering strengthens with the Gd concentration.

  12. Structural and dielectric properties of Cu doped CeO2

    NASA Astrophysics Data System (ADS)

    Kumar, Pawan; Chand, F.; Kumar, Parmod; Meena, R. C.; Kumar, Ashish; Asokan, K.

    2016-05-01

    In the present work, we report the structural and dielectric properties of Cu doped CeO2 compounds synthesized by solid state reaction method. X-ray diffraction study confirms the formation of cubic phase with Fm-3m space group corresponding to fluorite CeO2 structure. The crystallite size was found to decrease with Cu concentration. Furthermore, the dielectric measurements were carried out by varying frequency in the temperature range of 120 to 380 K. It has been found that the increase in Cu concentration in the host lattice leads to an enhancement in dielectric constant.

  13. Hydrothermally synthesized barium fluoride nanocubes for thermoluminescence dosimetry

    NASA Astrophysics Data System (ADS)

    Bhadane, Mahesh S.; Dahiwale, S. S.; Bhoraskar, V. N.; Dhole, S. D.

    2016-05-01

    In this work, we report a hydrothermally synthesized Dy doped BaF2 (BaF2:Dy) nanocubes and its Thermoluminescence studies. The synthesized BaF2:Dy samples was found to posses FCC structure and having average size ~ 60-70 nm, as revealed through X-Ray Diffraction. Cubical morphology having size ~90 nm was observed from TEM analysis. The 60Co γ- ray irradiated BaF2:Dy TL dosimetric experiments shows a pre-dominant single glow peak at 153 °C, indicating a single level trap present as a metastable state. Furthermore, BaF2:Dy nanophosphor shows a sharp linear response from 10 Gy to 3 kGy, thus it can be applicable as a gamma dosimeter.

  14. Alpha self-irradiation effect on the local structure of the U{sub 0.85}Am{sub 0.15}O{sub 2{+-}x} solid solution

    SciTech Connect

    Prieur, D.; Martin, P.M.; Scheinost, A.C.; Dehaudt, P.

    2012-10-15

    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, both 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

  15. Magnetic and structural properties of Mn-doped Bi2Se3 topological insulators

    NASA Astrophysics Data System (ADS)

    Tarasenko, R.; Vališka, M.; Vondráček, M.; Horáková, K.; Tkáč, V.; Carva, K.; Baláž, P.; Holý, V.; Springholz, G.; Sechovský, V.; Honolka, J.

    2016-01-01

    A thorough investigation is presented of the magnetic and structural properties of Mn-doped Bi2Se3 topological insulators grown by molecular beam epitaxy on top of insulating BaF2 (111) substrates. The magnetic properties have been studied in the temperature range from 2 K to 300 K in magnetic fields up to 7 T. The systems were further characterized by means of high-resolution X-ray diffraction, electron-microprobe analysis, and X-ray photoemission spectroscopy. Samples with the atomic concentration of Mn up to about 0.06 exhibit an almost perfect crystalline structure while, for higher Mn concentrations, diffuse scattering from defects is observed. Photoemission results suggest a localized non-metallic Mn 3d5 ground state which is weakly or intermediately coupled to the Bi2Se3 environment. The exchange interaction between the Mn moments leads to a ferromagnetic phase at low temperatures with a roughly linear relation between the Curie temperature and the atomic concentration of Mn.

  16. First-principles study of structural properties of alkaline earth metals methanides A2C(A = Be,Mg)

    NASA Astrophysics Data System (ADS)

    Paliwal, U.; Trivedi, D. K.; Galav, K. L.; Joshi, K. B.

    2013-06-01

    The structural properties of alkaline earth binary carbides A2C(A = Be,Mg) are evaluated using first-principles periodic linear combination of atomie orbitals method based on density functional theory implemented in the CRYSTAL06 code. The total energy is computed for the two binary carbides considering the anti-Fluorite structure. The computed total energy is coupled with the Murnaghan equation of states to report the equilibrium lattice constant and bulk modulus of the compounds. The cohesive energy and density are also reported for the two compounds.

  17. Structuralism.

    ERIC Educational Resources Information Center

    Piaget, Jean

    Provided is an overview of the analytical method known as structuralism. The first chapter discusses the three key components of the concept of a structure: the view of a system as a whole instead of so many parts; the study of the transformations in the system; and the fact that these transformations never lead beyond the system but always…

  18. The Crystal Structure of Thorium and Zirconium Dihydrides by X-ray and Neutron Diffraction

    DOE R&D Accomplishments Database

    Rundle, R.E.; Shull, C.G.; Wollan, E.O.

    1951-04-20

    Thorium forms a tetragonal lower hydride of composition ThH{sub 2}. The hydrides ThH{sub 2}, ThD{sub 2}, and ZrD{sub 2} have been studied by neutron diffraction in order that hydrogen positions could be determined. The hydrides are isomorphous, and have a deformed fluorite structure. Metal-hydrogen distances in thorium hydride are unusually large, as in UH{sub 3}. Thorium and zirconium scattering amplitudes and a revised scattering amplitude for deuterium are reported.

  19. Growth, structure and optical properties of nonlinear optical crystal BaZnBO3F

    NASA Astrophysics Data System (ADS)

    Xia, Mingjun; Li, R. K.

    2016-01-01

    Nonlinear optical (NLO) crystal BaZnBO3F (BZBF) with the size of about 20×20×0.5 mm3 is obtained from BaF2-NaF flux, and single crystal X-ray diffraction reveals that it belongs to space group P 6 ̅ with cell parameters of a=5.1045(6) Å, c=4.3116(10) Å and Z=1. In the structure of BZBF, the BO3 planar triangles are interconnected through O atoms from ZnO3F2 trigonal bipyramid to form (Zn3B3O6F6) twelve-membered rings (12-MRs), then the layers which are built with condensation from 12-MRs at ab plane, are further linked by the apical F from ZnO3F2 to form three dimensional framework along the c direction. The title crystal exhibits high transmittance in the range of 300-3000 nm with a UV transmission cutoff at 223 nm according to transmission spectra. Powder SHG tests indicate that the effective NLO coefficient of BZBF crystal is about 2.8 times that of KH2PO4 (KDP) crystal due to perfect alignment of the BO3 groups.

  20. Theoretical study of the properties of PtN with pyrite and marcasite structures

    NASA Astrophysics Data System (ADS)

    Zhu, Y.; Fan, C. Z.; Zhang, X. Y.; Zhang, S. H.; Li, L. X.; Zhang, S. L.; Jin, H. Y.; Liu, R. P.

    2009-07-01

    Pyrite and marcasite structures are both potential structures of platinum nitride. The mechanical properties of these two structures are similar, so we further investigate the thermodynamic properties of platinum nitride under high pressure and high temperature by the quasi-harmonic Debye model, in which phonon effects are considered. In the paper the important thermodynamic parameters, Debye temperature and heat capacity, have been investigated. The results show that the melting point is higher and the interatomic force is stronger in the pyrite structure than in the marcasite and fluorite structures. In addition, the marcasite structure has a much higher value of CV at the same T and P, and the change in CV is much sharper than that of the pyrite structure at low temperatures. Moreover, we notice that pressure has less influence on CV.

  1. A Hydrothermal System Associated with the Siljan Impact Structure, Sweden-Implications for the Search for Fossil Life on Mars

    NASA Astrophysics Data System (ADS)

    Hode, Tomas; von Dalwigk, Ilka; Broman, Curt

    2003-06-01

    The Siljan ring structure (368 +/- 1.1 Ma) is the largest known impact structure in Europe. It is a 65-km-wide, eroded, complex impact structure, displaying several structural units, including a central uplifted region surrounded by a ring-shaped depression. Associated with the impact crater are traces of a post-impact hydrothermal system indicated by precipitated and altered hydrothermal mineral assemblages. Precipitated hydrothermal minerals include quartz veins and breccia fillings associated with granitic rocks at the outer margin of the central uplift, and calcite, fluorite, galena, and sphalerite veins associated with Paleozoic carbonate rocks located outside the central uplift. Two-phase water/gas and oil/gas inclusions in calcite and fluorite display homogenization temperatures between 75°C and 137°C. With an estimated erosional unloading of ~1 km, the formation temperatures were probably not more than 10-15°C higher. Fluid inclusion ice-melting temperatures indicate a very low salt content, reducing the probability that the mineralization was precipitated during the Caledonian Orogeny. Our findings suggest that large impacts induce low-temperature hydrothermal systems that may be habitats for thermophilic organisms. Large impact structures on Mars may therefore be suitable targets in the search for fossil thermophilic organisms.

  2. Scheelite and coexisting F-rich zoned garnet, vesuvianite, fluorite, and apatite in calc-silicate rocks from the Mogok metamorphic belt, Myanmar: Implications for metasomatism in marble and the role of halogens in W mobilization and mineralization

    NASA Astrophysics Data System (ADS)

    Guo, Shun; Chen, Yi; Liu, Chuan-Zhou; Wang, Jian-Gang; Su, Bin; Gao, Yi-Jie; Wu, Fu-Yuan; Sein, Kyaing; Yang, Yue-Heng; Mao, Qian

    2016-03-01

    to a significant enrichment of F (up to 1.2 wt.%) and OH (up to 0.32 for nOH) and a negative correlation between F and Si in the garnet. Detailed petrographic observations show that the occurrence of scheelite in the MMB calc-silicate rocks is always associated with the growth of F-rich minerals such as garnet rims (0.8-1.2 wt.% F), vesuvianite (2.4-2.6 wt.% F), fluorite (48-49 wt.% F), apatite (3.9-4.1 wt.% F), and titanite (2.6-3.4 wt.% F). These textural characteristics, combined with the positive correlation of whole-rock F and W (as well as Sn, Mo) contents in the calc-silicate rocks, indicate that the elevated F contents increased the solubility of W in the infiltrating fluid, thereby allowing the W transfer in the hydrothermal-metasomatic system. The mineralization of scheelite was triggered by the crystallization of F-rich minerals during the formation of the calc-silicate rocks, which caused F depletion and consequent saturation of W in the metasomatic fluid. Our results suggest that, in the MMB metasomatic system, F rather than Cl is the key fluxing compound that facilitates the transfer of W and the mineralization of scheelite.

  3. Raman micro-spectroscopy of UOX and MOX spent nuclear fuel characterization and oxidation resistance of the high burn-up structure

    NASA Astrophysics Data System (ADS)

    Jegou, C.; Gennisson, M.; Peuget, S.; Desgranges, L.; Guimbretière, G.; Magnin, M.; Talip, Z.; Simon, P.

    2015-03-01

    Raman micro-spectroscopy was applied to study the structure and oxidation resistance of UO2 (burnup 60 GWd/tHM) and MOX (burnup 47 GWd/tHM) irradiated fuels. The Raman technique, adapted to working under extreme conditions, enabled structural information to be obtained at the cubic micrometer scale in various zones of interest within irradiated fuel (central and zones like the Rim for UOX60, and the plutonium-enriched agglomerates for MOX47 characterized by a high burn-up structure), and the study of their oxidation resistance. As regards the structural information after irradiation, the spectra obtained make up a set of data consistent with the systematic presence of the T2g band characteristic of the fluorite structure, and of a triplet band located between 500 and 700 cm-1. The existence of this triplet can be attributed to the presence of defects originating in changes to the fuel chemistry occurring in the reactor (presence of fission products) and to the accumulation of irradiation damage. As concerns the oxidation resistance of the different zones of interest, Raman spectroscopy results confirmed the good stability of the restructured zones (plutonium-enriched agglomerates and Rim) rich in fission products compared to the non-restructured UO2 grains. A greater structural stability was noticed in the case of high plutonium content agglomerates, as this element favors the maintenance of the fluorite structure.

  4. Percolating hierarchical defect structures drive phase transformation in Ce1−xGdxO2−x/2: a total scattering study

    PubMed Central

    Scavini, Marco; Coduri, Mauro; Allieta, Mattia; Masala, Paolo; Cappelli, Serena; Oliva, Cesare; Brunelli, Michela; Orsini, Francesco; Ferrero, Claudio

    2015-01-01

    A new hierarchical approach is presented for elucidating the structural disorder in Ce1−xGdxO2−x/2 solid solutions on different scale lengths. The primary goal of this investigation is to shed light on the relations between the short-range and the average structure of these materials via an analysis of disorder on the mesocopic scale. Real-space (pair distribution function) and reciprocal-space (Rietveld refinement and microstructure probing) analysis of X-ray powder diffraction data and electron spin resonance (ESR) investigations were carried out following this approach. On the local scale, Gd- and Ce-rich droplets (i.e. small regions a few ångströms wide) form, exhibiting either a distorted fluorite (CeO2) or a C-type (Gd2O3) structure in the whole compositional range. These droplets can then form C-type nanodomains which, for Gd concentrations x Gd ≤ 0.25, are embedded in the fluorite matrix. At the site percolation threshold p C for a cubic lattice (x Gd = p C ≃ 0.311), C-type nanodomains percolate inside each crystallite and a structural phase transformation is observed. When this occurs, the peak-to-peak ESR line width ΔH pp shows a step-like behaviour, which can be associated with the increase in Gd–Gd dipolar interactions. A general crystallographic rationale is presented to explain the fluorite-to-C-type phase transformation. The approach shown here could be adopted more generally in the analysis of disorder in other highly doped materials. PMID:26306193

  5. Enhanced anisotropic ionic diffusion in layered electrolyte structures from density functional theory

    NASA Astrophysics Data System (ADS)

    Hirschfeld, J. A.; Lustfeld, H.

    2014-01-01

    Electrolytes with high ionic diffusivity at temperatures distinctively lower than the presently used ones are the prerequisite for the success of, e.g., solid oxide fuel cells. We have found a promising structure having an asymmetric but superior ionic mobility in the direction of the oxygen-ion current. Using a layering of zirconium and yttrium in the fluorite structure of zirconia, a high vacancy concentration and a low migration barrier in two dimensions are obtained, while the mobility in the third direction is basically sacrificed. According to our density functional theory calculations an electrolyte made of this structure could operate at a temperature reduced by ≈200∘C. Thus a window to a different class of electrolytes has been flung open. In our structure the price paid is a more complicated manufacturing method.

  6. Preparation and structural study from neutron diffraction data of Pr{sub 5}Mo{sub 3}O{sub 16}

    SciTech Connect

    Martinez-Lope, M.J.; Alonso, J.A.; Sheptyakov, D.; Pomjakushin, V.

    2010-12-15

    The title compound has been prepared as polycrystalline powder by thermal treatments of mixtures of Pr{sub 6}O{sub 11} and MoO{sub 2} in air. In the literature, an oxide with a composition Pr{sub 2}MoO{sub 6} has been formerly described to present interesting catalytic properties, but its true stoichiometry and crystal structure are reported here for the first time. It is cubic, isostructural with CdTm{sub 4}Mo{sub 3}O{sub 16} (space group Pn-3n, Z=8), with a=11.0897(1) A. The structure contains MoO{sub 4} tetrahedral units, with Mo-O distances of 1.788(2) A, fully long-range ordered with PrO{sub 8} polyhedra; in fact it can be considered as a superstructure of fluorite (M{sub 8}O{sub 16}), containing 32 MO{sub 2} fluorite formulae per unit cell, with a lattice parameter related to that of cubic fluorite (a{sub f}=5.5 A) as a{approx}2a{sub f}. A bond valence study indicates that Mo exhibits a mixed oxidation state between 5+ and 6+ (perhaps accounting for the excellent catalytic properties). One kind of Pr atoms is trivalent whereas the second presents a mixed Pr{sup 3+}-Pr{sup 4+} oxidation state. The similarity of the XRD pattern with that published for Ce{sub 2}MoO{sub 6} suggests that this compound also belongs to the same structural type, with an actual stoichiometry Ce{sub 5}Mo{sub 3}O{sub 16}. -- Graphical Abstract: Formerly formulated as Pr{sub 2}MoO{sub 6}, the title compound is a cubic superstructure of fluorite (a=11.0897(1) A, space group Pn-3n) due to the long-range ordering of PrO{sub 8} scalenohedra and MoO{sub 4} tetrahedral units, showing noticeable shifts of the oxygen positions in order to provide a tetrahedral coordination for Mo ions. A mixed valence Mo{sup 5+}-Mo{sup 6+} is identified, which could account for the excellent catalytic properties of this material. Display Omitted

  7. Ab initio analysis of the defect structure of ceria

    NASA Astrophysics Data System (ADS)

    Zacherle, T.; Schriever, A.; De Souza, R. A.; Martin, M.

    2013-04-01

    We calculated the formation energies of all simple point defects in cubic fluorite structured CeO2 using density functional theory within the GGA+U approximation. All possible defect charge states were considered, and also polarons CeCe' and associates of polarons with oxygen vacancies: (VO··-CeCe')· and (CeCe'-VO··-CeCe')×. From the individual defect energies, we extracted Schottky, Frenkel, and anti-Frenkel energies: we find that anti-Frenkel disorder has the lowest energy in ceria. Energies for the reduction and the hydration of ceria are also computed, and the results are in good agreement with experiment. Finally, point-defect concentrations and conductivities are predicted for undoped and donor-doped systems as a function of oxygen partial pressure and temperature. The characteristic slopes found in experiment are reproduced.

  8. Pressure Effect on the Structural Transition and Suppression of the High-Spin State in the Triple-Layer T'-La₄Ni₃O₈

    DOE PAGESBeta

    Cheng, J.-G.; Zhou, J.-S.; Goodenough, J. B.; Zhou, H. D.; Matsubayashi, K.; Uwatoko, Y.; Kong, P. P.; Jin, C. Q.; Yang, W. G.; Shen, G. Y.

    2012-06-08

    We report a comprehensive high-pressure study on the triple-layer T'-La₄Ni₃O₈ with a suite of experimental probes, including structure determination, magnetic, and transport properties up to 50 GPa. Consistent with a recent ab inito calculation, application of hydrostatic pressure suppresses an insulator-metal spin-state transition at Pc≈6 GPa. However, a low-spin metallic phase does not emerge after the high-spin state is suppressed to the lowest temperature. For P>20 GPa, the ambient T' structure transforms gradually to a T†-type structure, which involves a structural reconstruction from fluorite La–O₂–La blocks under low pressures to rock-salt LaO-LaO blocks under high pressures. Absence of the metallicmore » phase under pressure has been discussed in terms of local displacements of O²⁻ ions in the fluorite block under pressure before a global T† phase is established.« less

  9. Pressure Effect on the Structural Transition and Suppression of the High-Spin State in the Triple-Layer T'-La₄Ni₃O₈

    SciTech Connect

    Cheng, J.-G.; Zhou, J.-S.; Goodenough, J. B.; Zhou, H. D.; Matsubayashi, K.; Uwatoko, Y.; Kong, P. P.; Jin, C. Q.; Yang, W. G.; Shen, G. Y.

    2012-06-08

    We report a comprehensive high-pressure study on the triple-layer T'-La₄Ni₃O₈ with a suite of experimental probes, including structure determination, magnetic, and transport properties up to 50 GPa. Consistent with a recent ab inito calculation, application of hydrostatic pressure suppresses an insulator-metal spin-state transition at Pc≈6 GPa. However, a low-spin metallic phase does not emerge after the high-spin state is suppressed to the lowest temperature. For P>20 GPa, the ambient T' structure transforms gradually to a T-type structure, which involves a structural reconstruction from fluorite La–O₂–La blocks under low pressures to rock-salt LaO-LaO blocks under high pressures. Absence of the metallic phase under pressure has been discussed in terms of local displacements of O²⁻ ions in the fluorite block under pressure before a global T† phase is established.

  10. Simultaneous measurement of (n,{gamma}) and (n,fission) cross sections with the DANCE 4{pi} BaF2 array

    SciTech Connect

    Bredeweg, T. A.; Fowler, M. M.; Bond, E. M.; Chadwick, M. B.; Hunt, L. F.; O'Donnell, J. M.; Rundberg, R. S.; Schwantes, J. M.; Ullmann, J. L.; Vieira, D. J.; Wilhelmy, J. B.; Wouters, J. M.; Becker, J. A.; Clement, R. R. C.; Esch, E.-I.; Macri, R. A.; Wu, C.-Y.; Ethvignot, T.; Granier, T.; Yurkon, J. E.

    2006-03-13

    Neutron capture cross section measurements on many of the actinides are complicated by low-energy neutron-induced fission, which competes with neutron capture to varying degrees depending on the nuclide of interest. Measurements of neutron capture on 235U using the Detector for Advanced Neutron Capture Experiments (DANCE) have shown that we can partially resolve capture from fission events based on total photon calorimetry (i.e. total {gamma}-ray energy and {gamma}-ray multiplicity per event). The addition of a fission-tagging detector to the DANCE array will greatly improve our ability to separate these two competing processes so that improved neutron capture and (n,{gamma})/(n,fission) cross section ratio measurements can be obtained. The addition of a fission-tagging detector to the DANCE array will also provide a means to study several important issues associated with neutron-induced fission, including (n,fission) cross sections as a function of incident neutron energy, and total energy and multiplicity of prompt fission photons. We have focused on two detector designs with complementary capabilities, a parallel-plate avalanche counter and an array of solar cells.

  11. The structure of Bi{sub 26}Mo{sub 10}O{sub 69}

    SciTech Connect

    Buttrey, D.J.; Yap, G.P.A.; Rheingold, A.L.; Vogt, T.

    1997-07-01

    The structure of Bi{sub 26}Mo{sub 10}O{sub 69} was solved using a combination of X-ray and neutron diffraction. The final refinement was completed using high resolution neutron powder diffraction in a monoclinic cell [a = 1.17456(3) nm, b = 0.57988(1) nm, c = 2.47919(5) nm, {beta} = 102.903(1){degree}, P2/c], neglecting a very subtle triclinic distortion resolved only with synchrotron X-ray data. This phase exhibits a solid solubility range of approximately 2.6 {le} Bi/Mo {le} 2.8, with the ideal ratio at 2.6 and one of the Bi sites disordered. The structure is rationalized by comparison with other bismuth molybdates using valence bond sums and Madelung site potentials. As with several other bismuth molybdates, there is significant charge transfer between Bi-rich channels and surrounding molybdenum tetrahedra in this fluorite-related structure.

  12. Alpha self-irradiation effect on the local structure of the U0.85Am0.15O2±x solid solution

    NASA Astrophysics Data System (ADS)

    Prieur, D.; Martin, P. M.; Lebreton, F.; Delahaye, T.; Jankowiak, A.; Laval, J.-P.; Scheinost, A. C.; Dehaudt, P.; Blanchart, P.

    2012-10-01

    Uranium-americium mixed oxides are promising fuels for achieving an efficient Am recycling. Previous studies on U0.85Am0.15O2±x materials showed that the high α activity of 241Am 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 U0.85Am0.15O2±x local structure and to correlate these results with those obtained at the macroscopic scale. For a cumulative α 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.

  13. Highly stable, mesoporous mixed lanthanum-cerium oxides with tailored structure and reducibility

    SciTech Connect

    Liang, Shuang; Broitman, Esteban; Wang, Yanan; Cao, Anmin; Veser, Goetz

    2011-05-01

    Pure and mixed lanthanum and cerium oxides were synthesized via a reverse microemulsion-templated route. This approach yields highly homogeneous and phase-stable mixed oxides with high surface areas across the entire range of La:Ce ratios from pure lanthana to pure ceria. Surprisingly, all mixed oxides show the fluorite crystal structure of ceria, even for lanthanum contents as high as 90%. Varying the La:Ce ratio not only allows tailoring of the oxide morphology (lattice parameter, pore structure, particle size, and surface area), but also results in a fine-tuning of the reducibility of the oxide which can be explained by the creation of oxygen vacancies in the ceria lattice upon La addition. Such finely controlled syntheses, which enable the formation of stable, homogeneous mixed oxides across the entire composition range, open the path towards functional tailoring of oxide materials, such as rational catalyst design via fine-tuning of redox activity.

  14. Structural, morphological, Raman, optical, magnetic, and antibacterial characteristics of CeO2 nanostructures

    NASA Astrophysics Data System (ADS)

    Abbas, Fazal; Iqbal, Javed; Jan, Tariq; Badshah, Noor; Mansoor, Qaisar; Ismail, Muhammad

    2016-01-01

    In this study, CeO2 nanostructures were synthesized by a soft chemical method. A hydrothermal treatment was observed to lead to an interesting morphological transformation of the nanoparticles into homogeneous microspheres composed of nanosheets with an average thickness of 40 nm. Structural analysis revealed the formation of a single-phase cubic fluorite structure of CeO2 for both samples. A Raman spectroscopic study confirmed the XRD results and furthermore indicated the presence of a large number of oxygen vacancies in the nanosheets. These oxygen vacancies led to room-temperature ferromagnetism (RTFM) of the CeO2 nanosheets with enhanced magnetic characteristics. Amazingly, the nanosheets exhibited substantially greater antibacterial activity than the nanoparticles. This greater antibacterial activity was attributed to greater exposure of high-surface-energy polar surfaces and to the presence of oxygen vacancies.

  15. Structural Phase Transitions in AuIn2 at High Pressure

    NASA Astrophysics Data System (ADS)

    Clark, S. M.; Speziale, S.; Voltolini, M.; Godwal, B. K.; Jeanloz, R.

    2007-12-01

    The intermetallic compound AuIn2 provides an analog for the high-pressure phases of SiO2, as it is initially in the Fm3m fluorite (CaF2) structure. Synchrotron-based angular-dispersive x-ray diffraction (Advanced Light Source beamline 12.2.2) reveals subtle anomalies in the pressure variation of normalized stress (F) versus Eulerian strain (f) around 3 GPa, coinciding with anomalies observed in fusion, transport and optical data, and potentially associated with the onset of an electronic phase transition. Our diamond-cell experiments (gasketted sample with methanol-ethanol pressure medium) show continuous broadening of diffraction peaks beyond 12 GPa, leading to amorphization near 24 GPa. On further increase of pressure, a crystalline phase appears around 28 GPa and persists upon unloading from 30 GPa to about 5 GPa, then reverting back to the original CaF2 phase. We find the sequence of pressure-induced phase transition documented for CaF2 (fluorite structure Fm3m - PbCl2 Pnma - Ni2In-type P63/mmc and a combination of PbCl2 and Ni2In) to be inadequate in fitting the observed high-pressure diffraction patterns of AuIn2. However, the post-cotunnite structure of PbCl2, BaCl2, BaBr2 and SnCl2 (P1121/c, Z=8) is able to account for most of the prominent peaks in our high-pressure diffraction patterns (a=10.983, b=9.875, c=4.350, À=96.6). Many oxides of geophysical interest occur in the CaF2 structure, and study of intermetallic compounds such as AuIn2 may prove useful in suggesting high-pressure metallic phases for these oxides.

  16. Fluorite Ce0.8Sm0.2O2- δ porous layer coating to enhance the oxygen permeation behavior of a BaCo0.7Fe0.2Nb0.1O3- δ mixed conductor

    NASA Astrophysics Data System (ADS)

    Wang, Tai-he; Song, Wei-jia; Li, Rong; Zhen, Qiang

    2016-06-01

    Fluorite Ce0.8Sm0.2O2- δ (SDC) nanopowder with a crystallite size of 15 nm was synthesized by a co-precipitation method. An SDC porous layer was coated onto a BaCo0.7Fe0.2Nb0.1O3- δ (BCFN) mixed conductor to improve its oxygen transport behavior. The results show that the SDC-coated BCFN membrane exhibits a remarkably higher oxygen permeation flux ({J_{{O_2}}}) than the uncoated BCFN in the partial oxidation of coke oven gas (COG). The maximum {J_{{O_2}}} value of the SDC-coated BCFN is 18.28 mL·min-1·cm-2 under a COG/air flux of 177 mL·min-1/353 mL·min-1 at 875°C when the thickness of the BCFN membrane is 1 mm; this {J_{{O_2}}} value is 23% higher than that of the uncoated BCFN membrane. This enhancement is likely because of the higher oxygen ionic conductivity of SDC, which supplies oxygen vacancies and accelerates oxygen exchange on the membrane/coating layer/gas three-phase boundary.

  17. Electronic structure and crystal phase stability of palladium hydrides

    SciTech Connect

    Houari, Abdesalem; Matar, Samir F.; Eyert, Volker

    2014-11-07

    The results of electronic structure calculations for a variety of palladium hydrides are presented. The calculations are based on density functional theory and used different local and semilocal approximations. The thermodynamic stability of all structures as well as the electronic and chemical bonding properties are addressed. For the monohydride, taking into account the zero-point energy is important to identify the octahedral Pd-H arrangement with its larger voids and, hence, softer hydrogen vibrational modes as favorable over the tetrahedral arrangement as found in the zincblende and wurtzite structures. Stabilization of the rocksalt structure is due to strong bonding of the 4d and 1s orbitals, which form a characteristic split-off band separated from the main d-band group. Increased filling of the formerly pure d states of the metal causes strong reduction of the density of states at the Fermi energy, which undermines possible long-range ferromagnetic order otherwise favored by strong magnetovolume effects. For the dihydride, octahedral Pd-H arrangement as realized, e.g., in the pyrite structure turns out to be unstable against tetrahedral arrangement as found in the fluorite structure. Yet, from both heat of formation and chemical bonding considerations, the dihydride turns out to be less favorable than the monohydride. Finally, the vacancy ordered defect phase Pd{sub 3}H{sub 4} follows the general trend of favoring the octahedral arrangement of the rocksalt structure for Pd:H ratios less or equal to one.

  18. Comparative XRPD and XAS study of the impact of the synthesis process on the electronic and structural environments of uranium–americium mixed oxides

    SciTech Connect

    Prieur, D.; Lebreton, F.; Somers, J.; Delahaye, T.

    2015-10-15

    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 U{sub 1−x}Am{sub x}O{sub 2±δ} 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 U{sub 1−x}Am{sub x}O{sub 2±δ} leads to the formation of similar fluorite solid solution indicating the presence of Am{sup +III} and U{sup +V} in equimolar proportions. - Graphical abstract: Formation of (U{sup IV/V},Am{sup III})O{sup 2} solid solution by sol–gel and by powder metallurgy. - Highlights: • Uranium–americium mixed oxides were synthesized by sol–gel and powder metallurgy. • Fluorite solid solutions with similar local environment have been obtained. • U{sup V} and Am{sup III} are formed in equimolar proportions.

  19. Phage-directed synthesis of copper sulfide: structural and optical characterization

    NASA Astrophysics Data System (ADS)

    Shahriar Zaman, Mohammed; Moon, Chung Hee; Bozhilov, Krassimir N.; Haberer, Elaine D.

    2013-08-01

    The growth of crystalline copper sulfide using a viral template was investigated using sequential incubation in CuCl2 and Na2S precursors. Non-specific electrostatic attraction between a genetically-modified M13 bacteriophage and copper cations in the CuCl2 precursor caused phage agglomeration and bundle formation. Following the addition of Na2S, polydisperse nanocrystals 2-7 nm in size were found along the length of the viral scaffold. The structure of the copper sulfide material was identified as cubic anti-fluorite type Cu1.8S, space group F m\\bar {3}m. Strong interband absorption was observed within the ultraviolet to visible range with an onset near 800 nm. Furthermore, free carrier absorption, associated with the localized surface plasmon resonance of the copper sulfide nanocrystals, was seen in the near infrared with absorbance maxima at 1060 nm and 3000 nm, respectively.

  20. Chemical expansion affected oxygen vacancy stability in different oxide structures from first principles calculations

    SciTech Connect

    Aidhy, Dilpuneet S.; Liu, Bin; Zhang, Yanwen; Weber, William J.

    2015-01-21

    We study the chemical expansion for neutral and charged oxygen vacancies in fluorite, rocksalt, perovskite and pyrochlores materials using first principles calculations. We show that the neutral oxygen vacancy leads to lattice expansion whereas the charged vacancy leads to lattice contraction. In addition, we show that there is a window of strain within which an oxygen vacancy is stable; beyond that range, the vacancy can become unstable. Using CeO2|ZrO2 interface structure as an example, we show that the concentration of oxygen vacancies can be manipulated via strain, and the vacancies can be preferentially stabilized. Furthermore, these results could serve as guiding principles in predicting oxygen vacancy stability in strained systems and in the design of vacancy stabilized materials.

  1. Chemical expansion affected oxygen vacancy stability in different oxide structures from first principles calculations

    SciTech Connect

    Aidhy, Dilpuneet S.; Liu, Bin; Zhang, Yanwen; Weber, William J.

    2015-03-01

    We study the chemical expansion for neutral and charged oxygen vacancies in fluorite, rocksalt, perovskite and pyrochlores materials using first principles calculations. We show that the neutral oxygen vacancy leads to lattice expansion whereas the charged vacancy leads to lattice contraction. In addition, we show that there is a window of strain within which an oxygen vacancy is stable; beyond that range, the vacancy can become unstable. Using CeO2|ZrO2 interface structure as an example, we show that the concentration of oxygen vacancies can be manipulated via strain, and the vacancies can be preferentially stabilized. These results could serve as guiding principles in predicting oxygen vacancy stability in strained systems and in the design of vacancy stabilized materials.

  2. Chemical expansion affected oxygen vacancy stability in different oxide structures from first principles calculations

    DOE PAGESBeta

    Aidhy, Dilpuneet S.; Liu, Bin; Zhang, Yanwen; Weber, William J.

    2015-01-21

    We study the chemical expansion for neutral and charged oxygen vacancies in fluorite, rocksalt, perovskite and pyrochlores materials using first principles calculations. We show that the neutral oxygen vacancy leads to lattice expansion whereas the charged vacancy leads to lattice contraction. In addition, we show that there is a window of strain within which an oxygen vacancy is stable; beyond that range, the vacancy can become unstable. Using CeO2|ZrO2 interface structure as an example, we show that the concentration of oxygen vacancies can be manipulated via strain, and the vacancies can be preferentially stabilized. Furthermore, these results could serve asmore » guiding principles in predicting oxygen vacancy stability in strained systems and in the design of vacancy stabilized materials.« less

  3. On the local electronic and atomic structure of Ce1-xPrxO2-δ epitaxial films on Si

    NASA Astrophysics Data System (ADS)

    Niu, Gang; Schubert, Markus Andreas; d'Acapito, Francesco; Zoellner, Marvin Hartwig; Schroeder, Thomas; Boscherini, Federico

    2014-09-01

    The local electronic and atomic structure of (111)-oriented, single crystalline mixed Ce1-xPrxO2-δ (x = 0, 0.1 and 0.6) epitaxial thin films on silicon substrates have been investigated in view of engineering redox properties of complex oxide films. Non-destructive X-ray absorption near edge structure reveals that Pr shows only +3 valence and Ce shows only nominal +4 valence in mixed oxides. Extended x-ray absorption fine structure (EXAFS) studies were performed at K edges of Ce and Pr using a specially designed monochromator system for high energy measurements. They demonstrate that the fluorite lattice of ceria (CeO2) is almost not perturbed for x = 0.1 sample, while higher Pr concentration (x = 0.6) not only generates a higher disorder level (thus more disordered oxygen) but also causes a significant reduction of Ce-O interatomic distances. The valence states of the cations were also examined by techniques operating in highly reducing environments: scanning transmission electron microscopy-electron energy loss spectroscopy and X-ray photoemission spectroscopy; in these reducing environments, evidence for the presence of Ce3+ was clearly found for the higher Pr concentration. Thus, the introduction of Pr3+ into CeO2 strongly enhances the oxygen exchange properties of CeO2. This improved oxygen mobility properties of CeO2 are attributed to the lattice disorder induced by Pr mixing in the CeO2 fluorite lattice, as demonstrated by EXAFS measurements. Thus, a comprehensive picture of the modifications of the atomic and electronic structure of Ce1-xPrxO2-δ epitaxial films and their relation is obtained.

  4. Epitaxial crystals of Bi{sub 2}Pt{sub 2}O{sub 7} pyrochlore through the transformation of δ–Bi{sub 2}O{sub 3} fluorite

    SciTech Connect

    Gutiérrez–Llorente, Araceli Holtz, Megan E.; Muller, David A.; Joress, Howie; Woll, Arthur; Ward, Matthew J.; Sullivan, Matthew C.; Brock, Joel D.

    2015-03-01

    Bi{sub 2}Pt{sub 2}O{sub 7} pyrochlore is thought to be one of the most promising oxide catalysts for application in fuel cell technology. Unfortunately, direct film growth of Bi{sub 2}Pt{sub 2}O{sub 7} has not yet been achieved, owing to the difficulty of oxidizing platinum metal in the precursor material to Pt{sup 4+}. In this work, in order to induce oxidation of the platinum, we annealed pulsed laser deposited films consisting of epitaxial δ–Bi{sub 2}O{sub 3} and co-deposited, comparatively disordered platinum. We present synchrotron x-ray diffraction results that show the nonuniform annealed films contain the first epitaxial crystals of Bi{sub 2}Pt{sub 2}O{sub 7}. We also visualized the pyrochlore structure by scanning transmission electron microscopy, and observed ordered cation vacancies in the epitaxial crystals formed in a bismuth-rich film but not in those formed in a platinum-rich film. The similarity between the δ–Bi{sub 2}O{sub 3} and Bi{sub 2}Pt{sub 2}O{sub 7} structures appears to facilitate the pyrochlore formation. These results provide the only route to date for the formation of epitaxial Bi{sub 2}Pt{sub 2}O{sub 7}.

  5. On the crystal structures of Ln{sub 3}MO{sub 7} (Ln=Nd, Sm, Y and M=Sb, Ta)-Rietveld refinement using X-ray powder diffraction data

    SciTech Connect

    Fu, W.T.; IJdo, D.J.W.

    2009-09-15

    We have investigated, using X-ray powder diffraction data, the crystal structures of some fluorite derivatives with the formula Ln{sub 3}MO{sub 7} (Ln=lanthanide or Y and M=Sb and Ta). In these compounds ordering of Ln and M occurs, leading to a parent structure in Cmmm. Tilting of the MO{sub 6} octahedra causes doubling of one of the cubic axes, leading to a number of non-isomorphic subgroups, e.g. Cmcm, Ccmm and Cccm. We have identified an alternative space group Ccmm instead of C222{sub 1} for those compounds containing a medium sized lanthanide or Y and M being Sb or Ta. Interestingly this is an alternative setting for the space group of the structure obtained when Ln is large (Cmcm). However, there tilting of the octahedra is around the a-axis of the parent structure, rather than around the b-axis as it is found in the compounds which we are reporting on here. In one compound, Nd{sub 3}TaO{sub 7}, both tilts occur. The phase transition between the two possible structures is a slow and difficult process above 80 K, allowing both phases to coexist. - Graphical abstract: (a) A projected view of Ln{sub 3}MO{sub 7} along the a-axis showing the ordering of Ln and M cations in the fluoride lattice. Note that the unit cells of the fluorite (dashed line), the parent Cmmm (dashed line) and the Cmcm/Ccmm structures (continuous line) are indicated. (b) Schematic representations of the crystal structures of Y{sub 3}SbO{sub 7} showing SbO{sub 6} octahedra and Y. Oxygens that do not bond to M cations are also shown.

  6. Nanostructured crystals of fluorite phases Sr{sub 1−x}R{sub x}F{sub 2+x} (R Are Rare Earth Elements) and their ordering: 10. Ordering under spontaneous crystallization and annealing of Sr{sub 1−x}R{sub x}F{sub 2+x} Alloys (R = Tb-Lu, Y) with 23.8–36.1 mol % RF{sub 3}

    SciTech Connect

    Sulyanova, E. A. Karimov, D. N.; Sulyanov, S. N.; Zhmurova, Z. I.; Golubev, A. M.; Sobolev, B. P.

    2015-01-15

    The products of spontaneous crystallization (at a cooling rate of ∼200 K/min) of Sr{sub 1−x}R{sub x}F{sub 2+x} melts in the homogeneity range of the fluorite phase have been investigated. Thirty-two irrational compositions with 23.8–36.1 mol % RF{sub 3} and eight rational Sr{sub 2}RF{sub 7} compositions are obtained. With respect to the RF{sub 3} content, these compositions form five groups: (1) Sr{sub 0.762}R{sub 0.238}F{sub 2.238} (23.8% RF{sub 3}), (2) Sr{sub 0.744}R{sub 0.256}F{sub 2.256} (25.6%), (3) Sr{sub 0.718}R{sub 0.282}F{sub 2.282} (28.2%), (4) Sr{sub 2}RF{sub 7} (33.3%), and (5) Sr{sub 0.639}R{sub 0.361}F{sub 2.361} (36.1%). R = Tb-Lu, Y for all groups. Quenching melts of group 5 with R = Tb, Dy, and Ho leads to the formation of ordered phases with the trigonal distortion of the rhβ-Na{sub 7}Zr{sub 6}F{sub 31} type, while for melts of group 5 with R = Lu, quenching yields a phase of the trigonal rhα′-Sr{sub 4}Lu{sub 3}F{sub 17} type. In group 5 with R = Y, Er, Tm, or Yb and in groups 1–4 with all REEs, fluorite phases are formed. Annealing at 900 ± 20°C for 96 h with subsequent cooling at a rate of ∼200 K/min expands the variety of ordered phases: a phase with a new r type of orthorhombic distortion is formed in group 1 with R = Lu, in group 2 with R = Tm or Lu, and in group 3 with R = Ho-Lu, Y; a t-Sr{sub 2}RF{sub 7} phase with tetragonal distortion is formed in group 4 with R = Tb-Er, Y; and a phase of trigonal rhα′ type is formed in group 5 with R = Y, Yb, or Lu. A fluorite phase arises in group 1 with R = Tb-Lu, Y as a result of quenching and annealing. The tendency to ordering becomes more pronounced with an increase in the RF{sub 3} content and REE atomic number. The annealing conditions do not provide equilibrium or the completely ordered state of all alloys.

  7. Local structure and charge distribution in mixed uranium-americium oxides: effects of oxygen potential and Am content.

    PubMed

    Prieur, Damien; Martin, Philippe M; Jankowiak, Aurélien; Gavilan, Elisabeth; Scheinost, Andreas C; Herlet, Nathalie; Dehaudt, Philippe; Blanchart, Philippe

    2011-12-19

    Partitioning and transmutation (P&T) of minor actinides (MA) is currently studied to reduce the nuclear waste inventory. In this context, the fabrication of MA bearing materials is of great interest to achieve an effective recycling of these highly radioactive elements. To ensure the in-pile behavior, nuclear oxide fuels have to respect several criteria including preservation of the fluorite structure and defined oxygen to metal ratio (O/M). In the case of Am bearing materials, such as U(1-y)Am(y)O(2±x) (y = 0.10, 0.15, 0.20), the O/M determination is quite challenging using conventional methods (TGA, XRD) because of the particular thermodynamic properties of Am. Despite the lack of experimental data in the U-Am-O system, thermodynamical models are currently developed to effectively assess the O/M ratio. In this work, the O/M ratios were calculated for various oxygen potentials using the cation molar fraction determined by XAS measurements. These results are an important addition to the experimental data available for the U-Am-O system. Moreover, XRD and XAS indicated that the fabrication of fluorite U(1-y)Am(y)O(2±x) solid solution was achieved for all Am content and oxygen potentials investigated. On the basis of the molar fraction, a description of the solid solution was proposed depending on the considered sintering conditions. Finally, the occurrence of an unexpected charge compensation mechanism was pointed out. PMID:22087707

  8. Structural and catalytic properties of lanthanide (La, Eu, Gd) doped ceria

    SciTech Connect

    Hernandez, W.Y.; Laguna, O.H.; Centeno, M.A.; Odriozola, J.A.

    2011-11-15

    Ce{sub 0.9}M{sub 0.1}O{sub 2-{delta}} mixed oxides (M=La, Eu and Gd) were synthesized by coprecipitation. Independent of the dopant cation, the obtained solids maintain the F-type crystalline structure, characteristic of CeO{sub 2} (fluorite structure) without phase segregation. The ceria lattice expands depending on the ionic radii of the dopant cation, as indicated by X-ray diffraction studies. This effect also agrees with the observed shift of the F{sub 2g} Raman vibrational mode. The presence of the dopant cations in the ceria lattice increases the concentration of structural oxygen vacancies and the reducibility of the redox pair Ce{sup 4+}/Ce{sup 3+}. All synthesized materials show higher catalytic activity for the CO oxidation reaction than that of bare CeO{sub 2}, being Eu-doped solid the one with the best catalytic performances despite of its lower surface area. - Graphical abstract: In this work, Ce{sub 0.9}M{sub 0.1}O{sub 2-{delta}} mixed oxides (M=La, Eu and Gd) were synthesized by coprecipitation. Independent of the dopant cation, the obtained solids maintain the F-type crystalline structure, characteristic of CeO{sub 2} (fluorite structure) without phase segregation. The ceria lattice expands depending on the ionic radii of the dopant cation, as indicated by X-ray diffraction studies. This effect also agrees with the observed shift of the F{sub 2g} Raman vibrational mode. The presence of the dopant cations in the ceria lattice increases the concentration of structural oxygen vacancies and the reducibility of the redox pair Ce{sup 4+}/Ce{sup 3+}. All synthesized materials show higher catalytic activity for the CO oxidation reaction than that of bare CeO{sub 2}, being Eu-doped solid the one with the best catalytic performances despite of its lower surface area. Highlights: > Lanthanide doped ceria as catalytic supports for CO oxidation reaction. > A higher concentration of oxygen vacancies promotes a higher catalytic activity. > Eu-doped ceria shows

  9. The response of the pyrochlore structure-type to ion-beam irradiation

    NASA Astrophysics Data System (ADS)

    Lian, Jie

    Pyrochlore with the general formula of A3+2B4+2O7 (Fd3m; Z = 8) has been proposed as the candidate waste form for the immobilization of actinides, particularly plutonium from dismantled nuclear weapons. Because actinides decay by alpha-decay events, radiation effects on the waste form are a concern. The effects of radiation on different pyrochlore compositions, A2B2O7 (A = La ˜ Lu, and Y; B = Ti, Sn, and Zr), have been investigated by 50 KeV He+, 600 KeV Ar+, 1.0 MeV Kr+, and 1.5 MeV Xe+ ion irradiations. Titanate pyrochlores are generally sensitive to ion beam damage and can be amorphized at a low damage level (˜0.2 dpa). The critical amorphization temperature, Tc, increases from ˜480 to ˜1120 K with increasing A-site cation size. A dramatically increasing radiation "resistance" to ion beam induced-amorphization has been observed with increasing Zr-content in the Gd2Ti2-xZrxO7 system. The pure end-member, Gd2Zr2O7, cannot be amorphized, even at doses as high as ˜100 dpa. Although zirconate pyrochlores are generally considered to be radiation "resistant", ion beam-induced amorphization occurs for La2Zr2O7 at a dose of ˜5.5 dpa at room temperature. Stannate pyrochlores A2Sn 2O7 (A = La, Nd, Gd) are readily amorphized by ion beam damage at a relatively low dose (˜1 dpa) at room temperature; while no evidence of amorphization has been observed in A2Sn2O7 (A = Er, Y, Lu) irradiated with 1 MeV Kr+ ions at a dose of ˜6 dpa at 25 K. The factors that influence the response of different pyrochlore compositions to ion irradiation-induced amorphization are discussed in terms of cation radius ratio, defect formation energies, and the tendency of the pyrochlore structure-type to undergo an order-disorder transition to the defect-fluorite structure. The "resistance" of the pyrochlore structure to ion beam-induced amorphization is not only affected by the relative sizes of the A- and B-site cations, but also the cation electronic configurations. Pyrochlore compositions

  10. Structural reinvestigation of Li3FeN2: Evidence of cationic disorder through XRD, solid-state NMR and Mössbauer spectroscopy

    NASA Astrophysics Data System (ADS)

    Panabière, E.; Emery, N.; Lorthioir, C.; Sougrati, M. T.; Jumas, J.-C.; Bach, S.; Pereira-Ramos, J.-P.; Smith, R. I.; Willmann, P.

    2016-08-01

    A significant cationic disorder is evidenced on Li3FeN2 prepared through solid-state reaction under controlled atmosphere. This derivative anti fluorite type structure (orthorhombic, space group Ibam, a=4.870(1) Å, b=9.652(1) Å and c=4.789(1) Å), solved first through single crystal X-ray diffraction [7], is usually described by Li+ and Fe+3 ordered distribution in tetrahedral sites formed by the nitrogen network, leading to [FeN4/2]3- edge-sharing tetrahedral chains. From 7Li/6Li Nuclear Magnetic Resonance spectroscopy, 57Fe Mössbauer spectroscopy and powder X-ray and neutron diffraction, we demonstrate that about 4% of lithium sites are filled by iron and about 11% of iron sites are occupied by Li, which can explain the discrepancy within the Gudat's model observed on larger scale solid-state synthesis samples.

  11. Comparative XRPD and XAS study of the impact of the synthesis process on the electronic and structural environments of uranium-americium mixed oxides

    NASA Astrophysics Data System (ADS)

    Prieur, D.; Lebreton, F.; Martin, P. M.; Caisso, M.; Butzbach, R.; Somers, J.; Delahaye, T.

    2015-10-01

    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-xAmxO2±δ 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±δ leads to the formation of similar fluorite solid solution indicating the presence of Am+III and U+V in equimolar proportions.

  12. Crystal structure of Mn{sub 2}Ln{sub 3}Sb{sub 3}O{sub 14} (Ln=La, Pr and Nd): A new ordered rhombohedral pyrochlore

    SciTech Connect

    Fu, W.T. IJdo, D.J.W.

    2014-05-01

    Manganese rare earth antimonates with the formula Mn{sub 2}Ln{sub 3}Sb{sub 3}O{sub 14} (Ln=La–Yb and Y) have been prepared and their structures were determined by the Rietveld method using X-ray diffraction data. The compounds with Ln=La, Pr and Nd crystallize in a rhombohedral supercell of the cubic fluorite with the space group R3{sup ¯}m and with the lattice parameters a{sub h}≈√2a{sub c} and c{sub h}≈2√3a{sub c}, where a{sub c} denotes the lattice constant of the cubic fluorite. The structure is pyrochlore-like but differs from the common cubic pyrochlore A{sub 2}B{sub 2}O{sub 7} in that it consists of fully ordered Mn:Ln in the A sites and Mn:Sb in the B sites with the ratio 1:3. The most interesting feature of Mn{sub 2}Ln{sub 3}Sb{sub 3}O{sub 14} is that the divalent Mn ions have different coordination numbers with oxygen and the Mn(II)O{sub 6} (octahedron) and Mn(II)O{sub 8} (hexagonal bipyramid) alternate along the parent cubic fluorite axes. For medium sized lanthanides, i.e. from Ln=Sm, the rhombohedral phase coexists with the cubic phase and Mn{sub 2}Y{sub 3}Sb{sub 3}O{sub 14} is cubic a pyrochlore. - Graphical abstract: Crystal structure of rhombohedral pyrochlore Mn{sub 2}Ln{sub 3}Sb{sub 3}O{sub 14} (Ln=La, Pr, and Nd) showing the staking of Ln{sub 3}Mn and MnSb{sub 3} layers (a). (b) and (c) show the connections between Mn1O{sub 6} and LnO{sub 8} and between Mn2O{sub 8} and SbO{sub 6} polyhedra, respectively. - Highlights: • Pyrochlores of the formula Mn{sub 2}Ln{sub 3}Sb{sub 3}O{sub 14} (Ln=La–Yb and Y) were synthesized for the first time. • Mn{sub 2}Ln{sub 3}Sb{sub 3}O{sub 14} with Ln=La, Pr, Nd are rhombohedral consisting of fully 1:3 ordering of metal ions. • With medium-sized Ln, rhombohedral phase co-exists with cubic phase. • Two divalent Mn ions have coordination numbers of 6 and 8, respectively.

  13. On the local electronic and atomic structure of Ce1-xPrxO2-δ epitaxial films on Si

    SciTech Connect

    Niu, Gang Schubert, Markus Andreas; Zoellner, Marvin Hartwig; D'Acapito, Francesco; Boscherini, Federico

    2014-09-28

    The local electronic and atomic structure of (111)-oriented, single crystalline mixed Ce1-xPrxO2-δ (x = 0, 0.1 and 0.6) epitaxial thin films on silicon substrates have been investigated in view of engineering redox properties of complex oxide films. Non-destructive X-ray absorption near edge structure reveals that Pr shows only +3 valence and Ce shows only nominal +4 valence in mixed oxides. Extended x-ray absorption fine structure (EXAFS) studies were performed at K edges of Ce and Pr using a specially designed monochromator system for high energy measurements. They demonstrate that the fluorite lattice of ceria (CeO₂) is almost not perturbed for x = 0.1 sample, while higher Pr concentration (x = 0.6) not only generates a higher disorder level (thus more disordered oxygen) but also causes a significant reduction of Ce–O interatomic distances. The valence states of the cations were also examined by techniques operating in highly reducing environments: scanning transmission electron microscopy-electron energy loss spectroscopy and X-ray photoemission spectroscopy; in these reducing environments, evidence for the presence of Ce³⁺ was clearly found for the higher Pr concentration. Thus, the introduction of Pr³⁺ into CeO₂ strongly enhances the oxygen exchange properties of CeO₂. This improved oxygen mobility properties of CeO₂ are attributed to the lattice disorder induced by Pr mixing in the CeO₂ fluorite lattice, as demonstrated by EXAFS measurements. Thus, a comprehensive picture of the modifications of the atomic and electronic structure of Ce1-xPrxO2-δ epitaxial films and their relation is obtained.

  14. Heterogeneous structure of the lithosphere of the Taimyr Peninsula

    NASA Astrophysics Data System (ADS)

    Litvinova, Tamara; Petrova, Alevtina

    2016-04-01

    Magnetic anomalies of the lower crust is well manifested in the satellite measurements and their reductions for the heights H = 100 and 400 km. Currently, however, a great interest is the area of negative magnetic anomalies, allocated to the same heights. They are confined to a special permeable zones of the crust and lithosphere, having increased geothermal activity and are associated with a variety of minerals. In digital magnetic anomalies and gravity anomalies circumpolar map of the Arctic Ocean (Total) was built geomagnetic and density sections along latitudinal and longitudinal cross sections of negative magnetic anomalies (n = 100 km). In the Taimyr Peninsula they capture the largest Fadyukudinsko Kotuiskaya-ring structure. In the north-central Siberia Fadyukudinsko Kotuiskaya ring structure is the "hub" articulation largest geoblocks (Anabar, Kureisko-Tunguska and North Kara). It is manifested in the gravity and magnetic field is also a ring structure. With Fadyukudinsko Kotui-ring structure formation associated injectors and high-carbonate metasomatic rocks tectonites controlling uranium and thorium-uranium-fluorite-barite-rare earth mineralization (VF Proskurnin, et al. 2010). It hypabyssal front of the hot spots. Fadyukudinsko-Kotuiskaya structure is defined posletrappovoe place in the north of the Eurasian plate, responding to a hot spot or a spot lower mantle plumes Triassic [Kravchenko SM, Hain VE 1996 Sazonov AM, Zvyagin EA, Leontiev SI et al., 2010]. Latitude and longitude revealed Profile permeable zones of low magnetic properties and density, confined to a weakened layer in the middle crust. Negative satellite magnetic anomalies (n = 100 km) at depths of 20 - 25-30 km weakly magnetic lens revealed a low density. The upper crust they overlap and dense magnetic rocks. At the bottom of the crust, these lenses are underlain by layers of dense and magnetic structures.

  15. Oxide-ion and proton conducting electrolyte materials for clean energy applications: structural and mechanistic features.

    PubMed

    Malavasi, Lorenzo; Fisher, Craig A J; Islam, M Saiful

    2010-11-01

    This critical review presents an overview of the various classes of oxide materials exhibiting fast oxide-ion or proton conductivity for use as solid electrolytes in clean energy applications such as solid oxide fuel cells. Emphasis is placed on the relationship between structural and mechanistic features of the crystalline materials and their ion conduction properties. After describing well-established classes such as fluorite- and perovskite-based oxides, new materials and structure-types are presented. These include a variety of molybdate, gallate, apatite silicate/germanate and niobate systems, many of which contain flexible structural networks, and exhibit different defect properties and transport mechanisms to the conventional materials. It is concluded that the rich chemistry of these important systems provides diverse possibilities for developing superior ionic conductors for use as solid electrolytes in fuel cells and related applications. In most cases, a greater atomic-level understanding of the structures, defects and conduction mechanisms is achieved through a combination of experimental and computational techniques (217 references). PMID:20848015

  16. Crystalline structure of ceria particles controlled by the oxygen partial pressure and STI CMP performances.

    PubMed

    Kim, Ye-Hwan; Kim, Sang-Kyun; Kim, Namsoo; Park, Jea-Gun; Paik, Ungyu

    2008-09-01

    The effect of the crystalline structures of nano-sized ceria particles on shallow trench isolation (STI) chemical mechanical planarization (CMP) performance was investigated. The ceria particles were synthesized via a solid-state displacement reaction method, and their crystalline structure was controlled by regulating the oxygen partial pressure at the reaction site on the precursor. The crystalline structures of ceria particles were analyzed by the high-resolution TEM nano-beam diffraction pattern. In a calcination process with a high oxygen concentration, the synthesized ceria particles had a cubic fluorite structure (CeO(2)), because of the decarbonation of the cerium precursor. However, a low oxygen concentration results in a hexagonal phase cerium oxide (Ce(2)O(3)) rather than the cubic phase due to the insufficient oxidation of Ce(3+) to Ce(4+). In the STI CMP evaluation, the ceria slurry prepared with the cubic CeO(2) shows enhanced performances of the oxide-to-nitride removal selectivity. PMID:18562111

  17. A relationship between three-dimensional surface hydration structures and force distribution measured by atomic force microscopy

    NASA Astrophysics Data System (ADS)

    Miyazawa, Keisuke; Kobayashi, Naritaka; Watkins, Matthew; Shluger, Alexander L.; Amano, Ken-Ichi; Fukuma, Takeshi

    2016-03-01

    Hydration plays important roles in various solid-liquid interfacial phenomena. Very recently, three-dimensional scanning force microscopy (3D-SFM) has been proposed as a tool to visualise solvated surfaces and their hydration structures with lateral and vertical (sub) molecular resolution. However, the relationship between the 3D force map obtained and the equilibrium water density, ρ(r), distribution above the surface remains an open question. Here, we investigate this relationship at an interface of an inorganic mineral, fluorite, and water. The force maps measured in pure water are directly compared to force maps generated using the solvent tip approximation (STA) model and from explicit molecular dynamics simulations. The results show that the simulated STA force map describes the major features of the experimentally obtained force image. The agreement between the STA data and the experiment establishes the correspondence between the water density used as an input to the STA model and the experimental hydration structure and thus provides a tool to bridge the experimental force data and atomistic solvation structures. Further applications of this method should improve the accuracy and reliability of both interpretation of 3D-SFM force maps and atomistic simulations in a wide range of solid-liquid interfacial phenomena.Hydration plays important roles in various solid-liquid interfacial phenomena. Very recently, three-dimensional scanning force microscopy (3D-SFM) has been proposed as a tool to visualise solvated surfaces and their hydration structures with lateral and vertical (sub) molecular resolution. However, the relationship between the 3D force map obtained and the equilibrium water density, ρ(r), distribution above the surface remains an open question. Here, we investigate this relationship at an interface of an inorganic mineral, fluorite, and water. The force maps measured in pure water are directly compared to force maps generated using the solvent

  18. Sum frequency generation spectroscopy of imidazolium-based ionic liquids with cyano-functionalized anions at the solid salt-liquid interface.

    PubMed

    Peñalber, Chariz Y; Baker, Gary A; Baldelli, Steven

    2013-05-16

    A surface-sensitive nonlinear vibrational spectroscopic technique, sum frequency generation (SFG), has been used to study cyano-containing ionic liquids in contact with two different solid salt surfaces. Specifically, the interfacial chemistry of BaF2(111) single-crystal and solid NaCl{100} surfaces in contact with ionic liquids such as [BMIM][SCN], [BMIM][DCA], [BMIM][TCM], and [EMIM][TCB] has been investigated. Spectral features in both C-H and C-N stretching regions were assigned, with a detailed discussion of the nature of surface interactions and ordering of the ionic liquid ions at the interface of the different crystals. Results showed that [BMIM](+) cations adhered closely via Coulombic interactions to the negatively charged NaCl{100} surface, while [SCN](-), [TCM](-), and [DCA](-) anions revealed a strong electrostatic affinity to the positively charged BaF2(111) surface. Ions of the ionic liquid adsorbed to the solid salt surface to form a Helmholtz-like electric double layer. The linear [SCN](-) anion has a particularly strong affinity to the BaF2(111) surface, resulting in a first layer of anions directly in contact with BaF2(111) containing an effective negative surface excess charge. This promoted ordering of the cations in the second layer to counter the charge excess. At the BaF2(111)-[EMIM][TCB] interface, however, a strongly bound layer of anions populating the first layer resulted in a much larger counterion charge delivered near the crystal salt surface than required to effectively neutralize the initial surface charge from the crystal. As a result, strong resonances from the cation were observed at the BaF2(111) surface, suggesting a more complicated structure of the double layer at the interface than a simple Helmholtz-type model. PMID:23650965

  19. Structural phase transitions in ionic conductor Bi2O3 by temperature dependent XPD and XAS

    NASA Astrophysics Data System (ADS)

    Zhu, Yingcai; An, Pengfei; Yu, Meijuan; Marcelli, Augusto; Liu, Yong; Hu, Tiandou; Xu, Wei

    2016-05-01

    The superionic behavior of cubic δ-phase Bi2O3, a metastable phase at high temperature, is of great interests from both scientific and technological perspectives. With the highest ionic conductivity among all known compounds, the δ-phase Bi2O3 possesses promising applications in solid-oxide fuel cells. Previous investigations pointed out the α to δ- phase transition occurs during the heating process, as supported by the X-ray and Neutron diffraction experiments. Through in situ measurements of the long-range order structure and the local structure by X-ray powder diffraction and X-ray absorption spectroscopy, we investigated the evolution of the structures under different temperatures. Both techniques provided ample evidence that the existence of meta-stable β-phase are crucial for forming the defective fluorite cubic δ phase. Our finding suggested that the phase transition from tetragonal β-phase to δ-phase is an influencing factor for the generation of the oxygen-ion pathways.

  20. Crystal structures of orthorhombic, hexagonal, and cubic compounds of the Sm{sub (x)}Yb{sub (2−x)}TiO{sub 5} series

    SciTech Connect

    Aughterson, Robert D.; Lumpkin, Gregory R.; Reyes, Massey de los; Sharma, Neeraj; Ling, Christopher D.; Gault, Baptiste; Smith, Katherine L.; Avdeev, Maxim; Cairney, Julie M.

    2014-05-01

    A series of single phase compounds with nominal stoichiometry Sm{sub (x)}Yb{sub (2−x)}TiO{sub 5} (x=2, 1.4, 1, 0.6, and 0) have been successfully fabricated to generate a range of crystal structures covering the most common polymorphs previously discovered in the Ln{sub 2}TiO{sub 5} series (Ln=lanthanides and yttrium). Four of the five samples have not been previously fabricated in bulk, single phase form so their crystal structures are refined and detailed using powder synchrotron and single crystal x-ray diffraction, neutron diffraction and transmission electron microscopy. Based on the phase information from diffraction data, there are four crystal structure types in this series; orthorhombic Pnma, hexagonal P6{sub 3}/mmc, cubic (pyrochlore-like) Fd-3m and cubic (fluorite-like) Fm-3m. The cubic materials show modulated structures with variation between long and short range ordering and the variety of diffraction techniques were used to describe these complex crystal structure types. - Graphical abstract: A high resolution image of the compound Sm{sub 0.6}Yb{sub 1.4}TiO{sub 5} showing contrast from lattice fringes and the corresponding fast Fourier transform (FFT) of the HREM image with pyrochlore related diffraction spots marked “P” and fluorite marked “F”. The crystal is oriented down the [1 1 0] zone axis based on the Fd-3m structure. The ideal crystal structure (no vacancies) of the cubic, pyrochlore-like (Sm{sub 0.6}Yb{sub 1.4}TiO{sub 5}). - Highlights: • First fabrication of bulk single-phase material with stoichiometry Sm{sub 2}TiO{sub 5}. • Systematic study of crystal structure types within Ln{sub 2}TiO{sub 5} series (Ln=lanthanides). • A novel technique using IFFT of HREM images to study cubic structures.

  1. Generality of the 18-n Rule: Intermetallic Structural Chemistry Explained through Isolobal Analogies to Transition Metal Complexes.

    PubMed

    Yannello, Vincent J; Fredrickson, Daniel C

    2015-12-01

    Intermetallic phases exhibit a vast structural diversity in which electron count is known to be one controlling factor. However, chemical bonding theory has yet to establish how electron counts and structure are interrelated for the majority of these compounds. Recently, a simple bonding picture for transition metal (T)-main group (E) intermetallics has begun to take shape based on isolobal analogies to molecular T complexes. This bonding picture is summarized in the 18-n rule: each T atom in a T-E intermetallic phase will need 18-n electrons to achieve a closed-shell 18-electron configuration, where n is the number of electron pairs it shares with other T atoms in multicenter interactions isolobal to T-T bonds. In this Article, we illustrate the generality of this rule with a survey over a wide range of T-E phases. First, we illustrate how three structural progressions with changing electron counts can be accounted for, both geometrically and electronically, with the 18-n rule: (1) the transition between the fluorite and complex β-FeSi2 types for TSi2 phases; (2) the sequence from the marcasite type to the arsenopyrite type and back to the marcasite type for TSb2 compounds; and (3) the evolution from the AuCu3 type to the ZrAl3 and TiAl3 types for TAl3 phases. We then turn to a broader survey of the applicability of the 18-n rule through a study of the following 34 binary structure types: PtHg4, CaF2 (fluorite), Fe3C, CoGa3, Co2Al5, Ru2B3, β-FeSi2, NiAs, Ni2Al3, Rh4Si5, CrSi2, Ir3Ga5, Mo3Al8, MnP, TiSi2, Ru2Sn3, TiAl3, MoSi2, CoSn, ZrAl3, CsCl, FeSi, AuCu3, ZrSi2, Mn2Hg5, FeS2 (oP6, marcasite), CoAs3 (skutterudite), PdSn2, CoSb2, Ir3Ge7, CuAl2, Re3Ge7, CrP2, and Mg2Ni. Through these analyses, the 18-n rule is established as a framework for interpreting the stability of 341 intermetallic phases and anticipating their properties. PMID:26581113

  2. Interlayer Communication in Aurivillius Vanadate to Enable Defect Structures and Charge Ordering.

    PubMed

    Zhang, Yaoqing; Yamamoto, Takafumi; Green, Mark A; Kageyama, Hiroshi; Ueda, Yutaka

    2015-11-16

    The fluorite-like [Bi2O2](2+) layer is a fundamental building unit in a great variety of layered compounds. Here in this contribution, we presented a comprehensive study on an unusual Aurivillius phase Bi3.6V2O10 with respect to its defect chemistry and polymorphism control as well as implications for fast oxide ion transport at lower temperatures. The bismuth oxide layer in Bi4V2O11 is found to tolerate a large number of Bi vacancies without breaking the high temperature prototype I4/mmm structure (γ-phase). On cooling, an orthorhombic distortion occurs to the γ-phase, giving rise to a different type of phase (B-phase) in the intermediate temperature region. Cooling to room temperature causes a further transition to an oxygen-vacancy ordered A-phase, which is accompanied by the charge ordering of V(4+) and V(5+) cations, providing magnetic (d(1)) and nonmagnetic (d(0)) chains along the a axis. This is a novel charge ordering transition in terms of the concomitant change of oxygen coordination. Interestingly, upon quenching, both the γ- and B-phase can be kinetically trapped, enabling the structural probing of the two phases at ambient temperature. Driven by the thermodynamic forces, the oxide anion in the γ-phase undergoes an interlayer diffusion process to reshuffle the compositions of both Bi-O and V-O layers. PMID:26502341

  3. Structural and spectroscopic study of a novel erbium titanate pink pigment prepared by sol-gel methodology.

    PubMed

    Martos, Mónica; Julian-López, Beatriz; Cordoncillo, Eloisa; Escribano, Purificación

    2008-02-28

    Pyrochlore oxides show a large variety of physical and chemical properties depending on the ordering/disordering of the cations and oxygen vacancies. Taking account of these structural features and the luminescent properties of lanthanides, a new family of colored materials is investigated. This paper studies the structural evolution of the erbium titanate system with temperature to establish its influence on the color properties. The success on the development of color is completely related to the sol-gel preparation method, underlining its higher reactivity compared to classical solid-state synthesis. After firing at 700 degrees C, the sol-gel material develops an intense pink coloration whose intensity significantly diminishes at 800 degrees C. X-ray diffraction and Rietveld refinements indicated the presence of nanocrystals with a fluorite-like structure at 700 degrees C, responsible for the intense coloration, which suffers a gradual atomic rearrangement toward an "ideal" pyrochlore phase. These results were corroborated by infrared and Raman measurements. UV-vis spectroscopy showed the influence of the Er(3+)-O bond covalence on the spectral properties. This study opens new perspectives to the development of more ecological colored sol-gel materials based on rare earth elements. Furthermore, the combination of the optical aspects with the classical pyrochlore properties (magnetization, heat capacity, conductivity, etc.) would provide new multifunctional materials for advanced applications. PMID:18247597

  4. Structure and phase composition of nanocrystalline Ce{sub 1-x}Lu{sub x}O{sub 2-y}

    SciTech Connect

    Malecka, Malgorzata A.; Kepinski, Leszek Maczka, Miroslaw

    2008-09-15

    The microstructure and phase stability of nanocrystalline mixed oxide Lu{sub x}Ce{sub 1-x}O{sub 2-y} (x=0-1) are described. Nano-sized (3-4 nm) oxide particles were prepared by the reverse microemulsion method. Morphological and structural changes upon heat treatment in an oxidizing atmosphere were studied by transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman and Yb{sup 3+} emission spectroscopy, the latter ion being present as an impurity in the Lu{sub 2}O{sub 3} starting material. Up to 950 deg. C, the samples were single phase, with structure changing smoothly with Lu content from fluorite type (F) to bixbyite type (C). For the samples heated at 1100 deg. C phase separation into coexisting F- and C-type structures was observed for 0.35

  5. Effect of annealing temperature on the structural and optical properties of CeO2:Ni thin films

    NASA Astrophysics Data System (ADS)

    Murugan, R.; Vijayaprasath, G.; Sakthivel, P.; Mahalingam, T.; Ravi, G.

    2016-05-01

    High quality Ni-doped CeO2 (CeO2:Ni) thin films were deposited on glass substrates at room temperature by using radio frequency magnetron sputtering. The effect of annealing temperature on structural and optical properties of the CeO2:Ni films was investigated. The structural, optical and vibrational properties of the films were determined using X-ray diffraction (XRD), photoluminescence spectrometer (PL) and Raman spectrometer. It was found that the as-deposited film has a fluorite cubic structure. By increasing annealing temperature from 100°C to 300°C, the crystalline quality of the thin films could be improved. The UV and visible band emissions were observed in the photoluminescence spectra, due to exciton, defect related emissions respectively. The micro-Raman results show the characteristic peak of CeO2 F2g at 465 cm-1 and 2L0 at 1142 cm-1. Defect peaks like D and 0 bands were observed at 641 cm-1 and 548 cm-1 respectively. It is found from the spectra that the peak intensity of the films increased with increase of annealing temperature.

  6. Structure of delta-Bi{sub 2}O{sub 3} from density functional theory: A systematic crystallographic analysis

    SciTech Connect

    Aidhy, Dilpuneet S.; Sinnott, Susan B.; Wachsman, Eric D.; Phillpot, Simon R.; Nino, Juan C.

    2009-05-15

    A systematic crystallographic analysis of the <110> and <111> vacancy-ordered structure of cubic delta-Bi{sub 2}O{sub 3} obtained from electronic-structure calculations is presented. The ordering of vacancies leads to a doubling of the unit-cell that results in a 2x2x2 fluorite super-structure, with an associated reduction in its space group symmetry from Fm3-barm to Fm3-bar. The Bi atoms present inside the <111> vacancy-ordered oxygen sublattice have equal Bi-O bond lengths, whereas, those present inside the <110> vacancy-ordered oxygen sublattice have three different pairs of Bi-O bond lengths. The specific ionic displacements and electronic charge configurations also depend on the nature of vacancy ordering in the oxygen sub-lattice. - Graphical abstract: 1/8 of a 2x2x2 delta-Bi{sub 2}O{sub 3} superstructure having Fm3-bar space group. Every oxygen (black) has three possible positions, only one of which is filled either by O1 (red) or O{sub 2} (blue).

  7. Electronic and structural properties of the surfaces and interfaces of indium oxide

    NASA Astrophysics Data System (ADS)

    Walsh, Aron

    2011-12-01

    Indium sesquioxide is a transparent conducting oxide material widely used in solar cell and solid-state lighting devices. Following our recent successes in modeling the electronic and defect properties of In2O3, we report an investigation of the surface physics of this material. In the ground-state bixbyite phase, the surface energies follow the order (100)>(110)>(111), with the charge neutral (111) termination being the lowest energy cleavage plane; the same ordering preferences have been established for materials adopting the parent fluorite (AB2) structure. Our first-principles predictions, based on density functional theory, are confirmed through collaboration with the group of Russell Egdell at Oxford University, who grew epitaxial In2O3 single crystals on lattice matched (100),(110) and (111) Y-stabilized zirconia substrates, and observed that (111) facets spontaneously form on other low index terminations. Furthermore, we have performed work function analysis of the low index In2O3 surfaces using a hybrid density functional, which is found to be in very good agreement with recent experiments.

  8. Effect of host structure on the photoluminescence properties of Ln3TaO7:Eu3+ red phosphors

    NASA Astrophysics Data System (ADS)

    Linda Francis, T.; Prabhakar Rao, P.; Mahesh, S. K.; Sreena, T. S.; Parvathi Babu, S.

    2016-02-01

    Eu3+ doped Ln3TaO7 (Ln = La, Gd, Y, Lu) red phosphors were prepared using a solid state route. The Ln3+ substitution induces variation of crystalline structure from a defect fluorite to weberite types with increased ordering of the cations from Lu to La. These phosphors show strong absorptions at near UV wavelength and emit orange-red luminescence. The increased trend in luminescence lifetime further surmises uniform distribution of Eu3+ ions from Lu to La. The luminescence intensity and quantum efficiency are closely related to the degree of ordering of the cations in the lattice. The Eu3+ luminescence in La3TaO7 embodies the structural variation through intense multiband 5D0 → 7F0,1,2,4 transitions to only dominant hypersensitive electric dipole 5D0 → 7F2 transition. All the Eu3+ emission transitions (5D0 → 7F0,1,2,4) are more intense in La3TaO7 host due to increased polarizability and covalent nature of Eu3+ bonding environment with the surrounding.

  9. DFT study on the electronic structure and chemical state of Americium in an (Am,U) mixed oxide

    NASA Astrophysics Data System (ADS)

    Suzuki, Chikashi; Nishi, Tsuyoshi; Nakada, Masami; Tsuru, Tomohito; Akabori, Mitsuo; Hirata, Masaru; Kaji, Yoshiyuki

    2013-12-01

    We investigated the electronic state of an (Am,U) mixed oxide with the fluorite structure using the all-electron full potential linear augmented plane wave method and compared it with those of Am2O3, AmO2, UO2, and La0.5U0.5O2. The valence of Am in the mixed oxide was close to that of Am2O3 and the valence of U in the mixed oxide was pentavalent. The electronic structure of AmO2 was different from that of Am2O3, particularly just above the Fermi level. In addition, the electronic states of Am and U in the mixed oxide were similar to those of trivalent Am and pentavalent U oxides. These electronic states reflected the high oxygen potential of AmO2 and the heightened oxygen potential resulting from the addition of Am to UO2 and also suggested the occurrence of charge transfer from Am to U in the solid solution process.

  10. High-pressure X-ray diffraction, Raman, and computational studies of MgCl2 up to 1 Mbar: Extensive pressure stability of the β-MgCl2 layered structure

    NASA Astrophysics Data System (ADS)

    Stavrou, Elissaios; Zaug, Joseph; Bastea, Sorin; Kuo, I.-Feng; Crowhurst, Jonathan; Kalkan, Bora; Kunz, Martin; Konopkova, Zuzana

    Magnesium chloride with the rhombohedral layered CdCl2-type structure (α-MgCl2) has been studied using x-ray diffraction and Raman spectroscopy up to 1 Mbar. The results reveal a second-order phase transition to a hexagonal layered CdI2-type structure at 0.7 GPa. This phase transition affects the stacking of the Cl anions, resulting to a shorter c-axis. An anisotropic compression along c-axis was observed during initial compression; altered above 10 GPa due to the repulsion between adjacent Cl-layers. According to previous theoretical studies, a series of phase transitions towards, initially, the 3D rutile (6-fold Mg cations) at 17 GPa and to fluorite structure (8-fold Mg cations) at 70 GPa are proposed. According to our experimental study MgCl2 remains in a 2D layered structure up to 1Mbar keeping the 6-fold coordination of Mg cations. This observation contradicts with the general structural behavior of compressed AB2 compounds; we conducted ab-initio calculations to elucidate the mechanisms that extend the remarkable structural stability of MgCl2. This work was performed under the auspices of the U. S. Department of Energy by Lawrence Livermore National Security, LLC under Contract DE-AC52-07NA27344.

  11. The influence of crystal structure on ion-irradiation tolerance in the Sm(x)Yb(2-x)TiO5 series

    NASA Astrophysics Data System (ADS)

    Aughterson, R. D.; Lumpkin, G. R.; de los Reyes, M.; Gault, B.; Baldo, P.; Ryan, E.; Whittle, K. R.; Smith, K. L.; Cairney, J. M.

    2016-04-01

    This ion-irradiation study covers the four major crystal structure types in the Ln2TiO5 series (Ln = lanthanide), namely orthorhombic Pnma, hexagonal P63/mmc, cubic (pyrochlore-like) Fd-3m and cubic (fluorite-like) Fm-3m. This is the first systematic examination of the complete Ln2TiO5 crystal system and the first reported examination of the hexagonal structure. A series of samples, based on the stoichiometry Sm(x)Yb(2-x)TiO5 (where x = 2, 1.4, 1, 0.6, and 0) have been irradiated using 1 MeV Kr2+ ions and characterised in-situ using a transmission electron microscope. Two quantities are used to define ion-irradiation tolerance: critical dose of amorphisation (Dc), which is the irradiating ion dose required for a crystalline to amorphous transition, and the critical temperature (Tc), above which the sample cannot be rendered amorphous by ion irradiation. The structure type plus elements of bonding are correlated to ion-irradiation tolerance. The cubic phases, Yb2TiO5 and Sm0.6Yb1.4TiO5, were found to be the most radiation tolerant, with Tc values of 479 and 697 K respectively. The improved radiation tolerance with a change in symmetry to cubic is consistent with previous studies of similar compounds.

  12. Local structure in solid solutions of stabilised zirconia with actinide dioxides (UO{sub 2}, NpO{sub 2})

    SciTech Connect

    Walter, Marcus; Somers, Joseph; Bouexiere, Daniel; Rothe, Joerg

    2011-04-15

    The local structure of (Zr,Lu,U)O{sub 2-x} and (Zr,Y,Np)O{sub 2-x} solid solutions has been investigated by extended X-ray absorption fine structure (EXAFS). Samples were prepared by mixing reactive (Zr,Lu)O{sub 2-x} and (Zr,Y)O{sub 2-x} precursor materials with the actinide oxide powders, respectively. Sintering at 1600 {sup o}C in Ar/H{sub 2} yields a fluorite structure with U(IV) and Np(IV). As typical for stabilised zirconia the metal-oxygen and metal-metal distances are characteristic for the different metal ions. The bond lengths increase with actinide concentration, whereas highest adaptation to the bulk stabilised zirconia structure was observed for U---O and Np---O bonds. The Zr---O bond shows only a slight increase from 2.14 A at 6 mol% actinide to 2.18 A at infinite dilution in UO{sub 2} and NpO{sub 2}. The short interatomic distance between Zr and the surrounding oxygen and metal atoms indicate a low relaxation of Zr with respect to the bulk structure, i.e. a strong Pauling behaviour. -- Graphical abstract: Metal-oxygen bond distances in (Zr,Lu,U)O{sub 2-x} solid solutions with different oxygen vacancy concentrations (Lu/Zr=1 and Lu/Zr=0.5). Display Omitted Research Highlights: {yields} EXAFS indicates high U and Np adaption to the bulk structure of stabilised zirconia. {yields} Zr---O bond length is 2.18 A at infinite Zr dilution in UO{sub 2} and NpO{sub 2}. {yields} Low relaxation (strong Pauling behaviour) of Zr explains its low solubility in UO{sub 2}.

  13. Mg Doping Induced Effects on Structural, Optical, and Electrical Properties as Well as Cytotoxicity of CeO2 Nanostructures

    NASA Astrophysics Data System (ADS)

    Iqbal, Javed; Jan, Tariq; Awan, M. S.; Naqvi, Sajjad Haider; Badshah, Noor; ullah, Asmat; Abbas, Fazzal

    2016-04-01

    Here, Mg x Ce1- x O2 (where x = 0, 0.01, 0.02, 0.03, 0.04, and 0.05) nanostructures have been successfully synthesized by using a simple, easy, and cost-effective soft chemical method. X-ray diffraction (XRD) patterns substantiate the single-phase formation of a CeO2 cubic fluorite structure for all samples. Infrared spectroscopy results depict the presence of peaks only related to Ce-O bonding, which confirms the XRD results. It has been observed via ultraviolet (UV)-visible spectroscopy that Mg doping has tuned the optical band gap of CeO2 significantly. The electrical conductivity of CeO2 nanostructures has been found to increase with Mg doping, which is attributed to enhancement in carrier concentration due to the different valance states of dopant and host ions. Selective cytotoxic behavior of Mg x Ce1- x O2 nanostructures has been determined for neuroblastoma (SH-SY5Y) cancerous and HEK-293 healthy cells. Both doped and undoped CeO2 nanostructures have been found to be toxic for cancer cells and safe toward healthy cells. This selective toxic behavior of the synthesized nanostructures has been assigned to the different levels of reactive oxygen species (ROS) generation in different types of cells. This makes the synthesized nanostructures a potential option for cancer therapy in the near future.

  14. Structural, optical and dielectric properties of Ce0.9Nd0.1O1.95 nanocrystalline oxygen ion conductors: Effect of sintering temperature

    NASA Astrophysics Data System (ADS)

    Anirban, Sk.; Dutta, A.

    2015-01-01

    Neodymium doped nanocrystalline ceria [Ce0.9Nd0.1O1.95] was prepared through citrate auto-ignition method. The prepared samples were sintered at five different temperatures starting from 400 °C up to 1200 °C. Rietveld's powder structure refinement analysis of XRD data confirmed the single phase cubic fluorite structure of the prepared samples with space group Fm 3 barm and the obtained particle size and lattice parameter values were found to vary with sintering temperature from 6.68 nm to 39.51 nm and from 5.39077 Å to 5.42317 Å respectively. The optical properties were studied using FT-IR and UV-vis absorption spectra. The FT-IR spectra confirm the presence of functional groups and chemical bonding in the material. The optical band gap was calculated from UV-vis spectra and its value was found to decrease from 3.70 eV to 2.46 eV with increase in sintering temperature. The dc conductivity was found to be thermally activated and decreased with increase in sintering temperature. The nature of impedance spectra reveals the presence of both grain and grain boundary effect. The tangent loss exhibited the presence of relaxation peaks due to the presence of defect pair in the synthesized samples.

  15. A TEM investigation of the nucleation, growth and structure of HWE grown lead-tin telluride films

    NASA Astrophysics Data System (ADS)

    Snyman, H. C.; Gouws, G. J.; Muller, R. J.

    1984-12-01

    The epitaxial growth of thin films is usually explained in terms of the interfacial energy of the critical nucleus. In a systematic TEM study of the nucleation and growth of (PbSn)Te on (111) BaF 2 substrates strong evidence is found that the post nucleation stage of recrystallisation and reorientation, rather than nucleation, is dominant in determining the degree of epitaxy. Thin films of various thicknesses were grown, in a hot wall epitaxial (HWE) system, onto (111) BaF 2 substrates at 250°C. Using dark field techniques and microdiffraction the recrystallisation processes and degree of epitaxy were studied as a function of overgrowth thickness. It was found that the degree of epitaxy was critically dependent on the film thickness. Films grown on pre-baked substrates changed from completely polycrystalline at an average thickness of 10 nm to a good epitaxially oriented overgrowth at 150 nm. The driving force for this recrystallisation process is explained in terms of the relative stability of (001) and (111) islands. Electron microscopy and microdiffraction provides direct confirmation of the proposed mechanism and its direction.

  16. Photoelectron Experiments and Studies of X-Ray Absorption Near Edge Structure in Alkaline-Earth and Rare - Fluorides.

    NASA Astrophysics Data System (ADS)

    Gao, Yuan

    Alkaline-earth fluorides and rare-earth trifluorides possess technological importance for applications in multi -layer electronic device structures and opto-electronic devices. Interfaces between thin films of YbF _3 and Si(111) substrates were studied by photoelectron spectroscopy and x-ray absorption spectroscopy using synchrotron radiation. Results of YbF_3 /Si(111) were compared with those of TmF _3/Si(111). While electrons in the Si valence band are prevented from occupying the empty 4f levels in TmF_3 at the interface by the on -site Coulomb repulsion energy, the charge transfer from Si to YbF_3 is possible because the totally filled 4f states in Yb still lie below the Si valence band maximum. The theory of x-ray absorption near edge structure (XANES) is incomplete except for a few particularly simple special cases. A Bragg reflection model was developed to qualitatively explain the oscillations in XANES, in terms of the scattering of the photoelectron wave between families of lattice planes as set out by the Bragg condition for backscattering. The model was found to represent the data for systems with nearly free electron like conduction bands reasonably well. High resolution CaF_2 fluorine K edge XANES was used as a prototype to understand XANES in more depth on systems with strong core hole effects. Unlike previous work which involved multiple scattering cluster calculations that include only short range order effects, both the long range order and the symmetry breaking core holes are included in a new bandstructure approach in which the core hole is treated with a supercell technique. A first principles calculation with the use of pseudopotentials successfully reproduced all the main features of the first 15 eV of the fluorine K edge in CaF_2 which had not been explained with the cluster calculations. A comparison of the theoretical and experimental fluorine K edges in CaF_2 and BaF _2 was used to identify the structure related features. The possibility

  17. Influence of the interfacial phase on the structural integrity and oxygen permeability of a dual-phase membrane.

    PubMed

    Sun, Ming; Chen, Xinwei; Hong, Liang

    2013-09-25

    Compositing fluorite Ce0.8Gd0.2O2-δ (CGO) oxide with perovskite La0.4Ba0.6Fe0.8Zn0.2O3-δ (LBFZ) oxide leads to the formation of a minor interfacial BaCeO3 phase upon sintering at 1400 °C. This interfacial composition assures a gastight ceramic membrane with fine grain-boundary structure, in which the LBFZ phase exhibits an improved oxygen permeability over the pristine LBFZ membrane on the same volumetric basis. The presence of the BaCeO3 phase effectively preserves the structural integrity of the composition by limiting the interfacial diffusion of barium ions between LBFZ and CGO. In comparison, replacing CGO with Y0.08Zr0.92O2-δ in the system results in a substantially low oxygen flux due to an overwhelming interfacial diffusion and, consequently, a heavy degradation of LBFZ. Besides structural reinforcement, the high interface between LBFZ and CGO benefits oxygen transport, as is proven through variation of the oxygen partial pressure on the feed side of the membrane and operation temperature. Furthermore, the trade-off between LBFZ loading and interfacial diffusion yields an optimal CGO loading at 40 wt %, which exhibits an oxygen flux of 0.84 cm(3)/cm(2)·min at 950 °C. In summary, the minor interfacial binding between CGO and LBFZ grains is constructive in easing oxygen crossover in the phase boundary with the exception of maintaining membrane structural stability under oxygen permeation conditions. PMID:23977996

  18. Cell Structure

    MedlinePlus

    ... Cells, Tissues, & Membranes Cell Structure & Function Cell Structure Cell Function Body Tissues Epithelial Tissue Connective Tissue Muscle Tissue ... apparatus , and lysosomes . « Previous (Cell Structure & Function) Next (Cell Function) » Contact Us | Privacy Policy | Accessibility | FOIA | File Formats ...

  19. HfO_2and ZrO2 : Comparison of Structures and Thermodynamic and Electronic Properties Based on Ab Initio Calculations and Experiment

    NASA Astrophysics Data System (ADS)

    Demkov, Alexander A.; Navrotsky, Alexandra

    2001-03-01

    The International Technology Roadmap for Semiconductors (ITRS) predicts that the strategy of scaling complementary metal-oxide-semiconductor (CMOS) devices will come to an abrupt end around the year 2012. The main reason for this will be the unacceptably high leakage current through the silicon dioxide gate with a thickness below 20 ÅFinding a gate insulator alternative to SiO2 has proven to be far from trivial. Hafnium and zirconium dioxides and silicates have been recently considered as gate dielectrics with intermediate dielectric constants. Hafnia and ziconia are important ceramic materials as well, and their phase relations are rather well studied. There is also interest in hafnia as a constituent of ceramic waste forms for plutonium, based on its refractory nature and high neutron absorption cross section. We use a combination of the ab-initio calculations and calorimetry to investigate thermodynamic and electronic properties of hafnia and zirconia. We describe the cubic to tetragonal phase transition in the fluorite structure by computing the total energy surface for zone-edge distortions correct to fourth order in the soft-mode displacement with the strain coupling renormalization included. We compare the two materials using some simple chemical concepts.

  20. Structural Analysis of the Combustion Synthesized Y3+ Doped Ceria (Ce0.9Y0.1O1.95)

    NASA Astrophysics Data System (ADS)

    Jeyanthi, C. Esther; Siddheswaran, R.; Kumar, Pushpendra; Mangalaraja, R. V.; Siva Shankar, V.; Rajarajan, K.

    2013-08-01

    Y3+ doped CeO2 nanopowders (Ce0.9Y0.1O1.95, abbreviated as YDC) were synthesized by citrate-nitrate-auto combustion process using cerium nitrate hexahydrate, yttrium nitrate hexahydrate and citric acid. The as-synthesized powders were calcined at 700°C and converted into dense bodies followed by sintering at 1200°C. The microstructure of the synthesized powders and sintered bodies were examined by scanning electron microscopy (SEM). The surface morphology of the nanoparticles and clusters were also analysed by transmission electron microscopy (TEM). The particles size of the YDC was found to be in the range from 10 to 30 nm, which is in good agreement with the crystallite size calculated from X-ray peak broadening method. Also, the X-ray diffraction confirmed that the Ce0.9Y0.1O1.95 crystallizes as the cubic fluorite structure of pure ceria. The optical absorption by functional molecules, impurities and oxygen vacancies were analysed by FTIR and Raman spectroscopic studies. From the FTIR spectrum, the absorption peak found at 530 cm-1 is attributed to the vibrations of metal-oxygen bonds. The characteristic Raman peak was found to be 468 cm-1, and the minute absorption of oxygen vacancies were observed in the region 500-640 cm-1.

  1. Information Structure and Linguistic Structure.

    ERIC Educational Resources Information Center

    Zierer, Ernesto

    1972-01-01

    This document describes a format for analyzing the information content of sentences and the language patterns that accompany particular information content. The author writes in terms of information structures, each information structure having a corresponding linguistic structure composed of distinctive features. The information structure of a…

  2. Electronic structures, hole-doping, and superconductivity of the s = 1, 2, 3, and 4 members of the (Cu, Mo)-12s2 homologous series of superconductive copper oxides.

    SciTech Connect

    Grigoraviciute, I.; Karppinen, M.; Chan, T.-S.; Liu, R.-S.; Chen , J.-M.; Chmaissem, O.; Yamauchi, H.; Materials Science Division; Tokyo Inst. of Tech.; Helsinki Univ. of Technology; National Taiwan Univ.; National Synchrotron Radiation Research Center; Northern Illinois Univ.

    2009-12-17

    We demonstrate that the T{sub c} value of superconductive copper oxides does not depend on the distance between two adjacent CuO{sub 2} planes as long as the hole-doping level and the immediate (crystal) chemical surroundings of the planes are kept the same. Experimental evidence is accomplished for the homologous series of (Cu,Mo)-12s2, the member phases of which differ from each other by the number (s) of cation layers in the fluorite-structured (Ce,Y)-[O{sub 2}-(Ce,Y)]{sub s-1} block between the CuO{sub 2} planes. X-ray absorption near-edge structure spectroscopy is employed as a probe for the hole states of these phases. The s = 1 member appears to be more strongly doped with holes than other phases of the series and accordingly to possess the highest T{sub c} value of 87 K. For s {ge} 2, unexpectedly, both the CuO{sub 2} plane hole concentration and the value of T{sub c} ({approx}55 K) remain constant, being independent of s.

  3. Rare earth niobium oxynitrides, LnNbON{sub 2-{delta}} (Ln = Y, La, Pr, Nd, Gd, Dy): Synthesis, structure and properties

    SciTech Connect

    Kumar, Nitesh; Sundaresan, A.; Rao, C.N.R.

    2011-11-15

    Graphical abstract: Ammonolysis of LnNbO{sub 4} (Ln = rare earth or Y) leads to the formation of oxynitrides of different structures depending on the size of the rare earth. Highlights: {yields} We have carried out ammonolysis of LnNbO{sub 4} (Ln = rare earth and Y) to form oxynitrides of different structures depending on the size of the rare earth. {yields} Infrared spectroscopy shows the marked difference between oxides and the corresponding oxynitrides. {yields} The oxynitrides are stable in air upto {approx}400 {sup o}C above which an intermediate phase with nitrogen molecules attached to the oxide lattice forms. {yields} Gadolinium niobium oxynitride shows paramagnetism. -- Abstract: Ammonolysis of rare earth niobates of the type LnNbO{sub 4} (Ln = Y, La, Pr, Nd, Gd, Dy) yields oxynitrides of different structures. When Ln = La, Nd and Pr, the structure is that of an orthorhombic perovskite of the general formula LnNbON{sub 2}. As the size of the rare earth decreases, the oxynitride has a nitrogen-deficient defect fluorite (Ln = Pr, Nd, Gd), or pyrochlore (Ln = Y) structure. The IR spectra of the oxynitrides and the corresponding oxides are significantly different. Thermogravimetric analysis suggests the formation of an intermediate phase wherein the N{sub 2} molecule is attached to the oxide lattice above 400 {sup o}C and decomposes to give the oxide on heating in an oxygen atmosphere. Raman spectra of the intermediate phases show evidence for the N{identical_to}N stretching vibration. Gadolinium niobium oxynitride is found to be paramagnetic.

  4. Classifying structures

    SciTech Connect

    Buslov, V.M.; Krahl, N.W.

    1985-01-01

    61 concepts are categorized and divided by structure type into bottom-mounted, floating, and island structures. They are either permanent systems or moving systems. They are further subdivided and listed in this paper. The structural designs are all distinguished by the consideration of sea ice. Bottom-mounted structures have been built in water depths from 30 to about 500 feet. To date, only a few steel or concrete structures have been built, but a number are being planned. A list of concrete structures now in operation is provided.

  5. Website Structure

    ERIC Educational Resources Information Center

    Jackson, Larry S.

    2009-01-01

    This dissertation reports the results of an exploratory data analysis investigation of the relationship between the structures used for information organization and access and the associated storage structures within state government websites. Extending an earlier claim that hierarchical directory structures are both the preeminent information…

  6. Structural, mineralogical, and paleoflow velocity constraints on Hercynian tin mineralization: the Achmmach prospect of the Moroccan Central Massif

    NASA Astrophysics Data System (ADS)

    Mahjoubi, El Mahjoub; Chauvet, Alain; Badra, Lakhlifi; Sizaret, Stanislas; Barbanson, Luc; El Maz, Abdelkader; Chen, Yan; Amann, Méderic

    2016-03-01

    The Achmmach tin mineralization (NE of the Moroccan Central Massif) is associated with tourmaline-rich alteration halos, veins, and faults hosted in sandstones and metapelites of the Upper Visean-Namurian. These deposits are reported to be late Hercynian in age and related to the emplacement of late-orogenic granite not outcropping in the studied area. Structural and paragenetic studies of the Achmmach tin deposit were conducted in order to establish a general model of the mineralization. From field constraints, the late Hercynian phase is marked by a transition from transpression to extension with deformation conditions evolving from ductile to brittle environments. The transpression (horizontal shortening direction roughly trending E-W) is coeval with the emplacement of the first tourmaline halos along several conjugated trends (N070, N020, and N120). Thereafter, a tourmaline-rich breccia formed in response to the fracturing of early tourmaline-altered rocks. Subsequently, during the extensional phase, these structures were reactivated as normal faults and breccias, allowing the formation of the main tin mineralization (cassiterite) associated with a wide variety of sulfides (arsenopyrite, chalcopyrite, sphalerite, galena, pyrrhotite, bismuthinite, pyrite, and stannite). This evolution ends with fluorite and carbonate deposition. The hydrothermal fluid flow velocity, calculated by applying statistical measures on the tourmaline growth bands, varies with the lithology. Values are lower in metapelites and higher in breccia. In the general evolution model proposed here, tourmaline alteration makes the rock more competent, allowing for brittle fracturing and generation of open space where the main Sn mineralization was precipitated.

  7. In-situ high temperature irradiation setup for temperature dependent structural studies of materials under swift heavy ion irradiation

    NASA Astrophysics Data System (ADS)

    Kulriya, P. K.; Kumari, Renu; Kumar, Rajesh; Grover, V.; Shukla, R.; Tyagi, A. K.; Avasthi, D. K.

    2015-01-01

    An in-situ high temperature (1000 K) setup is designed and installed in the materials science beam line of superconducting linear accelerator at the Inter-University Accelerator Centre (IUAC) for temperature dependent ion irradiation studies on the materials exposed with swift heavy ion (SHI) irradiation. The Gd2Ti2O7 pyrochlore is irradiated using 120 MeV Au ion at 1000 K using the high temperature irradiation facility and characterized by ex-situ X-ray diffraction (XRD). Another set of Gd2Ti2O7 samples are irradiated with the same ion beam parameter at 300 K and simultaneously characterized using in-situ XRD available in same beam line. The XRD studies along with the Raman spectroscopic investigations reveal that the structural modification induced by the ion irradiation is strongly dependent on the temperature of the sample. The Gd2Ti2O7 is readily amorphized at an ion fluence 6 × 1012 ions/cm2 on irradiation at 300 K, whereas it is transformed to a radiation-resistant anion-deficient fluorite structure on high temperature irradiation, that amorphized at ion fluence higher than 1 × 1013 ions/cm2. The temperature dependent ion irradiation studies showed that the ion fluence required to cause amorphization at 1000 K irradiation is significantly higher than that required at room temperature irradiation. In addition to testing the efficiency of the in-situ high temperature irradiation facility, the present study establishes that the radiation stability of the pyrochlore is enhanced at higher temperatures.

  8. Coilgun structures

    NASA Astrophysics Data System (ADS)

    Andrews, J. A.

    1993-01-01

    Recent research into the optimal design of 'coilgun' structures has indicated that structural requirements are strong functions of launcher classification as well as acceleration mode. Attention is presently given to both closed-form and numerical analytical techniques for coaxial DC accelerator (DCA) structural-design calculations. The DCA is a multistage pulsed-induction launcher that makes extensive use of composite materials technology; measured plastic deformations of the armature after a high energy experiment are compared to FEM analysis predictions.

  9. Aeropropulsion structures

    NASA Technical Reports Server (NTRS)

    Nichols, Lester D.

    1987-01-01

    The structural engineer is faced with unique problems when dealing with aeropropulsion systems. He is faced with extremes in operating temperatures, rotational effects, and behaviors of advanced material systems which combine into complexities that require advances in many scientific disciplines involved in structural analysis and design procedures. This presentation provides an overview of the complexities of aeropropulsion structures and the theoretical, computational, and experimental research conducted to achieve the needed advances.

  10. Structural crashworthiness

    SciTech Connect

    Jones, N.; Wierzbicki, T.

    1983-01-01

    Behind the quest for safety in all forms of transport lies a complex technology of which structural crashworthiness forms an important part. This volume contains the work of over twenty experts whose interests range from the fundamental principles of structural collapse to the application of those principles to the design of ships, aircraft, road vehicles, and rail vehicles. The text focuses on the application of analytical and experimental techniques to predict energy dissipation characteristics of thin-walled structures and structural members under quasi-static and dynamic loadings.