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Notes: [Auszug] The samples were prepared from mixtures of oxides and carbonates by melting at ~400 °C above liquidus temperatures in iron crucibles under an argon atmosphere. Optical examination revealed small blebs of Fe metal in an otherwise homogeneous, crystal-free glass phase. These Fe blebs ...

Notes: Abstract We have made use of the nearly complete linear polarization of synchrotron radiation to study the polarization dependence of X-ray absorption near-edge structure (XANES) and extended fine structure (EXAFS) in oriented single crystals of gillespite (BaFe2+ Si4O10; Fe2 + in square-planar coordination, point symmetry C 4), anatase (TiO2; Ti4+ in octahedral coordination, point symmetry D 2d), and epidote (Ca2(Al, Fe3+)3SiO4)3(OH); Fe3+ in distorted octahedral coordination, point symmetry (C s). For gillespite, the Fe K-XANES spectrum varies strongly with E-vector orientation of the incident X-ray beam. When the E-vector lies in the plane of the FeO4 group (i.e., perpendicular to the c-axis), multiple-scattering features at 7127 and 7131 eV intensify, whereas when the E-vector is perpendicular to the plane of the FeO4 group (i.e., parallel to the c-axis), a strongly-polarized 1s to 4p bound state transition occurs at 7116 eV and a localized continuum resonance occurs at 7122 eV. The Fe-K-EXAFS spectrum of gillespite is also highly polarization dependent. When the E-vector is perpendicular to c, all four nearest-neighbor oxygens around Fe2+ contribute to the EXAFS signal; when E is parallel to c, the EXAFS signal from nearest-neighbors is reduced by at least 86%. The unpolarized Ti K-XANES spectrum of anatase has three relatively strong pre-edge features at 4967.1, 4969.9, and 4972.7 eV which have resisted definitive interpretation in past studies. The lowest energy feature has a strong xy polarization dependence, suggesting a large amount of 4p x,y character, and it is also very sharp, indicating a well-defined transition energy. Both of these observations are consistent with an excitonic state with a binding energy of 2.8 eV. The two higher energy features, which are characteristic of octahedrally-coordinated Ti4+, show little polarization dependence and are probably due to 1s to 3d bound-state transitions, with a small degree of np character in the final state wavefunction. Interpretation of the polarization dependence of Fe K-XANES spectra for epidote is not as straightforward due to the lower space group symmetry (P21/m) relative to gillespite (P4/ncc) and anatase (I41/amd) and the lower point group symmetry (C s) of the M(3) site which contains most of the Fe3+ in the epidote structure. However, the presence of a shoulder at 7121 eV in the E parallel to b spectrum and its absence in the E normal to bc spectrum are consistent with it being a 1s to 4p z bound-state transition. Strong, weakly x, y polarized features near 7126 eV in both spectra are most likely due to localized continuum transitions. Also, the 1s to 3d pre-edge intensity varies in intensity with E-vector orientation which is consistent with displacement of Fe3+ from the center of the M(3) octahedral site. Analysis of EXAFS spectra of epidote in these two polarizations yields bond distances which are within 0.04 Å of previous single-crystal X-ray diffraction analysis. This study demonstrates the utility of polarized X-ray absorption spectroscopy in quantifying the energies and orbital compositions of final state wavefunctions associated with various X-ray induced transitions in transition-metal containing minerals. It also shows that reasonably accurate M-O distances can be obtained for individual bonds oriented in crystallographically non-equivalent directions.

Notes: Abstract Beryllium foil is important for a number of aerospace applications including honeycomb structures and metal-matrix composites. In this study, a method of producjng beryllium foil directly from powder or flake is demonstrated. A variety of foils were produced in the thickness range 90–300 μm, free from defects such as pinholes and excessive surface roughness, and exhibiting sufficient formability for honeycomb manufacture. Foil produced directly from powder or flake exhibits crystallographic texture, microstructure, and formability equivalent to foil produced from more massive precursors.