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Sample records for cu k-edge exafs

  1. Zn-K edge EXAFS study of human nails

    Energy Technology Data Exchange (ETDEWEB)

    Katsikini, M; Mavromati, E; Pinakidou, F; Paloura, E C [School of Physics, Aristotle University of Thessaloniki, 54124 Thessaloniki (Greece); Gioulekas, D, E-mail: katsiki@auth.g [Medical School, Aristotle University of Thessaloniki, 54124 Thessaloniki (Greece)

    2009-11-15

    Extended X-ray absorption fine structure (EXAFS) spectroscopy at the Zn - K edge is applied for the study of the bonding geometry of Zn in human nails. The studied nail clippings belong to healthy donors and donors who suffer from lung diseases. Fitting of the first nearest neighboring shell of Zn reveals that it is bonded with N and S, at distances that take values in the ranges 2.00-2.04 A and 2.23-2.28A, respectively. Zn is four - fold coordinated and the ratio of the number of sulfur and nitrogen atoms (N{sub S}/N{sub N}) in the first coordination shell ranges from 0.52 to 1. The sample that belongs to the donor who suffers from lung fibrosis, a condition that is related to keratinization of the lung tissue, is characterized by the highest number of N{sub S}/N{sub N}. Simulation, using the FEFF8 code, of the Zn - K edge EXAFS spectra with models of tetrahedrally coordinated Zn with 1 (or 2) cysteine and 3 (or 2) histidines is satisfactory.

  2. Iodine K-edge EXAFS analysis of iodide ion-cyclodextrin inclusion complexes in aqueous solution

    International Nuclear Information System (INIS)

    Kaneko, T; Ueda, M; Nagamatsu, S; Konishi, T; Fujikawa, T; Mizumaki, M

    2009-01-01

    We study the structure of inclusion complexes of α-, β-, γ-cyclodextrin with mono-iodide ion in aqueous solution by means of iodine K-edge EXAFS spectroscopy. The analysis is based on the assumption that two kinds of iodide ions exist in KI-cyclodextrin aqueous solution i.e. hydrated mono-iodide ions and one-one mono-iodide-cyclodextrin inclusion complexes. In KI-α-cyclodextrin system, iodine K-edge EXAFS analyse show that the average coordination number of the oxygen atoms in water molecules in the first hydration shell decreases as the fraction of included ions increases. This result suggests that dehydration process accompanies the formation of the inclusion complex. This is not found in the case of β-cyclodextrin, indicating that in this case the iodide ions are included together with the whole first hydration shell.

  3. In situ Ru K-edge EXAFS of CO adsorption on a Ru modified Pt/C fuel cell catalyst

    International Nuclear Information System (INIS)

    Rose, Abigail; Bilsborrow, Robert; King, Colin R.; Ravikumar, M.K.; Qian Yangdong; Wiltshire, Richard J.K.; Crabb, Eleanor M.; Russell, Andrea E.

    2009-01-01

    The Ru-CO bond of CO adsorbed on a Ru modified Pt/C fuel cell catalyst has been directly probed by in situ EXAFS at the Ru K-edge, providing evidence of a CO:metal surface atom ratio greater than 1:1 and that CO is adsorbed at bridging sites associated with Ru atoms at the surface of the catalyst nanoparticles. This result illustrates the limitations of single crystal models as representations of the bonding of adsorbed species at nanoparticle surfaces.

  4. EXAFS investigations of Cu-Mg-O compound

    CERN Document Server

    Sidorenko, A F; Babanov, Y A; Naumov, S V; Samokhvalov, A A

    2001-01-01

    The interest to systems containing copper oxide is connected with the problem of high-temperature superconductivity because of the closeness of its basic physical properties and properties of superconductor mother Cu-compounds. In this work, EXAFS study of the Cu sub 0 sub . sub 2 Mg sub 0 sub . sub 8 O compound is presented. A new iterative algorithm of the solution of ill-posed problem on determining three partial pair correlation functions from one EXAFS-data set near the Cu K-edge is described. The results of X-ray scattering study of a given sample show a presence of a single phase with the MgO structure and a lattice parameter of 4.219 A instead of 4.208 A for pure MgO. From the EXAFS investigations, we find the local distortion of the lattice. We revealed that the short range order differs both from a hypothetical alloy with the MgO structure and from copper oxide.

  5. New insight on the local structure of Cu2+ ion in the solution of CuBr2 by EXAFS studies

    International Nuclear Information System (INIS)

    Yu Meijuan; Chu Wangsheng; Chen Xing; Wu Ziyu

    2009-01-01

    CuBr 2 solutions at different concentrations were studied by extended X-ray absorption fine structure (EXAFS) at the Cu K edge. In the saturated solution Cu 2+ ions have chemical bonds with 3.0 oxygen atoms and 0.9 Br ion at about 1.96 A and 2.42 A, respectively. It indicates that the CuBr 4 -2 configuration exists with a ratio of 25% under this condition. In the dilute solutions no evidence of Br ions contributions in the first shell around Cu 2+ ions occurs. The almost identical X-ray absorption near edge structure (XANES) and EXAFS characters address similar local environments around Cu 2+ in agreement with results of the EXAFS fit taking into account only the contributions of Cu-O bonds.

  6. New insight on the local structure of Cu{sup 2+} ion in the solution of CuBr{sub 2} by EXAFS studies

    Energy Technology Data Exchange (ETDEWEB)

    Yu Meijuan; Chu Wangsheng; Chen Xing; Wu Ziyu, E-mail: wuzy@ustc.edu.c [Institute of High Energy Physics, Chinese Academy of Sciences, Beijing, 100049 (China)

    2009-11-15

    CuBr{sub 2} solutions at different concentrations were studied by extended X-ray absorption fine structure (EXAFS) at the Cu K edge. In the saturated solution Cu{sup 2+} ions have chemical bonds with 3.0 oxygen atoms and 0.9 Br ion at about 1.96 A and 2.42 A, respectively. It indicates that the CuBr{sub 4}{sup -2} configuration exists with a ratio of 25% under this condition. In the dilute solutions no evidence of Br ions contributions in the first shell around Cu{sup 2+} ions occurs. The almost identical X-ray absorption near edge structure (XANES) and EXAFS characters address similar local environments around Cu{sup 2+} in agreement with results of the EXAFS fit taking into account only the contributions of Cu-O bonds.

  7. Bimagnon studies in cuprates with resonant inelastic x-ray scattering at the O K edge. I. Assessment on La2CuO4 and comparison with the excitation at Cu L3 and Cu K edges

    Science.gov (United States)

    Bisogni, V.; Simonelli, L.; Ament, L. J. P.; Forte, F.; Moretti Sala, M.; Minola, M.; Huotari, S.; van den Brink, J.; Ghiringhelli, G.; Brookes, N. B.; Braicovich, L.

    2012-06-01

    We assess the capabilities of magnetic resonant inelastic x-ray scattering (RIXS) at the O K edge in undoped cuprates by taking La2CuO4 as a benchmark case, based on a series of RIXS measurements that we present here. By combining the experimental results with basic theory we point out the fingerprints of bimagnon excitation in the O K edge RIXS spectra. These are a dominant peak around 450 meV, the almost complete absence of dispersion both with π and σ polarization, and the almost constant intensity vs the transferred momentum with σ polarization. This behavior is quite different from Cu L3 edge RIXS giving a strongly dispersing bimagnon tending to zero at the center of the Brillouin zone. This is clearly shown by RIXS measurements at the Cu L3 edge that we present. The Cu L3 bimagnon spectra and those at the Cu K edge—both from the literature and from our data—however, have the same shape. These similarities and differences are understood in terms of different sampling of the bimagnon continuum. This panorama points out the unique possibilities offered by O K RIXS in the study of magnetic excitations in cuprates near the center of the BZ.

  8. EXAFS analysis of a human Cu,Zn SOD isoform focused using non-denaturing gel electrophoresis

    Energy Technology Data Exchange (ETDEWEB)

    Chevreux, Sylviane; Roudeau, Stephane; Deves, Guillaume; Ortega, Richard [Laboratoire de Chimie Nucleaire Analytique et Bioenvironnementale, CNRS UMR5084, Universite Bordeaux 1, Chemin du Solarium, F-33175 Gradignan cedex (France); Solari, Pier Lorenzo [Synchrotron SOLEIL, L' Orme des Merisiers, BP 48, F-91192 Gif-sur-Yvette cedex, Saint-Aubin (France); Alliot, Isabelle; Testemale, Denis; Hazemann, Jean Louis, E-mail: ortega@cenbg.in2p3.f [FAME, ESRF, 6 rue Jules Horowitz, BP220, F-38043 Grenoble cedex (France)

    2009-11-15

    Isoelectric point isoforms of a metalloprotein, copper-zinc superoxide dismutase (CuZnSOD), separated on electrophoresis gels were analyzed using X-ray Absorption Spectroscopy. Mutations of this protein are involved in familial cases of amyotrophic lateral sclerosis. The toxicity of mutants could be relied to defects in the metallation state. Our purpose is to establish analytical protocols to study metallation state of protein isoforms such as those from CuZnSOD. We previously highlighted differences in the copper oxidation state between CuZnSOD isoforms using XANES. Here, we present the first results for EXAFS analyses performed at Cu and Zn K-edge on the majoritary expressed isoform of human CuZnSOD separated on electrophoresis gels.

  9. EXAFS analysis of a human Cu,Zn SOD isoform focused using non-denaturing gel electrophoresis

    Science.gov (United States)

    Chevreux, Sylviane; Solari, Pier Lorenzo; Roudeau, Stéphane; Deves, Guillaume; Alliot, Isabelle; Testemale, Denis; Hazemann, Jean Louis; Ortega, Richard

    2009-11-01

    Isoelectric point isoforms of a metalloprotein, copper-zinc superoxide dismutase (CuZnSOD), separated on electrophoresis gels were analyzed using X-ray Absorption Spectroscopy. Mutations of this protein are involved in familial cases of amyotrophic lateral sclerosis. The toxicity of mutants could be relied to defects in the metallation state. Our purpose is to establish analytical protocols to study metallation state of protein isoforms such as those from CuZnSOD. We previously highlighted differences in the copper oxidation state between CuZnSOD isoforms using XANES. Here, we present the first results for EXAFS analyses performed at Cu and Zn K-edge on the majoritary expressed isoform of human CuZnSOD separated on electrophoresis gels.

  10. EXAFS analysis of a human Cu,Zn SOD isoform focused using non-denaturing gel electrophoresis

    International Nuclear Information System (INIS)

    Chevreux, Sylviane; Roudeau, Stephane; Deves, Guillaume; Ortega, Richard; Solari, Pier Lorenzo; Alliot, Isabelle; Testemale, Denis; Hazemann, Jean Louis

    2009-01-01

    Isoelectric point isoforms of a metalloprotein, copper-zinc superoxide dismutase (CuZnSOD), separated on electrophoresis gels were analyzed using X-ray Absorption Spectroscopy. Mutations of this protein are involved in familial cases of amyotrophic lateral sclerosis. The toxicity of mutants could be relied to defects in the metallation state. Our purpose is to establish analytical protocols to study metallation state of protein isoforms such as those from CuZnSOD. We previously highlighted differences in the copper oxidation state between CuZnSOD isoforms using XANES. Here, we present the first results for EXAFS analyses performed at Cu and Zn K-edge on the majoritary expressed isoform of human CuZnSOD separated on electrophoresis gels.

  11. Local Environment Sensitivity of the Cu K-Edge XANES Features in Cu-SSZ-13: Analysis from First-Principles.

    Science.gov (United States)

    Zhang, Renqin; McEwen, Jean-Sabin

    2018-05-22

    Cu K-edge X-ray absorption near-edge spectra (XANES) have been widely used to study the properties of Cu-SSZ-13. In this Letter, the sensitivity of the XANES features to the local environment for a Cu + cation with a linear configuration and a Cu 2+ cation with a square-linear configuration in Cu-SSZ-13 is reported. When a Cu + cation is bonded to H 2 O or NH 3 in a linear configuration, the XANES has a strong peak at around 8983 eV. The intensity of this peak decreases as the linear configuration is broken. As for the Cu 2+ cations in a square-planar configuration with a coordination number of 4, two peaks at around 8986 and 8993 eV are found. An intensity decrease for both peaks at around 8986 and 8993 eV is found in an NH 3 _4_Z 2 Cu model as the N-Cu-N angle changes from 180 to 100°. We correlate these features to the variation of the 4p state by PDOS analysis. In addition, the feature peaks for both the Cu + cation and Cu 2+ cation do not show a dependence on the Cu-N bond length. We further show that the feature peaks also change when the coordination number of the Cu cation is varied, while these feature peaks are independent of the zeolite topology. These findings help elucidate the experimental XANES features at an atomic and an electronic level.

  12. Effect of atomic vibrations in XANES: polarization-dependent damping of the fine structure at the Cu K-edge of (creat)2CuCl4.

    Science.gov (United States)

    Šipr, Ondřej; Vackář, Jiří; Kuzmin, Alexei

    2016-11-01

    Polarization-dependent damping of the fine structure in the Cu K-edge spectrum of creatinium tetrachlorocuprate [(creat) 2 CuCl 4 ] in the X-ray absorption near-edge structure (XANES) region is shown to be due to atomic vibrations. These vibrations can be separated into two groups, depending on whether the respective atoms belong to the same molecular block; individual molecular blocks can be treated as semi-rigid entities while the mutual positions of these blocks are subject to large mean relative displacements. The effect of vibrations can be efficiently included in XANES calculations by using the same formula as for static systems but with a modified free-electron propagator which accounts for fluctuations in interatomic distances.

  13. Removal of Cu from aqueous solutions by synthetic hydroxyapatite: EXAFS investigation

    International Nuclear Information System (INIS)

    Corami, Alessia; D'Acapito, Francesco; Mignardi, Silvano; Ferrini, Vincenzo

    2008-01-01

    The sorption of aqueous Cu on synthetic hydroxyapatite has been investigated by means of the results of a combined structural simulation and extended X-ray absorption fine structure (EXAFS) analysis. The removal of Cu was studied in batch experiments at 25 ± 2 deg. C. The sorption of Cu follows Langmuir behaviour and was attributed to a two-step mechanism involving surface complexation and ion exchange with Ca resulting in the formation of a copper-containing hydroxyapatite. EXAFS results suggest that the heavy metal is present in the Cu 2+ form. The structural experimental and theoretical analysis shows that Cu is bond to about four O atoms at a distance of about 1.95 A. In all the studied cases the immobilization site of Cu is the same. The fixation of Cu occurs in the surface sites of hydroxyapatite whereas the sorption in the Ca sites in the inner part of the structure is unlikely

  14. Multiple Scattering Analysis of Cu - K EXAFS in Bi2Sr1.5 Cu2O8+δ

    International Nuclear Information System (INIS)

    Roehler, J.; Cruesemann, R.

    1995-01-01

    We have analyzed the Cu K-EXAFS of Bi 2 Sr 1.5 Ca 1.5 Cu 2 O 8+δ using a full multiple scattering analysis in a cluster with diameter d∼ 7.6 A. The layered structure has numerous quasi one-dimensional structural elements which give rise to significant multiple scattering contributions in the EXAFS. We confirm the Sr/Ca ratio of the sample is 1:1, and one Ca atom is located close to a nominal Sr-site. At 40 K the dimpling angle in the CuO 2 -plane is found to be ≤ 3.5 . (author)

  15. Local atomic structure of Zr-Cu and Zr-Cu-Al amorphous alloys investigated by EXAFS method

    International Nuclear Information System (INIS)

    Antonowicz, J.; Pietnoczka, A.; Zalewski, W.; Bacewicz, R.; Stoica, M.; Georgarakis, K.; Yavari, A.R.

    2011-01-01

    Research highlights: → Coordination number, interatomic distances and mean square atomic displacement in Zr-Cu and Zr-Cu-Al glasses. → Icosahedral symmetry in local atomic structure. → Deviation from random mixing behavior resulting from Al addition. - Abstract: We report on extended X-ray absorption fine structure (EXAFS) study of rapidly quenched Zr-Cu and Zr-Cu-Al glassy alloys. The local atomic order around Zr and Cu atoms was investigated. From the EXAFS data fitting the values of coordination number, interatomic distances and mean square atomic displacement were obtained for wide range of compositions. It was found that icosahedral symmetry rather than that of corresponding crystalline analogs dominates in the local atomic structure of Zr-Cu and Zr-Cu-Al amorphous alloys. Judging from bonding preferences we conclude that addition of Al as an alloying element results in considerable deviation from random mixing behavior observed in binary Zr-Cu alloys.

  16. Reduction and re-oxidation of Cu/Al{sub 2}O{sub 3} catalysts investigated with quick-scanning XANES and EXAFS

    Energy Technology Data Exchange (ETDEWEB)

    Stoetzel, J; Luetzenkirchen-Hecht, D; Frahm, R [Department of Physics, University of Wuppertal, Gaussstr. 20, D-42097 Wuppertal (Germany); Kimmerle, B; Baiker, A [Department of Chemistry and Applied Biosciences, ETH Zuerich, CH-8093 Zuerich (Switzerland); Nachtegaal, M [Paul Scherrer Institut, CH-5232 Villigen (Switzerland); Beier, M J; Grunwaldt, J-D, E-mail: j.stoetzel@uni-wuppertal.d, E-mail: jdg@kt.dtu.d [Department of Chemical and Biochemical Engineering, Technical University of Denmark, Building 229, DK-2800 Kgs. Lyngby (Denmark)

    2009-11-15

    In the present study the structure of copper catalysts on alumina support were investigated in situ and time resolved during reduction and re-oxidation at different temperatures with the quick-scanning EXAFS (QEXAFS) technique. Different impregnation times (2 min and 90 min) were chosen for the preparation which resulted in different copper species that show a strong variation in the reduction/re-oxidation behaviour. These dynamic changes as well as possible intermediate phases during the gas atmospheres changes were followed with up to 20 EXAFS spectra per second at the copper K-edge covering an energy range of 450 eV. The high time resolution provided new insights into the dynamics of the catalysts e.g. revealing Cu(I) as intermediate state during re-oxidation. Latest advances in the data acquisition hardware are leading to an improved data quality of spectra collected at the SuperXAS beamline. Thus, not only accurate analysis of the catalysts via XANES but also by EXAFS was possible. This is also due to the recent upgrade to monitor the Bragg angle directly with an encoder during the experiments.

  17. Effect of Cu insertion on structural, local electronic/atomic structure and photocatalyst properties of TiO{sub 2}, ZnO and Ni(OH){sub 2} nanostructures: XANES-EXAFS study

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, Aditya; Varshney, Mayora [Advanced Analysis Centre, Korea Institute of Science and Technology, Seoul, 02792 (Korea, Republic of); Shin, Hyun Joon, E-mail: shj001@postech.ac.kr [Pohang Accelerator Laboratory (POSTECH), Pohang, 37673 (Korea, Republic of); Lee, Byeong-Hyeon [Advanced Analysis Centre, Korea Institute of Science and Technology, Seoul, 02792 (Korea, Republic of); Chae, Keun Hwa, E-mail: khchae@kist.re.kr [Advanced Analysis Centre, Korea Institute of Science and Technology, Seoul, 02792 (Korea, Republic of); Won, Sung Ok, E-mail: sowon@kist.re.kr [Advanced Analysis Centre, Korea Institute of Science and Technology, Seoul, 02792 (Korea, Republic of)

    2017-04-15

    We report detailed investigations on the synthesis, structural, morphology, electronic/atomic structure and photocatalyst properties of Cu doped TiO{sub 2}, ZnO and Ni(OH){sub 2} nanostructures. All of the samples were synthesized by using the chemical precipitation method. Samples were characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), X-ray absorption near edge structure (XANES), extended X-ray absorption fine structure (EXAFS) and photocatalyst measurements. XRD studies revealed single phase nature of the samples and omitted the presence of trivial metallic or binary oxide phases. TiO{sub 2} set of samples have shown nanorod kind of morphology, however TEM images of ZnO and Ni(OH){sub 2} set of samples depicted the spherical morphology of particles. XANES spectra at the Cu K-edge and Cu L-edge, along with the atomic multiplet calculations, revealed the predominance of Cu{sup 2+} ions in all of the samples, within the entire doping range. Ti L-edge and Ti K-edge XANES confirmed the existence of Ti{sup 4+} ions in the pure and Cu doped TiO{sub 2} samples with anatase local structure. Zn L-edge XANES results confirmed the divalent character of Zn ions in the pure and Cu doped ZnO, which is further validated by the Zn K-edge XANES. Ni L-edge and Ni K-edge XANES conveyed the +2 valence state of Ni ions in the pure and Cu doped Ni (OH){sub 2} samples. EXAFS analysis at the Cu K-edge nullifies the formation of Cu metallic clusters and other trivial phases, suggesting random distribution of Cu atoms in the oxide materials. Though, local atomic arrangement of Cu ions is disparate in the different oxide compounds. As an application of the pure and Cu doped TiO{sub 2}, ZnO and Ni(OH){sub 2} nanostructures, towards the degradation of water pollutant dyes, we demonstrate that all of the samples can serve as effective photocatalyst materials towards the degradation of methyl orange aqueous pollutant dye under the UV-light irradiation

  18. Study of apical oxygen atoms in a spin-ladder cuprate compound by X-ray absorption spectroscopy near the Cu K edge

    Energy Technology Data Exchange (ETDEWEB)

    Hatterer, C.J.; Eustache, B.; Collin, L.; Beuran, C.F.; Partiot, C.; Germain, P.; Xu, X.Z.; Lagues, M. [CNRS, Paris (France). Surfaces et Supraconducteurs; Michalowicz, A. [Laboratoire de Physique des Milieux Desordonnes, Universite Paris XII Val-de-Marne, 61 avenue du general de Gaulle, 94010, Creteil Cedex (France)]|[LURE, Universite Paris Sud, 91405, Orsay Cedex (France); Moscovici, J. [Laboratoire de Physique des Milieux Desordonnes, Universite Paris XII Val-de-Marne, 61 avenue du general de Gaulle, 94010, Creteil Cedex (France); Deville Cavellin, C. [CNRS, Paris (France). Surfaces et Supraconducteurs]|[Laboratoire d`Electronique, Universite Paris XII Val-de-Marne, 61 av. du general de Gaulle, 94010, Creteil Cedex (France); Traverse, A. [LURE, Universite Paris Sud, 91405, Orsay Cedex (France)

    1997-04-01

    The structure of high-T{sub c} superconducting cuprate compounds is based on CuO{sub 2} planes alternating with blocks that behave as charge reservoirs. The apical oxygen atoms which belong to these reservoirs are suspected to play a role in the mechanism of superconductivity. It thus seems necessary to measure the amount of apical oxygen atoms in various compounds, as a function of the superconducting properties. Polarisation dependent X-ray absorption spectroscopy (XAS) measurements were performed near the Cu K-edge on three types of phases. We collected information about the neighbourhood of the copper atom in the cuprate planes and in the direction perpendicular to these planes. Two of these phases have well known structures: Bi2212 in which copper atoms are on a pyramidal site and infinite layer phase, a square planar cuprate without apical oxygen. We used the obtained results as reference data to study a new copper-rich phase related to the spin-ladder series. (orig.)

  19. Structure of bimetallic clusters. Extended x-ray absorption fine structure (EXAFS) studies of Rh--Cu clusters

    International Nuclear Information System (INIS)

    Meitzner, G.; Via, G.H.; Lytle, F.W.; Sinfelt, J.H.

    1983-01-01

    An investigation of the structure of the bimetallic clusters present in rhodium--copper catalysts was conducted with the use of extended x-ray absorption fine structure (EXAFS) measurements. Two catalysts were studied, both employing silica as a support for the clusters and both containing 1 wt. % rhodium. In one catalyst the Cu:Rh atomic ratio was 1:2 and in the other 1:1. Studies were made of the EXAFS associated with the K absorption edges of the rhodium and copper. The results of the EXAFS studies indicate that copper concentrates at the surface of the rhodium--copper clusters. In this regard the results are similar to our earlier reported results on ruthenium--copper clusters. However, the extent of surface segregation of the copper appears to be less pronounced for rhodium--copper clusters. This result is reasonable on the basis that rhodium and copper, unlike ruthenium and copper, exhibit at least some miscibility in the bulk

  20. K-edge densitometer (KED)

    Energy Technology Data Exchange (ETDEWEB)

    Sprinkle, J.K.; Hansen, W.J.

    1993-02-11

    In 1979, a K-edge densitometer (KED) was installed by the Safeguards Assay group from Los Alamos National Laboratory in the PNC reprocessing plant at Tokai-mura, Japan. It uses an active nondestructive assay technique, KED, to measure the plutonium concentration of the product solution. The measurement uncertainty of an assay depends on the count time chosen, but can be 0.5% or better. The computer hardware and software were upgraded in 1992. This manual describes the operation of the instrument, with an emphasis on the user interface to the software.

  1. Laboratory EXAFS using photographic method

    International Nuclear Information System (INIS)

    Joshi, S K; Gaur, A; Johari, A; Shrivastava, B D

    2009-01-01

    Laboratory EXAFS facilities have been used since long. However, EXAFS data analysis has not been reported as yet for the spectra recorded photographically. Though from our laboratory we have been reporting various studies employing X-ray spectrographs using the photographic method of registration of EXAFS spectra, but the data has never been analyzed using the Fourier transformation method and fitting with standards. This paper reports the study of copper metal EXAFS spectra at the K-edge recorded photographically employing a 400 mm curved mica crystal Cauchois type spectrograph with 0.5 kW tungsten target X-ray tube. The data obtained in digital form with the help of a microphotometer has been processed using EXAFS data analysis programs Athena and Artemis. The experimental data for copper metal foil have been fitted with the theoretical standards. The results have been compared with those obtained from another laboratory EXAFS set up employing 12 kW Rigaku rotating anode, Johansson-type spectrometer with Si(311) monochromator crystal and scintillation counter. The results have also been compared with those obtained from SSRL. The parameters obtained for the first two shells from the photographic method are comparable with those obtained from the other two methods. The present work shows that the photographic method of registering EXAFS spectra in laboratory set up using fixed target X-ray tubes can also be used for getting structural information at least for the first two coordination shells.

  2. Laboratory EXAFS using photographic method

    Energy Technology Data Exchange (ETDEWEB)

    Joshi, S K [Government College, Badnawar (Dhar)-454660 (India); Gaur, A; Johari, A; Shrivastava, B D, E-mail: joshisantoshk@yahoo.co [School of Studies in Physics, Vikram University, Ujjain-456010 (India)

    2009-11-15

    Laboratory EXAFS facilities have been used since long. However, EXAFS data analysis has not been reported as yet for the spectra recorded photographically. Though from our laboratory we have been reporting various studies employing X-ray spectrographs using the photographic method of registration of EXAFS spectra, but the data has never been analyzed using the Fourier transformation method and fitting with standards. This paper reports the study of copper metal EXAFS spectra at the K-edge recorded photographically employing a 400 mm curved mica crystal Cauchois type spectrograph with 0.5 kW tungsten target X-ray tube. The data obtained in digital form with the help of a microphotometer has been processed using EXAFS data analysis programs Athena and Artemis. The experimental data for copper metal foil have been fitted with the theoretical standards. The results have been compared with those obtained from another laboratory EXAFS set up employing 12 kW Rigaku rotating anode, Johansson-type spectrometer with Si(311) monochromator crystal and scintillation counter. The results have also been compared with those obtained from SSRL. The parameters obtained for the first two shells from the photographic method are comparable with those obtained from the other two methods. The present work shows that the photographic method of registering EXAFS spectra in laboratory set up using fixed target X-ray tubes can also be used for getting structural information at least for the first two coordination shells.

  3. Atomic structure of glassy Mg60Cu30Y10 investigated with EXAFS, x-ray and neutron diffraction, and reverse Monte Carlo simulations

    DEFF Research Database (Denmark)

    Jovari, P.; Saksl, K.; Pryds, Nini

    2007-01-01

    Short range order of amorphous Mg60Cu30Y10 was investigated by x-ray and neutron diffraction, Cu and Y K-edge x-ray absorption fine structure measurements, and the reverse Monte Carlo simulation technique. We found that Mg-Mg and Mg-Cu nearest neighbor distances are very similar to values found...... in crystalline Mg2Cu. The Cu-Y coordination number is 1.1 +/- 0.2, and the Cu-Y distance is similar to 4% shorter than the sum of atomic radii, suggesting that attraction between Cu and Y plays an important role in stabilizing the glassy state. Thermal stability and structure evolution upon annealing were also...

  4. Polarized XANES and EXAFS spectroscopic investigation into copper(II) complexes on vermiculite

    Science.gov (United States)

    Furnare, Luca J.; Vailionis, Arturas; Strawn, Daniel G.

    2005-11-01

    Interaction of heavy metals with clay minerals can dominate solid-solution reactions in soil, controlling the fate of the metals in the environment. In this study we used powdered and polarized extended X-ray absorption fine structure (EXAFS) spectroscopy and X-ray absorption near edge spectroscopy (XANES) to investigate Cu sorbed on Llano vermiculite and compare the results to reported Cu sorption mechanism on Wyoming (WY) smectite and reduced South African (SA) vermiculite. Analysis of the Cu K-edge spectra revealed that Cu sorbed on Llano vermiculite at high ionic strength ( I) has the greatest degree of covalent bond character, followed by Cu sorbed on montmorillonite at high I, and Cu sorbed on reduced SA vermiculite at high I. Cu sorbed on clay minerals at low I has the least covalent character. EXAFS data from Cu sorbed Ca- and K-equilibrated Llano vermiculites showed the presence of a second-shell Al, Si, or Mg backscatterer at 3.02 Å. This distance is consistent with Cu sorbing via a corner-sharing monodentate or bidentate bond. Polarized XANES and EXAFS results revealed that the angle between the Cu atom and the mineral sorption sites is 68° with respect to the [001] direction. From the bond angle and the persistence of the second-shell backscatterer when the interlayer is collapsed (K-equilibration), we conclude that Cu adsorption on the Llano vermiculite is not occurring in the interlayer but rather Cu is adsorbing onto the edges of the vermiculite. Results from this research provide evidence that Cu forms inner-sphere and outer-sphere complexes on clay minerals, and does not form the vast multinuclear surface precipitates that have been observed for Co, Zn, and Ni.

  5. Cu k-edge studies of the charge carries in Th-doped cuprate system R2-xThxCuO4-δ (R = Nd, Sm and Gd)

    International Nuclear Information System (INIS)

    Liang, G.; Yi, Y.; Jardim, R.F.; Wang, L.V.

    1999-01-01

    To further study the charge carrier concentration in electron doped cuprate superconductors, a systematic x-ray absorption near edge structure (XANES) measurement has been carried out on Th-doped superconductor system R 2-x Th x CuO 4-δ (R = Nd, Sm, and Gd). The XANES results show that, similar to the Ce-doped compounds, while the intensity of the Cu 1+ 4p π feature increase with the increase of the Th doping level x, the intensities of the Cu 2+ 4p π and 4p σ features decreases. This clearly indicates that the electrons doped by the Th atoms are injected into the local Cu 3d-orbitals. The normalized Cu 1+ 4p π intensity data show that the Cu 1+ concentration in the Th-doped compound series with different R-elements is linearly proportional to the Th doping-level x. The data suggest that both Ce and Th donate the same fraction of electrons into the Cu sites

  6. Magnetic properties and EXAFS study of nanocrystalline Fe2Mn0.5Cu0.5Al synthesized using mechanical alloying technique

    International Nuclear Information System (INIS)

    Nanto, Dwi; Yang, Dong-Seok; Yu, Seong-Cho

    2014-01-01

    Nanocrystalline Fe 2 Mn 0.5 Cu 0.5 Al has been synthesized by the mechanical alloying technique and studied as a function of milling time. Alloy nature of Fe 2 Mn 0.5 Cu 0.5 Al was observed in a sample milled for 96 h. The magnetic saturation is 4.0 μ B /f.u., which coincidently follows Slater–Pauling rule at 5 K. Nanocrystalline Fe 2 Mn 0.5 Cu 0.5 Al has enhanced saturate magnetization compared to any other fabrication of Fe 2 MnAl reported. Cu element plays an important role in site competes with other elements and may result in the enhancement of saturate magnetization. In accordance to the magnetic results and EXAFS pattern, it was revealed that the dynamics of magnetic properties were confirmed as structural changes of nanocrystalline Fe 2 Mn 0.5 Cu 0.5 Al

  7. EXAFS cumulants of CdSe

    International Nuclear Information System (INIS)

    Diop, D.

    1997-04-01

    EXAFS functions had been extracted from measurements on the K edge of Se at different temperatures between 20 and 300 K. The analysis of the EXAFS of the filtered first two shells has been done in the wavevector range laying between 2 and 15.5 A -1 in terms of the cumulants of the effective distribution of distances. The cumulants C 3 and C 4 obtained from the phase difference and the amplitude ratio methods have shown the anharmonicity in the vibrations of atoms around their equilibrium position. (author). 13 refs, 3 figs

  8. Laser EXAFS

    International Nuclear Information System (INIS)

    Mallozzi, P.J.; Epstein, H.M.; Schwenzel, R.E.; Campbell, B.E.

    1983-01-01

    Apparatus for obtaining EXAFS data of a material, comprising means for directing radiant energy from a laser onto a target in such manner as to produce X-rays at the target of a selected spectrum and intensity, suitable for obtaining the EXAFS spectrum of the material, means for directing X-rays from the target onto spectral dispersive means so located as to direct the spectrally resolved X-rays therefrom onto recording means, and means for positioning a sample of material in the optical path of the X-rays, the recording means providing a reference spectrum of X-rays not affected by the sample and absorption spectrum of X-rays modified by transmission through the sample

  9. XANES at the silicon k-edge in the kaolin-meta kaolin-geopolymer system

    International Nuclear Information System (INIS)

    Lima, F.T.; Silva, F.J.; Thaumaturgo, C.

    2005-01-01

    The geo polymer synthesis process optimization pretends to control the re logical and mechanical properties. The Al/Si ratio is the main variable that governs the geo polymerization process. This control occurs by changing temperature, pressure and chemical composition of the geo polymer. Thermal analysis (DTA/DSC), microscopic (SEM/TEM) and spectroscopic (FTIR, XRD, SAXS, EXAFS and XANES) techniques have been used to characterize these inorganic systems. In this work, XANES spectra of the k-edge silicon (Si) of the kaolin-meta kaolin-geo polymer are presented. The XANES spectra provides the oxidation state and structural information about the present studied atom: Silicon (Si). (author)

  10. EXAFS spectroscopy of quasicrystals

    International Nuclear Information System (INIS)

    Menushenkov, A. P.; Rakshun, Ya. V.

    2007-01-01

    The results of the investigation of the features of the local structure of quasicrystalline materials by extended X-ray absorption fine structure (EXAFS) spectroscopy with the use of synchrotron radiation are analyzed. The advantages of this method from the point of view of deriving information about the local shifts of the atoms forming an icosahedral structure are demonstrated. The rearrangement of the local environment of copper and iron in Al-Fe-Cu ternary alloys at a transition from the crystalline to the quasicrystalline phase has been investigated. It is established that the nearest copper coordination retains the symmetry characteristic of the crystal; however, rotation and small displacements of copper matrix atoms lead to significant rearrangement of aluminum atoms around iron atoms. As a result, icosahedral clusters with pentagonal symmetry are formed around iron atoms and violation of the translational symmetry is accompanied by the transition of Al-Fe-Cu to the quasicrystalline state

  11. K-edge Radiography and applications to Cultural Heritage

    OpenAIRE

    Albertin, Fauzia

    2011-01-01

    The present work of thesis is focused on application of X-ray K-edge technique to paintings. This technique allows one to achieve a topographic map of a pigment on the whole surface of the painting. The digital acquisition of radiographic images by using monochromatic X-ray beams allows to take advantage of the sharp rise of X-ray absorption coefficient of the elements, the K-edge discontinuity. Working at different energies, bracketing the K-edge peak, allows recognition ...

  12. Silicon K-edge XANES spectra of silicate minerals

    Science.gov (United States)

    Li, Dien; Bancroft, G. M.; Fleet, M. E.; Feng, X. H.

    1995-03-01

    Silicon K-edge x-ray absorption near-edge structure (XANES) spectra of a selection of silicate and aluminosilicate minerals have been measured using synchrotron radiation (SR). The spectra are qualitatively interpreted based on MO calculation of the tetrahedral SiO{4/4-}cluster. The Si K-edge generally shifts to higher energy with increased polymerization of silicates by about 1.3 eV, but with considerable overlap for silicates of different polymerization types. The substitution of Al for Si shifts the Si K-edge to lower energy. The chemical shift of Si K-edge is also sensitive to cations in more distant atom shells; for example, the Si K-edge shifts to lower energy with the substitution of Al for Mg in octahedral sites. The shifts of the Si K-edge show weak correlation with average Si-O bond distance (dSi-O), Si-O bond valence (sSi-O) and distortion of SiO4 tetrahedra, due to the crystal structure complexity of silicate minerals and multiple factors effecting the x-ray absorption processes.

  13. Material Discrimination Based on K-edge Characteristics

    Directory of Open Access Journals (Sweden)

    Peng He

    2013-01-01

    Full Text Available Spectral/multienergy CT employing the state-of-the-art energy-discriminative photon-counting detector can identify absorption features in the multiple ranges of photon energies and has the potential to distinguish different materials based on K-edge characteristics. K-edge characteristics involve the sudden attenuation increase in the attenuation profile of a relatively high atomic number material. Hence, spectral CT can utilize material K-edge characteristics (sudden attenuation increase to capture images in available energy bins (levels/windows to distinguish different material components. In this paper, we propose an imaging model based on K-edge characteristics for maximum material discrimination with spectral CT. The wider the energy bin width is, the lower the noise level is, but the poorer the reconstructed image contrast is. Here, we introduce the contrast-to-noise ratio (CNR criterion to optimize the energy bin width after the K-edge jump for the maximum CNR. In the simulation, we analyze the reconstructed image quality in different energy bins and demonstrate that our proposed optimization approach can maximize CNR between target region and background region in reconstructed image.

  14. The efficacy of K-edge filters in diagnostic radiology

    International Nuclear Information System (INIS)

    Williamson, B.D.P.; van Doorn, T.

    1994-01-01

    The application of K-edge filters in diagnostic has been investigated by many workers for over twenty years. These investigations have analysed the effects of such filters on image quality and radiation dose as well as the practicalities of their application. This paper presents a synopsis of the published works and concludes that K-edge filters do not perceptibly improve image quality and make only limited reductions in patient dose. K-edge filters are also costly to purchase and potentially result in a reduction in the cost effectiveness of x-ray examinations by increasing the x-ray tube loading. Equivalent contrast enhancement and dose reductions can be achieved by the assiduous choice of non-selective filters. 51 refs., 2 tab., 6 figs

  15. Solid energy calibration standards for P K-edge XANES: electronic structure analysis of PPh4Br.

    Science.gov (United States)

    Blake, Anastasia V; Wei, Haochuan; Donahue, Courtney M; Lee, Kyounghoon; Keith, Jason M; Daly, Scott R

    2018-03-01

    P K-edge X-ray absorption near-edge structure (XANES) spectroscopy is a powerful method for analyzing the electronic structure of organic and inorganic phosphorus compounds. Like all XANES experiments, P K-edge XANES requires well defined and readily accessible calibration standards for energy referencing so that spectra collected at different beamlines or under different conditions can be compared. This is especially true for ligand K-edge X-ray absorption spectroscopy, which has well established energy calibration standards for Cl (Cs 2 CuCl 4 ) and S (Na 2 S 2 O 3 ·5H 2 O), but not neighboring P. This paper presents a review of common P K-edge XANES energy calibration standards and analysis of PPh 4 Br as a potential alternative. The P K-edge XANES region of commercially available PPh 4 Br revealed a single, highly resolved pre-edge feature with a maximum at 2146.96 eV. PPh 4 Br also showed no evidence of photodecomposition when repeatedly scanned over the course of several days. In contrast, we found that PPh 3 rapidly decomposes under identical conditions. Density functional theory calculations performed on PPh 3 and PPh 4 + revealed large differences in the molecular orbital energies that were ascribed to differences in the phosphorus oxidation state (III versus V) and molecular charge (neutral versus +1). Time-dependent density functional theory calculations corroborated the experimental data and allowed the spectral features to be assigned. The first pre-edge feature in the P K-edge XANES spectrum of PPh 4 Br was assigned to P 1s → P-C π* transitions, whereas those at higher energy were P 1s → P-C σ*. Overall, the analysis suggests that PPh 4 Br is an excellent alternative to other solid energy calibration standards commonly used in P K-edge XANES experiments.

  16. Spatial structure of transition metal complexes in solution determined by EXAFS spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Erenburg, S.B. E-mail: simon@che.nsk.su; Bausk, N.V.; Zemskova, S.M.; Mazalov, L.N

    2000-06-21

    CdK EXAFS, ZnK and CuK EXAFS and XANES spectra were measured for solutions of cadmium, zinc and copper dialkyldithiocarbamates in organic solvents with varying donating abilities: tributylphosphine, methylene chloride, benzene, dibutylsulfide, pyridine, dimethylsulfoxide and for some model compounds. The parameters of the local surroundings of the Cd, Zn and Cu atoms for complex forms in solutions were determined using EXAFS spectroscopy. Spatial structure models of the complex forms in a metal chelate - nonaqueous solvent system are suggested.

  17. Spatial structure of transition metal complexes in solution determined by EXAFS spectroscopy

    International Nuclear Information System (INIS)

    Erenburg, S.B.; Bausk, N.V.; Zemskova, S.M.; Mazalov, L.N.

    2000-01-01

    CdK EXAFS, ZnK and CuK EXAFS and XANES spectra were measured for solutions of cadmium, zinc and copper dialkyldithiocarbamates in organic solvents with varying donating abilities: tributylphosphine, methylene chloride, benzene, dibutylsulfide, pyridine, dimethylsulfoxide and for some model compounds. The parameters of the local surroundings of the Cd, Zn and Cu atoms for complex forms in solutions were determined using EXAFS spectroscopy. Spatial structure models of the complex forms in a metal chelate - nonaqueous solvent system are suggested

  18. EXAFS analysis of intermediate phases in the synthesis of the YBa2Cu3O7-x high-Tc superconductor from xerogel

    International Nuclear Information System (INIS)

    Arcon, I.; Bele, M.; Hribar, M.; Kodre, A.; Pejovnik, S.; Stuhec, M.; Drube, W.

    1994-01-01

    In the synthesis of superconducting cuprate ceramics starting from gels, the advantage of stoichiometric homogeneity of the constituent atoms on the molecular level is exploited. However, x-ray diffraction analysis of samples taken in consecutive temperature points in the process of calcination shows formation of a number of well-crystalized intermediary products. EXAFS spectrometry gives additional insight into the process, providing the information on the neighborhood of constituent atoms in the crystalline as well as amorphous phase. (orig.)

  19. Carbon K-edge spectra of carbonate minerals.

    Science.gov (United States)

    Brandes, Jay A; Wirick, Sue; Jacobsen, Chris

    2010-09-01

    Carbon K-edge X-ray spectroscopy has been applied to the study of a wide range of organic samples, from polymers and coals to interstellar dust particles. Identification of carbonaceous materials within these samples is accomplished by the pattern of resonances in the 280-320 eV energy region. Carbonate minerals are often encountered in the study of natural samples, and have been identified by a distinctive resonance at 290.3 eV. Here C K-edge and Ca L-edge spectra from a range of carbonate minerals are presented. Although all carbonates exhibit a sharp 290 eV resonance, both the precise position of this resonance and the positions of other resonances vary among minerals. The relative strengths of the different carbonate resonances also vary with crystal orientation to the linearly polarized X-ray beam. Intriguingly, several carbonate minerals also exhibit a strong 288.6 eV resonance, consistent with the position of a carbonyl resonance rather than carbonate. Calcite and aragonite, although indistinguishable spectrally at the C K-edge, exhibited significantly different spectra at the Ca L-edge. The distinctive spectral fingerprints of carbonates provide an identification tool, allowing for the examination of such processes as carbon sequestration in minerals, Mn substitution in marine calcium carbonates (dolomitization) and serpentinization of basalts.

  20. Carbon K-edge Spectra of Carbonate Minerals

    Energy Technology Data Exchange (ETDEWEB)

    Brandes, J.; Wirick, S; Jacobsen, C

    2010-01-01

    Carbon K-edge X-ray spectroscopy has been applied to the study of a wide range of organic samples, from polymers and coals to interstellar dust particles. Identification of carbonaceous materials within these samples is accomplished by the pattern of resonances in the 280-320 eV energy region. Carbonate minerals are often encountered in the study of natural samples, and have been identified by a distinctive resonance at 290.3 eV. Here C K-edge and Ca L-edge spectra from a range of carbonate minerals are presented. Although all carbonates exhibit a sharp 290 eV resonance, both the precise position of this resonance and the positions of other resonances vary among minerals. The relative strengths of the different carbonate resonances also vary with crystal orientation to the linearly polarized X-ray beam. Intriguingly, several carbonate minerals also exhibit a strong 288.6 eV resonance, consistent with the position of a carbonyl resonance rather than carbonate. Calcite and aragonite, although indistinguishable spectrally at the C K-edge, exhibited significantly different spectra at the Ca L-edge. The distinctive spectral fingerprints of carbonates provide an identification tool, allowing for the examination of such processes as carbon sequestration in minerals, Mn substitution in marine calcium carbonates (dolomitization) and serpentinization of basalts.

  1. Low Z elements (Mg, Al, and Si) K-edge X-ray absorption spectroscopy in minerals and disordered systems

    International Nuclear Information System (INIS)

    Ildefonse, P.; Calas, G.; Flank, A.M.; Lagarde, P.

    1995-01-01

    Soft X-ray absorption near edge spectroscopy (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy have been performed at the Mg-, Al- and Si-K edges in order to establish the ability of this spectroscopy to derive structural information in disordered solids such as glasses and gels. Mg- and Al-K XANES are good structural probes to determine the coordination state of these elements in important minerals, glasses and gels. In a CaO-MgO-2SiO 2 glass Mg XANES spectra differ from that found in the crystalline equivalent, with a significant shift of the edge maxima to lower energy, consistent with a CN lower than 6. Mg-EXAFS on the same sample are in agreement and indicate the presence of 5-coordinated Mg with Mg-O distances of 2.01 A. In aluminosilicate gels, Al-K XANES has been used to investigate the [4]Al/Al total ratios. These ratios increase as the Al/Si ratios decrease. Aluminosilicate and ferric-silicate gels were studied by using Si-K edge XANES. XANES spectra differ significantly among the samples studied. Aluminosilicate gels with Al/Si=1 present a different Al and Si local environment from that known in clay minerals with the same Al/Si ratio. The gel-to-mineral transformation thus implies a dissolution-recrystallization mechanism. On the contrary, ferric-silicate gel presents a Si local environment close to that found in nontronite which may be formed by a long range ordering of the initial gels. (orig.)

  2. Low Z elements (Mg, Al, and Si) K-edge X-ray absorption spectroscopy in minerals and disordered systems

    Science.gov (United States)

    Ildefonse, Ph.; Calas, G.; Flank, A. M.; Lagarde, P.

    1995-05-01

    Soft X-ray absorption near edge spectroscopy (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy have been performed at the Mg-, Al- and Si-K edges in order to establish the ability of this spectroscopy to derive structural information in disordered solids such as glasses and gels. Mg- and Al-K XANES are good structural probes to determine the coordination state of these elements in important minerals, glasses and gels. In a CaOsbnd MgOsbnd 2SiO2 glass Mg XANES spectra differ from that found in the crystalline equivalent, with a significant shift of the edge maxima to lower energy, consistent with a CN lower than 6. Mg-EXAFS on the same sample are in agreement and indicate the presence of 5-coordinated Mg with Mgsbnd O distances of 2.01Å. In aluminosilicate gels, Alsbnd K XANES has been used to investigate the [4]Al/Altotal ratios. These ratios increase as the Al/Si ratios decrease. Aluminosilicate and ferric-silicate gels were studied by using Sisbnd K edge XANES. XANES spectra differ significantly among the samples studied. Aluminosilicate gels with Al/Si= 1 present a different Al and Si local environment from that known in clay minerals with the same Al/Si ratio. The gel-to-mineral transformation thus implies a dissolution-recrystallization mechanism. On the contrary, ferric-silicate gel presents a Si local environment close to that found in nontronite which may be formed by a long range ordering of the initial gels.

  3. EXAFS study on dynamic structural property of porous morph-genetic SiC

    International Nuclear Information System (INIS)

    Ding, J.; Sun, B.H.; Fan, T.X.; Zhang, D.; Kamada, M.; Ogawa, H.; Guo, Q.X.

    2005-01-01

    Novel porous morph-genetic silicon carbide has been fabricated through sintering treatment, after infiltrating the methyl organic silicone resin to the bio-template. Its dynamic transition of structure during sintering process is investigated by extended X-ray absorption fine structure (EXAFS) for the first time. By analyzing Si K-edge EXAFS, it is found that the coordination number of the nearest C shell remains almost unchanged while that of the nearest Si shell dramatically changes when the structure is transformed from amorphous into crystalline state

  4. Characterization of isolated Ag cations in homoionic Ag-Y zeolites: A combined anomalous XRPD and EXAFS study

    International Nuclear Information System (INIS)

    Lamberti, C.; Prestipino, C.; Bordiga, S.; Fitch, A.N.; Marra, G.L.

    2003-01-01

    In this contribution we report a structural characterization of a homoionic Ag-Y zeolite (Si/Al=2.63) on both short (EXAFS) and long range (XRD) scales. Our study shows that the zeolite is a near-100% exchanged silver faujasite, showing almost isolated Ag + counterions (EXAFS estimates that clustered species represent less than 2% of the whole silver). Synchrotron radiation XRPD measurements (ESRF, BM16), performed at the Ag-K edge (λ=0.486103(2) A), just before (λ=0.486093(2) A) and far away (λ=0.491153(2) A), allowed us to locate the near totality of the expected Ag + counterions: 51.9(4) out of 52.9 per unit cell, located in five different sites. The output of the Rietveld refinement has been used successfully to simulate the Ag-K edge EXAFS spectra (ESRF, BM29)

  5. Calcium EXAFS establishes the Mn-Ca cluster in the oxygen-evolving complex of Photosystem II

    Energy Technology Data Exchange (ETDEWEB)

    Cinco, Roehl M.; McFarlane Holman, Karen L.; Robblee, John H.; Yano, Junko; Pizarro, Shelly A.; Bellacchio, Emanuele; Sauer, Kenneth; Yachandra, Vittal K.

    2002-08-02

    The proximity of Ca to the Mn cluster of the photosynthetic water-oxidation complex is demonstrated by X-ray absorption spectroscopy. We have collected EXAFS data at the Ca K-edge using active PS II membrane samples that contain approximately 2 Ca per 4 Mn. These samples are much less perturbed than previously investigated Sr-substituted samples, which were prepared subsequent to Ca depletion. The new Ca EXAFS clearly shows backscattering from Mn at 3.4 angstroms, a distance that agrees with that surmised from previously recorded Mn EXAFS. This result is also consistent with earlier related experiments at the Sr K-edge, using samples that contained functional Sr, that show Mn is {approx}; 3.5 angstroms distant from Sr. The totality of the evidence clearly advances the notion that the catalytic center of oxygen evolution is a Mn-Ca heteronuclear cluster.

  6. Comparison of EXAFS Foil Spectra from Around the World

    International Nuclear Information System (INIS)

    Kelly, S.D.; Bare, S.R.; Greenlay, N.; Azevedo, G.; Balasubramanian, M.; Barton, D.; Chattopadhyay, S.; Fakra, S.; Johannessen, B.; Newville, M.; Pena, J.; Pokrovski, G.S; Proux, O.; Priolkar, K.; Ravel, B.; Webb, S.M.

    2010-01-01

    The EXAFS spectra of Cu and Pd foil from many different beamlines and synchrotrons are compared to address the dependence of the amplitude reduction factor (S 0 2 ) on beamline specific parameters. Even though S 0 2 is the same parameter as the EXAFS coordination number, the value for S 0 2 is given little attention, and is often unreported. The S 0 2 often differs for the same material due to beamline and sample attributes, such that no importance is given to S 0 2 -values within a general range of 0.7 to 1.1. EXAFS beamlines have evolved such that it should now be feasible to use standard S 0 2 values for all EXAFS measurements of a specific elemental environment. This would allow for the determination of the imaginary energy (Ei) to account for broadening of the EXAFS signal rather than folding these errors into an effective S 0 2 -value. To test this concept, we model 11 Cu-foil and 6 Pd-foil EXAFS spectra from around the world to compare the difference in S 0 2 - and Ei-values.

  7. K-Edge Subtraction Angiography with Synchrotron X-Rays

    International Nuclear Information System (INIS)

    Giacomini, John C.

    1996-01-01

    The purpose of this project was to utilize dual energy, monochromatic X-rays produced from synchrotrons radiation in order to obtain noninvasive medical imaging. The application of synchrotrons radiation to medical imaging is based on the principle of iodine dichromography, first described by Bertil Jacobson of the Karolinska Institute in 1953. Medical imaging using synchrotrons radiation and K-edge dichromography was pioneered at Stanford University under the leadership of Dr. Ed Rubenstein, and the late Nobel Laureate in Physics, Dr. Robert Hofstadter. With progressive refinements in hardware, clinical-quality images were obtained of human coronary arteries utilizing peripheral injections of iodinated contrast agent. These images even now are far superior to those being presented by investigators using MRI as an imaging tool for coronary arteries. However, new supplies and instruments in the cardiac catheterization laboratory have served to transform coronary angiography into an outpatient procedure, with relatively little morbidity. We extended the principles learned with coronary angiography to noninvasive imaging of the human bronchial tree. For these images, we utilized xenon as the contrast agent, as it has a K-edge very similar to that of iodine. In this case, there is no true competing diagnostic test, and pulmonary neoplasm is an enormous public health concern. In early experiments, we demonstrated remarkably clear images of the human bronchial tree. These images have been shown internationally; however, funding difficulties primarily with the Department of Energy have not allowed for progression of this promising avenue of research. One potential criticism of the project is that in order to obtain these images, we utilized national laboratories. Some have questioned whether this would lead to a practical imaging modality. However, we have shown that the technology exists to allow for construction of a miniature storage ring, with a superconducting

  8. K-Edge Subtraction Angiography with Synchrotron X-Rays

    CERN Document Server

    Giacomini, J C

    1996-01-01

    The purpose of this project was to utilize dual energy, monochromatic X-rays produced from synchrotrons radiation in order to obtain noninvasive medical imaging. The application of synchrotrons radiation to medical imaging is based on the principle of iodine dichromography, first described by Bertil Jacobson of the Karolinska Institute in 1953. Medical imaging using synchrotrons radiation and K-edge dichromography was pioneered at Stanford University under the leadership of Dr. Ed Rubenstein, and the late Nobel Laureate in Physics, Dr. Robert Hofstadter. With progressive refinements in hardware, clinical-quality images were obtained of human coronary arteries utilizing peripheral injections of iodinated contrast agent. These images even now are far superior to those being presented by investigators using MRI as an imaging tool for coronary arteries. However, new supplies and instruments in the cardiac catheterization laboratory have served to transform coronary angiography into an outpatient procedure, with r...

  9. Portable X-Ray, K-Edge Heavy Metal Detector

    International Nuclear Information System (INIS)

    Fricke, V.

    1999-01-01

    The X-Ray, K-Edge Heavy Metal Detection System was designed and built by Ames Laboratory and the Center for Nondestructive Evaluation at Iowa State University. The system uses a C-frame inspection head with an X-ray tube mounted on one side of the frame and an imaging unit and a high purity germanium detector on the other side. the inspection head is portable and can be easily positioned around ventilation ducts and pipes up to 36 inches in diameter. Wide angle and narrow beam X-ray shots are used to identify the type of holdup material and the amount of the contaminant. Precise assay data can be obtained within minutes of the interrogation. A profile of the containerized holdup material and a permanent record of the measurement are immediately available

  10. Local structure in LaMnO3 and CaMnO3 perovskites: A quantitative structural refinement of Mn K-edge XANES data

    International Nuclear Information System (INIS)

    Monesi, C.; Meneghini, C.; Bardelli, F.; Benfatto, M.; Mobilio, S.; Manju, U.; Sarma, D.D.

    2005-01-01

    Hole-doped perovskites such as La 1-x Ca x MnO 3 present special magnetic and magnetotransport properties, and it is commonly accepted that the local atomic structure around Mn ions plays a crucial role in determining these peculiar features. Therefore experimental techniques directly probing the local atomic structure, like x-ray absorption spectroscopy (XAS), have been widely exploited to deeply understand the physics of these compounds. Quantitative XAS analysis usually concerns the extended region [extended x-ray absorption fine structure (EXAFS)] of the absorption spectra. The near-edge region [x-ray absorption near-edge spectroscopy (XANES)] of XAS spectra can provide detailed complementary information on the electronic structure and local atomic topology around the absorber. However, the complexity of the XANES analysis usually prevents a quantitative understanding of the data. This work exploits the recently developed MXAN code to achieve a quantitative structural refinement of the Mn K-edge XANES of LaMnO 3 and CaMnO 3 compounds; they are the end compounds of the doped manganite series La x Ca 1-x MnO 3 . The results derived from the EXAFS and XANES analyses are in good agreement, demonstrating that a quantitative picture of the local structure can be obtained from XANES in these crystalline compounds. Moreover, the quantitative XANES analysis provides topological information not directly achievable from EXAFS data analysis. This work demonstrates that combining the analysis of extended and near-edge regions of Mn K-edge XAS spectra could provide a complete and accurate description of Mn local atomic environment in these compounds

  11. Generalized Multi-Edge Analysis for K-Edge Densitometry

    International Nuclear Information System (INIS)

    Collins, M.

    1998-01-01

    In K-edge densitometry (KED), a continuous-energy x-ray beam is transmitted through a liquid sample. The actinide content of the sample can be measured through analysis of the transmitted portion of the x-ray beam. Traditional methods for KED analysis allow the simultaneous calculation of, at most, two actinide concentrations. A generalized multi-edge KED analytical method is presented, allowing up to six actinide concentrations to be calculated simultaneously. Applications of this method for hybrid KED/x-ray fluorescence (HKED) systems are discussed. Current HKED systems require the operator to know the approximate actinide content of each sample, and manually select the proper analysis mode. The new multi-edge KED technique allows rapid identification of the major actinide components in a sample, independent of actinide content. The proper HKED analysis mode can be selected automatically, without requiring sample content information from the user. Automatic HKED analysis would be especially useful in an analytical laboratory setting, where samples with truly unknown characteristics are encountered. Because this technique requires no hardware modifications, several facilities that use HKED may eventually benefit from this approach

  12. Sulfur K-edge absorption spectroscopy on selected biological systems

    International Nuclear Information System (INIS)

    Lichtenberg, Henning

    2008-07-01

    Sulfur is an essential element in organisms. In this thesis investigations of sulfur compounds in selected biological systems by XANES (X-ray Absorption Near Edge Structure) spectroscopy are reported. XANES spectroscopy at the sulfur K-edge provides an excellent tool to gain information about the local environments of sulfur atoms in intact biological samples - no extraction processes are required. Spatially resolved measurements using a Kirkpatrick-Baez mirror focusing system were carried out to investigate the infection of wheat leaves by rust fungi. The results give information about changes in the sulfur metabolism of the host induced by the parasite and about the extension of the infection into visibly uninfected plant tissue. Furthermore, XANES spectra of microbial mats from sulfidic caves were measured. These mats are dominated by microbial groups involved in cycling sulfur. Additionally, the influence of sulfate deprivation and H 2 S exposure on sulfur compounds in onion was investigated. To gain an insight into the thermal degradation of organic material the influence of roasting of sulfur compounds in coffee beans was studied. (orig.)

  13. Methods in carbon K-edge NEXAFS: Experiment and analysis

    International Nuclear Information System (INIS)

    Watts, B.; Thomsen, L.; Dastoor, P.C.

    2006-01-01

    Near-edge X-ray absorption spectroscopy (NEXAFS) is widely used to probe the chemistry and structure of surface layers. Moreover, using ultra-high brilliance polarised synchrotron light sources, it is possible to determine the molecular alignment of ultra-thin surface films. However, the quantitative analysis of NEXAFS data is complicated by many experimental factors and, historically, the essential methods of calibration, normalisation and artefact removal are presented in the literature in a somewhat fragmented manner, thus hindering their integrated implementation as well as their further development. This paper outlines a unified, systematic approach to the collection and quantitative analysis of NEXAFS data with a particular focus upon carbon K-edge spectra. As a consequence, we show that current methods neglect several important aspects of the data analysis process, which we address with a combination of novel and adapted techniques. We discuss multiple approaches in solving the issues commonly encountered in the analysis of NEXAFS data, revealing the inherent assumptions of each approach and providing guidelines for assessing their appropriateness in a broad range of experimental situations

  14. Fe K-edge XANES of Maya blue pigment

    Science.gov (United States)

    Río, M. Sánchez del; Sodo, A.; Eeckhout, S. G.; Neisius, T.; Martinetto, P.; Dooryhée, E.; Reyes-Valerio, C.

    2005-08-01

    The utilization of techniques used in Materials Science for the characterization of artefacts of interest for cultural heritage is getting more and more attention nowadays. One of the products of the ancient Maya chemistry is the "Maya blue" pigment, made with natural indigo and palygorskite. This pigment is different from any other pigment used in other parts of the world. It is durable and acid-resistant, and still keeps many secrets to scientists even though it has been studied for more than 50 years. Although the pigment is basically made of palygorskite Si8(Mg2Al2)O20(OH)2(OH2)4.4H2O and an organic colourant (indigo: C16H10N2O2), a number of other compounds have been found in previous studies on archaeological samples, like other clays and minerals, iron nanoparticles, iron oxides, impurities of transition metals (Cr, Mn, Ti, V), etc. We measured at the ESRF ID26 beamline the Fe K-edge XANES spectra of the blue pigment in ancient samples. They are compared to XANES spectra of Maya blue samples synthesized under controlled conditions, and iron oxides usually employed as pigments (hematite and goethite). Our results show that the iron found in ancient Maya blue pigment is related to the Fe exchanged in the palygorskite clay. We did not find iron in metallic form or goethite in archaeological Maya blue.

  15. Fe K-edge XANES of Maya blue pigment

    International Nuclear Information System (INIS)

    Rio, M. Sanchez del; Sodo, A.; Eeckhout, S.G.; Neisius, T.; Martinetto, P.; Dooryhee, E.; Reyes-Valerio, C.

    2005-01-01

    The utilization of techniques used in Materials Science for the characterization of artefacts of interest for cultural heritage is getting more and more attention nowadays. One of the products of the ancient Maya chemistry is the 'Maya blue' pigment, made with natural indigo and palygorskite. This pigment is different from any other pigment used in other parts of the world. It is durable and acid-resistant, and still keeps many secrets to scientists even though it has been studied for more than 50 years. Although the pigment is basically made of palygorskite Si 8 (Mg 2 Al 2 )O 20 (OH) 2 (OH 2 ) 4 .4H 2 O and an organic colourant (indigo: C 16 H 10 N 2 O 2 ), a number of other compounds have been found in previous studies on archaeological samples, like other clays and minerals, iron nanoparticles, iron oxides, impurities of transition metals (Cr, Mn, Ti, V), etc. We measured at the ESRF ID26 beamline the Fe K-edge XANES spectra of the blue pigment in ancient samples. They are compared to XANES spectra of Maya blue samples synthesized under controlled conditions, and iron oxides usually employed as pigments (hematite and goethite). Our results show that the iron found in ancient Maya blue pigment is related to the Fe exchanged in the palygorskite clay. We did not find iron in metallic form or goethite in archaeological Maya blue

  16. Fragmentation of HCl following excitation at the chlorine K edge

    Energy Technology Data Exchange (ETDEWEB)

    Hansen, D.L.; Arrasate, M.E. [Univ. of Nevada, Las Vegas, NV (United States); Cotter, J.P. [Univ. of Nevada, Reno, NV (United States)] [and others

    1997-04-01

    A space-focused time-of-flight (TOF) mass spectrometer was used to study the relaxation dynamics of HCl following excitation in the vicinity of the Cl-K edge ({approximately}2.8 keV) using x-rays from B.L. 9.3.1. At the lowest resonant excitation to a {sigma}{sup *} antibonding orbital (1{sigma} {r_arrow} 6{sigma}), a significant fraction of the excited molecules decay by emission of a neutral H atom. While neutral-H emission has been observed for shallow core levels (e.g., Cl 2p in HCl), the authors believe this to be the first observation of neutral-atom emission as a significant decay channel following resonant excitation of a deep core hole. The dissociation of neutral hydrogen atoms raises the issue of how effectively dissociation competes with Auger decay in the relaxation of these deep core levels (i.e., Cl 1s). Graphical evidence is presented to support the dissociation agrument. In addition, trends in fractional ion yields from Photo-Ion Photo-Ion COincidence (PIPICO) spectra suggest the presence of post-collision interaction (PCI). While, electron spectroscopy studies are required to confirm the observation of this effect, the authors believe this to be the first evidence of PCI moderated dissociation in molecules.

  17. Tungsten anode tubes with K-edge filters for mammography

    Energy Technology Data Exchange (ETDEWEB)

    Beaman, S.; Lillicrap, S.C. (Wessex Regional Medical Physics Service, Bath (UK)); Price, J.L. (Jarvis Screening Centre, Guildford (UK))

    1983-10-01

    Optimum X-ray energies for mammography have previously been calculated using the maximum signal to noise ratio (SNR) per unit dose to the breast, or the minimum exposure for constant SNR. Filters having absorption edges at appropriate energy positions have been used to modify the shape of tungsten anode spectra towards the calculated optimum. The suitability of such spectra for practical use has been assessed by comparing the film image quality and the incident breast dose obtained using a K-edge filtered tungsten anode tube with that obtained using a molybdenum anode. Image quality has been assessed by using a 'random' phantom and by comparing mammograms where one breast was radiographed using a filtered tungsten anode tube and the other using a standard molybdenum anode unit. Relative breast doses were estimated from both ionisation chamber measurements with a phantom and thermoluminescent dosimetry measurements on the breast. Film image quality assessment indicated that the filtered tungsten anode tube gave results not significantly different from those obtained with a molybdenum anode tube for a tissue thickness of about 4 cm and which were better for larger breast thicknesses. Doses could be reduced to between one-half and one-third with the filtered tungsten anode tube.

  18. Tungsten anode tubes with K-edge filters for mammography

    International Nuclear Information System (INIS)

    Beaman, S.; Lillicrap, S.C.; Price, J.L.

    1983-01-01

    Optimum X-ray energies for mammography have previously been calculated using the maximum signal to noise ratio (SNR) per unit dose to the breast, or the minimum exposure for constant SNR. Filters having absorption edges at appropriate energy positions have been used to modify the shape of tungsten anode spectra towards the calculated optimum. The suitability of such spectra for practical use has been assessed by comparing the film image quality and the incident breast dose obtained using a K-edge filtered tungsten anode tube with that obtained using a molybdenum anode. Image quality has been assessed by using a 'random' phantom and by comparing mammograms where one breast was radiographed using a filtered tungsten anode tube and the other using a standard molybdenum anode unit. Relative breast doses were estimated from both ionisation chamber measurements with a phantom and thermoluminescent dosimetry measurements on the breast. Film image quality assessment indicated that the filtered tungsten anode tube gave results not significantly different from those obtained with a molybdenum anode tube for a tissue thickness of abut 4 cm and which were better for larger breast thicknesses. Doses could be reduced to between one-half and one-third with the filtered tungsten anode tube. (U.K.)

  19. Pressure effects in Debye-Waller factors and in EXAFS

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen Van Hung, E-mail: hungnv@vnu.edu.v [University of Science, VNU Hanoi, 334 Nguyen Trai, Thanh Xuan, Hanoi (Viet Nam); Vu Van Hung [Hanoi National University of Education, 136 Xuan Thuy, Cau Giay, Hanoi (Viet Nam); Ho Khac Hieu [University of Science, VNU Hanoi, 334 Nguyen Trai, Thanh Xuan, Hanoi (Viet Nam); National University of Civil Engineering, 55 Giai Phong, Hai Ba Trung, Hanoi (Viet Nam); Frahm, Ronald R. [Bergische Universitaet-Gesamthochschule Wuppertal, FB: 8-Physik, Gauss Strasse 20, 42097 Wuppertal (Germany)

    2011-02-01

    Anharmonic correlated Einstein model (ACEM) and statistical moment method (SMM) have been developed to derive analytical expressions for pressure dependence of the lattice bond length, effective spring constant, correlated Einstein frequency and temperature, Debye-Waller factors (DWF) or second cumulant, first and third cumulants in Extended X-ray Absorption Fine Structure (EXAFS) at a given temperature. Numerical results for pressure-dependent DWF of Kr and Cu agree well with experiment and other theoretical values. Simulated EXAFS of Cu and its Fourier transform magnitude using our calculated pressure-induced change in the 1st shell are found to be in a reasonable agreement with those using X-ray diffraction (XRD) experimental results. -- Research Highlights: {yields} We have developed anharmonic correlated Einstein model and statistical moment method. {yields} The pressure effects in cumulants including DWF and in EXAFS has been investigated. {yields} Calculated pressure-dependent DWF for Kr, Cu agree with experiment and other results. {yields} Simulated EXAFS and Fourier transform magnitude of Cu agree with those using XRD data.

  20. Pressure effects in Debye-Waller factors and in EXAFS

    International Nuclear Information System (INIS)

    Nguyen Van Hung; Vu Van Hung; Ho Khac Hieu; Frahm, Ronald R.

    2011-01-01

    Anharmonic correlated Einstein model (ACEM) and statistical moment method (SMM) have been developed to derive analytical expressions for pressure dependence of the lattice bond length, effective spring constant, correlated Einstein frequency and temperature, Debye-Waller factors (DWF) or second cumulant, first and third cumulants in Extended X-ray Absorption Fine Structure (EXAFS) at a given temperature. Numerical results for pressure-dependent DWF of Kr and Cu agree well with experiment and other theoretical values. Simulated EXAFS of Cu and its Fourier transform magnitude using our calculated pressure-induced change in the 1st shell are found to be in a reasonable agreement with those using X-ray diffraction (XRD) experimental results. -- Research Highlights: → We have developed anharmonic correlated Einstein model and statistical moment method. → The pressure effects in cumulants including DWF and in EXAFS has been investigated. → Calculated pressure-dependent DWF for Kr, Cu agree with experiment and other results. → Simulated EXAFS and Fourier transform magnitude of Cu agree with those using XRD data.

  1. EXAFS measurements under high pressure conditions using a combination of a diamond anvil cell and synchrotron radiation

    International Nuclear Information System (INIS)

    Sueno, Shigeho; Nakai, Izumi; Imafuku, Masayuki; Morikawa, Hideki; Kimata, Mitsuyoshi; Ohsumi, Kazumasa; Nomura, Masaharu; Shimomura, Osamu.

    1986-01-01

    EXAFS spectra for Fe, Co, Ni K-edges were successfully measured under high pressure conditions using a combination of a set of normal 1/8 carat diamond anvils, synchrotron radiation and a scintillation counter. A newly developed motor controlled goniometer stage was used for adjusting the position of a miniature diamond anvil cell. On the measurement of Cr and Mn spectra, specially designed thinner diamond anvil was necessary. EXAFS analysis of bis(dimethylglyoximato)nickel(II) at pressures from 1 atm to 5.6 GPa was made. (author)

  2. Fe K-edge XANES of Maya blue pigment

    Energy Technology Data Exchange (ETDEWEB)

    Rio, M. Sanchez del [ESRF, Experiments Division, B.P. 220, F-38043, Grenoble Cedex (France)]. E-mail: srio@esrf.fr; Sodo, A. [ESRF, Experiments Division, B.P. 220, F-38043, Grenoble Cedex (France); Eeckhout, S.G. [ESRF, Experiments Division, B.P. 220, F-38043, Grenoble Cedex (France); Neisius, T. [ESRF, Experiments Division, B.P. 220, F-38043, Grenoble Cedex (France); Martinetto, P. [Laboratoire de Cristallographie, CNRS, Grenoble B.P. 166, F-38042, Grenoble Cedex 09 (France); Dooryhee, E. [Laboratoire de Cristallographie, CNRS, Grenoble B.P. 166, F-38042, Grenoble Cedex 09 (France); Reyes-Valerio, C. [INAH, Mexico DF (Mexico)

    2005-08-15

    The utilization of techniques used in Materials Science for the characterization of artefacts of interest for cultural heritage is getting more and more attention nowadays. One of the products of the ancient Maya chemistry is the 'Maya blue' pigment, made with natural indigo and palygorskite. This pigment is different from any other pigment used in other parts of the world. It is durable and acid-resistant, and still keeps many secrets to scientists even though it has been studied for more than 50 years. Although the pigment is basically made of palygorskite Si{sub 8}(Mg{sub 2}Al{sub 2})O{sub 20}(OH){sub 2}(OH{sub 2}){sub 4}.4H{sub 2}O and an organic colourant (indigo: C{sub 16}H{sub 10}N{sub 2}O{sub 2}), a number of other compounds have been found in previous studies on archaeological samples, like other clays and minerals, iron nanoparticles, iron oxides, impurities of transition metals (Cr, Mn, Ti, V), etc. We measured at the ESRF ID26 beamline the Fe K-edge XANES spectra of the blue pigment in ancient samples. They are compared to XANES spectra of Maya blue samples synthesized under controlled conditions, and iron oxides usually employed as pigments (hematite and goethite). Our results show that the iron found in ancient Maya blue pigment is related to the Fe exchanged in the palygorskite clay. We did not find iron in metallic form or goethite in archaeological Maya blue.

  3. Electron-beam induced amorphization of stishovite: Silicon-coordination change observed using Si K-edge extended electron energy-loss fine structure

    International Nuclear Information System (INIS)

    Aken, P.A. van; Sharp, T.G.; Seifert, F.

    1998-01-01

    The analysis of the extended energy-loss fine structure (EXELFS) of the Si K-edge for sixfold-coordinated Si in synthetic stishovite and fourfold-coordinated Si in natural α-quartz is reported by using electron energy-loss spectroscopy (EELS) in combination with transmission electron microscopy (TEM). The stishovite Si K-edge EXELFS spectra were measured as a time-dependent series to document irradiation-induced amorphization. The amorphization was also investigated through the change in Si K- and O K-edge energy-loss near edge structure (ELNES). For α-quartz, in contrast to stishovite, electron irradiation-induced vitrification, produced no detectable changes of the EXELFS. The Si K-edge EXELFS were analysed with the classical extended X-ray absorption fine structure (EXAFS) treatment and compared to ab initio curve-waved multiple-scattering (MS) calculations of EXAFS spectra for stishovite and α-quartz. Highly accurate information on the local atomic environment of the silicon atoms during the irradiation-induced amorphization of stishovite is obtained from the EXELFS structure parameters The mean Si-O bond distance R and mean Si coordination number N changes from R=0.1775 nm and N=6 for stishovite through a disordered intermediate state (R∼0.172 nm and N∼5) to R∼0.167 nm and N∼4.5 for a nearly amorphous state similar to α-quartz (R=0.1609 nm and N=4). During the amorphization process, the Debye-Waller factor (DWF) passes through a maximum value of σ N 2 ∼83.8pm 2 as it changes from σ st 2 =51.8pm 2 for sixfold to σ qu 2 =18.4pm 2 for fourfold coordination of Si. This increase in Debye-Waller factor indicates an increase in mean-square relative displacement (MSRD) between the central silicon atom and its oxygen neighbours. Using the EXELFS data for amorphization, a new method is developed to derive the relative amounts of Si coordinations in high-pressure minerals with mixed coordination. For the radiation-induced amorphization process of

  4. Electron-beam induced amorphization of stishovite: Silicon-coordination change observed using Si K-edge extended electron energy-loss fine structure

    Science.gov (United States)

    van Aken, P. A.; Sharp, T. G.; Seifert, F.

    The analysis of the extended energy-loss fine structure (EXELFS) of the Si K-edge for sixfold-coordinated Si in synthetic stishovite and fourfold-coordinated Si in natural α-quartz is reported by using electron energy-loss spectroscopy (EELS) in combination with transmission electron microscopy (TEM). The stishovite Si K-edge EXELFS spectra were measured as a time-dependent series to document irradiation-induced amorphization. The amorphization was also investigated through the change in Si K- and O K-edge energy-loss near edge structure (ELNES). For α-quartz, in contrast to stishovite, electron irradiation-induced vitrification, verified by selected area electron diffraction (SAED), produced no detectable changes of the EXELFS. The Si K-edge EXELFS were analysed with the classical extended X-ray absorption fine structure (EXAFS) treatment and compared to ab initio curve-waved multiple-scattering (MS) calculations of EXAFS spectra for stishovite and α-quartz. Highly accurate information on the local atomic environment of the silicon atoms during the irradiation-induced amorphization of stishovite is obtained from the EXELFS structure parameters (Si-O bond distances, coordination numbers and Debye-Waller factors). The mean Si-O bond distance R and mean Si coordination number N changes from R=0.1775 nm and N=6 for stishovite through a disordered intermediate state (R 0.172 nm and N 5) to R 0.167 nm and N 4.5 for a nearly amorphous state similar to α-quartz (R=0.1609 nm and N=4). During the amorphization process, the Debye-Waller factor (DWF) passes through a maximum value of as it changes from for sixfold to for fourfold coordination of Si. This increase in Debye-Waller factor indicates an increase in mean-square relative displacement (MSRD) between the central silicon atom and its oxygen neighbours that is consistent with the presence of an intermediate structural state with fivefold coordination of Si. The distribution of coordination states can be estimated by

  5. Strong excitonic interactions in the oxygen K-edge of perovskite oxides

    Energy Technology Data Exchange (ETDEWEB)

    Tomita, Kota; Miyata, Tomohiro [Institute of Industrial Science, The University of Tokyo, 4-6-1 Komaba, Meguro, Tokyo 153-8505 (Japan); Olovsson, Weine [Department of Physics, Chemistry and Biology (IFM), Linköping University, SE-581 83 Linköping (Sweden); Mizoguchi, Teruyasu, E-mail: teru@iis.u-tokyo.ac.jp [Institute of Industrial Science, The University of Tokyo, 4-6-1 Komaba, Meguro, Tokyo 153-8505 (Japan)

    2017-07-15

    Excitonic interactions of the oxygen K-edge electron energy-loss near-edge structure (ELNES) of perovskite oxides, CaTiO{sub 3}, SrTiO{sub 3}, and BaTiO{sub 3}, together with reference oxides, MgO, CaO, SrO, BaO, and TiO{sub 2}, were investigated using a first-principles Bethe–Salpeter equation calculation. Although the transition energy of oxygen K-edge is high, strong excitonic interactions were present in the oxygen K-edge ELNES of the perovskite oxides, whereas the excitonic interactions were negligible in the oxygen K-edge ELNES of the reference compounds. Detailed investigation of the electronic structure suggests that the strong excitonic interaction in the oxygen K-edge ELNES of the perovskite oxides is caused by the directionally confined, low-dimensional electronic structure at the Ti–O–Ti bonds. - Highlights: • Excitonic interaction in oxygen-K edge is investigated. • Strong excitonic interaction is found in the oxygen-K edge of perovskite oxides. • The strong excitonic interaction is ascribed to the low-dimensional and confined electronic structure.

  6. A study of the Nb3Ge system by Ge K-edge extended x-ray absorption fine structure and x-ray absorption near-edge structure spectroscopy

    International Nuclear Information System (INIS)

    Saini, N L; Filippi, M; Wu Ziyu; Oyanagi, H; Ihara, H; Iyo, A; Agrestini, S; Bianconi, A

    2002-01-01

    The local structure of Nb 3 Ge intermetallic superconductor has been studied by Ge K-edge absorption spectroscopy. Extended x-ray absorption fine structure (EXAFS) experiments show two Ge-Nb distances. In addition to the crystallographic distance of ∼2.87 A, there exists a second Ge-Nb distance, shorter than the first by ∼0.2 A, assigned to a phase with short-range symmetry related to local displacements in the Nb-Nb chains. The x-ray absorption near-edge structure (XANES) spectrum has been simulated by full multiple-scattering calculations considering the local displacements determined by the EXAFS analysis. The XANES spectrum has been well reproduced by considering a cluster of 99 atoms within a radius of about 7 A from the central Ge atom and introducing determined local displacements

  7. Manganese in photosynthetic oxygen evolution: An edge and EXAFS study

    International Nuclear Information System (INIS)

    Yachandra, V.K.; Guiles, R.D.; McDermott, A.; Britt, R.D.; Dexheimer, S.L.; Saver, K.; Klein, M.P.

    1985-01-01

    The authors edge studies have previously shown that the Mn edges in photosynthetic samples in the S 1 and S 2 states fall into the range for Mn III and Mn IV complexes, and that the K-edge energy increases appreciably on advancing S 1 to S 2 . This was the first evidence that manganese is directly involved in the storage of oxidizing equivalents. More recently, they have extended this result with better quality data from both spinach and a thermophilic cyanobacterium. The newer results show an interesting structure to the edges, including a 1s to 3d transition. The EXAFS results for spinach membranes show that the salient features of the Mn structure are the same in the S 1 and S 2 states. These features are a Mn neighbor at approx. =2.7 A and O or N neighbors at approx. =1.75 A and approx. =2.0 A. The EXAFS spectrum of the S 1 state of the thermophilic blue green algae are strikingly similar to that of spinach

  8. Application of X-ray K-edge densitometry in D and D operations

    International Nuclear Information System (INIS)

    Jensen, T.; Aljundi, T.; Gray, J.N.; Iowa State Univ., Ames, IA

    1998-01-01

    K-edge densitometry is a nondestructive assay technique which provides accurate measurement of heavy metal contamination in pipes, containers, and other items encountered in D and D operations. A prototype mobile K-edge instrument has been built and demonstrated in several applications. Results from measurements of uranium in pipes and spent reactor fuel plates, and quantification of mercury and lead in waste drums are presented. In this report the authors briefly describe the theory behind K-edge densitometry. They follow that with a description of the prototype system they have developed, and a presentation of results from demonstrations of this system. They conclude with a discussion of the potential for application of K-edge analysis in D and D operations

  9. An EXAFS spectrometer on beam line 10B at the Photon Factory

    International Nuclear Information System (INIS)

    Oyanagi, Hiroyuki; Matsushita, Tadashi; Ito, Masahisa; Kuroda, Haruo.

    1984-03-01

    An EXAFS spectrometer installed on the beam line 10B at the Photon Factory is designed to cover the photon energy between 4 and 30 keV. Utilizing either a channel-cut or two flat silicon crystals as a monochromator, a beam intensity between 10 8 and 10 9 photons/sec is obtained at 9 keV with a resolution of 1 eV. The performance of the spectrometer, such as a signal-to-noise ratio or an energy resolution is demonstrated with examples of K edge absorption spectra of bromine, germanium, gallium arsenide, and zinc selenide. (author)

  10. EXAFS Study of Disorder in SrTiO3 Perovskite

    International Nuclear Information System (INIS)

    Kodre, Alojz; Arcon, Iztok; Gomilsek, Jana Padeznik; Zalar, Bostjan

    2007-01-01

    Ti K-edge EXAFS spectra of SrTiO3 at room temperature and at N2 boiling point are measured to detect the Ti ion displacement above and below the antiferrodistortive phase transition occurring at Tc = 105 K. The data yield a definite value of the displacement, only slightly dependent on the temperature. The sensitive dependence of the amplitude of Ti-O-Ti focusing paths on the scattering angle is used to infer the correlation of Ti displacements. A preference to alternating displacements is indicated

  11. Ion charge-state production and photoionization near the K edge in argon and potassium

    International Nuclear Information System (INIS)

    Berry, H.G.; Azuma, Y.; Cowan, P.L.; Gemmell, D.S.; LeBrun, T.; Amusia, M.Y.

    1994-01-01

    We have measured the time-of-flight charge distributions of ions of argon and potassium following x-ray absorption at energies near their respective K edges. We confirm previously observed enhancements of the higher charge states at energies up to 100 eV below the K edge in argon. The measurements confirm recent calculations suggesting excitation of a virtual 1s state in this energy range

  12. Field demonstration of a portable, X-ray, K-edge heavy-metal detector

    International Nuclear Information System (INIS)

    Jensen, T.; Aljundi, T.; Whitmore, C.; Zhong, H.; Gray, J.N.

    1997-01-01

    Under the Characterization, Monitoring, and Sensor Technology Crosscutting Program, the authors have designed and built a K-edge heavy metal detector that measures the level of heavy metal contamination inside closed containers in a nondestructive, non-invasive way. The device employs a volumetric technique that takes advantage of the X-ray absorption characteristics of heavy elements, and is most suitable for characterization of contamination inside pipes, processing equipment, closed containers, and soil samples. The K-edge detector is a fast, efficient, and cost-effective in situ characterization tool. More importantly, this device will enhance personnel safety while characterizing radioactive and toxic waste. The prototype K-edge system was operated at the Materials and Chemistry Laboratory User Facility at the Oak Ridge K-25 Site during February 1997. Uranium contaminated pipes and valves from a UF 6 feed facility were inspected using the K-edge technique as well as a baseline nondestructive assay method. Operation of the K-edge detector was demonstrated for uranium contamination ranging from 10 to 6,000 mg/cm 2 and results from the K-edge measurements were found to agree very well with nondestructive assay measurements

  13. Redox chemistry of a binary transition metal oxide (AB2O4): a study of the Cu(2+)/Cu(0) and Fe(3+)/Fe(0) interconversions observed upon lithiation in a CuFe2O4 battery using X-ray absorption spectroscopy.

    Science.gov (United States)

    Cama, Christina A; Pelliccione, Christopher J; Brady, Alexander B; Li, Jing; Stach, Eric A; Wang, Jiajun; Wang, Jun; Takeuchi, Esther S; Takeuchi, Kenneth J; Marschilok, Amy C

    2016-06-22

    Copper ferrite, CuFe2O4, is a promising candidate for application as a high energy electrode material in lithium based batteries. Mechanistic insight on the electrochemical reduction and oxidation processes was gained through the first X-ray absorption spectroscopic study of lithiation and delithiation of CuFe2O4. A phase pure tetragonal CuFe2O4 material was prepared and characterized using laboratory and synchrotron X-ray diffraction, Raman spectroscopy, and transmission electron microscopy. Ex situ X-ray absorption spectroscopy (XAS) measurements were used to study the battery redox processes at the Fe and Cu K-edges, using X-ray absorption near-edge structure (XANES), extended X-ray absorption fine structure (EXAFS), and transmission X-ray microscopy (TXM) spectroscopies. EXAFS analysis showed upon discharge, an initial conversion of 50% of the copper(ii) to copper metal positioned outside of the spinel structure, followed by a migration of tetrahedral iron(iii) cations to octahedral positions previously occupied by copper(ii). Upon charging to 3.5 V, the copper metal remained in the metallic state, while iron metal oxidation to iron(iii) was achieved. The results provide new mechanistic insight regarding the evolution of the local coordination environments at the iron and copper centers upon discharging and charging.

  14. Interaction between crystal lattice and mobile ions in copper selenides studied by EXAFS spectroscopy

    International Nuclear Information System (INIS)

    Asylgushina, G.N.; Bikkulova, N.N.; Titova, S.G.; Kochubey, D.I.

    2005-01-01

    Interaction between crystal lattice and mobile Cu ions has been studied in Cu 2- x Se in superionic and in normal state using EXAFS-spectroscopy. It has been found that the transition from normal to superionic state and change of mobile Cu ion concentration practically do not have an influence on local state of Cu atoms, but change of both these parameters is accompanied by a change of Se-sublattice state

  15. K-edge x-ray dichroism investigation of Fe1−xCoxSi: Experimental evidence for spin polarization crossover

    International Nuclear Information System (INIS)

    Hearne, G.R.; Diguet, G.; Baudelet, F.; Itié, J.-P.; Manyala, N.

    2015-01-01

    Both Fe and Co K-edge x-ray magnetic circular dichroism (XMCD) have been employed as element-specific probes of the magnetic moments in the composition series of the disordered ferromagnet Fe 1−x Co x Si (for x=0.2, 0.3, 0.4, 0.5). A definitive single peaked XMCD profile occurs for all compositions at both Fe and Co K-edges. The Fe 4p orbital moment, deduced from the integral of the XMCD signal, has a steep dependence on x at low doping levels and evolves to a different (weaker) dependence at x≥0.3, similar to the behavior of the magnetization in the Co composition range studied here. It is systematically higher, by at least a factor of two, than the corresponding Co orbital moment for most of the composition series. Fine structure beyond the K-edge absorption (limited range EXAFS) suggests that the local order (atomic environment) is very similar across the series, from the perspective of both the Fe and Co absorbing atom. The variation in the XMCD integral across the Co composition range has two regimes, that which occurs below x=0.3 and then evolves to different behavior at higher doping levels. This is more conspicuously present in the Fe contribution. This is rationalized as the evolution from a half-metallic ferromagnet at low Co doping to that of a strong ferromagnet at x>0.3 and as such, spin polarization crossover occurs. The Fermi level is tuned from the majority spin band for x<0.3 where a strongly polarized majority spin electron gas prevails, to a regime where minority spin carriers dominate at higher doping. The evolution of the Fe-derived spin polarized (3d) bands, indirectly probed here via the 4p states, is the primary determinant of the doping dependence of the magnetism in this alloy series. - Highlights: • Element-specific probing of the electronic structure of the Fe 1−x Co x Si series. • XMCD at the level of 10 −4 at the K-edge in such low-moment systems. • Element-specific probing of magnetic contributions from both Fe and Co

  16. Macroscopic and molecular approaches of enrofloxacin retention in soils in presence of Cu(II).

    Science.gov (United States)

    Graouer-Bacart, Mareen; Sayen, Stéphanie; Guillon, Emmanuel

    2013-10-15

    The co-adsorption of copper and the fluoroquinolone antibiotic enrofloxacin (ENR) at the water-soil interface was studied by means of batch adsorption experiments, and extended X-ray absorption fine structure (EXAFS) spectroscopy. The system was investigated over a pH range between 6 and 10, at different contact times, ionic strengths, and ENR concentrations. Adsorption coefficient - Kd - was determined at relevant environmental concentrations and the value obtained in water at a ionic strength imposed by the soil and at soil natural pH was equal to 0.66Lg(-1). ENR adsorption onto the soil showed strong pH dependence illustrating the influence of the electrostatic interactions in the sorption processes. The simultaneous co-adsorption of ENR and Cu(II) on the soil was also investigated. The presence of Cu(II) strongly influenced the retention of the antibiotic, leading to an increase up to 35% of adsorbed ENR amount. The combined quantitative and spectroscopic results showed that Cu(II) and ENR directly interacted at the water-soil interface to form ternary surface complexes. Cu K-edge EXAFS data indicated a molecular structure where the carboxylate and carbonyl groups of ENR coordinate to Cu(II) to form a 6-membered chelate ring and where Cu(II) bridges between ENR and the soil surface sites. Cu(II) bonds bidentately to the surface in an inner-sphere mode. Thus, the spectroscopic data allowed us to propose the formation of ternary surface complexes with the molecular architecture soil-Cu(II)-ENR. Copyright © 2013 Elsevier Inc. All rights reserved.

  17. Small changes in Cu redox state and speciation generate large isotope fractionation during adsorption and incorporation of Cu by a phototrophic biofilm

    Science.gov (United States)

    Coutaud, Margot; Méheut, Merlin; Glatzel, Pieter; Pokrovski, Gleb S.; Viers, Jérôme; Rols, Jean-Luc; Pokrovsky, Oleg S.

    2018-01-01

    Despite the importance of phototrophic biofilms in metal cycling in freshwater systems, metal isotope fractionation linked to metal adsorption and uptake by biofilm remains very poorly constrained. Here, copper isotope fractionation by a mature phototrophic biofilm during Cu surface adsorption and incorporation was studied in batch reactor (BR) and open drip flow reactor (DFR) systems at ambient conditions. X-ray Absorption Spectroscopy (both Near Edge Structure, XANES, and Extended Fine Structure, EXAFS) at Cu K-edge of the biofilm after its interaction with Cu in BR experiments allowed characterizing the molecular structure of assimilated Cu and quantifying the degree of CuII to CuI reduction linked to Cu assimilation. For both BR and DFR experiments, Cu adsorption caused enrichment in heavy isotope at the surface of the biofilm relative to the aqueous solution, with an apparent enrichment factor for the adsorption process, ε65Cuads, of +1.1 ± 0.3‰. In contrast, the isotope enrichment factor during copper incorporation into the biofilm (ε65Cuinc) was highly variable, ranging from -0.6 to +0.8‰. This variability of the ε65Cuinc value was likely controlled by Cu cellular uptake via different transport pathways resulting in contrasting fractionation. Specifically, the CuII storage induced enrichment in heavy isotope, whereas the toxicity response of the biofilm to Cu exposure resulted in reduction of CuII to CuI, thus yielding the biofilm enrichment in light isotope. EXAFS analyses suggested that a major part of the Cu assimilated by the biofilm is bound to 5.1 ± 0.3 oxygen or nitrogen atoms, with a small proportion of Cu linked to sulfur atoms (NS biofilm exhibited a similar trend over time of exposure. Our study demonstrates the complexity of biological processes associated with live phototrophic biofilms, which produce large and contrasting isotope fractionations following rather small Cu redox and speciation changes during uptake, storage or release of

  18. Strong excitonic interactions in the oxygen K-edge of perovskite oxides.

    Science.gov (United States)

    Tomita, Kota; Miyata, Tomohiro; Olovsson, Weine; Mizoguchi, Teruyasu

    2017-07-01

    Excitonic interactions of the oxygen K-edge electron energy-loss near-edge structure (ELNES) of perovskite oxides, CaTiO 3 , SrTiO 3 , and BaTiO 3 , together with reference oxides, MgO, CaO, SrO, BaO, and TiO 2 , were investigated using a first-principles Bethe-Salpeter equation calculation. Although the transition energy of oxygen K-edge is high, strong excitonic interactions were present in the oxygen K-edge ELNES of the perovskite oxides, whereas the excitonic interactions were negligible in the oxygen K-edge ELNES of the reference compounds. Detailed investigation of the electronic structure suggests that the strong excitonic interaction in the oxygen K-edge ELNES of the perovskite oxides is caused by the directionally confined, low-dimensional electronic structure at the Ti-O-Ti bonds. Copyright © 2016 Elsevier B.V. All rights reserved.

  19. X-ray K-edge analysis of drain lines in Wilhelm Hall, Ames Laboratory

    International Nuclear Information System (INIS)

    Jensen, T.; Whitmore, C.; Iowa State Univ., Ames, IA

    1999-01-01

    From August 12--27, 1998 X-ray K-edge measurements were made on drain lines in seven rooms in Wilhelm Hall, Ames Laboratory. The purpose of these measurements was to determine the extent of thorium (and other heavy metal) contamination inside these pipes. The K-edge method is a noninvasive inspection technique that can provide accurate quantification of heavy metal contamination interior to an object. Of the seven drain lines inspected, one was found to have no significant contamination, three showed significant thorium deposits, two showed mercury contamination, and one line was found to contain mercury, thorium and uranium. The K-edge measurements were found to be consistent with readings from hand-held survey meters, and provided much greater detail on the location and amount of heavy metal contamination

  20. Theoretical Mn K-edge XANES for Li2MnO3: DFT + U study

    International Nuclear Information System (INIS)

    Tamura, Tomoyuki; Ohwaki, Tsukuru; Ito, Atsushi; Ohsawa, Yasuhiko; Kobayashi, Ryo; Ogata, Shuji

    2012-01-01

    Spectral features of Mn K-edge x-ray absorption near-edge structure (XANES) for Li 2 MnO 3 were calculated using the first-principles full projector augmented wave method with the general gradient approximation plus U method. We demonstrated that the U parameter affects the spectral features in the pre-edge region while it does not affect those in the major absorption region. From the comparison with the experimental spectra and those of reference compounds, we showed that the spectral features of Mn K-edge XANES and the differences in the valence state can be reproduced well. (paper)

  1. Mammographic x-ray unit kilovoltage test tool based on k-edge absorption effect.

    Science.gov (United States)

    Napolitano, Mary E; Trueblood, Jon H; Hertel, Nolan E; David, George

    2002-09-01

    A simple tool to determine the peak kilovoltage (kVp) of a mammographic x-ray unit has been designed. Tool design is based on comparing the effect of k-edge discontinuity of the attenuation coefficient for a series of element filters. Compatibility with the mammography accreditation phantom (MAP) to obtain a single quality control film is a second design objective. When the attenuation of a series of sequential elements is studied simultaneously, differences in the absorption characteristics due to the k-edge discontinuities are more evident. Specifically, when the incident photon energy is higher than the k-edge energy of a number of the elements and lower than the remainder, an inflection may be seen in the resulting attenuation data. The maximum energy of the incident photon spectra may be determined based on this inflection point for a series of element filters. Monte Carlo photon transport analysis was used to estimate the photon transmission probabilities for each of the sequential k-edge filter elements. The photon transmission corresponds directly to optical density recorded on mammographic x-ray film. To observe the inflection, the element filters chosen must have k-edge energies that span a range greater than the expected range of the end point energies to be determined. For the design, incident x-ray spectra ranging from 25 to 40 kVp were assumed to be from a molybdenum target. Over this range, the k-edge energy changes by approximately 1.5 keV between sequential elements. For this design 21 elements spanning an energy range from 20 to 50 keV were chosen. Optimum filter element thicknesses were calculated to maximize attenuation differences at the k-edge while maintaining optical densities between 0.10 and 3.00. Calculated relative transmission data show that the kVp could be determined to within +/-1 kV. To obtain experimental data, a phantom was constructed containing 21 different elements placed in an acrylic holder. MAP images were used to determine

  2. Image reconstruction for x-ray K-edge imaging with a photon counting detector

    Science.gov (United States)

    Meng, Bo; Cong, Wenxiang; Xi, Yan; Wang, Ge

    2014-09-01

    Contrast agents with high-Z elements have K-absorption edges which significantly change X-ray attenuation coefficients. The K-edge characteristics is different for various kinds of contrast agents, which offers opportunities for material decomposition in biomedical applications. In this paper, we propose a new K-edge imaging method, which not only quantifies a distribution of a contrast agent but also provides an optimized contrast ratio. Our numerical simulation tests demonstrate the feasibility and merits of the proposed methodology.

  3. Si K-edge XANES study of SiOxCyHz amorphous polymeric materials

    International Nuclear Information System (INIS)

    Chaboy, J.; Barranco, A.; Yanguas-Gil, A.; Yubero, F.; Gonzalez-Elipe, A. R.

    2007-01-01

    This work reports on x-ray absorption spectroscopy study at the Si K edge of several amorphous SiO x C y H z polymers prepared by plasma-enhanced chemical-vapor deposition with different C/O ratios. SiO 2 and SiC have been used as reference materials. The comparison of the experimental Si K-edge x-ray absorption near-edge structure spectra with theoretical computations based on multiple scattering theory has allowed us to monitor the modification of the local coordination around Si as a function of the overall C/O ratio in this kind of materials

  4. Mammographic x-ray unit kilovoltage test tool based on k-edge absorption effect

    International Nuclear Information System (INIS)

    Napolitano, Mary E.; Trueblood, Jon H.; Hertel, Nolan E.; David, George

    2002-01-01

    A simple tool to determine the peak kilovoltage (kVp) of a mammographic x-ray unit has been designed. Tool design is based on comparing the effect of k-edge discontinuity of the attenuation coefficient for a series of element filters. Compatibility with the mammography accreditation phantom (MAP) to obtain a single quality control film is a second design objective. When the attenuation of a series of sequential elements is studied simultaneously, differences in the absorption characteristics due to the k-edge discontinuities are more evident. Specifically, when the incident photon energy is higher than the k-edge energy of a number of the elements and lower than the remainder, an inflection may be seen in the resulting attenuation data. The maximum energy of the incident photon spectra may be determined based on this inflection point for a series of element filters. Monte Carlo photon transport analysis was used to estimate the photon transmission probabilities for each of the sequential k-edge filter elements. The photon transmission corresponds directly to optical density recorded on mammographic x-ray film. To observe the inflection, the element filters chosen must have k-edge energies that span a range greater than the expected range of the end point energies to be determined. For the design, incident x-ray spectra ranging from 25 to 40 kVp were assumed to be from a molybdenum target. Over this range, the k-edge energy changes by approximately 1.5 keV between sequential elements. For this design 21 elements spanning an energy range from 20 to 50 keV were chosen. Optimum filter element thicknesses were calculated to maximize attenuation differences at the k-edge while maintaining optical densities between 0.10 and 3.00. Calculated relative transmission data show that the kVp could be determined to within ±1 kV. To obtain experimental data, a phantom was constructed containing 21 different elements placed in an acrylic holder. MAP images were used to determine

  5. Plutonium isotopic assay of reprocessing product solutions in the KfK K-edge densitometer

    International Nuclear Information System (INIS)

    Eberle, H.; Ottmar, H.; Matussek, P.

    1985-04-01

    The KfK K-edge densiometer, designed for accurate element concentration measurements using the technique of X-ray absorptiometry at the K absorption edge, provides as an additional option the possibility to determine the isotopic composition of freshly separated plutonium from an gamma-spectrometric analysis of its self-radiation. This report describes the underlying methodology and experimental procedures for the isotopic analysis in the K-edge densitometer. The paper also presents and discusses the experimental results so far obtained from routine measurements on reprocessing product solutions. (orig.)

  6. X-ray absorption spectroscopic studies of the blue copper site: Metal and ligand K-edge studies to probe the origin of the EPR hyperfine splitting in plastocyanin

    International Nuclear Information System (INIS)

    Shadle, S.E.; Penner-Hahn, J.E.; Schugar, H.J.; Hedman, B.; Hodgson, K.O.; Solomon, E.I.

    1993-01-01

    X-ray absorption spectra for the oxidized blue copper protein plastocyanin and several Cu(II) model complexes have been measured at both the Cu K-edge and the ligand K-edges (Cl and S) in order to elucidate the source of the small parallel hyperfine splitting in the EPR spectra of blue copper centers. Assignment and analysis of a feature in the Cu K-edge X-ray absorption spectrum at ∼8,987 eV as the Cu 1s → 4p + ligand-to-metal charge-transfer shakedown transition has allowed for quantitation of 4p mixing into the ground-state wave function as reflected in the 1s →3d (+4p) intensity at ∼8,979 eV. The results show that distorted tetrahedral (D 2d )CuCl 4 2- is characterized by z mixing, while plastocyanin has only Cu 4p xy mixing. Thus, the small parallel hyperfine splitting in the EPR spectra of D 2d CuCl 4 2- and of oxidized plastocyanin cannot be explained by 12% 4p z mixing into the 3d x 2 -y 2 orbital as had been previously postulated. Data collected at the Cl K-edge for CuCl 4 2- show that the intensity of the ligand pre-edge feature at ∼2,820 eV reflects the degree of covalency between the metal half-occupied orbital and the ligands. The data show that D 2d CuCl 4 2- is not unusually covalent. The source of the small parallel splitting in the EPR of D 2d CuCl 4 2- is discussed. Experiments at the S K-edge (∼2,470 eV) show that plastocyanin is characterized by a highly covalent Cu-S(cysteine) bond relative to the cupric-thiolate model complex [Cu(tet b)(o-SC 6 H 4 CO 2 )]·H 2 O. The XAS results demonstrate that the small parallel hyperfine splitting in the EPR spectra of blue copper sites reflects the high degree of covalency of the copper-thiolate bond. 34 refs., 12 figs., 3 tabs

  7. Chemical shift of Mn and Cr K-edges in X-ray absorption

    Indian Academy of Sciences (India)

    ... Lecture Workshops · Refresher Courses · Symposia · Live Streaming. Home; Journals; Bulletin of Materials Science; Volume 36; Issue 6. Chemical shift of Mn and Cr K-edges in X-ray absorption spectroscopy with synchrotron radiation. D Joseph A K Yadav S N Jha D Bhattacharyya. Volume 36 Issue 6 November 2013 pp ...

  8. Investigation of Prussian Blue Analogs by XMCD at the K-edge of transition metals

    International Nuclear Information System (INIS)

    Bordage, A; Bleuzen, A; Nataf, L; Baudelet, F

    2016-01-01

    Despite transition metal (TM) K-edge x-ray magnetic circular dichroism (XMCD) seems an interesting tool to get magnetic and structural information at the atomic scale, the effects originating this signal are still poorly understood. We thus initiated a deep investigation of the TM K-edge XMCD using Prussian Blue analogs (PBA) as model-compounds. In a recent study of the NiFe PBA family, we demonstrated that the XMCD signals at the TM K-edges strongly vary with external (mechanical) or internal (chemical) pressure and so that they are highly sensitive to small structural distortions. Following these first results, we extended this approach to the MnFe and CoFe families to evaluate the effect of electronic parameters (number of unpaired electrons of the M II TM) on the XMCD signal. All the results set milestones in the disentanglement of the components originating the XMCD signals at the K-edge of TM and will eventually help in a better understanding of the photomagnetic properties of PBAs. (paper)

  9. EXAFS Study on LiFePO4 Powders Produced From Two Sol-Gel Routes

    Science.gov (United States)

    Negara, V. S. I.; Latif, C.; Wongtepa, W.; Pratapa, S.

    2018-04-01

    The local structure of LiFePO4 powders has been investigated using Fe K-edge Extended X-Ray Absorption Fine Structure (EXAFS) Spectroscopy data. The synthesis of LFP powders was carried out using two different sol-gel methods. The raw materials for Fe source were ironstone and commercial precursor of FeCl2·4H2O. Synthesis using natural materials produced two phases, namely LiFePO4 olivine and Li3Fe2(PO4)3 nasicon, whereas that using a commercial product produced a single phase of LiFePO4 olivine. The EXAFS data for both samples were collected at Synchrotron Light Research Institute (SLRI), Thailand. Fitting of the model on the experimental curve provided parameters that can be interpreted as the distance between Fe as the absorber and the nearest atoms on the LFP materials. The EXAFS data analysis has shown that synthesis of LFPs using different Fe sources gives slightly different nearest-neighbor distances, namely Fe-O of 0.21% -0.23%, Fe-P of 0.14% - 0.16%, Fe-Fe of 0.12% for both samples, respectively.

  10. Local structure in (MnS)2x(CuInS2)1-x alloys

    International Nuclear Information System (INIS)

    Pietnoczka, A.; Bacewicz, R.; Schorr, S.

    2006-01-01

    Local structure around Mn atoms in (MnS) 2x (CuInS 2 ) 1-x alloys for x≤0.09 has been determined using near-edge and extended X-ray absorption fine structure (XANES and EXAFS) measured at the Mn K-edge. We found that for the Mn concentration up to 9 at% Mn atoms substitute preferentially for indium in the chalcopyrite lattice. The Mn-S bond length is 2.43±0.015 Aa, and is about 2% shorter than the In-S bond length. (copyright 2006 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (Abstract Copyright [2006], Wiley Periodicals, Inc.)

  11. Interpretation of the U L3-edge EXAFS in uranium dioxide using molecular dynamics and density functional theory simulations

    International Nuclear Information System (INIS)

    Bocharov, Dmitry; Chollet, Melanie; Krack, Matthias; Bertsch, Johannes; Grolimund, Daniel; Martin, Matthias; Kuzmin, Alexei; Purans, Juris; Kotomin, Eugene

    2016-01-01

    X-ray absorption spectroscopy is employed to study the local structure of pure and Cr-doped UO 2 at 300 K. The U L 3 -edge EXAFS spectrum is interpreted within the multiplescattering (MS) theory using the results of the classical and ab initio molecular dynamics simulations, allowing us to validate the accuracy of theoretical models. The Cr K-edge XANES is simulated within the full-multiple-scattering formalism considering a substitutional model (Cr at U site). It is shown that both unrelaxed and relaxed structures, produced by ab initio density functional theory (DFT) calculations, fail to describe the experiment. (paper)

  12. Oxygen K-edge absorption spectra of small molecules in the gas phase

    Energy Technology Data Exchange (ETDEWEB)

    Yang, B.X.; Kirz, J.; Sham, T.K.

    1986-01-01

    The absorption spectra of O/sub 2/, CO, CO/sub 2/ and OCS have been recorded in a transmission mode in the energy region from 500 to 950 eV. Recent observation of EXAFS in these molecules is confirmed in this study. 7 refs., 3 figs.

  13. Oxygen K-edge absorption spectra of small molecules in the gas phase

    International Nuclear Information System (INIS)

    Yang, B.X.; Kirz, J.; Sham, T.K.

    1986-01-01

    The absorption spectra of O 2 , CO, CO 2 and OCS have been recorded in a transmission mode in the energy region from 500 to 950 eV. Recent observation of EXAFS in these molecules is confirmed in this study. 7 refs., 3 figs

  14. In situ, Cr K-edge XAS study on the Phillips catalyst : activation and ethylene polymerization

    NARCIS (Netherlands)

    Groppo, E.; Prestipino, C.; Cesano, F.; Bonino, F.; Bordiga, S.; Lamberti, C.; Thuene, P.C.; Niemantsverdriet, J.W.; Zecchina, A.

    2005-01-01

    In this in situ EXAFS and XANES study on the Phillips ethylene-polymerization Cr/SiO2 catalyst, two polymerization routes are investigated and compared. The first mimics that adopted in industrial plants, where ethylene is dosed directly on the oxidized catalyst, while in the second the oxidized

  15. Composition-driven Cu-speciation and reducibility in Cu-CHA zeolite catalysts: a multivariate XAS/FTIR approach to complexity† †Electronic supplementary information (ESI) available: Sample description and synthesis details, experimental setup for in situ XAS and FTIR spectroscopy, details on the MCR-ALS method, details on DFT-assisted XANES simulations, details on the determination of N pure by PCA, MCR-ALS results for downsized and upsized component spaces, additional information to support the assignment of theoretical XANES curves, details on EXAFS analysis, details on IR spectral deconvolution. See DOI: 10.1039/c7sc02266b Click here for additional data file.

    Science.gov (United States)

    Martini, A.; Lomachenko, K. A.; Pankin, I. A.; Negri, C.; Berlier, G.; Beato, P.; Falsig, H.; Bordiga, S.; Lamberti, C.

    2017-01-01

    The small pore Cu-CHA zeolite is attracting increasing attention as a versatile platform to design novel single-site catalysts for deNOx applications and for the direct conversion of methane to methanol. Understanding at the atomic scale how the catalyst composition influences the Cu-species formed during thermal activation is a key step to unveil the relevant composition–activity relationships. Herein, we explore by in situ XAS the impact of Cu-CHA catalyst composition on temperature-dependent Cu-speciation and reducibility. Advanced multivariate analysis of in situ XANES in combination with DFT-assisted simulation of XANES spectra and multi-component EXAFS fits as well as in situ FTIR spectroscopy of adsorbed N2 allow us to obtain unprecedented quantitative structural information on the complex dynamics during the speciation of Cu-sites inside the framework of the CHA zeolite. PMID:29147509

  16. Probing ultrafast ππ*/nπ* internal conversion in organic chromophores via K-edge resonant absorption

    DEFF Research Database (Denmark)

    Wolf, T. J. A.; Myhre, Rolf H.; Cryan, J. P.

    2017-01-01

    -edge soft X-ray absorption spectroscopy. As a hole forms in the n orbital during ππ*/nπ* internal conversion, the absorption spectrum at the heteroatom K-edge exhibits an additional resonance. We demonstrate the concept using the nucleobase thymine at the oxygen K-edge, and unambiguously show that ππ...

  17. Visualization of pigment distributions in paintings using synchrotron K-edge imaging

    International Nuclear Information System (INIS)

    Krug, K.; Dik, J.; Leeuw, M.; Whitson, A. den; Tortora, J.; Coan, P.; Nemoz, C.; Bravin, A.

    2006-01-01

    X-ray radiography plays an important role in the study of artworks and archaeological artifacts. The internal structure of objects provides information on genesis, authenticity, painting technique, material condition and conservation history. Transmission radiography, however, does not provide information on the exact elemental composition of objects and heavy metal layers can shadow or obscure the ones including lighter elements. This paper presents the first application of synchrotron-based K-edge absorption imaging applied to paintings. Using highly monochromatic radiation, K-edge imaging is used to obtain elemental distribution images over large areas. Such elemental maps visualize the distribution of an individual pigment throughout the paint stratigraphy. This provides color information on hidden paint layers, which is of great relevance to art historians and painting conservators. The main advantage is the quick data acquisition time and the sensitivity to elements throughout the entire paint stratigraphy. The examination of a test painting is shown and further instrumental developments are discussed. (orig.)

  18. Phosphorus Speciation of Forest-soil Organic Surface Layers using P K-edge XANES Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    J Prietzel; J Thieme; D Paterson

    2011-12-31

    The phosphorus (P) speciation of organic surface layers from two adjacent German forest soils with different degree of water-logging (Stagnosol, Rheic Histosol) was analyzed by P K-edge XANES and subsequent Linear Combination Fitting. In both soils, {approx}70% of the P was inorganic phosphate and {approx}30% organic phosphate; reduced P forms such as phosphonate were absent. The increased degree of water-logging in the Histosol compared to the Stagnosol did not affect P speciation.

  19. Surface EXAFS - A mathematical model

    International Nuclear Information System (INIS)

    Bateman, J.E.

    2002-01-01

    Extended X-ray absorption fine structure (EXAFS) studies are a powerful technique for studying the chemical environment of specific atoms in a molecular or solid matrix. The study of the surface layers of 'thick' materials introduces special problems due to the different escape depths of the various primary and secondary emission products which follow X-ray absorption. The processes are governed by the properties of the emitted fluorescent photons or electrons and of the material. Their interactions can easily destroy the linear relation between the detected signal and the absorption cross-section. Also affected are the probe depth within the surface and the background superimposed on the detected emission signal. A general mathematical model of the escape processes is developed which permits the optimisation of the detection modality (X-rays or electrons) and the experimental variables to suit the composition of any given surface under study

  20. EXAFS studies of metamict materials

    International Nuclear Information System (INIS)

    Greegor, R.B.; Lytle, F.W.; Ewing, R.C.; Haaker, R.F.

    1984-01-01

    An important approach in the evaluation of crystalline wasteforms for nuclear waste storage is to study the long term stabilities of closely related radioactive mineral species which have become metamict (radiation damaged) and have been exposed to weathering processes for geologic periods of time. The metamictization and alteration effects can then be used for comparison with the results of short term laboratory leaching and irradiation experiments which have been designed to simulate long term effects. Phosphates, the Ti-Nb-Ta complex oxide minerals and various selected silicates are natural analogues for phases in proposed radioactive wasteforms. Because of the geochemical similarities with wasteforms, a study of the metamict state and annealing in complex mineral phosphates, silicates and oxides will yield data that is important in evaluating the long term stability of radioactive wasteforms. The investigation reported here is an application of EXAFS and XANES spectroscopy to the study of the structure of the metamict state. The nearest neighbor environment of Ti and Ca in metamict AB 2 O 6 -type complex oxides has been examined using SSRL Beam Line VII-3 in order to evaluate the effect of alpha-recoil damage on these structures. Comparison of the EXAFS/XANES data for metamict samples with data for annealed and crystalline samples suggests minor changes in the first coordination sphere, Ca-O or Ti-O, (a slight decrease in coordination number and bond lengths, and increased distortion of the coordination polyhedron), but major disruption of the second coordination sphere, for the material in the metamict state. These data suggest a mechanism for the transition from the crystalline to the metamict state in which tilting of cation coordiantion polyhedra is a possible effect of damage caused by alpha-recoil events

  1. Parameters Influencing Sulfur Speciation in Environmental Samples Using Sulfur K-Edge X-Ray Absorption Near-Edge Structure

    Directory of Open Access Journals (Sweden)

    Siwatt Pongpiachan

    2012-01-01

    Full Text Available This paper aims to enhance the credibility of applying the sulfur K-edge XANES spectroscopy as an innovative “fingerprint” for characterizing environmental samples. The sensitivities of sulfur K-edge XANES spectra of ten sulfur compound standards detected by two different detectors, namely, Lytle detector (LyD and Germanium detector (GeD, were studied and compared. Further investigation on “self-absorption” effect revealed that the maximum sensitivities of sulfur K-edge XANES spectra were achieved when diluting sulfur compound standards with boron nitride (BN at the mixing ratio of 0.1%. The “particle-size” effect on sulfur K-edge XANES spectrum sensitivities was examined by comparing signal-to-noise ratios of total suspended particles (TSP and particulate matter of less than 10 millionths of a meter (PM10 collected at three major cities of Thailand. The analytical results have demonstrated that the signal-to-noise ratios of sulfur K-edge XANES spectra were positively correlated with sulfate content in aerosols and negatively connected with particle sizes. The combination of hierarchical cluster analysis (HCA and principal component analysis (PCA has proved that sulfur K-edge XANES spectrum can be used to characterize German terrestrial soils and Andaman coastal sediments. In addition, this study highlighted the capability of sulfur K-edge XANES spectra as an innovative “fingerprint” to distinguish tsunami backwash deposits (TBD from typical marine sediments (TMS.

  2. (EXAFS) X-ray absorption spectroscopy

    International Nuclear Information System (INIS)

    Craievich, A.F.

    1983-01-01

    The technique EXAFS (Extended X-Ray Absorption Fine Structure) is presented and its applications using the synchrotron radiation as an incidente beam in Science of Materials and Biophysics are shown. (L.C.) [pt

  3. The thermal behaviour of cuprite: An XRD-EXAFS combined approach

    International Nuclear Information System (INIS)

    Dapiaggi, M.; Tiano, W.; Artioli, G.; Sanson, A.; Fornasini, P.

    2003-01-01

    Cuprite (Cu 2 O) is a low thermal expansion material with a negative thermal expansion coefficient below room temperature. Its peculiar thermal behaviour encompasses the increase of the shear modulus with increasing temperature, and the presence of rather intense symmetry-forbidden eeo reflections below room temperature. The thermal expansion of cuprite was studied at low temperature (between 5 and 298 K) by means of high-resolution (10 -5 A) X-ray powder diffraction at European Synchrotron Radiation Facility (Grenoble, BM16) and extended X-ray absorption fine structure (EXAFS) (BM29). Negative thermal expansion is confirmed up to 200 K, by EXAFS as well as by XRD measurements, and no sign of transition was found in XRD data. The comparison between EXAFS and XRD results provides a valuable insight into vibrational behaviour of cuprite at low temperature

  4. EXAFS-spectroscopy on synchrotron radiation beam

    CERN Document Server

    Aksenov, V L; Kuzmin, A Y; Purans, Y

    2001-01-01

    In the review the basis theoretical principles of EXAFS spectroscopy are given, as one of principal directions of an absorption spectroscopy permitting with a high accuracy to gain parameters of the short-range order in multicomponent amorphous and quasi-crystal mediums. The methods of the analysis of EXAFS spectra with allowance of effects of multiply scattering are featured. The exposition of the experimental set-ups, which realize the method of EXAFS spectroscopy on beams of SR, requirement of the monochromatization of radiation beams are given. For investigation of phase transition and external effects the energy-dispersive EXAFS spectrometer is creating at the National center of SR Kurchatov Institute which can measure the EXAFS spectrum with a time resolution 3-5 ms. The experimental results on investigation (by the EXAFS spectroscopy method) of oxides of tungsten and molybdenum are given, which have unique property: the variable valence of an ion of metal is depending on external action. The most inter...

  5. Actinide L-line ED-XRF and Hybrid K-edge Densitometer Spectra Processing

    International Nuclear Information System (INIS)

    Esbelin, E.

    2015-01-01

    The analysis laboratory in the CEA Atalante complex at Marcoule (France) performs numerous R and D studies carried out in glove-boxes or in hot cells. Most of the samples are measured in liquid phase, aqueous or organic. The concentration of the main actinides of interest (U, Np, Pu, Am and Cm) are determined by XRF in a hot cell via their L-line X-ray between 13 and 15 keV. In order to limit the counting rate of many radioactive emitters (X-ray and gamma emitters) in the analysis solution and the continuous spectrum, a graphite monochromator is placed between the sample and detector. Commercial or free, the software packages available for processing X-ray spectra are designed and dedicated to a specific instrument and/or do not take into account the specific feature of our system, in other words, the presence of a monochromator. Therefore, a new X-ray analysis software programme was developed for this particular system which takes into account matrix effects corrections. For sample with U and/or Pu in high concentrations, the hybrid K-edge densitometer is used. A new software programme was also developed. For K-edge densitometry spectra processing, no calibration process is used. Spectra processing is based on theoretical equation and uses XCOM database for mass attenuation coefficients. Measured spectra on K-edge densitometer of Rokkasho Safeguards Analytical Laboratory were processed with this software and a very good agreement was found with IDTIMS results. The new graphical user interface allows to manually correct the defined edge. For the XRF spectra processing, new algorithms are used to define the base line and to find/integrate peaks. With these two analytical devices in laboratory, U and Pu concentrations can be measured from 0.5 mg/l to several hundred of g/l. (author)

  6. Comparison of iodine K-edge subtraction and fluorescence subtraction imaging in an animal system

    International Nuclear Information System (INIS)

    Zhang, H.; Zhu, Y.; Bewer, B.; Zhang, L.; Korbas, M.; Pickering, I.J.; George, G.N.; Gupta, M.; Chapman, D.

    2008-01-01

    K-Edge Subtraction (KES) utilizes the discontinuity in the X-ray absorption across the absorption edge of the selected contrast element and creates an image of the projected density of the contrast element from two images acquired just above and below the K-edge of the contrast element. KES has proved to be powerful in coronary angiography, micro-angiography, bronchography, and lymphatic imaging. X-ray fluorescence imaging is a successful technique for the detection of dilute quantities of elements in specimens. However, its application at high X-ray energies (e.g. at the iodine K-edge) is complicated by significant Compton background, which may enter the energy window set for the contrast material's fluorescent X-rays. Inspired by KES, Fluorescence Subtraction Imaging (FSI) is a technique for high-energy (>20 keV) fluorescence imaging using two different incident beam energies just above and below the absorption edge of a contrast element (e.g. iodine). The below-edge image can be assumed as a 'background' image, which includes Compton scatter and fluorescence from other elements. The above-edge image will contain nearly identical spectral content as the below-edge image but will contain the additional fluorescence of the contrast element. This imaging method is especially promising with thick objects with dilute contrast materials, significant Compton background, and/or competing fluorescence lines from other materials. A quality factor is developed to facilitate the comparison. The theoretical value of the quality factor sets the upper limit that an imaging method can achieve when the noise is Poisson limited. The measured value of this factor makes two or more imaging methods comparable. Using the Hard X-ray Micro-Analysis (HXMA) beamline at the Canadian Light Source (CLS), the techniques of FSI and KES were critically compared, with reference to radiation dose, image acquisition time, resolution, signal-to-noise ratios, and quality factor

  7. Spectral K-edge subtraction imaging of experimental non-radioactive barium uptake in bone.

    Science.gov (United States)

    Panahifar, Arash; Samadi, Nazanin; Swanston, Treena M; Chapman, L Dean; Cooper, David M L

    2016-12-01

    To evaluate the feasibility of using non-radioactive barium as a bone tracer for detection with synchrotron spectral K-edge subtraction (SKES) technique. Male rats of 1-month old (i.e., developing skeleton) and 8-month old (i.e., skeletally mature) were orally dosed with low dose of barium chloride (33mg/kg/day Ba 2+ ) for 4weeks. The fore and hind limbs were dissected for imaging in projection and computed tomography modes at 100μm and 52μm pixel sizes. The SKES method utilizes a single bent Laue monochromator to prepare a 550eV energy spectrum to encompass the K-edge of barium (37.441keV), for collecting both 'above' and 'below' the K-edge data sets in a single scan. The SKES has a very good focal size, thus limits the 'crossover' and motion artifacts. In juvenile rats, barium was mostly incorporated in the areas of high bone turnover such as at the growth plate and the trabecular surfaces, but also in the cortical bone as the animals were growing at the time of tracer administration. However, the adults incorporated approximately half the concentration and mainly in the areas where bone remodeling was predominant and occasionally in the periosteal and endosteal layers of the diaphyseal cortical bone. The presented methodology is simple to implement and provides both structural and functional information, after labeling with barium, on bone micro-architecture and thus has great potential for in vivo imaging of pre-clinical animal models of musculoskeletal diseases to better understand their mechanisms and to evaluate the efficacy of pharmaceuticals. Copyright © 2016 Associazione Italiana di Fisica Medica. Published by Elsevier Ltd. All rights reserved.

  8. The hybrid K-edge/K-XRF densitometer: Principles - design - performance

    International Nuclear Information System (INIS)

    Ottmar, H.; Eberle, H.

    1991-02-01

    The Euratom Safeguards Directorate (ESD) has recently installed a hybrid K-edge/K-XRF densitometer in a commerical reprocessing plant for the safeguarding of nuclear materials. This instrument, developed at KfK Karlsruhe, offers for the first time analytical measurement capabilities for timely on-site input accountancy verification. Lectures providing informations on measurement principles, instrument design features and performance data have been given to inspectors of ESD to make them familiar with the new instrument. This report summarizes the essential materials presented during these courses. (orig.) [de

  9. Sensitivity of photon-counting based K-edge imaging in X-ray computed tomography.

    Science.gov (United States)

    Roessl, Ewald; Brendel, Bernhard; Engel, Klaus-Jürgen; Schlomka, Jens-Peter; Thran, Axel; Proksa, Roland

    2011-09-01

    The feasibility of K-edge imaging using energy-resolved, photon-counting transmission measurements in X-ray computed tomography (CT) has been demonstrated by simulations and experiments. The method is based on probing the discontinuities of the attenuation coefficient of heavy elements above and below the K-edge energy by using energy-sensitive, photon counting X-ray detectors. In this paper, we investigate the dependence of the sensitivity of K-edge imaging on the atomic number Z of the contrast material, on the object diameter D , on the spectral response of the X-ray detector and on the X-ray tube voltage. We assume a photon-counting detector equipped with six adjustable energy thresholds. Physical effects leading to a degradation of the energy resolution of the detector are taken into account using the concept of a spectral response function R(E,U) for which we assume four different models. As a validation of our analytical considerations and in order to investigate the influence of elliptically shaped phantoms, we provide CT simulations of an anthropomorphic Forbild-Abdomen phantom containing a gold-contrast agent. The dependence on the values of the energy thresholds is taken into account by optimizing the achievable signal-to-noise ratios (SNR) with respect to the threshold values. We find that for a given X-ray spectrum and object size the SNR in the heavy element's basis material image peaks for a certain atomic number Z. The dependence of the SNR in the high- Z basis-material image on the object diameter is the natural, exponential decrease with particularly deteriorating effects in the case where the attenuation from the object itself causes a total signal loss below the K-edge. The influence of the energy-response of the detector is very important. We observed that the optimal SNR values obtained with an ideal detector and with a CdTe pixel detector whose response, showing significant tailing, has been determined at a synchrotron differ by factors of

  10. Effect of BSO addition on Cu-O bond of GdBa{sub 2}Cu{sub 3}O{sub 7-x} films with varying thickness probed by extended x-ray absorption fine structure

    Energy Technology Data Exchange (ETDEWEB)

    Jeon, H. K.; Lee, J. K.; Yang, D. S.; Kang, B. [Chungbuk National University, Cheongju (Korea, Republic of); Kang, W. N. [Dept. of Physics, Sungkyunkwan University, Suwon (Korea, Republic of)

    2016-12-15

    We investigated the relation between the Cu-O bond length and the superconducting properties of BaSnO{sub 3} (BSO)-added GdBa{sub 2}Cu{sub 3}O{sub 7-x} (GdBCO) thin films by using extended x-ray absorption fine structure (EXAFS) spectroscopy. 4 wt.% BaSnO{sub 3} (BSO) added GdBa{sub 2}Cu{sub 3}O{sub 7-x} (GdBCO) thin films with varying thickness from 0.2 μm to 1.0 μm were fabricated by using pulsed laser deposition (PLD) method. The transition temperature (T{sub c}) and the residual resistance ratio (RRR) of the GdBCO films increased with increasing thickness up to 0.8 μm, where the crystalline BSO has the highest peak intensity, and then decreased. This uncommon behaviors of T{sub c} and RRR are likely to be created by the addition of BSO, which may change the ordering of GdBCO atomic bonds. Analysis from the Cu K-edge EXAFS spectroscopy showed an interesting thickness dependence of ordering behavior of BSO-added GdBCO films. It is noticeable that the ordering of Cu-O bond and the transition temperature are found to show opposite behaviors in the thickness dependence. Based on these results, the growth of BSO seemingly have evident effect on the alteration of the local structure of GdBCO film.

  11. K-edge subtraction synchrotron X-ray imaging in bio-medical research.

    Science.gov (United States)

    Thomlinson, W; Elleaume, H; Porra, L; Suortti, P

    2018-05-01

    High contrast in X-ray medical imaging, while maintaining acceptable radiation dose levels to the patient, has long been a goal. One of the most promising methods is that of K-edge subtraction imaging. This technique, first advanced as long ago as 1953 by B. Jacobson, uses the large difference in the absorption coefficient of elements at energies above and below the K-edge. Two images, one taken above the edge and one below the edge, are subtracted leaving, ideally, only the image of the distribution of the target element. This paper reviews the development of the KES techniques and technology as applied to bio-medical imaging from the early low-power tube sources of X-rays to the latest high-power synchrotron sources. Applications to coronary angiography, functional lung imaging and bone growth are highlighted. A vision of possible imaging with new compact sources is presented. Copyright © 2018 Associazione Italiana di Fisica Medica. Published by Elsevier Ltd. All rights reserved.

  12. K-edge energy-based calibration method for photon counting detectors

    Science.gov (United States)

    Ge, Yongshuai; Ji, Xu; Zhang, Ran; Li, Ke; Chen, Guang-Hong

    2018-01-01

    In recent years, potential applications of energy-resolved photon counting detectors (PCDs) in the x-ray medical imaging field have been actively investigated. Unlike conventional x-ray energy integration detectors, PCDs count the number of incident x-ray photons within certain energy windows. For PCDs, the interactions between x-ray photons and photoconductor generate electronic voltage pulse signals. The pulse height of each signal is proportional to the energy of the incident photons. By comparing the pulse height with the preset energy threshold values, x-ray photons with specific energies are recorded and sorted into different energy bins. To quantitatively understand the meaning of the energy threshold values, and thus to assign an absolute energy value to each energy bin, energy calibration is needed to establish the quantitative relationship between the threshold values and the corresponding effective photon energies. In practice, the energy calibration is not always easy, due to the lack of well-calibrated energy references for the working energy range of the PCDs. In this paper, a new method was developed to use the precise knowledge of the characteristic K-edge energy of materials to perform energy calibration. The proposed method was demonstrated using experimental data acquired from three K-edge materials (viz., iodine, gadolinium, and gold) on two different PCDs (Hydra and Flite, XCounter, Sweden). Finally, the proposed energy calibration method was further validated using a radioactive isotope (Am-241) with a known decay energy spectrum.

  13. Spin-Polarization-Induced Preedge Transitions in the Sulfur K-Edge XAS Spectra of Open-Shell Transition-Metal Sulfates: Spectroscopic Validation of σ-Bond Electron Transfer.

    Science.gov (United States)

    Frank, Patrick; Szilagyi, Robert K; Gramlich, Volker; Hsu, Hua-Fen; Hedman, Britt; Hodgson, Keith O

    2017-02-06

    Sulfur K-edge X-ray absorption spectroscopy (XAS) spectra of the monodentate sulfate complexes [M II (itao)(SO 4 )(H 2 O) 0,1 ] (M = Co, Ni, Cu) and [Cu(Me 6 tren)(SO 4 )] exhibit well-defined preedge transitions at 2479.4, 2479.9, 2478.4, and 2477.7 eV, respectively, despite having no direct metal-sulfur bond, while the XAS preedge of [Zn(itao)(SO 4 )] is featureless. The sulfur K-edge XAS of [Cu(itao)(SO 4 )] but not of [Cu(Me 6 tren)(SO 4 )] uniquely exhibits a weak transition at 2472.1 eV, an extraordinary 8.7 eV below the first inflection of the rising K-edge. Preedge transitions also appear in the sulfur K-edge XAS of crystalline [M II (SO 4 )(H 2 O)] (M = Fe, Co, Ni, and Cu, but not Zn) and in sulfates of higher-valent early transition metals. Ground-state density functional theory (DFT) and time-dependent DFT (TDDFT) calculations show that charge transfer from coordinated sulfate to paramagnetic late transition metals produces spin polarization that differentially mixes the spin-up (α) and spin-down (β) spin orbitals of the sulfate ligand, inducing negative spin density at the sulfate sulfur. Ground-state DFT calculations show that sulfur 3p character then mixes into metal 4s and 4p valence orbitals and various combinations of ligand antibonding orbitals, producing measurable sulfur XAS transitions. TDDFT calculations confirm the presence of XAS preedge features 0.5-2 eV below the rising sulfur K-edge energy. The 2472.1 eV feature arises when orbitals at lower energy than the frontier occupied orbitals with S 3p character mix with the copper(II) electron hole. Transmission of spin polarization and thus of radical character through several bonds between the sulfur and electron hole provides a new mechanism for the counterintuitive appearance of preedge transitions in the XAS spectra of transition-metal oxoanion ligands in the absence of any direct metal-absorber bond. The 2472.1 eV transition is evidence for further radicalization from copper(II), which

  14. K-Edge Subtraction Angiography with Synchrotron X-Rays; TOPICAL

    International Nuclear Information System (INIS)

    Giacomini, John C.

    1996-01-01

    The purpose of this project was to utilize dual energy, monochromatic X-rays produced from synchrotrons radiation in order to obtain noninvasive medical imaging. The application of synchrotrons radiation to medical imaging is based on the principle of iodine dichromography, first described by Bertil Jacobson of the Karolinska Institute in 1953. Medical imaging using synchrotrons radiation and K-edge dichromography was pioneered at Stanford University under the leadership of Dr. Ed Rubenstein, and the late Nobel Laureate in Physics, Dr. Robert Hofstadter. With progressive refinements in hardware, clinical-quality images were obtained of human coronary arteries utilizing peripheral injections of iodinated contrast agent. These images even now are far superior to those being presented by investigators using MRI as an imaging tool for coronary arteries. However, new supplies and instruments in the cardiac catheterization laboratory have served to transform coronary angiography into an outpatient procedure, with relatively little morbidity. We extended the principles learned with coronary angiography to noninvasive imaging of the human bronchial tree. For these images, we utilized xenon as the contrast agent, as it has a K-edge very similar to that of iodine. In this case, there is no true competing diagnostic test, and pulmonary neoplasm is an enormous public health concern. In early experiments, we demonstrated remarkably clear images of the human bronchial tree. These images have been shown internationally; however, funding difficulties primarily with the Department of Energy have not allowed for progression of this promising avenue of research. One potential criticism of the project is that in order to obtain these images, we utilized national laboratories. Some have questioned whether this would lead to a practical imaging modality. However, we have shown that the technology exists to allow for construction of a miniature storage ring, with a superconducting

  15. K-edge x-ray-absorption spectroscopy of laser-generated Kr+ and Kr2+

    International Nuclear Information System (INIS)

    Southworth, S. H.; Arms, D. A.; Dufresne, E. M.; Dunford, R. W.; Ederer, D. L.; Hoehr, C.; Kanter, E. P.; Kraessig, B.; Landahl, E. C.; Peterson, E. R.; Rudati, J.; Santra, R.; Walko, D. A.; Young, L.

    2007-01-01

    Tunable, polarized, microfocused x-ray pulses were used to record x-ray absorption spectra across the K edges of Kr + and Kr 2+ produced by laser ionization of Kr. Prominent 1s→4p and 5p excitations are observed below the 1s ionization thresholds in accord with calculated transition energies and probabilities. Due to alignment of 4p hole states in the laser-ionization process, the Kr + 1s→4p cross section varies with respect to the angle between the laser and x-ray polarization vectors. This effect is used to determine the Kr + 4p 3/2 and 4p 1/2 quantum state populations, and these are compared with results of an adiabatic strong-field ionization theory that includes spin-orbit coupling

  16. Using X-ray, K-edge densitometry in spent fuel characterization

    International Nuclear Information System (INIS)

    Jensen, T.; Aljundi, T.; Gray, J.N.

    1998-01-01

    There are instances where records for spent nuclear fuel are incomplete, as well as cases where fuel assemblies have deteriorated during storage. To bring these materials into compliance for long term storage will require determination of parameters such as enrichment, total fissionable material, and burnup. To obtain accurate estimates of these parameters will require the combination of information from different inspection techniques. A method which can provide an accurate measure of the total uranium in the spent fuel is X-ray K-edge densitometry. To assess the potential for applying this method in spent fuel characterization, the authors have measured the amount of uranium in stacks of reactor fuel plates containing nuclear materials of different enrichments and alloys. They have obtained good agreement with expected uranium concentrations ranging from 60 mg/cm 2 to 3,000 mg/cm 2 , and have demonstrated that these measurements can be made in a high radiation field (> 200 mR/hr)

  17. Exotic sources of x-rays for iodine K-edge angiography

    International Nuclear Information System (INIS)

    Carr, R.

    1993-08-01

    Digital Subtractive Angiography (DSA) has been performed to image human coronary arteries using wiggler radiation from electron storage rings. The significant medical promise of this procedure motivates the development of smaller and less costly x-ray sources. Several exotic sources are candidates for consideration, using effects such as Cherenkov, channeling, coherent bremsstrahlung, laser backscattering, microundulator, parametric, Smith-Purcell, and transition radiation. In this work we present an analysis of these effects as possible sources of intense x-rays at the iodine K-edge at 33.169 key. The criteria we use are energy, efficiency, flux, optical properties, and technical realizability. For each of the techniques, we find that they suffer either from low flux, a low energy cutoff, target materials heating, too high electron beam energy requirement, optical mismatch to angiography, or a combination of these. We conclude that the foreseeable state-of-the-art favors a compact storage ring design

  18. Extended software for the KfK K-edge densitometer

    International Nuclear Information System (INIS)

    Eberle, H.

    1985-04-01

    In order to further exploit the possibilities of the KfK K-edge densitometer, and to enlarge the range of its application, we have extended and modified the instrument's software. With the new software packages the instrument can now be used for analysis of the actinide elemments Th, U, Np, Pu and Am in single element solutions, and for the simultaneous assay of U and Pu in mixed U/Pu solutions. Provisions have been made for later extensions, allowing the analysis of additional elements combinations, if necessary. The report gives a short description of the new programs, and of the modifications to the previous programs. The listings and the corresponding programs are given in the Appendix. (orig./HP)

  19. Three dimensional mapping of strontium in bone by dual energy K-edge subtraction imaging

    International Nuclear Information System (INIS)

    Cooper, D M L; Chapman, L D; Carter, Y; Zhouping, W; Wu, Y; Panahifar, A; Duke, M J M; Doschak, M; Britz, H M; Bewer, B

    2012-01-01

    The bones of many terrestrial vertebrates, including humans, are continually altered through an internal process of turnover known as remodeling. This process plays a central role in bone adaptation and disease. The uptake of fluorescent tetracyclines within bone mineral is widely exploited as a means of tracking new tissue formation. While investigation of bone microarchitecture has undergone a dimensional shift from 2D to 3D in recent years, we lack a 3D equivalent to fluorescent labeling. In the current study we demonstrate the ability of synchrotron radiation dual energy K-edge subtraction (KES) imaging to map the 3D distribution of elemental strontium within rat vertebral samples. This approach has great potential for ex vivo analysis of preclinical models and human tissue samples. KES also represents a powerful tool for investigating the pharmokinetics of strontium-based drugs recently approved in many countries around the globe for the treatment of osteoporosis. (paper)

  20. Si K EDGE STRUCTURE AND VARIABILITY IN GALACTIC X-RAY BINARIES

    Energy Technology Data Exchange (ETDEWEB)

    Schulz, Norbert S.; Corrales, Lia; Canizares, Claude R. [Kavli Institute for Astrophysics and Space Research, Massachusetts Institute of Technology, Cambridge, MA 02139 (United States)

    2016-08-10

    We survey the Si K edge structure in various absorbed Galactic low-mass X-ray binaries (LMXBs) to study states of silicon in the inter- and circum-stellar medium. The bulk of these LMXBs lie toward the Galactic bulge region and all have column densities above 10{sup 22} cm{sup −2}. The observations were performed using the Chandra High Energy Transmission Grating Spectrometer. The Si K edge in all sources appears at an energy value of 1844 ± 0.001 eV. The edge exhibits significant substructure that can be described by a near edge absorption feature at 1849 ± 0.002 eV and a far edge absorption feature at 1865 ± 0.002 eV. Both of these absorption features appear variable with equivalent widths up to several mÅ. We can describe the edge structure using several components: multiple edge functions, near edge absorption excesses from silicates in dust form, signatures from X-ray scattering optical depths, and a variable warm absorber from ionized atomic silicon. The measured optical depths of the edges indicate much higher values than expected from atomic silicon cross sections and interstellar medium abundances, and they appear consistent with predictions from silicate X-ray absorption and scattering. A comparison with models also indicates a preference for larger dust grain sizes. In many cases, we identify Si xiii resonance absorption and determine ionization parameters between log ξ = 1.8 and 2.8 and turbulent velocities between 300 and 1000 km s{sup −1}. This places the warm absorber in close vicinity of the X-ray binaries. In some data, we observe a weak edge at 1.840 keV, potentially from a lesser contribution of neutral atomic silicon.

  1. The potential for neurovascular intravenous angiography using K-edge digital subtraction angiography

    International Nuclear Information System (INIS)

    Schueltke, E.; Fiedler, S.; Kelly, M.; Griebel, R.; Juurlink, B.; LeDuc, G.; Esteve, F.; Le Bas, J.-F.; Renier, M.; Nemoz, C.; Meguro, K.

    2005-01-01

    Background: Catheterization of small-caliber blood vessels in the central nervous system can be extremely challenging. Alternatively, intravenous (i.v.) administration of contrast agent is minimally invasive and therefore carries a much lower risk for the patient. With conventional X-ray equipment, volumes of contrast agent that could be safely administered to the patient do not allow acquisition of high-quality images after i.v. injection, because the contrast bolus is extremely diluted by passage through the heart. However, synchrotron-based digital K-edge subtraction angiography does allow acquisition of high-quality images after i.v. administration of relatively small doses of contrast agent. Materials and methods: Eight adult male New Zealand rabbits were used for our experiments. Animals were submitted to both angiography with conventional X-ray equipment and synchrotron-based digital subtraction angiography. Results: With conventional X-ray equipment, no contrast was seen in either cerebral or spinal blood vessels after i.v. injection of iodinated contrast agent. However, using K-edge digital subtraction angiography, as little as 1 ml iodinated contrast agent, when administered as i.v. bolus, yielded images of small-caliber blood vessels in the central nervous system (both brain and spinal cord). Conclusions: If it would be possible to image blood vessels of the same diameter in the central nervous system of human patients, the synchrotron-based technique could yield high-quality images at a significantly lower risk for the patient than conventional X-ray imaging. Images could be acquired where catheterization of feeding blood vessels has proven impossible

  2. Stability of Working Reference Standards for Hybrid K-Edge Densitometer Quality Assurance

    International Nuclear Information System (INIS)

    Guzzardo, T.; Pickett, C.A.; McElroy, R.; Croft, S.; Garrison, J.; Venkataraman, R.

    2015-01-01

    The relatively short working life of aqueous solution standards of actinides for the calibration and quality control of Hybrid K-Edge Densitometer (HKED) measurements necessitates the development of a stable matrix material less susceptible to degradation. Degradation in the form of evaporation, radiolysis, settling, sloshing, and sediment formation can all reduce the reliability and working life of an aqueous standard. These factors make aqueous solutions inadequate for long-term quality assurance measurements designed to detect weak or subtle trends in system performance. Epoxy, studied here, is an alternative matrix material that may be less vulnerable to degradation. An additional benefit of epoxy is that standards can easily be characterized as sealed sources which allows for simplified administrative controls during shipping and storage. The stability of working reference standards consisting of U 3 O 8 in an epoxy matrix for use in the HKED has been tracked for over three years through repeated X-ray Fluorescence (XRF) and K-Edge (KED) measurements. A set of six epoxy standards ranging in concentration from 1 g/l to 76 g/l uranium were determined to be stable, within the expected accuracy of the system, over the period of analysis. During this time, no effort was made to enhance the stability of the epoxy standards; the radial measurement position was not controlled and in the middle of the analysis period the HKED system and standards were shipped from the vendor's factory to the customer. Epoxy standards afford numerous benefits over those created from aqueous solutions and should be considered when developing HKED standards for quality assurance measurements. The stability of the epoxy allows the development of working standards of a stability and robustness sufficient for use in a proposed international round-robin exercise based on the exchange of such standards. (author)

  3. X-ray absorption spectroscopy (EXAFS)

    International Nuclear Information System (INIS)

    Craievich, A.F.

    1983-01-01

    The experimental technics of Extended X-ray Absorption Fine Structure (EXAFS) is presented and several uses of it in atomic, molecular and bio physics are shown. The recent progresses of this technics, both theoretical and experimental, are discussed and the future perspectives on this subject are commented. (L.C.) [pt

  4. Structure of spinel at high temperature using in-situ XANES study at the Al and Mg K-edge

    Energy Technology Data Exchange (ETDEWEB)

    Ligny, D de [Universite Claude Bernard Lyon 1, LPCML, 69622 Villeurbanne (France); Neuville, D R [Physique des Mineraux et Magmas, Geochimie-Cosmochimie, CNRS-IPGP, 4 place Jussieu, 75005 Paris (France); Flank, A-M; Lagarde, P, E-mail: deligny@pcml.univ-lyon1.f [Synchrotron SOLEIL, L' Orme des Merisiers, Saint Aubin, 91192 France (France)

    2009-11-15

    We present structural information obtained on spinel at high temperature (298-2400 K) using in situ XANES at the Mg and Al K-edge. Spinel, {sup [4]}(Al{sub x},Mg{sub 1-x}){sup [6]}(Al{sub 2-x},Mg{sub x})O{sub 4}, with increasing temperature, show a substitution of Mg by Al and Al by Mg in their respective sites. This substitution corresponds to an inversion of the Mg and Al sites. Furthermore, both experiments at the Al and Mg K-edges are in good agreement with XANES calculation made using FDMNES code.

  5. The use of the hybrid K-edge densitometer for routine analysis of safeguards verification samples of reprocessing input liquor

    International Nuclear Information System (INIS)

    Ottmar, H.; Eberle, H.

    1991-01-01

    Following successful tests of a hybrid K-edge instrument at TUI Karlsruhe and the routine use of a K-edge densitometer for safeguards verification at the same laboratory, the Euratom Safeguards Directorate of the Commission of the European Communities decided to install the first such instrument into a large industrial reprocessing plant for the routine verification of samples taken from the input accountancy tanks. This paper reports on the installation, calibration, sample handling procedure and the performance of this instrument after one year of routine operation

  6. Molecular anisotropy effects in carbon K-edge scattering: depolarized diffuse scattering and optical anisotropy

    Energy Technology Data Exchange (ETDEWEB)

    Stone, Kevin H.

    2014-07-14

    Some polymer properties, such as conductivity, are very sensitive to short- and intermediate-range orientational and positional ordering of anisotropic molecular functional groups, and yet means to characterize orientational order in disordered systems are very limited. We demonstrate that resonant scattering at the carbon K-edge is uniquely sensitive to short-range orientation correlations in polymers through depolarized scattering at high momentum transfers, using atactic polystyrene as a well-characterized test system. Depolarized scattering is found to coexist with unpolarized fluorescence, and to exhibit pronounced anisotropy. We also quantify the spatially averaged optical anisotropy from low-angle reflectivity measurements, finding anisotropy consistent with prior visible, x-ray absorption, and theoretical studies. The average anisotropy is much smaller than that in the depolarized scattering and the two have different character. Both measurements exhibit clear spectral signatures from the phenyl rings and the polyethylene-like backbone. Discussion focuses on analysis considerations and prospects for using this depolarized scattering for studies of disorder in soft condensed matter.

  7. New K-edge-balanced contrast phantom for image quality assurance in projection radiography

    Science.gov (United States)

    Cresens, Marc; Schaetzing, Ralph

    2003-06-01

    X-ray-absorber step-wedge phantoms serve in projection radiography to assess a detection system's overall exposure-related signal-to-noise ratio performance and contrast response. Data derived from a phantom image, created by exposing a step-wedge onto the image receptor, are compared with predefined acceptance criteria during periodic image quality assurance (QA). For contrast-related measurements, in particular, the x-ray tube potential requires accurate setting and low ripple, since small deviations from the specified kVp, causing energy spectrum changes, lead to significant image signal variation at high contrast ratios. A K-edge-balanced, rare-earth-metal contrast phantom can generate signals that are significantly more robust to the spectral variability and instability of exposure equipment in the field. The image signals from a hafnium wedge, for example, are up to eight times less sensitive to spectral fluctuations than those of today"s copper phantoms for a 200:1 signal ratio. At 120 kVp (RQA 9), the hafnium phantom still preserves 70% of the subject contrast present at 75 kVp (RQA 5). A copper wedge preserves only 7% of its contrast over the same spectral range. Spectral simulations and measurements on prototype systems, as well as potential uses of this new class of phantoms (e.g., QA, single-shot exposure response characterization) are described.

  8. Surface modification study of borate materials from B K-edge X-ray absorption spectroscopy

    Science.gov (United States)

    Kasrai, Masoud; Fleet, Michael E.; Muthupari, Swaminathan; Li, D.; Bancroft, G. M.

    The B K-edge X-ray absorption near-edge structure (XANES) spectra of two borates with tetrahedrally-coordinated B [[4]B; natural danburite (CaB2Si2O8) and synthetic boron phosphate (BPO4)] have been recorded in total electron yield (TEY) and fluorescence yield (FY) modes to investigate the surface and bulk structure of these materials. The TEY XANES measurement shows that danburite is susceptible to surface damage involving conversion of [4]B sites to [3]B sites by reaction with moisture and/or mechanical abrasion (grinding, polishing, etc.). The bulk of the mineral is essentially unaffected. Commercial boron phosphate powder exhibits more extensive surface and bulk damage, which increases with air exposure but is recovered on heating at 650°C. In contrast to ELNES, the XANES technique is not affected by beam damage and when collected in the FY mode is capable of yielding meaningful information on the coordination and intermediate-range structure of B in borate and borosilicate materials.

  9. The optical properties of boron carbide near boron K-edge inside periodical multilayers

    Energy Technology Data Exchange (ETDEWEB)

    Ksenzov, Dmitriy; Schlemper, Christoph; Pietsch, Ullrich [University of Siegen (Germany)

    2010-07-01

    Multilayer mirrors made for the use in the wavelength range near K-edge of boron (188 eV) are of great interest for X-ray fluorescence analysis of boron content in doped semiconductors, plasma diagnostics, astronomy and lithography. Moreover, multilayer mirrors composed by a metal and a low Z element like boron are used as optical elements in both the soft x-ray spectral range as well as at higher photon energies on 3rd generation synchrotron beamlines. Using an energy-resolved photon-in-photon-out method we reconstructed the optical data from energy dependence of both integrated peak intensity and FWHM of the 1st order ML Bragg peak measured at the UHV triple axis soft-x-ray reflectometer at BESSY II. The experiments clearly demonstrate that the peak shape of the ML Bragg peak is most sensitive to any kind of electronic excitation and recombination in solid. The soft-ray reflectivity can give detailed information for MLs with thickness up to several tens of nanometers. In addition, measurements close to a resonance edge probe the chemical state of the respective constituent accompanied with a high sensitivity of changes close to the sample surface.

  10. Photoabsorption spectra of potassium and rubidium near the K-edge

    International Nuclear Information System (INIS)

    Azuma, Y.; Berry, H.G.; Cowan, P.L.

    1995-01-01

    We have used a high-temperature circulating heat-pipe absorption cell together with monochromatized X-ray beams at the X24A and X23A2 beam lines at the NSLS to obtain photoabsorption spectra of potassium and rubidium at their K- and KM-edges. The photon-energy ranges lay near 3600 eV and 15200 eV, respectively. We have also obtained first measurements of the LII and LIII edges in cesium. Although the K-edge photoabsorptions of the rare gases have been studied, there is little previous work on other atomic vapors. Most of the edges and resonance peaks that we observed have now been identified using Dirac Hartree-Fock calculations. As a check, we have compared these results with those obtained previously in closed-shell rare-gas absorption spectra. The absolute energies were obtained through a calibration of the X24A systems using measurements of several metal L-edges in the 3200-5000 eV energy range. We found that the 4p resonance in potassium is significantly enhanced compared with the corresponding situation in argon. Likewise, the 5p resonance in krypton is unresolved from the background ionization cross section, whereas it is well resolved in rubidium. As suggested by Amusia, these enhancements may be due to the enhanced potential seen in the excited state of the alkali systems as a result of the presence of an s-electron which reduces the nuclear shielding

  11. K-edge resonant x-ray magnetic scattering from a transition-metal oxide: NiO

    DEFF Research Database (Denmark)

    Hill, J.P.; Kao, C.C.; McMorrow, D.F.

    1997-01-01

    We report the observation of resonant x-ray magnetic scattering in the vicinity of the Ni K edge in the antiferromagnet NiO. An approximately twofold increase in the scattering is observed as the incident photon energy is tuned through a pre-edge feature in the absorption spectrum, associated...

  12. Off-line NDA measurement of actinides in reprocessing solution using hybrid K-edge/K-XRF densitometer

    International Nuclear Information System (INIS)

    Bootharajan, M.; Swaminathan, K.; Venkata Subramani, C.R.; Kumar, R.

    2015-01-01

    A versatile, nondestructive assay (NDA) system of a hybrid K-edge/K-XRF facility adapted to a glove box facility has been developed at RCL, IGCAR for the analysis of U and Pu in process solutions obtained from the reprocessing of spent nuclear fuels. This paper describes i) The development of a hybrid K-edge/K-XRF facility adapted to a glove box system ii) The results obtained using conditioner solution of burn up 155 GWd/t with a dose of 20 R/h and iii) Comparison of the results with the parallel analyses of the same by Isotope dilution mass spectrometry. The hybrid K-edge cum K-XRF densitometer is ideally suited for dissolver solutions as well as U and Pu product solutions from reprocessing plant. This method can be useful in the analysis of mixed solution of Special Nuclear Materials (SNM) without chemical separation. To assay solutions with high radiation background, the hybrid K-edge/K-XRF system is designed and fabricated inside a glove box with adequate shielding from both source X-rays and the sample radiation. The theory and preliminary experiments are described elsewhere. Around 5 mL of the conditioner solution (burn up of 155 GWd/t with a dose of 20 R/h) was taken in a poly propylene vial placed concentrically in to another poly propylene vial. The concentration was estimated by K-edge densitometry with X-ray tube operated with 150 kV and 1 mA and counting period of 3000s. Background correction was obtained with the X-ray tube in OFF condition. The solution was analysed parallelly using isotopic dilution mass spectrometry

  13. Determination of two- and three-body correlation functions in ionic solutions by means of MD and EXAFS investigations

    International Nuclear Information System (INIS)

    D'Angelo, P.; Pavel, N.V.

    1999-01-01

    The solvation structure of Sr 2+ ions in acetonitrile has been studied by x-ray absorption spectroscopy (XAS) and molecular dynamics (MD) simulations. The extended x-ray absorption fine structure (EXAFS) above the Sr K-edge has been interpreted in the framework of the multiple scattering (MS) formalism and, for the first time, clear evidence of MS contributions has been found for non-complexing ions in solution. Molecular dynamics has been used to generate the partial pair g(r) and the three-body g(r 1 , r 2 , θ) distribution functions from which a model χ(k) has been constructed. An excellent agreement has been found between the theoretical and experimental data. This result demonstrates the ability of the XAS technique in probing three-body correlation functions in solutions. (au)

  14. EXAFS and principal component analysis : a new shell game

    International Nuclear Information System (INIS)

    Wasserman, S.

    1998-01-01

    The use of principal component (factor) analysis in the analysis EXAFS spectra is described. The components derived from EXAFS spectra share mathematical properties with the original spectra. As a result, the abstract components can be analyzed using standard EXAFS methodology to yield the bond distances and other coordination parameters. The number of components that must be analyzed is usually less than the number of original spectra. The method is demonstrated using a series of spectra from aqueous solutions of uranyl ions

  15. EXAFS study of short range order in Fe-Zr amorphous alloys

    International Nuclear Information System (INIS)

    Fernandez-Gubieda, M.L.; Gorria, P.; Barandiaran, J.M.; Barquin, L.F.

    1995-01-01

    Room temperature X-ray absorption spectra on Fe K-edge have been performed in Fe 100-x-y Zr x B y and Fe 86 Zr 7 Cu 1 B 6 alloys (x=7, 7.7, 9; y=0, 2, 4, 6). Fe-Fe coordination number and interatomic distances do not change in any sample. However, small changes in the Fe-Zr short range order, which could explain the evolution of the magnetic properties, have been observed. (orig.)

  16. Probing single magnon excitations in Sr₂IrO₄ using O K-edge resonant inelastic x-ray scattering.

    Science.gov (United States)

    Liu, X; Dean, M P M; Liu, J; Chiuzbăian, S G; Jaouen, N; Nicolaou, A; Yin, W G; Rayan Serrao, C; Ramesh, R; Ding, H; Hill, J P

    2015-05-27

    Resonant inelastic x-ray scattering (RIXS) at the L-edge of transition metal elements is now commonly used to probe single magnon excitations. Here we show that single magnon excitations can also be measured with RIXS at the K-edge of the surrounding ligand atoms when the center heavy metal elements have strong spin-orbit coupling. This is demonstrated with oxygen K-edge RIXS experiments on the perovskite Sr2IrO4, where low energy peaks from single magnon excitations were observed. This new application of RIXS has excellent potential to be applied to a wide range of magnetic systems based on heavy elements, for which the L-edge RIXS energy resolution in the hard x-ray region is usually poor.

  17. Sulfur K-edge X-ray absorption spectroscopy as an experimental probe for S-nitroso proteins

    International Nuclear Information System (INIS)

    Szilagyi, Robert K.; Schwab, David E.

    2005-01-01

    X-ray absorption spectroscopy at the sulfur K-edge (2.4-2.6 keV) provides a sensitive and specific technique to identify S-nitroso compounds, which have significance in nitric oxide-based cell signaling. Unique spectral features clearly distinguish the S-nitroso-form of a cysteine residue from the sulfhydryl-form or from a methionine thioether. Comparison of the sulfur K-edge spectra of thiolate, thiol, thioether, and S-nitroso thiolate compounds indicates high sensitivity of energy positions and intensities of XAS pre-edge features as determined by the electronic environment of the sulfur absorber. A new experimental setup is being developed for reaching the in vivo concentration range of S-nitroso thiol levels in biological samples

  18. Feasibility study of X-ray K-edge analysis of RCRA heavy metal contamination of sludge packaged in drums

    International Nuclear Information System (INIS)

    Jensen, T.

    1999-01-01

    A study has been completed to assess the capabilities of X-ray K-edge analysis in the measurement of RCRA metal contamination of sludge packaged in drums. Results were obtained for mercury and lead contamination. It was not possible to measure cadmium contamination using this technique. No false positive signals were observed. In cases where uniformity of the sludge can be assumed, this analysis can provide a quick, accurate measurement of heavy-metal contamination

  19. X-ray spectroscopy at the Mn K edge in LaMnO3 : An ab initio study

    NARCIS (Netherlands)

    Hozoi, L.; Vries, A.H. de; Broer, R.

    2001-01-01

    We present ab initio quantum chemical embedded cluster calculations of Mn core-valence and d-d transitions in LaMnO3. The results are also important for the analysis of recent x-ray absorption and x-ray scattering experiments at the Mn K edge in LaMnO3. We find that the first two peaks of the

  20. Operating software for plutonium measurements in the KfK K-edge densitometer. A user's guide

    International Nuclear Information System (INIS)

    Eberle, H.

    1983-09-01

    A set of computer programs has been developed for the execution of plutonium concentration measurements in the KfK K-edge photon absorptiometer for performance evaluation. The programs are implemented on a ND-6620 data acquisition and processing system. A short description of the programs and commands for data accumulation and analysis is given. Nevertheless, the user should be familiar with the ND-6620 data acquisition and processing system, its system software, and with the FORTRAN programming language. (orig./HP)

  1. Chemical shift of Mn and Cr K-edges in X-ray absorption ...

    Indian Academy of Sciences (India)

    particularly on Mn and Cr compounds (Ghatikar et al 1977;. Padalia and Nayak 1977; ... conventional X-ray sources and hence may lack reliability. 2. Experimental ..... with the result obtained by Hinge et al (2011) for Cu com- pounds and is ... Chem. 84 2200. Nietubyc R, Sobczak E and Attenkofer K E 2001 J. Alloys Compd.

  2. EXAFS analysis of the L3 edge of Ce in CeO2: effects of multielectron excitations and final-state mixed valence

    International Nuclear Information System (INIS)

    Fonda, E.; Andreatta, D.; Colavita, P.E.; Vlaic, G.

    1999-01-01

    Cerium oxide (IV) (CeO 2 ) is extensively employed in heterogeneous catalysis, particularly as a promoter of noble metal action in three-way catalysts. For this reason there is a great scientific and economical interest in the development of any possible chemical or structural analysis technique that could provide information on these systems. EXAFS spectroscopy has revealed itself as a powerful technique for structural characterization of such catalysts. Unfortunately, good quality K-edge spectra of cerium are not yet easily obtainable because of the high photon energy required (>40 keV). On the other hand, at lower energies it is easy to collect very good spectra of the L 3 edge (5.5 keV), but L 3 -edge spectra of cerium (IV) are characterized by the presence of two undesired additional phenomena that interfere with EXAFS analysis: final-state mixed-valence behaviour and intense multi-electron excitations. Here, a comparative analysis of the K, L 3 , L 2 and L 1 edges of Ce in CeO 2 has been made and a procedure for obtaining structural parameters from L 3 -edge EXAFS, even in the presence of these features, has been developed. This procedure could allow further studies of catalytic compounds containing tetravalent cerium surrounded by oxygen ligands. (au)

  3. Interpolation of Gamma-ray buildup Factors for Arbitrary Source Energies in the Vicinity of the K-edge

    International Nuclear Information System (INIS)

    Michieli, I.

    1998-01-01

    Recently, a new buildup factors approximation formula based on the expanded polynomial set (E-P function) was successfully introduced (Michieli 1994.) with the maximum approximation error below 4% throughout the standard data domain. Buildup factors interpolation in E-P function parameters for arbitrary source energies, near the K-edge in lead, was satisfactory. Maximum interpolation error, for lead, lays within 12% what appears to be acceptable for most Point Kernel application. 1991. Harima at. al., showed that, near the K-edge, fluctuation in energy of exposure rate attenuation factors i.e.: D(E)B(E, μ E r)exp(-μ E r), given as a function of penetration depth (r) in ordinary length units (not mfps.), is not nearly as great as that of buildup factors. That phenomenon leads to the recommendation (ANSI/ANS-6.4.3) that interpolations in that energy range should be made in the attenuation factors B(E, μ E r)exp(-μ E r) rather than in the buildup factors alone. In present article, such interpolation approach is investigated by applying it to the attenuation factors in lead, with E-P function representation of exposure buildup factors. Simple form of the E-P function leads to strait calculation of new function parameters for arbitrary source energy near the K-edge and thus allowing the same representation form of buildup factors as in the standard interpolation procedure. results of the interpolation are discussed and compared with those from standard approach. (author)

  4. Adsorption behavior of sulfur-containing amino acid molecule on transition metal surface studied by S K-edge NEXAFS

    International Nuclear Information System (INIS)

    Yagi, S.; Matsumura, K.; Nakano, Y.; Ikenaga, E.; Sardar, S.A.; Syed, J.A.; Soda, K.; Hashimoto, E.; Tanaka, K.; Taniguchi, M.

    2003-01-01

    Adsorption behavior of a sulfur-containing amino acid L-cysteine molecule on transition metal surface have been investigated by S K-edge near-edge X-ray absorption fine structure. The L-cysteine molecule for first adsorption layer was found to dissociate on polycrystalline nickel surface, whereas molecularly adsorbed on copper surface at room temperature. Most of the L-cysteine molecules have been dissociated on nickel surface in annealing condition up to 353 K. On the other hand, the L-cysteine molecule did not dissociate on copper surface and the elongation of the S-C bonding occurred at 353 K

  5. Pressure-induced magnetic transition in Fe sub 4 N probed by Fe K-edge XMCD measurement

    CERN Document Server

    Ishimatsu, N; Maruyama, H; Kawamura, N; Suzuki, M; Ohishi, Y; Ito, M; Nasu, S; Kawakami, T

    2003-01-01

    X-ray magnetic circular dichroism (XMCD) of gamma'-iron nitride (Fe sub 4 N) was recorded at Fe K-edge under high pressure up to 27 GPa. The XMCD intensity decreased remarkably with pressure, and vanished at 24 GPa. Compressibility was measured by the X-ray diffraction method. These results indicate that Fe sub 4 N undergoes a second-order phase transition from the ferromagnetic state to a paramagnetic state without any structural change. The pressure-induced demagnetizing process is discussed in terms of the Fe magnetic states in the local environment.

  6. Sulfur K-edge X-ray absorption spectroscopy and time-dependent density functional theory of arsenic dithiocarbamates.

    Science.gov (United States)

    Donahue, Courtney M; Pacheco, Juan S Lezama; Keith, Jason M; Daly, Scott R

    2014-06-28

    S K-edge X-ray absorption spectroscopy (XAS) and time-dependent density functional theory (TDDFT) calculations were performed on a series of As[S2CNR2]3 complexes, where R2 = Et2, (CH2)5 and Ph2, to determine how dithiocarbamate substituents attached to N affect As[S2CNR2]3 electronic structure. Complimentary [PPh4][S2CNR2] salts were also studied to compare dithiocarbamate bonding in the absence of As. The XAS results indicate that changing the orientation of the alkyl substituents from trans to cis (R2 = Et2vs. (CH2)5) yields subtle variations whereas differences associated with a change from alkyl to aryl are much more pronounced. For example, despite the differences in As 4p mixing, the first features in the S K-edge XAS spectra of [PPh4][S2CNPh2] and As[S2CNPh2]3 were both shifted by 0.3 eV compared to their alkyl-substituted derivatives. DFT calculations revealed that the unique shift observed for [PPh4][S2CNPh2] is due to phenyl-induced splitting of the π* orbitals delocalized over N, C and S. A similar phenomenon accounts for the shift observed for As[S2CNPh2]3, but the presence of two unique S environments (As-S and As···S) prevented reliable analysis of As-S covalency from the XAS data. In the absence of experimental values, DFT calculations revealed a decrease in As-S orbital mixing in As[S2CNPh2]3 that stems from a redistribution of electron density to S atoms participating in weaker As···S interactions. Simulated spectra obtained from TDDFT calculations reproduce the experimental differences in the S K-edge XAS data, which suggests that the theory is accurately modeling the experimental differences in As-S orbital mixing. The results highlight how S K-edge XAS and DFT can be used cooperatively to understand the electronic structure of low symmetry coordination complexes containing S atoms in different chemical environments.

  7. Multiple Scattering Approach to Polarization Dependence of F K-Edge XANES Spectra for Highly Oriented Polytetrafluoroethylene (PTFE) Thin Film

    International Nuclear Information System (INIS)

    Nagamatsu, S.; Ono, M.; Kera, S.; Okudaira, K. K.; Fujikawa, T.; Ueno, N.

    2007-01-01

    The polarization dependence of F K-edge X-ray absorption near edge structure (XANES) spectra of highly-oriented thin-film of polytetrafluoroethylene (PTFE) has been analyzed by using multiple scattering theory. The spectra show clear polarization dependence due to the highly-oriented structure. The multiple scattering calculations reflects a local structure around an absorbing atom. The calculated results obtained by considering intermolecular-interactions are in good agreement with the observed polarization-dependence. We have also analyzed structural models of the radiation damaged PTFE films

  8. EXAFS of dilute systems: fluorescence detection

    International Nuclear Information System (INIS)

    Hastings, J.B.

    1979-01-01

    Since the first observations of the variation of the absorption coefficient for x-rays above the energy thresholds in the thirties until the early seventies, measurements and analysis of these variations were merely intended for the understanding of the underlying physics. Recently, with the understanding of the information available about the local atomic structure in the neighborhood of the absorbing species and the availability of high intensity synchrotron radiation sources, EXAFS has become a powerful structural tool. In these discussions, the details of the measurements for very dilute species are presented. It is shown that for the more dilute systems the measurement of the emission rather than the direct absorption is a more favorable technique

  9. EXAFS study of plutonium sorption onto kaolinite

    International Nuclear Information System (INIS)

    Reich, T.Y.; Banik, L.; Buda, R.A.; Amayri, S.; Drebert, J.; Kratz, J.V.; Trautmann, N.; Reich, T.; Ageev, A.L.; Korshunov, M.E.

    2007-01-01

    The uptake mechanism of plutonium by kaolinite was investigated by applying X-ray absorption spectroscopy to batch sorption samples (total Pu concentrations 1 and 10 μM; 4 g kaolinite/L in 0.1 M NaClO 4 ; 1 ≤ pH ≤ 9; presence and absence of ambient CO 2 ). For XAFS measurements, one sample was prepared from a Pu(III) solution at pH 6 under argon atmosphere. Three samples were obtained by sorption of Pu(IV) at pH I, 4, and 9 in an air-equilibrated system. The Pu L III -edge XANES spectra indicated that in all samples, including the Pu(III) sample, plutonium is sorbed at the kaolinite surface as Pu(IV). The Pu L III -edge k 3 -weighted EXAFS spectra showed eight oxygen atoms at an average Pu-O distance of 2.3 angstrom. Two Pu atoms were detected at ∼ 3.7 angstrom in all spectra, indicating the formation of polynuclear Pu(IV) species at the kaolinite surface. For the sample prepared from Pu(III) solution, an additional Pu-O shell at 3.2 angstrom was observed. The spectra of samples prepared from Pu(IV) included a Pu-Al/Si co-ordination shell at approximately 3.6 angstrom, indicating formation of inner-sphere sorption complexes. The structural models used in the least-squares fits were confirmed by an alternative EXAFS data analysis approach based on a modified Tikhonov regularization method. (authors)

  10. Feasibility of photon-counting K-edge imaging in X-ray and computed tomographic systems: Monte Carlo simulation studies

    International Nuclear Information System (INIS)

    Lee, Seung-Wan; Choi, Yu-Na; Cho, Hyo-Min; Lee, Young-Jin; Ryu, Hyun-Ju; Kim, Hee-Joung

    2011-01-01

    Conventional X-ray systems and X-ray computed tomography (CT) systems, which use detectors operated in the integrating mode, are not able to reflect spectral information because the detector output is proportional to the energy fluence integrated over the whole spectrum. Photon-counting detectors have been considered as alternative devices. These detectors can measure the photon energy deposited by each event and improve the image quality. In this study, we investigated the feasibility of K-edge imaging using a photon-counting detector and evaluated the capability of material decomposition in X-ray images. The geometries of X-ray imaging systems equipped with cadmium telluride (CdTe) detectors and phantoms consisting of different materials were designed using Geant4 Application for Tomographic Emission (GATE) version 6.0. To observe the effect of a discontinuity in the attenuation due to the K-edge of a high atomic number material, we chose the energy windows to be one below and one above the K-edge absorption energy of the target material. The contrast-to-noise ratios (CNRs) of the target materials were increased at selective energy levels above the K-edge absorption energy because the attenuation is more dramatically increased at energies above the K-edge absorption energy of the material than at energies below that. The CNRs for the target materials in the K-edge image were proportional to the material concentration. The results of this study show that K-edge imaging can be carried out in conventional X-ray systems and X-ray CT systems using CdTe photon-counting detectors and that the target materials can be separated from background materials by using K-edge imaging. The photon-counting detector has potential to provide improved image quality, and this study will be used as a basis for future studies on photon-counting X-ray imaging.

  11. Novel digital K-edge imaging system with transition radiation from an 855-MeV electron beam

    CERN Document Server

    Hagenbuck, F; Clawiter, N; Euteneuer, H; Görgen, F; Holl, P; Johann, K; Kiser, K H; Kemmer, J; Kerschner, T; Kettig, O; Koch, H; Kube, G; Lauth, W; Mauhay, H; Schütrumpf, M; Stotter, R; Strüder, L; Walcher, T; Wilms, A; von Zanthier, C; Zemter, M

    2001-01-01

    A novel K-edge imaging method has been developed at the Mainz Microtron MAMI aiming at a very efficient use of the transition radiation (TR) flux generated by the external 855-MeV electron beam in a foil stack. A fan-like quasi-monochromatic hard X-ray beam is produced from the +or-1-mrad-wide TR cone with a highly oriented pyrolytic graphite (HOPG) crystal. The absorption of the object in front of a 30 mm*10 mm pn charge-coupled device (pn-CCD) photon detector is measured at every pixel by a broad-band energy scan around the K-absorption edge. This is accomplished by a synchronous variation of the lateral crystal position and the electron beam direction which defines also the direction of the TR cone. The system has been checked with a phantom consisting of a 2.5- mu m thick molybdenum sample embedded in a 136- or 272- mu m-thick copper bulk foil. A numerical analysis of the energy spectrum for every pixel demonstrates that data as far as +or-0.75 keV away from the K edge of molybdenum at 20 keV still improv...

  12. Augmentation of Quick-EXAFS measurement facility at the energy scanning EXAFS beamline at INDUS-2 SRS

    Energy Technology Data Exchange (ETDEWEB)

    Poswal, A. K., E-mail: poswalashwini@gmail.com; Agrawal, Ankur; Bhattachryya, D.; Jha, S. N.; Sahoo, N. K. [Atomic and Molecular Physics Division, Bhabha Atomic Research Centre, Mumbai -400085 (India)

    2015-06-24

    In this paper implementation of Quick-EXAFS data acquisition facility at the Energy Scanning EXAFS beamline(BL-09) at INDUS-2 synchrotron source, Indore is presented. By adopting a continuous-scan mode in the Double Crystal monochromator (DCM), a high signal-to-noise ratio is maintained and the acquisition time is reduced to few seconds. The quality of spectra and repeatability is checked by measuring standards. The present mode of data acquisition would enable EXAFS measurement for in-situ studies even in fluorescence mode.

  13. Ca and S K-edge XANES studies of calcite-acid mine water interactions

    International Nuclear Information System (INIS)

    Myneni, S.C.B.; Perera, R.C.C.

    1997-01-01

    Heavy metal-rich acidic waters (SO 4 2- , AsO 4 3- , SeO 4 2- , Fe 2+ , Fe 3+ , Al 3+ , Cu 2+ , Zn 2+ , Cd 2+ ) and related ochreous coatings are common around abandoned sulfide and coal mine sites. This is mainly caused by the natural weathering of pyrite (FeS 2 ), arsenopyrite (FeAsS), and other metal sulfide containing shales. Acid generation in the case of pyrite can be explained by a general reaction: FeS 2 + 3.5 O 2 + H 2 O ↔ Fe 2+ + SO 4 2- + 2H + . Also, these low pH waters interact with the soils, and mobilize their soluble elements. One of the common remediation strategies is to allow these acid waters to react with limestone (CaCO 3 -rich rock) and neutralize the pH and precipitate out soluble metals. Yet, the associated problem is the precipitation of Fe and Al oxides and hydroxy sulfate coatings on limestone surfaces, which block calcite reactive sites, and make them ineffective a few hours after initiation of treatment. The main objectives of this research are to examine: (1) the chemistry of limestone surface coatings, and (2) their toxic metal uptake and the conditions that inhibit their formation. Previous molecular studies using X-ray diffraction, and vibrational spectroscopy on limestone surface coatings (sampled from Athens, OH) indicate that the surface-most layer (the layer in contact with water) is composed of schwertmannite (Fe(III)-hydroxy sulfate) like phases. However, white, X-ray amorphous; Al-, sulfate- and carbonate-rich; and Ca-poor phases appeared at the interface between the limestone and the iron oxide coatings. The structure, morphology, and coordination chemistry of component major and trace elements of these white precipitate phases have not previously been examined

  14. K-XANES study of YBa2Cu3O6.96 system

    International Nuclear Information System (INIS)

    Mishra, A.; Varshney, D.; Shivkumar, K.M.; Pandey, D.

    1998-01-01

    The copper K-edge x-ray absorption near edge structure (XANES) has been recorded in both CuO and YBaCuO samples on Cauchois type spectrograph with 0.4 m radius of curvature and a laboratory source of x-rays. The sample of YBa 2 Cu 3 ) 6.96 (T c =91K) were prepared by solid state route. The Cu K-XANES measurements were made on the powdered sample. The x-ray parameters, e.g., K-edge shift (ΔE k ), shift of principal absorption maximum (δE K ) and edge-width (δE A ) with reference to metal K-edge have been reported. The value of edge-shift of YBaCuO is larger than parent CuO. Also the smaller value of edge-width in YBaCuO is indicative of its ionic character. (author)

  15. Trace metal analysis by laser ablation-inductively coupled plasmamass spectrometry and x-ray K-edge densitometry of forensic samples

    Energy Technology Data Exchange (ETDEWEB)

    Berry, Jonna Elizabeth [Iowa State Univ., Ames, IA (United States)

    2016-10-25

    This dissertation describes a variety of studies on the determination of trace elements in samples with forensic importance. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) was used to determine the trace element composition of numerous lipstick samples. Lipstick samples were determined to be homogeneous. Most lipstick samples of similar colors were readily distinguishable at a 95% confidence interval based on trace element composition. Numerous strands of a multi-strand speaker cable were analyzed by LA-ICP-MS. The strands in this study are spatially heterogeneous in trace element composition. In actual forensic applications, the possibility of spatial heterogeneity must be considered, especially in cases where only small samples (e.g., copper wire fragments after an explosion) are available. The effects of many unpredictable variables, such as weather, temperature, and human activity, on the retention of gunshot residue (GSR) around projectile wounds were assessed with LAICP- MS. Skin samples around gunshot and stab wounds and larvae feeding in and around the wounds on decomposing pig carcasses were analyzed for elements consistent with GSR (Sb, Pb, Ba, and Cu). These elements were detected at higher levels in skin and larvae samples around the gunshot wounds compared to the stab wounds for an extended period of time throughout decomposition in both a winter and summer study. After decomposition, radiographic images of the pig bones containing possible damage from bullets revealed metallic particles embedded within a number of bones. Metallic particles within the bones were analyzed with x-ray, K-edge densitometry and determined to contain lead, indicating that bullet residue can be retained throughout decomposition and detected within bones containing projectile trauma.

  16. Ca and S K-edge XANES studies of calcite-acid mine water interactions

    Energy Technology Data Exchange (ETDEWEB)

    Myneni, S.C.B.; Perera, R.C.C. [Lawrence Berkeley National Lab., CA (United States)

    1997-04-01

    Heavy metal-rich acidic waters (SO{sub 4}{sup 2{minus}}, AsO{sub 4}{sup 3{minus}}, SeO{sub 4}{sup 2{minus}}, Fe{sup 2+}, Fe{sup 3+}, Al{sup 3+}, Cu{sup 2+}, Zn{sup 2+}, Cd{sup 2+}) and related ochreous coatings are common around abandoned sulfide and coal mine sites. This is mainly caused by the natural weathering of pyrite (FeS{sub 2}), arsenopyrite (FeAsS), and other metal sulfide containing shales. Acid generation in the case of pyrite can be explained by a general reaction: FeS{sub 2} + 3.5 O{sub 2} + H{sub 2}O {leftrightarrow} Fe{sup 2+} + SO{sub 4}{sup 2{minus}} + 2H{sup +}. Also, these low pH waters interact with the soils, and mobilize their soluble elements. One of the common remediation strategies is to allow these acid waters to react with limestone (CaCO{sub 3}-rich rock) and neutralize the pH and precipitate out soluble metals. Yet, the associated problem is the precipitation of Fe and Al oxides and hydroxy sulfate coatings on limestone surfaces, which block calcite reactive sites, and make them ineffective a few hours after initiation of treatment. The main objectives of this research are to examine: (1) the chemistry of limestone surface coatings, and (2) their toxic metal uptake and the conditions that inhibit their formation. Previous molecular studies using X-ray diffraction, and vibrational spectroscopy on limestone surface coatings (sampled from Athens, OH) indicate that the surface-most layer (the layer in contact with water) is composed of schwertmannite (Fe(III)-hydroxy sulfate) like phases. However, white, X-ray amorphous; Al-, sulfate- and carbonate-rich; and Ca-poor phases appeared at the interface between the limestone and the iron oxide coatings. The structure, morphology, and coordination chemistry of component major and trace elements of these white precipitate phases have not previously been examined.

  17. The local structure of Ca-Na pyroxenes. 2-Xanes studies at the Mg and A1 K edges

    International Nuclear Information System (INIS)

    Mottana, A.; Cibin, G.; Paris, E.; Giuli, G.; Florence Univ., Florence

    1999-01-01

    X-ray absorption spectra at the Mg and A1 K edges have been recorded on synthetic endmember diopside (Di) and jadeite (Jd) and on a series of natural Fe-poor Ca-Na clinopyroxenes compositionally straddling the Jd-Di join. The spectra of C2/c members of the series (C-omphacites) are different from having P2/n symmetry (P-omphacites). Differences can be explained by theoretical spectra calculated via the multiple-scattering formalism on atomic clusters with at least 89 atoms, extending to a. 0.62 nm away from the Mg viz. A1 absorber: Xanes detects in these systems medium- rather than short-range order-disorder relationships. Near-edge features of C-omphacites reflect the single-type of octahedral arrangement of the back scattering nearest-neighbours (six O atoms) around the absorber (Mg resp. A1) at the centre of the cluster (site M1). Others arise again from medium-range order. P-omphacites show more complicated spectra than C-omphacites. Their additional features reflect the increased local disorder around the probed atom (Mg resp. A1) induced by the two alternative M1, M11 configurations of the six O atoms forming the first co-ordination spheres. Mg and A1 are confirmed to be preferentially partitioned in the M1 resp. M11 site of the P-omphacite crystal structure, however never exclusively, but in a ratio close to 85:15 (plus or minus 10%) that implies a certain degree of local disorder. Changes in the relative heights of some prominent features are more evident in the A1 than in the Mg K-edge spectra. They are diagnostic to qualitatively distinguish C-from P-omphacites

  18. The local structure of Ca-Na pyroxenes. 2-Xanes studies at the Mg and A1 K edges

    Energy Technology Data Exchange (ETDEWEB)

    Mottana, A. [Rome Univ. Roma Tre, Rome (Italy). Dipt. di Scienze Geologiche; Murata, T. [Kyoto University of Education, Kyoto (Japan). Dept. of Physics; Marcelli, A. [Istituto Nazionale di Fisica Nucleare, Frascati, RM (Italy). Laboratori Nazionali di Frascati; Wu, Z.Y. [Istituto Nazionale di Fisica Nucleare, Frascati, RM (Italy). Laboratori Nazionali di Frascati]|[Laboratoire Piere Suee, Gif-sur Yvette Cedex, (France); Cibin, G. [Istituto Nazionale di Fisica Nucleare, Frascati, RM (Italy). Laboratori Nazionali di Frascati; Paris, E. [Camerino Univ., Camerino, MC (Italy). Dipt. di Scienze della Terra; Giuli, G. [Camerino Univ., Camerino, MC (Italy). Dipt. di Scienze della Terra]|[Florence Univ., Florence (Italy). Dipt. di Scienze della Terra

    1999-07-01

    X-ray absorption spectra at the Mg and A1 K edges have been recorded on synthetic end member diopside (Di) and jadeite (Jd) and on a series of natural Fe-poor Ca-Na clinopyroxenes compositionally straddling the Jd-Di join. The spectra of C2/c members of the series (C-omphacites) are different from having P2/n symmetry (P-omphacites). Differences can be explained by theoretical spectra calculated via the multiple-scattering formalism on atomic clusters with at least 89 atoms, extending to a. 0.62 nm away from the Mg viz. A1 absorber: Xanes detects in these systems medium- rather than short-range order-disorder relationships. Near-edge features of C-omphacites reflect the single-type of octahedral arrangement of the back scattering nearest-neighbours (six O atoms) around the absorber (Mg resp. A1) at the centre of the cluster (site M1). Others arise again from medium-range order. P-omphacites show more complicated spectra than C-omphacites. Their additional features reflect the increased local disorder around the probed atom (Mg resp. A1) induced by the two alternative M1, M11 configurations of the six O atoms forming the first co-ordination spheres. Mg and A1 are confirmed to be preferentially partitioned in the M1 resp. M11 site of the P-omphacite crystal structure, however never exclusively, but in a ratio close to 85:15 (plus or minus 10%) that implies a certain degree of local disorder. Changes in the relative heights of some prominent features are more evident in the A1 than in the Mg K-edge spectra. They are diagnostic to qualitatively distinguish C-from P-omphacites.

  19. Structural and thermal investigations of an amorphous GaSe9 alloy using EXAFS, cumulant expansion, and reverse Monte Carlo simulations

    International Nuclear Information System (INIS)

    Siqueira, M. C.; Maia, R. N. A.; Araujo, R. M. T.; Machado, K. D.; Stolf, S. F.

    2015-01-01

    In this article, we investigated structural and thermal properties of an amorphous alloy of the Ga–Se system. The amorphous GaSe 9 alloy was produced by mechanical alloying and it was studied using EXAFS spectroscopy and cumulant expansion method. We also made reverse Monte Carlo simulations using the total structure factor S(K) obtained from x-ray diffraction and the EXAFS χ(k) oscillations on Se and Ga K edges as input data. Several parameters, such as average coordination numbers and interatomic distances, structural and thermal disorders, asymmetry of the partial distribution functions g ij (r), and Einstein and Debye temperatures, were determined. The g ij E (r) functions were reconstructed from the cumulants C 1 , C 2 , and C 3 obtained from the Einstein model, and they were compared to the g ij RMC (r) functions obtained from the simulations. The simulations also furnished the partial bond angle distribution functions Θ ijℓ (cosθ), which describe the angular distribution of bonds between first neighbors, and give information about the kind of structural units present in the alloy

  20. The Difficult Chore of Measuring Coordination by EXAFS

    International Nuclear Information System (INIS)

    Ravel, B.; Kelly, S. D.

    2007-01-01

    Neither the theory nor the interpretation of Extended X-Ray-Absorption Fine-Structure (EXAFS) spectroscopy requires assumptions of crystalline symmetry or periodicity. As a result, EXAFS is a tool applied to a wide range of scientific disciplines and to a wide variety of experimental systems. A simple enumeration of the atoms in the coordination environment of the absorber is often the primary goal of an EXAFS experiment. There are, however, a number of pitfalls in the way of an accurate determination of coordination number (CN). These include statistical limitations of the EXAFS fitting problem, empirical effects due to sample preparation, and the assumptions made about the physical structure surrounding the absorber in the course of data analysis. In this paper we examine several of these pitfalls and their effects upon the determination of CN. Where possible, we offer suggestions for avoiding or mitigating the pitfalls. We hope this paper will help guide the general EXAFS practitioner through the difficult chore of accurately determining CN

  1. Synchrotron-based intra-venous K-edge digital subtraction angiography in a pig model: A feasibility study

    Energy Technology Data Exchange (ETDEWEB)

    Schueltke, Elisabeth [Departments of Surgery, University of Saskatchewan, Saskatoon, SK (Canada); Anatomy and Cell Biology, University of Saskatchewan, Saskatoon, SK (Canada); Department of Neurological Sciences, Walton Medical Centre, University of Liverpool, Liverpool L97 LJ (United Kingdom)], E-mail: e.schultke@usask.ca; Fiedler, Stefan [European Molecular Biology Laboratory (EMBL), Nottkestrasse 85, 22603 Hamburg (Germany); Nemoz, Christian [European Synchrotron Radiation Facility (ESRF), 6 rue Horowitz, 38043 Grenoble (France); Ogieglo, Lissa [Departments of Surgery, University of Saskatchewan, Saskatoon, SK (Canada); Kelly, Michael E. [Departments of Surgery, University of Saskatchewan, Saskatoon, SK (Canada); Department of Neurosurgery, Section of Cerebrovascular and Endovascular Neurosurgery, Cleveland Clinic, 9500 Euclid Avenue, Cleveland, OH (United States); Crawford, Paul [Royal Veterinary College, Hawkshead Lane, North Mymms, Hatfield, Herfordshire AL9 7TA (United Kingdom); Esteve, Francois [INSERM U836-ESRF, 6 rue Horowitz, 38043 Grenoble (France); Brochard, Thierry; Renier, Michel; Requardt, Herwig; Le Duc, Geraldine [European Synchrotron Radiation Facility (ESRF), 6 rue Horowitz, 38043 Grenoble (France); Juurlink, Bernhard [Anatomy and Cell Biology, University of Saskatchewan, Saskatoon, SK (Canada); Meguro, Kotoo [Departments of Surgery, University of Saskatchewan, Saskatoon, SK (Canada)

    2010-03-15

    Background: K-edge digital subtraction angiography (KEDSA) combined with the tunability of synchrotron beam yields an imaging technique that is highly sensitive to low concentrations of contrast agents. Thus, contrast agent can be administered intravenously, obviating the need for insertion of a guided catheter to deliver a bolus of contrast agent close to the target tissue. With the high-resolution detectors used at synchrotron facilities, images can be acquired at high spatial resolution. Thus, the KEDSA appears particularly suited for studies of neurovascular pathology in animal models, where the vascular diameters are significantly smaller than in human patients. Materials and methods: This feasibility study was designed to test the suitability of KEDSA after intravenous injection of iodine-based contrast agent for use in a pig model. Four adult male pigs were used for our experiments. Neurovascular angiographic images were acquired using KEDSA with a solid state Germanium (Ge) detector at the European Synchrotron Radiation Facility (ESRF) in Grenoble, France. Results: After intravenous injection of 0.9 ml/kg iodinated contrast agent (Xenetix), the peak iodine concentrations in the internal carotid and middle cerebral arteries reached 35 mg/ml. KEDSA images in radiography mode allowed the visualization of intracranial arteries of less than 1.5 mm diameter.

  2. Sulfur K-edge absorption spectroscopy on selected biological systems; Schwefel-K-Kanten-Absorptionsspektroskopie an ausgewaehlten biologischen Systemen

    Energy Technology Data Exchange (ETDEWEB)

    Lichtenberg, Henning

    2008-07-15

    Sulfur is an essential element in organisms. In this thesis investigations of sulfur compounds in selected biological systems by XANES (X-ray Absorption Near Edge Structure) spectroscopy are reported. XANES spectroscopy at the sulfur K-edge provides an excellent tool to gain information about the local environments of sulfur atoms in intact biological samples - no extraction processes are required. Spatially resolved measurements using a Kirkpatrick-Baez mirror focusing system were carried out to investigate the infection of wheat leaves by rust fungi. The results give information about changes in the sulfur metabolism of the host induced by the parasite and about the extension of the infection into visibly uninfected plant tissue. Furthermore, XANES spectra of microbial mats from sulfidic caves were measured. These mats are dominated by microbial groups involved in cycling sulfur. Additionally, the influence of sulfate deprivation and H{sub 2}S exposure on sulfur compounds in onion was investigated. To gain an insight into the thermal degradation of organic material the influence of roasting of sulfur compounds in coffee beans was studied. (orig.)

  3. Resonant soft x-ray reflectivity of Me/B4C multilayers near the boron K edge

    Energy Technology Data Exchange (ETDEWEB)

    Ksenzov, Dmitriy; Schlemper, Christoph; Pietsch, Ullrich

    2010-09-01

    Energy dependence of the optical constants of boron carbide in the short period Ru/B4C and Mo/B4C multilayers (MLs) are evaluated from complete reflectivity scans across the boron K edge using the energy-resolved photon-in-photon-out method. Differences between the refractive indices of the B4Cmaterial inside and close to the surface are obtained from the peak profile of the first order ML Bragg peak and the reflection profile near the critical angle of total external reflection close to the surface. Where a Mo/B4C ML with narrow barrier layers appears as a homogeneous ML at all energies, a Ru/B4C ML exhibits another chemical nature of boron at the surface compared to the bulk. From evaluation of the critical angle of total external reflection in the energy range between 184 and 186 eV, we found an enriched concentration of metallic boron inside the Ru-rich layer at the surface, which is not visible in other energy ranges.

  4. Synchrotron-based intra-venous K-edge digital subtraction angiography in a pig model: A feasibility study

    International Nuclear Information System (INIS)

    Schueltke, Elisabeth; Fiedler, Stefan; Nemoz, Christian; Ogieglo, Lissa; Kelly, Michael E.; Crawford, Paul; Esteve, Francois; Brochard, Thierry; Renier, Michel; Requardt, Herwig; Le Duc, Geraldine; Juurlink, Bernhard; Meguro, Kotoo

    2010-01-01

    Background: K-edge digital subtraction angiography (KEDSA) combined with the tunability of synchrotron beam yields an imaging technique that is highly sensitive to low concentrations of contrast agents. Thus, contrast agent can be administered intravenously, obviating the need for insertion of a guided catheter to deliver a bolus of contrast agent close to the target tissue. With the high-resolution detectors used at synchrotron facilities, images can be acquired at high spatial resolution. Thus, the KEDSA appears particularly suited for studies of neurovascular pathology in animal models, where the vascular diameters are significantly smaller than in human patients. Materials and methods: This feasibility study was designed to test the suitability of KEDSA after intravenous injection of iodine-based contrast agent for use in a pig model. Four adult male pigs were used for our experiments. Neurovascular angiographic images were acquired using KEDSA with a solid state Germanium (Ge) detector at the European Synchrotron Radiation Facility (ESRF) in Grenoble, France. Results: After intravenous injection of 0.9 ml/kg iodinated contrast agent (Xenetix), the peak iodine concentrations in the internal carotid and middle cerebral arteries reached 35 mg/ml. KEDSA images in radiography mode allowed the visualization of intracranial arteries of less than 1.5 mm diameter.

  5. Synchrotron-based intra-venous K-edge digital subtraction angiography in a pig model: a feasibility study.

    Science.gov (United States)

    Schültke, Elisabeth; Fiedler, Stefan; Nemoz, Christian; Ogieglo, Lissa; Kelly, Michael E; Crawford, Paul; Esteve, Francois; Brochard, Thierry; Renier, Michel; Requardt, Herwig; Le Duc, Geraldine; Juurlink, Bernhard; Meguro, Kotoo

    2010-03-01

    K-edge digital subtraction angiography (KEDSA) combined with the tunability of synchrotron beam yields an imaging technique that is highly sensitive to low concentrations of contrast agents. Thus, contrast agent can be administered intravenously, obviating the need for insertion of a guided catheter to deliver a bolus of contrast agent close to the target tissue. With the high-resolution detectors used at synchrotron facilities, images can be acquired at high spatial resolution. Thus, the KEDSA appears particularly suited for studies of neurovascular pathology in animal models, where the vascular diameters are significantly smaller than in human patients. This feasibility study was designed to test the suitability of KEDSA after intravenous injection of iodine-based contrast agent for use in a pig model. Four adult male pigs were used for our experiments. Neurovascular angiographic images were acquired using KEDSA with a solid state Germanium (Ge) detector at the European Synchrotron Radiation Facility (ESRF) in Grenoble, France. After intravenous injection of 0.9 ml/kg iodinated contrast agent (Xenetix), the peak iodine concentrations in the internal carotid and middle cerebral arteries reached 35 mg/ml. KEDSA images in radiography mode allowed the visualization of intracranial arteries of less than 1.5mm diameter. Copyright 2009 Elsevier Ireland Ltd. All rights reserved.

  6. High-resolution molybdenum K-edge X-ray absorption spectroscopy analyzed with time-dependent density functional theory.

    Science.gov (United States)

    Lima, Frederico A; Bjornsson, Ragnar; Weyhermüller, Thomas; Chandrasekaran, Perumalreddy; Glatzel, Pieter; Neese, Frank; DeBeer, Serena

    2013-12-28

    X-ray absorption spectroscopy (XAS) is a widely used experimental technique capable of selectively probing the local structure around an absorbing atomic species in molecules and materials. When applied to heavy elements, however, the quantitative interpretation can be challenging due to the intrinsic spectral broadening arising from the decrease in the core-hole lifetime. In this work we have used high-energy resolution fluorescence detected XAS (HERFD-XAS) to investigate a series of molybdenum complexes. The sharper spectral features obtained by HERFD-XAS measurements enable a clear assignment of the features present in the pre-edge region. Time-dependent density functional theory (TDDFT) has been previously shown to predict K-pre-edge XAS spectra of first row transition metal compounds with a reasonable degree of accuracy. Here we extend this approach to molybdenum K-edge HERFD-XAS and present the necessary calibration. Modern pure and hybrid functionals are utilized and relativistic effects are accounted for using either the Zeroth Order Regular Approximation (ZORA) or the second order Douglas-Kroll-Hess (DKH2) scalar relativistic approximations. We have found that both the predicted energies and intensities are in excellent agreement with experiment, independent of the functional used. The model chosen to account for relativistic effects also has little impact on the calculated spectra. This study provides an important calibration set for future applications of molybdenum HERFD-XAS to complex catalytic systems.

  7. Composing complex EXAFS problems with severe information constraints

    International Nuclear Information System (INIS)

    Ravel, B

    2009-01-01

    In recent work, a model for the structural environment of Hg bound to a catalytic DNA sensor was proposed on the basis of EXAFS data analysis. Although severely constrained by limited data quality and scant supporting structural data, a compelling structural model was found which agreed with a similar but less detailed model proposed on the basis on NMR data. I discuss in detail the successes and limitations of the analytical strategy that were implemented in the earlier work. I then speculate on future software requirements needed to make this and similarly complex analytical strategies more available to the wider audience of EXAFS practitioners.

  8. Automating an EXAFS facility: hardware and software considerations

    International Nuclear Information System (INIS)

    Georgopoulos, P.; Sayers, D.E.; Bunker, B.; Elam, T.; Grote, W.A.

    1981-01-01

    The basic design considerations for computer hardware and software, applicable not only to laboratory EXAFS facilities, but also to synchrotron installations, are reviewed. Uniformity and standardization of both hardware configurations and program packages for data collection and analysis are heavily emphasized. Specific recommendations are made with respect to choice of computers, peripherals, and interfaces, and guidelines for the development of software packages are set forth. A description of two working computer-interfaced EXAFS facilities is presented which can serve as prototypes for future developments. 3 figures

  9. EXAFS determination of cation local order in layered perovskites

    Energy Technology Data Exchange (ETDEWEB)

    Montero C, M. E.; Fuentes M, L.; Duarte M, J. A.; Fuentes C, L. [Centro de Investigacion en Materiales Avanzados S. C., Miguel de Cervantes Saavedra 120, Complejo Industrial Chihuahua, 31109 Chihuahua (Mexico); Garcia G, M. [Instituto de Fisica, UNAM, Ciudad Universitaria, 04510 Mexico D. F. (Mexico); Mehta, A.; Webb, S. [Stanford Synchrotron Radiation Laboratory, CA (United States)

    2008-02-15

    EXAFS analysis of Bi{sub 6}Ti{sub 3}Fe{sub 2}O{sub 18} Aurivillius ceramic was performed to elucidate the local environment of Fe cations. Experiments were performed at Stanford Synchrotron Radiation Laboratory, at T = 10, 30, 50, 75, 100 and 298 K, in fluorescence regime. EXAFS spectra were processed using the ab initio multiple scattering program FEFF6. Distances among representative atomic pairs were refined. As a basic result, the previous hypothesis suggested by X-ray diffraction experiments, regarding a preference of iron atoms for the centered perovskite layer of the unit cell, was confirmed. (Author)

  10. EXAFS as a tool for catalyst characterization: a review of the data analysis methods

    Directory of Open Access Journals (Sweden)

    NORONHA F. B.

    1999-01-01

    Full Text Available A review of the EXAFS data analysis methods is presented. A detailed description of the EXAFS signal extraction and the Fourier transform of the data are discussed. The procedure for determining interatomic distances, coordination numbers and disorder effects from EXAFS data is described. This paper also discusses the data analysis statistics. Finally, one example of catalyst characterization by the EXAFS technique is reported.

  11. Measurement of X-ray mass attenuation coefficient of nickel around the K-edge using synchrotron radiation based X-ray absorption study

    International Nuclear Information System (INIS)

    Roy, Bunty Rani; Rajput, Parasmani; Jha, S.N.; Nageswara Rao, A.S.

    2015-01-01

    The work presents the X-ray absorption fine structure (XAFS) technique for measuring the X-ray mass attenuation coefficient of nickel metal foil in the X-ray energy range of 8271.2–8849.4 eV using scanning XAFS beam line (BL-09) at Indus-2 synchrotron radiation source facility, Raja Ramanna Centre for Advanced Technology (RRCAT) at Indore, India. The result represents the X-ray mass attenuation coefficient data for 0.02 mm thick Ni metal foil in the XAFS region of Ni K-edge. However, the results are compared to theoretical values using X-COM. There is a maximum deviation which is found exactly near the K-edge jump and decreases as we move away from the absorption edge. Oscillatory structure appears just above the observed absorption edge i.e., 8348.7 eV and is confined to around 250 eV above the edge. - Highlights: • Mass attenuation coefficient measurements of nickel using synchrotron radiation. • The measurements were taken exactly near the Ni K-edge at an energy step of 1 eV. • A maximum deviation is found near the K-edge

  12. Unexpected covalency from actinide 5f orbital interactions (An = Th, U, Np, Pu) determined from chlorine K-edge X-ray absorption spectroscopy and electronic structure theory

    International Nuclear Information System (INIS)

    Clark, D.L.; Batista, E.R.; Boland, K.S.

    2010-01-01

    We have employed Cl K-edge XAS and multiple levels of sophisticated electronic structure calculations on a series of simple octahedral light actinide (Th, U, Np, Pu) chloride salts, AnCl 6 n- in order to assess the relative roles of the valence 5f and 6d orbitals in chemical bonding. Chlorine K-edge X-ray absorption spectroscopy on AnCl 6 n- (An = Th, U, Np, Pu) systems indicates the presence of covalent interactions between both Cl 3p and An 5f and 6d orbitals, with the relative contributions changing across the series. Electronic structure calculations indicate the predominant covalent interactions are expected to occur through An-Cl bonding via t 1u and t 2u interactions with the An 5f orbitals, and through t 2g and e g interactions with An 6d orbitals. For the Cl K-edge data therefore, we expect bound state transitions from Cl 1s → e g (σ), t 2g (π), and t 1u (σ + π) orbitals. Qualitatively, the Cl K-edge data fulfills these expectations

  13. Origin of the chemical shift in X-ray absorption near-edge spectroscopy at the Mn K-Edge in manganese oxide compounds

    NARCIS (Netherlands)

    de Vries, AH; Hozoi, L.; Broer, R.

    2003-01-01

    The absorption edge in Mn K-edge X-ray absorption spectra of manganese oxide compounds shows a shift of several electronvolts in going from MnO through LaMnO3 to CaMnO3. On the other hand, in X-ray photoelectron spectra much smaller shifts are observed. To identify the mechanisms that cause the

  14. Multifunctional synchrotron spectrometer of NRC Kurchatov Institute. Part 1. EXAFS in dispersive mode

    International Nuclear Information System (INIS)

    Aksenov, V.L.; Tyutyunnikov, S.I.; Shalyapin, V.N.; Belyaev, A.D.; Artem'ev, A.N.; Kirillov, B.F.; Demkiv, A.A.; Knyazev, G.A.; Koval'chuk, M.V.; Artem'ev, N.A.

    2017-01-01

    The improved X-ray optical scheme, the system of registration and measurement procedure of multifunctional synchrotron radiation spectrometer in dispersive EXAFS mode are described. The results of the energy permission measurements of spectrometer are given. The advantages and disadvantages in the traditional and dispersion schematics of spectrometers EXAFS are analyzed. Examples of the EXAFS spectra measured in the dispersion mode are given.

  15. Investigation of radiation defects in solids using the EXAFS method

    International Nuclear Information System (INIS)

    Eritsyan, G.N.

    1983-01-01

    The exafs method is proposed as a more informative, universal one to investigate the radiation defects in solids. The successful results as obtained by the author using the synchrotron radiation source are reported for the first time. The measurements were carried out in GaAsP crystals irradiated with 50 MeV electrons

  16. The influence of coordination geometry and valency on the K-edge absorption near edge spectra of selected chromium compounds

    International Nuclear Information System (INIS)

    Pantelouris, A.; Modrow, H.; Pantelouris, M.; Hormes, J.; Reinen, D.

    2004-01-01

    X-ray absorption spectra at the chromium K-edge are reported for a number of selected chromium compounds of known chemical structure. The spectra were obtained with use of synchrotron radiation available at the ELectron Stretcher Accelerator ELSA in Bonn. The compounds studied include the tetrahedrally coordinated compounds Ca 2 Ge 0.8 Cr 0.2 O 4 , Ba 2 Ge 0.1 Cr 0.9 O 4 , Sr 2 CrO 4 , Ca 2 (PO 4 ) x (CrO 4 ) 1-x Cl (x=0.25,0.5), Ca 5 (CrO 4 ) 3 Cl, CrO 3 , the octahedrally coordinated compounds Cr(II)-acetate, CrCl 3 , CrF 3 , Cr 2 O 3 , KCr(SO 4 ) 2 · 12H 2 O, CrO 2 and cubic coordinated metallic chromium. In these compounds chromium exhibits a wide range of formal oxidation states (0 to VI). The absorption features in the near edge region are shown to be characteristic of the spatial environment of the absorbing atom. The occurrence of a single pre-edge line easily allows one to distinguish between tetrahedral and octahedral coordination geometry, whereas the energy position of the absorption edge is found to be very sensitive to the valency of the excited chromium atom. Calculations of the ionisation potential of Cr in different oxidation states using the non-relativistic Hartree-Fock method (Froese-Fischer) confirm that the ionisation limit shifts to higher energy with increasing Cr valency. More detailed information on the electronic structure of the different compounds is gained by real-space full multiple scattering calculations using the FEFF8 code

  17. The local structure of CaNa pyroxenes. I. XANES study at the Na K-edge

    International Nuclear Information System (INIS)

    Mottana, Annibale; Murata, T.; Wu, Ziyu; Marcelli, Augusto; Paris, E.

    1996-07-01

    X-ray absorption Na K-edge spectra have been recorded on synthetic end member jadeite and on a series of natural Ca-Na pyroxenes compositionally straddling the Jd-Di. The disordered C2/c members of the series are systematically different from the ordered P2/n members. These differences can be interpreted and explained by comparing the experimental spectra with theoretical spectra. These have been calculated by the multiple-scattering formalism from the atomic positional parameters determined by single-crystal X-ray diffraction structure refinement on the same samples. In the full multiple scattering region of the spectrum (1075 to 1095 eV) C-pyroxenes exhibit three features which reflect the 6-2 configuration of the O back-scattering atoms around the Na absorber located at the center of the cluster (site M2 of the jadeite structure). P-pyroxenes show more complicated spectra in which at least four features can be recognized; they reflect the two types of the configuration (6-2 and 4-2-2) of the oxygens around Na in the two independent M2 and M21 eight-fold coordinated sites of the omphacite structure. A weak, sometimes poorly resolved peak at 1079 eV diagnostic and discriminates C- from P-pyroxenes. The Garnet Ridge C2/c impure jadeite exhibits a spectrum which is intermediate between those of jadeite and omphacite. The Hedin-Lundqist potential proves best for these insulating materials and allows multiple-scattering calculations agreeing well with experiments. The assessment of the local electronic properties of compositionally and structurally complex minerals such as clinopyroxenes is thus enhanced

  18. The local structure of Ca{sub N}a pyroxenes. I. XANES study at the Na K-edge

    Energy Technology Data Exchange (ETDEWEB)

    Mottana, Annibale [Rome, Univ. III (Italy). Dipt. di Scienze Geologiche; Murata, T. [Kyoto, Univ. of Education (Japan). Dept. of Physics; Wu, Ziyu; Marcelli, Augusto [INFN, Frascati (Italy). Laboratori Nazionali di Frascati; Paris, E. [Camerino, Univ. (Italy). Dipt. di Scienze della Terra

    1996-07-01

    X-ray absorption Na K-edge spectra have been recorded on synthetic end member jadeite and on a series of natural Ca-Na pyroxenes compositionally straddling the Jd-Di. The disordered C2/c members of the series are systematically different from the ordered P2/n members. These differences can be interpreted and explained by comparing the experimental spectra with theoretical spectra. These have been calculated by the multiple-scattering formalism from the atomic positional parameters determined by single-crystal X-ray diffraction structure refinement on the same samples. In the full multiple scattering region of the spectrum (1075 to 1095 eV) C-pyroxenes exhibit three features which reflect the 6-2 configuration of the O back-scattering atoms around the Na absorber located at the center of the cluster (site M2 of the jadeite structure). P-pyroxenes show more complicated spectra in which at least four features can be recognized; they reflect the two types of the configuration (6-2 and 4-2-2) of the oxygens around Na in the two independent M2 and M21 eight-fold coordinated sites of the omphacite structure. A weak, sometimes poorly resolved peak at 1079 eV diagnostic and discriminates C- from P-pyroxenes. The Garnet Ridge C2/c impure jadeite exhibits a spectrum which is intermediate between those of jadeite and omphacite. The Hedin-Lundqist potential proves best for these insulating materials and allows multiple-scattering calculations agreeing well with experiments. The assessment of the local electronic properties of compositionally and structurally complex minerals such as clinopyroxenes is thus enhanced.

  19. The influence of coordination geometry and valency on the K-edge absorption near edge spectra of selected chromium compounds

    Energy Technology Data Exchange (ETDEWEB)

    Pantelouris, A.; Modrow, H.; Pantelouris, M.; Hormes, J.; Reinen, D

    2004-05-10

    X-ray absorption spectra at the chromium K-edge are reported for a number of selected chromium compounds of known chemical structure. The spectra were obtained with use of synchrotron radiation available at the ELectron Stretcher Accelerator ELSA in Bonn. The compounds studied include the tetrahedrally coordinated compounds Ca{sub 2}Ge{sub 0.8}Cr{sub 0.2}O{sub 4}, Ba{sub 2}Ge{sub 0.1}Cr{sub 0.9}O{sub 4}, Sr{sub 2}CrO{sub 4}, Ca{sub 2}(PO{sub 4}){sub x}(CrO{sub 4}){sub 1-x}Cl (x=0.25,0.5), Ca{sub 5}(CrO{sub 4}){sub 3}Cl, CrO{sub 3}, the octahedrally coordinated compounds Cr(II)-acetate, CrCl{sub 3}, CrF{sub 3}, Cr{sub 2}O{sub 3}, KCr(SO{sub 4}){sub 2} {center_dot} 12H{sub 2}O, CrO{sub 2} and cubic coordinated metallic chromium. In these compounds chromium exhibits a wide range of formal oxidation states (0 to VI). The absorption features in the near edge region are shown to be characteristic of the spatial environment of the absorbing atom. The occurrence of a single pre-edge line easily allows one to distinguish between tetrahedral and octahedral coordination geometry, whereas the energy position of the absorption edge is found to be very sensitive to the valency of the excited chromium atom. Calculations of the ionisation potential of Cr in different oxidation states using the non-relativistic Hartree-Fock method (Froese-Fischer) confirm that the ionisation limit shifts to higher energy with increasing Cr valency. More detailed information on the electronic structure of the different compounds is gained by real-space full multiple scattering calculations using the FEFF8 code.

  20. The influence of coordination geometry and valency on the K-edge absorption near edge spectra of selected chromium compounds

    Science.gov (United States)

    Pantelouris, A.; Modrow, H.; Pantelouris, M.; Hormes, J.; Reinen, D.

    2004-05-01

    X-ray absorption spectra at the chromium K-edge are reported for a number of selected chromium compounds of known chemical structure. The spectra were obtained with use of synchrotron radiation available at the ELectron Stretcher Accelerator ELSA in Bonn. The compounds studied include the tetrahedrally coordinated compounds Ca 2Ge 0.8Cr 0.2O 4, Ba 2Ge 0.1Cr 0.9O 4, Sr 2CrO 4, Ca 2(PO 4) x(CrO 4) 1- xCl ( x=0.25,0.5), Ca 5(CrO 4) 3Cl, CrO 3, the octahedrally coordinated compounds Cr(II)-acetate, CrCl 3, CrF 3, Cr 2O 3, KCr(SO 4) 2 · 12H 2O, CrO 2 and cubic coordinated metallic chromium. In these compounds chromium exhibits a wide range of formal oxidation states (0 to VI). The absorption features in the near edge region are shown to be characteristic of the spatial environment of the absorbing atom. The occurrence of a single pre-edge line easily allows one to distinguish between tetrahedral and octahedral coordination geometry, whereas the energy position of the absorption edge is found to be very sensitive to the valency of the excited chromium atom. Calculations of the ionisation potential of Cr in different oxidation states using the non-relativistic Hartree-Fock method (Froese-Fischer) confirm that the ionisation limit shifts to higher energy with increasing Cr valency. More detailed information on the electronic structure of the different compounds is gained by real-space full multiple scattering calculations using the FEFF8 code.

  1. Covellite CuS as a matrix for "invisible" gold: X-ray spectroscopic study of the chemical state of Cu and Au in synthetic minerals

    Science.gov (United States)

    Tagirov, Boris R.; Trigub, Alexander L.; Kvashnina, Kristina O.; Shiryaev, Andrey A.; Chareev, Dmitriy A.; Nickolsky, Maximilian S.; Abramova, Vera D.; Kovalchuk, Elena V.

    2016-10-01

    Geological processes leading to formation of sulfide ores often result in precipitation of gold-bearing sulfides which can contain high concentrations of this metal in ;invisible; (or ;refractory;) state. Covellite (CuS) is ubiquitous mineral in many types of the ore deposits, and numerous studies of the natural ores show that covellite can contain high concentrations of Au. At the same time, Au-bearing covellite withstands cooling in contrast to other minerals of the Cu-Fe-S system (chalcocite, bornite, chalcopyrite), where Au exsolves at low temperatures. This makes covellite a convenient model system for investigation of the chemical state (local environment and valence) of the ;invisible; Au in copper-sulfide ores (copper-porphyry, epithermal, volcanogenic massive sulfide, SEDEX deposits). Therefore, it is necessary to determine the location of Au in the covellite matrix as it will have important implications for the methods employed by mineral processing industry to extract Au from sulfide ores. Here we investigate the chemical state of Cu and Au in synthetic covellite containing up to 0.3 wt.% of Au in the ;invisible; state. The covellite crystals were synthesized by hydrothermal and salt flux methods. Formation of the chemically bound Au is indicated by strong dependence of the concentration of Au in covellite on the sulfur fugacity in the experimental system (d(log C(Au))/d(log f(S2)) ∼ 0.65). The Au concentration of covellite grows with increasing temperature from 400 to 450 °C, whereas further temperature increase to 500 °C has only minor effect. The synthesized minerals were studied using X-ray absorption fine structure spectroscopy (XAFS) in high energy resolution fluorescence detection (HERFD) mode. Ab initio simulations of Cu K edge XANES spectra show that the Cu oxidation state in two structural positions in covellite (tetrahedral and triangular coordination with S atoms) is identical: the total loss of electronic charge for the 3d shell is ∼0

  2. Probing single magnon excitations in Sr2IrO4 using O K-edge resonant inelastic x-ray scattering

    International Nuclear Information System (INIS)

    Liu, X; Ding, H; Dean, M P M; Yin, W G; Hill, J P; Liu, J; Ramesh, R; Chiuzbăian, S G; Jaouen, N; Nicolaou, A; Serrao, C Rayan

    2015-01-01

    Resonant inelastic x-ray scattering (RIXS) at the L-edge of transition metal elements is now commonly used to probe single magnon excitations. Here we show that single magnon excitations can also be measured with RIXS at the K-edge of the surrounding ligand atoms when the center heavy metal elements have strong spin–orbit coupling. This is demonstrated with oxygen K-edge RIXS experiments on the perovskite Sr 2 IrO 4 , where low energy peaks from single magnon excitations were observed. This new application of RIXS has excellent potential to be applied to a wide range of magnetic systems based on heavy elements, for which the L-edge RIXS energy resolution in the hard x-ray region is usually poor. (fast track communication)

  3. Optical properties of boron carbide near the boron K edge evaluated by soft-x-ray reflectometry from a Ru/B4C multilayer

    Energy Technology Data Exchange (ETDEWEB)

    Ksenzov, Dmitriy; Panzner, Tobias; Schlemper, Christoph; Morawe, Christian; Pietsch, Ullrich

    2009-12-10

    Soft-x-ray Bragg reflection from two Ru/B4C multilayers with 10 and 63 periods was used for independent determination of both real and imaginary parts of the refractive index n = 1 -{delta} + i{beta} close to the boron K edge ({approx}188 eV). Prior to soft x-ray measurements, the structural parameters of the multilayers were determined by x-ray reflectometry using hard x rays. For the 63-period sample, the optical properties based on the predictions made for elemental boron major deviations were found close to the K edge of boron for the 10-period sample explained by chemical bonding of boron to B4C and various boron oxides.

  4. User's guide for the portable microprocessor equipment: 'KfK K-edge densitometer' for quantitative determination of Th, U, Np, Pu, Am in solutions

    International Nuclear Information System (INIS)

    Michel-Piper, I.; Matussek, P.

    1985-06-01

    This report describes the hardware and software features, and the use of the microprocessor-controlled multichannel analyzer system SILENA + IRIS. The self-contained portable system, which permits independent accumulation and evaluation of spectral data from the KfK K-edge densitometer, provides one of the possible means for the authentication of resident instruments by safeguards inspectors. The 'K-Edge' program, written in PL/M language for compatibility with the system's firmware, allows fully automated assays of heavy element concentrations in solutions by means of X-ray absorption edge spectrometry. It is primarily intended for highly accurate determinations of the U and Pu content in process- and product solutions of a reprocessing plant. (orig.)

  5. Sn-L3 EDGE and Fe K edge XANES spectra of the surface layer of ancient Chinese black mirror Heiqigu

    International Nuclear Information System (INIS)

    Gaowei Mengjia; Liu Yuzhen; Chu Wangsheng; Wu Ziyu; Wang Changsui

    2009-01-01

    The Chinese ancient black mirror known as Heiqigu was studied by x-ray-absorption near-edge structure spectroscopy and results were reported. The Sn-L 3 edge and Fe K edge spectra further confirmed the Schottky-type defect model in the Heiqigu surface system. And it was suggested that the surface layer of the mirror was a combined structure of oxidation of Sn(IV) and Sn(II). (authors)

  6. Mn K-edge XANES spectroscopy of photosynthetic water oxidation enzyme in the S0-, S1-, S2- and S3-states induced by flash excitation

    International Nuclear Information System (INIS)

    Ono, Taka-aki; Noguchi, Takumi; Inoue, Yorinao; Kusunoki, Masami; Matsushita, Tadashi; Oyanagi, Hiroyuki.

    1993-01-01

    Electronic and structural rearrangement of the Mn-cluster during the four step oxidation of water in photosynthetic oxygen evolution was studied by XANES spectroscopy. The Mn K-edge energy of the spectrum was changed with flash number to show a clear quadruple oscillation, indicating a periodic change in oxidation and electronic state of the Mn-cluster depending on Joliot and Kok's oxygen clock. (author)

  7. Intermediate phases in the formation of the Cu-Ba-Y high-Tc superconductor from xerogel

    International Nuclear Information System (INIS)

    Arcon, I.; Bele, M.; Hribar, M.; Kodre, A.; Stuhec, M.; Pejovnik, S.; Frahm, R.

    1995-01-01

    In the synthesis of YBa 2 Cu 3 O 7-x superconductor ceramics by the sol-gel method, yttrium K EXAFS spectra of the intermediate products give evidence of the dynamics of the Y ion in the reaction. Together with previous data on Cu K and Ba L 3 EXAFS, the results give information on the processes in the amorphous phase, complementing the diffraction data on crystallite growth. ((orig.))

  8. Determining metal ion distributions using resonant scattering at very high-energy K-edges: Bi/Pb in Pb5Bi6Se14

    International Nuclear Information System (INIS)

    Zhang Yuegang; Lee, P.L.; Shastri, S.D.; Shu Deming; Wilkinson, A.P.; Chung Duck-Young; Kanatzidis, M.G.

    2005-01-01

    Powder diffraction data collected at ∝ 86 keV, and just below both the Pb and the Bi K-edges, on an imaging plate detector using synchrotron radiation from the Advanced Photon Source have been used to examine the Pb/Bi distribution over the 11 crystallographically distinct sites in Pb 5 Bi 6 Se 14 [space group P2 1 /m, a=16.0096(2) Aa, b=4.20148(4) Aa, c=21.5689(3) Aa and β=97.537(1) 0 ]. The scattering factors needed for the analyses were determined both by Kramers- Kronig transformation of absorption spectra and by analyses of diffraction patterns from reference compounds. Even with the relatively low scattering contrast that is available at the K-edges, it was possible to determine the Pb/Bi distribution and probe the presence of cation site vacancies in the material. The current results indicate that resonant scattering measurements at high-energy K-edges are a viable, and perhaps preferable, route to site occupancies when absorption from the sample or sample environment/container is a major barrier to the acquisition of high-quality resonant scattering data at lower-energy edges

  9. Performance of computed tomography for contrast agent concentration measurements with monochromatic x-ray beams: comparison of K-edge versus temporal subtraction

    International Nuclear Information System (INIS)

    Elleaume, H.; Charvet, A.M.; Corde, S.; Esteve, F.; Le Bas, J.F.

    2002-01-01

    We investigated the performance of monochromatic computed tomography for the quantification of contrast agent concentrations. Two subtraction methods (K-edge subtraction and temporal subtraction) were evaluated and compared theoretically and experimentally in terms of detection limit, precision and accuracy. Measurements were performed using synchrotron x-rays with Lucite phantoms (10 cm and 17.5 cm in diameter) containing iodine or gadolinium solutions ranging from 50 μg ml -1 to 5 mg ml -1 . The experiments were carried out using monochromators developed at the European Synchrotron Radiation Facility (ESRF) medical beamline. The phantoms were imaged either above and below the contrast agent K-edge, or before and after the addition of the contrast agent. Both methods gave comparable performance for phantoms less than 10 cm in diameter. For large phantoms, equivalent to a human head, the temporal subtraction is more suitable for detecting elements such as iodine, keeping a reasonable x-ray dose delivered to the phantom. A good agreement was obtained between analytical calculations, simulations and measurements. The beam harmonic content was taken into account in the simulations. It explains the performance degradation with high contrast agent concentrations. The temporal subtraction technique has the advantage of energy tunability and is well suited for imaging elements, such as iodine or gadolinium, in highly absorbing samples. For technical reasons, the K-edge method is preferable when the imaged organ is moving since the two measurements can be performed simultaneously, which is mandatory for obtaining a good subtraction. (author)

  10. Vibrationally resolved NEXAFS at C and N K-edges of pyridine, 2-fluoropyridine and 2,6-difluoropyridine: A combined experimental and theoretical assessment

    Energy Technology Data Exchange (ETDEWEB)

    Baiardi, Alberto; Mendolicchio, Marco; Barone, Vincenzo, E-mail: vincenzo.barone@sns.it [Scuola Normale Superiore, Piazza dei Cavalieri 7, 56125 Pisa (Italy); Fronzoni, Giovanna; Cardenas Jimenez, Gustavo Adolfo; Stener, Mauro; Grazioli, Cesare [Dipartimento di Scienze Chimiche e Farmaceutiche, Universita’ di Trieste, Via Giorgieri 1, 34127 Trieste (Italy); Simone, Monica de [CNR-IOM, Laboratorio TASC, Area Science Park Basovizza, 34149 Trieste (Italy); Coreno, Marcello [CNR-ISM, UOS Trieste, Area Science Park Basovizza, 34149 Trieste (Italy)

    2015-11-28

    In the present work, the near edge X-ray absorption spectroscopy (NEXAFS) spectra at both C and N K-edges of pyridine, 2-fluoropyridine, and 2,6-difluoropyridine have been studied both experimentally and theoretically. From an electronic point of view, both transition potential density functional theory and time-dependent density functional theory approaches lead to reliable results provided that suitable basis sets and density functionals are employed. In this connection, the global hybrid B3LYP functional in conjunction with the EPR-III basis set appears particularly suitable after constant scaling of the band positions. For the N K-edge, vertical energies obtained at these levels and broadened by symmetric Gaussian distributions provide spectra in reasonable agreement with the experiment. Vibronic contributions further modulate the band-shapes leading to a better agreement with the experimental results, but are not strictly necessary for semi-quantitative investigations. On the other hand, vibronic contributions are responsible for strong intensity redistribution in the NEXAFS C K-edge spectra, and their inclusion is thus mandatory for a proper description of experiments. In this connection, the simple vertical gradient model is particularly appealing in view of its sufficient reliability and low computational cost. For more quantitative results, the more refined vertical Hessian approach can be employed, and its effectiveness has been improved thanks to a new least-squares fitting approach.

  11. Metal and ligand K-edge XAS of organotitanium complexes: metal 4p and 3d contributions to pre-edge intensity and their contributions to bonding.

    Science.gov (United States)

    George, Serena DeBeer; Brant, Patrick; Solomon, Edward I

    2005-01-19

    Titanium cyclopentadienyl (Cp) complexes play important roles as homogeneous polymerization catalysts and have recently received attention as potential anticancer agents. To systematically probe the contribution of the Cp to bonding in organotitanium complexes, Ti K-edge XAS has been applied to TiCl(4) and then to the mono- and bis-Cp complexes, TiCpCl(3) and TiCp(2)Cl(2). Ti K-edge XAS is used as a direct probe of metal 3d-4p mixing and provides insight into the contribution of the Cp to bonding. These data are complimented by Cl K-edge XAS data, which provide a direct probe of the effect of the Cp on the bonding to the spectator chloride ligand. The experimental results are correlated to DFT calculations. A model for metal 3d-4p mixing is proposed, which is based on covalent interactions with the ligands and demonstrates that metal K-pre-edge intensities may be used as a measure of ligand-metal covalency in molecular Ti(IV) systems in noncentrosymmetric environments.

  12. In situ removal of carbon contamination from a chromium-coated mirror: ideal optics to suppress higher-order harmonics in the carbon K-edge region.

    Science.gov (United States)

    Toyoshima, Akio; Kikuchi, Takashi; Tanaka, Hirokazu; Mase, Kazuhiko; Amemiya, Kenta

    2015-11-01

    Carbon-free chromium-coated optics are ideal in the carbon K-edge region (280-330 eV) because the reflectivity of first-order light is larger than that of gold-coated optics while the second-order harmonics (560-660 eV) are significantly suppressed by chromium L-edge and oxygen K-edge absorption. Here, chromium-, gold- and nickel-coated mirrors have been adopted in the vacuum ultraviolet and soft X-ray branch beamline BL-13B at the Photon Factory in Tsukuba, Japan. Carbon contamination on the chromium-coated mirror was almost completely removed by exposure to oxygen at a pressure of 8 × 10(-2) Pa for 1 h under irradiation of non-monochromated synchrotron radiation. The pressure in the chamber recovered to the order of 10(-7) Pa within a few hours. The reflectivity of the chromium-coated mirror of the second-order harmonics in the carbon K-edge region (560-660 eV) was found to be a factor of 0.1-0.48 smaller than that of the gold-coated mirror.

  13. Silicon Detector System for High Rate EXAFS Applications.

    Science.gov (United States)

    Pullia, A; Kraner, H W; Siddons, D P; Furenlid, L R; Bertuccio, G

    1995-08-01

    A multichannel silicon pad detector for EXAFS (Extended X-ray Absorption Fine Structure) applications has been designed and built. The X-ray spectroscopic measurements demonstrate that an adequate energy resolution of 230 eV FWHM (corresponding to 27 rms electrons in silicon) can be achieved reliably at -35 °C. A resolution of 190 eV FWHM (corresponding to 22 rms electrons) has been obtained from individual pads at -35 °C. At room temperature (25 °C) an average energy resolution of 380 eV FWHM is achieved and a resolution of 350 eV FWHM (41 rms electrons) is the best performance. A simple cooling system constituted of Peltier cells is sufficient to reduce the reverse currents of the pads and their related shot noise contribution, in order to achieve resolutions better than 300 eV FWHM which is adequate for the EXAFS applications.

  14. EXAFS investigation on microstructure of La-based alloy deuteride

    CERN Document Server

    Chen Bo Fei; Xie Chao Mei; Chen Xi Ping; Liu Li Juan; Xie Ya Ning; Hu Tian Dou; Zhang Jing

    2002-01-01

    Extended X-ray absorption fine structure (EXAFS) spectra were measured to investigate the microstructure of La-based alloy deuteride. The radial structural functions of LaNi sub 4 sub . sub 2 sub 5 Al sub 0 sub . sub 7 sub 5 D sub x samples were obtained and the comparisons among different samples were performed. The results show that removal of deuterium is fast in La-Ni-Al hydrogen storage alloys under non-airtight condition

  15. Temperature-dependent magnetic EXAFS investigation of Gd

    CERN Document Server

    Wende, H; Poulopoulos, P N; Rogalev, A; Goulon, J; Schlagel, D L; Lograsso, T A; Baberschke, K

    2001-01-01

    Magnetic EXAFS (MEXAFS) is the helicity-dependent counterpart of the well-established EXAFS technique. By means of MEXAFS it is possible not only to analyze the local magnetic structure but also to learn about magnetic fluctuations. Here we present the MEXAFS of a Gd single crystal at the L sub 3 sub , sub 2 -edges in the temperature range of 10-250 K. For the first time MEXAFS was probed over a large range in reduced temperature of 0.04<=T/T sub C<=0.85 with T sub C =293 K. We show that the vibrational damping described by means of a Debye temperature of theta sub D =160 K must be taken into account for the spin-dependent MEXAFS before analyzing magnetic fluctuations. For a detailed analysis of the MEXAFS and the EXAFS, the experimental data are compared to ab initio calculations. This enables us to separate the individual single- from the multiple-scattering contributions. The MEXAFS data have been recorded at the ID 12A beamline of the European Synchrotron Radiation Facility (ESRF). To ensure that th...

  16. Zinc adsorption on clays inferred from atomistic simulations and EXAFS spectroscopy

    International Nuclear Information System (INIS)

    Churakov, S.V.; Daehn, R.

    2012-01-01

    Document available in extended abstract form only. Clay minerals such as illite and montmorillonite are ubiquitous in the environment. Because of their large specific area and high structural charge, they control the migration of heavy metals in the geosphere via different uptake mechanisms. The main processes for the sequestration of trace concentrations of heavy metals are sorption to clay edge sites and incorporation into clay structures. Whereas, sorption is a fast process occurring nearly instantaneously, the incorporation of metal ions into clay minerals occurs over geological time scales. Zn is a divalent transition metal, which shows similar chemical behavior to Ni and Co and can thus also be considered as a natural analogue for radioactive Ni and Co arising from nuclear fuel and radioactive waste from the decommissioning of nuclear power plants. The release of radionuclides from a repository can be considerably retarded due to interactions with clay minerals. For example, bentonite containing >70 wt% di-octahedral alumino-silicate clays is foreseen as a backfill material in the Swiss concept for a high level radioactive waste repository (NAGRA, 2002). Knowing the uptake mechanism of these elements on clays can help to protect the natural environment. In this study ab initio molecular dynamics (MD) calculations were applied to simulate the molecular mechanism of Zn uptake on the edge surfaces of montmorillonite, a di-octahedral clay, and to explain the measured K-edge extended X-ray absorption fine structure (EXAFS) spectra of Zn adsorbed on montmorillonite at different loadings. Two different montmorillonites were chosen for the experimental part of this study: Milos (Island of Milos, Greece) and STx-1 (Gonzales County, Texas, USA) (VANTELON et al., 2003). As a reference for Zn substituted for Al in the clay octahedral sheet a MILOS sample was prepared without adding any Zn. Milos was chosen because it contains 1.8 [mmol/kg] Zn incorporated into the

  17. Local structural changes in paramagnetic and charge-ordered phases of Sm0.2Pr0.3Sr0.5MnO3: an EXAFS study

    International Nuclear Information System (INIS)

    Priolkar, K R; Kulkarni, Vishwajeet; Sarode, P R; Emura, S

    2008-01-01

    Sm 0.5-x Pr x Sr 0.5 MnO 3 exhibits a variety of ground states as x is varied from 0 to 0.5. At an intermediate doping of x = 0.3 a charge-ordered CE-type antiferromagnetic insulating (AFI) ground state is seen. The transition to this ground state is from a paramagnetic-insulating (PMI) phase through a ferromagnetic-metallic phase (FMM). Local structures in PMI and AFI phases of the x = 0.3 sample have been investigated using Pr K-edge and Sm K-edge extended x-ray absorption fine structure (EXAFS). It can be seen that the tilting and rotation of the MnO 6 octahedra about the b-axis are responsible for the charge-ordered CE-type antiferromagnetic ground state at low temperatures. In addition a shift in the position of the rare-earth ion along the c-axis has to be considered to account for observed distribution of bond distances around the rare-earth ion

  18. EXAFS analysis of uranium speciation in plants using the difference technique

    International Nuclear Information System (INIS)

    Rossberg, A.; Reich, T.; Guenther, A.; Bernhard, G.

    2002-01-01

    An EXAFS spectrum is the sum of the signals of scattering contributions from single atoms and multiple scattering (MS) between atoms. The scattering contributions with high intensity are the major and such with low intensity are the minor components in an EXAFS spectrum. A chi-squared fit algorithm is not sensitive enough to the minor components. A difference technique has been developed /1/ to isolate the minor components from the whole EXAFS spectrum to increase the accuracy in determinating of their EXAFS structural parameters. (orig.)

  19. An EXAFS Study on the Local Structure Around Iron in Atmospheric Aerosols Collected in the Qingdao Area

    Directory of Open Access Journals (Sweden)

    Tiandou Hu

    2003-01-01

    Full Text Available The existing forms of Fe are of great interest since they have a profound effect on the biological availability of Fe. In this work, aerosol samples collected in different seasons and at different locations in the Qingdao region were examined by means of extended X-ray absorption fine structure (EXAFS K-edge analysis of Fe, X-ray diffraction (XRD and Fe content analysis. The results showed that an iron ion in aerosol particles is surrounded on average by 5.8 (coordinated O ions. For the six samples examined, the coordination number of the first Fe-O coordination subshell is always 3 with a coordination distance (with O in the range of 1.952~1.966±0.002 Å, while the coordination number of the second subshell varies from 2.2 to 3.0 with a coordination distance of 2.108±0.002 Å. The coordination is approximately consistent with that of a-Fe2O3, suggesting that iron in aerosol samples is mainly present in the form of a-Fe2O3. The fact that the coordination number in the second subshell is smaller than that of a-Fe2O3 might be an indication that there is a small amount of FeO mixed with a-Fe2O3 in aerosol particles. Existence of FeO is confirmed by a later XRD experiment.

  20. Difference between Cr and Ni K-edge XANES spectra of rust layers formed on Fe-based binary alloys exposed to Cl-rich environment

    International Nuclear Information System (INIS)

    Konishi, Hiroyuki; Mizuki, Jun'ichiro; Yamashita, Masato; Uchida, Hitoshi

    2005-01-01

    The rust layer formed on weathering steel possesses a strong protective ability against corrosives in an atmospheres. This ability is related to the structure of the rust layer. The difference in the protective ability of a rust layer. The difference in the protective ability of a rust layer in a Cl-rich environment between conventional weathering steel containing Cr and advanced weathering steel containing Ni is believed to be caused by the differences in local structural and chemical properties between alloying elements. Cr and Ni, in the rust layer. In order to examine the effect of these alloying elements on the structure of the rust layer formed on steel in a Cl-rich environment, we have performed Cr and Ni K-edge X-ray absorption near-edge structure (XANES) measurements for the rust layer of Fe-Cr and Fe-Ni binary alloys exposed to a Cl-rich atmosphere using synchrotron radiation. The results of the Cr K-edge XANES measurements for the rust layer of Fe-Cr binary alloys show that the atomic geometry around Cr depends on the concentration of Cr. Therefore, it is expected that the local structure around Cr in the rust layer is unstable. On the other hand, from the results of the Ni K-edge XANES measurements for the rust layer of Fe-Ni binary alloys. Ni is considered to be positioned at a specific site in the crystal structure of a constituent of the rust layer, such as akaganeite or magnetite. As a consequence, Ni negligibly interacts with Cl - ions in the rust layer. (author)

  1. Demonstration of iodine K-edge imaging by use of an energy-discrimination X-ray computed tomography system with a cadmium telluride detector.

    Science.gov (United States)

    Abudurexiti, Abulajiang; Kameda, Masashi; Sato, Eiichi; Abderyim, Purkhet; Enomoto, Toshiyuki; Watanabe, Manabu; Hitomi, Keitaro; Tanaka, Etsuro; Mori, Hidezo; Kawai, Toshiaki; Takahashi, Kiyomi; Sato, Shigehiro; Ogawa, Akira; Onagawa, Jun

    2010-07-01

    An energy-discrimination K-edge X-ray computed tomography (CT) system is useful for increasing the contrast resolution of a target region by utilizing contrast media. The CT system has a cadmium telluride (CdTe) detector, and a projection curve is obtained by linear scanning with use of the CdTe detector in conjunction with an X-stage. An object is rotated by a rotation step angle with use of a turntable between the linear scans. Thus, CT is carried out by repetition of the linear scanning and the rotation of an object. Penetrating X-ray photons from the object are detected by the CdTe detector, and event signals of X-ray photons are produced with use of charge-sensitive and shaping amplifiers. Both the photon energy and the energy width are selected by use of a multi-channel analyzer, and the number of photons is counted by a counter card. For performing energy discrimination, a low-dose-rate X-ray generator for photon counting was developed; the maximum tube voltage and the minimum tube current were 110 kV and 1.0 microA, respectively. In energy-discrimination CT, the tube voltage and the current were 60 kV and 20.0 microA, respectively, and the X-ray intensity was 0.735 microGy/s at 1.0 m from the source and with a tube voltage of 60 kV. Demonstration of enhanced iodine K-edge X-ray CT was carried out by selection of photons with energies just beyond the iodine K-edge energy of 33.2 keV.

  2. MO-FG-CAMPUS-IeP1-01: Alternative K-Edge Filters for Low-Energy Image Acquisition in Contrast Enhanced Spectral Mammography

    Energy Technology Data Exchange (ETDEWEB)

    Shrestha, S; Vedantham, S; Karellas, A [University of Massachusetts Medical School, Worcester, MA (United States)

    2016-06-15

    Purpose: In Contrast Enhanced Spectral Mammography (CESM), Rh filter is often used during low-energy image acquisition. The potential for using Ag, In and Sn filters, which exhibit K-edge closer to, and just below that of Iodine, instead of the Rh filter, was investigated for the low-energy image acquisition. Methods: Analytical computations of the half-value thickness (HVT) and the photon fluence per mAs (photons/mm2/mAs) for 50µm Rh were compared with other potential K-edge filters (Ag, In and Sn), all with K-absorption edge below that of Iodine. Two strategies were investigated: fixed kVp and filter thickness (50µm for all filters) resulting in HVT variation, and fixed kVp and HVT resulting in variation in Ag, In and Sn thickness. Monte Carlo simulations (GEANT4) were conducted to determine if the scatter-to-primary ratio (SPR) and the point spread function of scatter (scatter PSF) differed between Rh and other K-edge filters. Results: Ag, In and Sn filters (50µm thick) increased photon fluence/mAs by 1.3–1.4, 1.8–2, and 1.7–2 at 28-32 kVp compared to 50µm Rh, which could decrease exposure time. Additionally, the fraction of spectra closer to and just below Iodine’s K-edge increased with these filters, which could improve post-subtraction image contrast. For HVT matched to 50µm Rh filtered spectra, the thickness range for Ag, In, and Sn were (41,44)µm, (49,55)µm and (45,53)µm, and increased photon fluence/mAs by 1.5–1.7, 1.6–2, and 1.6–2.2, respectively. Monte Carlo simulations showed that neither the SPR nor the scatter PSF of Ag, In and Sn differed from Rh, indicating no additional detriment due to x-ray scatter. Conclusion: The use of Ag, In and Sn filters for low-energy image acquisition in CESM is potentially feasible and could decrease exposure time and may improve post-subtraction image contrast. Effect of these filters on radiation dose, contrast, noise and associated metrics are being investigated. Funding Support: Supported in

  3. Cl K-edge XANES spectra of atmospheric rust on Fe, Fe-Cr and Fe-Ni alloys exposed to saline environment

    International Nuclear Information System (INIS)

    Konishi, Hiroyuki; Mizuki, Jun'ichiro; Yamashita, Masato; Uchida, Hitoshi

    2004-01-01

    Cl K-edge XANES measurements of atmospheric corrosion products (rust) formed on Fe, Fe-Ni and Fe-Cr alloys in chloride pollution have been performed using synchrotron radiation in order to clarify roles of anticorrosive alloying elements and of Cl in the corrosion resistance of weathering steel. The spectra of binary alloys show a shoulder structure near the absorption edge. The intensity of the shoulder peak depends on the kind and amount of the alloying element, whereas the energy position is invariant. This indicates that Cl is not combined directly with alloying elements in the rust. (author)

  4. Resonant inelastic x-ray scattering on iso-C2H2Cl2 around the chlorine K-edge: Structural and dynamical aspects

    International Nuclear Information System (INIS)

    Kawerk, Elie; Carniato, Stéphane; Journel, Loïc; Marchenko, Tatiana; Simon, Marc; Piancastelli, Maria Novella; Žitnik, Matjaž; Bučar, Klemen; Bohnic, Rok

    2014-01-01

    We report a theoretical and experimental study of the high resolution resonant K α X-ray emission lines around the chlorine K-edge in gas phase 1,1-dichloroethylene. With the help of ab initio electronic structure calculations and cross section evaluation, we interpret the lowest lying peak in the X-ray absorption and emission spectra. The behavior of the K α emission lines with respect to frequency detuning highlights the existence of femtosecond nuclear dynamics on the dissociative Potential Energy Surface of the first K-shell core-excited state

  5. Resonant inelastic x-ray scattering on iso-C2H2Cl2 around the chlorine K-edge: Structural and dynamical aspects

    Science.gov (United States)

    Kawerk, Elie; Carniato, Stéphane; Journel, Loïc; Marchenko, Tatiana; Piancastelli, Maria Novella; Žitnik, Matjaž; Bučar, Klemen; Bohnic, Rok; Kavčič, Matjaž; Céolin, Denis; Khoury, Antonio; Simon, Marc

    2014-10-01

    We report a theoretical and experimental study of the high resolution resonant Kα X-ray emission lines around the chlorine K-edge in gas phase 1,1-dichloroethylene. With the help of ab initio electronic structure calculations and cross section evaluation, we interpret the lowest lying peak in the X-ray absorption and emission spectra. The behavior of the Kα emission lines with respect to frequency detuning highlights the existence of femtosecond nuclear dynamics on the dissociative Potential Energy Surface of the first K-shell core-excited state.

  6. Resonant inelastic x-ray scattering on iso-C₂H₂Cl₂ around the chlorine K-edge: structural and dynamical aspects.

    Science.gov (United States)

    Kawerk, Elie; Carniato, Stéphane; Journel, Loïc; Marchenko, Tatiana; Piancastelli, Maria Novella; Žitnik, Matjaž; Bučar, Klemen; Bohnic, Rok; Kavčič, Matjaž; Céolin, Denis; Khoury, Antonio; Simon, Marc

    2014-10-14

    We report a theoretical and experimental study of the high resolution resonant K(α) X-ray emission lines around the chlorine K-edge in gas phase 1,1-dichloroethylene. With the help of ab initio electronic structure calculations and cross section evaluation, we interpret the lowest lying peak in the X-ray absorption and emission spectra. The behavior of the K(α) emission lines with respect to frequency detuning highlights the existence of femtosecond nuclear dynamics on the dissociative Potential Energy Surface of the first K-shell core-excited state.

  7. Silicon Detector System for High Rate EXAFS Applications

    OpenAIRE

    Pullia, A.; Kraner, H. W.; Siddons, D. P.; Furenlid, L. R.; Bertuccio, G.

    1995-01-01

    A multichannel silicon pad detector for EXAFS (Extended X-ray Absorption Fine Structure) applications has been designed and built. The X-ray spectroscopic measurements demonstrate that an adequate energy resolution of 230 eV FWHM (corresponding to 27 rms electrons in silicon) can be achieved reliably at −35 °C. A resolution of 190 eV FWHM (corresponding to 22 rms electrons) has been obtained from individual pads at −35 °C. At room temperature (25 °C) an average energy resolution of 380 eV FWH...

  8. Charge-transfer and Mott-Hubbard Excitations in FeBo3: Fe K-edge resonant Inelastic x-ray scattering study

    International Nuclear Information System (INIS)

    Kim, J.; Shvydko, Y.

    2011-01-01

    Momentum-resolved resonant inelastic x-ray scattering (RIXS) spectroscopy has been carried out successfully at the Fe K-edge for the first time. The RIXS spectra of a FeBO 3 single crystal reveal a wealth of information on ∼ 1-10 eV electronic excitations. The IXS signal resonates when the incident photon energy approaches the pre-edge (1s - -3d) and the main-edge (1s - -4p) of the Fe K-edge absorption spectrum. The RIXS spectra measured at the pre-edge and the main-edge show quantitatively different dependences on the incident photon energy, momentum transfer, photon polarization, and temperature. We present a multielectron analysis of the Mott-Hubbard (MH) and charge transfer (CT) excitations, and calculate their energies. Electronic excitations observed in the pre-edge and main-edge RIXS spectra are interpreted as MH and CT excitations, respectively. We propose the electronic structure around the chemical potential in FeBO 3 based on the experimental data.

  9. Arsenic K-edge X-ray absorption near-edge spectroscopy to determine oxidation states of arsenic of a coastal aquifer–aquitard system

    International Nuclear Information System (INIS)

    Wang, Ya; Jiao, Jiu Jimmy; Zhu, Sanyuan; Li, Yiliang

    2013-01-01

    Determination of oxidation states of solid-phase arsenic in bulk sediments is a valuable step in the evaluation of its bioavailability and environmental fate in deposits, but is difficult when the sediments have low arsenic contents and heterogeneous distribution of arsenic species. As K-edge X-ray absorption near-edge spectroscopy (XANES) was used to determine quantitatively the oxidation states of arsenic in sediments collected from different depths of boreholes in the Pearl River Delta, China, where the highest aquatic arsenic concentration is 161.4 μg/L, but the highest solid arsenic content only 39.6 mg/kg. The results demonstrated that XANES is efficient in determining arsenic oxidation states of the sediments with low arsenic contents and multiple arsenic species. The study on the high-resolution vertical variations of arsenic oxidation states also indicated that these states are influenced strongly by groundwater activities. With the help of geochemical data, solid arsenic speciation, toxicity and availability were further discussed. -- Highlights: •XANES is efficient in determining arsenic oxidation states of the bulk sediments. •Distribution of arsenic oxidation states is consistent with geochemical conditions. •Arsenic oxidation states are influenced strongly by groundwater activities. -- As K-edge X-ray absorption near-edge spectroscopy is efficient in determining arsenic oxidation states of the bulk sediments with low arsenic contents and heterogeneous distribution of arsenic species

  10. Nitrogen K-edge X-ray absorption near edge structure (XANES) spectra of purine-containing nucleotides in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Shimada, Hiroyuki; Fukao, Taishi; Minami, Hirotake; Ukai, Masatoshi [Department of Applied Physics, Tokyo University of Agriculture and Technology, Koganei-shi, Tokyo 184-8588 (Japan); Fujii, Kentaro; Yokoya, Akinari [Advanced Science Research Center, Japan Atomic Energy Agency, Tokai-mura, Naka-gun, Ibaraki 319-1195 (Japan); Fukuda, Yoshihiro; Saitoh, Yuji [Synchrotron Radiation Research Center, Japan Atomic Energy Agency, Sayo-gun, Hyougo 679-5148 (Japan)

    2014-08-07

    The N K-edge X-ray absorption near edge structure (XANES) spectra of the purine-containing nucleotide, guanosine 5{sup ′}-monophosphate (GMP), in aqueous solution are measured under various pH conditions. The spectra show characteristic peaks, which originate from resonant excitations of N 1s electrons to π* orbitals inside the guanine moiety of GMP. The relative intensities of these peaks depend on the pH values of the solution. The pH dependence is explained by the core-level shift of N atoms at specific sites caused by protonation and deprotonation. The experimental spectra are compared with theoretical spectra calculated by using density functional theory for GMP and the other purine-containing nucleotides, adenosine 5{sup ′}-monophosphate, and adenosine 5{sup ′}-triphosphate. The N K-edge XANES spectra for all of these nucleotides are classified by the numbers of N atoms with particular chemical bonding characteristics in the purine moiety.

  11. Non-destructive assay system for uranium and plutonium in reprocessing input solutions. Hybrid K-edge/XRF Densitometer. JASPAS JC-11 final report

    International Nuclear Information System (INIS)

    Surugaya, N.; Abe, K.; Kurosawa, A.; Ikeda, H.; Kuno, Y.

    1997-05-01

    As a part of JASPAS programme, a non-radioactive assay system for the accountability of uranium and plutonium in input dissolver solutions of a spent fuel reprocessing plant, called Hybrid K-edge/XRF Densitometer, has been developed at the Tokai Reprocessing plant (TRP) since 1991. The instrument is the one of the hybrid type combined K-edge densitometry (KED) and X-ray fluorescence (XRF) analysis. The KED is used to determine the uranium concentration and the XRF is used to determine the U/Pu ratio. These results give the plutonium concentration in consequence. It is considered that the instrument has the capability of timely on-site verification for input accountancy. The instrument had been installed in the analytical hot cell at the TRP and the experiments comparing with Isotope Dilution Mass Spectrometry (IDMS) method have been carried out. As the results of measurements for the actual input solutions in the acceptance and performance tests, it was typically confirmed that the precision for determining uranium concentration by the KED was within 0.2%, whereas the XRF for plutonium performed within 0.7%. This final report summarizes the design information and performance data so as to end the JASPAS programme. (author)

  12. Moessbauer and EXAFS spectroscopy investigation of iron and arsenic adsorption to lettuce leaves

    International Nuclear Information System (INIS)

    Vasconcelos, Igor F.; Silva, Gabriela C.; Carvalho, Regina P.; Dantas, Maria Sylvia S.; Ciminelli, Virginia S. T.

    2010-01-01

    The accumulation of iron and arsenic from aqueous solution by lettuce leaves biomass was investigated using Moessbauer and EXAFS spectroscopic techniques. Moessbauer spectroscopy results show that iron is oxidized during sorption while EXAFS results indicate that iron is coordinated by approximately 6 oxygen and 2 carbon atoms while arsenic is coordinated by approximately 4 oxygen atoms with iron as a second neighbor.

  13. Moessbauer and EXAFS spectroscopy investigation of iron and arsenic adsorption to lettuce leaves

    Energy Technology Data Exchange (ETDEWEB)

    Vasconcelos, Igor F., E-mail: ifvasco@ufc.br [Universidade Federal do Ceara, Dep. Eng. Metalurgica e de Materiais (Brazil); Silva, Gabriela C.; Carvalho, Regina P.; Dantas, Maria Sylvia S.; Ciminelli, Virginia S. T. [Universidade Federal de Minas Gerais, Dep. Eng. Metalurgica e de Materiais (Brazil)

    2010-01-15

    The accumulation of iron and arsenic from aqueous solution by lettuce leaves biomass was investigated using Moessbauer and EXAFS spectroscopic techniques. Moessbauer spectroscopy results show that iron is oxidized during sorption while EXAFS results indicate that iron is coordinated by approximately 6 oxygen and 2 carbon atoms while arsenic is coordinated by approximately 4 oxygen atoms with iron as a second neighbor.

  14. EXAFS investigations on PbMoO4 single crystals grown under ...

    Indian Academy of Sciences (India)

    Abstract. Extended X-ray absorption fine structure (EXAFS) measurements on PbMoO4 (LMO) crystals have been performed at the recently-commissioned dispersive EXAFS beamline (BL-8) of INDUS-2 Synchrotron facility at Indore, India. The LMO samples were prepared under three different conditions viz. (i) grown from ...

  15. Local atomic and crystal structure rearrangement during the martensitic transformation in Ti50Ni25Cu25 shape memory alloy

    International Nuclear Information System (INIS)

    Menushenkov, Alexey; Grishina, Olga; Shelyakov, Alexander; Yaroslavtsev, Alexander; Zubavichus, Yan; Veligzhanin, Alexey; Bednarcik, Jozef; Chernikov, Roman; Sitnikov, Nikolay

    2014-01-01

    Highlights: • Local crystalline structure of TiNiCu SMA is investigated using EXAFS. • Peculiarities of Ni and Cu local environment are found. • Ti atoms show greater mobility relative to Ni atoms. • Ni local environment change is significant for shape memory effect. -- Abstract: The changes of crystal structure and local crystalline environment of Ti, Ni and Cu atoms in Ti 50 Ni 25 Cu 25 shape memory alloy are investigated using X-ray diffraction and extended X-ray absorption fine structure spectroscopy (EXAFS) in temperature range of martensite transformation. The analysis of the EXAFS-spectra shows that the bonds involving Ni atoms have the highest degree of disorder and the change in the local environment around Ni atoms is significant for the occurrence of the shape memory effect, while Cu atoms occupy the normal positions in the crystallographic structure and have the lowest displacement amplitude leading to the stabilization of both phases

  16. SAXS and EXAFS studies of ion beam synthesized Au nanocrystals

    International Nuclear Information System (INIS)

    Kluth, P.; Johannessen, B.; Cookson, D.J.; Foran, G.J.; Ridgway, M.C.

    2006-01-01

    We have used small-angle X-ray scattering (SAXS) and extended X-ray absorption fine structure (EXAFS) spectroscopy to investigate Au nanocrystals (NCs) fabricated by high dose ion implantation into thin SiO 2 and subsequent annealing at different temperatures. Size distributions were determined from SAXS and structural parameters were extracted from EXAFS measurements, the latter analyzed as a function of NC size. Increasing implantation dose leads to an increasing average NC size and broadening of the size distribution. A significant size-dependent bond length contraction with respect to bulk material was observed. For samples annealed at 1100 deg. C our analysis suggests that an increased structural disorder is predominantly located at the NC surface. Post-implantation annealing at temperatures of 500 deg. C and 800 deg. C for 1 h in forming gas had no detectable influence on the NC size distribution, however, a significant influence on the structural parameters, in particular increased disorder was observed. This is potentially the result of stress induced disorder due to the different thermal expansion of the NC and matrix materials

  17. A Monte Carlo simulation study of an improved K-edge log-subtraction X-ray imaging using a photon counting CdTe detector

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Youngjin, E-mail: radioyoungj@gmail.com [Department of Radiological Science, Eulji University, 553, Sanseong-daero, Sujeong-gu, Seongnam-si, Gyeonggi-do (Korea, Republic of); Lee, Amy Candy [Department of Mathematics and Statistics, McGill University (Canada); Kim, Hee-Joung [Department of Radiological Science and Radiation Convergence Engineering, Yonsei University (Korea, Republic of)

    2016-09-11

    Recently, significant effort has been spent on the development of photons counting detector (PCD) based on a CdTe for applications in X-ray imaging system. The motivation of developing PCDs is higher image quality. Especially, the K-edge subtraction (KES) imaging technique using a PCD is able to improve image quality and useful for increasing the contrast resolution of a target material by utilizing contrast agent. Based on above-mentioned technique, we presented an idea for an improved K-edge log-subtraction (KELS) imaging technique. The KELS imaging technique based on the PCDs can be realized by using different subtraction energy width of the energy window. In this study, the effects of the KELS imaging technique and subtraction energy width of the energy window was investigated with respect to the contrast, standard deviation, and CNR with a Monte Carlo simulation. We simulated the PCD X-ray imaging system based on a CdTe and polymethylmethacrylate (PMMA) phantom which consists of the various iodine contrast agents. To acquired KELS images, images of the phantom using above and below the iodine contrast agent K-edge absorption energy (33.2 keV) have been acquired at different energy range. According to the results, the contrast and standard deviation were decreased, when subtraction energy width of the energy window is increased. Also, the CNR using a KELS imaging technique is higher than that of the images acquired by using whole energy range. Especially, the maximum differences of CNR between whole energy range and KELS images using a 1, 2, and 3 mm diameter iodine contrast agent were acquired 11.33, 8.73, and 8.29 times, respectively. Additionally, the optimum subtraction energy width of the energy window can be acquired at 5, 4, and 3 keV for the 1, 2, and 3 mm diameter iodine contrast agent, respectively. In conclusion, we successfully established an improved KELS imaging technique and optimized subtraction energy width of the energy window, and based on

  18. Lattice positions of Sn in Cu2ZnSnS4 nanoparticles and thin films studied by synchrotron X-ray absorption near edge structure analysis

    Science.gov (United States)

    Zillner, E.; Paul, A.; Jutimoosik, J.; Chandarak, S.; Monnor, T.; Rujirawat, S.; Yimnirun, R.; Lin, X. Z.; Ennaoui, A.; Dittrich, Th.; Lux-Steiner, M.

    2013-06-01

    Lattice positions of Sn in kesterite Cu2ZnSnS4 and Cu2SnS3 nanoparticles and thin films were investigated by XANES (x-ray absorption near edge structure) analysis at the S K-edge. XANES spectra were analyzed by comparison with simulations taking into account anti-site defects and vacancies. Annealing of Cu2ZnSnS4 nanoparticle thin films led to a decrease of Sn at its native and defect sites. The results show that XANES analysis at the S K-edge is a sensitive tool for the investigation of defect sites, being critical in kesterite thin film solar cells.

  19. Pramana – Journal of Physics | Indian Academy of Sciences

    Indian Academy of Sciences (India)

    Keywords. Energy-dispersive extended X-ray absorption fine-structure spectroscopy; beamline BL-8; Cu metal; Cu complex. ... Further, EXAFS spectra at Cu K-edge in a copper complex have also been recorded at BL-8 beamline and beamline 11.1 at ELETTRA (Italy). The obtained experimental () data have been ...

  20. Structural disorder and electronic hybridization in NicMg1-cO solid solutions probed by XANES at the oxygen K edge

    International Nuclear Information System (INIS)

    Chen Dongliang; Zhong Jun; Chu Wangsheng; Wu Ziyu; Kuzmin, Alexei; Mironova-Ulmane, Nina; Marcelli, Augusto

    2007-01-01

    A series of Ni c Mg 1-c O solid solutions has been studied for the first time looking at the structural disorder by means of x-ray absorption near-edge-structure (XANES) spectroscopy at the oxygen K edge. The experimental XANES signals were analysed within the full multiple scattering formalism and were interpreted taking into account clusters of up to 15 coordination shells around an absorbing oxygen atom. The substitution of nickel atoms by magnesium atoms results in a dramatic decrease of the empty density of states in the conduction band close to the Fermi level due to an exchange of the 3d(Ni)-2p(O) interaction with 3p(Mg)-2p(O). Besides, a simultaneous small decrease of the 3d(Ni)-2p(O) hybridization is also induced by the lattice expansion, determined by the difference in ionic radii between nickel and magnesium ions

  1. Structural disorder and electronic hybridization in Ni{sub c}Mg{sub 1-c}O solid solutions probed by XANES at the oxygen K edge

    Energy Technology Data Exchange (ETDEWEB)

    Chen Dongliang [Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China); Zhong Jun [Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China); Chu Wangsheng [Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China); Wu Ziyu [Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China); Kuzmin, Alexei [Institute of Solid State Physics, University of Latvia, Kengaraga 8, LV-1063 Riga (Latvia); Mironova-Ulmane, Nina [Institute of Solid State Physics, University of Latvia, Kengaraga 8, LV-1063 Riga (Latvia); Marcelli, Augusto [Laboratori Nazionali di Frascati, Istituto Nazionale di Fisica Nucleare, PO Box 13, 00044 Frascati (Italy)

    2007-09-05

    A series of Ni{sub c}Mg{sub 1-c}O solid solutions has been studied for the first time looking at the structural disorder by means of x-ray absorption near-edge-structure (XANES) spectroscopy at the oxygen K edge. The experimental XANES signals were analysed within the full multiple scattering formalism and were interpreted taking into account clusters of up to 15 coordination shells around an absorbing oxygen atom. The substitution of nickel atoms by magnesium atoms results in a dramatic decrease of the empty density of states in the conduction band close to the Fermi level due to an exchange of the 3d(Ni)-2p(O) interaction with 3p(Mg)-2p(O). Besides, a simultaneous small decrease of the 3d(Ni)-2p(O) hybridization is also induced by the lattice expansion, determined by the difference in ionic radii between nickel and magnesium ions.

  2. Order-disorder in olivine minerals by synchrotron X-ray absorption near-edge structure (Xane) spectroscopy at the Mg, Fe and Ca K edges

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Z.; Marcelli, A.; Cibin, G. [Istituto Nazionale di Fisica Nucleare, Frascati, RM (Italy). Laboratori Nazionali di Frascati; Mottana, A. [Istituto Nazionale di Fisica Nucleare, Frascati, RM (Italy). Laboratori Nazionali di Frascati; Rome Univ. Roma Tre, Rome (Italy). Dipt. di Scienze Geologiche; Paris, E.; Giuli, G [INFM, Camerino Univ., Camerino, MC (Italy). Dipt. di Scienze della Terra

    1999-07-01

    In this paper, are presented new, high-resolution experimental spectra at the Mg and Fe K edges for the two Fe-Mg end members F o and F a, and for three other olivines. Two are the Ca end members of the family, namely monticellite (Mtc: CaMgSiO4) and kirschsteinite (Krs: CaFeSiO4). The main purpose of this work is to investigate the effects of Mg, Fe, and Ca partition in the Pbnm (or {alpha}) olivine structure on the electronic properties, as well as the relationships that exist between chemical substitutions and features occurring in Xanes spectra. One wants to explore the relationships that intervene between LRO, as determined by XRD, and SRO, as determined by Xanes, on the endmembers and on a well-known intermediate member as well, and deduce from it a model for the behavior of the entire olivine solid-solution system.

  3. Optimization of the k-edge filters utilization in the dental radiographs; Otimizacao da utilizacao dos filtros de aresta K na radiografias dentarias

    Energy Technology Data Exchange (ETDEWEB)

    Reyes, Luis M.G.; Almeida, Adelaide de [Sao Paulo Univ., Ribeirao Preto, SP (Brazil). Faculdade de Filosofia, Ciencias e Letras. Dept. de Fisica e Matematica

    2001-07-01

    The signal to noise ratio (S/N) of radiographic film images may be optimized if the thicknesses and atomic composition of the structures to be analyzed are known. With specifications and a knowledge of the interaction of photons with the materials, the photon energy for maximum contrast may be determined. We propose a K-edge filter in addition to the normal aluminum filter, to reduce the dose to the patient by the transmission of a narrow spectrum of photons with energies to optimize the image contrast. The optimum photon energy to obtain the best contrast between dental pulp and dentine and between dentine and dental enamel was determined to be 29-34 and 22-26 keV respectively. The filter material, which closely approximates these spectra, is made of Ce (Z=58) whose thickness is shown do depend on the parameters of the X-ray generator. (author)

  4. Pyrimidine and halogenated pyrimidines near edge x-ray absorption fine structure spectra at C and N K-edges: experiment and theory

    International Nuclear Information System (INIS)

    Bolognesi, P.; O'Keeffe, P.; Ovcharenko, Y.; Coreno, M.; Avaldi, L.; Feyer, V.; Plekan, O.; Prince, K. C.; Zhang, W.; Carravetta, V.

    2010-01-01

    The inner shell excitation of pyrimidine and some halogenated pyrimidines near the C and N K-edges has been investigated experimentally by near edge x-ray absorption fine structure spectroscopy and theoretically by density functional theory calculations. The selected targets, 5-Br-pyrimidine, 2-Br-pyrimidine, 2-Cl-pyrimidine, and 5-Br-2-Cl-pyrimidine, allow the effects of the functionalization of the pyrimidine ring to be studied either as a function of different halogen atoms bound to the same molecular site or as a function of the same halogen atom bound to different molecular sites. The results show that the individual characteristics of the different spectra of the substituted pyrimidines can be rationalized in terms of variations in electronic and geometrical structures of the molecule depending on the localization and the electronegativity of the substituent.

  5. Order-disorder in olivine minerals by synchrotron X-ray absorption near-edge structure (Xane) spectroscopy at the Mg, Fe and Ca K edges

    International Nuclear Information System (INIS)

    Wu, Z.; Marcelli, A.; Cibin, G.; Mottana, A.; Rome Univ. Roma Tre, Rome; Paris, E.; Giuli, G.

    1999-01-01

    In this paper, are presented new, high-resolution experimental spectra at the Mg and Fe K edges for the two Fe-Mg endmembers F o and F a, and for three other olivines. Two are the Ca endmembers of the family, namely monticellite (Mtc: CaMgSiO4) and kirschsteinite (Krs: CaFeSiO4). The main purpose of this work is to investigate the effects of Mg, Fe, and Ca partition in the Pbnm (or α) olivine structure on the electronic properties, as well as the relationships that exist between chemical substitutions and features occurring in Xanes spectra. One wants to explore the relationships that intervene between LRO, as determined by XRD, and SRO, as determined by Xanes, on the endmembers and on a well-known intermediate member as well, and deduce from it a model for the behavior of the entire olivine solid-solution system

  6. Near K-edge measurement of the X-ray attenuation coefficient of heavy elements using a tuneable X-ray source based on an electron LINAC

    CERN Document Server

    Materna, T; Mondelaers, W; Masschaele, B

    2000-01-01

    The X-ray attenuation coefficients of bismuth and of uranium were measured in the regions of 40-240 and 70-240 keV, respectively, using a tuneable hard X-ray source based on the linear electron accelerator at the University of Ghent. Results were compared with the semi-empirical values of Storm and Israel and to the theoretical values of Berger and Hubbell. We also propose a simple function for the attenuation coefficient in the vicinity of the K-edge for uranium and in an extended range of energy for bismuth. The set-up of the source at Ghent is described and the future improvements are explained.

  7. MULTI ELEMENT SI SENSOR WITH READOUT ASIC FOR EXAFS SPECTROSCOPY.

    Energy Technology Data Exchange (ETDEWEB)

    DE GERONIMO,G.; O CONNOR,P.; BEUTTENMULLER,R.H.; LI,Z.; KUCZEWSKI,A.J.; SIDDONS,D.P.

    2002-09-09

    Extended X-ray Absorption Fine Structure (EXAFS) experiments impose stringent requirements on a detection system, due to the need for processing ionizing events at a high rate, typically above of 10Mcps/cm{sup 2}, and with a high resolution, typically better than 300eV. The detection system here presented is being developed targeting these stringent requirements. It is the result of a cooperation between the Instrumentation Division and the National Synchrotron Light Source (NSLS) of the Brookhaven National Laboratory (BNL). The system is composed of a multi-element Si sensor with dedicated per pixel electronics. The combination of high rate, high resolution and moderate complexity makes this system attractive when compared to other multi-element solutions. In sections 2, 3 and 4 the sensor, the interconnect and the electronics are briefly described. Section 5 reports on the first experimental results.

  8. Radiation damage in A-15 materials: EXAFS studies

    International Nuclear Information System (INIS)

    Knapp, G.S.; Kampwirth, R.T.; Georgopoulos, P.; Brown, B.S.

    1980-01-01

    EXAFS measurements are useful in determining the local atomic environment of a particular element in a solid. Since there has been some controversy about the nature of the defects produced in A-15 materials by radiation damage, such studies were carried out on some A-15 compounds, V 3 Ga which was damaged by neutrons, as well as Nb 3 Ge damaged by 2.5 MeV a particles. In the V 3 Ga sample, site exchange disorder seems to be the most important result of the neutron damage with less than 20% of the vanadium atoms on wrong sites. However, in the Nb 3 Ge samples in addition to site exchange disorder, an unusual splitting of the first near-neighbor distance between the Ge and Nb is found. This splitting, approximately 0.2 A, may explain the large Debye Waller factors observed by Burbank et al

  9. Tetrahalide complexes of the [U(NR)2]2+ ion: synthesis, theory, and chlorine K-edge X-ray absorption spectroscopy.

    Science.gov (United States)

    Spencer, Liam P; Yang, Ping; Minasian, Stefan G; Jilek, Robert E; Batista, Enrique R; Boland, Kevin S; Boncella, James M; Conradson, Steven D; Clark, David L; Hayton, Trevor W; Kozimor, Stosh A; Martin, Richard L; MacInnes, Molly M; Olson, Angela C; Scott, Brian L; Shuh, David K; Wilkerson, Marianne P

    2013-02-13

    Synthetic routes to salts containing uranium bis-imido tetrahalide anions [U(NR)(2)X(4)](2-) (X = Cl(-), Br(-)) and non-coordinating NEt(4)(+) and PPh(4)(+) countercations are reported. In general, these compounds can be prepared from U(NR)(2)I(2)(THF)(x) (x = 2 and R = (t)Bu, Ph; x = 3 and R = Me) upon addition of excess halide. In addition to providing stable coordination complexes with Cl(-), the [U(NMe)(2)](2+) cation also reacts with Br(-) to form stable [NEt(4)](2)[U(NMe)(2)Br(4)] complexes. These materials were used as a platform to compare electronic structure and bonding in [U(NR)(2)](2+) with [UO(2)](2+). Specifically, Cl K-edge X-ray absorption spectroscopy (XAS) and both ground-state and time-dependent hybrid density functional theory (DFT and TDDFT) were used to probe U-Cl bonding interactions in [PPh(4)](2)[U(N(t)Bu)(2)Cl(4)] and [PPh(4)](2)[UO(2)Cl(4)]. The DFT and XAS results show the total amount of Cl 3p character mixed with the U 5f orbitals was roughly 7-10% per U-Cl bond for both compounds, which shows that moving from oxo to imido has little effect on orbital mixing between the U 5f and equatorial Cl 3p orbitals. The results are presented in the context of recent Cl K-edge XAS and DFT studies on other hexavalent uranium chloride systems with fewer oxo or imido ligands.

  10. Application of a high intensity laboratory X-ray source to EXAFS spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Cohen, G G; Deslattes, R D [National Bureau of Standards, Washington, DC (USA)

    1982-02-15

    A practically oriented summary for the design and operation of a high-performance laboratory EXAFS system is presented. Emphasis is on an evaluation of total system performance, including both geometrical and crystal diffraction effects.

  11. Predetermining acceptable noise limits of EXAFS spectra in the limit of stochastic noise

    International Nuclear Information System (INIS)

    Hu, Yung-Jin; Booth, Corwin H

    2009-01-01

    The effect of stochastic noise on Extended X-ray Absorption Fine Structure (EXAFS) data measurement, analysis, and fitting is discussed. Stochastic noise reduces the ability to uniquely fit a calculated model to measured EXAFS data. Such noise can be reduced by common methods that increase the signal-to-noise ratio; however, these methods are not always practical. Therefore, predetermined, quantitative knowledge of the level of acceptable stochastic noise when fitting for a particular model system is essential in maximizing the chances of a successful EXAFS experiment and minimizing wasted beamtime. This paper outlines a method to estimate, through simulation, the acceptable level of stochastic noise in EXAFS spectra that still allows a successful test of a proposed model compound.

  12. Uranium speciation in 30-year old Freital mine tailings: an EXAFS, {mu}-XRD, and {mu}-XRF study

    Energy Technology Data Exchange (ETDEWEB)

    Scheinost, A.C.; Hennig, C. [Institute of Radiochemistry, FZR, D-01314 Dresden (Germany); Somogyi, A. [Synchrotron Soleil, F-91192 Gif-sur-Yvette (France); Martinez-Criado, G. [ESRF, ID-22, F-38043 Grenoble (France); Knappik, R. [VKTA Rossendorf, D-01314 Dresden (Germany)

    2005-07-01

    Full text of publication follows: Risk assessments of actinide-contaminated soils and sediments require detailed knowledge of actinide speciation and its long-term kinetics. Former Saxonian mine tailings, which have been covered but else left undisturbed, are ideally suited to study changes in uranium speciation over timescales of decades. We investigated the major uranium species in two samples from buried mine tailings using a combination of Synchrotron-based microfocus-techniques ({mu}-XRF, {mu}-XRD with micrometer resolution), bulk EXAFS spectroscopy, and chemical extractions. In sample F1 (5 m depth, oxic, pH 8, U = 440 mg/kg, high Ca, S, Pb, Cu, Zn concentrations), uranium is diffusely distributed among aggregates of layer silicates (muscovite, illite and kaolinite). The chemical extractions and EXAFS results confirm that uranium is sorbed to these minerals, but is not incorporated into their crystal structure. Sorption is also in line with the high pH and low carbonate concentrations in pore water. In sample F3 (12 m depth, oxic, pH 4, U = 430 mg/kg), the combination of {mu}-XRF and {mu}-XRD enabled us to identify several U(IV) and U(VI) containing minerals like coffinite, uraninite, uranyl hydroxide, and vanuralite. Only a minor part of U is sorbed to layer silicates as confirmed by chemical extractions and EXAFS spectroscopy. At smaller depth (F1, 5 m), sulfuric acid from the ore extraction procedure was completely neutralized by the construction waste used as cover material, resulting in precipitation of jarosite and gypsum. Even 30 years after the ore extraction, uranium remains highly soluble. At greater depth (F3, 12 m), the low pH from ore extraction was conserved. The presence of U(IV) minerals suggest either precipitation of secondary (IV) minerals due to microbial redox activity, or incomplete dissolution of primary (IV) minerals due to ore processing inefficiency of these older sediments. The U(IV) minerals were recalcitrant during chemical

  13. Uranium speciation in 30-year old Freital mine tailings: an EXAFS, μ-XRD, and μ-XRF study

    International Nuclear Information System (INIS)

    Scheinost, A.C.; Hennig, C.; Somogyi, A.; Martinez-Criado, G.; Knappik, R.

    2005-01-01

    Full text of publication follows: Risk assessments of actinide-contaminated soils and sediments require detailed knowledge of actinide speciation and its long-term kinetics. Former Saxonian mine tailings, which have been covered but else left undisturbed, are ideally suited to study changes in uranium speciation over timescales of decades. We investigated the major uranium species in two samples from buried mine tailings using a combination of Synchrotron-based microfocus-techniques (μ-XRF, μ-XRD with micrometer resolution), bulk EXAFS spectroscopy, and chemical extractions. In sample F1 (5 m depth, oxic, pH 8, U = 440 mg/kg, high Ca, S, Pb, Cu, Zn concentrations), uranium is diffusely distributed among aggregates of layer silicates (muscovite, illite and kaolinite). The chemical extractions and EXAFS results confirm that uranium is sorbed to these minerals, but is not incorporated into their crystal structure. Sorption is also in line with the high pH and low carbonate concentrations in pore water. In sample F3 (12 m depth, oxic, pH 4, U = 430 mg/kg), the combination of μ-XRF and μ-XRD enabled us to identify several U(IV) and U(VI) containing minerals like coffinite, uraninite, uranyl hydroxide, and vanuralite. Only a minor part of U is sorbed to layer silicates as confirmed by chemical extractions and EXAFS spectroscopy. At smaller depth (F1, 5 m), sulfuric acid from the ore extraction procedure was completely neutralized by the construction waste used as cover material, resulting in precipitation of jarosite and gypsum. Even 30 years after the ore extraction, uranium remains highly soluble. At greater depth (F3, 12 m), the low pH from ore extraction was conserved. The presence of U(IV) minerals suggest either precipitation of secondary (IV) minerals due to microbial redox activity, or incomplete dissolution of primary (IV) minerals due to ore processing inefficiency of these older sediments. The U(IV) minerals were recalcitrant during chemical extractions

  14. Carbon K-edge X-ray absorption spectroscopy and time-dependent density functional theory examination of metal-carbon bonding in metallocene dichlorides.

    Science.gov (United States)

    Minasian, Stefan G; Keith, Jason M; Batista, Enrique R; Boland, Kevin S; Kozimor, Stosh A; Martin, Richard L; Shuh, David K; Tyliszczak, Tolek; Vernon, Louis J

    2013-10-02

    Metal-carbon covalence in (C5H5)2MCl2 (M = Ti, Zr, Hf) has been evaluated using carbon K-edge X-ray absorption spectroscopy (XAS) as well as ground-state and time-dependent hybrid density functional theory (DFT and TDDFT). Differences in orbital mixing were determined experimentally using transmission XAS of thin crystalline material with a scanning transmission X-ray microscope (STXM). Moving down the periodic table (Ti to Hf) has a marked effect on the experimental transition intensities associated with the low-lying antibonding 1a1* and 1b2* orbitals. The peak intensities, which are directly related to the M-(C5H5) orbital mixing coefficients, increase from 0.08(1) and 0.26(3) for (C5H5)2TiCl2 to 0.31(3) and 0.75(8) for (C5H5)2ZrCl2, and finally to 0.54(5) and 0.83(8) for (C5H5)2HfCl2. The experimental trend toward increased peak intensity for transitions associated with 1a1* and 1b2* orbitals agrees with the calculated TDDFT oscillator strengths [0.10 and 0.21, (C5H5)2TiCl2; 0.21 and 0.73, (C5H5)2ZrCl2; 0.35 and 0.69, (C5H5)2HfCl2] and with the amount of C 2p character obtained from the Mulliken populations for the antibonding 1a1* and 1b2* orbitals [8.2 and 23.4%, (C5H5)2TiCl2; 15.3 and 39.7%, (C5H5)2ZrCl2; 20.1 and 50.9%, (C5H5)2HfCl2]. The excellent agreement between experiment, theory, and recent Cl K-edge XAS and DFT measurements shows that C 2p orbital mixing is enhanced for the diffuse Hf (5d) and Zr (4d) atomic orbitals in relation to the more localized Ti (3d) orbitals. These results provide insight into how changes in M-Cl orbital mixing within the metallocene wedge are correlated with periodic trends in covalent bonding between the metal and the cyclopentadienide ancillary ligands.

  15. X-ray absorption spectroscopic studies on novel microporous copper containing catalytic systems

    International Nuclear Information System (INIS)

    Bhargava, Suresh K.; Akolekar, Deepak B.; Foran, Garry

    2006-01-01

    Novel copper metal modified microporous aluminosilicate and aluminophosphate catalysts with the high phase purity were synthesized and characterized. CuK-edge XAS measurements were carried out over a series of copper containing SAPO-34 and ZSM-5 catalysts. EXAFS technique was used to obtain specific climacteric information related to the copper atomic distances, coordination and near neighbour environments. EXAFS studies indicated the presence of different of Cu species on ZSM-5/SAPO34 catalysts

  16. Exafs studies of coprecipitation and adsorption reactions of Tc

    Energy Technology Data Exchange (ETDEWEB)

    Bunker, D.J.; Jones, M.J.; Livens, F.R.; Collison, D. [Manchester Univ. (United Kingdom). Dept. of Chemistry; Pattrick, R.A.D. [Manchester Univ., Dept. of Earth Sciences (United Kingdom); Charnock, J.M. [CLRC Daresbury Laboratoire, Warrington Cheshire (United Kingdom)

    2000-07-01

    Adsorption and coprecipitation reactions may be a simple way of removing [TcO{sub 4}]{sup -} from aqueous solution. The effectiveness of a range of potential adsorbents and precipitants has been evaluated and some are capable of near quantitative (>98%) removal of [TcO{sub 4}){sup -} from solution. X-ray absorption near edge structure (XANES) has been used to determine Tc oxidation states and extended X-ray absorption fine structure spectroscopy (EXAFS) has been used to identify the local environment of Tc. The absorption edge position has been determined, using [PPh{sub 4}][TcO{sub 4}], TcS{sub 2} and Tc{sub 2}S{sub 7} as model compounds, and is diagnostic of Tc oxidation state. In a series of experiments investigating FeS coprecipitation, Tc was reduced to oxidation state (IV) and its local environment resembled that in TcO{sub 2} (6 O atoms at approximately 2.0 Angstrom). (authors)

  17. EXAFS and XANES analysis of oxides at the nanoscale

    Directory of Open Access Journals (Sweden)

    Alexei Kuzmin

    2014-11-01

    Full Text Available Worldwide research activity at the nanoscale is triggering the appearance of new, and frequently surprising, materials properties in which the increasing importance of surface and interface effects plays a fundamental role. This opens further possibilities in the development of new multifunctional materials with tuned physical properties that do not arise together at the bulk scale. Unfortunately, the standard methods currently available for solving the atomic structure of bulk crystals fail for nanomaterials due to nanoscale effects (very small crystallite sizes, large surface-to-volume ratio, near-surface relaxation, local lattice distortions etc.. As a consequence, a critical reexamination of the available local-structure characterization methods is needed. This work discusses the real possibilities and limits of X-ray absorption spectroscopy (XAS analysis at the nanoscale. To this end, the present state of the art for the interpretation of extended X-ray absorption fine structure (EXAFS is described, including an advanced approach based on the use of classical molecular dynamics and its application to nickel oxide nanoparticles. The limits and possibilities of X-ray absorption near-edge spectroscopy (XANES to determine several effects associated with the nanocrystalline nature of materials are discussed in connection with the development of ZnO-based dilute magnetic semiconductors (DMSs and iron oxide nanoparticles.

  18. First-Principles Fe L 2,3 -Edge and O K-Edge XANES and XMCD Spectra for Iron Oxides

    Energy Technology Data Exchange (ETDEWEB)

    Sassi, Michel [Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Pearce, Carolyn I. [Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Bagus, Paul S. [Department; Arenholz, Elke [Advanced; Rosso, Kevin M. [Pacific Northwest National Laboratory, Richland, Washington 99352, United States

    2017-10-02

    X-ray absorption near-edge structure (XANES) and X-ray magnetic circular dichroism (XMCD) spectroscopies are tools in widespread use for providing detailed local atomic structure, oxidation state, and magnetic structure information for materials and organometallic complexes. The analysis of these spectra for transition-metal L-edges is routinely performed on the basis of ligand-field multiplet theory because one- and two-particle mean-field ab initio methods typically cannot describe the multiplet structure. Here we show that multireference configuration interaction (MRCI) calculations can satisfactorily reproduce measured XANES spectra for a range of complex iron oxide materials including hematite and magnetite. MRCI Fe L2,3-edge XANES and XMCD spectra of Fe(II)O6, Fe(III)O6, and Fe(III)O4 in magnetite are found to be in very good qualitative agreement with experiment and multiplet calculations. Point-charge embedding and small distortions of the first-shell oxygen ligands have only small effects. Oxygen K-edge XANES/XMCD spectra for magnetite investigated by a real-space Green’s function approach complete the very good qualitative agreement with experiment. Material-specific differences in local coordination and site symmetry are well reproduced, making the approach useful for assigning spectral features to specific oxidation states and coordination environments.

  19. Evolution of phosphorus complexation and mineralogy during (hydro)thermal treatments of activated and anaerobically digested sludge: Insights from sequential extraction and P K-edge XANES.

    Science.gov (United States)

    Huang, Rixiang; Tang, Yuanzhi

    2016-09-01

    (Hydro)thermal treatments of sewage sludge is a promising option that can simultaneously target safe waste disposal, energy recovery, and nutrient recovery/recycling. The speciation of phosphorus (P) in sludge is of great relevance to P reclamation/recycling and soil application of sludge-derived products, thus it is critical to understand the effects of different treatment techniques and conditions on P speciation. This study systematically characterized P speciation (i.e. complexation and mineral forms) in chars derived from pyrolysis and hydrothermal carbonization (HTC) of municipal sewage sludges. Combined sequential extraction and P K-edge X-ray absorption near edge structure (XANES) spectroscopy analysis revealed the dependence of P transformation on treatment conditions and metal composition in the feedstocks. Pyrolysis of sludges decreased the relative abundance of phytic acid while increased the abundance of Al-associated P. HTC thoroughly homogenized and exposed P for interaction with various metals/minerals, with the final P speciation closely related to the composition/speciation of metals and their affinities to P. Results from this study revealed the mechanisms of P transformation during (hydro)thermal treatments of sewage sludges, and might be applicable to other biosolids. It also provided fundamental knowledge basis for the design and selection of waste management strategies for better P (re)cycling and reclamation. Copyright © 2016 Elsevier Ltd. All rights reserved.

  20. Hydrogen bonding interaction of small acetaldehyde clusters studied with core-electron excitation spectroscopy in the oxygen K-edge region

    Science.gov (United States)

    Tabayashi, K.; Chohda, M.; Yamanaka, T.; Tsutsumi, Y.; Takahashi, O.; Yoshida, H.; Taniguchi, M.

    2010-06-01

    In order to examine inner-shell electron excitation spectra of molecular clusters with strong multipole interactions, excitation spectra and time-of-flight (TOF) fragment-mass spectra of small acetaldehyde (AA) clusters have been studied under the beam conditions. The TOF spectra at the oxygen K-edge region showed an intense growth of the protonated clusters, MnH+ (M=CH3CHO) in the cluster beams. "cluster-specific" excitation spectra could be generated by monitoring partial-ion-yields of the protonated clusters. The most intense band of O1s→π*CO was found to shift to a higher energy by 0.15 eV relative to the monomer band upon clusterization. X-ray absorption spectra (XAS) were also calculated for the representative dimer configurations using a computer modelling program based on the density functional theory. The XAS prediction for the most stable (non-planar) configuration was found to give a close comparison with the cluster-band shift observed. The band shift was interpreted as being due to the HOMO-LUMO interaction within the complex where a contribution of vibrationally blue-shifting hydrogen bonding could be identified.

  1. Organometallic model complexes elucidate the active gallium species in alkane dehydrogenation catalysts based on ligand effects in Ga K-edge XANES

    Energy Technology Data Exchange (ETDEWEB)

    Getsoian, Andrew “Bean”; Das, Ujjal; Camacho-Bunquin, Jeffrey; Zhang, Guanghui; Gallagher, James R.; Hu, Bo; Cheah, Singfoong; Schaidle, Joshua A.; Ruddy, Daniel A.; Hensley, Jesse E.; Krause, Theodore R.; Curtiss, Larry A.; Miller, Jeffrey T.; Hock, Adam S.

    2016-01-01

    Gallium-modified zeolites are known catalysts for the dehydrogenation of alkanes, reactivity that finds industrial application in the aromatization of light alkanes by Ga-ZSM5. While the role of gallium cations in alkane activation is well known, the oxidation state and coordination environment of gallium under reaction conditions has been the subject of debate. Edge shifts in Ga K-edge XANES spectra acquired under reaction conditions have long been interpreted as evidence for reduction of Ga(III) to Ga(I). However, a change in oxidation state is not the only factor that can give rise to a change in the XANES spectrum. In order to better understand the XANES spectra of working catalysts, we have synthesized a series of molecular model compounds and grafted surface organometallic Ga species and compared their XANES spectra to those of gallium-based catalysts acquired under reducing conditions. We demonstrate that changes in the identity and number of gallium nearest neighbors can give rise to changes in XANES spectra similar to those attributed in literature to changes in oxidation state. Specifically, spectral features previously attributed to Ga(I) may be equally well interpreted as evidence for low-coordinate Ga(III) alkyl or hydride species. These findings apply both to gallium-impregnated zeolite catalysts and to silica-supported single site gallium catalysts, the latter of which is found to be active and selective for dehydrogenation of propane and hydrogenation of propylene.

  2. X-ray absorption study at the Mg and O K edges of ultrathin MgO epilayers on Ag(001)

    International Nuclear Information System (INIS)

    Luches, P.; D'Addato, S.; Valeri, S.; Groppo, E.; Prestipino, C.; Lamberti, C.; Boscherini, F.

    2004-01-01

    We determined the local atomic structure of MgO epilayers on Ag(001) by means of polarization-dependent x-ray absorption spectroscopy measurements at the Mg and O K edges. A quantitative analysis of the data in the extended energy range has been performed using multiple scattering simulations. We found that, even in the ultrathin limit, the local structure of the films is rocksalt and we obtained a quantitative evaluation of the average in-plane and out-of-plane film strain at the different thicknesses investigated. An in-plane compressive strain, due to lattice mismatch with the Ag substrate, is clearly present for the 3 ML film. The out-of-plane lattice constant is found to be expanded, in agreement with the expected behavior for a tetragonal distortion of the unit cell. This growth-induced strain is gradually released with increasing thickness and it is almost completely relaxed at 20 ML. Any significant intermixing with the Ag substrate can be ruled out. An expansion of the interplanar distance at the MgO-Ag interface is detected and its sign and magnitude are found to be in agreement with recent ab initio simulations. This work provides previously unavailable input for modeling the physical properties of the system and supports the hypothesis that the different electronic properties of MgO films on Ag(001) are not related to structural or compositional differences at the ultrathin limit

  3. Surface structure of alpha-Fe sub 2 O sub 3 nanocrystal observed by O K-edge X-ray absorption spectroscopy

    CERN Document Server

    Zhang, J; Ibrahim, K; Abbas, M I; Ju, X

    2003-01-01

    X-ray absorption near edge structure (XANES) spectra is used as a probe of surface structure of alpha-Fe sub 2 O sub 3 nanocrystal, prepared by sol-gel method. We present O K-edge XANES of alpha-Fe sub 2 O sub 3 in nanocrystal and bulk by total electron yield at the photoemission station of Beijing Synchrotron Radiation Facility. The spectrum of alpha-Fe sub 2 O sub 3 shows a splitting of the pre-edge structure, which is interpreted as two subsets of Fe 3d t sub 2 sub g and e sub g orbitals in oxygen octahedral (O sub h) crystal field, and is also sensitive to long-range order effects. However, no distinguishable splitting of the pre-edge peak of nanocrystal alpha-Fe sub 2 O sub 3 is observed. This suggests that there exists the distorted octahedral coordination around Fe sites and also the long-range disorder due to the surface as compared with bulk alpha-Fe sub 2 O sub 3.

  4. Redox Reaction in Silicate Melts Monitored by ''Static'' In-Situ Fe K-Edge XANES up to 1180 deg. C

    International Nuclear Information System (INIS)

    Wilke, Max; Partzsch, Georg M.; Welter, Edmund; Farges, Francois

    2007-01-01

    A new experimental setup to measure in-situ kinetics of redox reactions in silicate melts is presented. To study the progress of the Fe-redox reaction, the variation of the signal is recorded at an energy, where the difference between the spectra of the oxidized and reduced Fe in the melt is largest (''static XANES''). To control the redox conditions, the gas atmosphere could be changed between to types of gases using computer-controlled valves (N2:H2 and air, respectively). In this way, a number of reduction/oxidation cycles can be monitored in-situ and continuously. Applied at the Fe K-edge in molten silicates, we obtained a set of high quality data, which includes the very first steps of the redox reaction. An Avrami-type equation is used to investigate rate-controlling parameters for the iron oxidation/reduction kinetics for two melts (basaltic and Na trisilicate) for temperatures up to 1180 deg. C

  5. UV-Photochemistry of the Disulfide Bond: Evolution of Early Photoproducts from Picosecond X-ray Absorption Spectroscopy at the Sulfur K-Edge.

    Science.gov (United States)

    Ochmann, Miguel; Hussain, Abid; von Ahnen, Inga; Cordones, Amy A; Hong, Kiryong; Lee, Jae Hyuk; Ma, Rory; Adamczyk, Katrin; Kim, Tae Kyu; Schoenlein, Robert W; Vendrell, Oriol; Huse, Nils

    2018-05-30

    We have investigated dimethyl disulfide as the basic moiety for understanding the photochemistry of disulfide bonds, which are central to a broad range of biochemical processes. Picosecond time-resolved X-ray absorption spectroscopy at the sulfur K-edge provides unique element-specific insight into the photochemistry of the disulfide bond initiated by 267 nm femtosecond pulses. We observe a broad but distinct transient induced absorption spectrum which recovers on at least two time scales in the nanosecond range. We employed RASSCF electronic structure calculations to simulate the sulfur-1s transitions of multiple possible chemical species, and identified the methylthiyl and methylperthiyl radicals as the primary reaction products. In addition, we identify disulfur and the CH 2 S thione as the secondary reaction products of the perthiyl radical that are most likely to explain the observed spectral and kinetic signatures of our experiment. Our study underscores the importance of elemental specificity and the potential of time-resolved X-ray spectroscopy to identify short-lived reaction products in complex reaction schemes that underlie the rich photochemistry of disulfide systems.

  6. Influence of 300°C thermal conversion of Fe-Ce hydrous oxides prepared by hydrothermal precipitation on the adsorptive performance of five anions: Insights from EXAFS/XANES, XRD and FTIR (companion paper)

    KAUST Repository

    Chubar, Natalia; Gerda, Vasyl; Banerjee, Dipanjan

    2016-01-01

    In this work, we report atomic-scale reconstruction processes in Fe-Ce oxide-based composites (hydrothermally precipitated at Fe-to-Ce dosage ratios of 1:0, 2:1, 1:1, 1:2, and 0:1), upon treatment at 300 °C. The structural changes are correlated with the adsorptive removal of arsenate, phosphate, fluoride, bromide, and bromate. The presence of the carbonate-based Ce-component and surface sulfate in precursor samples creates favorable conditions for phase transformation, resulting in the formation of novel (unknown) layered compounds of Fe and Ce. These compounds are of the layered double hydroxide type, with sulfate in the interlayer space. In spite of general awareness of the importance of surface area in adsorptive removal, the increase in surface area upon thermal treatment did not increase adsorption of the studied anions. However, EXAFS simulations and the adsorption tests provided evidence of regularities between local structures of Fe in composites obtained at 80 and 300 °C and adsorption performance of most studied anions. The best adsorption of tetrahedral anions was demonstrated by samples whose simulated outer Fe shells resulted from oscillations from both O and Fe atoms. In contrast, the loss of extended x-ray absorption fine structure was correlated with the decrease of adsorptive removal. Both Fe K-edge and Ce L3 -edge EXAFS suggested the formation of solid solutions. For the first time, the utilization of extended x-ray absorption fine structure is suggested as a methodological approach (first expressed in the companion paper) to estimate the surface reactivity of inorganic materials intended for use as anion exchange adsorbents.

  7. Influence of 300°C thermal conversion of Fe-Ce hydrous oxides prepared by hydrothermal precipitation on the adsorptive performance of five anions: Insights from EXAFS/XANES, XRD and FTIR (companion paper)

    KAUST Repository

    Chubar, Natalia

    2016-12-07

    In this work, we report atomic-scale reconstruction processes in Fe-Ce oxide-based composites (hydrothermally precipitated at Fe-to-Ce dosage ratios of 1:0, 2:1, 1:1, 1:2, and 0:1), upon treatment at 300 °C. The structural changes are correlated with the adsorptive removal of arsenate, phosphate, fluoride, bromide, and bromate. The presence of the carbonate-based Ce-component and surface sulfate in precursor samples creates favorable conditions for phase transformation, resulting in the formation of novel (unknown) layered compounds of Fe and Ce. These compounds are of the layered double hydroxide type, with sulfate in the interlayer space. In spite of general awareness of the importance of surface area in adsorptive removal, the increase in surface area upon thermal treatment did not increase adsorption of the studied anions. However, EXAFS simulations and the adsorption tests provided evidence of regularities between local structures of Fe in composites obtained at 80 and 300 °C and adsorption performance of most studied anions. The best adsorption of tetrahedral anions was demonstrated by samples whose simulated outer Fe shells resulted from oscillations from both O and Fe atoms. In contrast, the loss of extended x-ray absorption fine structure was correlated with the decrease of adsorptive removal. Both Fe K-edge and Ce L3 -edge EXAFS suggested the formation of solid solutions. For the first time, the utilization of extended x-ray absorption fine structure is suggested as a methodological approach (first expressed in the companion paper) to estimate the surface reactivity of inorganic materials intended for use as anion exchange adsorbents.

  8. Fischer-Tropsch synthesis: study of the promotion of Pt on the reduction property of Co/Al2O3 catalysts by in situ EXAFS of Co K and Pt LIII edges and XPS

    International Nuclear Information System (INIS)

    Jacobs, G.; Chaney, J.A.; Patterson, P.M.; Das, T.K.; Maillot, J.C.; Davis, B.H.

    2004-01-01

    The addition of platinum metal to cobalt/alumina-based Fischer-Tropsch synthesis (FTS) catalysts increases both the reduction rate and, consequently, the density of active cobalt sites. Platinum also lowers the temperature of the two-step conversion of cobalt oxide to cobalt metal observed in temperature programmed reduction (TPR) as Co 3 O 4 to CoO and CoO to Co 0 . The interaction of the alumina support with cobalt oxide ultimately determines the active site density of the catalyst surface. This interaction can be controlled by varying the cobalt loading and dispersion, selecting supports with differing surface areas or pore sizes, or changing the noble metal promoter. However, the active site density is observed to depend primarily on the cluster size and extent of reduction, and there is a direct relationship between site density and FTS rate. In this work, in situ extended X-ray absorption fine structure (EXAFS) at the L III edge of Pt was used to show that isolated Pt atoms interact with supported cobalt clusters without forming observable Pt-Pt bonds. K-edge EXAFS was also used to verify that the cobalt cluster size increases slightly for those systems with Pt promotion. X-ray absorption near-edge spectroscopy (XANES) was used to examine the remaining cobalt clusters after the first stage of TPR, and it revealed that the species were almost entirely cobalt (II) oxide. After the second stage of TPR to form cobalt metal, a residual oxide persists in the sample, and this oxide has been identified as cobalt (II) aluminate using X-ray photoelectron spectroscopy (XPS). Sequential in situ reduction of promoted and unpromoted systems was also monitored through XPS, and Pt was seen to increase the extent of cobalt reduction by a factor of two. (orig.)

  9. Imaging Taurine in the Central Nervous System Using Chemically Specific X-ray Fluorescence Imaging at the Sulfur K-Edge

    Energy Technology Data Exchange (ETDEWEB)

    Hackett, Mark J.; Paterson, Phyllis G.; Pickering, Ingrid J.; George, Graham N. (Curtin U.); (Saskatchewan)

    2016-11-15

    A method to image taurine distributions within the central nervous system and other organs has long been sought. Since taurine is small and mobile, it cannot be chemically “tagged” and imaged using conventional immuno-histochemistry methods. Combining numerous indirect measurements, taurine is known to play critical roles in brain function during health and disease and is proposed to act as a neuro-osmolyte, neuro-modulator, and possibly a neuro-transmitter. Elucidation of taurine’s neurochemical roles and importance would be substantially enhanced by a direct method to visualize alterations, due to physiological and pathological events in the brain, in the local concentration of taurine at or near cellular spatial resolution in vivo or in situ in tissue sections. We thus have developed chemically specific X-ray fluorescence imaging (XFI) at the sulfur K-edge to image the sulfonate group in taurine in situ in ex vivo tissue sections. To our knowledge, this represents the first undistorted imaging of taurine distribution in brain at 20 μm resolution. We report quantitative technique validation by imaging taurine in the cerebellum and hippocampus regions of the rat brain. Further, we apply the technique to image taurine loss from the vulnerable CA1 (cornus ammonis 1) sector of the rat hippocampus following global brain ischemia. The location-specific loss of taurine from CA1 but not CA3 neurons following ischemia reveals osmotic stress may be a key factor in delayed neurodegeneration after a cerebral ischemic insult and highlights the significant potential of chemically specific XFI to study the role of taurine in brain disease.

  10. X-ray absorption near edge spectroscopy at the Mn K-edge in highly homogeneous GaMnN diluted magnetic semiconductors

    Energy Technology Data Exchange (ETDEWEB)

    Sancho-Juan, O.; Cantarero, A.; Garro, N.; Cros, A. [Materials Science Institute, University of Valencia, PO Box 22085, 46071 Valencia (Spain); Martinez-Criado, G.; Salome, M.; Susini, J. [ESRF, Polygone Scientifique Louis Neel, 6 rue Jules Horowitz, 38000 Grenoble (France); Olguin, D. [Dept. de Fisica, CINVESTAV-IPN, 07300 Mexico D.F. (Mexico); Dhar, S.; Ploog, K. [Paul Drude Institute, Hausvogteiplatz 5-7, 10117 Berlin (Germany)

    2006-06-15

    We have studied by X-ray absorption spectroscopy the local environment of Mn in highly homogeneous Ga{sub 1-x}Mn{sub x}N (0.06K-edges. In this report, we focus our attention to the X-ray absorption near edge spectroscopy (XANES) results. The comparison of the XANES spectra corresponding to the Ga and Mn edges indicates that Mn is substitutional to Ga in all samples studied. The XANES spectra measured at the Mn absorption edge shows in the near-edge region a double peak and a shoulder below the absorption edge and the main absorption peak after the edge, separated around 15 eV above the pre-edge structure. We have compared the position of the edge with that of MnO (Mn{sup 2+}) and Mn{sub 2}O{sub 3} (Mn{sup 3+}). All samples studied present the same Mn oxidation state, 2{sup +}. In order to interprete the near-edge structure, we have performed ab initio calculations with a 2 x 2 x 1supercell ({proportional_to}6% Mn) using the full potential linear augmented plane wave method as implemented in the Wien2k code. The calculations show the appearance of Mn anti-bonding t{sub 2g} bands, which are responsible for the pre-edge absorption. The shoulder and main absorption peaks are due to transitions from the valence band 1s-states of Mn to the p-contributions of the conduction bands. (copyright 2006 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  11. Atomic resolution chemical bond analysis of oxygen in La2CuO4

    Science.gov (United States)

    Haruta, M.; Nagai, T.; Lugg, N. R.; Neish, M. J.; Nagao, M.; Kurashima, K.; Allen, L. J.; Mizoguchi, T.; Kimoto, K.

    2013-08-01

    The distorted CuO6 octahedron in La2CuO4 was studied using aberration-corrected scanning transmission electron microscopy at atomic resolution. The near-edge structure in the oxygen K-edge electron energy-loss spectrum was recorded as a function of the position of the electron probe. After background subtraction, the measured spectrum image was processed using a recently developed inversion process to remove the mixing of signals on the atomic columns due to elastic and thermal scattering. The spectra were then compared with first-principles band structure calculations based on the local-density approximation plus on-site Coulomb repulsion (LDA + U) approach. In this article, we describe in detail not only anisotropic chemical bonding of the oxygen 2p state with the Cu 3d state but also with the Cu 4p and La 5d/4f states. Furthermore, it was found that buckling of the CuO2 plane was also detectable at the atomic resolution oxygen K-edge. Lastly, it was found that the effects of core-hole in the O K-edge were strongly dependent on the nature of the local chemical bonding, in particular, whether it is ionic or covalent.

  12. Effect of atomic vibrations in XANES: polarization-dependent damping of the fine structure at the Cu K-edge of (creat).sub.2./sub.CuCl.sub.4./sub.

    Czech Academy of Sciences Publication Activity Database

    Šipr, Ondřej; Vackář, Jiří; Kuzmin, A.

    2016-01-01

    Roč. 23, č. 6 (2016), s. 1433-1439 ISSN 1600-5775 R&D Projects: GA MŠk LD15097 Institutional support: RVO:68378271 Keywords : XANES * vibrations * multiple-scattering formalism Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.011, year: 2016

  13. X-ray absorption edges and E.X.A.F.S.: application to the study of electronic and atomic structures of titanium and vanadium carbides TiC(1-x) and VC(1-x)

    International Nuclear Information System (INIS)

    Moisy-Maurice, Virginie.

    1980-09-01

    This text presents a systematic study of the X-ray absorption fine structures evolution, at the K edge of titanium, with vacancy concentration in TiC(1-x). The absorption edges are situated in the 50 eV following the coefficient discontinuity: from the evaluation of their general aspect, it is deduced that the positive charge of titanium atoms decreases when vacancy concentration increases in TiC(1-x). This allowed us to determine the best band structure calculation model. The interpretation of EXAFS spectra (modulation of the absorption coefficient until 1500 eV above the edge) gives indications about the local atomic structure. Here, the contraction of the average titanium-carbon interatomic distances compared to the distances between crystallographic sites is of the order of the experimental resolution 0.02 A for Ti C(0.8). The study of the damping of the spectra in terms of Debye-Waller factors gave an evaluation of the relative static atomic mean square displacements between first neighbours. Last, it has been established that the disordering of vacancies in the order-disorder transition of V 8 C 7 is an atomic scale phenomenon [fr

  14. Characterisation of zinc in slags originated from a contaminated sediment by coupling /μ-PIXE, /μ-RBS, /μ-EXAFS and powder EXAFS spectroscopy

    Science.gov (United States)

    Isaure, M. P.; Laboudigue, A.; Manceau, A.; Sarret, G.; Tiffreau, C.; Trocellier, P.

    2001-07-01

    Depositing dredged sediments on soils is usual but it is a hazardous practice for the local environment when these sediments are polluted by heavy metals. This chemical hazard can be assessed by determining the speciation of metals. In this study, slags highly polluted with Zn and originated from a contaminated dredged sediment were investigated. Zn speciation was studied by laterally resolved techniques such as μ-particle induced X-ray emission (μ-PIXE), μ-Rutherford backscattering spectrometry (μ-RBS), μ-extended X-ray absorption fine structure (μ-EXAFS), and bulk analyses such as powder EXAFS spectroscopy. μ-PIXE and μ-RBS results showed that high concentrations of Zn were associated with S in localised areas at the surface of the slags while moderate amounts of Zn were mainly associated with Fe in the matrix. EXAFS results allowed to identify ZnS and Zn sorbed on ferrihydrite (5Fe 2O 3·9H 2O), proxy for iron oxy-hydroxides, as the main Zn-bearing phases. The occurrence of this Zn-iron oxy-hydroxide is interpreted as a mobilisation of Zn released from ZnS oxidation.

  15. Characterisation of zinc in slags originated from a contaminated sediment by coupling μ-PIXE, μ-RBS, μ-EXAFS and powder EXAFS spectroscopy

    International Nuclear Information System (INIS)

    Isaure, M.P.; Laboudigue, A.; Manceau, A.; Sarret, G.; Tiffreau, C.; Trocellier, P.

    2001-01-01

    Depositing dredged sediments on soils is usual but it is a hazardous practice for the local environment when these sediments are polluted by heavy metals. This chemical hazard can be assessed by determining the speciation of metals. In this study, slags highly polluted with Zn and originated from a contaminated dredged sediment were investigated. Zn speciation was studied by laterally resolved techniques such as μ-particle induced X-ray emission (μ-PIXE), μ-Rutherford backscattering spectrometry (μ-RBS), μ-extended X-ray absorption fine structure (μ-EXAFS), and bulk analyses such as powder EXAFS spectroscopy. μ-PIXE and μ-RBS results showed that high concentrations of Zn were associated with S in localised areas at the surface of the slags while moderate amounts of Zn were mainly associated with Fe in the matrix. EXAFS results allowed to identify ZnS and Zn sorbed on ferrihydrite (5Fe 2 O 3 ·9H 2 O), proxy for iron oxy-hydroxides, as the main Zn-bearing phases. The occurrence of this Zn-iron oxy-hydroxide is interpreted as a mobilisation of Zn released from ZnS oxidation

  16. Ru-core/Cu-shell bimetallic nanoparticles with controlled size formed in one-pot synthesis.

    Science.gov (United States)

    Helgadottir, I; Freychet, G; Arquillière, P; Maret, M; Gergaud, P; Haumesser, P H; Santini, C C

    2014-12-21

    Suspensions of bimetallic nanoparticles (NPs) of Ru and Cu have been synthesized by simultaneous decomposition of two organometallic compounds in an ionic liquid. These suspensions have been characterized by Anomalous Small-Angle X-ray Scattering (ASAXS) at energies slightly below the Ru K-edge. It is found that the NPs adopt a Ru-core, a Cu-shell structure, with a constant Ru core diameter of 1.9 nm for all Ru : Cu compositions, while the Cu shell thickness increases with Cu content up to 0.9 nm. The formation of RuCuNPs thus proceeds through rapid decomposition of the Ru precursor into RuNPs of constant size followed by the reaction of the Cu precursor and agglomeration as a Cu shell. Thus, the different decomposition kinetics of precursors make possible the elaboration of core-shell NPs composed of two metals without chemical affinity.

  17. Determining metal ion distributions using resonant scattering at very high-energy K-edges: Bi/Pb in Pb{sub 5}Bi{sub 6}Se{sub 14}

    Energy Technology Data Exchange (ETDEWEB)

    Yuegang, Zhang; Lee, P L; Shastri, S D; Deming, Shu [Argonne National Lab., IL (United States). XOR, Advanced Photon Source; Wilkinson, A P [Georgia Inst. of Tech., Atlanta (United States). School of Chemistry and Biochemistry; Duck-Young, Chung; Kanatzidis, M G [Michigan State Univ., East Lansing (United States). Dept. of Chemistry

    2005-06-01

    Powder diffraction data collected at {proportional_to} 86 keV, and just below both the Pb and the Bi K-edges, on an imaging plate detector using synchrotron radiation from the Advanced Photon Source have been used to examine the Pb/Bi distribution over the 11 crystallographically distinct sites in Pb{sub 5}Bi{sub 6}Se{sub 14} [space group P2{sub 1}/m, a=16.0096(2) Aa, b=4.20148(4) Aa, c=21.5689(3) Aa and {beta}=97.537(1){sup 0}]. The scattering factors needed for the analyses were determined both by Kramers- Kronig transformation of absorption spectra and by analyses of diffraction patterns from reference compounds. Even with the relatively low scattering contrast that is available at the K-edges, it was possible to determine the Pb/Bi distribution and probe the presence of cation site vacancies in the material. The current results indicate that resonant scattering measurements at high-energy K-edges are a viable, and perhaps preferable, route to site occupancies when absorption from the sample or sample environment/container is a major barrier to the acquisition of high-quality resonant scattering data at lower-energy edges.

  18. In situ EXAFS study of Ru-containing electrocatalysts of oxygen reduction

    International Nuclear Information System (INIS)

    Malakhov, I.V.; Nikitenko, S.G.; Savinova, E.R.; Kochubey, D.I.; Alonso-Vante, N.

    2000-01-01

    The series of Ru chalcogenide compounds is obtained by varying the nature of the chalcogen with the transition metal (Ru) matrix. The EXAFS technique reveals that the electrocatalytic centre is Ru in a cluster matrix. Furthermore, a reversible change in the structure of the active centre as a function of the applied electrode potential appears

  19. Structural characterization of Am(III) formate complexes. Combining EXAFS spectroscopy with DFT and thermodynamical calculations

    Energy Technology Data Exchange (ETDEWEB)

    Rossberg, Andre [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Molecular Structures; Froehlich, D.R. [Heidelberg Univ. (Germany). Physikalisch-Chemisches Inst.

    2017-06-01

    We used iterative transformation factor analysis (ITFA) in order to isolate the EXAFS spectral contributions of the complexing ligand from a Am(III)/formate pH-series. Thermodynamic calculations were used as constraint for ITFA and for density functional theory (DFT) calculations to identify the coordination mode within the formed complexes.

  20. EXAFS: New tool for study of battery and fuel cell materials

    Science.gov (United States)

    Mcbreen, James; Ogrady, William E.; Pandya, Kaumudi I.

    1987-01-01

    Extended X ray absorption fine structure (EXAFS) is a powerful technique for probing the local atomic structure of battery and fuel cell materials. The major advantages of EXAFS are that both the probe and the signal are X rays and the technique is element selective and applicable to all states of matter. This permits in situ studies of electrodes and determination of the structure of single components in composite electrodes, or even complete cells. EXAFS specifically probes short range order and yields coordination numbers, bond distances, and chemical identity of nearest neighbors. Thus, it is ideal for structural studies of ions in solution and the poorly crystallized materials that are often the active materials or catalysts in batteries and fuel cells. Studies on typical battery and fuel cell components are used to describe the technique and the capability of EXAFS as a structural tool in these applications. Typical experimental and data analysis procedures are outlined. The advantages and limitations of the technique are also briefly discussed.

  1. EXAFS study of Mo2N and Mo nitrides supported on zeolites

    International Nuclear Information System (INIS)

    Liu Zhenlin; Meng Ming; Fu Yilu; Jiang Ming; Hu Tiandou; Xie Yaning; Liu Tao

    2002-01-01

    In the present study, the reaction is applied to prepare molybdenum nitrides with high surface area, and zeolites are used as supports. The EXAFS of the Mo K-absorption edge is measured and the change of coordination environment of Mo atoms before and after the nitridation is revealed

  2. EXAFS, Determination of Short Range Order and Local Structures in Materials

    NARCIS (Netherlands)

    Koningsberger, D.C.; Prins, R.

    1981-01-01

    Extended X-ray Absorption Fine Structure (EXAFS) is a powerful method of determining short range order and local structures in materials using X-ray photons produced by a synchrotron light source, or in-house by a high intensity rotating anode X-ray generator. The technique has provided valuable

  3. EXAFS Studies of Ga Doped Pb1-xMnxTe

    International Nuclear Information System (INIS)

    Radisavljevic, I.; Ivanovic, N.; Novakovic, N.; Romcevic, N.; Mahnke, H.-E.

    2007-01-01

    We have employed the X-Rays Absorption Fine Structure (EXAFS) technique to resolve the local structure of Pb1-xMnxTe (Ga) in order to provide answers on questions concerning the exact positions and charge states of constitutive and impurity atoms, possibilities and features of their ordering and (or) clustering, as well as configurational and thermal disorder in the system

  4. The structural analysis of zinc borate glass by laboratory EXAFS and X-ray diffraction measurements

    International Nuclear Information System (INIS)

    Kajinami, Akihiko; Harada, Yasushi; Inoue, Shinsuke; Deki, Shigehito; Umesaki, Norimasa

    1999-01-01

    The structure of zinc borate glass has been investigated by laboratory EXAFS and X-ray diffraction measurement as preliminary investigations for the detailed study in SPring-8. The zinc borate glass was prepared in the range from 40 to 65 mol% of zinc oxide content. The X-ray diffraction was measured by horizontal θ-θ goniometer with 60 kV and 300 mA output of Mo target. The EXAFS of zinc borate glass was measured by laboratory EXAFS system with 20 kV, 100 mA output of Mo target for the K absorption edge of zinc atom. From the X-ray diffraction and the EXAFS measurements, it is found that the zinc ion is surrounded by four oxygen atoms and formed a tetrahedral structure whose (Zn-O) distance is about 2 A and that the structure is unchanged with the zinc oxide content. The diffraction data show that the neighboring structure of boron atom transforms from BO 4 tetrahedra to BO 3 tetragonal planar structure with increasing of the zinc oxide content. (author)

  5. PySpline: A Modern, Cross-Platform Program for the Processing of Raw Averaged XAS Edge and EXAFS Data

    International Nuclear Information System (INIS)

    Tenderholt, Adam; Hedman, Britt; Hodgson, Keith O.

    2007-01-01

    PySpline is a modern computer program for processing raw averaged XAS and EXAFS data using an intuitive approach which allows the user to see the immediate effect of various processing parameters on the resulting k- and R-space data. The Python scripting language and Qt and Qwt widget libraries were chosen to meet the design requirement that it be cross-platform (i.e. versions for Windows, Mac OS X, and Linux). PySpline supports polynomial pre- and post-edge background subtraction, splining of the EXAFS region with a multi-segment polynomial spline, and Fast Fourier Transform (FFT) of the resulting k3-weighted EXAFS data

  6. Structural studies of Nd1.85Ce0.15CuO4 + Ag superconducting ...

    Indian Academy of Sciences (India)

    Nd1.85Ce0.15CuO4, on its crystal structure and local structural features, using synchrotron X-ray diffraction. (SXRD) and ..... extended X-ray absorption fine structure (EXAFS). ... [1] Zhang and Chongmin 1991 Thesis, University of British.

  7. Universal energy-dispersive EXAFS spectrometer based on SR beam of `Kurchatovskij Institute` and scientific program of investigations; Universal`nyj ehnergodispersionnyj EXAFS-spektrometr v Natsional`nom tsentre sinkhrotronnogo izlucheniya (`Kurchatovskij institut`) i nauchnaya programma issledovanij

    Energy Technology Data Exchange (ETDEWEB)

    Aksenov, V L; Ivanov, I N [Laboratory of Particle Physics, Joint Institute for Nuclear Research, Dubna (Russian Federation); Koval` chuk, M V [Institut Kristallografii, RAN, Moscow (Russian Federation); and others

    1997-12-31

    The scheme of the energy-dispersive EXAFS spectrometer is discussed. The spectrometer will be used for the solid state investigations on the Kurchatov Synchrotron Radiation Source KSRS. The main elements of the universal station are described, including the results of the positive-sensitive X-ray detector testing. The experimental investigations are presented which are supposed to be carried out with this EXAFS spectrometer. (author). 4 refs., 14 figs., 1 tab. Submitted to Poverkhnost`. Rentgenovskie, Sinkhrotronnye i Nejtronnye Issledovaniya.

  8. Effects of Cu over Pd based catalysts supported on silica or niobia

    Directory of Open Access Journals (Sweden)

    Roma M.N.S.C.

    2000-01-01

    Full Text Available Palladium and palladium-copper catalysts supported on silica and niobia were characterized by H2 chemisorption and H2-O2 titration. Systems over silica were also analyzed by transmission electron microscopy and EXAFS. The metallic dispersion decreased from 20% to 7% when the content of Pd was increased from 0.5wt.-% to 3wt.-% in monometallic catalysts. The addition of 3 wt.-% Cu to obtain Pd-Cu catalysts caused a remarkable capacity loss of hydrogen chemisorption. TPR analysis suggested an interaction between the two metals and EXAFS characterization of the catalyst supported on silica confirmed the formation of Pd-Cu alloy. Pd/Nb2O5 catalysts showed turnover numbers higher than those obtained with the Pd/SiO2 systems in the cyclohexane dehydrogenation. However, the bimetallic catalysts showed very low turnover numbers.

  9. Resonant inelastic x-ray scattering on iso-C{sub 2}H{sub 2}Cl{sub 2} around the chlorine K-edge: Structural and dynamical aspects

    Energy Technology Data Exchange (ETDEWEB)

    Kawerk, Elie, E-mail: eliekawerk@hotmail.com, E-mail: ekawerk@units.it [CNRS, UMR 7614, Laboratoire de Chimie Physique-Matière et Rayonnement, F-75005 Paris (France); Sorbonne Universités, UPMC Université Paris 06, UMR 7614, Laboratoire de Chimie Physique-Matière et Rayonnement, F-75005 Paris (France); Laboratoire de Physique Appliquée, Faculté des Sciences II, Université Libanaise, 90656 Jdeidet el Metn, Liban (Libya); Dipartimento di Scienze Chimiche, Università di Trieste, Via L. Giorgieri 1, I-34127 Trieste (Italy); Carniato, Stéphane; Journel, Loïc; Marchenko, Tatiana; Simon, Marc [CNRS, UMR 7614, Laboratoire de Chimie Physique-Matière et Rayonnement, F-75005 Paris (France); Sorbonne Universités, UPMC Université Paris 06, UMR 7614, Laboratoire de Chimie Physique-Matière et Rayonnement, F-75005 Paris (France); Piancastelli, Maria Novella [CNRS, UMR 7614, Laboratoire de Chimie Physique-Matière et Rayonnement, F-75005 Paris (France); Sorbonne Universités, UPMC Université Paris 06, UMR 7614, Laboratoire de Chimie Physique-Matière et Rayonnement, F-75005 Paris (France); Department of Physics and Astronomy, Uppsala University, P.O. Box 516, SE-751 20 Uppsala (Sweden); Žitnik, Matjaž; Bučar, Klemen; Bohnic, Rok [Jožef Stefan Institute, Jamova cesta 39, SI-1000 Ljubljana (Slovenia); and others

    2014-10-14

    We report a theoretical and experimental study of the high resolution resonant K{sub α} X-ray emission lines around the chlorine K-edge in gas phase 1,1-dichloroethylene. With the help of ab initio electronic structure calculations and cross section evaluation, we interpret the lowest lying peak in the X-ray absorption and emission spectra. The behavior of the K{sub α} emission lines with respect to frequency detuning highlights the existence of femtosecond nuclear dynamics on the dissociative Potential Energy Surface of the first K-shell core-excited state.

  10. Evidence of icosahedral short-range order in Zr70Cu30 and Zr70Cu29Pd1 metallic glasses

    DEFF Research Database (Denmark)

    Saksl, K.; Franz, H.; Jovari, P.

    2003-01-01

    Change in local atomic environment during crystallization of Zr-based glassy alloys was studied by extended x-ray absorption fine structure (EXAFS) spectroscopy. The formation of icosahedral quasicrystalline phase followed by crystallization of tetragonal CuZr2 has been observed in the Zr70Cu29Pd1...... glassy alloy during annealing up to 850 K. On the other hand, the binary Zr70Cu30 alloy shows a single glassy to crystalline CuZr2 phase transformation. The local atomic environment of as-quenched Zr70Cu30 alloy is matched to an icosahedral local atomic configuration, which is similar to that of the as......-quenched Zr70Cu29Pd1 alloy and the alloy annealed at 593 K containing icosahedral phase. Considering that the supercooled liquid region appears prior to crystallization in the Zr70Cu30 glassy alloy, the observed results support the theory claiming a strong correlation between the existence of local...

  11. Electronic structure of nanoscale Cu/Pt alloys: A combined X-ray diffraction and X-ray absorption investigations

    International Nuclear Information System (INIS)

    Chen Xing; Chu Wangsheng; Cai Quan; Xia Dingguo; Wu Zhonghua; Wu Ziyu

    2006-01-01

    PVP-protected Cu/Pt clusters were prepared by glycol/water reduction method and characterized with transmission electron microscopy (TEM), X-ray diffraction (XRD) and absorption spectra. TEM and XRD analysis show that the Cu/Pt clusters with different molar ratio have fcc structure with particle size of about 4 nm, while the lattice parameters in these clusters reduce with increasing Cu concentration. From the X-ray absorption near edge structure (XANES) at Cu-K edge and Pt-L 2,3 edge, we demonstrate that the d-electronic states of Cu and Pt are affected by the local environment as a function of Cu/Pt molar ratio. With increasing Cu concentration, Pt loses a fraction of 5d electrons and the hybridization between p- and d-states at Cu sites is enhanced

  12. Electronic structure of nanoscale Cu/Pt alloys: A combined X-ray diffraction and X-ray absorption investigations

    Energy Technology Data Exchange (ETDEWEB)

    Chen Xing [Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, CAS, Beijing (China); Graduate School of the Chinese Academy of Sciences, 100864 Beijing (China); Chu Wangsheng [Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, CAS, Beijing (China); University of Science and Technology of China, Hefei, 230036 (China); Cai Quan [Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, CAS, Beijing (China); Graduate School of the Chinese Academy of Sciences, 100864 Beijing (China); Xia Dingguo [College of Environmental and Energy Engineering, Beijing University of Technology, 100022 Beijing (China); Wu Zhonghua [Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, CAS, Beijing (China); Wu Ziyu [Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, CAS, Beijing (China) and National Center for Nanoscience and Technology (China)]. E-mail: wuzy@ihep.ac.cn

    2006-11-15

    PVP-protected Cu/Pt clusters were prepared by glycol/water reduction method and characterized with transmission electron microscopy (TEM), X-ray diffraction (XRD) and absorption spectra. TEM and XRD analysis show that the Cu/Pt clusters with different molar ratio have fcc structure with particle size of about 4 nm, while the lattice parameters in these clusters reduce with increasing Cu concentration. From the X-ray absorption near edge structure (XANES) at Cu-K edge and Pt-L{sub 2,3} edge, we demonstrate that the d-electronic states of Cu and Pt are affected by the local environment as a function of Cu/Pt molar ratio. With increasing Cu concentration, Pt loses a fraction of 5d electrons and the hybridization between p- and d-states at Cu sites is enhanced.

  13. EXAFS study influence of pH on microscopic structure of zinc

    International Nuclear Information System (INIS)

    Li Xianliang; Chongqing Entry-Exit Inspection and Quarantine Bureau, Chongqing; Pan Gang; Zhu Mengqiang; Chen Hao; Hu Tiandou; Wu Ziyu; Xie Yaning; Du Yonghua

    2004-01-01

    Microscopic local structures of Zn(II) were studied using extended X-ray absorption fine structure (EXAFS) spectroscopy under different pH conditions. When pH 2+ (aq) was coordinated with six water molecules and the average Zn-O distance was measured to be 2.08 Angstrom, which indicated that hydrated Zn 2+ (aq) ions were in octahedral geometry under acid conditions. Under alkaline conditions, Zn 2+ (aq) was coordinated with four water molecules and the average Zn-O distance was measured to be 1.96 Angstrom, which indicated that hydrated Zn 2+ (aq) ions were in tetrahedral geometry. EXAFS results provided detailed information on the form and microscopic structure of hydrated Zn(II) ions under different pH conditions, which were fundamental for understanding the reactivity of Zn(II) in solutions and at particle-water interfaces. (authors)

  14. Commissioning and first results of scanning type EXAFS beamline (BL-09) at INDUS-2 synchrotron source

    Energy Technology Data Exchange (ETDEWEB)

    Poswal, A. K., E-mail: poswalashwini@gmail.com; Agrawal, A., E-mail: poswalashwini@gmail.com; Yadav, A. K., E-mail: poswalashwini@gmail.com; Nayak, C., E-mail: poswalashwini@gmail.com; Basu, S., E-mail: poswalashwini@gmail.com; Bhattachryya, D.; Jha, S. N.; Sahoo, N. K. [Atomic and Molecular Physics Division, Bhabha Atomic Research Centre, Mumbai -400085 (India); Kane, S. R.; Garg, C. K. [Indus Synchrotrons Utilization Division, Raja Ramanna Centre for Advanced Technology, Indore- 452013 (India)

    2014-04-24

    An Energy Scanning X-ray Absorption Fine Structure spectroscopy beamline has recently been installed and commissioned at BL-09 bending magnet port of INDUS-2 synchrotron source, Indore. The beamline uses an UHV compatible fixed exit double crystal monochromator (DCM) with two Si (111) crystals. Two grazing incidence cylindrical mirrors are also used in this beamline; the pre-mirror is used as a collimating mirror while the post mirror is used for vertical focusing and higher harmonic rejection. In this beamline it is possible to carry out EXAFS measurements both in transmission and fluorescence mode on various types of samples, using Ionization chamber detectors and solid state drift detector respectively. In this paper, results from first experiments of the Energy Scanning EXAFS beamline are presented.

  15. A gas microstrip X-ray detector for soft energy fluorescence EXAFS

    CERN Document Server

    Smith, A D; Derbyshire, G E; Duxbury, D M; Lipp, J; Spill, E J; Stephenson, R

    2001-01-01

    Gas microstrip detectors have been previously developed by the particle physics community, where their robustness, compactness and high counting speed have been recognised. These features are particularly attractive to synchrotron radiation use. In this paper, we describe a gas microstrip detector employing multi-element readout and specifically developed for high count rate fluorescence EXAFS at soft X-ray energies below 4 keV.

  16. EXAFS and RDF studies of Ge27S53I20 glass

    International Nuclear Information System (INIS)

    Nasu, H.; Myoren, H.; Makida, S.; Imura, T.; Osaka, Y.

    1988-01-01

    Detailed X-ray diffraction measurements and extended X-ray absorption fine structure (EXAFS) have been applied to Ge 23 S 57 I 20 glass as a typical chalcohalide glass and to GeS 2 glass for comparison, in order to investigate the structure of Ge-S-I glass system. From the derived curves against atomic distance, the formation of Ge-I bonds is evidenced in the glass structure. (author) 4 refs., 2 figs., 1 tab

  17. EXAFS study of the stability of amorphous TbFe thin films

    International Nuclear Information System (INIS)

    Samant, M.G.; Marinero, E.E.; Robinson, C.; Cargill, G.S.

    1989-01-01

    This paper discusses the measurement of the local atomic structure of Fe in Au doped Tb-Fe thin film alloys by the use of EXAFS. The as deposited sample shows structural features which are essentially identical to those of the undoped films. Au additions stabilizes the amorphous structure against recrystallization, however, the loss of magnetic anisotropy under thermal annealing is not reduced. This demonstrates that magnetic relaxation in these alloys does not involve crystallization of the amorphous structure

  18. Self-consistent EXAFS PDF Projection Method by Matched Correction of Fourier Filter Signal Distortion

    International Nuclear Information System (INIS)

    Lee, Jay Min; Yang, Dong-Seok

    2007-01-01

    Inverse problem solving computation was performed for solving PDF (pair distribution function) from simulated data EXAFS based on data FEFF. For a realistic comparison with experimental data, we chose a model of the first sub-shell Mn-0 pair showing the Jahn Teller distortion in crystalline LaMnO3. To restore the Fourier filtering signal distortion, involved in the first sub-shell information isolated from higher shell contents, relevant distortion matching function was computed initially from the proximity model, and iteratively from the prior-guess during consecutive regularization computation. Adaptive computation of EXAFS background correction is an issue of algorithm development, but our preliminary test was performed under the simulated background correction perfectly excluding the higher shell interference. In our numerical result, efficient convergence of iterative solution indicates a self-consistent tendency that a true PDF solution is convinced as a counterpart of genuine chi-data, provided that a background correction function is iteratively solved using an extended algorithm of MEPP (Matched EXAFS PDF Projection) under development

  19. A theoretical and experimental XAS study of monolayer dispersive supported CuO/γ-Al2O3 catalysts

    International Nuclear Information System (INIS)

    Chen Dongliang; Wu Ziyu

    2006-01-01

    The local structures of supported CuO/γ-Al 2 O 3 monolayer dispersive catalysts with different CuO loadings have been investigated by EXAFS and multiple scattering XANES simulations. The EXAFS results show that the first nearest neighbors around the Cu atoms in the CuO/γ-Al 2 O 3 catalysts are similar to that of the polycrystalline CuO powder, which is independent of the CuO loadings. Moreover, the Cu K-XANES FEFF8 calculations for CuO reveal that the monolayer-dispersed CuO species are of small distorted (CuO 4 ) m n+ clusters, which is mainly composed of a distorted CuO 6 octahedron incorporated in the surface octahedral vacant sites of the γ-Al 2 O 3 support. We consider that the CuO species for the CuO/γ-Al 2 O 3 catalysts with loadings of 0.4 and 0.8 mmol/100 m 2 are distorted (CuO 4 ) m n+ clusters composed mainly of a distorted CuO 6 octahedron incorporated in the surface octahedral vacant sites of the γ-Al 2 O 3 support after calcinations at high temperature in air for a few hours. On the contrary, for the CuO/γ-Al 2 O 3 with loading of 1.2 mmol/100 m 2 , the local structure of Cu atoms in CuO/γ-Al 2 O 3 is similar to that of polycrystalline CuO powder

  20. In-plant measurements of gamma-ray transmissions for precise K-edge and passive assay of plutonium concentration and isotopic abundance in product solutions at the Tokai Reprocessing Plant

    International Nuclear Information System (INIS)

    Asakura, Y.; Kondo, I.; Masui, J.; Shoji, K.; Russo, P.A.; Hsue, S.T.; Sprinkle, J.K. Jr.; Johnson, S.S.

    1982-01-01

    A field test has been carried out for more than 2 years for determination of plutonium concentration by K-edge absorption densitometry and for determination of plutonium isotopic abundance by transmission-corrected passive gamma-ray spectrometry. This system was designed and built at Los Alamos National Laboratory and installed at the Tokai reprocessing plant of the Power Reactor and Nuclear Fuel Development Corporation as a part of the Tokai Advanced Safeguards Technology Exercise (TASTEX). For K-edge measurement of plutonium concentration, the transmissions at two discrete gamma-ray energies are measured using the 121.1- and 122.1-keV gamma rays from 75 Se and 57 Co. Intensities of the plutonium passive gamma rays in the energy regions between 38 and 51 keV and between 129 and 153 keV are used for determination of the isotopic abundances. More than 200 product solution samples have been measured in a timely fashion during these 2 years. The relative precisions and accuracies of the plutonium concentration measurement are shown to be within 0.6% (1 sigma) in these applications, and those for plutonium isotopic abundances are within 3% for 238 Pu, 0.4% for 239 Pu, 1.2% for 240 Pu, 1.3% for 241 Pu, and 7% for 242 Pu. The time required is 10 min for the concentration assay, 10 min for the isotopics assay, and about 15 min for handling procedures in the laboratory

  1. XANES- and EXAFS-Investigations on Chromium-Doped Mullite Precursors

    OpenAIRE

    Arzberger , I.; Küper , G.; Pantelouris , A.; Peitz , B.; Hormes , J.; Schneider , H.; Saruhan , B.

    1997-01-01

    Chromium-doped non-crystalline mullite precursors for ceramics were investigated with x-ray absorption spectroscopy at the Cr K edge. They were prepared using a sol-gel-route. 3 wt% Cr2O3 were added to partially substitute aluminium by chromium in the aluminosilicate network. The aim of the study was to characterize the development of the electronic and geometric structure of the precursor at different temperatures prior to its crystallization to mullite. The x-ray absorption spectra of the p...

  2. The local structure of U(VI)-ferri-hydrite sorption complexes revisited: EXAFS spectroscopy and Monte-Carlo simulations

    International Nuclear Information System (INIS)

    Rossberg, A.; Ulrich, K.U.; Scheinost, A.C.

    2005-01-01

    Full text of publication follows: EXAFS analysis of actinyl sorption complexes is a complicated task due to the presence of overlapping shells, structural disorder and the presence of multiple scattering paths due to the specific actinyl structure. Hence often controversial interpretations arise from conventional shell fitting. A typical example is the proposed formation of ternary uranyl carbonato surface complexes on ferri-hydrite, where a peak at ∼2.4 Angstrom in the Fourier transform is explained by backscattering carbon atoms at 2.86-2.94 Angstrom. While such ternary carbonate complexes have been confirmed by complementary techniques like FTIR and electrophoretic mobility measurements, the EXAFS peak shows even up in those uranyl ferri-hydrite systems, where great care has been taken to keep the system carbonate-free, rendering an EXAFS fit with carbon meaningless. To overcome this common problem of EXAFS shell fitting, we developed a new analysis approach based on Monte-Carlo simulations coupled to theoretical EXAFS modeling using FEFF. Here, the position of the uranyl atom is first refined in relation to a given ferri-hydrite surface structure. In a second step, the whole complex structure is refined to allow for e.g. surface relaxation effects. Using this approach, a match to the experimental EXAFS spectra of U(VI) ferri-hydrite complexes without carbonate could be achieved. The local structure indicates a mononuclear bidentate (edge-sharing) surface complex, which was identified for the first time by EXAFS spectroscopy. Further fits were performed to elucidate the influence of carbonate and other anions on the structure of the surface complex. The results demonstrate the potential of the Monte-Carlo approach for determining the structure of actinyl surface complexes. (authors)

  3. EXAFS and FTIR studies of selenite and selenate sorption by alkoxide-free sol–gel generated Mg–Al–CO 3 layered double hydroxide with very labile interlayer anions

    KAUST Repository

    Chubar, Natalia

    2014-01-01

    © the Partner Organisations 2014. Current research on Layered Double Hydroxides (LDHs, also known as hydrotalcites, HTs) is predominantly focused on their intercalations, but the industrial application of LDHs for anion exchange adsorption has not yet been achieved. It was recently recognized that, to develop LDH applications, these materials should be produced using methods other than direct co-precipitation. Mg-Al-CO3LDH produced using an alkoxide-free sol-gel synthesis showed exceptional removal properties for aqueous selenium species. Se K-edge EXAFS/XANES and FTIR studies (supporting the data by XRD patterns) were performed to explain the unusual adsorptive performance of Mg-Al LDH by revealing the molecular-level mechanism of HSeO3 -, SeO4 2-and {HSeO3 -+ SeO4 2-} uptake at pH 5, 7 and 8.5. The role of inner-sphere complexation (exhibited by inorganic adsorbents with good performance) in adsorption of both selenium aqueous species was not confirmed. However, Mg-Al LDH fully met the other expectations regarding the involvement of the interlayer anions. The interlayer carbonate (due to its favorable speciation and generous HT hydration) gave a "second breath" to selenite sorption and was the only mechanism that controlled the removal of Se(vi). Because inner sphere complexation was the leading mechanism for selenite removal, ion exchange via surface OH-and interlayer CO3 2-species was the only mechanism for selenate removal; both of these species were easily bound to Mg-Al LDH (on its surface and gently parked into the interlayer forming a multilayer without violation of the structure of Mg-Al-CO3LDH). This work provides the first theoretical explanation of why it is more difficult to sorb selenate than selenite and which material should be used for this purpose. This journal is

  4. EXAFS and FTIR studies of selenite and selenate sorption by alkoxide-free sol–gel generated Mg–Al–CO 3 layered double hydroxide with very labile interlayer anions

    KAUST Repository

    Chubar, Natalia

    2014-08-08

    © the Partner Organisations 2014. Current research on Layered Double Hydroxides (LDHs, also known as hydrotalcites, HTs) is predominantly focused on their intercalations, but the industrial application of LDHs for anion exchange adsorption has not yet been achieved. It was recently recognized that, to develop LDH applications, these materials should be produced using methods other than direct co-precipitation. Mg-Al-CO3LDH produced using an alkoxide-free sol-gel synthesis showed exceptional removal properties for aqueous selenium species. Se K-edge EXAFS/XANES and FTIR studies (supporting the data by XRD patterns) were performed to explain the unusual adsorptive performance of Mg-Al LDH by revealing the molecular-level mechanism of HSeO3 -, SeO4 2-and {HSeO3 -+ SeO4 2-} uptake at pH 5, 7 and 8.5. The role of inner-sphere complexation (exhibited by inorganic adsorbents with good performance) in adsorption of both selenium aqueous species was not confirmed. However, Mg-Al LDH fully met the other expectations regarding the involvement of the interlayer anions. The interlayer carbonate (due to its favorable speciation and generous HT hydration) gave a "second breath" to selenite sorption and was the only mechanism that controlled the removal of Se(vi). Because inner sphere complexation was the leading mechanism for selenite removal, ion exchange via surface OH-and interlayer CO3 2-species was the only mechanism for selenate removal; both of these species were easily bound to Mg-Al LDH (on its surface and gently parked into the interlayer forming a multilayer without violation of the structure of Mg-Al-CO3LDH). This work provides the first theoretical explanation of why it is more difficult to sorb selenate than selenite and which material should be used for this purpose. This journal is

  5. Theory and X-ray Absorption Spectroscopy for Aluminum Coordination Complexes – Al K-Edge Studies of Charge and Bonding in (BDI)Al, (BDI)AlR2, and (BDI)AlX2 Complexes.

    Science.gov (United States)

    Altman, Alison B; Pemmaraju, C D; Camp, Clément; Arnold, John; Minasian, Stefan G; Prendergast, David; Shuh, David K; Tyliszczak, Tolek

    2015-08-19

    Polarized aluminum K-edge X-ray absorption near edge structure (XANES) spectroscopy and first-principles calculations were used to probe electronic structure in a series of (BDI)Al, (BDI)AlX2, and (BDI)AlR2 coordination compounds (X = F, Cl, I; R = H, Me; BDI = 2,6-diisopropylphenyl-β-diketiminate). Spectral interpretations were guided by examination of the calculated transition energies and polarization-dependent oscillator strengths, which agreed well with the XANES spectroscopy measurements. Pre-edge features were assigned to transitions associated with the Al 3p orbitals involved in metal-ligand bonding. Qualitative trends in Al 1s core energy and valence orbital occupation were established through a systematic comparison of excited states derived from Al 3p orbitals with similar symmetries in a molecular orbital framework. These trends suggested that the higher transition energies observed for (BDI)AlX2 systems with more electronegative X(1-) ligands could be ascribed to a decrease in electron density around the aluminum atom, which causes an increase in the attractive potential of the Al nucleus and concomitant increase in the binding energy of the Al 1s core orbitals. For (BDI)Al and (BDI)AlH2 the experimental Al K-edge XANES spectra and spectra calculated using the eXcited electron and Core-Hole (XCH) approach had nearly identical energies for transitions to final state orbitals of similar composition and symmetry. These results implied that the charge distributions about the aluminum atoms in (BDI)Al and (BDI)AlH2 are similar relative to the (BDI)AlX2 and (BDI)AlMe2 compounds, despite having different formal oxidation states of +1 and +3, respectively. However, (BDI)Al was unique in that it exhibited a low-energy feature that was attributed to transitions into a low-lying p-orbital of b1 symmetry that is localized on Al and orthogonal to the (BDI)Al plane. The presence of this low-energy unoccupied molecular orbital on electron-rich (BDI)Al distinguishes

  6. EXAFS investigation of uranium(6) complexes formed at Acidithiobacillus ferro oxidans types

    International Nuclear Information System (INIS)

    Merroun, M.; Reich, T.; Hennig, Ch.; Selenska-Pobell, S.

    2002-01-01

    Mining activities have brought excessive amounts of uranium into the environment. In uranium deposits a number of acidophilic chemo-litho-autotrophic bacteria have been identified which are able to oxidize sulphide minerals, elemental sulphur, ferrous iron and also (in the presence of uranium mineral) U(IV). In particular, the interaction of one representative of the group Acidithiobacillus ferro oxidans (new designation of Thiobacillus ferro oxidans) with uranium has been investigated. Uranium(VI) complex formations at the surfaces of Acidithiobacillus ferro oxidans were studied using uranium L III -edge extended X-ray absorption fine structure (EXAFS) spectroscopy. In all samples uranium is co-ordinated by two axial oxygen atoms (O ax ) at a distance of 1.77-1.78 angstrom. The average distance between uranium and the equatorial oxygen atoms (O eq ) is 2.35 angstrom. The co-ordination number for O eq is 5-6. In comparison to the uranium crystal structure data, the U-O eq distance indicates a co-ordination number of the equatorial oxygen of 5. Within the experimental error, there are no differences in the U-O bond distances between samples from the three types of A. ferro oxidans investigated. The fit to the EXAFS data of samples measured as wet pastes gave the same results as for dried samples. No significant structural differences were observed for the uranium complexes formed by the eco-types of A. ferro oxidans. However, the EXAFS spectra do indicate a formation of uranium complexes which are different from those formed by Bacilli where the bond length of 2.28 angstrom indicates a co-ordination number of 4 for the equatorial oxygen atoms. (authors)

  7. A new cell for high temperature EXAFS measurements in molten rare earth fluorides

    International Nuclear Information System (INIS)

    Rollet, Anne-Laure; Bessada, Catherine; Auger, Yannick; Melin, Philippe; Gailhanou, Marc; Thiaudiere, Dominique

    2004-01-01

    A new cell with simple design has been developed for high temperature X-rays absorption measurements in both solid and molten lanthanide fluorides. Two plates of pyrolitic boron nitride are fixed hermetically together around the samples in order to avoid any evaporation and atmosphere interaction. EXAFS spectra of molten mixtures of LiF-LaF 3 measured at the La L III absorption edge are reported up to 900 deg C, and show the ability of this cell to keep the salt and to perform long time acquisition improving the signal to noise ratio

  8. Local structure and speciation of uranium in strontium orthosilicate: TRFS and EXAFS studies

    International Nuclear Information System (INIS)

    Gupta, Santosh K.; Thulasidas, S.K.; Natarajan, V.; Yadav, A.K.; Bhattacharya, D.

    2015-01-01

    TRFS is used to investigate the valence state and coordination behavior of uranium in strontium orthosilicate. From TRFS measurement it was observed that uranium exists as U(VI) in the form of UO 2 2+ in Sr 2 SiO 4 . Based on life time measurement and EXAFS studies it was inferred that uranyl is stabilized on both 9- and 10- coordinated strontium polyhedra. Majority of uranyl ion occupy relatively asymmetric site in strontium silicate most probably 9-coordinated Sr sites. (author)

  9. Extended X-ray absorption fine structure (EXAFS) studies of supported catalysts

    International Nuclear Information System (INIS)

    Joyner, R.W.

    1979-01-01

    Since the rebirth of interest in extended X-ray absorption fine structure there have been several studies of systems of catalytic interest. This note is a preliminary account of an investigation of supported platinum catalysts and NiO/Al 2 O 3 catalysts. Experiments were performed on pressed disc samples at the DESY synchrotron, Hamburg, using the EXAFS spectrometer. The synchrotron operated at 7 GeV energy with a circulating current of approximately 4 mA; spectrum accumulation time was typically 45 minutes. (author)

  10. EXAFS Determination of the Structure of Cobalt in Carbon-Supported Cobalt and Cobalt-Molybdenum Sulfide Hydrodesulfurization Catalysts.

    NARCIS (Netherlands)

    Koningsberger, D.C.; Bouwens, S.M.A.M.; Veen, J.A.R. van; Beer, V.H.J. de; Prins, R.

    1991-01-01

    The structure of the cobalt present in carbon-supported Co and Co-Mo sulfide catalysts was studied by means of X-ray absorption spectroscopy at the Co K-edge and by X-ray photoelectron spectroscopy (XPS). Thiophene hydrodesulfurization activities were used to measure the catalytic properties of

  11. STRUCTURAL STUDY OF BIS(2,6-BIS(PYRAZOL-3-YLPYRIDINENICKEL(II BY CALORIMETRY AND EXAFS SPECTROMETRY

    Directory of Open Access Journals (Sweden)

    Kristian H Sugiyarto

    2010-06-01

    Full Text Available The main aim of this work is to reveal the complex formation of 2,6-bis(pyrazol-3-ylpyridine, bpp, with nickel(II perchlorate in DMF by calorimetric stepwise complex formation and then followed by EXAFS spectrometry. It was found that the complex formation follows two stepwise pathways namely the formation of mono pyrazolyl-pyridine, [Ni(DMF3 bpp]2+, and bis pyrazolyl-pyridine, [Ni(bpp2]2+;  the formation constants being  log β1 = 6.57, and log β2 = 5.02, and the total value of log β  = 11.58. The final formation of six-coordinated compound was confirmed by EXAFS analysis with the mean Ni-Nbpp bond length of 2.0646(0.0014 Å.   Keywords: nickel(II, bpp, EXAFS

  12. Extended x-ray absorption fine structure (EXAFS): a novel probe for local structure of glassy solids

    International Nuclear Information System (INIS)

    Wong, J.

    1979-01-01

    The extended x-ray absorption fine structure (EXAFS) is the oscillation in the absorption coefficient extending a few hundred eVs on the high energy side of an x-ray absorption edge. This mode of spectroscopy has recently been realized to be a powerful tool in probing the local atomic structure of all states of matter, particularly with the advent of intense synchrotron radiation. More importantly is the unique ability of EXAFS to probe the structure and dynamics around individual atomic species in a multi-atomic system. In this paper, the physical processes associated with the EXAFS phenomenon will be discussed. Experimental results obtained at the Stanford Synchrotron Radiation Laboratory on some oxide and metallic glasses will be presented. The local structure in these materials are elucidated using a Fourier transform technique

  13. Controlled Oxygen Chemisorption on an Alumina Supported Rhodium Catalyst. The Formation of a New Metal-Metal Oxide Interface Determined with EXAFS.

    NARCIS (Netherlands)

    Koningsberger, D.C.; Martens, J.H.A.; Prins, R.

    1989-01-01

    An alumina-supported rhodium catalyst has been studied with EXAFS. After reduction and evacuation, oxygen was admitted at 100 and 300 K. EXAFS spectra of the catalyst after oxygen admission at 100 K indicated the beginning of oxidation. At 300 K only a small part of the rhodium particles remained

  14. A theoretical and experimental XAS study of monolayer dispersive supported CuO/{gamma}-Al{sub 2}O{sub 3} catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Chen Dongliang [Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, CAS, 100049 Beijing (China); Wu Ziyu [Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, CAS, 100049 Beijing (China)]. E-mail: wuzy@ihep.ac.cn

    2006-11-15

    The local structures of supported CuO/{gamma}-Al{sub 2}O{sub 3} monolayer dispersive catalysts with different CuO loadings have been investigated by EXAFS and multiple scattering XANES simulations. The EXAFS results show that the first nearest neighbors around the Cu atoms in the CuO/{gamma}-Al{sub 2}O{sub 3} catalysts are similar to that of the polycrystalline CuO powder, which is independent of the CuO loadings. Moreover, the Cu K-XANES FEFF8 calculations for CuO reveal that the monolayer-dispersed CuO species are of small distorted (CuO{sub 4}) {sub m} {sup n+} clusters, which is mainly composed of a distorted CuO{sub 6} octahedron incorporated in the surface octahedral vacant sites of the {gamma}-Al{sub 2}O{sub 3} support. We consider that the CuO species for the CuO/{gamma}-Al{sub 2}O{sub 3} catalysts with loadings of 0.4 and 0.8 mmol/100 m{sup 2} are distorted (CuO{sub 4}) {sub m} {sup n+} clusters composed mainly of a distorted CuO{sub 6} octahedron incorporated in the surface octahedral vacant sites of the {gamma}-Al{sub 2}O{sub 3} support after calcinations at high temperature in air for a few hours. On the contrary, for the CuO/{gamma}-Al{sub 2}O{sub 3} with loading of 1.2 mmol/100 m{sup 2}, the local structure of Cu atoms in CuO/{gamma}-Al{sub 2}O{sub 3} is similar to that of polycrystalline CuO powder.

  15. X-ray-scattering study of copper magnetism in nonsuperconducting PrBa2Cu3O6.92

    DEFF Research Database (Denmark)

    Hill, J.P.; McMorrow, D.F.; Boothroyd, A.T.

    2000-01-01

    X-ray magnetic scattering from ordered Cu spins has been observed in a high-T-c compound. The measurements were made on the anomalous cuprate PrBa2Cu3O6.92 with x-ray photon energies tuned in the vicinity of the Cu K edge. The high wave-vector resolution enabled us to observe an incommensurate...... double-Q Cu spin structure below T-Pr = 19 K that forms as a result of coupling between the magnetically ordered Cu and Pr sublattices. Above T-Pr, the Cu ordering is commensurate, ruling out static spin-charge stripe order as an explanation for the absence of superconductivity in this material....

  16. EXAFS and XANES analysis of plutonium and cerium edges from titanate ceramics for fissile materials disposal

    International Nuclear Information System (INIS)

    Fortner, J. A.; Kropf, A. J.; Bakel, A. J.; Hash, M. C.; Aase, S. B.; Buck, E. C.; Chamerlain, D. B.

    1999-01-01

    We report x-ray absorption near edge structure (XANES) and extended x-ray absorption fine structure (EXAFS) spectra from the plutonium L III edge and XANES from the cerium L II edge in prototype titanate ceramic hosts. The titanate ceramics studied are based upon the hafnium-pyrochlore and zirconolite mineral structures and will serve as an immobilization host for surplus fissile materials, containing as much as 10 weight % fissile plutonium and 20 weight % (natural or depleted) uranium. Three ceramic formulations were studied: one employed cerium as a ''surrogate'' element, replacing both plutonium and uranium in the ceramic matrix, another formulation contained plutonium in a ''baseline'' ceramic formulation, and a third contained plutonium in a formulation representing a high-impurity plutonium stream. The cerium XANES from the surrogate ceramic clearly indicates a mixed III-IV oxidation state for the cerium. In contrast, XANES analysis of the two plutonium-bearing ceramics shows that the plutonium is present almost entirely as Pu(IV) and occupies the calcium site in the zirconolite and pyrochlore phases. The plutonium EXAFS real-space structure shows a strong second-shell peak, clearly distinct from that of PuO 2 , with remarkably little difference in the plutonium crystal chemistry indicated between the baseline and high-impurity formulations

  17. In-situ EXAFS study on the thermal decomposition of TiH2

    International Nuclear Information System (INIS)

    Zhou Yingli; Wu Min; An Pengfei; Zheng Lirong; Chu Shengqi; Zhang Jing; Hu Tiandou

    2014-01-01

    Thermal decomposition behaviors of TiH 2 powder under a flowing helium atmosphere and in a low vacuum condition have been studied using an in situ EXAFS technique. By an EXAFS analysis containing the multiple scattering paths including H atoms, the changes of the hydrogen stoichiometric ratio and the phase transformation sequence are obtained. The results demonstrate that the initial decomposition temperature is dependent on experimental conditions, which occurs, respectively, at about 300 and 400 °C in a low vacuum condition and under a flowing helium atmosphere. During the decomposition process of TiH 2 in a low vacuum condition, the sample experiences a phase change process: δ(TiH 2 ) → δ (TiH x ) → δ(TiH x )+ β(TiH x ) → δ(TiH x )+ β(TiH x ) + α(Ti) → β(TiH x ) + α(Ti) → α(Ti) + β(Ti). This study offers a way to detect the structural information of hydrogen. A detailed discussion about the decomposition process of TiH 2 is given in this paper. (authors)

  18. Characterization of U(VI)-carbonato ternary complexes on hematite: EXAFS and electrophoretic mobility measurements

    Science.gov (United States)

    Bargar, John R.; Reitmeyer, Rebecca; Lenhart, John J.; Davis, James A.

    2000-01-01

    We have measured U(VI) adsorption on hematite using EXAFS spectroscopy and electrophoresis under conditions relevant to surface waters and aquifers (0.01 to 10 μM dissolved uranium concentrations, in equilibrium with air, pH 4.5 to 8.5). Both techniques suggest the existence of anionic U(VI)-carbonato ternary complexes. Fits to EXAFS spectra indicate that U(VI) is simultaneously coordinated to surface FeO6 octahedra and carbonate (or bicarbonate) ligands in bidentate fashions, leading to the conclusion that the ternary complexes have an inner-sphere metal bridging (hematite-U(VI)-carbonato) structure. Greater than or equal to 50% of adsorbed U(VI) was comprised of monomeric hematite-U(VI)-carbonato ternary complexes, even at pH 4.5. Multimeric U(VI) species were observed at pH ≥ 6.5 and aqueous U(VI) concentrations approximately an order of magnitude more dilute than the solubility of crystalline β-UO2(OH)2. Based on structural constraints, these complexes were interpreted as dimeric hematite-U(VI)-carbonato ternary complexes. These results suggest that Fe-oxide-U(VI)-carbonato complexes are likely to be important transport-limiting species in oxic aquifers throughout a wide range of pH values.

  19. An EXAFS study of the structure of Co-Mo hydrodesulfurization catalysts

    International Nuclear Information System (INIS)

    Clausen, B.S.; Topsoe, H.; Candia, R.; Villadsen, J.; Lengeler, B.

    1981-05-01

    By analysing the extended X-ray absorption fine structure (EXAFS) of the Mo absorption edge, structural information about both calcined and sulfided Mo/Al 2 O 3 and Co-Mo/Al 2 O 3 catalysts has been obtained. The calcined catalysts show only one strong backscatterer peak in the radial distribution function, which indicates that molybdenum is present in a highly disordered structure. For the Co-Mo/Al 2 O 3 catalyst the presence of cobalt seems to have some effect on the immediate surroundings of molybdenum. Upon sulfiding the catalysts, an ordering of the molybdenum-containing phase takes place as evidenced by the observation of a contribution from the second coordination shell. From a comparison with EXAFS data obtained on well-crystallized MoS 2 it is concluded that the molybdenum atoms in the catalysts are present in MoS 2 -like structures. Furthermore, from a comparison of the amplitude of the Mo-backscatterer peak it is found that these MoS 2 -like structures are ordered in very small domains. (orig.)

  20. EXAFS: Possibilities, advantages and limitations for the investigation of local order in metallic glasses

    International Nuclear Information System (INIS)

    Haensel, R.; Rabe, P.; Tolkiehn, G.; Werner, A.

    1980-06-01

    Throughout this book many examples for the close relationship between the macroscopic properties and the local structure of liquid and amorphous metals and alloys are given. Complementing the conventional X-ray, electron and neutron scattering techniques the analysis of the Extended X-ray Absorption Fine Structure (EXAFS) has been developed to a reliable method for structural analysis. Although the phenomenon is known since the thirties of the century, its application for the determination of local geometrical parameters has only been introduced about ten years ago. The development of the method has been greatly stimulated by extensive theoretical work, e.g. more refined calculations of complex scattering amplitudes and by the availability of synchrotron radiation as an intense X-ray continuum source. Two aspects are discussed in this paper: i) the basic principles of EXAFS and the usual data evaluation techniques demonstrated for crystalline Fe; ii) Applications on amorphous systems, the modifications of the data evaluation due to nonsymmetric pair distributions and the comparison with other methods for structure determination. (orig.)

  1. Silver and copper nanoclusters in the lustre decoration of Italian Renaissance pottery: an EXAFS study

    Science.gov (United States)

    Padovani, S.; Borgia, I.; Brunetti, B.; Sgamellotti, A.; Giulivi, A.; D'Acapito, F.; Mazzoldi, P.; Sada, C.; Battaglin, G.

    Lustre is one of the most important decorative techniques of the Medieval and Renaissance pottery of the Mediterranean basin, capable of producing brilliant metallic reflections and iridescence. Following the recent finding that the colour of lustre decorations is mainly determined by copper and silver nanoclusters dispersed in the glaze layer, the local environment of copper and silver atoms has been studied by extended X-ray absorption fine structure (EXAFS) spectroscopy on original samples of gold and red lustre. It has been found that, in gold lustre, whose colour is attributed mainly to the silver nanocluster dispersion, silver is only partially present in the metallic form and copper is almost completely oxidised. In the red lustre, whose colour is attributed mainly to the copper nanocluster dispersion, only a fraction of copper is present in the metallic form. EXAFS measurements on red lustre, carried out in the total electron yield mode to probe only the first 150 nm of the glaze layer, indicated that in some cases lustre nanoclusters may be confined in a very thin layer close to the surface.

  2. Sorption Speciation of Lanthanides/Actinides on Minerals by TRLFS, EXAFS and DFT Studies: A Review

    Directory of Open Access Journals (Sweden)

    Xiaoli Tan

    2010-11-01

    Full Text Available Lanthanides/actinides sorption speciation on minerals and oxides by means of time resolved laser fluorescence spectroscopy (TRLFS, extended X-ray absorption fine structure spectroscopy (EXAFS and density functional theory (DFT is reviewed in the field of nuclear disposal safety research. The theoretical aspects of the methods are concisely presented. Examples of recent research results of lanthanide/actinide speciation and local atomic structures using TRLFS, EXAFS and DFT are discussed. The interaction of lanthanides/actinides with oxides and minerals as well as their uptake are also of common interest in radionuclide chemistry. Especially the sorption and inclusion of radionuclides into several minerals lead to an improvement in knowledge of minor components in solids. In the solid-liquid interface, the speciation and local atomic structures of Eu(III, Cm(III, U(VI, and Np(IV/VI in several natural and synthetic minerals and oxides are also reviewed and discussed. The review is important to understand the physicochemical behavior of lanthanides/actinides at a molecular level in the natural environment.

  3. EXAFS and XPS Study of Rutile-Type Difluorides of First-Row Transition Metals

    International Nuclear Information System (INIS)

    Murai, Kei-ichiro; Suzuki, Yohei; Moriga, Toshihiro; Yoshiasa, Akira

    2007-01-01

    Although most rutile-type difluorides (MnF2, CoF2 and NiF2) have a positive thermal expansion coefficient, FeF2 has a negative thermal expansion (NTE) along the c-axis in the high temperature region. In this study, we give an explanation of that behavior with Extended X-ray Absorption Fine Structure (EXAFS) and X-ray Photoelectron Spectroscopy (XPS) techniques. From EXAFS results, it has become apparent that the length of the share-edge (Fe-Fe) of FeF6 octahedra increased with the rise of temperature in the high temperature region. We have revealed that the force constant between nearest neighbor atoms (Fe-F) was much larger than that between second-nearest neighbor atoms (Fe-Fe) in FeF2. In XPS measurements, it was discovered that the peak of F 1s of FeF2 was located at the lowest binding energy position as compared to that of other difluorides. This means that the charge density around the F atom in FeF2 was higher than that in other difluorides. It follows from this that the share-edge repulsive force in FeF2 is larger than that in other difluorides. On account of the large repulsive force and the large force constant between nearest neighbor atoms, Fe atoms are attracted to share-edge with the rise of temperature

  4. DFT and EXAFS, mutually enhancing tools for structure elucidation of Tc complexes

    International Nuclear Information System (INIS)

    Breynaert, E.; Bruggeman, C.; Maes, A.

    2005-01-01

    Full text of publication follows: The redox-sensitive fission product technetium-99 (Tc) is of great interest in nuclear waste disposal studies because of its potential for contaminating the geosphere due to its very long half-life (2.13 x 10 5 year) and high mobility under oxidising conditions, where technetium forms pertechnetate (TcO 4 - ). Under suitable reducing conditions, e.g. in the presence of an iron(II) containing solid phase which can act as an electron donor, the solubility can be limited by the reduction of pertechnetate followed by the formation of a surface precipitate [1]. However, by association with mobile humic substances (HS) or other associating/complexing species, the solubility of reduced Tc species may be drastically enhanced [2]. The elucidation of the identity and geometrical structure of the species causing this enhanced solubility often remains a difficult issue. Extended X-Ray Absorption Fluorescence Spectroscopy/ X-Ray Absorption Near Edge Spectroscopy (EXAFS/XANES) analysis can be very helpful to determine the molecular surroundings of reduced Tc organic complexes of Tc(IV) colloid-HS-associations. The interpretation of the EXAFS spectra is however not a straightforward process due to the possibly strong influence of multiple scattering paths on the spectra. Contrary to single scattering analysis which can be easily performed on the experimental EXAFS spectra, multiple scattering analysis can only be done, based on good approximations of the possible geometrical structures of the species under consideration. It has been shown that the Density Functional Theory (DFT) can be used to perform geometry optimizations of technetium species and therefore can be utilized to predict the structure of technetium complexes [3]. The success and computational effort needed for such structure predictions are however highly dependant on the quality of the initial structure from which the geometry optimization is started. Single scattering analysis of

  5. Multiple rare-earth ion environments in amorphous (Gd2O3)0.230(P2O5)0.770 revealed by gadolinium K-edge anomalous X-ray scattering

    Energy Technology Data Exchange (ETDEWEB)

    Cole, Jacqueline M.; Cramer, Alisha J.; Shastri, Sarvjit D.; Mukaddem, Karim T.; Newport, Robert J

    2018-04-26

    A Gd K-edge anomalous X-ray scattering (AXS) study is performed on the rare-earth (R) phosphate glass, (Gd2O3)0.230(P2O5)0.770, in order to determine Gd…Gd separations in its local structure. The minimum rare-earth separation is of particular interest given that the optical properties of these glasses can quench when rare-earth ions become too close to each other. To this end, a weak Gd…Gd pairwise correlation is located at 4.2(1) Å which is representative of a meta-phosphate R…R separation. More intense first neighbor Gd…Gd pairwise correlations are found at the larger radial distributions, 4.8(1) Å, 5.1(1) Å and 5.4(1) Å. These reflect a mixed ultra-phosphate and meta-phosphate structural character, respectively. A second neighbor Gd…Gd pairwise correlation lies at 6.6(1) Å which is indicative of meta-phosphate structures. Meta- and ultra-phosphate classifications are made by comparing the R…R separations against those of rare-earth phosphate crystal structures, R(PO3)3 and RP5O14 respectively, or difference pair distribution function (PDF) features determined on similar glasses using difference neutron scattering methods. The local structure of this glass is therefore found to display multiple rare-earth ion environments, presumably because its composition lies between these two stoichiometric formulae. These Gd…Gd separations are well resolved in the PDFs that represent the AXS signal. Indeed, the spatial resolution is so good that it also enables the identification of R…X (X = R, P, O) pairwise correlations up to r ~ 9 Å; their average separations lie at r ~ 7.1(1) Å, 7.6(1) Å 7.9(1) Å, 8.4(1) Å and 8.7(1) Å. This is the first report of a Gd K-edge AXS study on an amorphous material. Its demonstrated ability to characterize the local structure of a glass up to such a long-range of r, heralds exciting prospects for AXS studies on other ternary non-crystalline materials. However, the technical challenge of such an experiment

  6. REDOX state analysis of platinoid elements in simulated high-level radioactive waste glass by synchrotron radiation based EXAFS

    Energy Technology Data Exchange (ETDEWEB)

    Okamoto, Yoshihiro, E-mail: okamoto.yoshihiro@jaea.go.jp [Condensed Matter Chemistry Group, Quantum Beam Science Center, Japan Atomic Energy Agency, Shirakata 2-4, Tokai-mura, Ibaraki 319-1195 (Japan); Shiwaku, Hideaki [Quantum Beam Science Center, Japan Atomic Energy Agency, Kouto 1-1-1, Sayo-cho, Hyogo 679-5143 (Japan); Nakada, Masami [Nuclear Engineering Science Center, Japan Atomic Energy Agency, Shirakata 2-4, Tokai-mura, Ibaraki 319-1195 (Japan); Komamine, Satoshi; Ochi, Eiji [Japan Nuclear Fuel Limited, 4-108 Aza Okitsuke, Oaza Obuchi, Rokkasho-mura, Aomori 030-3212 (Japan); Akabori, Mitsuo [Nuclear Engineering Science Center, Japan Atomic Energy Agency, Shirakata 2-4, Tokai-mura, Ibaraki 319-1195 (Japan)

    2016-04-01

    Extended X-ray Absorption Fine Structure (EXAFS) analyses were performed to evaluate REDOX (REDuction and OXidation) state of platinoid elements in simulated high-level nuclear waste glass samples prepared under different conditions of temperature and atmosphere. At first, EXAFS functions were compared with those of standard materials such as RuO{sub 2}. Then structural parameters were obtained from a curve fitting analysis. In addition, a fitting analysis used a linear combination of the two standard EXAFS functions of a given elements metal and oxide was applied to determine ratio of metal/oxide in the simulated glass. The redox state of Ru was successfully evaluated from the linear combination fitting results of EXAFS functions. The ratio of metal increased at more reducing atmosphere and at higher temperatures. Chemical form of rhodium oxide in the simulated glass samples was RhO{sub 2} unlike expected Rh{sub 2}O{sub 3}. It can be estimated rhodium behaves according with ruthenium when the chemical form is oxide.

  7. Structure of Rhodium in an Ultradispersed Rhodium/Alumina Catalyst as Studied by EXAFS and Other Technique

    NARCIS (Netherlands)

    Koningsberger, D.C.; Blik, H.F.J. van 't; Zon, J.B.A.D. van; Huizinga, T.; Vis, J.C.; Prins, R.

    1985-01-01

    The structure of rhodium in an ultradispersed 0.57 wt % Rh/y-Al,O, catalyst before and after CO adsorption was studied with extended X-ray absorption fine structure (EXAFS), X-ray photoelectron spectroscopy (XPS), electron spin resonance (ESR), temperature programmed reduction (TPR), CO infrared

  8. Using solution- and solid-state S K-edge X-ray absorption spectroscopy with density functional theory to evaluate M-S bonding for MS4(2-) (M = Cr, Mo, W) dianions.

    Science.gov (United States)

    Olson, Angela C; Keith, Jason M; Batista, Enrique R; Boland, Kevin S; Daly, Scott R; Kozimor, Stosh A; MacInnes, Molly M; Martin, Richard L; Scott, Brian L

    2014-12-14

    Herein, we have evaluated relative changes in M-S electronic structure and orbital mixing in Group 6 MS4(2-) dianions using solid- and solution-phase S K-edge X-ray absorption spectroscopy (XAS; M = Mo, W), as well as density functional theory (DFT; M = Cr, Mo, W) and time-dependent density functional theory (TDDFT) calculations. To facilitate comparison with solution measurements (conducted in acetonitrile), theoretical models included gas-phase calculations as well as those that incorporated an acetonitrile dielectric, the latter of which provided better agreement with experiment. Two pre-edge features arising from S 1s → e* and t electron excitations were observed in the S K-edge XAS spectra and were reasonably assigned as (1)A1 → (1)T2 transitions. For MoS4(2-), both solution-phase pre-edge peak intensities were consistent with results from the solid-state spectra. For WS4(2-), solution- and solid-state pre-edge peak intensities for transitions involving e* were equivalent, while transitions involving the t orbitals were less intense in solution. Experimental and computational results have been presented in comparison to recent analyses of MO4(2-) dianions, which allowed M-S and M-O orbital mixing to be evaluated as the principle quantum number (n) for the metal valence d orbitals increased (3d, 4d, 5d). Overall, the M-E (E = O, S) analyses revealed distinct trends in orbital mixing. For example, as the Group 6 triad was descended, e* (π*) orbital mixing remained constant in the M-S bonds, but increased appreciably for M-O interactions. For the t orbitals (σ* + π*), mixing decreased slightly for M-S bonding and increased only slightly for the M-O interactions. These results suggested that the metal and ligand valence orbital energies and radial extensions delicately influenced the orbital compositions for isoelectronic ME4(2-) (E = O, S) dianions.

  9. The time-resolved and extreme conditions XAS (TEXAS) facility at the European Synchrotron Radiation Facility: the general-purpose EXAFS bending-magnet beamline BM23

    Energy Technology Data Exchange (ETDEWEB)

    Mathon, O., E-mail: mathon@esrf.fr; Beteva, A.; Borrel, J.; Bugnazet, D.; Gatla, S.; Hino, R.; Kantor, I.; Mairs, T. [European Synchrotron Radiation Facility, CS 40220, 38043 Grenoble Cedex 9 (France); Munoz, M. [European Synchrotron Radiation Facility, CS 40220, 38043 Grenoble Cedex 9 (France); Université Joseph Fourier, 1381 rue de la Piscine, BP 53, 38041 Grenoble Cedex 9 (France); Pasternak, S.; Perrin, F.; Pascarelli, S. [European Synchrotron Radiation Facility, CS 40220, 38043 Grenoble Cedex 9 (France)

    2015-10-17

    BM23 is the general-purpose EXAFS bending-magnet beamline at the ESRF, replacing the former BM29 beamline in the framework of the ESRF upgrade. Its mission is to serve the whole XAS user community by providing access to a basic service in addition to the many specialized instruments available at the ESRF. BM23 offers high-signal-to-noise ratio EXAFS in a large energy range (5–75 keV), continuous energy scanning for quick-EXAFS on the second timescale and a micro-XAS station delivering a spot size of 4 µm × 4 µm FWHM. BM23 is the general-purpose EXAFS bending-magnet beamline at the ESRF, replacing the former BM29 beamline in the framework of the ESRF upgrade. Its mission is to serve the whole XAS user community by providing access to a basic service in addition to the many specialized instruments available at the ESRF. BM23 offers high signal-to-noise ratio EXAFS in a large energy range (5–75 keV), continuous energy scanning for quick-EXAFS on the second timescale and a micro-XAS station delivering a spot size of 4 µm × 4 µm FWHM. It is a user-friendly facility featuring a high degree of automation, online EXAFS data reduction and a flexible sample environment.

  10. Comparative EXAFS study of uranium(VI) and neptunium(V) sorption onto kaolinite

    International Nuclear Information System (INIS)

    Reich, T.; Amayri, S.; Reich, Ta.; Jermolajev, J.

    2005-01-01

    Full text of publication follows: We investigated the surface sorption process of U(VI) and Np(V) on kaolinite by extended X-ray absorption fine structure (EXAFS) spectroscopy in the 10 μM concentration range. Batch experiments with kaolinite in CO 2 -equilibrated systems showed that the adsorption edge of U(VI) occurs at pH 5.5, i.e., near the pH PZC of kaolinite. The adsorption edge of Np(V) occurs well above the pH PZC value at pH 8.5. This may indicate that the bonds between Np(V) and the surface functional groups of kaolinite are not as strong as in the case of U(VI). U(VI) and Np(V) have in common that the amount which is adsorbed decreases when the pH is increased beyond the absorption maximum. This behavior can be attributed to the formation of U(VI) and Np(V) carbonato complexes in the aqueous solutions. The aim of this comparative EXAFS study was to investigate the reason for the different affinities of U(VI) and Np(V) for kaolinite by measuring their local environments at the clay surface. Samples were prepared from 4 g/L kaolinite, 0.1 M NaClO 4 , pH 3.0 - 10.5, presence and absence of ambient CO 2 . The U L 3 - and Np L 2 -edge EXAFS spectra of the wet paste samples were measured at room temperature in fluorescence mode at the Rossendorf Beamline (ROBL) at the European Synchrotron Radiation Facility. The measured U-O and U-Al/Si distances indicate inner-sphere sorption of U(VI) on kaolinite. There was no evidence of uranium neighbors in the EXAFS spectra, suggesting that the adsorbed U(VI) complexes were predominantly monomeric. The average distance between uranium and its equatorial oxygen atoms, O eq , increased from 2.32 to 2.38 Angstrom in the presence of atmospheric CO 2 when the pH was increased from 5.0 to 8.5. In the CO 2 -free system, the U-O eq distance was independent from pH and equal to 2.32 Angstrom. The lengthening of the average U-O eq distance in the presence of carbonate (or bicarbonate) suggests the formation of ternary U

  11. The Mn site in Mn-doped GaAs nanowires: an EXAFS study

    International Nuclear Information System (INIS)

    D’Acapito, F; Rovezzi, M; Boscherini, F; Jabeen, F; Bais, G; Piccin, M; Rubini, S; Martelli, F

    2012-01-01

    We present an EXAFS study of the Mn atomic environment in Mn-doped GaAs nanowires. Mn doping has been obtained either via the diffusion of the Mn used as seed for the nanowire growth or by providing Mn during the growth of Au-induced wires. As a general finding, we observe that Mn forms chemical bonds with As but is not incorporated in a substitutional site. In Mn-induced GaAs wires, Mn is mostly found bonded to As in a rather disordered environment and with a stretched bond length, reminiscent of that exhibited by MnAs phases. In Au-seeded nanowires, along with stretched MnAs coordination, we have found the presence of Mn in a MnAu intermetallic compound. (paper)

  12. A study on the structures of hemoglobin of diabetic patients by EXAFS technique

    International Nuclear Information System (INIS)

    Wang Yinsong; Tan Mingguang; Zhang Guilin

    2001-01-01

    Hemoglobin was the carrier of oxygen in blood circulation. For the patients with diabetes mellitus the enhancement of glycidate hemoglobin in blood causes the decrease of oxygen transmission function. The local atomic structures of iron in hemoglobin were determined by EXAFS techniques. The relationship between diabetes mellitus and hemoglobin structures was observed. The blood samples were taken from normal people, slight and serious diabetic patients. The results show that the coordination number of iron atoms and Fe-O bond length were almost the same for the three samples. However, for the samples of serious diabetic patients the Fe-N bond length increases by about 0.002 nm, the possible reasons were the increase of deoxyhemoglobin contents in their blood

  13. EXAFS Phase Retrieval Solution Tracking for Complex Multi-Component System: Synthesized Topological Inverse Computation

    International Nuclear Information System (INIS)

    Lee, Jay Min; Yang, Dong-Seok; Bunker, Grant B

    2013-01-01

    Using the FEFF kernel A(k,r), we describe the inverse computation from χ(k)-data to g(r)-solution in terms of a singularity regularization method based on complete Bayesian statistics process. In this work, we topologically decompose the system-matched invariant projection operators into two distinct types, (A + AA + A) and (AA + AA + ), and achieved Synthesized Topological Inversion Computation (STIC), by employing a 12-operator-closed-loop emulator of the symplectic transformation. This leads to a numerically self-consistent solution as the optimal near-singular regularization parameters are sought, dramatically suppressing instability problems connected with finite precision arithmetic in ill-posed systems. By statistically correlating a pair of measured data, it was feasible to compute an optimal EXAFS phase retrieval solution expressed in terms of the complex-valued χ(k), and this approach was successfully used to determine the optimal g(r) for a complex multi-component system.

  14. Characterization of mercury based Indian herbomineral drug by radioisotope induced EDXRF and synchrotron based EXAFS

    International Nuclear Information System (INIS)

    Joseph, Daisy; Saxena, A.; Joseph, Rajeeta; Rajput, P.; Nayak, C.; Bhattacharya, D.; Jha, S.N.; Natrajan, V.

    2014-01-01

    An Indian herbomineral drug was characterized for its trace elements by radioisotope induced EDXRF. The drug contains minerals like mercury, sulfur and arsenic disulfide, along with herbs such as dhaturra, bhrami, vacha etc. All the above ingredients were processed together in a step wise manner (6 steps). Hence the motive was to expect some change in the drug molecule at every step of processing it. The 6 samples are the samples collected at every step of drug preparation. These 6 samples which are collected as intermediatary samples would be then evaluated for its role in various neuropsychological (psychosis, depression etc) disorders in experimental animals such as rats/mice. Hence it was required to find the elements/trace elements composition, details of chemical components present in the drug samples. It was seen that using EDXRF it was possible to determine As and Hg. The EXAFS results also showed the presence of As in their sulphide form. (author)

  15. High pressure and high temperature EXAFS and diffraction study of AgI

    International Nuclear Information System (INIS)

    Yoshiasa, Akira; Arima, Hiroshi; Fukui, Hiroshi; Okube, Maki; Katayama, Yoshinori; Ohtaka, Osamu

    2009-01-01

    We have determined the precise P-T phase diagram of AgI by in-situ high-pressure high-temperature synchrotron experiments. X-ray diffraction and XAFS measurements were performed up to 6.0 GPa and 1100 K using a multi-anvil high-pressure device and synchrotron radiation from SPring-8. In the disordered rock-salt phase, Ag ions occupy both octahedral and tetrahedral sites and twenty percent of Ag ions occupy the tetrahedral site as a maximum value at 2 GPa. From the viewpoint of the local structure analyses, some sudden changes are recognized near broad phase transition point. Analysis of EXAFS Debye-Waller factor is useful because the force constant can be decided directly even at high pressure and high temperature. Pressure influences greatly the effective potential and anharmonicity decreases with increasing pressure. (author)

  16. Fe K-Edge X-ray absorption near-edge spectroscopy (XANES) and X-ray diffraction (XRD) analyses of LiFePO4 and its base materials

    Science.gov (United States)

    Latif, C.; Negara, V. S. I.; Wongtepa, W.; Thamatkeng, P.; Zainuri, M.; Pratapa, S.

    2018-03-01

    XANES analysis has been performed with the aim of knowing the Fe oxidation state in a synthesized LiFePO4 and its base materials. XANES measurements were performed at SLRI on energy around Fe K-edge. An XRD analysis has also been performed with the aim of knowing the phase composition, lattice parameters and crystallite size of the LiFePO4 as well as the base materials. From the XRD analysis, it was found that the dominating phase in the iron sand sample was Fe3O4 and the only phase found after calcination was LiFePO4. The latter phase exhibited crystallite size of 100 nm and lattice parameters a = 10.169916 Å, b = 5.919674 Å, c = 4.627893 Å. Qualitative analysis of XANES data revealed that the oxidation number of Fe in the sample before calcination was greater than that after calcination and Fe in the natural iron sand, indicated by the E0 values of 7129.2 eV, 7120.6 eV and 7124.4 eV respectively.

  17. Chemical kinetics of Cs species in an alkali-activated municipal solid waste incineration fly ash and pyrophyllite-based system using Cs K-edge in situ X-ray absorption fine structure analysis

    Science.gov (United States)

    Shiota, Kenji; Nakamura, Takafumi; Takaoka, Masaki; Nitta, Kiyofumi; Oshita, Kazuyuki; Fujimori, Takashi; Ina, Toshiaki

    2017-05-01

    We conducted in situ X-ray absorption fine structure (in situ XAFS) analysis at the Cs K-edge to investigate the chemical kinetics of Cs species during reaction in an alkali-activated municipal solid waste incineration fly ash (MSWIFA) and pyrophyllite-based system. Understanding the kinetics of Cs is essential to the design of appropriate conditions for Cs stabilization. In situ XAFS analysis of four pastes, prepared from NaOHaq, sodium silicate solution, pyrophyllite, and MSWIFA with the addition of CsCl, was conducted in custom-built reaction cells at four curing temperatures (room temperature, 60 °C, 80 °C, 105 °C) for approximately 34 h. The results indicated that the change in Cs species during reaction at room temperature was small, while changes at higher temperatures were faster and more extreme, with the fastest conversion to pollucite occurring at 105 °C. Further analysis using a leaching test and a simple reaction model for Cs species during reaction showed that the pollucite formation rate was dependent on the curing temperature and had a significant negative correlation with Cs leaching. The activation energy of pollucite formation was estimated to be 31.5 kJ/mol. These results revealed that an important change in the chemical state of Cs occurs during reaction in the system.

  18. Combined mineralogical and EXAFS characterization of polluted sediments for the definition of technological variables and constraints

    Science.gov (United States)

    Brigatti, M. F.; Elmi, C.; Laurora, A.; Malferrari, D.; Medici, L.

    2009-04-01

    An extremely severe aspect, both from environmental and economic viewpoint, is the management of polluted sediments removed from drainage and irrigation canals. Canals, in order to retain their functionality over the time, need to have their beds, periodically cleaned from sediments there accumulating. The management of removed sediments is extremely demanding, also from an economical perspective, if these latter needs to be treated as dangerous waste materials, as stated in numerous international standards. Furthermore the disposal of such a large amount of material may introduce a significant environmental impact as well. An appealing alternative is the recovery or reuse of these materials, for example in brick and tile industry, after obviously the application of appropriate techniques and protocols that could render these latter no longer a threat for human health. The assessment of the effective potential danger for human health and ecosystem of sediments before and after treatment obviously requires both a careful chemical and mineralogical characterization and, even if not always considered in the international standards, the definition of the coordination shell of heavy metals dangerous for human health, as a function of their oxidation state and coordination (e.g. Cr and Pb), and introducing technological constraints or affecting the features of the end products. Fe is a good representative for this second category, as the features of the end product, such as color, strongly depend not only from Fe concentration but also from its oxidation state, speciation and coordination. This work will first of all provide mineralogical characterization of sediments from various sampling points of irrigation and drainage canals of Po river region in the north-eastern of Italy. Samples were investigated with various approaches including X-ray powder diffraction under non-ambient conditions, thermal analysis and EXAFS spectroscopy. Obtained results, and in particular

  19. Colloidal diatomite, radionickel, and humic substance interaction: a combined batch, XPS, and EXAFS investigation.

    Science.gov (United States)

    Sheng, Guodong; Shen, Runpu; Dong, Huaping; Li, Yimin

    2013-06-01

    This work determined the influence of humic acid (HA) and fulvic acid (FA) on the interaction mechanism and microstructure of Ni(II) onto diatomite by using batch experiments, X-ray photoelectron spectroscopy (XPS), and extended X-ray absorption fine structure (EXAFS) methods. Macroscopic and spectroscopic experiments have been combined to see the evolution of the interaction mechanism and microstructure of Ni(II) in the presence of HA/FA as compared with that in the absence of HA/FA. The results indicated that the interaction of Ni(II) with diatomite presents the expected solution pH edge at 7.0, which is modified by addition of HA/FA. In the presence of HA/FA, the interaction of Ni(II) with diatomite increased below solution pH 7.0, while Ni(II) interaction decreased above solution pH 7.0. XPS analysis suggested that the enrichment of Ni(II) onto diatomite may be due to the formation of (≡SO)2Ni. EXAFS results showed that binary surface complexes and ternary surface complexes of Ni(II) can be simultaneously formed in the presence of HA/FA, whereas only binary surface complexes of Ni(II) are formed in the absence of HA/FA, which contribute to the enhanced Ni(II) uptake at low pH values. The results observed in this work are important for the evaluation of Ni(II) and related radionuclide physicochemical behavior in the natural soil and water environment.

  20. The time-resolved and extreme conditions XAS (TEXAS) facility at the European Synchrotron Radiation Facility: the general-purpose EXAFS bending-magnet beamline BM23.

    Science.gov (United States)

    Mathon, O; Beteva, A; Borrel, J; Bugnazet, D; Gatla, S; Hino, R; Kantor, I; Mairs, T; Munoz, M; Pasternak, S; Perrin, F; Pascarelli, S

    2015-11-01

    BM23 is the general-purpose EXAFS bending-magnet beamline at the ESRF, replacing the former BM29 beamline in the framework of the ESRF upgrade. Its mission is to serve the whole XAS user community by providing access to a basic service in addition to the many specialized instruments available at the ESRF. BM23 offers high signal-to-noise ratio EXAFS in a large energy range (5-75 keV), continuous energy scanning for quick-EXAFS on the second timescale and a micro-XAS station delivering a spot size of 4 µm × 4 µm FWHM. It is a user-friendly facility featuring a high degree of automation, online EXAFS data reduction and a flexible sample environment.

  1. Characterization of rust layer formed on Fe, Fe-Ni and Fe-Cr alloys exposed to Cl-rich environment by Cl and Fe K-edge XANES measurements

    International Nuclear Information System (INIS)

    Konishi, Hiroyuki; Mizuki, Jun'ichiro; Yamashita, Masato; Uchida, Hitoshi

    2005-01-01

    Chloride in atmosphere considerably reduces the corrosion resistance of conventional weathering steel containing a small amount of Cr. Ni is an effective anticorrosive element for improving the corrosion resistance of steel in a Cl-rich environment. In order to clarify the structure of the protective rust layer of weathering steel, Cl and Fe K-edge X-ray absorption near edge structure (XANES) spectra of atmospheric corrosion products (rust) formed on Fe, Fe-Ni and Fe-Cr alloys exposed to Cl-rich atmosphere were measured. The Fe K-XANES measurements enable the characterization of mixture of iron oxides such as rust. The chemical composition of the rust was determined by performing pattern fitting of the measured spectra. All the rust is composed mainly of goethite, akaganeite, lepidocrocite and magnetite. Among these iron oxides, akaganeite in particular is the major component in the rust. Additionally, the amount of akaganeite in the rust of Fe-Ni alloy is much greater than that in rust of Fe-Cr alloy. Akaganeite is generally considered to facilitate the corrosion of steel, but our results indicate that akaganeite in the rust of Fe-Ni alloy is quantitatively different from that in rust of Fe-Cr alloy and does not facilitate the corrosion of steel. The shoulder peak observed in Cl K-XANES spectra reveals that the rust contains a chloride other than akaganeite. The energy of the shoulder peak does not correspond to that of any well-known chlorides. In the measured spectra, there is no proof that Cl, by combining with the alloying element, inhibits the alloying element from acting in corrosion resistance. The shoulder peak appears only when the content of the alloying element is lower than a certain value. This suggests that the generation of the unidentified chloride is related to the corrosion rate of steel. (author)

  2. WE-FG-207B-01: BEST IN PHYSICS (IMAGING): Abdominal CT with Three K-Edge Contrast Materials Using a Whole-Body Photon-Counting Scanner: Initial Results of a Large Animal Experiment

    Energy Technology Data Exchange (ETDEWEB)

    Lakshmanan, M; Symons, R; Cork, T; Davies-Venn, C; Rice, K; Malayeri, A; Sandfort, V; Bluemke, D; Pourmorteza, A [National Institutes of Health Clinical Center, Bethesda, MD (United States)

    2016-06-15

    Purpose: To demonstrate the feasibility of in vivo three-material decomposition techniques using photon-counting CT (PCCT) with possible advantage of resolving arterial and venous flow of an organ simultaneously. Methods: Abdominal PCCT scans were acquired using a prototype whole-body PCCT with four energy thresholds (25/50/75/90keV) in a canine. Bismuth subsalicylate (60 mg) was administered orally one day prior to scanning. Immediately prior to CT scan, gadoteric acid (60 ml, Dotarem, Guerbet) was intravenously injected, followed in ten minutes by a 20mL injection of iodinated contrast (iopamidol 370 mg/mL, Bracco). Scans were acquired every ∼20 seconds, starting from the time of iodine injection. Linear material decomposition was performed using the least mean squares method to create concentration maps of iodine, gadolinium, and bismuth. The method was calibrated to vials with known concentrations of materials placed next to the animal. The accuracy of this method was tested on vials with known concentrations. Results: The material decomposition algorithm’s accuracy was confirmed to be within ±4mM in the test vials. In the animal, we could estimate the concentration of gadolinium in delayed-enhanced phase (10 minutes post-injection) in the abdomen. We could follow the wash-in and wash-out of iodine in arterial, venous, and excretory flow of the kidneys (20s, 80s, and 120s post-iodine injection) while gadolinium was present in the delayed-enhanced phase. Bismuth, which was used as a contrast agent for the gastro-intestinal tract, was easily differentiable from the other two contrast agents in the small intestine. Conclusion: This study shows the feasibility of using photon-counting CT with four energy thresholds to differentiate three k-edge contrast agents in vivo. This can potentially reduce radiation dose to patients by combining arterial and venous phases into a single acquisition.

  3. Impact of S fertilizers on pore-water Cu dynamics and transformation in a contaminated paddy soil with various flooding periods.

    Science.gov (United States)

    Yang, Jianjun; Zhu, Shenhai; Zheng, Cuiqing; Sun, Lijuan; Liu, Jin; Shi, Jiyan

    2015-04-09

    Impact of S fertilization on Cu mobility and transformation in contaminated paddy soils has been little reported. In this study, we investigated the dynamics and transformation of dissolved and colloidal Cu in the pore water of a contaminated paddy soil after applying ammonium sulphate (AS) and sulfur coated urea (SCU) with various flooding periods (1, 7 and 60 days). Compared to the control soil, the AS-treated soil released more colloidal and dissolved Cu over the entire flooding period, while the SCU-treated soil had lower colloidal Cu after 7-day flooding but higher colloidal and dissolved Cu after 60-day flooding. Microscopic X-ray fluorescence (μ-XRF) analysis found a close relationship between Fe and Cu distribution on soil colloids after 60-day flooding, implying the formation of colloidal Fe/Cu sulphide coprecipitates. Cu K-edge X-ray absorption near-edge structure (XANES) spectroscopy directly revealed the transformation of outer-sphere complexed Cu(II) species to Cu(II) sulphide and reduced Cu2O in the colloids of S-treated soils after 60-day flooding. These results demonstrated the great influence of S fertilization on pore-water Cu mobility by forming Cu sulphide under flooding conditions, which facilitated our understanding and control of Cu loss in contaminated paddy soils under S fertilization. Copyright © 2015 Elsevier B.V. All rights reserved.

  4. Limitations on the extent of off-center displacements in TbMnO3 from EXAFS measurements

    International Nuclear Information System (INIS)

    Bridges, F.; Downs, C.; O'Brien, T.; Jeong, Il-K; Kimura, T.

    2007-01-01

    We present extended x-ray-absorption fine structure (EXAFS) data at the Mn K and Tb L 3 edges that provide upper limits on the possible displacements of any atoms in TbMnO 3 . The displacements must be less than 0.005-0.01 A for all atoms, which eliminates the possibility of moderate distortions (0.02 A) with a small c-axis component, but for which the displacements in the ab plane average to zero. Assuming the polarization arises from a displacement of the O2 atoms along the c axis, the measured polarization then leads to an O2 displacement that is at least 6x10 -4 A, well below our experimental limit. Thus, a combination of the EXAFS and the measured electrical polarization indicate that the atomic displacements likely lie in the range 6x10 -4 -5x10 -3 A

  5. High covalence in CuSO4 and the radicalization of sulfate: an X-ray absorption and density functional study.

    Science.gov (United States)

    Szilagyi, Robert K; Frank, Patrick; DeBeer George, Serena; Hedman, Britt; Hodgson, Keith O

    2004-12-27

    Sulfur K-edge X-ray absorption spectroscopy (XAS) of anhydrous CuSO(4) reveals a well-resolved preedge transition feature at 2478.8 eV that has no counterpart in the XAS spectra of anhydrous ZnSO(4) or copper sulfate pentahydrate. Similar but weaker preedge features occur in the sulfur K-edge XAS spectra of [Cu(itao)SO(4)] (2478.4 eV) and [Cu[(CH(3))(6)tren]SO(4)] (2477.7 eV). Preedge features in the XAS spectra of transition metal ligands are generally attributed to covalent delocalization of a metal d-orbital hole into a ligand-based orbital. Copper L-edge XAS of CuSO(4) revealed that 56% of the Cu(II) 3d hole is delocalized onto the sulfate ligand. Hybrid density functional calculations on the two most realistic models of the covalent delocalization pathways in CuSO(4) indicate about 50% electron delocalization onto the sulfate oxygen-based 2p orbitals; however, at most 14% of that can be found on sulfate sulfur. Both experimental and computational results indicated that the high covalence of anhydrous CuSO(4) has made sulfate more like the radical monoanion, inducing an extensive mixing and redistribution of sulfur 3p-based unoccupied orbitals to lower energy in comparison to sulfate in ZnSO(4). It is this redistribution, rather than a direct covalent interaction between Cu(II) and sulfur, that is the origin of the observed sulfur XAS preedge feature. From pseudo-Voigt fits to the CuSO(4) sulfur K-edge XAS spectrum, a ground-state 3p character of 6% was quantified for the orbital contributing to the preedge transition, in reasonable agreement with the DFT calculation. Similar XAS fits indicated 2% sulfur 3p character for the preedge transition orbitals in [Cu(itao)SO(4)] and [Cu[(CH(3))(6)tren]SO(4)]. The covalent radicalization of ligands similar to sulfate, with consequent energy redistribution of the virtual orbitals, represents a new mechanism for the induction of ligand preedge XAS features. The high covalence of the Cu sites in CuSO(4) was found to be

  6. Relationship between the adsorption species of cesium and radiocesium interception potential in soils and minerals: an EXAFS study

    International Nuclear Information System (INIS)

    Fan, Qiaohui; Yamaguchi, Noriko; Tanaka, Masato; Tsukada, Hirofumi; Takahashi, Yoshio

    2014-01-01

    This study examined the radiocesium (RCs) interception potential (RIP), cation exchange capacity (CEC), total organic carbon (TOC) content, and adsorption species in soils and minerals by using extended X-ray absorption fine structure (EXAFS) spectroscopy. The RIP related to Cs + adsorption by frayed-edge site (FES) has often been used to measure the mobility and bioavailability of RCs in the environment. This study found that the presence of organic matter (OM) can reduce RIP to a certain extent. The adsorption amount (=Q T ) in soil was obviously correlated to RIP at a small [Cs + ] region, whereas a linear relationship between Q T and CEC was observed at a large [Cs + ] region. Both the inner-sphere (IS) and outer-sphere (OS) complexes of Cs + were observed through EXAFS at a molecular scale. The linear correlation between log (RIP/CEC) and the ratio of the coordination number (CN) of IS (=CN IS ) and OS (=CN OS ) complexes noted as CN IS /(CN IS + CN OS ) suggested that the ratio of CN is very sensitive to Cs + adsorption species with variable RIP and CEC. The adsorption species of Cs + in soil was mainly dependent on the clay mineral content of soil. RIP was affected not only by FES but also by other strong adsorption sites, such as the interlayers and cavities identified as the IS complex in EXAFS analysis. Findings indicated that the EXAFS approach is a powerful and efficient tool to explore the behavior of Cs + in a given environment. - Highlights: • The relationship of Cs + species on soils and minerals and RIP was firstly clarified in this study. • Coordination number of Cs + was very sensitive to Cs + adsorption species with variable RIP and CEC. • This finding can be used as a basis for understanding of Cs + behavior in nature

  7. X-ray photoemission spectroscopy (XPS) and extended x-ray absorption fine structure (EXAFS) studies of silicate based glasses

    International Nuclear Information System (INIS)

    Karim, D.; Lam, D.J.

    1979-01-01

    The application of the x-ray photoemission spectroscopy (XPS) technique to study the electronic structure and bonding of heavy metal oxides in alkali- and alkali-earth-silicate glasses had been demonstrated. The bonding characteristics of the iron oxide and uranium oxide in sodium silicate glasses were deduced from the changes in the oxygen 1s levels and the heavy metal core levels. It is reasonable to expect that the effect of leaching on the heavy metal ions can be monitored using the appropriate core levels of these ions. To study the effect of leaching on the glass forming network, the valence band structure of the bridging and nonbridging oxygens in sodium silicate glasses were investigated. The measurement of extended x-ray absorption fine-structure (EXAFS) is a relatively new analytical technique for obtaining short range (<5 A) structural information around atoms of a selected species in both solid and fluid systems. Experiments have recently begun to establish the feasibility of using EXAFS to study the bonding of actinides in silicate glasses. Because of the ability of EXAFS to yield specific structural data even in complex multicomponent systems, it could prove to be an invaluable tool in understanding glass structure

  8. EXAFS as a tool for investigation of the local environment of Ge atoms in buried low-dimensional structures

    International Nuclear Information System (INIS)

    Demchenko, I.N.; Lawniczak-Jablonska, K.; Liliental-Weber, Z.; Zakharov, D.N.; Zhuravlev, K.S.

    2005-01-01

    In spite of large number of articles dedicated to the investigation of GeSi islands, a lot of problems concerning growth mechanism and island composition, as well as elastic strains inside the QDs, are still unsolved. To solve such problems, the GeSi low dimensional structures were studied by Extended X-Ray Absorption Fine Structure (EXAFS). The aim of this investigation was to get knowledge about the local structure around Ge atoms inside formed quantum dots. The paper presents a series of measurements performed for a single Ge layer buried in the silicon matrix at A1 station at the HASYLAB/DESY (Germany) with the angle of 45 o between the incident beam and sample surface. The fluorescence, total electron yield and the transmission modes of detection were used. To confirm the EXAFS analysis conclusion more measurements were performed using transmission electron microscopy (TEM). The low temperature samples with 8-20 ML of Ge were investigated by cross-section and plan-view TEM. The reported results of TEM studies of the local structure of germanium quantum dots (QDs) in Si/Ge/Si '' sandwich '' structures are in good correlation with EXAFS conclusion

  9. Quick EXAFS experiments using a now GDA eclipse RCP GUI with EPICS hardware control

    International Nuclear Information System (INIS)

    Woolliscroft, R.J.; Coles, C.; Gerring, M.; Pearson, M.

    2012-01-01

    The Generic Data Acquisition (GDA) framework is an open source, Java and Eclipse RCP based, data acquisition software framework for synchrotron and neutron facilities. A new implementation of the GDA on the B18 X-ray beamline at the Diamond synchrotron will be discussed. This beamline performs energy scanning Xray Absorption Spectroscopy (XAS) experiments. It includes a continuous-scan mode of the monochromator synchronized with various detectors for Quick EXAFS (QEXAFS) experiments. XAS energy scans may now be performed in 30 s, where the equivalent step scans take approximately 40 minutes. A new generic perspective for the GDA client has been developed in which graphical editors are used to write XML files which hold experimental parameters. The XML files are marshalled by the GDA server to create Java beans used by Jython scripts which run on the GDA server. Underlying this, a new generic continuous scanning mechanism for the GDA has been developed. The new Eclipse RCP UI, the new continuous scanning mechanism, new hardware development and integration between the two systems shall be covered. (authors)

  10. EXAFS and XRD studies of nanocrystalline cerium oxide: the effect of preparation method on the microstructure

    International Nuclear Information System (INIS)

    Savin, S.L.P.; Chadwick, A.V.; Smith, M.E.; O'Dell, L.A.

    2007-01-01

    There is considerable interest in nanocrystalline materials due to their unusual properties, such as enhanced ionic conductivity in the case of nanocrystalline ionic solids. This has potential commercial applications, particularly for oxide ion conductors. However, a detailed knowledge of the microstructure is important in fully understanding the novel properties exhibited by nanocrystalline materials. The final microstructure of a material is dependent on the preparation method used, for example, sol-gel and ball-milling methods are commonly used in the preparation of nanocrystalline oxides. Additionally, there is a problem in maintaining the materials in nanocrystalline form when they are subjected to elevated temperatures. We have been exploring strategies to restrict the growth of nanocrystalline oxides and have found that adding a small amount of an inert material, e.g. SiO 2 or Al 2 O 3 , is particularly effective. We will report XRD and EXAFS studies of nanocrystalline ceria prepared by sol-gel, sol-gel pinned and ball-milling methods and the effect of preparation method on the final microstructure. (copyright 2007 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  11. DEVELOPMENT OF A HIGH RATE HIGH RESOLUTION DETECTOR FOR EXAFS EXPERIMENTS.

    Energy Technology Data Exchange (ETDEWEB)

    DE GERONIMO,G.; O CONNOR,P.; BEUTTENMULLER,R.H.; LI,Z.; KUCZEWSKI,A.J.; SIDDONS,D.P.

    2002-11-10

    A new detector for EXAFS experiments is being developed. It is based on a multi-element Si sensor and dedicated readout ASICs. The sensor is composed of 384 pixels, each having 1 mm{sup 2} area, arranged in four quadrants of 12 x 8 elements, and wire-bonded to 32-channel front-end ASICs. Each channel implements low noise preamplification with self-adaptive continuous reset, high order shaper, band-gap referenced baseline stabilizer, one threshold comparator and two DAC adjustable window comparators, each followed by a 24-bit counter. Fabricated in 0.35{micro}m CMOS dissipates about 8mW per channel. First measurements show at room temperature a resolution of 14 rms electrons without the detector and of 40 rms electrons (340eV) with the detector connected and biased. Cooling at -35C a FWHM of 205eV (167eV from electronics) was measured at the Mn-K{alpha} line. A resolution of about 300eV was measured for rates approaching 100kcps/cm{sup 2} per channel, corresponding to an overall rate in excess of 10MHz/cm{sup 2}. A channel-to-channel threshold dispersion after DACs adjustment of 2.5 rms electrons was also measured.

  12. EXAFS studies on the reaction of gold (III) chloride complex ions with sodium hydroxide and glucose.

    Science.gov (United States)

    Pacławski, K; Zajac, D A; Borowiec, M; Kapusta, Cz; Fitzner, K

    2010-11-11

    EXAFS and QEXAFS experiments were carried out at Hasylab laboratory in DESY center (X1 beamline, Hamburg, Germany) to monitor the course of the hydrolysis reactions of [AuCl(4)](-) complex ions as well as their reduction using glucose. As a result, changes in the spectra of [AuCl(4)](-) ions and disappearance of absorption Au-L(3) edge were registered. From the results of the experiments we have carried out, the changes in bond lengths between Au(3+) central ion and Cl(-) ligands as well as the reduction of Au(3+) to metallic form (colloidal gold was formed in the system) are evident. Good quality spectra obtained before and after the reactions gave a chance to determine the bond length characteristic of Au-Cl, Au-OH and Au-Au pairs. Additionally, the obtained results were compared with the simulated spectra of different gold (III) complex ions, possibly present in the solution. Finally, the mechanism of these reactions was suggested. Unfortunately, it was not possible to detect the changes in the structure of gold (III) complex ions within the time of reaction, because of too high rates of both processes (hydrolysis and reduction) as compared with the detection time.

  13. Characterization of atmospheric aerosols using Synchroton radiation total reflection X-ray fluorescence and Fe K-edge total reflection X-ray fluorescence-X-ray absorption near-edge structure

    Energy Technology Data Exchange (ETDEWEB)

    Fittschen, U.E.A. [Department of Chemistry, University of Hamburg, Martin-Luther-King-Platz 6, 20146 Hamburg (Germany)], E-mail: ursula.fittschen@chemie.uni-hamburg.de; Meirer, F. [Atominstitut, Vienna University of Technology, Stadionallee 2, 1020 Wien (Austria)], E-mail: fmeirer@ati.ac.at; Streli, C. [Atominstitut, Vienna University of Technology, Stadionallee 2, 1020 Wien (Austria)], E-mail: streli@ati.ac.at; Wobrauschek, P. [Atominstitut, Vienna University of Technology, Stadionallee 2, 1020 Wien (Austria)], E-mail: wobi@ati.ac.at; Thiele, J. [Department of Chemistry, University of Hamburg, Martin-Luther-King-Platz 6, 20146 Hamburg (Germany)], E-mail: Julian.Thiele@gmx.de; Falkenberg, G. [Hamburger Synchrotronstrahlungslabor at Deutsches Elektronen-Synchrotron DESY, Notkestr. 85, 22603 Hamburg (Germany)], E-mail: falkenbe@mail.desy.de; Pepponi, G. [ITC-irst, Via Sommarive 18, 38050 Povo (Trento) (Italy)], E-mail: pepponi@itc.it

    2008-12-15

    In this study a new procedure using Synchrotron total reflection X-ray fluorescence (SR-TXRF) to characterize elemental amounts in atmospheric aerosols down to particle sizes of 0.015 um is presented. The procedure was thoroughly evaluated regarding bounce off effects and blank values. Additionally the potential of total reflection X-ray fluorescence-X-ray absorption near edge structure (SR-TXRF-XANES) for speciation of FeII/III down to amounts of 34 pg in aerosols which were collected for 1 h is shown. The aerosols were collected in the city of Hamburg with a low pressure Berner impactor on Si carriers covered with silicone over time periods of 60 and 20 min each. The particles were collected in four and ten size fractions of 10.0-8.0 {mu}m, 8.0-2.0 {mu}m, 2.0-0.13 {mu}m 0.13-0.015 {mu}m (aerodynamic particle size) and 15-30 nm, 30-60 nm, 60-130 nm, 130-250 nm, 250-500 nm, 0.5-1 {mu}m, 1-2 {mu}m, 2-4 {mu}m, 4-8 {mu}m, 8-16 {mu}m. Prior to the sampling 'bounce off' effects on Silicone and Vaseline coated Si carriers were studied with total reflection X-ray fluorescence. According to the results silicone coated carriers were chosen for the analysis. Additionally, blank levels originating from the sampling device and the calibration procedure were studied. Blank levels of Fe corresponded to 1-10% of Fe in the aerosol samples. Blank levels stemming from the internal standard were found to be negligible. The results from the Synchroton radiation total reflection X-ray fluorescence analysis of the aerosols showed that 20 min of sampling time gave still enough sample material for elemental determination of most elements. For the determination of the oxidation state of Fe in the aerosols different Fe salts were prepared as a reference from suspensions in isopropanol. The results from the Fe K-edge Synchroton radiation total reflection X-ray fluorescence-X-ray absorption near-edge structure analysis of the aerosol samples showed that mainly Fe(III) was present in

  14. Characterization of atmospheric aerosols using Synchroton radiation total reflection X-ray fluorescence and Fe K-edge total reflection X-ray fluorescence-X-ray absorption near-edge structure

    International Nuclear Information System (INIS)

    Fittschen, U.E.A.; Meirer, F.; Streli, C.; Wobrauschek, P.; Thiele, J.; Falkenberg, G.; Pepponi, G.

    2008-01-01

    In this study a new procedure using Synchrotron total reflection X-ray fluorescence (SR-TXRF) to characterize elemental amounts in atmospheric aerosols down to particle sizes of 0.015 um is presented. The procedure was thoroughly evaluated regarding bounce off effects and blank values. Additionally the potential of total reflection X-ray fluorescence-X-ray absorption near edge structure (SR-TXRF-XANES) for speciation of FeII/III down to amounts of 34 pg in aerosols which were collected for 1 h is shown. The aerosols were collected in the city of Hamburg with a low pressure Berner impactor on Si carriers covered with silicone over time periods of 60 and 20 min each. The particles were collected in four and ten size fractions of 10.0-8.0 μm, 8.0-2.0 μm, 2.0-0.13 μm 0.13-0.015 μm (aerodynamic particle size) and 15-30 nm, 30-60 nm, 60-130 nm, 130-250 nm, 250-500 nm, 0.5-1 μm, 1-2 μm, 2-4 μm, 4-8 μm, 8-16 μm. Prior to the sampling 'bounce off' effects on Silicone and Vaseline coated Si carriers were studied with total reflection X-ray fluorescence. According to the results silicone coated carriers were chosen for the analysis. Additionally, blank levels originating from the sampling device and the calibration procedure were studied. Blank levels of Fe corresponded to 1-10% of Fe in the aerosol samples. Blank levels stemming from the internal standard were found to be negligible. The results from the Synchroton radiation total reflection X-ray fluorescence analysis of the aerosols showed that 20 min of sampling time gave still enough sample material for elemental determination of most elements. For the determination of the oxidation state of Fe in the aerosols different Fe salts were prepared as a reference from suspensions in isopropanol. The results from the Fe K-edge Synchroton radiation total reflection X-ray fluorescence-X-ray absorption near-edge structure analysis of the aerosol samples showed that mainly Fe(III) was present in all particle size fractions

  15. Crystal and electronic structure study of AgAu and AgCu bimetallic alloy thin films by X-ray techniques

    Energy Technology Data Exchange (ETDEWEB)

    Ozkendir, O. Murat, E-mail: ozkendir@gmail.com [Mersin University, Faculty of Technology, Energy Systems Engineering, Tarsus (Turkey); Mersin University, Institute of Natural Science, Department of Nanotechnology and Advanced Materials, Mersin (Turkey); Cengiz, E. [Karadeniz Technical University, Faculty of Science, Department of Physics, Trabzon (Turkey); Yalaz, E. [Mersin University, Institute of Natural Science, Department of Nanotechnology and Advanced Materials, Mersin (Turkey); Söğüt, Ö.; Ayas, D.H. [Kahramanmaraş Sütçü İmam Üniversitesi, Faculty of Science and Letters, Department of Physics, Kahramanmaraş (Turkey); Thammajak, B. Nirawat [Synchrotron Light Research Institute (Public Organisation), 111 University Avenue, T. Suranaree, A. Muang, Nakhon Ratchasima 30000 (Thailand)

    2016-05-15

    Highlights: • Crystal and electronic properties of bimetallic AgCu and AgAu alloy thin films were studied. • Both AgCu and AgAu bimetallic samples were determined to have cubic crystal geometry. • Strong influence of Cu and Au atoms on the electronic structure of the Ag atoms were determined. - Abstract: Crystal and electronic structure properties of bimetallic AgAu and AgCu alloy thin films were investigated by X-ray spectroscopic techniques. The aim of this study is to probe the influence of Au or Cu atoms on the electronic behaviors of Ag ions in bimetallic alloy materials that yields different crystal properties. To identify the mechanisms causing crystal phase transitions, study were supported by the collected EXAFS (Extended X-ray Absorption Fine Structure) data. Crystal structures of both Cu and Au doped bimetallic Ag samples were determined mainly in cubic geometry with “Fm3m” space group. Through the Ag–Au and Ag–Cu molecular interactions during bimetallic alloy formations, highly overlapped electronic levels that supports large molecular band formations were observed with different ionization states. Besides, traces of the d–d interactions in Au rich samples were determined as the main interplay in the broad molecular bond formations. The exact atomic locations and types in the samples were determined by EXAFS studies and supported by the performed calculations with FEFF scientific code.

  16. Spectroscopic investigation on the chemical forms of Cu during the synthesis of zeolite X at low temperature

    International Nuclear Information System (INIS)

    Terzano, Roberto; Spagnuolo, Matteo; Medici, Luca; Tateo, Fabio; Vekemans, Bart; Janssens, Koen; Ruggiero, Pacifico

    2006-01-01

    The direct synthesis of zeolites in polluted soils has proved to be a promising process for the stabilization of metals inside these minerals. Nevertheless, more detailed information about this process is still needed in order to better foresee the fate of metals in treated soils. In this work, zeolite X has been synthesized under alkaline conditions in an aqueous solution containing 2500 mg kg -1 of Cu, starting from Na silicate and Al hydroxide at 60 deg. C. Aluminium, Si and Cu concentrations in the aqueous phase, during zeolite synthesis, were measured over a period of 160 h. The solid products have been characterized over time by XRD, SEM-EDX, ESR, FT-IR, and synchrotron radiation X-ray microbeam absorption near edge structure (μ-XANES) and extended X-ray absorption fine structure (μ-EXAFS) spectroscopy. It appears that the marked reduction of Cu concentration in solution is not only due to a simple precipitation effect, but also to processes connected with the formation of zeolite X which could entrap, inside its porous structure, nano- or micro-occlusions of precipitated Cu hydroxides and/or oxides. In addition, EXAFS observations strengthen the hypothesis of the presence of different Cu phases even at a short-range molecular level and suggest that some of these occlusions could be even bound to the zeolite framework. The results suggest that zeolite formation could be used to reduce the availability of metals in polluted soils

  17. XANES, EXAFS and Kbeta spectroscopic studies of the oxygen-evolving complex in Photosystem II

    Energy Technology Data Exchange (ETDEWEB)

    Robblee, John Henry [Univ. of California, Berkeley, CA (United States)

    2000-12-01

    A key question for the understanding of photosynthetic water oxidation is whether the four oxidizing equivalents necessary to oxidize water to dioxygen are accumulated on the four Mn ions of the oxygen evolving complex (OEC), or whether some ligand-centered oxidations take place before the formation and release of dioxygen during the S3 → [S4] → S0 transition. Progress in instrumentation and flash sample preparation allowed us to apply Mn Kβ X-ray emission spectroscopy (Kb XES) to this problem for the first time. The Kβ XES results, in combination with Mn X-ray absorption near-edge structure (XANES) and electron paramagnetic resonance (EPR) data obtained from the same set of samples, show that the S2 → S3 transition, in contrast to the S0 → S1 and S1 → S2 transitions, does not involve a Mn-centered oxidation. This is rationalized by manganese μ-oxo bridge radical formation during the S2 → S3 transition. Using extended X-ray absorption fine structure (EXAFS) spectroscopy, the local environment of the Mn atoms in the S0 state has been structurally characterized. These results show that the Mn-Mn distance in one of the di-μ-oxo-bridged Mn-Mn moieties increases from 2.7 Å in the S1} state to 2.85 Å in the S0 state. Furthermore, evidence is presented that shows three di-μ-oxo binuclear Mn2 clusters may be present in the OEC, which is contrary to the widely held theory that two such clusters are present in the OEC. The EPR properties of the S0 state have been investigated and a characteristic ''multiline'' signal in the S0 state has been discovered in the presence of methanol. This provides the first direct confirmation that the native S0 state is paramagnetic. In addition, this signal was simulated using parameters derived from three

  18. EXAFS analysis of full color glasses and glass ceramics: local order and color

    International Nuclear Information System (INIS)

    Santa Cruz, Petrus A.; Sa, Gilberto F. de; Malta, Oscar L.; Silva, Jose expedito Cavalcante

    1996-01-01

    The generation and control of the relative intensities of the primary additive colors in solid state light emitters is very important to the development of higher resolution media, used in color monitors, solid state sensors, large area and flat displays and other optoelectronic devices. We have developed a multi-doped glassy material named FCG (full color glass, to generate and to control the primary light colors, allowing the simulation of any color of light by additive synthesis. Tm(III), Tb(III) and Eu(III) ions were used (0.01 to 5.0 mol%) as blue, green and red narrow emitters. A wide color gamut was obtained under ultraviolet excitation by varying the material composition. The chromaticity diagram is covered, including the white simulation. We proposed a mechanism to control the chromaticity of a fixed composition of the material, using the Er (III) as a selective quencher that may be deactivated by infrared excitation. Although this new material presents at this time a high efficiency, it may be improved because the energy transfer between the rare earth triad may be still reduced. Optical spectroscopy measurements confirms that it is still possible to improve the efficiency of the FCC material. EXAFS analysis will be used to probe the local environment around the triad of rare earth that generates the primary colors. For this purpose we have prepared single doped glasses with each component of the triad with the same concentration than FCG. The devitrification of these glasses will be analyzed in order to produce glassceramics with ion segregation. (author)

  19. Geological and anthropogenic factors influencing mercury speciation in mine wastes: An EXAFS spectroscopy study

    Science.gov (United States)

    Kim, C.S.; Rytuba, J.J.; Brown, Gordon E.

    2004-01-01

    The speciation of Hg is a critical determinant of its mobility, reactivity, and potential bioavailability in mine-impacted regions. Furthermore, Hg speciation in these complex natural systems is influenced by a number of physical, geological, and anthropogenic variables. In order to investigate the degree to which several of these variables may affect Hg speciation, extended X-ray absorption fine structure (EXAFS) spectroscopy was used to determine the Hg phases and relative proportions of these phases present in Hg-bearing wastes from selected mine-impacted regions in California and Nevada. The geological origin of Hg ore has a significant effect on Hg speciation in mine wastes. Specifically, samples collected from hot-spring Hg deposits were found to contain soluble Hg-chloride phases, while such phases were largely absent in samples from silica-carbonate Hg deposits; in both deposit types, however, Hg-sulfides in the form of cinnabar (HgS, hex.) and metacinnabar (HgS, cub.) dominate. Calcined wastes in which Hg ore was crushed and roasted in excess of 600??C, contain high proportions of metacinnabar while the main Hg-containing phase in unroasted waste rock samples from the same mines is cinnabar. The calcining process is thought to promote the reconstructive phase transformation of cinnabar to metacinnabar, which typically occurs at 345??C. The total Hg concentration in calcines is strongly correlated with particle size, with increases of nearly an order of magnitude in total Hg concentration between the 500-2000 ??m and process, identified the presence of Hg-sulfides and schuetteite (Hg3O2SO4), which may have formed as a result of long-term Hg(0) burial in reducing high-sulfide sediments. ?? 2003 Elsevier Ltd. All rights reserved.

  20. The geochemical behaviour of selenium in the Boom Clay system - a XANES and EXAFS study

    International Nuclear Information System (INIS)

    2S, KULeuven, B-3001Leuven (Belgium))" data-affiliation=" (Center for surface Chemistry and Catalysis - M2S, KULeuven, B-3001Leuven (Belgium))" >Breynaert, Eric; 2S, KULeuven, B-3001Leuven (Belgium))" data-affiliation=" (Center for surface Chemistry and Catalysis - M2S, KULeuven, B-3001Leuven (Belgium))" >Dom, Dirk; 2S, KULeuven, B-3001Leuven (Belgium))" data-affiliation=" (Center for surface Chemistry and Catalysis - M2S, KULeuven, B-3001Leuven (Belgium))" >Vancluysen, Jacqueline; 2S, KULeuven, B-3001Leuven (Belgium))" data-affiliation=" (Center for surface Chemistry and Catalysis - M2S, KULeuven, B-3001Leuven (Belgium))" >Kirschhock, Christine E.A.; 2S, KULeuven, B-3001Leuven (Belgium))" data-affiliation=" (Center for surface Chemistry and Catalysis - M2S, KULeuven, B-3001Leuven (Belgium))" >Maes, Andre; Scheinost, Andreas C.

    2010-01-01

    Document available in extended abstract form only. In Belgium, the Boom Clay formation is studied as a reference host formation for the geological disposal of high-level and long-lived radioactive waste for more than 30 years. This formation mainly consists of mixed clay minerals (illite, inter-stratified illite-smectite), pyrite and immobile and dissolved natural organic matter. Since it provides good sorption capacities, very low permeability, and chemically reducing conditions due to the presence of pyrite (FeS 2 ), the Boom clay formation itself is considered to be the main barrier preventing radionuclide migration from the geological repository. Within this concept for geological storage Se 79 has been identified as one of the critical elements contributing to the final dose to man. Although the sorption and migration behaviour of Se in the Boom Clay system has been thoroughly studied, the speciation of Se in the Boom Clay system has never been identified spectroscopically. In all previous studies, the interpretation of the behaviour of Se in Boom Clay conditions has always been based on circumstantial evidence such as solubility measurements or comparison with the spectroscopically identified speciation of Se in model systems. Based on the XANES analysis, selenite is transformed into Se 0 confirming the previously proposed reduction of selenite in the Boom Clay system. Combination of the mass-balance for Se with the results from linear combination analysis of the XANES spectra provided new evidence for the sorption-reduction mechanism proposed to explain the interaction between Se(IV) and the BC solid phase. In addition, evidence was found that that the fate of Se(IV) in the BC system is completely dominated by its interaction with pyrite present in the Boom Clay. The combined EXAFS analysis of Se in Se 0 reference phases (hexagonal, monoclinic, Se-loaded pyrite) allowed to elucidate further details on the short-range structure of the reaction products formed

  1. EXAFS Characterization of Dendrimer-Derived Pt/γ-Al2O3

    International Nuclear Information System (INIS)

    Siani, A.; Alexeev, O. S.; Williams, C. T.; Ploehn, H. J.; Amiridis, M. D.

    2007-01-01

    The various steps involved in the preparation of a Pt/γ-Al2O3 material using hydroxyl-terminated generation four (G4OH) PAMAM dendrimers as templates were monitored by EXAFS. The results indicate that Cl ligands in the Pt precursors (H2PtCl6 and K2PtCl4) were partially replaced by aquo ligands upon hydrolysis to form [PtCl3(H2O)3]+ and [PtCl2(H2O)2] species. After interaction of such species with G4OH, Cl ligands from the first coordination shell of Pt were further replaced by nitrogen atoms from the dendrimer interior, indicating the complexation of Pt with the dendrimer. This process was accompanied by a transfer of the electron density from the dendrimer to Pt, indicating that the former plays the role of a ligand. Following treatment of the H2PtCl6/G4OH and K2PtCl4/G4OH composites with NaBH4, no substantial changes were detecteded in the electronic or coordination environment of Pt, and no formation of metal nanoparticles was observed. However, when the reduction treatment was performed with H2, the formation of extremely small Pt clusters incorporating no more than 4 Pt atoms was observed. These Pt species remained strongly bonded to the dendrimer and their nuclearity depends on the length of the H2 treatment. Formation of Pt nanoparticles with an average diameter of approximately 10 A was finally observed after the deposition of H2PtCl6/G4OH on γ-Al2O3 and drying, suggesting that their formation may be related to the collapse of the dendrimer structure. The Pt nanoparticles formed appear to have high mobility, since subsequent thermal treatment in O2/H2 led to further sintering

  2. Macroscopic and microscopic investigation of Ni(II) sequestration on diatomite by batch, XPS, and EXAFS techniques.

    Science.gov (United States)

    Sheng, Guodong; Yang, Shitong; Sheng, Jiang; Hu, Jun; Tan, Xiaoli; Wang, Xiangke

    2011-09-15

    Sequestration of Ni(II) on diatomite as a function of time, pH, and temperature was investigated by batch, XPS, and EXAFS techniques. The ionic strength-dependent sorption at pH < 7.0 was consistent with outer-sphere surface complexation, while the ionic strength-independent sorption at pH = 7.0-8.6 was indicative of inner-sphere surface complexation. EXAFS results indicated that the adsorbed Ni(II) consisted of ∼6 O at R(Ni-O) ≈ 2.05 Å. EXAFS analysis from the second shell suggested that three phenomena occurred at the diatomite/water interface: (1) outer-sphere and/or inner-sphere complexation; (2) dissolution of Si which is the rate limiting step during Ni uptake; and (3) extensive growth of surface (co)precipitates. Under acidic conditions, outer-sphere complexation is the main mechanism controlling Ni uptake, which is in good agreement with the macroscopic results. At contact time of 1 h or 1 day or pH = 7.0-8.0, surface coprecipitates occur concurrently with inner-sphere complexes on diatomite surface, whereas at contact time of 1 month or pH = 10.0, surface (co)precipitates dominate Ni uptake. Furthermore, surface loading increases with temperature increasing, and surface coprecipitates become the dominant mechanism at elevated temperature. The results are important to understand Ni interaction with minerals at the solid-water interface, which is helpful to evaluate the mobility of Ni(II) in the natural environment.

  3. Mechanism of superconductivity in Yb sub 1 sub - sub x Ca sub x (Ba sub 0 sub . sub 8 Sr sub O sub . sub 2) sub 2 Cu sub 3 O sub 6 sub + subdelta

    CERN Document Server

    Anvekar, T S; Sarode, P R; Kamat-Dalal, V N; Narlikar, Anant V

    2002-01-01

    EXAFS, X-ray Rietveld refinement and infra-red absorption measurements have been made on Yb sub 1 sub - sub x Ca sub x (Ba sub 0 sub . sub 8 Sr sub 0 sub . sub 2) sub 2 Cu sub 3 O sub 6 sub + subdelta in order to understand the effect of Ca doping on the local structure of planar Cu ion. The study indicates that restoration of superconductivity is due to oxidation of copper ions in the CuO sub 2 planes. (author)

  4. Selenium Sequestration in a Cationic Layered Rare Earth Hydroxide: A Combined Batch Experiments and EXAFS Investigation.

    Science.gov (United States)

    Zhu, Lin; Zhang, Linjuan; Li, Jie; Zhang, Duo; Chen, Lanhua; Sheng, Daopeng; Yang, Shitong; Xiao, Chengliang; Wang, Jianqiang; Chai, Zhifang; Albrecht-Schmitt, Thomas E; Wang, Shuao

    2017-08-01

    Selenium is of great concern owing to its acutely toxic characteristic at elevated dosage and the long-term radiotoxicity of 79 Se. The contents of selenium in industrial wastewater, agricultural runoff, and drinking water have to be constrained to a value of 50 μg/L as the maximum concentration limit. We reported here the selenium uptake using a structurally well-defined cationic layered rare earth hydroxide, Y 2 (OH) 5 Cl·1.5H 2 O. The sorption kinetics, isotherms, selectivity, and desorption of selenite and selenate on Y 2 (OH) 5 Cl·1.5H 2 O at pH 7 and 8.5 were systematically investigated using a batch method. The maximum sorption capacities of selenite and selenate are 207 and 124 mg/g, respectively, both representing the new records among those of inorganic sorbents. In the low concentration region, Y 2 (OH) 5 Cl·1.5H 2 O is able to almost completely remove selenium from aqueous solution even in the presence of competitive anions such as NO 3 - , Cl - , CO 3 2- , SO 4 2- , and HPO 4 2- . The resulting concentration of selenium is below 10 μg/L, well meeting the strictest criterion for the drinking water. The selenate on loaded samples could be desorbed by rinsing with concentrated noncomplexing NaCl solutions whereas complexing ligands have to be employed to elute selenite for the material regeneration. After desorption, Y 2 (OH) 5 Cl·1.5H 2 O could be reused to remove selenate and selenite. In addition, the sorption mechanism was unraveled by the combination of EDS, FT-IR, Raman, PXRD, and EXAFS techniques. Specifically, the selenate ions were exchanged with chloride ions in the interlayer space, forming outer-sphere complexes. In comparison, besides anion exchange mechanism, the selenite ions were directly bound to the Y 3+ center in the positively charged layer of [Y 2 (OH) 5 (H 2 O)] + through strong bidentate binuclear inner-sphere complexation, consistent with the observation of the higher uptake of selenite over selenate. The results presented in

  5. Spin Equilibria in Monomeric Manganocenes: Solid State Magnetic and EXAFS Studies

    Energy Technology Data Exchange (ETDEWEB)

    Walter, M. D.; Sofield, C. D.; Booth, C. H.; Andersen, R. A.

    2009-02-09

    Magnetic susceptibility measurements and X-ray data confirm that tert-butyl-substituted manganocenes [(Me{sub 3}C){sub n}C{sub 5}H{sub 5?n}]{sub 2}Mn (n = 1, 2) follow the trend previously observed with the methylated manganocenes; that is, electron-donating groups attached to the Cp ring stabilize the low-spin (LS) electronic ground state relative to Cp{sub 2}Mn and exhibit higher spin-crossover (SCO) temperatures. However, introducing three CMe{sub 3} groups on each ring gives a temperature-invariant high-spin (HS) state manganocene. The origin of the high-spin state in [1,2,4-(Me{sub 3}C){sub 3}C{sub 5}H{sub 2}]{sub 2}Mn is due to the significant bulk of the [1,2,4-(Me{sub 3}C){sub 3}C{sub 5}H{sub 2}]{sup -} ligand, which is sufficient to generate severe inter-ring steric strain that prevents the realization of the low-spin state. Interestingly, the spin transition in [1,3-(Me{sub 3}C){sub 2}C{sub 5}H{sub 3}]{sub 2}Mn is accompanied by a phase transition resulting in a significant irreversible hysteresis ({Delta}T{sub c} = 16 K). This structural transition was also observed by extended X-ray absorption fine-structure (EXAFS) measurements. Magnetic susceptibility studies and X-ray diffraction data on SiMe{sub 3}-substituted manganocenes [(Me{sub 3}Si){sub n}C{sub 5}H{sub 5-n}]{sub 2}Mn (n = 1, 2, 3) show high-spin configurations in these cases. Although tetra- and hexasubstituted manganocenes are high-spin at all accessible temperatures, the disubstituted manganocenes exhibit a small low-spin admixture at low temperature. In this respect it behaves similarly to [(Me{sub 3}C)(Me{sub 3}Si)C{sub 5}H{sub 3}]{sub 2}Mn, which has a constant low-spin admixture up to 90 K and then gradually converts to high-spin. Thermal spin-trapping can be observed for [(Me{sub 3}C)(Me{sub 3}Si)C{sub 5}H{sub 3}]{sub 2}Mn on rapid cooling.

  6. Energy and polarization dependence of resonant inelastic X-ray scattering in Nd2CuO4

    International Nuclear Information System (INIS)

    Hill, J.P.; Kao, C.C.; Haemaelaeinen, K.

    1998-01-01

    The authors report the energy and polarization dependence of resonant inelastic x-ray scattering from Nd 2 CuO 4 . An energy loss feature at ∼6 eV is observed in the vicinity of the Cu K-edge. Numerical calculations based on the Anderson impurity model identify this as a charge transfer excitation to the anti-bonding state. The incident polarization is shown to select the intermediate states participating in the resonance process. Resonances are observed at 8,990 eV and 9,000 eV with the incident polarization perpendicular and parallel to the CuO planes, respectively. In contrast to the single-site model calculations, no resonances are observed associated with the 1s3d 10 L intermediate states, suggesting non-local effects play a role

  7. X-ray absorption spectroscopy: EXAFS and XANES - A versatile tool to study the atomic and electronic structure of materials

    International Nuclear Information System (INIS)

    Alp, E.E.; Mini, S.M.; Ramanathan, M.

    1990-01-01

    X-ray absorption spectroscopy (XAS) had been an essential tool to gather spectroscopic information about atomic energy level structure in the early decades of this century. The correct interpretation of the oscillatory structure in the x-ray absorption cross-section above the absorption edge has transformed XAS from a spectroscopic tool to a structural technique. EXAFS (Extended X-ray Absorption Fine Structure) yields information about the interatomic distances, near neighbor coordination numbers, and lattice dynamics. XANES (X-ray Absorption Near Edge Structure), on the other hand, gives information about the valence state, energy bandwidth and bond angles. Today, there are about 50 experimental stations in various synchrotrons around the world dedicated to collecting x-ray absorption data from the bulk and surfaces of solids and liquids. In this chapter, they will give the basic principles of XAS, explain the information content of essentially two different aspects of the absorption process leading to EXAFS and XANES, and discuss the source and sample limitations

  8. Shape resonances and EXAFS scattering in the $Pt L_{2,3}$ XANES from a Pt electrode

    CERN Document Server

    O'Grady, W E

    1999-01-01

    Atomic hydrogen and oxygen adsorption on a platinum electrode in H /sub 2/SO/sub 4/ and HClO/sub 4/ electrolytes were studied by Pt L /sub 23/ XANES. The Pt electrode was formed of highly dispersed 1.5-3.0 nm particles supported on $9 carbon. A difference procedure utilizing the L/sub 2/ and L/sub 3/ spectra at various applied voltages was used to isolate the electronic and geometric effects in the XANES spectra. At 0.54 V (relative to RHE) the Pt electrode in $9 HClO/sub 4/ is assumed to be "clean". By taking the difference between the spectra at 0.0 and 0.54 V, the Pt-H antibonding state (electronic effect) is isolated and found to have a Fano-resonance line shape. In addition, a $9 significant Pt-H EXAFS scattering (geometric effect) was found for photon energies 0 to 20 eV above the edge. The difference between the spectra at 1.14 and 0.54 V allows isolation of the Pt-O antibonding state and the Pt-O EXAFS $9 scattering. (7 refs).

  9. Towards accurate structural characterization of metal centres in protein crystals: the structures of Ni and Cu T6 bovine insulin derivatives

    DEFF Research Database (Denmark)

    Frankær, Christian Grundahl; Mossin, Susanne; Ståhl, Kenny

    2014-01-01

    Using synchrotron radiation (SR), the crystal structures of T6 bovine insulin complexed with Ni2+ and Cu2+ were solved to 1.50 and 1.45 Å resolution, respectively. The level of detail around the metal centres in these structures was highly limited, and the coordination of water in Cu site II...... of the copper insulin derivative was deteriorated as a consequence of radiation damage. To provide more detail, X-ray absorption spectroscopy (XAS) was used to improve the information level about metal coordination in each derivative. The nickel derivative contains hexacoordinated Ni2+ with trigonal symmetry...... by electron paramagnetic resonance (EPR). The coordination distances were refined from EXAFS with standard deviations within 0.01 Å. The insulin derivative containing Cu2+ is sensitive towards photoreduction when exposed to SR. During the reduction of Cu2+ to Cu+, the coordination geometry of copper changes...

  10. Characterization of Binary Ag-Cu Ion Mixtures in Zeolites: Their Reduction Products and Stability to Air Oxidation

    International Nuclear Information System (INIS)

    Fiddy, Steven; Petranovskii, Vitalii; Ogden, Steve; Iznaga, Inocente Rodriguez

    2007-01-01

    A series of Ag+-Cu2+ binary mixtures with different Ag/Cu ratios were supported on mordenite with different Si/Al ratios and were subsequently reduced under hydrogen in the temperature range 323K - 473K. Ag and Cu K-edge X-ray Absorption Spectroscopy (XAS) was conducted on these systems in-situ to monitor the reduction species formed and the kinetics of their reduction. In-situ XANES clearly demonstrates that the formation of silver particles is severely impeded by the addition of copper and that the copper is converted from Cu(II) to Cu(I) during reduction and completely reverts back to Cu(II) during cooling. There are no indications at any stage of the formation of bimetallic Ag-Cu clusters. Interestingly, the Ag/Cu ratio appears to have no influence of the reduction kinetics and reduction products formed with only the highest Si/Al ratio (MR = 128) investigated during this study having an influence on the reduction and stability to air oxidation

  11. The application of iterative transformation factor analysis to resolve multi-component EXAFS spectra of uranium(6) complexes with acetic acid as a function of pH

    International Nuclear Information System (INIS)

    Robberg, A.; Reich, T.

    2002-01-01

    Synchrotron-based EXAFS spectroscopy is a powerful technique to obtain structural information on radionuclide complexes in solution. Depending on the chemical conditions of the samples several radionuclide species can coexist in the solution as is often the case for environmentally related samples. All radionuclide species, which may have different near-neighbour environments, contribute to the measured EXAFS signal. In order to isolate the EXAFS spectra of the individual species (pure spectral components), it is necessary, in a first step, to measure a series of samples where their composition is changed by variation of one physico-chemical parameter (e.g. pH, concentration, etc.). For the spectral decomposition it is necessary that the EXAFS signal change as a function of the chosen physico-chemical parameter. In a second step, the series of EXAFS spectra is analysed with Eigen analysis and Iterative Transformation Factor Analysis (ITFA). As a result of the ITFA one obtains: a) for each sample the relative concentration of the structural distinguishable species and b) their corresponding pure spectral components. From the information obtained in a), one can construct a speciation diagram. The pure spectral components contain the structural information of the individual species, which can be extracted by conventional EXAFS analysis. To evaluate our ITFA algorithm for EXAFS analysis of mixtures, we prepared a series of eight solution samples of 0.05 M uranium(VI) and 1 M acetate (Ac) in the pH range of 0.1 to 4.5. From thermodynamic constants it is known that under these conditions up to four species can occur: uranyl hydrate, and the 1:1, 1:2 and 1:3 complexes of uranyl acetate. The uranium L III -edge EXAFS spectra were measured at room temperature in transmission mode at the Rossendorf Beamline (ROBL) at the ESRF. The average bond length between uranium and the equatorial oxygen atoms (O eq ) increases from 2.40 to 2.46 angstrom with increasing pH. This increase

  12. Relation between interfacial structure and mechanical properties in AlN/TiN bilayers investigated by EXAFS

    International Nuclear Information System (INIS)

    Ersen, O.; Tuilier, M.-H.; Thobor-Keck, A.; Rousselot, C.; Cortes, R.

    2005-01-01

    The relation between the mechanical properties and the structure of AlN/TiN bilayers prepared by reactive magnetron sputtering in the 600 nm range is investigated. Al and Ti K-edge extended X-ray absorption fine structure is used in order to determine the local order around Al and Ti by comparison with 300 nm thick AlN and TiN single layers. The use of this powerful local probe allows the evidence of intermixing between AlN and TiN deposited layers, which is suggested by glow discharge optical emission spectroscopy experiments. The effect of ionic bombardment applied at various steps of the deposition process is studied. The ionic bombardment applied during the deposit induces substantial changes in the absorption spectra that are assigned to a decrease of intermixing and an improvement of local order. Simulations of (Al, Ti)N ternary alloys Al and Ti K-edge absorption spectra for increasing mean occupation factors C Ti (C Al ) of Ti(Al) substituting Al(Ti) in hexagonal AlN (cubic TiN) lattice are performed in order to determine the initial parameters for the fit of the experimental data. The refinements performed by using FEFFIT software demonstrate that an ionic bombardment applied during the deposition phase results in a significant reduction of the number of Al-Ti pairs within the bilayer and an improvement of the local order around Ti and Al, which is quantified by a decrease of the Debye-Waller parameters. This structural evolution is tentatively correlated with the improvement of mechanical properties of the bilayers

  13. Relation between interfacial structure and mechanical properties in AlN/TiN bilayers investigated by EXAFS

    Energy Technology Data Exchange (ETDEWEB)

    Ersen, O. [Equipe de Recherche Mecanique, Materiaux et Procedes de Fabrication, 61, rue Albert Camus, F-68093 Mulhouse (France)]. E-mail: ovidiu.ersen@ipcms.u-strasbg.fr; Tuilier, M.-H. [Equipe de Recherche Mecanique, Materiaux et Procedes de Fabrication, 61, rue Albert Camus, F-68093 Mulhouse (France); Thobor-Keck, A. [Centre de Recherche sur les Ecoulements les Surfaces et les Transferts (UMR CNRS 6000), ITSFC, 4, place Tharradin, BP 71427, F-25211 Montbeliard (France); Rousselot, C. [Centre de Recherche sur les Ecoulements les Surfaces et les Transferts (UMR CNRS 6000), ITSFC, 4, place Tharradin, BP 71427, F-25211 Montbeliard (France); Cortes, R. [Laboratoire de Physique de la Matiere Condensee (UMR CNRS 7643), Ecole Polytechnique, F-91128 Palaiseau cedex (France)

    2005-06-01

    The relation between the mechanical properties and the structure of AlN/TiN bilayers prepared by reactive magnetron sputtering in the 600 nm range is investigated. Al and Ti K-edge extended X-ray absorption fine structure is used in order to determine the local order around Al and Ti by comparison with 300 nm thick AlN and TiN single layers. The use of this powerful local probe allows the evidence of intermixing between AlN and TiN deposited layers, which is suggested by glow discharge optical emission spectroscopy experiments. The effect of ionic bombardment applied at various steps of the deposition process is studied. The ionic bombardment applied during the deposit induces substantial changes in the absorption spectra that are assigned to a decrease of intermixing and an improvement of local order. Simulations of (Al, Ti)N ternary alloys Al and Ti K-edge absorption spectra for increasing mean occupation factors C {sub Ti} (C {sub Al}) of Ti(Al) substituting Al(Ti) in hexagonal AlN (cubic TiN) lattice are performed in order to determine the initial parameters for the fit of the experimental data. The refinements performed by using FEFFIT software demonstrate that an ionic bombardment applied during the deposition phase results in a significant reduction of the number of Al-Ti pairs within the bilayer and an improvement of the local order around Ti and Al, which is quantified by a decrease of the Debye-Waller parameters. This structural evolution is tentatively correlated with the improvement of mechanical properties of the bilayers.

  14. Hydration effects on the molecular structure of silica-supported vanadium oxide catalysts: A combined IR, Raman, UV–vis and EXAFS study

    NARCIS (Netherlands)

    Keller, D.E.; Visser, T.; Soulimani, F.; Koningsberger, D.C.; Weckhuysen, B.M.

    2007-01-01

    The effect of hydration on the molecular structure of silica-supported vanadium oxide catalysts with loadings of 1–16 wt.% V has been systematically investigated by infrared, Raman, UV–vis and EXAFS spectroscopy. IR and Raman spectra recorded during hydration revealed the formation of V–OH groups,

  15. Structural studies of ZnS:Cu (5 at %) nanocomposites in porous Al{sub 2}O{sub 3} of different thicknesses

    Energy Technology Data Exchange (ETDEWEB)

    Valeev, R. G., E-mail: rishatvaleev@mail.ru; Trigub, A. L.; Chukavin, A. I.; Beltiukov, A. N. [Physical-Technical Institute, Russian Academy of Sciences (Ural Branch) (Russian Federation)

    2017-02-15

    We present EXAFS, XANES, and X-ray diffraction data on nanoscale ZnS:Cu (5 at %) structures fabricated by the thermal deposition of a ZnS and Cu powder mixture in porous anodic alumina matrices with a pore diameter of 80 nm and thicknesses of 1, 3, and 5 μm. The results obtained are compared with data on ZnS:Cu films deposited onto a polycor surface. According to X-ray diffraction data, the samples contain copper and zinc compounds with sulfur (Cu{sub 2}S and ZnS, respectively); the ZnS compound is in the cubic (sphalerite) and hexagonal (wurtzite) modifications. EXAFS and XANES studies at the K absorption edges of zinc and copper showed that, in samples deposited onto polycor and alumina with thicknesses of 3 and 5 μm, most copper atoms form the Cu{sub 2}S compound, while, in the sample deposited onto a 1-μm-thick alumina layer, copper atoms form metallic particles on the sample surface. Copper crystals affect the Zn–S interatomic distance in the sample with a 1-μm-thick porous Al{sub 2}O{sub 3} layer; this distance is smaller than in the other samples.

  16. Growth control, structure, chemical state, and photoresponse of CuO-CdS core-shell heterostructure nanowires.

    Science.gov (United States)

    El Mel, A A; Buffière, M; Bouts, N; Gautron, E; Tessier, P Y; Henzler, K; Guttmann, P; Konstantinidis, S; Bittencourt, C; Snyders, R

    2013-07-05

    The growth of single-crystal CuO nanowires by thermal annealing of copper thin films in air is studied. We show that the density, length, and diameter of the nanowires can be controlled by tuning the morphology and structure of the copper thin films deposited by DC magnetron sputtering. After identifying the optimal conditions for the growth of CuO nanowires, chemical bath deposition is employed to coat the CuO nanowires with CdS in order to form p-n nanojunction arrays. As revealed by high-resolution TEM analysis, the thickness of the polycrystalline CdS shell increases when decreasing the diameter of the CuO core for a given time of CdS deposition. Near-edge x-ray absorption fine-structure spectroscopy combined with transmission x-ray microscopy allows the chemical analysis of isolated nanowires. The absence of modification in the spectra at the Cu L and O K edges after the deposition of CdS on the CuO nanowires indicates that neither Cd nor S diffuse into the CuO phase. We further demonstrate that the core-shell nanowires exhibit the I-V characteristic of a resistor instead of a diode. The electrical behavior of the device was found to be photosensitive, since increasing the incident light intensity induces an increase in the collected electrical current.

  17. Determination of sorption mechanisms of radionuclides onto clay minerals using extended x-ray absorption fine structure (EXAFS) spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Daehn, R.; Scheidegger, A.; Baeyens, B.; Bradbury, M.H

    2001-03-01

    Much of the experimental work in the Waste Management Laboratory at PSI concentrates on trying to understand the processes and mechanisms which govern the release of safety-relevant radionuclides from waste matrices, and their transport through engineered barrier systems and the surrounding geosphere. For this reason, detailed sorption studies of radionuclides (Cs, Sr, Ni, Zn, Eu, Am, Th and Se) in clay and cement systems are being conducted. The sorption and modelling studies are combined with kinetic investigations and advanced spectroscopic and microscopic methods in order to understand the sorption mechanism on an atomic level. This approach is part of a new multidisciplinary research field called Molecular Environmental Science (MES). In this paper, a case study of Ni sorption on montmorillonite is presented to illustrate how EXAFS can be used successfully to better understand sorption processes. (author)

  18. Determination of sorption mechanisms of radionuclides onto clay minerals using extended x-ray absorption fine structure (EXAFS) spectroscopy

    International Nuclear Information System (INIS)

    Daehn, R.; Scheidegger, A.; Baeyens, B.; Bradbury, M.H.

    2001-01-01

    Much of the experimental work in the Waste Management Laboratory at PSI concentrates on trying to understand the processes and mechanisms which govern the release of safety-relevant radionuclides from waste matrices, and their transport through engineered barrier systems and the surrounding geosphere. For this reason, detailed sorption studies of radionuclides (Cs, Sr, Ni, Zn, Eu, Am, Th and Se) in clay and cement systems are being conducted. The sorption and modelling studies are combined with kinetic investigations and advanced spectroscopic and microscopic methods in order to understand the sorption mechanism on an atomic level. This approach is part of a new multidisciplinary research field called Molecular Environmental Science (MES). In this paper, a case study of Ni sorption on montmorillonite is presented to illustrate how EXAFS can be used successfully to better understand sorption processes. (author)

  19. EXAFS study on the neptunium(V) complexation by various humic acids under neutral pH conditions

    Energy Technology Data Exchange (ETDEWEB)

    Sachs, S.; Schmeide, K.; Brendler, V.; Heise, K.H.; Bernhard, G. [Forschungszentrum Rossendorf e.V., Inst. of Radiochemistry, Dresden (Germany); Reich, T. [Forschungszentrum Rossendorf e.V., Inst. of Radiochemistry, Dresden (Germany); Univ. Mainz, Inst. of Nuclear Chemistry (Germany)

    2005-07-01

    The structure of Np(V) humic acid (HA) complexes at pH 7 was studied by extended X-ray absorption fine structure analysis (EXAFS). For the first time, the influence of phenolic OH groups on the complexation of HA and Np(V) in the neutral pH range was investigated using modified HAs with blocked phenolic OH groups and Bio-Rex70, a cation exchange resin having only carboxyl groups as proton exchanging sites. The formation of Np(V) humate complexes was verified by near-infrared (NIR) spectroscopy. Axial Np-O bond distances of 1.84-1.85 Aa were determined for the studied Np(V) humate complexes and the Np(V)-Bio-Rex70 sorbate. In the equatorial plane Np(V) is surrounded by about 3 oxygen atoms with bond lengths of 2.48-2.49 Aa. The comparison of the structural parameters of the Np(V) humates with those of Np(V)-Bio-Rex70 points to the fact that the interaction between HA and Np(V) in the neutral pH range is dominated by carboxylate groups. However, up to now a contribution of phenolic OH groups to the interaction process cannot be excluded completely. The comparison of the obtained structural data for the Np(V) humates to those of Np(V) carboxylates and Np(V) aquo ions reported in the literature indicates that humic acid carboxylate groups predominantly act as monodentate ligands. A differentiation between equatorial coordinated carboxylate groups and water molecules using EXAFS spectroscopy is impossible. (orig.)

  20. Size-dependent structural disorder in nanocrystalline Cu probed by synchrotron-based X-ray techniques

    International Nuclear Information System (INIS)

    Johannessen, B.; Kluth, P.; Cookson, D.J.; Foran, G.J.; Ridgway, M.C.

    2006-01-01

    Elemental Cu nanocrystals were synthesized in thin film SiO 2 by ion implantation and thermal annealing. The local atomic structure and nanocrystal size distribution were investigated by means of extended X-ray absorption fine structure (EXAFS) spectroscopy and small angle X-ray scattering (SAXS), respectively. We quantify the bondlength contraction and increased structural disorder in the nanocrystals as compared to a bulk Cu reference. Both are proportional to the inverse of the nanocrystal diameter, which in turn is proportional to the surface-area-to-volume ratio. In particular we show that a simple liquid-drop model can explain the bondlength contraction and estimate the surface tension of nanocrystalline Cu to be 3.8 ± 0.4 J/m 2

  1. Diffusion limited Cu and Au nanocrystal formation in thin film SiO2

    International Nuclear Information System (INIS)

    Johannessen, B.; Kluth, P.; Glover, C.J.; Foran, G.J.; Ridgway, M.C.

    2006-01-01

    Elemental Cu and Au nanocrystals (NCs) were produced by high-energy ion-implantations into amorphous silica (SiO 2 ) and subsequent thermal annealing. By a combination of X-ray diffraction (XRD) and cross-sectional transmission electron microscopy (XTEM) we confirm both NC species to have the bulk face-centered cubic phase and estimate their average diameter. We concentrate on the investigation of the concentration and size-dependent coordination number (China) of these matrix embedded NCs utilising extended X-ray absorption fine structure (EXAFS) spectroscopy. The CN is found to be suppressed compared to that of a bulk standard. The CN in Au NCs is found to be lower than that of Cu NCs in agreement with smaller average Au NC sizes. We explain this difference by the difference in diffusivity for the two atomic species in SiO 2

  2. Ni-induced local distortions in La1.85Sr0.15Cu1-yNiyO4 and their relevance to Tc suppression: An angular-resolved XAFS study

    International Nuclear Information System (INIS)

    Haskel, Daniel; Stern, Edward A.; Polinger, Victor; Dogan, Fatih

    2001-01-01

    We present results from angular-resolved x-ray-absorption fine-structure (XAFS) measurements at the Ni, La, and Sr K edges of oriented powders of La 1.85 Sr 0.15 Cu 1-y Ni y O 4 , with y=0.01, 0.03, 0.06. A special magnetic alignment procedure allowed us to measure pure c- and ab-oriented XAFS at the Ni K edge in identical fluorescence geometries. Both the x-ray-absorption near-edge structure and the XAFS unequivocally show that the NiO 6 octahedra are contracted along the c axis by ∼0.32 angstrom relative to CuO 6 octahedra while the in-plane distances of NiO 6 and CuO 6 octahedra are the same within 0.01 angstrom. The NiO 6 octahedral contraction drives the average c axis contraction measured by diffraction with increasing content of Ni. The local c axis shows strong spatial fluctuations, due to the different NiO 6 and CuO 6 octahedral configurations and the stronger bonding of a La 3+ ion than a Sr 2+ ion to the O(2) apical oxygens of such octahedra. We discuss the relevance of these findings to the mechanisms of loss of superconductivity at y∼0.03 and hole localization above y∼0.05 by Ni dopants

  3. Suppression of superconductivity in La1.85Sr0.15Cu1-yNiyO4: The relevance of local lattice distortions

    International Nuclear Information System (INIS)

    Haskel, D.; Stern, E.A.; Polinger, V.; Dogan, F.

    2001-01-01

    The effect of Ni substitution upon the local structure of La 1.85 Sr 0.15 Cu 1-y Ni y O 4 is commonly neglected when addressing the Ni-induced destruction of the superconducting state at y≅0.03 and a metal-insulator transition at y≅0.05. It is also sometimes assumed that direct substitution of a dopant into the CuO 2 planes has a detrimental effect on superconductivity due to in-plane lattice distortions around the dopants. We present here results from angular-dependent x-ray absorption fine structure (XAFS) measurements at the Ni, La and Sr K-edges of oriented powders of La 1.85 Sr 0.15 Cu 1-y Ni y O 4 with y=0.01, 0.03, 0.06. A special magnetic alignment geometry allowed us to measure pure c and (subform(ab)) oriented XAFS at the Ni K-edge in identical fluorescence geometries. Both the near-edge absorption spectra (XANES) and the XAFS unequivocally show that the NiO 6 octahedra are largely contracted along the c-axis, by ≅ 0.16 Aa. Surprisingly, the Ni-O planar bonds and the Ni-O-Cu/Ni planar buckling angle are nearly identical to their Cu counterparts. The NiO 6 octahedral contraction drives the macroscopic c-axis contraction observed with Ni-doping. The local c-axis strongly fluctuates, due to the different NiO 6 and CuO 6 octahedral configurations and the much stronger bonding of a La +3 ion than a Sr +2 ion to the O(2) apical oxygens. We discuss the relevance of these findings to the mechanisms of T c suppresion and hole-localization by Ni dopants

  4. Solution Structures of Highly Active Molecular Ir Water-Oxidation Catalysts from Density Functional Theory Combined with High-Energy X-ray Scattering and EXAFS Spectroscopy.

    Science.gov (United States)

    Yang, Ke R; Matula, Adam J; Kwon, Gihan; Hong, Jiyun; Sheehan, Stafford W; Thomsen, Julianne M; Brudvig, Gary W; Crabtree, Robert H; Tiede, David M; Chen, Lin X; Batista, Victor S

    2016-05-04

    The solution structures of highly active Ir water-oxidation catalysts are elucidated by combining density functional theory, high-energy X-ray scattering (HEXS), and extended X-ray absorption fine structure (EXAFS) spectroscopy. We find that the catalysts are Ir dimers with mono-μ-O cores and terminal anionic ligands, generated in situ through partial oxidation of a common catalyst precursor. The proposed structures are supported by (1)H and (17)O NMR, EPR, resonance Raman and UV-vis spectra, electrophoresis, etc. Our findings are particularly valuable to understand the mechanism of water oxidation by highly reactive Ir catalysts. Importantly, our DFT-EXAFS-HEXS methodology provides a new in situ technique for characterization of active species in catalytic systems.

  5. The structure of well defined SiO2 supported MoO3 clusters during sulfidation : an in situ EXAFS-study

    NARCIS (Netherlands)

    Boer, de M.; Dillen, van A.J.; Koningsberger, D.C.; Geus, J.W.; Kuroda, H.; Ohta, T.

    1993-01-01

    The sulfidation of a well defined MoO3/SiO2 catalyst has been examd. by means of TPS, EXAFS, and TEM. The oxidic clusters in a 5.6 wt% MoO3/SiO2 catalyst are transformed into almost completely sulfided particles (MoOxSy) by O-S exchange at RT. A molybdenum-sulfido particle that resembles the MoS3

  6. In-Plane Structure of Underpotentially Deposited Copper on Gold (111) Determined by Surface EXAFS (Extended X-Ray Absorption Fine Structure).

    Science.gov (United States)

    1988-01-28

    EXAFS is the inverse transform of the two peaks in the RSF using a filtering a12 function to isolate the range between I and 4A. Both the frequency...backscattering of different neighbors. This inverse transform contains only one frequency and its envelope of intensity is the backscattering amplitude function...and the inverse transform of the RSF using a fourier filter between 1 and 4A (Solid line). Insert: Radial Structure Function (RSF) analyzed between

  7. Lanthanide complexes of macrocyclic polyoxovanadates by VO4 units: synthesis, characterization, and structure elucidation by X-ray crystallography and EXAFS spectroscopy.

    Science.gov (United States)

    Nishio, Masaki; Inami, Shinnosuke; Katayama, Misaki; Ozutsumi, Kazuhiko; Hayashi, Yoshihito

    2012-01-16

    Reactions of a tetravanadate anion, [V(4)O(12)](4-), with a series of lanthanide(III) salts yield three types of lanthanide complexes of macrocyclic polyoxovanadates: (Et(4)N)(6)[Ln(III)V(9)O(27)] [Ln = Nd (1), Sm (2), Eu (3), Gd (4), Tb (5), Dy (6)], (Et(4)N)(5)[(H(2)O)Ho(III)(V(4)O(12))(2)] (7), and (Et(4)N)(7)[Ln(III)V(10)O(30)] [Ln = Er (8), Tm (9), Yb (10), Lu (11)]. Lanthanide complexes 1-11 are isolated and characterized by IR, elemental analysis, single-crystal X-ray diffraction, and extended X-ray absorption fine structure spectroscopy (EXAFS). Lanthanide complexes 1-6 are composed of a square-antiprism eight-coordinated Ln(III) center with a macrocyclic polyoxovanadate that is constructed from nine VO(4) tetrahedra through vertex sharing. The structure of 7 is composed of a seven-coordinated Ho(III) center, which exhibits a capped trigonal-prism coordination environment by the sandwiching of two cyclic tetravanadates with a capping H(2)O ligand. Lanthanide complexes 8-11 have a six-coordinated Ln(III) center with a 10-membered vanadate ligand. The structural trend to adopt a larger coordination number for a larger lanthanide ion among the three types of structures is accompanied by a change in the vanadate ring sizes. These lanthanide complexes are examined by EXAFS spectroscopies on lanthanide L(III) absorption edges, and the EXAFS oscillations of each of the samples in the solid state and in acetonitrile are identical. The Ln-O and Ln···V bond lengths obtained from fits of the EXAFS data are consistent with the data from the single-crystal X-ray studies, reflecting retention of the structures in acetonitrile.

  8. Behavior and mechanism of Ni(II) uptake on MnO2 by a combination of macroscopic and EXAFS investigation

    International Nuclear Information System (INIS)

    Guodong Sheng; Jiang Sheng; Shitong Yang; Ju Hu; Xiangke Wang

    2011-01-01

    The effects of pH, ionic strength, competing ions and initial metal concentrations on the uptake behavior and mechanism of radioactive Ni(II) onto MnO 2 was investigated using a combination of classical macroscopic methods and the extended X-ray absorption fine structure (EXAFS) spectroscopy technique. The results indicated that the uptake of Ni(II) on MnO 2 is obviously dependent on pH but independent of ionic strength, which suggested that the uptake of Ni(II) onto MnO 2 is attributed to an inner-sphere surface complex rather than an outer-sphere surface complex. EXAFS analysis shows that the hydrated Ni(II) is adsorbed through six-fold coordination with an average Ni-O interatomic distance of 2.04 ± 0.01 A. It can be inferred from the EXAFS analysis that the inner-sphere surface complex of Ni(II) onto MnO 2 is involved in both edge-sharing and corner-sharing linkages. Both the macroscopic uptake data and the molecular level evidence of Ni(II) surface speciation at the MnO 2 -water interfaces should be factored into better prediction of the bioavailability and mobility of Ni(II) in soil and water environment. (author)

  9. Location of rare-earth dopants on LiCAF and LiSAF laser hosts via XRD, EXAFS and computer modeling technique

    International Nuclear Information System (INIS)

    Valerio, Mario Ernesto Giroldo; Amaral, Jomar Batista de; Baldochi, Sonia Licia Vera; Mazzocchi, L.; Sasaki, Jose Marcos; Jackson, Robert A.

    2004-01-01

    Full text: Cr-doped LiCaAlF 6 (LiCAF) and LiSrAlF 6 (LiSAF) were used as laser operating in the near infrared region. Ce-doped LiCAF and LiSAF have been reported as leading candidates for tunable all-solid-state lasers in the UV region. Spectroscopic properties of LiCaAlF 6 : Nd suggest that this crystal can be used as selective optical filter and refractive element for 157 nm photolithography. The question of whether the RE dopant will prefer the Li + , the M 2+ site or the Al 3+ site is not yet known. Nevertheless most of the optical properties of these hosts including their laser action depend on the local symmetry, charge compensation mechanism and possible deformation of the lattice. In the present work, Powder X-ray Diffraction (XRD), X-ray Absorption Spectroscopy (XAS), Spectro fluorimetry, combined with computer modeling, were used to study the local structure around the dopant and determine the site occupied by them and also the distance and nature of the co-ordinating atoms. The compounds were prepared from commercially available CaF2 and SrF2 powders of high purity; LiF previously purified by the zone melting method, and AlF3 and RE dopants obtained from the hydro fluorination of commercial Al 2 O 3 . The synthesis of 2 mol % RE doped LiCAF and LiSAF samples were performed in a platinum reactor. The compositions were 2 mol % LiF and AlF3 enriched to compensate for their high vaporization. Powder XRD measurements were performed at room temperature in a Rigaku DMAX diffractometer in step scan mode using Cu K radiation. The Rietveld method (DBWS-9807a software) was employed in the analysis of the patterns. It was found that in the doped samples the concentration of the LiCAF or LiSAF phases are 84-95% and a small amount of AlF 3 and α - Li 3 AlF 6 were formed. The XAS experiments were performed on and above the L III absorption edge of the Er, Ho and Nd ions in fluorescence and transmission mode at room temperature in the XAS station at the LNLS, Campinas

  10. Evidence from EXAFS for Different Ta/Ti Site Occupancy in High Critical Current Density Nb3Sn Superconductor Wires.

    Science.gov (United States)

    Heald, Steve M; Tarantini, Chiara; Lee, Peter J; Brown, Michael D; Sung, ZuHawn; Ghosh, Arup K; Larbalestier, David C

    2018-03-19

    To meet critical current density, J c , targets for the Future Circular Collider (FCC), the planned replacement for the Large Hadron Collider (LHC), the high field performance of Nb 3 Sn must be improved, but champion J c values have remained static for the last 10 years. Making the A15 phase stoichiometric and enhancing the upper critical field H c2 by Ti or Ta dopants are the standard strategies for enhancing high field performance but detailed recent studies show that even the best modern wires have broad composition ranges. To assess whether further improvement might be possible, we employed Extended X-ray Absorption Fine Structure (EXAFS) to determine the lattice site location of dopants in modern high-performance Nb 3 Sn strands with J c values amongst the best so far achieved. Although Ti and Ta primarily occupy the Nb sites in the A15 structure, we also find significant Ta occupancy on the Sn site. These findings indicate that the best performing Ti-doped stand is strongly sub-stoichiometric in Sn and that antisite disorder likely explains its high average H c2 behavior. These new results suggest an important role for dopant and antisite disorder in minimizing superconducting property distributions and maximizing high field J c properties.

  11. Hard real-time quick EXAFS data acquisition with all open source software on a commodity personal computer

    International Nuclear Information System (INIS)

    So, I.; Siddons, D.P.; Caliebe, W.A.; Khalid, S.

    2007-01-01

    We describe here the data acquisition subsystem of the Quick EXAFS (QEXAFS) experiment at the National Synchrotron Light Source of Brookhaven National Laboratory. For ease of future growth and flexibility, almost all software components are open source with very active maintainers. Among them, Linux running on x86 desktop computer, RTAI for real-time response, COMEDI driver for the data acquisition hardware, Qt and PyQt for graphical user interface, PyQwt for plotting, and Python for scripting. The signal (A/D) and energy-reading (IK220 encoder) devices in the PCI computer are also EPICS enabled. The control system scans the monochromator energy through a networked EPICS motor. With the real-time kernel, the system is capable of deterministic data-sampling period of tens of micro-seconds with typical timing-jitter of several micro-seconds. At the same time, Linux is running in other non-real-time processes handling the user-interface. A modern Qt-based controls-frontend enhances productivity. The fast plotting and zooming of data in time or energy coordinates let the experimenters verify the quality of the data before detailed analysis. Python scripting is built-in for automation. The typical data-rate for continuous runs are around 10 M bytes/min

  12. Electron microscopy and EXAFS studies on oxide-supported gold-silver nanoparticles prepared by flame spray pyrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Hannemann, Stefan [Institute of Chemical and Bioengineering, Swiss Federal Institute of Technology, ETH Hoenggerberg, CH-8093 Zurich (Switzerland); Grunwaldt, Jan-Dierk [Institute of Chemical and Bioengineering, Swiss Federal Institute of Technology, ETH Hoenggerberg, CH-8093 Zurich (Switzerland)]. E-mail: grunwaldt@chem.ethz.ch; Krumeich, Frank [Laboratory of Inorganic Chemistry, Swiss Federal Institute of Technology, ETH Hoenggerberg, CH-8093 Zurich (Switzerland); Kappen, Peter [Department of Physics, La Trobe University, Victoria 3086 (Australia); Baiker, Alfons [Institute of Chemical and Bioengineering, Swiss Federal Institute of Technology, ETH Hoenggerberg, CH-8093 Zurich (Switzerland)

    2006-09-15

    Gold and gold-silver nanoparticles prepared by flame spray pyrolysis (FSP) were characterized by electron microscopy, in situ X-ray absorption spectroscopy (XANES and EXAFS), X-ray diffraction (XRD) and their catalytic activity in CO oxidation. Within this one-step flame-synthesis procedure, precursor solutions of dimethyl gold(III) acetylacetonate and silver(I) benzoate together with the corresponding precursor of the silica, iron oxide or titania support, were sprayed and combusted. In order to prepare small metal particles, a low noble metal loading was required. A loading of 0.1-1 wt.% of Au and Ag resulted in 1-6 nm particles. The size of the noble metal particles increased with higher loadings of gold and particularly silver. Both scanning transmission electron microscopy (STEM) combined with energy dispersive X-ray spectroscopy (EDXS) and X-ray absorption spectroscopy (XAS) studies proved the formation of mixed Au-Ag particles. In case of 1% Au-1% Ag/SiO{sub 2}, TEM combined with electron spectroscopic imaging (ESI) using an imaging filter could be used in addition to prove the presence of silver and gold in the same noble metal particle. CO oxidation in the presence of hydrogen was chosen as a test reaction sensitive to small gold particles. Both the influence of the particle size and the alloying of gold and silver were reflected in the CO oxidation activity.

  13. Electron microscopy and EXAFS studies on oxide-supported gold-silver nanoparticles prepared by flame spray pyrolysis

    International Nuclear Information System (INIS)

    Hannemann, Stefan; Grunwaldt, Jan-Dierk; Krumeich, Frank; Kappen, Peter; Baiker, Alfons

    2006-01-01

    Gold and gold-silver nanoparticles prepared by flame spray pyrolysis (FSP) were characterized by electron microscopy, in situ X-ray absorption spectroscopy (XANES and EXAFS), X-ray diffraction (XRD) and their catalytic activity in CO oxidation. Within this one-step flame-synthesis procedure, precursor solutions of dimethyl gold(III) acetylacetonate and silver(I) benzoate together with the corresponding precursor of the silica, iron oxide or titania support, were sprayed and combusted. In order to prepare small metal particles, a low noble metal loading was required. A loading of 0.1-1 wt.% of Au and Ag resulted in 1-6 nm particles. The size of the noble metal particles increased with higher loadings of gold and particularly silver. Both scanning transmission electron microscopy (STEM) combined with energy dispersive X-ray spectroscopy (EDXS) and X-ray absorption spectroscopy (XAS) studies proved the formation of mixed Au-Ag particles. In case of 1% Au-1% Ag/SiO 2 , TEM combined with electron spectroscopic imaging (ESI) using an imaging filter could be used in addition to prove the presence of silver and gold in the same noble metal particle. CO oxidation in the presence of hydrogen was chosen as a test reaction sensitive to small gold particles. Both the influence of the particle size and the alloying of gold and silver were reflected in the CO oxidation activity

  14. Towards advanced structural analysis of iron oxide clusters on the surface of γ-Al{sub 2}O{sub 3} using EXAFS

    Energy Technology Data Exchange (ETDEWEB)

    Boubnov, Alexey [Institute for Chemical Technology and Polymer Chemistry, Karlsruhe Institute of Technology, Kaiserstr. 12, D-76131 Karlsruhe (Germany); Institute of Catalysis Research and Technology, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, D-76344 Eggenstein-Leopoldshafen (Germany); Roppertz, Andreas [Institute of Energy Process Engineering and Chemical Engineering, Chair of Reaction Engineering, Technical University of Freiberg, Fuchsmuehlenweg 9, D-09599 Freiberg (Germany); Kundrat, Matthew D. [Center for Functional Nanostructures and Institute of Physical Chemistry, Karlsruhe Institute of Technology, Kaiserstr. 12, D-76131 Karlsruhe (Germany); Mangold, Stefan [Institut für Beschleunigerphysik und Technologie (IBPT), Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, D-76344 Eggenstein-Leopoldshafen (Germany); Reznik, Boris [Institute of Applied Geosciences, Karlsruhe Institute of Technology, Kaiserstr. 12, D-76131 Karlsruhe (Germany); Jacob, Christoph R. [Center for Functional Nanostructures and Institute of Physical Chemistry, Karlsruhe Institute of Technology, Kaiserstr. 12, D-76131 Karlsruhe (Germany); Institute of Physical and Theoretical Chemistry, TU Braunschweig, Hans-Sommer-Str. 10, D-38106 Braunschweig (Germany); Kureti, Sven [Institute of Energy Process Engineering and Chemical Engineering, Chair of Reaction Engineering, Technical University of Freiberg, Fuchsmuehlenweg 9, D-09599 Freiberg (Germany); Grunwaldt, Jan-Dierk, E-mail: grunwaldt@kit.edu [Institute for Chemical Technology and Polymer Chemistry, Karlsruhe Institute of Technology, Kaiserstr. 12, D-76131 Karlsruhe (Germany); Institute of Catalysis Research and Technology, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, D-76344 Eggenstein-Leopoldshafen (Germany)

    2016-11-15

    Highlights: • Analysis of isolated and oligomeric FeOx (x = 4, 5) on Al{sub 2}O{sub 3} by XANES and EXAFS. • Iron is trivalent and is mainly located at octahedral lattice sites of Al{sub 2}O{sub 3}. • Low Fe loading (0.1%) guarantees high dispersion of catalytically active iron sites. • Surface Fe-cluster on Al{sub 2}O{sub 3} and DFT-optimised Fe-doped Al{sub 2}O{sub 3} as input models for EXAFS. • Interactions of iron with support are well-accounted for using realistic models. - Abstract: Iron oxide centres are structurally investigated in 0.1% Fe/γ-Al{sub 2}O{sub 3}, which is known as highly active catalyst, for instance in the oxidation of CO. The sample was characterised by using X-ray absorption spectroscopy (XAS) in terms of X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS), Mössbauer spectroscopy, X-ray diffraction (XRD) and transmission electron microscopy (TEM). These analyses evidenced high dispersion of the iron oxide entities without significant presence of bulk-like aggregates associated with the low Fe content of the catalyst. A library of structural models of Al{sub 2}O{sub 3}-supported surface Fe was created as input for EXAFS fitting. Additionally, several model structures of Fe substituting Al ions in bulk γ-Al{sub 2}O{sub 3} were created with optimised geometry based on density-functional theory (DFT) calculations. From EXAFS refinement of the best 8 out of 24 models, it was found that the trivalent Fe ions are coordinated by 4–5 oxygen atoms and are located on octahedral lattice sites of the exposed surfaces of γ-Al{sub 2}O{sub 3}. These iron oxide species exist mainly as a mixture of monomeric and binuclear species and due to the low concentration represent suitable model systems as alternative to single crystal systems for structure-function relationships.

  15. EXAFS study of Mn1.28Fe0.67P0.46Si0.54 compound with first-order phase transition

    International Nuclear Information System (INIS)

    L, Yingjie; Huliyageqi, B; Haschaolu, W; Song, Zhiqiang; Tegus, O; Nakai, Ikuo

    2014-01-01

    Highlights: • We have investigated the Fe and Mn K edge XAFS spectra of the Mn 1.28 Fe 0.67 P 0.46 Si 0.54 compound at 25 K and 295 K. • The site occupation of the Fe and Mn atoms and local structure of Mn 1.28 Fe 0.67 P 0.46 Si 0.54 are determined. • The atomic distances between Fe–Fe in c-plane for the ferromagnetic state are larger than those in the paramagnetic state. - Abstract: The Fe 2 P-type MnFe(P,Si) compounds are investigated by means of magnetic measurements and X-ray absorption fine structure spectroscopy. Magnetic measurements show that the Mn 1.28 Fe 0.67 P 0.46 Si 0.54 compound undergoes a first-order phase transition at the Curie temperature of 254 K. The Fe K-edge and Mn K-edge X-ray absorption fine structure spectra show that Mn atom mainly located at the 3g sites, while the 3f sites are occupied by Fe atoms and Mn atom randomly. The distances between the Fe atom and its nearest neighbor atoms in a triangle Fe–Mn–Fe change from 2.80 Å at 25 K to 2.74 Å at 300 K. On the other hand, the distances between Fe atom and its second neighbor atoms change from 4.06 Å at 25 K to 4.02 Å at 300 K

  16. Dendritic chelating agents. 1. Cu(II) binding to ethylene diamine core poly (amidoamine) denderimers in aqueous solutions

    International Nuclear Information System (INIS)

    Diallo, Mamadou S.; Christie, Simone; Swaminathan, Pirabalini; Balogh, Lajos; Shi, XIANGYANG; Um, Wooyong; Papelis, Charalambos; Goddard, William A.; Johnson, J. H.

    2004-01-01

    The overall results of the proton and metal ion binding measurements suggest that the uptake of Cu(II) by EDA core PAMAM dendrimers involves both the dendrimer tertiary amine and terminal groups. However, the extents of protonation of these groups control the ability of the dentrimers to bind Cu(II). Analysis of the EXAFS spectra suggests that Cu(II) forms octahedral complexes involving the tertiary amine groups of Gx-NH2 EDA core PAMAM dendrimers at pH 7.0. The central Cu(II) metal ion of each of these complexes appears to be coordinated to 2-4 dendrimer tertiary amine groups located in the equatorial plane and 2 axial water molecules. Finally, we combine the results of our experiments with literature data to formulate and evaluate a phenomenological model of Cu(II) uptake by Gx-NH2 PAMAM dendrimers in aqueous solutions. At low metal ion-dendrimer loadings, the model provides a good fit of the measured extent of binding of Cu(II) in aqueous solutions of G4-NH2 PAMAM dendrimers at pH 7.0

  17. X AFS analysis of ancient chinese porcelain of honglvcai

    International Nuclear Information System (INIS)

    Wang Lihua; Zhu Jian; Wang Changsui; Duan Huiping; Yan Yan; Xie Yaning

    2010-01-01

    Structure analysis of Honglvcai, an overglaze ploychrome porcelain produced in China from the Song Dynasty to Ming Dynasty, has been a blank in studies on ancient Chinese ceramics. This work was focused on the oxidation state and local environment of colorants in red, yellow and green decorations on Honglvcai by X-ray absorption fine structure (XAFS). The analysis of Fe K-edge XANES and EXAFS spectra of the red-colored samples indicated that Fe 3+ was mainly located at a distorted octahedral site in a hematite phase, while that if the yellow-colored samples showed that iron was present as both trivalent and divalent cations coordinated with oxygen atoms in an amorphous phase. And Cu K-edge XAFS analysis of the green-colored samples revealed that Cu 2+ was the main constituent coordinated with oxygen atoms in an amorphous phase. (authors)

  18. Inelastic scattering at the B K edge of hexagonal BN

    Energy Technology Data Exchange (ETDEWEB)

    Jia, J.J.; Callcott, T.A.; Zhou, L. [Univ. of Tennessee, Knoxville, TN (United States)] [and others

    1997-04-01

    Many recent soft x-ray fluorescence (SXF) studies have shown that inelastic scattering processes make important contributions to the observed spectra for excitation near the x-ray threshold. These effects are all attributed to a process, usually called an electronic Raman scattering (ERS) process, in which energy is lost to an electronic excitation. The theory has been described using second order perturbation theory by Tulkki and Aberg. In different materials, the detailed nature of the electronic excitation producing the energy loss may be very different. In crystalline Si, diamond and graphite, changes in spectral shape and dispersion of spectral features with variation of the excitation energy are observed, which are attributed to k conservation between the photoelectron generated in the excitation process and the valence hole remaining after the coupled emission process. Hence the process is strongly localized in k-space. In haxagonal boron nitride, which has a lattice and band structure very similar to graphite, inelastic scattering produces very different effects on the observed spectra. Here, the inelastic losses are coupled to a strong resonant elastic scattering process, in which the intermediate state is a localized core exciton and the final state is a localized valence exciton, so that the electronic excitation is strongly localized in real rather than reciprocal space.

  19. F K-edge soft X-ray absorption spectroscopy

    International Nuclear Information System (INIS)

    Sugimura, Tetsuro; Kawai, Jun; Maeda, Kuniko; Fukushima, Akiko; Shin, S.; Motoyama, Muneyuki; Nakajima Tsuyoshi

    2001-01-01

    We measured F X-ray absorption spectra of various fluorine compounds using a synchrotron radiation at KEK-PF. The absorption spectra were measured using X-ray fluorescence yield (XFY) and total electron yield (TEY) methods. Change of the spectral shape has a relation to the metal-fluorine bond distance. By comparing with the experimental spectrum and calculated spectrum, F 2p state density is divined into up and down states. (author)

  20. Double-electron excitation above Xe K-edge

    International Nuclear Information System (INIS)

    Ito, Y.; Tochio, T.; Vlaicu, A.M.; Mutaguchi, K.; OhHashi, H.; Shigeoka, N.; Nakata, Y.; Akahama, Y.; Uruga, T.; Emura, Sh.

    2000-01-01

    When X-rays fall on any substance, whether solid, liquid, or gaseous, a photoabsorption occurs. Photoabsorption in atoms has been generally treated as a single-electron excitation process. However, the existence of the multi-electron excitation process, where the removal of a core electron by photoabsorption causes excitation of additional electrons in the same atoms, has been known in x-ray absorption spectra for a long time. In x-ray absorption spectra, experimental investigations of the shake processes in inner-shell ionization phenomena have been performed by detecting discontinuities. The shake effect which is a consequence of rearrangement of the atomic electrons, occurs in association with inner-shell excitation and ionization phenomena in x-ray absorption. The shake process has been studied extensively in various gases, because it is usually considered that the measurement of the multi-electron excitation is only possible for monatomic gases or vapors. The x-ray absorption spectra in Kr gas were measured by Ito et al. in order to observe precisely x-ray absorption spectra and to investigate the multi-electron excitation cross sections in Kr as a function of photon energy using synchrotron radiation. However, no suitable measured K x-ray absorption spectra was available to elucidate the shake processes. In the present work, the photoabsorption cross sections in Xe have been precisely measured in order to determine the features on the shake processes resulting from multiple electron excitations as a function of photon energy. Double-electron transitions of [1s4d], [1s4p], [1s4s], and [1s3d] are first detected. (author)

  1. X-ray diffraction and X-ray K absorption near edge studies of copper (II) complexes with amino acids

    Science.gov (United States)

    Sharma, P. K.; Mishra, Ashutosh; Malviya, Varsha; Kame, Rashmi; Malviya, P. K.

    2017-05-01

    Synthesis of copper (II) complexes [CuL1L2X].nH2O, where n=1, 2,3 (X=Cl,Br,NO3) (L1is 2,2’-bipyridine and L2 is L-tyrosine) by the chemical root method. The XRD data for the samples have been recorded. EXAFS spectra have also been recorded at the K-edge of Cu using the dispersive beam line BL-8 at 2.5 Gev Indus-2 Synchrotron radiation source at RRCAT, Indore, India. XRD and EXAFS data have been analysed using the computer software. X-ray diffraction studies of all complexes indicate their crystalline nature. Lattice parameter, bond length, particle size have been determined from XRD data.

  2. THE STATE OF MANGANESE IN THE PHOTOSYNTHETIC APPARATUS. I. EXAFS STUDIES ON CHLOROPLASTS AND di-u-oxo BRIDGED di-MANGANESE MODEL COMPOUNDS

    Energy Technology Data Exchange (ETDEWEB)

    Kirby, J. A.; Robertson, A. S.; Smith, J. P.; Thompson, A. C.; Thompson, A. C.; Klein, M. P.

    1980-11-01

    Extended X-ray Absorption Fine Structure (EXAFS) studies on the manganese contained in spinach chloroplasts and on certain di-u-oxo bridged manganese dimers of the form (X{sub 2}Mn)O{sub 2}(MnX{sub 2} (X=2,2'-bypyridine and 1,10-phenanthroline) are reported. From these studies, the manganese associated with photosynthetic oxygen evolution is suggested to occur as a bridged transition metal dimer with most likely another manganese. Extensive details on the analysis are included.

  3. Sulfur K-edge X-ray absorption spectroscopy and density functional theory calculations on monooxo Mo(IV) and bisoxo Mo(VI) bis-dithiolenes: insights into the mechanism of oxo transfer in sulfite oxidase and its relation to the mechanism of DMSO reductase.

    Science.gov (United States)

    Ha, Yang; Tenderholt, Adam L; Holm, Richard H; Hedman, Britt; Hodgson, Keith O; Solomon, Edward I

    2014-06-25

    Sulfur K-edge X-ray absorption spectroscopy (XAS) and density functional theory (DFT) calculations have been used to determine the electronic structures of two complexes [Mo(IV)O(bdt)2](2-) and [Mo(VI)O2(bdt)2](2-) (bdt = benzene-1,2-dithiolate(2-)) that relate to the reduced and oxidized forms of sulfite oxidase (SO). These are compared with those of previously studied dimethyl sulfoxide reductase (DMSOr) models. DFT calculations supported by the data are extended to evaluate the reaction coordinate for oxo transfer to a phosphite ester substrate. Three possible transition states are found with the one at lowest energy, stabilized by a P-S interaction, in good agreement with experimental kinetics data. Comparison of both oxo transfer reactions shows that in DMSOr, where the oxo is transferred from the substrate to the metal ion, the oxo transfer induces electron transfer, while in SO, where the oxo transfer is from the metal site to the substrate, the electron transfer initiates oxo transfer. This difference in reactivity is related to the difference in frontier molecular orbitals (FMO) of the metal-oxo and substrate-oxo bonds. Finally, these experimentally related calculations are extended to oxo transfer by sulfite oxidase. The presence of only one dithiolene at the enzyme active site selectively activates the equatorial oxo for transfer, and allows facile structural reorganization during turnover.

  4. Characterization of electron beam deposited thin films of HfO2 and binary thin films of (HfO2:SiO2) by XRD and EXAFS measurements

    International Nuclear Information System (INIS)

    Das, N.C.; Sahoo, N.K.; Bhattacharyya, D.; Thakur, S.; Kamble, N.M.; Nanda, D.; Hazra, S.; Bal, J.K.; Lee, J.F.; Tai, Y.L.; Hsieh, C.A.

    2009-10-01

    In this report, we have discussed the microstructure and the local structure of composite thin films having varying hafnia and silica compositions and prepared by reactive electron beam evaporation. XRD and EXAFS studies have confirmed that the pure hafnium oxide thin film has crystalline microstructure whereas the films with finite hafnia and silica composition are amorphous. The result of EXAFS analysis has shown that the bond lengths as well as coordination numbers around hafnium atom change with the variation of hafnia and silica compositions in the thin film. Finally, change of bond lengths has been correlated with change of refractive index and band gap of the composite thin films. (author)

  5. Momentum Dependence of Charge Excitations in YBa2Cu3O7-δ and Nd2-xCexCuO4

    Science.gov (United States)

    Ishii, Kenji

    2006-03-01

    Resonant inelastic x-ray scattering (RIXS) studies at Cu K-edge on high-Tc superconducting cuprates, YBa2Cu3O7-δ and Nd2-xCexCuO4 are presented. The superconductivity occurs in the vicinity of the Mott insulating state and it is important to clarify the nature of the Mott gap and its doping dependence. Because RIXS has an advantage that we can measure charge excitation in a wide energy-momentum space, it gives a unique opportunity to study the electronic structure of materials. We apply this technique to high-Tc superconducting cuprates. In particular the electronic structure of strongly correlated metals is in the focus of our RIXS study. The experiments were performed at BL11XU of SPring-8, Japan, where a specially designed spectrometer for inelastic x-ray scattering is installed. In optimally doped YBa2Cu3O7-δ, anisotropic spectra are observed in the ab plane of a twin-free crystal. The Mott gap excitation from the one-dimensional CuO chain is enhanced at 2 eV near the zone boundary of the chain direction, while the excitation from the CuO2 plane is broad at 1.5-4 eV and almost independent of momentum. Theoretical calculation based on the one-dimensional and two-dimensional Hubbard model reproduces the observed features in the RIXS spectra when smaller values of the on-site Coulomb energy of the chain than that of the plane are assumed. This means that the charge transfer gap of the chain is smaller than that of the plane. On the other hand, both interband excitation across the Mott gap and intraband excitation in the upper Hubbard band are observed in the electron-doped Nd2-xCexCuO4. The intensity of the interband excitation is concentrated at ˜ 2 eV near the zone boundary while a dispersion relation with a momentum-dependent width emerges in the intraband excitation. The author would like to acknowledge to his collaborators, K. Tsutsui, Y. Endoh, T. Tohyama, K. Kuzushita, T. Inami, K. Ohwada, M. Hoesch, M. Tsubota, Y. Murakami, J. Mizuki, S. Maekawa, T

  6. EX6AFS: A data acquisition system for high-speed dispersive EXAFS measurements implemented using object-oriented programming techniques

    International Nuclear Information System (INIS)

    Jennings, G.; Lee, P.L.

    1995-01-01

    In this paper we describe the design and implementation of a computerized data-acquisition system for high-speed energy-dispersive EXAFS experiments on the X6A beamline at the National Synchrotron Light Source. The acquisition system drives the stepper motors used to move the components of the experimental setup and controls the readout of the EXAFS spectra. The system runs on a Macintosh IIfx computer and is written entirely in the object-oriented language C++. Large segments of the system are implemented by means of commercial class libraries, specifically the MacApp application framework from Apple, the Rogue Wave class library, and the Hierarchical Data Format datafile format library from the National Center for Supercomputing Applications. This reduces the amount of code that must be written and enhances reliability. The system makes use of several advanced features of C++: Multiple inheritance allows the code to be decomposed into independent software components and the use of exception handling allows the system to be much more reliable in the event of unexpected errors. Object-oriented techniques allow the program to be extended easily as new requirements develop. All sections of the program related to a particular concept are located in a small set of source files. The program will also be used as a prototype for future software development plans for the Basic Energy Science Synchrotron Radiation Center Collaborative Access Team beamlines being designed and built at the Advanced Photon Source

  7. Structure of a Rh/TiO2 catalyst in the strong metal-support interaction state as determined by EXAFS

    International Nuclear Information System (INIS)

    Koningsberger, D.C.; Martens, J.H.A.; Prins, R.; Short, D.R.; Sayers, D.E.

    1986-01-01

    Reduction of a highly dispersed 2.85 wt% Rh/TiO 2 catalyst at 473 K after previous calcination at 623 K resulted in EXAFS whose primary contributions are due to nearest rhodium (average coordination number of 3.1 and distance of 2.67 A) and oxygen neighbors (coordination 2.5 and distance 2.71 A). These oxygen neighbors originated at the metal-support interface. The average rhodium-rhodium coordination number did not change in the SMSI state produced by reducing the catalyst at 673 K. However, the average coordination distance contracted by 0.04 A with an accompanying decrease of the Debye-Waller factor of the Rh-Rh bond of 0.0012 A 2 . This is due to the fact that in the SMSI state the surface of the metal particles is not covered with chemisorbed hydrogen. The SMSI state leads to a structural reorganization of the support in the vicinity of the rhodium metal particles. This can be concluded from the appearance of a Rh-Ti bond at 3.42 A in the SMSI state coupled with the fact that the average coordination number of the rhodium-support oxygen bonds does not increase. Other types of rhodium-oxygen bonds could not be detected with EXAFS in this state. Thus, these results provide no evidence for coverage of the metal particle by a suboxide of TiO 2 in the SMSI state

  8. Alternative difference analysis scheme combining R-space EXAFS fit with global optimization XANES fit for X-ray transient absorption spectroscopy.

    Science.gov (United States)

    Zhan, Fei; Tao, Ye; Zhao, Haifeng

    2017-07-01

    Time-resolved X-ray absorption spectroscopy (TR-XAS), based on the laser-pump/X-ray-probe method, is powerful in capturing the change of the geometrical and electronic structure of the absorbing atom upon excitation. TR-XAS data analysis is generally performed on the laser-on minus laser-off difference spectrum. Here, a new analysis scheme is presented for the TR-XAS difference fitting in both the extended X-ray absorption fine-structure (EXAFS) and the X-ray absorption near-edge structure (XANES) regions. R-space EXAFS difference fitting could quickly provide the main quantitative structure change of the first shell. The XANES fitting part introduces a global non-derivative optimization algorithm and optimizes the local structure change in a flexible way where both the core XAS calculation package and the search method in the fitting shell are changeable. The scheme was applied to the TR-XAS difference analysis of Fe(phen) 3 spin crossover complex and yielded reliable distance change and excitation population.

  9. Structural Transformations in High-Capacity Li 2 Cu 0.5 Ni 0.5 O 2 Cathodes

    Energy Technology Data Exchange (ETDEWEB)

    Ruther, Rose; Pandian, Amaresh S.; Yan, Pengfei; Weker, Johanna N.; Wang, Chongmin; Nanda, Jagjit

    2017-03-21

    Cathode materials that can cycle > 1 Li+ per transition metal are of substantial interest to increase the overall energy density of lithium-ion batteries. Li2Cu0.5Ni0.5O2 has a very high theoretical capacity of ~ 500 mAh/g assuming both Li+ are cycled reversibly. The Cu2+/3+ and Ni2+/3+/4+ redox couples are also at high voltage, which could further boost the energy density of this system. Despite such promise, Li2Cu0.5Ni0.5O2 undergoes irreversible phase changes during charge (delithiation) that result in large first-cycle irreversible loss and poor long-term cycling stability. Oxygen is evolved before the Cu2+/3+ or Ni3+/4+ transitions are accessed. In this contribution, XRD, TEM, and TXM-XANES are used to follow the chemical and structural changes that occur in Li2Cu0.5Ni0.5O2 during electrochemical cycling. Li2Cu0.5Ni0.5O2 is a solid solution of orthorhombic Li2CuO2 and Li2NiO2, but the structural changes more closely mimic the Li2NiO2 endmember. Li2Cu0.5Ni0.5O2 loses long-range order during charge, but TEM analysis provides clear evidence for particle exfoliation and the transformation from orthorhombic to a partially layered structure. Linear combination fitting and principal component analysis of TXM-XANES are used to map the different phases that emerge during cycling ex situ and in situ. Significant changes in the XANES at the Cu and Ni K-edges correlate with the onset of oxygen evolution.

  10. Cu(I), Ag(I), Cd(II), and Pb(II) binding to biomolecules studied by perturbed angular correlation of $\\gamma$-rays (PAC) spectroscopy

    CERN Multimedia

    Metal ions display diverse functions in biological systems and are essential components in both protein and nucleic acid structure and function, and in control of biochemical reaction paths and signalling. Similarly, metal ions may be used to control structure and function of synthetic biomolecules, and thus be a tool in the design of molecules with a desired function. In this project we address a variety of questions concerning both the function of metal ions in natural systems, in synthetic biomolecules, and the toxic effect of some metal ions. All projects involve other experimental techniques such as NMR, EXAFS, UV-Vis, fluorescence, and CD spectroscopies providing complementary data, as well as interpretation of the experimental data by quantum mechanical calculations of spectroscopic properties. The isotopes to be employed in the proposal are the following: $^{111m}$Cd, $^{111}$Ag, $^{199m}$Hg, $^{204m}$Pb, $^{61}$Cu, $^{68m}$Cu

  11. Evidence of a splitting of the Mn-O distance and of a large lattice disorder in the charge-ordered phase of LiMn2O4 obtained by EXAFS

    International Nuclear Information System (INIS)

    Paolone, A.; Castellano, C.; Cantelli, R.; Rousse, G.; Masquelier, C.

    2003-01-01

    We measured the extended x-ray-absorption fine-structure (EXAFS) spectrum of LiMn 2 O 4 below room temperature in the charge-ordered phase and for comparison at room temperature in the cubic phase. By means of a standard fit procedure we verified that, as reported by neutron-scattering experiments, also at the local level there are two different Mn-O distances below room temperature, which correspond to the surroundings of well-defined Mn 3+ and Mn 4+ ions. This result is different from the ones obtained from previous EXAFS measurements and confirms the physical picture of the phase transition caused by the ordering of charges in contrast to a cooperative Jahn-Teller phenomenon. Moreover a large lattice disorder in the charge-ordered state, which determines a significant static contribution to the EXAFS Debye-Waller factor, has been found. This last result can be considered as the EXAFS spectral mark of charge-order transitions, even in those materials in which there is no clear evidence of the splitting of bond lengths

  12. Study on accumulation mechanism of Cu and Pb in moss, Scopelophila cataractae, by micro-XRF imaging and XAFS analysis

    International Nuclear Information System (INIS)

    Yoshii, Yuichi; Nakai, Izumi; Hokura, Akiko; Abe, Tomoko; Itouga, Misao; Sakakibara, Hitoshi; Terada, Yasuko

    2011-01-01

    Scopelophila cataractae is known as a 'copper moss'. It is known as a peculiar moss which can accumulate high level of metals (Cu, Pb, etc.) in its plant body. This moss is expected as a material to collect metals from water. In this study, gametophyte's leaf of the moss was examined by μ-XRF imaging, and Cu K-edge and Pb L 1 -, L 3 -edge XAFS analyses to reveal the accumulation behavior of Cu and Pb. μ-XRF imaging was carried out utilizing X-ray microbeam at BL37XU, SPring-8 from the undulator source, and at BL-4A, Photon Factory KEK from the bending magnet. The results have revealed that Cu and Pb were accumulated on the cell wall of the leaf, and especially at the stereid cells of midrib. It was found that Cu-XANES spectra of the leaf were similar to that of copper(II) acetate, a reference substance. On the other hand, Pb XANES spectra of the leaf were similar to that of a reference, lead(II) stearate. These results suggested that these metals were bound to oxygen of carboxyl group in the plant. Consequently, it is assumed that Cu and Pb could be bound to acidic sugar which is a component of its cell wall such as pectic acid, polygalacturonic acid and others. Furthermore, to compare with other heavy-metal accumulating moss (Scopelophila ligulata and Sphagnum palustre), their gametophyte's leaves were also examined by μ-XRF imaging. S. ligulata accumulated Pb in its stereid cells of midlib, while S. palustre accumulated Pb in its hyaline cells. (author)

  13. Interaction of Zn(II) with hematite nanoparticles and microparticles: Part 2. ATR-FTIR and EXAFS study of the aqueous Zn(II)/oxalate/hematite ternary system.

    Science.gov (United States)

    Ha, Juyoung; Trainor, Thomas P; Farges, François; Brown, Gordon E

    2009-05-19

    Sorption of Zn(II) to hematite nanoparticles (HN) (av diam=10.5 nm) and microparticles (HM) (av diam=550 nm) was studied in the presence of oxalate anions (Ox2-(aq)) in aqueous solutions as a function of total Zn(II)(aq) to total Ox2-(aq) concentration ratio (R=[Zn(II)(aq)]tot/[Ox2-(aq)]tot) at pH 5.5. Zn(II) uptake is similar in extent for both the Zn(II)/Ox/HN and Zn(II)/Ox/HM ternary systems and the Zn(II)/HN binary system at [Zn(II)(aq)](tot)system than for the Zn(II)/Ox/HM ternary and the Zn(II)/HN and Zn(II)/HM binary systems at [Zn(II)(aq)]tot>4 mM. In contrast, Zn(II) uptake for the Zn(II)/HM binary system is a factor of 2 greater than that for the Zn(II)/Ox/HM and Zn(II)/Ox/HN ternary systems and the Zn(II)/HN binary system at [Zn(II)(aq)]totternary system at both R values examined (0.16 and 0.68), attenuated total reflectance Fourier transform infrared (ATR-FTIR) results are consistent with the presence of inner-sphere oxalate complexes and outer-sphere ZnOx(aq) complexes, and/or type A ternary complexes. In addition, extended X-ray absorption fine structure (EXAFS) spectroscopic results suggest that type A ternary surface complexes (i.e., >O2-Zn-Ox) are present. In the Zn(II)/Ox/HN ternary system at R=0.15, ATR-FTIR results indicate the presence of inner-sphere oxalate and outer-sphere ZnOx(aq) complexes; the EXAFS results provide no evidence for inner-sphere Zn(II) complexes or type A ternary complexes. In contrast, ATR-FTIR results for the Zn/Ox/HN sample with R = 0.68 are consistent with a ZnOx(s)-like surface precipitate and possibly type B ternary surface complexes (i.e., >O2-Ox-Zn). EXAFS results are also consistent with the presence of ZnOx(s)-like precipitates. We ascribe the observed increase of Zn(II)(aq) uptake in the Zn(II)/Ox/HN ternary system at [Zn(II)(aq)]tot>or=4 mM relative to the Zn(II)/Ox/HM ternary system to formation of a ZnOx(s)-like precipitate at the hematite nanoparticle/water interface.

  14. Angle and Polarization Dependent Fluorescence EXAFS Measurements on Al-doped Single Crystal V_2O3 Above and Below the Transition Temperature

    Science.gov (United States)

    Müller, O.; Pfalzer, P.; Schramme, M.; Urbach, J.-P.; Klemm, M.; Horn, S.; Frenkel, A. I.; Denboer, M. L.

    1998-03-01

    We present angle and polarisation dependent flourescence EXAFS measured on Al-doped single crystal V_2O3 below and above the structural phase transition from monoclinic to trigonal. Strong self-absorption distorted the spectra; this was corrected by using the procedure described by Tröger et al. (L. Tröger, D. Arvantis, K. Baberschke, H. Michaelis, U. Grimm, and E. Zschech, Phys. Rev. B,.46), 3238 (1992), generalized to the Lytle detector employed in our work. The spectra show pronounced dependence on the angle between the threefold symmetry axes and the polarization of the incident photons, making it possible to measure the local atomic distances in different directions. We compare our results with the measurements of Frenkel et al. (A. I. Frenkel, E. A. Stern, and F. A. Chudnovsky, Sol. State Comm.102), 637 (1997) on pure V_2O3 They found that locally the monoclinic distortion persists in the trigonal metallic phase.

  15. High pressure study of nanostructured Cu2Sb by X-ray Diffraction, Extended X-ray Absorption fine structure and Raman measurements

    International Nuclear Information System (INIS)

    Souza, Sergio Michielon de; Triches, Daniela Menegon; Lima, Joao Cardoso de; Polian, Alain

    2016-01-01

    Full text: Nanostructured tetragonal Cu 2 Sb was prepared by mechanical alloying and its stability was studied as a function of pressure using synchrotron X-ray diffraction (XRD) Extended X-Ray Absorption Fine Structure (EXAFS) and Raman spectroscopy. The high pressure XRD data were collected at 0.6, 1.1, 2.2, 3.4, 5.0, 7.1, 8.0, 9.9, 14.8, 18.7, 23.2, 29.3 and 40.6 GPa in the ELETTRA synchrotron (Italy) with λ = 0.68881 Å. The high pressure EXAFS measurements were carried out in the Soleil synchrotron (France) in 0.6, 1.8, 3.0, 4.5, 6.1, 8.0, 10.3, 12.7, 15.5, 18.0, 19.0, 20.0, 22.1, 23.9, 26.3 and 29.4 GPa and the high pressure Raman spectroscopy in the Institut de Mineralogie et de Physique des Milieux Condenses (France) collected at 0.1, 1.6, 3.7, 6.7, 11.2, 15.1, 19.4, 24.5, 30.8, 36.3, 41.3 and 44.5 GPa. The results show high structural and optical phase stability. The moduli bulk and its derivatives were obtained by using the Birch-Murnaghan equation of states to the XRD and EXAFS results. The evolution of the Raman modes and the bulk moduli were used to obtain the Grueneisen parameters. (author)

  16. An energy-dispersive X-ray monochromator for measurements in the soft X-ray spectra: design, construction and first measurements. Ein energiedispersiver Roentgenmonochromator mit der Moeglichkeit von Messungen im weichen Roentgenbereich: Entwurf, Aufbau und erste Messungen

    Energy Technology Data Exchange (ETDEWEB)

    Steil, S.

    1993-12-01

    An Energy-Dispersive X-ray Monochromator (EDM) for time-resolved X-ray absorption spectroscopy was built in the Synchrotron radiation laboratory at the 3.5 GeV ELectron Stretcher and Accelerator (ELSA). Bragg angles up to 70 and a specially designed vacuum system allow measurements down to an energy of 2.149 keV (P K-edge) with a Si(111)-crystal. Compared to a standard double crystal monochromator and for an EXAFS spectrum at the Cu K-edge at 8.979 keV for concentrated samples, the EDM boosts time resolution by 3 orders of magnitude. The time resolution increases by a factor of 50 for a XANES spectrum at the S K-edge at 2.472 keV for a rubber sample with 4% sulfur. The energy resolution of the EDM is limited by the Darwin width [Omega] of the Bragg crystal. The harmonics in the 'monochromatized' beam, which increase to lower energies, could be nearly eliminated by using a quartz mirror. The spherical aberration of the focus was described theoretically for a cylindrically bent crystal and compared with measurements. In a first time-resolved measurement at the S K-edge, which comprehended about 120 spectra taken in 40 minutes, the thermal ageing of a rubber sample was investigated to demonstrate the performance of the monochromator. (orig.)

  17. Depth distribution of secondary phases in kesterite Cu2ZnSnS4 by angle-resolved X-ray absorption spectroscopy

    Directory of Open Access Journals (Sweden)

    J. Just

    2017-12-01

    Full Text Available The depth distribution of secondary phases in the solar cell absorber material Cu2ZnSnS4 (CZTS is quantitatively investigated using X-ray Absorption Near Edge Structure (XANES analysis at the K-edge of sulfur at varying incidence angles. Varying information depths from several nanometers up to the full thickness is achieved. A quantitative profile of the phase distribution is obtained by a self-consistent fit of a multilayer model to the XANES spectra for different angles. Single step co-evaporated CZTS thin-films are found to exhibit zinc and copper sulfide secondary phases preferentially at the front or back interfaces of the film.

  18. /Cu-Al System

    Science.gov (United States)

    Kish, Orel; Froumin, Natalya; Aizenshtein, Michael; Frage, Nachum

    2014-05-01

    Wettability and interfacial interaction of the Ta2O5/Cu-Al system were studied. Pure Cu does not wet the Ta2O5 substrate, and improved spreading is achieved when relatively a high fraction of the active element (~40 at.% Al) was added. The Al2O3 and AlTaO4 phases were observed at the Ta2O5/Cu-Al interface. A thermodynamic evaluation allowed us to suggest that the lack of wetting bellow 40 at.% Al is due to the presence of a native oxide, which covers the drop. The conditions of the native oxide decomposition and the formation of the volatile Al2O suboxide strongly depend on the vacuum level during sessile drop experiments and the composition of the Cu-Al alloy. In our case, Al contents greater than 40% provides thermodynamic conditions for the formation of Al2O (as a result of Al reaction with Al2O3) and the drop spreading. It was suggested that the final contact angle in the Ta2O5/Cu-Al system (50°) is determined by Ta adsorption on the newly formed alumina interlayer.

  19. P-EXAFS investigations of Zn uptake by montmorillonite. The strong and weak sites concept in the 2SPNE SC/CE sorption model

    International Nuclear Information System (INIS)

    Daehn, R.; Baeyens, B.; Bradbury, M.H.

    2012-01-01

    Document available in extended abstract form only. The sorption of radioactive elements on the immobile components in the near- and far-fields of a deep geological radioactive waste repository is a significant process in retarding their aqueous phase transport and an important component in safety assessment studies. The development of robust and well-founded mechanistic sorption models to predict the uptake of radionuclides under different geochemical conditions would enhance the justification and defensibility of the sorption values used in safety studies and thereby represent a considerable contribution to the scientific basis for radioactive waste disposal. The 2 site proto-lysis non electrostatic surface complexation and cation exchange (2SPNE SC/CE) sorption model has been used over the past decade or so to quantitatively describe the uptake of metals with oxidation states from II to VI on 2:1 clay minerals; montmorillonite and illite (Bradbury and Baeyens, 1997). One of the main features in this model is that there are two broad categories of amphoteric edge sorption sites; the so called strong (≡SSOH) and weak (≡SW1OH) sites. Because of their different sorption characteristics, it was expected that the coordination environments of the surface complexes on the two site types would be different. Although the 2SPNE SC/CE model uses different mechanistic uptake processes to describe sorption, it can only be described as a 'quasi mechanistic' model because the exact nature of the surface binding sites and surface complexes is not known. In order to check the 'strong site / weak site' sorption sites hypothesis in the 2SPNE SC/CE sorption model, it was essential to perform polarised extended X-ray absorption fine structure (P-EXAFS) measurements on an uptake system, in which it was possible to obtain good spectra particularly at the low metal loadings (∼2 mmol kg-1 or less) corresponding to occupancies dominated by strong sites. The Zn-montmorillonite system

  20. An anomalous X-ray scattering study on glassy superionic conductor (As2Se3)1-x(CuI) x using a third-generation synchrotron radiation facility

    International Nuclear Information System (INIS)

    Usuki, T.; Hosokawa, S.; Berar, J.-F.

    2005-01-01

    Anomalous X-ray scattering experiments on glassy superionic conductor (As 2 Se 3 ) 0.4 (CuI) 0.6 were performed at energies close to the As, Se, and Cu K edges using a new detecting system and a third-generation synchrotron radiation facility. The detecting system was composed of a graphite-crystal energy-analyzer and a NaI(Tl) detector on a 40-cm-long arm. The overall energy resolution was about 60 eV, which can discriminate the elastic signal from the fluorescence and Compton contributions, and a sufficient number of scattered X-ray photons were acquired within a reasonable data collection time. The differential structure factors, Δ i S(Q), were obtained from the detailed analyses, indicating that Δ As S(Q) and Δ Se S(Q) are similar to those of glassy As 2 Se 3 except at the prepeak position, and Δ Cu S(Q) that in liquid CuI. From these findings, it can be concluded that a pseudo-binary mixture of the As 2 Se 3 network matrix and CuI-related conduction pathways would be a good structural model for this superionic glass

  1. Binuclear Pt-Tl bonded complex with square pyramidal coordination around Pt: a combined multinuclear NMR, EXAFS, UV-Vis, and DFT/TDDFT study in dimethylsulfoxide solution.

    Science.gov (United States)

    Purgel, Mihály; Maliarik, Mikhail; Glaser, Julius; Platas-Iglesias, Carlos; Persson, Ingmar; Tóth, Imre

    2011-07-04

    The structure and bonding of a new Pt-Tl bonded complex formed in dimethylsulfoxide (dmso), (CN)(4)Pt-Tl(dmso)(5)(+), have been studied by multinuclear NMR and UV-vis spectroscopies, and EXAFS measurements in combination with density functional theory (DFT) and time dependent density functional theory (TDDFT) calculations. This complex is formed following the equilibrium reaction Pt(CN)(4)(2-) + Tl(dmso)(6)(3+) ⇆ (CN)(4)Pt-Tl(dmso)(5)(+) + dmso. The stability constant of the Pt-Tl bonded species, as determined using (13)C NMR spectroscopy, amounts to log K = 2.9 ± 0.2. The (NC)(4)Pt-Tl(dmso)(5)(+) species constitutes the first example of a Pt-Tl bonded cyanide complex in which the sixth coordination position around Pt (in trans with respect to the Tl atom) is not occupied. The spectral parameters confirm the formation of the metal-metal bond, but differ substantially from those measured earlier in aqueous solution for complexes (CN)(5)Pt-Tl(CN)(n)(H(2)O)(x)(n-) (n = 0-3). The (205) Tl NMR chemical shift, δ = 75 ppm, is at extraordinary high field, while spin-spin coupling constant, (1)J(Pt-Tl) = 93 kHz, is the largest measured to date for a Pt-Tl bond in the absence of supporting bridging ligands. The absorption spectrum is dominated by two strong absorption bands in the UV region that are assigned to MMCT (Pt → Tl) and LMCT (dmso → Tl) bands, respectively, on the basis of MO and TDDFT calculations. The solution of the complex has a bright yellow color as a result of a shoulder present on the low energy side of the band at 355 nm. The geometry of the (CN)(4)Pt-Tl core can be elucidated from NMR data, but the particular stoichiometry and structure involving the dmso ligands are established by using Tl and Pt L(III)-edge EXAFS measurements. The Pt-Tl bond distance is 2.67(1) Å, the Tl-O bond distance is 2.282(6) Å, and the Pt-C-N entity is linear with Pt-C and Pt···N distances amounting to 1.969(6) and 3.096(6) Å, respectively. Geometry optimizations on

  2. CuO reduction induced formation of CuO/Cu2O hybrid oxides

    Science.gov (United States)

    Yuan, Lu; Yin, Qiyue; Wang, Yiqian; Zhou, Guangwen

    2013-12-01

    Reduction of CuO nanowires results in the formation of a unique hierarchical hybrid nanostructure, in which the parent oxide phase (CuO) works as the skeleton while the lower oxide (Cu2O) resulting from the reduction reaction forms as partially embedded nanoparticles that decorate the skeleton of the parent oxide. Using in situ transmission electron microscopy observations of the reduction process of CuO nanowires, we demonstrate that the formation of such a hierarchical hybrid oxide structure is induced by topotactic nucleation and growth of Cu2O islands on the parent CuO nanowires.

  3. Iron environment in ferritin with large amounts of phosphate, from Azotobacter vinelandii and horse spleen, analyzed using Extended X-ray Absorption fine Structure (EXAFS)

    International Nuclear Information System (INIS)

    Rohrer, J.S.; Islam, Q.T.; Sayes, D.E.; Theil, E.C.; Watt, G.D.

    1990-01-01

    The iron core of proteins in the ferritin family displays structural variations that includes phosphate content was well as the number and the degree of ordering of the iron atoms. Earlier studies had shown that ferritin iron cores naturally high in phosphate, e.g., Azotobacter vinelandii (AV) ferritin had decreased long-range order. Here, the influence of phosphate on the local structure around iron in ferritin cores is reported, comparing the EXAFS of AV ferritin, reconstituted ferritin and native horse spleen ferritin. In contrast, when the phosphate content was high in AV ferritin and horse spleen ferritin reconstituted with phosphate, the average iron atom had five to six phosphorus neighbors at 3.17 angstrom. Moreover, the number of detectable iron neighbors was lower when phosphate was high or present during reconstitution and the interatomic distance was longer indicating that some phosphate bridges neighboring iron atoms. However, the decrease in the number of detectable iron-iron neighbors compared to HSF and the higher number of Fe-P interactions relative to Fe-Fe interactions suggest that some phosphate ligands were chain termini, or blocked crystal growth, and/or introduced defects which contributed both to the long-range disorder and to altered redox properties previously observed in AV ferritin

  4. The double-well oscillating potential of oxygen atoms in perovskite system Ba(K)BiO sub 3 : EXAFS - analysis results

    CERN Document Server

    Menushenkov, A P; Konarev, P V; Meshkov, A A; Benazeth, S; Purans, J

    2000-01-01

    Temperature-dependent X-ray absorption investigations were made on the Bi L sub 3 -edge in Ba sub 1 sub - sub x K sub x BiO sub 3 with x=0.0, 0.4 and 0.5. For the superconducting samples (x=0.4 and 0.5) it has been found that the local structure differs from the ideal cubic in contrast to the neutron and X-ray diffraction data. The provided analysis of the EXAFS spectra indicates that the oxygen atoms move in double-well potential produced by the existence of two non-equivalent octahedral types of the oxygen environment of bismuth. The vibrations in such a potential lead to modulations of the Bi-O lengths with low frequency which is determined by the soft oxygen octahedron rotation mode frequency. This induces strong electron-phonon interaction and may be the reason for relatively high-temperature transition (T sub c approx 30 K) to the superconducting state.

  5. EXAFS analysis of cations distribution in structure of Co1-xNixFe2O4 nanoparticles obtained by hydrothermal method in aloe vera extract solution

    Science.gov (United States)

    Wongpratat, Unchista; Maensiri, Santi; Swatsitang, Ekaphan

    2016-09-01

    Effect of cations distribution upon EXAFS analysis on magnetic properties of Co1-xNixFe2O4 (x = 0, 0.25, 0.50, 0.75 and 1.0) nanoparticles prepared by the hydrothermal method in aloe vera extract solution were studied. XRD analysis confirmed a pure phase of cubic spinel ferrite of all samples. Changes in lattice parameter and particle size depended on the Ni content with partial substitution and site distributions of Co2+, Ni2+ ions of different ionic radii at both tetrahedral and octahedral sites in the crystal structure. Particle sizes of samples estimated by TEM images were found to be in the range of 10.87-62.50 nm. The VSM results at room temperature indicated the ferrimagnetic behavior of all samples. Superparamagnetic behavior was observed in NiFe2O4 sample. The coercivity (Hc) and remanance (Mr) values were related to the particle sizes of samples. The saturation magnetization (Ms) was increased by a factor of 1.4 to a value of 57.57 emu/g, whereas the coercivity (Hc) was decreased by a factor of 20 to a value of 63.15 Oe for a sample with x = 0.75. In addition to the cations distribution, the increase of aspect ratio (surface to volume ratio) due to the decrease of particle size could significantly affect the magnetic properties of the materials.

  6. Structure of the Hydrated Platinum(II) Ion And the Cis-Diammine-Platinum(II) Complex in Acidic Aqueous Solution: An EXAFS Study

    Energy Technology Data Exchange (ETDEWEB)

    Jalilehvand, F.; Laffin, L.J.

    2009-05-18

    Careful analysis of Pt L{sub 3}-edge extended X-ray absorption fine structure (EXAFS) spectra shows that the hydrated platinum(II) ion in acidic (HClO{sub 4}) aqueous solution binds four water molecules with the Pt-O bond distance 2.01(2) {angstrom} and one (or two) in the axial position at 2.39(2) {angstrom}. The weak axial water coordination is in accordance with the unexpectedly small activation volume previously reported for water exchange in an interchange mechanism with associative character. The hydrated cis-diammineplatinum(II) complex has a similar coordination environment with two ammine and two aqua ligands strongly bound with Pt-O/N bond distances of 2.01(2) {angstrom} and, in addition, one (or two) axial water molecule at 2.37(2) {angstrom}. This result provides a new basis for theoretical computational studies aiming to connect the function of the anticancer drug cis-platin to its ligand exchange reactions, where usually four-coordinated square planar platinum(II) species are considered as the reactant and product. {sup 195}Pt NMR spectroscopy has been used to characterize the Pt(II) complexes.

  7. Optical and mechanical design of the extended x-ray absorption fine structure (EXAFS) beam-line at Indus-II synchrotron source

    International Nuclear Information System (INIS)

    Das, N.C.; Jha, S.N.; Bhattacharyya, D.; Sinha, A.K.; Mishra, V.K.; Verma, Vishnu; Ghosh, A.K.

    2002-11-01

    An extended x-ray absorption fine structure (EXAFS) beam line for x-ray absorption studies using energy dispersive geometry and position sensitive detector is being designed for the INDUS-II Synchrotron source. The beam line would be used for doing x-ray absorption experiments involving measurements of fme structures above the absorption edge of different species of atoms in a material The results of the above experiments would lead to the determination of different important structural parameters of materials viz.. inter-atomic distance. co-ordination number, degree of disorder and radial distribution function etc. The optical design of the beam line has been completed based on the working principle that a single crystal bent in the shape of an ellipse by a crystal bender would act as a dispersing as well as focusing element. The mechanical design of the beam line including the crystal bender has also been completed and discussed here. Calculations have been done to detennine the temperature profile on the different components of the beam line under exposure to synchrotron radiation and proper cooling channels have been designed to bring down the heat load on the components. (author)

  8. Kα resonance fluorescence in Al, Ti, Cu and potential applications for X-ray sources

    Science.gov (United States)

    Nahar, Sultana N.; Pradhan, Anil K.

    2015-04-01

    The Kα resonance fluorescence (RFL) effect via photoabsorptions of inner shell electrons as the element goes through multiple ionization states is studied. We demonstrate that the resonances observed recently in Kα (1s-2p) fluorescence in aluminum plasmas by using a high-intensity X-ray free-electron laser [1] are basically K-shell resonances in hollow atoms going through multiple ionization states at resonant energies as predicted earlier for gold and iron ions [2]. These resonances are formed below the K-shell ionization edge and shift toward higher energies with ionization states, as observed. Fluorescence emission intensities depend on transition probabilities for each ionization stage of the given element for all possible Kα (1 s → 2 p) transition arrays. The present calculations for resonant photoabsorptions of Kα photons in Al have reproduced experimentally observed features. Resonant cross sections and absorption coefficients are presented for possible observation of Kα RFL in the resonant energy ranges of 4.5-5.0 keV for Ti ions and 8.0-8.7 keV for Cu ions respectively. We suggest that theoretically the Kα RFL process may be driven to enhance the Auger cycle by a twin-beam monochromatic X-ray source, tuned to the K-edge and Kα energies, with potential applications such as the development of narrow-band biomedical X-ray devices.

  9. EXAFS study of Mn{sub 1.28}Fe{sub 0.67}P{sub 0.46}Si{sub 0.54} compound with first-order phase transition

    Energy Technology Data Exchange (ETDEWEB)

    L, Yingjie; Huliyageqi, B; Haschaolu, W; Song, Zhiqiang [Inner Mongolia Key Laboratory for Physics and Chemistry of Functional Materials, Physics and Electronic Information College, Inner Mongolia Normal University, Hohhot 010022 (China); Tegus, O, E-mail: tegusph@imnu.edu.cn [Inner Mongolia Key Laboratory for Physics and Chemistry of Functional Materials, Physics and Electronic Information College, Inner Mongolia Normal University, Hohhot 010022 (China); Nakai, Ikuo [Department of Electrical and Electronic Engineering, Tottori University, Tottori 680-8552 (Japan)

    2014-10-15

    Highlights: • We have investigated the Fe and Mn K edge XAFS spectra of the Mn{sub 1.28}Fe{sub 0.67}P{sub 0.46}Si{sub 0.54} compound at 25 K and 295 K. • The site occupation of the Fe and Mn atoms and local structure of Mn{sub 1.28}Fe{sub 0.67}P{sub 0.46}Si{sub 0.54} are determined. • The atomic distances between Fe–Fe in c-plane for the ferromagnetic state are larger than those in the paramagnetic state. - Abstract: The Fe{sub 2}P-type MnFe(P,Si) compounds are investigated by means of magnetic measurements and X-ray absorption fine structure spectroscopy. Magnetic measurements show that the Mn{sub 1.28}Fe{sub 0.67}P{sub 0.46}Si{sub 0.54} compound undergoes a first-order phase transition at the Curie temperature of 254 K. The Fe K-edge and Mn K-edge X-ray absorption fine structure spectra show that Mn atom mainly located at the 3g sites, while the 3f sites are occupied by Fe atoms and Mn atom randomly. The distances between the Fe atom and its nearest neighbor atoms in a triangle Fe–Mn–Fe change from 2.80 Å at 25 K to 2.74 Å at 300 K. On the other hand, the distances between Fe atom and its second neighbor atoms change from 4.06 Å at 25 K to 4.02 Å at 300 K.

  10. Active Ti Species in TiCl3-Doped NaAlH4. Mechanism for Catalyst Deactivation

    NARCIS (Netherlands)

    Balde, C.P.; Stil, H.A.; van der Eerden, A.M.J.; de Jong, K.P.; Bitter, J.H.

    2007-01-01

    The nature of the active Ti species in TiCl3-doped NaAlH4, a promising hydrogen storage material, was studied as a function of the desorption temperature with Ti K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy, Ti K-edge X-ray absorption near-edge structure (XANES) spectroscopy,

  11. Hydrodynamic evolution and jet energy loss in Cu + Cu collisions

    International Nuclear Information System (INIS)

    Schenke, Bjoern; Jeon, Sangyong; Gale, Charles

    2011-01-01

    We present results from a hybrid description of Cu + Cu collisions using (3 + 1)-dimensional hydrodynamics (music) for the bulk evolution and a Monte Carlo simulation (martini) for the evolution of high-momentum partons in the hydrodynamical background. We explore the limits of this description by going to small system sizes and determine the dependence on different fractions of wounded nucleon and binary collisions scaling of the initial energy density. We find that Cu + Cu collisions are well described by the hybrid description at least up to 20% central collisions.

  12. Magnetic Moment of $^{59}$Cu

    CERN Multimedia

    2002-01-01

    Experiment IS358 uses the intense and pure beams of copper isotopes provided by the ISOLDE RILIS (resonance ionization laser ion source). The isotopes are implanted and oriented in the low temperature nuclear orientation set-up NICOLE. Magnetic moments are measured by $\\beta$-NMR. Copper (Z=29), with a single proton above the proton-magic nickel isotopes provides an ideal testground for precise shell model calculations of magnetic moments and their experimental verification. In the course of our experiments we already determined the magnetic moments of $^{67}$Ni, $^{67}$Cu, $^{68g}$Cu, $^{69}$Cu and $^{71}$Cu which provide important information on the magicity of the N=40 subshell closure. In 2001 we plan to conclude our systematic investigations by measuring the magnetic moment of the neutron-deficient isotope $^{59}$Cu. This will pave the way for a subsequent study of the magnetic moment of $^{57}$Cu with a complementary method.

  13. Effect of Fe(II)/Ce(III) dosage ratio on the structure and anion adsorptive removal of hydrothermally precipitated composites: Insights from EXAFS/XANES, XRD and FTIR

    KAUST Repository

    Chubar, Natalia

    2016-10-24

    In this work, we present material chemistry in the hydrothermal synthesis of new complex structure materials based on various dosage ratios of Fe and Ce (1:0, 2:1, 1:1, 1:2, 0:1), characterize them by the relevant methods that allow characterization of both crystalline and amorphous phases and correlate their structure/surface properties with the adsorptive performance of the five toxic anions. The applied synthesis conditions resulted in the formation of different compounds of Fe and Ce components. The Fe-component was dominated by various phases of Fe hydrous oxides, whereas the Ce-component was composed of various phases of Ce carbonates. The presence of two metal salts in raw materials resulted in the formation of a mesoporous structure and averaged the surface area compared to one metal-based material. The surface of all Fe-Ce composites was abundant in Fe component phases. Two-metal systems showed stronger anion removal performance than one-metal materials. The best adsorption was demonstrated by Fe-Ce based materials that had low crystallinity, that were rich in phases and that exhibited surfaces were abundant in greater number of surface functional groups. Notably, Fe extended fine structures simulated by EXAFS in these better adsorbents were rich from oscillations from both heavy and light atoms. This work provides new insights on the structure of composite inorganic materials useful to develop their applications in adsorption and catalysis. It also presents new inorganic anion exchangers with very high removal potential to fluoride and arsenate.

  14. Effect of Fe(II)/Ce(III) dosage ratio on the structure and anion adsorptive removal of hydrothermally precipitated composites: Insights from EXAFS/XANES, XRD and FTIR

    KAUST Repository

    Chubar, Natalia; Gerda, Vasyl; Banerjee, Dipanjan; Yablokova, Ganna

    2016-01-01

    In this work, we present material chemistry in the hydrothermal synthesis of new complex structure materials based on various dosage ratios of Fe and Ce (1:0, 2:1, 1:1, 1:2, 0:1), characterize them by the relevant methods that allow characterization of both crystalline and amorphous phases and correlate their structure/surface properties with the adsorptive performance of the five toxic anions. The applied synthesis conditions resulted in the formation of different compounds of Fe and Ce components. The Fe-component was dominated by various phases of Fe hydrous oxides, whereas the Ce-component was composed of various phases of Ce carbonates. The presence of two metal salts in raw materials resulted in the formation of a mesoporous structure and averaged the surface area compared to one metal-based material. The surface of all Fe-Ce composites was abundant in Fe component phases. Two-metal systems showed stronger anion removal performance than one-metal materials. The best adsorption was demonstrated by Fe-Ce based materials that had low crystallinity, that were rich in phases and that exhibited surfaces were abundant in greater number of surface functional groups. Notably, Fe extended fine structures simulated by EXAFS in these better adsorbents were rich from oscillations from both heavy and light atoms. This work provides new insights on the structure of composite inorganic materials useful to develop their applications in adsorption and catalysis. It also presents new inorganic anion exchangers with very high removal potential to fluoride and arsenate.

  15. Hydrous ferric oxide: evaluation of Cd-HFO surface complexation models combining Cd(K) EXAFS data, potentiometric titration results, and surface site structures identified from mineralogical knowledge.

    Science.gov (United States)

    Spadini, Lorenzo; Schindler, Paul W; Charlet, Laurent; Manceau, Alain; Vala Ragnarsdottir, K

    2003-10-01

    The surface properties of ferrihydrite were studied by combining wet chemical data, Cd(K) EXAFS data, and a surface structure and protonation model of the ferrihydrite surface. Acid-base titration experiments and Cd(II)-ferrihydrite sorption experiments were performed within 3titration data could be adequately modeled by triple bond Fe- OH(2)(+1/2)-H(+)triple bond Fe-OH(-1/2),logk((int))=-8.29, assuming the existence of a unique intrinsic microscopic constant, logk((int)), and consequently the existence of a single significant type of acid-base reactive functional groups. The surface structure model indicates that these groups are terminal water groups. The Cd(II) data were modeled assuming the existence of a single reactive site. The model fits the data set at low Cd(II) concentration and up to 50% surface coverage. At high coverage more Cd(II) ions than predicted are adsorbed, which is indicative of the existence of a second type of site of lower affinity. This agrees with the surface structure and protonation model developed, which indicates comparable concentrations of high- and low-affinity sites. The model further shows that for each class of low- and high-affinity sites there exists a variety of corresponding Cd surface complex structure, depending on the model crystal faces on which the complexes develop. Generally, high-affinity surface structures have surface coordinations of 3 and 4, as compared to 1 and 2 for low-affinity surface structures.

  16. Solvent phase characterisation of lanthanide(3) and americium(3) complexes with malonamide (tema) and ter-pyridine ligands by EXAFS: comparison with single crystals

    International Nuclear Information System (INIS)

    Den Auwer, C.; Presson, M.T.; Grigoriev, M.; Madic, C.; Nierlich, M.; Thuery, P.; David, F.; Hubert, S.; Drew, M.G.B.; Hudson, M.J.; Iveson, P.B.; Russell, M.L.

    2002-01-01

    In order to develop molecules that will be good candidates for the extractive separation of the various elements contained within nuclear fuels, 4f and 5f molecular chemistry has been the subject of numerous studies. Thus, to better understand the ligand to cation interaction and to fine tune the theoretical models, precise knowledge about the cation co-ordination sphere must be obtained. More precisely, both structural and electronic data must be acquired in order to define the role of the cation frontier orbitals within the complex. To do so, various structural probes must be used, from vibrational and nuclear techniques to X-ray spectroscopies. In the field of actinide solvent extraction, the species of interest are in the solvent phase and both solid state diffraction methods and solvent phase X-ray absorption spectroscopy have become of primary importance lately. A number of Ln(III) and Am(III) complexes of the type M(NO 3 ) 3 L 1,2 (where M is either Ln 3+ or Am 3+ and L is either the 2,2',6',2 - ter-pyridine (Tpy) or the N,N,N',N' tetraethyl-malonamide (TEMA) ligand) have been crystallographically characterised in the solid state. In order to obtain structural information in the solvent phase, EXAFS L III edge measurements have been performed on the cation (DCI ring at the LURE facility). The overall contraction (-0.05 Angstrom) of the cation co-ordination sphere from Nd 3+ to Lu 3+ reflects the decrease in the lanthanide ionic radii. With the TEMA ligand, this steric constraint generates the elongation of one nitrate bond, leading to one formally monodendate nitrate for the late Ln ions. Comparison is made with the Tpy ligand. In the case of Am 3+ cation, comparison with isostructural Nd 3+ shows that similar co-ordination spheres are obtained, either with the TEMA or the Tpy ligands. (authors)

  17. Towards accurate structural characterization of metal centres in protein crystals: the structures of Ni and Cu T6 bovine insulin derivatives

    International Nuclear Information System (INIS)

    Frankaer, Christian Grundahl; Mossin, Susanne; Ståhl, Kenny; Harris, Pernille

    2013-01-01

    The level of structural detail around the metal sites in Ni 2+ and Cu 2+ T 6 insulin derivatives was significantly improved by using a combination of single-crystal X-ray crystallography and X-ray absorption spectroscopy. Photoreduction and subsequent radiation damage of the Cu 2+ sites in Cu insulin was followed by XANES spectroscopy. Using synchrotron radiation (SR), the crystal structures of T 6 bovine insulin complexed with Ni 2+ and Cu 2+ were solved to 1.50 and 1.45 Å resolution, respectively. The level of detail around the metal centres in these structures was highly limited, and the coordination of water in Cu site II of the copper insulin derivative was deteriorated as a consequence of radiation damage. To provide more detail, X-ray absorption spectroscopy (XAS) was used to improve the information level about metal coordination in each derivative. The nickel derivative contains hexacoordinated Ni 2+ with trigonal symmetry, whereas the copper derivative contains tetragonally distorted hexacoordinated Cu 2+ as a result of the Jahn–Teller effect, with a significantly longer coordination distance for one of the three water molecules in the coordination sphere. That the copper centre is of type II was further confirmed by electron paramagnetic resonance (EPR). The coordination distances were refined from EXAFS with standard deviations within 0.01 Å. The insulin derivative containing Cu 2+ is sensitive towards photoreduction when exposed to SR. During the reduction of Cu 2+ to Cu + , the coordination geometry of copper changes towards lower coordination numbers. Primary damage, i.e. photoreduction, was followed directly by XANES as a function of radiation dose, while secondary damage in the form of structural changes around the Cu atoms after exposure to different radiation doses was studied by crystallography using a laboratory diffractometer. Protection against photoreduction and subsequent radiation damage was carried out by solid embedment of Cu insulin

  18. Stability of Cu-Precipitates in Al-Cu Alloys

    Directory of Open Access Journals (Sweden)

    Torsten E. M. Staab

    2018-06-01

    Full Text Available We present first principle calculations on formation and binding energies for Cu and Zn as solute atoms forming small clusters up to nine atoms in Al-Cu and Al-Zn alloys. We employ a density-functional approach implemented using projector-augmented waves and plane wave expansions. We find that some structures, in which Cu atoms are closely packed on {100}-planes, turn out to be extraordinary stable. We compare the results with existing numerical or experimental data when possible. We find that Cu atoms precipitating in the form of two-dimensional platelets on {100}-planes in the fcc aluminum are more stable than three-dimensional structures consisting of the same number of Cu-atoms. The preference turns out to be opposite for Zn in Al. Both observations are in agreement with experimental observations.

  19. Beta decay of Cu-56

    NARCIS (Netherlands)

    Borcea, R; Aysto, J; Caurier, E; Dendooven, P; Doring, J; Gierlik, M; Gorska, M; Grawe, H; Hellstrom, M; Janas, Z; Jokinen, A; Karny, M; Kirchner, R; La Commara, M; Langanke, K; Martinez-Pinedo, G; Mayet, P; Nieminen, A; Nowacki, F; Penttila, H; Plochocki, A; Rejmund, M; Roeckl, E; Schlegel, C; Schmidt, K; Schwengner, R; Sawicka, M

    2001-01-01

    The proton-rich isotope Cu-56 was produced at the GSI On-Line Mass Separator by means of the Si-28(S-32, p3n) fusion-evaporation reaction. Its beta -decay properties were studied by detecting beta -delayed gamma rays and protons. A half-Life of 93 +/- 3 ms was determined for Cu-56. Compared to the

  20. The hydrolysis and precipitation of Pd(II) in 0.6 mol kg-1 NaCl: A potentiometric, spectrophotometric, and EXAFS study

    International Nuclear Information System (INIS)

    Boily, Jean-Francois F.; Seward, Terry M.; Charnock, John M.

    2007-01-01

    The hydrolysis of palladium was investigated in 0.6 mol kg -1 NaCl at 298.2 K. Potentiometric titrations of solutions at various total concentrations of palladium(II) revealed that dilute (millimolar) conditions can be used to monitor the proton release due to hydrolysis reactions up to 2 protons per palladium(II) as long as the equilibration time is kept small. Spectrophotometric titrations were used to corroborate the homogeneous changes in speciation for the PdCl 3 OH 2- species and to extract its correlative molar absorption coefficients in the 210-320 nm range. The molar absorption coefficients are similar to those of PdCl42- but exhibit a broader distribution of excitation energies resulting from the blue shift of the dominant charge transfer bands due to the presence of OH-. The longer-term potentiometric titrations systematically yielded, on the other hand, precipitates which matured over a period of 6 weeks and resulted in a more extensive release of protons to the solution. Precipitation experiments at six different total palladium(II) concentrations in the 3-11 pH range showed the dominant precipitating phase as Pd(OH)1.72Cl0.28. The coordination environment of Pd in this solid was investigated by extended X-ray absorption fine structure spectroscopy (EXAFS) and yielded an average 1.75 O and 0.25 Cl per Pd atoms with a Pd-O distance of 2.0 (angstrom) and Pd-Cl of 2.1 (angstrom). Finally, the precipitation experiments showed the final products to be of larger solubility than a literature Pd(OH)2 solubility study in which the KCl media induced a solid phase transformation to Pd(OH)1.72Cl0.28. Polynuclear complexes Pdq(OH)r2q-r with q=r=[3,9] explain the combined precipitation and hydrolysis data and may represent subsets of [Pd(OH)2]n and/or [Pd(OH)1.72Cl0.28]n chains coiled into nanometer-sized spheroids previously described in the literature

  1. Deuterium transport in Cu, CuCrZr, and Cu/Be

    Science.gov (United States)

    Anderl, R. A.; Hankins, M. R.; Longhurst, G. R.; Pawelko, R. J.

    This paper presents the results of deuterium implantation/permeation experiments and TMAP4 simulations for a CuCrZr alloy, for OFHC-Cu and for a Cu/Be bi-layered structure at temperatures from 700 to 800 K. Experiments used a mass-analyzed, 3-keV D 3+ ion beam with particle flux densities of 5 × 10 19 to 7 × 10 19 D/m 2 s. Effective diffusivities and surface molecular recombination coefficients were derived giving Arrhenius pre-exponentials and activation energies for each material: CuCrZr alloy, (2.0 × 10 -2 m 2/s, 1.2 eV) for diffusivity and (2.9 × x10 -14 m 4/s, 1.92 eV) for surface molecular recombination coefficients; OFHC Cu, (2.1 × 10 -6 m 2/s, 0.52 eV) for diffusivity and (9.1 × 10 -18 m 4/s, 0.99 eV) for surface molecular recombination coefficients. TMAP4 simulation of permeation data measured for a Cu/Be bi-layer sample was achieved using a four-layer structure (Cu/BeO interface/Be/BeO back surface) and recommended values for diffusivity and solubility in Be, BeO and Cu.

  2. Cu-Cr Literature Review

    Energy Technology Data Exchange (ETDEWEB)

    Need, Ryan F. [Los Alamos National Laboratory

    2012-08-09

    Cu-Cr alloys are part of a class of face-centered cubic (FCC)-body-centered cubic (BCC) composites that includes similar alloys, such as Cu-Nb and Cu-Ta. When heavily deformed, these FCC-BCC materials create 'in situ' composites with a characteristic structure-nanoscale BCC filaments in a ductile FCC matrix. The strength of these composites is vastly greater than predicted by the rule of mixtures, and has been shown to be inversely proportional to the filament spacing. Lower raw materials costs suggest that Cu-Cr alloys may offer more economical solution to high-strength, high-conductivity wire than either their Nb or Ta counterparts. However, Cr is also more brittle and soluble in Cu than Nb or Ta. These qualities necessitate thermal treatments to remove solute atoms from the Cu matrix, improve conductivity, and maintain the ductility of the Cr filaments. Through the use of different thermomechanical processing routes or the addition of select dopants, alloys with strength in excess of 1 GPa at 70% IACS have been achieved. To date, previous research on Cu-Cr alloys has focused on a relatively small number of alloy compositions and processing methods while the effects of dopants and ageing treatments have only been studied independently. Consequently, there remains considerable opportunity for the development and optimization of these alloys as a leading high-strength, high-conductivity material.

  3. EXAFS and EPR study of La0.6Sr0.2Ca0.2MnO3 and La0.6Sr0.2Ba0.2MnO3

    International Nuclear Information System (INIS)

    Yang, D.-K.Dong-Seok; Ulyanov, A.N.; Phan, Manh-Huong; Kim, Ikgyun; Ahn, Byong-Keun; Rhee, Jang Roh; Kim, Jung Sun; Nguyen, Chau; Yu, Seong-Cho

    2003-01-01

    Extended X-ray absorption fine structure (EXAFS) analysis and electron-paramagnetic resonance (EPR) have been used to examine the local structure and the internal dynamics of La 0.6 Sr 0.2 Ca 0.2 MnO 3 and La 0.6 Sr 0.2 Ba 0.2 MnO 3 lanthanum manganites. The Mn-O bond distance (∼1.94 Angst for both samples) and the Debye-Waller factors (0.36x10 -2 and 0.41x10 -2 Angst 2 for La 0.6 Sr 0.2 Ca 0.2 MnO 3 and for La 0.6 Sr 0.2 Ba 0.2 MnO 3 , respectively) were obtained from the EXAFS analysis. The dependence of the EPR line width on dopant kind (Ca or Ba) showed a decrease of the spin-lattice interaction with an increase of the Curie temperature. For both compositions, the EPR line intensity followed the exponential law I(T)=I 0 exp(E a /k B T), deduced on the basis of the adiabatic polaron hopping model

  4. Effects of out-of-plane disorder on the superconductivity of Bi{sub 2}Sr{sub 2-x}La{sub x}CuO{sub 6+{delta}}

    Energy Technology Data Exchange (ETDEWEB)

    Roehler, Juergen; Trabant, Christoph; Frielingsdorf, Johanna; Djemour, Rabia [Universitaet Koeln, 50937 Koeln (Germany); Martovitsky, Victor [Lebedev-Institute, 119991 Moscow (Russian Federation); Dudy, Lenart; Dwelk, Helmut; Krapf, Alica [Humboldt Universitaet Berlin, 12489 Berlin (Germany)

    2008-07-01

    The effects of out-of-plane substitutional order/disorder on cuprate superconductivity remains to a large extent an unresolved issue. We have investigated the connection between superconductivity and the lattice effects arising from the heterovalent doping of Bi{sub 2}Sr{sub 2-x}La{sub x}CuO{sub 6+{delta}}, x = 0.8-0.1. Decreasing lanthanum content tunes the compound through the entire underdoped and overdoped regimes. Cu-K and La- K EXAFS served as local structural probes, and single crystal X-ray diffraction for the determination of the basic unit cell, and the symmetry of the supercell. The oxygen atoms in the CuO{sub 2} planes were found significantly disordered, dependent on doping, and to exhibit minimum disorder around x{sub opt}=0.33. But the degree of substitutional disorder in the out-of-plane La environment turned out independent on the concentration of the La dopants, the superstructure symmetry, and the crystal growth parameters, whereas T{sub c} depends sensitively on them. No evidence was found for possible concentration dependent site changes of the La dopant from the nominal Sr to the Bi sites. We discuss the probably crucial role of the interstitial oxygen atoms for the superconducting properties of the Bi{sub 2}Sr{sub 2-x}La{sub x}CuO{sub 6+{delta}} system.

  5. In-plane polarization dependence of (Bi,Pb){sub 2}Sr{sub 2}CaCu{sub 2}O{sub 8+δ} single crystals studied by X-ray absorption spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Ghafari, A., E-mail: ghafari@physik.hu-berlin.de [Institute of Physics, Humboldt University of Berlin, Newtonstr., 15, D-12489 Berlin (Germany); Elettra Sincrotrone Trieste, Strada Statale 14 km 163.5, I-34149 Trieste (Italy); Ariffin, A.K. [Institute of Physics, Humboldt University of Berlin, Newtonstr., 15, D-12489 Berlin (Germany); Department of Physics, Universiti Pendidikan Sultan Idris, 35900 Tanjong Malim (Malaysia); Janowitz, C., E-mail: christoph.janowitz@physik.hu-berlin.de [Institute of Physics, Humboldt University of Berlin, Newtonstr., 15, D-12489 Berlin (Germany); Dwelk, H.; Krapf, A.; Manzke, R. [Institute of Physics, Humboldt University of Berlin, Newtonstr., 15, D-12489 Berlin (Germany)

    2014-06-15

    The effects of in-plane polarization change on the determination of the hole density of weakly under-doped (Bi, Pb)-2212 single crystals has been studied by x-ray absorption spectroscopy (XAS). The XAS signal at the CuL{sub 3} edge (925–940 eV) and O K edge (525 eV to 539 eV) were recorded under continuous rotation of the CuO{sub 2} plane from 0° to 180° with a minimum increment of 1.8°, yielding experimentally an in-plane polarization dependence for the absorption signals at the respective threshold. From that the in-plane angular dependence of the hole density (n{sub H}(φ)) could be determined. Fermi's golden rule was then used for the evaluation of the in-plane polarization dependence showing the expected polarization independence in disaccord to the experimental observations. Possible scenarios to solve this issue are discussed. Our results propose that polarization dependence could be due to inhomogeneous distribution of holes in the CuO{sub 2} planes which is also supported by models. Second, the role of out of plane orbitals has to be taken into account for interpretation.

  6. Cu-ZSM-5, Cu-ZSM-11, and Cu-ZSM-12 Catalysts for Direct NO Decomposition

    DEFF Research Database (Denmark)

    Kustova, Marina; Kustov, Arkadii; Christiansen, Sofie E.

    2006-01-01

    Cu-ZSM-5 has for many years been recognized as a unique catalyst for direct NO decomposition. Here, it is discovered that both Cu-ZSM-11 and Cu-ZSM-12 are about twice as active as Cu-ZSM-5. This difference is attributed to the active sites located almost exclusively in the straight zeolite pores...

  7. Physical mechanisms of Cu-Cu wafer bonding

    International Nuclear Information System (INIS)

    Rebhan, B.

    2014-01-01

    Modern manufacturing processes of complex integrated semiconductor devices are based on wafer-level manufacturing of components which are subsequently interconnected. When compared with classical monolithic bi-dimensional integrated circuits (2D ICs), the new approach of three-dimensional integrated circuits (3D ICs) exhibits significant benefits in terms of signal propagation delay and power consumption due to the reduced metal interconnection length and allows high integration levels with reduced form factor. Metal thermo-compression bonding is a process suitable for 3D interconnects applications at wafer level, which facilitates the electrical and mechanical connection of two wafers even processed in different technologies, such as complementary metal oxide semiconductor (CMOS) and microelectromechanical systems (MEMS). Due to its high electrical conductivity, copper is a very attractive material for electrical interconnects. For Cu-Cu wafer bonding the process requires typically bonding for around 1 h at 400°C and high contact pressure applied during bonding. Temperature reduction below such values is required in order to solve issues regarding (i) throughput in the wafer bonder, (ii) wafer-to-wafer misalignment after bonding and (iii) to minimise thermo-mechanical stresses or device degradation. The aim of this work was to study the physical mechanisms of Cu-Cu bonding and based on this study to further optimise the bonding process for low temperatures. The critical sample parameters (roughness, oxide, crystallinity) were identified using selected analytical techniques and correlated with the characteristics of the bonded Cu-Cu interfaces. Based on the results of this study the impact of several materials and process specifications on the bonding result were theoretically defined and experimentally proven. These fundamental findings subsequently facilitated low temperature (LT) metal thermo-compression Cu-Cu wafer bonding and even room temperature direct

  8. The influence of dietary Cu and diabetes on tissue 67Cu retention kinetics in rats

    International Nuclear Information System (INIS)

    Uriu-Hare, J.Y.; Rucker, R.B.; Keen, C.L.

    1991-01-01

    Compared to controls, diabetes results in higher plasma, liver and kidney Cu concentrations. Since alterations in Cu metabolism may be associated with diabetic pathology, the authors investigated how Cu metabolism is affected by diabetes and dietary Cu intake. Nondiabetic and STZ diabetic rats were fed Cu suppl. or Cu def. diets for 5 wks. Rats were intubated with 28 μCi 67 Cu and killed after 8, 16, 24, 32, 64, or 128 h. There were marked effects of both diet and diabetes on 67 Cu metabolism. Independent of diabetes, deficient rats had a higher % of retained 67 Cu, in liver, plasma, RBC, muscle, spleen, brain, lung, uterus, and intestine than adequate Cu rats. Independent of dietary Cu, diabetic rats had a lower % of retained 67 Cu in liver, plasma, RBC, muscle, spleen, lung, bone, pancreas, skin, uterus and heart than controls. Differential effects were noted for kidney; adequate Cu diabetic rats had a higher % of retained 67 Cu than all other groups. Marked effects of both diet and diabetes were evident when tissue Cu turnover was examined. Compared to Cu suppl. rats, Cu def. rats had a slower turnover of 67 Cu, in liver, plasma, intestine, pancreas, eye, brain, muscle, spleen, lung and heart. Diabetic rats had a slower turnover of 67 Cu than nondiabetic rats in liver, plasma, intestine, pancreas, eye, kidney, RBC and uterus. The data imply that a focus on Cu metabolism with regard to cellular Cu trafficking and pathology may be warranted

  9. Renal Cu and Na excretion and hepatic Cu metabolism in both Cu acclimated and non acclimated rainbow trout (Oncorhynchus mykiss)

    DEFF Research Database (Denmark)

    Grosell, M.; Hogstrand, C.; Wood, C.M.

    1998-01-01

    protein depending on whether the Cu is derived from recent branchial uptake or is already present in the plasma prior to Cu-64 exposure. The plasma Cu pool derived from recent branchial uptake and the Cu pool present in the plasma prior to Cu-64 exposure is accessible to renal excretion to different...... Na+ efflux decreased by 40%, which was largely due to increased tubular Na+ reabsorption. Renal compensation for the impaired branchial Na+ uptake, seen during Cu exposure, thus seems to be involved in Cu acclimation in rainbow trout. (C) 1998 Elsevier Science B.V....

  10. Cu-62, Cu-64 and Cu-66 production with 4.2 MeV deuterons

    International Nuclear Information System (INIS)

    Avila, Mario; Morales, J.R.; Riquelme, H.O.

    1996-01-01

    Full text: The natural copper irradiation with deuterons produces the Cu-62, Cu-64 and Cu-66 radionuclides. Of two radioisotopes, those with deficiencies in neutrons, are applied in nuclear medicine diagnostic processes, mainly for the nuclear characteristic of the decay modes. The positron emitters, of short life mean Cu-62 (9.1 min, β + ) and Cu(12.7 h), are radionuclides applied in radio pharmacological preparation for brain, core, blood flux studies. The radiochemical process consists in the de solution of the irradiated metallic copper target, in acid medium. The result solution, can be neutralized with a base or a buffer at wished pH. Using a deuteron beam of 4,2 ± 0,1 MeV energy has been obtained total yields of 1,103 ± 0,011 μCl/μAh medium for 62 Cu and of 0,148 ± 0,015 μCl/μAh for 64 Cu

  11. Tailoring Graphene Morphology and Orientation on Cu(100), Cu(110), and Cu(111)

    Science.gov (United States)

    Jacobberger, Robert; Arnold, Michael

    2013-03-01

    Graphene CVD on Cu is phenomenologically complex, yielding diverse crystal morphologies, such as lobes, dendrites, stars, and hexagons, of various orientations. We present a comprehensive study of the evolution of these morphologies as a function of Cu surface orientation, pressure, H2:CH4, and nucleation density. Growth was studied on ultra-smooth, epitaxial Cu films inside Cu enclosures to minimize factors that normally complicate growth. With low H2:CH4, Mullins-Sekerka instabilities propagate to form dendrites, indicating transport limited growth. In LPCVD, the dendrites extend hundreds of microns in the 100, 111, and 110 directions on Cu(100), (110), and (111) and are perturbed by twin boundaries. In APCVD, multiple preferred dendrite orientations exist. With increasing H2:CH4, the dendritic nature of growth is suppressed. In LPCVD, square, rectangle, and hexagon crystals form on Cu(100), (110) and (111), reflecting the Cu crystallography. In APCVD, the morphology becomes hexagonal on each surface. If given ample time, every growth regime yields high-quality monolayers with D:G Raman ratio rationally tailor the graphene crystal morphology and orientation.

  12. Morphology and chemical composition of Cu/Sn/Cu and Cu(5 at-%Ni)/Sn/Cu(5 at-%Ni) interconnections

    NARCIS (Netherlands)

    Wierzbicka-Miernik, A.; Wojewoda-Budka, J.; Litynska-Dobrzynska, L.; Kodentsov, A.; Zieba, P.

    2012-01-01

    In the present paper, scanning and transmission electron microscopies as well as energy dispersive X-ray spectroscopy investigations were performed to describe the morphology and chemical composition of the intermetallic phases growing in Cu/Sn/Cu and Cu(Ni)/Sn/Cu(Ni) interconnections during the

  13. Compound cuing in free recall.

    Science.gov (United States)

    Lohnas, Lynn J; Kahana, Michael J

    2014-01-01

    According to the retrieved context theory of episodic memory, the cue for recall of an item is a weighted sum of recently activated cognitive states, including previously recalled and studied items as well as their associations. We show that this theory predicts there should be compound cuing in free recall. Specifically, the temporal contiguity effect should be greater when the 2 most recently recalled items were studied in contiguous list positions. A meta-analysis of published free recall experiments demonstrates evidence for compound cuing in both conditional response probabilities and interresponse times. To help rule out a rehearsal-based account of these compound cuing effects, we conducted an experiment with immediate, delayed, and continual-distractor free recall conditions. Consistent with retrieved context theory but not with a rehearsal-based account, compound cuing was present in all conditions, and was not significantly influenced by the presence of interitem distractors.

  14. Cu/Cu{sub 2}O/CuO nanoparticles: Novel synthesis by exploding wire technique and extensive characterization

    Energy Technology Data Exchange (ETDEWEB)

    Sahai, Anshuman [Department of Physics and Materials Science and Engineering, Jaypee Institute of Information Technology, A-10, Sector-62, Noida 201307 (India); Goswami, Navendu, E-mail: navendugoswami@gmail.com [Department of Physics and Materials Science and Engineering, Jaypee Institute of Information Technology, A-10, Sector-62, Noida 201307 (India); Kaushik, S.D. [UGC-DAE-Consortium for Scientific Research Mumbai Centre, R5 Shed, BARC, Mumbai 400085 (India); Tripathi, Shilpa [UGC-DAE Consortium for Scientific Research, Indore, M.P. (India)

    2016-12-30

    Highlights: The salient features of this research article are following: • Mixed phase synthesis of Cu/Cu{sub 2}O/CuO nanoparticles prepared by Exploding Wire Technique (EWT). • Predominant Cu/Cu{sub 2}O phases along with minor CuO phase revealed through XRD, TEM, Raman, FTIR, UV–Visible and PL analyses. • XPS analysis provided direct evidences of Cu{sup 2+} and Cu{sup +} along with O deficiency for prepared nanoparticles. • Room temperature weak ferromagnetic behaviour was demonstrated for Cu/Cu{sub 2}O/CuO nanoparticles. - Abstract: In this article, we explore potential of Exploding Wire Technique (EWT) to synthesize the copper nanoparticles using the copper metal in a plate and wire geometry. Rietveld refinement of X-ray diffraction (XRD) pattern of prepared material indicates presence of mixed phases of copper (Cu) and copper oxide (Cu{sub 2}O). Agglomerates of copper and copper oxide comprised of ∼20 nm average size nanoparticles observed through high resolution transmission electron microscope (HRTEM) and energy dispersive x-ray (EDX) spectroscopy. Micro-Raman (μR) and Fourier transform infrared (FTIR) spectroscopies of prepared nanoparticles reveal existence of additional minority CuO phase, not determined earlier through XRD and TEM analysis. μR investigations vividly reveal cubic Cu{sub 2}O and monoclinic CuO phases based on the difference of space group symmetries. In good agreement with μRaman analysis, FTIR stretching modes corresponding to Cu{sub 2}-O and Cu-O were also distinguished. Investigations of μR and FTIR vibrational modes are in accordance and affirm concurrence of CuO phases besides predominant Cu and Cu{sub 2}O phase. Quantum confinement effects along with increase of band gaps for direct and indirect optical transitions of Cu/Cu{sub 2}O/CuO nanoparticles are reflected through UV–vis (UV–vis) spectroscopy. Photoluminescence (PL) spectroscopy spots the electronic levels of each phase and optical transitions processes

  15. X-ray absorption spectroscopic studies of the active sites of nickel- and copper-containing metalloproteins

    International Nuclear Information System (INIS)

    Tan, G.O.

    1993-06-01

    X-ray absorption spectroscopy (XAS) is a useful tool for obtaining structural and chemical information about the active sites of metalloproteins and metalloenzymes. Information may be obtained from both the edge region and the extended X-ray absorption fine structure (EXAFS) or post-edge region of the K-edge X-ray absorption spectrum of a metal center in a compound. The edge contains information about the valence electronic structure of the atom that absorbs the X-rays. It is possible in some systems to infer the redox state of the metal atom in question, as well as the geometry and nature of ligands connected to it, from the features in the edge in a straightforward manner. The EXAFS modulations, being produced by the backscattering of the ejected photoelectron from the atoms surrounding the metal atom, provide, when analyzed, information about the number and type of neighbouring atoms, and the distances at which they occur. In this thesis, analysis of both the edge and EXAFS regions has been used to gain information about the active sites of various metalloproteins. The metalloproteins studied were plastocyanin (Pc), laccase and nickel carbon monoxide dehydrogenase (Ni CODH). Studies of Cu(I)-imidazole compounds, related to the protein hemocyanin, are also reported here

  16. Thermochemical properties of oxides in Y-Ba-Cu-O, Sr-Bi-O, Cu-Nb-O, Sr-Cu-O, Ca-Cu-O, Cu-O and Hg-Ba-Ca-Cu-O systems

    International Nuclear Information System (INIS)

    Moiseev, G.K.; Vatolin, N.A.; Il'inykh, N.I.

    2000-01-01

    Thermochemical properties (ΔH 0 298 , S 0 298 , H 0 298 -H 0 0 , C p (T), C p at T>T melt ) of complex oxides in Y-Ba-Cu-O, Sr-Bi-O, Cu-Nb-O, Sr-Cu-O, Ca-Cu-O, Cu-O and Hg-Ba-Ca-Cu-O systems obtained with application of calculation methods are presented. Nonexperimental methods of estimation, revision and correction of standard formation enthalpies of inorganic compounds are described [ru

  17. Comparative study of Cu-Zr and Cu-Ru alloy films for barrier-free Cu metallization

    International Nuclear Information System (INIS)

    Wang Ying; Cao Fei; Zhang Milin; Liu Yuntao

    2011-01-01

    The properties of Cu-Zr and Cu-Ru alloy films were comparatively studied to evaluate their potential use as alloying elements. Cu alloy films were deposited on SiO 2 /Si substrates by magnetron sputtering. Samples were subsequently annealed and analyzed by four-point probe measurement, X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy and Auger electron spectroscopy. X-ray diffraction data suggest that Cu film has preferential (111) crystal orientation and no extra peak corresponding to any compound of Cu, Zr, Ru, and Si. According to transmission electron microscopy results, Cu grains grow in size for both systems but the grain sizes of the Cu alloy films are smaller than that of pure Cu films. These results indicate that Cu-Zr film is suitable for advanced barrier-free metallization in terms of interfacial stability and lower resistivity.

  18. Spin dynamics in CuO and Cu[sub 1[minus][ital x

    Energy Technology Data Exchange (ETDEWEB)

    Carretta, P.; Corti, M.; Rigamonti, A. (Department of Physics Alessandro Volta,' ' University of Pavia, Via Bassi 6, 27100 Pavia (Italy))

    1993-08-01

    [sup 63]Cu nuclear quadrupole resonance (NQR), nuclear antiferromagnetic resonance (AFNMR), and spin-lattice relaxation, as well as [sup 7]Li NMR and relaxation measurements in CuO and in Cu[sub 1[minus][ital x

  19. Direct Observation of Reduction of Cu(II) to Cu(I) by Terminal Alkynes

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Guanghui; Yi, Hong; Zhang, Guoting; Deng, Yi; Bai, Ruopeng; Zhang, Heng; Miller, Jeffrey T.; Kropf, Arthur J.; Bunel, Emilio E.; Lei, Aiwen

    2014-01-06

    ABSTRACT: X-ray absorption spectroscopy and in situ electron paramagnetic resonance evidence were provided for the reduction of Cu(II) to Cu(I) species by alkynes in the presence of tetramethylethylenediamine (TMEDA), in which TMEDA plays dual roles as both ligand and base. The structures of the starting Cu(II) species and the obtained Cu(I) species were determined as (TMEDA)- CuCl2 and [(TMEDA)CuCl]2 dimer, respectively.

  20. Controllable synthesis and enhanced photocatalytic properties of Cu2O/Cu31S16 composites

    International Nuclear Information System (INIS)

    Liu, Xueqin; Li, Zhen; Zhang, Qiang; Li, Fei

    2012-01-01

    Highlights: ► Facile sonochemical route. ► The content of Cu 31 S 16 in the Cu 2 O/Cu 31 S 16 can be easily controlled. ► Structure and optical properties of Cu 2 O/Cu 31 S 16 were discussed. ► Enhanced photocatalytic property of Cu 2 O/Cu 31 S 16 . ► Cu 2 O/Cu 31 S 16 core/shell structures were more stable than single Cu 2 O particles. -- Abstract: The controlled synthesis of Cu 2 O/Cu 31 S 16 microcomposites with hierarchical structures had been prepared via a convenient sonochemical route. Ultrasonic irradiation of a mixture of Cu 2 O and (NH 2 ) 2 CS in an aqueous medium yielded Cu 2 O/Cu 31 S 16 composites. The content of Cu 31 S 16 in the Cu 2 O/Cu 31 S 16 can be easily controlled by adjusting the synthesis time. The Cu 31 S 16 layer not only protected and stabilized Cu 2 O particles, but also prohibited the recombination of photogenerated electrons–holes pair between Cu 31 S 16 and Cu 2 O. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR) spectra, ultraviolet–visible (UV–Vis) spectroscopy and photoluminescence (PL) spectroscopy were used to characterize the products. Photocatalytic performance of the Cu 2 O/Cu 31 S 16 hierarchical structures was evaluated by measuring the decomposition rate of methyl orange solution under natural light. To the best of our knowledge, this is the first report on the preparation and photocatalytic activity of Cu 2 O/Cu 31 S 16 microcomposite. Additionally, the Cu 2 O/Cu 31 S 16 core/shell structures were more stable than single Cu 2 O particles during photocatalytic process since the photocatalytic activity of the second reused architecture sample was much higher than that of pure Cu 2 O. The Cu 2 O/Cu 31 S 16 microcomposites may be a good promising candidate for wastewater treatment.

  1. Mechanism of Catalytic Behavior and Structure of Active Centers in CuY Zeolite

    OpenAIRE

    Tanabe, Shuji; Matsumoto, Hiroshige

    1990-01-01

    The experimental and theoretical basis for the activated coppere xchanged Y zeolite system have been studied by the observation and analysis in the electronspin resonanace (ESR) , infrared (IR) and extended X-ray absorption fine structure (EXAFS) spectroscopies.

  2. Anomalous x-ray attenuation coefficients around the absorption edges using Mn Ksub(α) and Cu Ksub(α) x-rays

    International Nuclear Information System (INIS)

    Kerur, B.R.; Thontadarya, S.R.; Hanumaiah, B.

    1994-01-01

    The x-ray attenuation coefficients for three elements and for eight compounds are determined, adopting the method developed by employing a proportional counter, with a view to study the effect of fine structure on the mass attenuation coefficient values using Mn K α and Cu K α x-rays derived from K x-ray emitters, 55 Fe and 65 Zn radioactive sources, by a differential absorption technique. It is experimentally established that a small difference in energy between K α1 and K α2 (11 eV in the case of Mn K α and 24 eV in the case of the Cu K α x-ray) is inconsequential by comparing the measured and theoretical values of μ/ρ for standard elements, aluminium, copper and tantalum. The effect of fine structure on μ/ρ values is studied using the compounds containing one element with its absorption edge close to the incident photon energy. Results obtained in the present investigation show the nonvalidity of the mixture rule above the edge and also below the edge, ranging from about 600 eV below the edge to about 1500 eV about the edge. The contribution of resonance Raman scattering to the attenuation coefficient and indications to the presence of pre-edge structure similar to EXAFS are discussed. (author)

  3. On the molecular basis of the activity of the antimalarial drug chloroquine: EXAFS-assisted DFT evidence of a direct Fe–N bond with free heme in solution

    International Nuclear Information System (INIS)

    Macetti, Giovanni; Rizzato, Silvia; Beghi, Fabio; Presti, Leonardo Lo; Silvestrini, Lucia

    2016-01-01

    4-aminoquinoline antiplasmodials interfere with the biocrystallization of the malaria pigment, a key step of the malaria parasite metabolism. It is commonly believed that these drugs set stacking π···π interactions with the Fe-protoporphyrin scaffold of the free heme, even though the details of the heme:drug recognition process remain elusive. In this work, the local coordination of Fe(III) ions in acidic solutions of hematin at room temperature was investigated by extended x-ray absorption fine structure (EXAFS) spectroscopy in the 4.0–5.5 pH range, both in the presence and in the absence of the antimalarial drug chloroquine. EXAFS results were complemented by DFT simulations in polarizable continuum media to model solvent effects. We found evidence that a complex where the drug quinoline nitrogen is coordinated with the iron center might coexist with formerly proposed adduct geometries, based on stacking interactions. Charge-assisted hydrogen bonds among lateral chains of the two molecules play a crucial role in stabilizing this complex, whose formation is favored by the presence of lipid micelles. The direct Fe–N bond could reversibly block the axial position in the Fe 1st coordination shell in free heme, acting as an inhibitor for the crystallization of the malaria pigment without permanently hampering the catalytic activity of the redox center. These findings are discussed in the light of possible implications on the engineering of drugs able to thwart the adaptability of the malaria parasite against classical aminoquinoline-based therapies. (invited comment)

  4. On the molecular basis of the activity of the antimalarial drug chloroquine: EXAFS-assisted DFT evidence of a direct Fe-N bond with free heme in solution

    Science.gov (United States)

    Macetti, Giovanni; Rizzato, Silvia; Beghi, Fabio; Silvestrini, Lucia; Lo Presti, Leonardo

    2016-02-01

    4-aminoquinoline antiplasmodials interfere with the biocrystallization of the malaria pigment, a key step of the malaria parasite metabolism. It is commonly believed that these drugs set stacking π···π interactions with the Fe-protoporphyrin scaffold of the free heme, even though the details of the heme:drug recognition process remain elusive. In this work, the local coordination of Fe(III) ions in acidic solutions of hematin at room temperature was investigated by extended x-ray absorption fine structure (EXAFS) spectroscopy in the 4.0-5.5 pH range, both in the presence and in the absence of the antimalarial drug chloroquine. EXAFS results were complemented by DFT simulations in polarizable continuum media to model solvent effects. We found evidence that a complex where the drug quinoline nitrogen is coordinated with the iron center might coexist with formerly proposed adduct geometries, based on stacking interactions. Charge-assisted hydrogen bonds among lateral chains of the two molecules play a crucial role in stabilizing this complex, whose formation is favored by the presence of lipid micelles. The direct Fe-N bond could reversibly block the axial position in the Fe 1st coordination shell in free heme, acting as an inhibitor for the crystallization of the malaria pigment without permanently hampering the catalytic activity of the redox center. These findings are discussed in the light of possible implications on the engineering of drugs able to thwart the adaptability of the malaria parasite against classical aminoquinoline-based therapies.

  5. Photonuclear spallation reactions in Cu

    International Nuclear Information System (INIS)

    Shibata, S.; Imamura, M.; Miyachi, T.

    1986-06-01

    Formation yields of 24 radioactive nuclides by the interaction of bremsstrahlung in the maximum end-point energies of 100 MeV - 1 GeV with Cu have been measured by direct γ-ray counting of irradiated targets. The yields in the mass range of 42 to 60 except for 60 Cu were analysed by non-linear least-squares fit to construct the mass yield and charge dispersion curves in spallation reactions. From the parameter values obtained, the energy dependence of the slope of the mass yield curve and the relationship between target N/Z and the most probable product N/Z were investigated in comparison with the results of proton, α and heavy ion-induced spallations of Cu. The characteristics of photon-induced spallations are discussed. (author)

  6. Diffusion of Cu+ in β-phase CuI

    International Nuclear Information System (INIS)

    Johansson, J.X.M.Z.; Skoeld, K.; Joergensen, J.E.

    1992-01-01

    Measurements of ionic diffusion of Cu + in solid CuI in the β-phase is carried out with a non-destructive radioactive tracer technique, utilizing coincidence counting of the annihilation gammas from the positron decay of 64 Cu. The diffusion coefficient and the activation energy for the diffusion are evaluated. The experimental results show distinct diffusion character in the β-phase which differs from those in the γ- and α-phases. The β-phase diffusion properties together with the previous results for γ-and α-phases will provide valuable guidance for MD calculations, in which the diffusion coefficients and activation energies have been overestimated and the γ-β phase transition does not appear. The ionic conductivity of CuI estimated from tracer diffusion results and the Nernst-Einstein relation are compared with values from electro-chemical methods. In all three phases the conductivities obtained from electro-chemical methods are much lower than those calculated from the measured tracer diffusion coefficients. (author). 7 refs.; 4 figs.; 2 tabs

  7. Cu/Cu2O/CuO nanoparticles: Novel synthesis by exploding wire technique and extensive characterization

    Science.gov (United States)

    Sahai, Anshuman; Goswami, Navendu; Kaushik, S. D.; Tripathi, Shilpa

    2016-12-01

    In this article, we explore potential of Exploding Wire Technique (EWT) to synthesize the copper nanoparticles using the copper metal in a plate and wire geometry. Rietveld refinement of X-ray diffraction (XRD) pattern of prepared material indicates presence of mixed phases of copper (Cu) and copper oxide (Cu2O). Agglomerates of copper and copper oxide comprised of ∼20 nm average size nanoparticles observed through high resolution transmission electron microscope (HRTEM) and energy dispersive x-ray (EDX) spectroscopy. Micro-Raman (μR) and Fourier transform infrared (FTIR) spectroscopies of prepared nanoparticles reveal existence of additional minority CuO phase, not determined earlier through XRD and TEM analysis. μR investigations vividly reveal cubic Cu2O and monoclinic CuO phases based on the difference of space group symmetries. In good agreement with μRaman analysis, FTIR stretching modes corresponding to Cu2-O and Cu-O were also distinguished. Investigations of μR and FTIR vibrational modes are in accordance and affirm concurrence of CuO phases besides predominant Cu and Cu2O phase. Quantum confinement effects along with increase of band gaps for direct and indirect optical transitions of Cu/Cu2O/CuO nanoparticles are reflected through UV-vis (UV-vis) spectroscopy. Photoluminescence (PL) spectroscopy spots the electronic levels of each phase and optical transitions processes occurring therein. Iterative X-ray photoelectron spectroscopy (XPS) fitting of core level spectra of Cu (2p3/2) and O (1s), divulges presence of Cu2+ and Cu+ in the lattice with an interesting evidence of O deficiency in the lattice structure and surface adsorption. Magnetic analysis illustrates that the prepared nanomaterial demonstrates ferromagnetic behaviour at room temperature.

  8. CH{sub 4} dehydrogenation on Cu(1 1 1), Cu@Cu(1 1 1), Rh@Cu(1 1 1) and RhCu(1 1 1) surfaces: A comparison studies of catalytic activity

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Riguang; Duan, Tian [Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, Shanxi (China); Ling, Lixia [Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, Shanxi (China); Research Institute of Special Chemicals, Taiyuan University of Technology, Taiyuan 030024, Shanxi (China); Wang, Baojun, E-mail: wangbaojun@tyut.edu.cn [Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, Shanxi (China)

    2015-06-30

    Highlights: • Adsorbed Rh atom on Cu catalyst exhibits better catalytic activity for CH{sub 4} dehydrogenation. • The adsorbed Rh atom is the reaction active center for CH{sub 4} dehydrogenation. • The morphology of Cu substrate has negligible effect on CH{sub 4} dehydrogenation. - Abstract: In the CVD growth of graphene, the reaction barriers of the dehydrogenation for hydrocarbon molecules directly decide the graphene CVD growth temperature. In this study, density functional theory method has been employed to comparatively probe into CH{sub 4} dehydrogenation on four types of Cu(1 1 1) surface, including the flat Cu(1 1 1) surface (labeled as Cu(1 1 1)) and the Cu(1 1 1) surface with one surface Cu atom substituted by one Rh atom (labeled as RhCu(1 1 1)), as well as the Cu(1 1 1) surface with one Cu or Rh adatom (labeled as Cu@Cu(1 1 1) and Rh@Cu(1 1 1), respectively). Our results show that the highest barrier of the whole CH{sub 4} dehydrogenation process is remarkably reduced from 448.7 and 418.4 kJ mol{sup −1} on the flat Cu(1 1 1) and Cu@Cu(1 1 1) surfaces to 258.9 kJ mol{sup −1} on RhCu(1 1 1) surface, and to 180.0 kJ mol{sup −1} on Rh@Cu(1 1 1) surface, indicating that the adsorbed or substituted Rh atom on Cu catalyst can exhibit better catalytic activity for CH{sub 4} complete dehydrogenation; meanwhile, since the differences for the highest barrier between Cu@Cu(1 1 1) and Cu(1 1 1) surfaces are smaller, the catalytic behaviors of Cu@Cu(1 1 1) surface are very close to the flat Cu(1 1 1) surface, suggesting that the morphology of Cu substrate does not obviously affect the dehydrogenation of CH{sub 4}, which accords with the reported experimental observations. As a result, the adsorbed or substituted Rh atom on Cu catalyst exhibit a better catalytic activity for CH{sub 4} dehydrogenation compared to the pure Cu catalyst, especially on Rh-adsorbed Cu catalyst, we can conclude that the potential of synthesizing high-quality graphene with the

  9. Compound Cuing in Free Recall

    Science.gov (United States)

    Lohnas, Lynn J.; Kahana, Michael J.

    2014-01-01

    According to the retrieved context theory of episodic memory, the cue for recall of an item is a weighted sum of recently activated cognitive states, including previously recalled and studied items as well as their associations. We show that this theory predicts there should be compound cuing in free recall. Specifically, the temporal contiguity…

  10. The effect of inducing uniform Cu growth on formation of electroless Cu seed layer

    International Nuclear Information System (INIS)

    Lim, Taeho; Kim, Myung Jun; Park, Kyung Ju; Kim, Kwang Hwan; Choe, Seunghoe; Lee, Young-Soo; Kim, Jae Jeong

    2014-01-01

    The uniformity of Cu growth on Pd nanocatalysts was controlled by using organic additives in the formation of electroless Cu seed layers. Polyethylene glycol (PEG, Mw. 8000) not only reduced the deposition rate but also improved the uniformity of Cu growth on each Pd nanocatalyst during the seed layer formation. The stronger suppression effect of PEG on Cu than on Pd reduced the difference in the deposition rate between the two surfaces, resulting in the uniform deposition. Meanwhile, bis(3-sulfopropyl) disulfide degraded the uniformity by strong and nonselective suppression. The sheet resistance measurement and atomic force microscopy imaging revealed that the uniform Cu growth by PEG was more advantageous for the formation of a thin and smooth Cu seed layer than the non-uniform growth. The uniform Cu growth also had a positive influence on the subsequent Cu electrodeposition: the 60-nm-thick electrodeposited Cu film on the Cu seed layer showed low resistivity (2.70 μΩ·cm), low surface roughness (6.98 nm), and good adhesion strength. - Highlights: • Uniform Cu growth on Pd was achieved in formation of electroless Cu seed layer. • PEG addition to electroless bath improved the uniformity of Cu growth on Pd. • A thin, smooth and continuous Cu seed layer was obtained with PEG. • Adhesion strength of the Cu seed layer was also improved with PEG. • The uniformity improvement positively affected subsequent Cu electrodeposition

  11. Punicalagin Green Functionalized Cu/Cu2O/ZnO/CuO Nanocomposite for Potential Electrochemical Transducer and Catalyst

    Science.gov (United States)

    Fuku, X.; Kaviyarasu, K.; Matinise, N.; Maaza, M.

    2016-09-01

    A novel ternary Punica granatum L-Cu/Cu2O/CuO/ZnO nanocomposite was successfully synthesised via green route. In this work, we demonstrate that the green synthesis of metal oxides is more viable and facile compare to other methods, i.e., physical and chemical routes while presenting a potential electrode for energy applications. The prepared nanocomposite was characterised by both microscopic and spectroscopic techniques. High-resolution scanning electron microscopy (HRSEM) and X-ray diffraction (XRD) techniques revealed different transitional phases with an average nanocrystallite size of 29-20 mm. It was observed that the nanocomposites changed from amorphous-slightly crystalline Cu/Cu2O to polycrystalline Cu/Cu2O/CuO/ZnO at different calcination temperatures (room temperature-RT- 600 °C). The Cu/Cu2O/ZnO/CuO metal oxides proved to be highly crystalline and showed irregularly distributed particles with different sizes. Meanwhile, Fourier transform infrared (FTIR) spectroscopy confirmed the purity while together with ultraviolet-visible (UV-Vis) spectroscopy proved the proposed mechanism of the synthesised nanocomposite. UV-Vis showed improved catalytic activity of the prepared metal oxides, evident by narrow band gap energy. The redox and electrochemical properties of the prepared nanocomposite were achieved by cyclic voltammetry (CV), electrochemical impedance (EIS) and galvanostatic charge-discharge (GCD). The maximum specific capacitance ( C s) was calculated to be 241 F g-1 at 50 mV s-1 for Cu/Cu2O/CuO/ZnO nanoplatelets structured electrode. Moreover, all the CuO nanostructures reveal better power performance, excellent rate as well as long term cycling stability. Such a study will encourages a new design for a wide spectrum of materials for smart electronic device applications.

  12. Preparation of Cu Nanoclusters within Dendrimer Templates

    National Research Council Canada - National Science Library

    Zhao, M

    1998-01-01

    ... (16-atom Cu cluster in G4 and 64-atom Cu cluster in G6 dendrimers). The clusters remain trapped within the dendrimers for extended periods of time, do not agglomerate, and do not precipitate. The clusters can also be oxidized to yield dendrimer-encapsulated Cu(2+).

  13. Growth of intermetallics between Sn/Ni/Cu, Sn/Ag/Cu and Sn/Cu layered structures

    International Nuclear Information System (INIS)

    Horváth, Barbara; Illés, Balázs; Shinohara, Tadashi

    2014-01-01

    Intermetallic growth mechanisms and rates are investigated in Sn/Ni/Cu, Sn/Ag/Cu and Sn/Cu layer systems. An 8–10 μm thick Sn surface finish layer was electroplated onto a Cu substrate with a 1.5–2 μm thick Ni or Ag barrier layer. In order to induce intermetallic layer growth, the samples were aged in elevated temperatures: 50 °C and 125 °C. Intermetallic layer growth was checked by focused ion beam–scanning ion microscope. The microstructures and chemical compositions of the intermetallic layers were observed with a transmission electron microscope. It has been found that Ni barrier layers can effectively block the development of Cu 6 Sn 5 intermetallics. The intermetallic growth characteristics in the Sn/Cu and Sn/Ni/Cu systems are very similar. The intermetallic layer grows towards the Sn layer and forms a discrete layer. Differences were observed only in the growth gradients and surface roughness of the intermetallic layer which may explain the different tin whiskering properties. It was observed that the intermetallic layer growth mechanisms are completely different in the Ag barrier layers compared to the Ni layers. In the case of Sn/Ag/Cu systems, the Sn and Cu diffused through the Ag layer, formed Cu 6 Sn 5 intermetallics mainly at the Sn/Ag interface and consumed the Ag barrier layer. - Highlights: • Intermetallic growth was characterised in Sn/Ni/Cu, Sn/Ag/Cu and Sn/Cu layer systems. • Intermetallic growth rates and roughness are similar in the Sn/Cu and Sn/Ni/Cu systems. • Sn/Ni/Cu system contains the following intermetallic layer structure Sn–Ni3Sn4–Ni3Sn2–Ni3Sn–Ni. • In the case of Sn/Ag/Cu systems the Sn and Cu diffusion consumes the Ag barrier layer. • When Cu reaches the Sn/Ag interface a large amount of Cu 6 Sn 5 forms above the Ag layer

  14. Influence of Cu content on the cell biocompatibility of Ti–Cu sintered alloys

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Erlin, E-mail: zhangel@atm.neu.edu.cn [Key Lab. for Anisotropy and Texture of Materials, Education Ministry of China, Northeastern University, Shenyang 110819 (China); Jiamusi University, Jiamusi 154007 (China); Zheng, Lanlan [Jiamusi University, Jiamusi 154007 (China); Liu, Jie [Key Lab. for Anisotropy and Texture of Materials, Education Ministry of China, Northeastern University, Shenyang 110819 (China); Dept. of Prosthodontics, The Affiliated Hospital of Medical College, Qingdao University, Qingdao 266003 (China); Bai, Bing [Dept. of Prosthodontics, School of Stomatology, China Medical University, Liaoning Institute of Dental Research, Shenyang 110001 (China); Liu, Cong [Jiamusi University, Jiamusi 154007 (China)

    2015-01-01

    The cell toxicity and the cell function of Ti–Cu sintered alloys with different Cu contents (2, 5, 10 and 25 wt.%, respectively) have been investigated in comparison with commercial pure titanium in order to assess the influence of Cu content on the cell biocompatibility of the Ti–Cu alloys. The cytotoxicity was studied by examining the MG63 cell response by CCK8 assessment. The cell morphology was evaluated by acridine orange/ethidium bromide (AO/EB) fluorescence and observed under scanning electronic microscopy (SEM). The cell function was monitored by measuring the AKP activity. It has been shown by the AO/EB morphology results that the cell death on both cp-Ti sample and Ti–Cu samples is due to apoptosis rather than necrosis. Although more apoptotic cells were found on the Ti–2Cu and Ti–5Cu samples, no evidence of Cu content dependent manner of apoptosis has been found. SEM observation indicated very good cell adhesion and spread on the cp-Ti sample and the Ti–Cu samples with different Cu contents. CCK8 results displayed that increase in the Cu content in Ti–Cu alloys does not bring about any difference in the cell viability. In addition, AKP test results indicated that no difference in the differentiation of MG63 was found between the cp-Ti and the Ti–Cu samples and among the Ti–Cu samples. All results indicated that Ti–Cu alloys exhibit very good cell biocompatibility and the Cu content up to 25 wt.% in the Ti–Cu alloys has no influence on the cell proliferation and differentiation. - Highlights: • The effect of Cu content on the cell biocompatibility has been investigated. • Cu content shows no influence on the cell proliferation. • Cu content shows no effect on the cell differentiation.

  15. Influence of Cu content on the cell biocompatibility of Ti–Cu sintered alloys

    International Nuclear Information System (INIS)

    Zhang, Erlin; Zheng, Lanlan; Liu, Jie; Bai, Bing; Liu, Cong

    2015-01-01

    The cell toxicity and the cell function of Ti–Cu sintered alloys with different Cu contents (2, 5, 10 and 25 wt.%, respectively) have been investigated in comparison with commercial pure titanium in order to assess the influence of Cu content on the cell biocompatibility of the Ti–Cu alloys. The cytotoxicity was studied by examining the MG63 cell response by CCK8 assessment. The cell morphology was evaluated by acridine orange/ethidium bromide (AO/EB) fluorescence and observed under scanning electronic microscopy (SEM). The cell function was monitored by measuring the AKP activity. It has been shown by the AO/EB morphology results that the cell death on both cp-Ti sample and Ti–Cu samples is due to apoptosis rather than necrosis. Although more apoptotic cells were found on the Ti–2Cu and Ti–5Cu samples, no evidence of Cu content dependent manner of apoptosis has been found. SEM observation indicated very good cell adhesion and spread on the cp-Ti sample and the Ti–Cu samples with different Cu contents. CCK8 results displayed that increase in the Cu content in Ti–Cu alloys does not bring about any difference in the cell viability. In addition, AKP test results indicated that no difference in the differentiation of MG63 was found between the cp-Ti and the Ti–Cu samples and among the Ti–Cu samples. All results indicated that Ti–Cu alloys exhibit very good cell biocompatibility and the Cu content up to 25 wt.% in the Ti–Cu alloys has no influence on the cell proliferation and differentiation. - Highlights: • The effect of Cu content on the cell biocompatibility has been investigated. • Cu content shows no influence on the cell proliferation. • Cu content shows no effect on the cell differentiation

  16. Porous HKUST-1 derived CuO/Cu2O shell wrapped Cu(OH)2 derived CuO/Cu2O core nanowire arrays for electrochemical nonenzymatic glucose sensors with ultrahigh sensitivity

    Science.gov (United States)

    Yu, Cuiping; Cui, Jiewu; Wang, Yan; Zheng, Hongmei; Zhang, Jianfang; Shu, Xia; Liu, Jiaqin; Zhang, Yong; Wu, Yucheng

    2018-05-01

    Self-supported CuO/Cu2O@CuO/Cu2O core-shell nanowire arrays (NWAs) are successfully fabricated by a simple and efficient method in this paper. Anodized Cu(OH)2 NWAs could in-situ convert to HKUST-1 at room temperature easily. Cu(OH)2 NWAs cores and HKUST-1 shells transform into CuO/Cu2O simultaneously after calcinations and form CuO/Cu2O@CuO/Cu2O core-shell NWAs. This smart configuration of the core-shell structure not only avoids the agglomeration of the traditional MOF-derived materials in particle-shape, but also facilitates the ion diffusion and increases the active sites. This novel structure is employed as substrate to construct nonenzymatic glucose sensors. The results indicate that glucose sensor based on CuO/Cu2O@CuO/Cu2O core-shell NWAs presents ultrahigh sensitivity (10,090 μA mM-1 cm-2), low detection limit (0.48 μM) and wide linear range (0.99-1,330 μM). In addition, it also shows excellent anti-interference ability toward uric acid, ascorbic acid and L-Cysteine co-existing with glucose, good reproducibility and superior ability of real sample analysis.

  17. Synthesis of Cu2O, CuCl, and Cu2OCl2 nanoparticles by ultrafast ...

    Indian Academy of Sciences (India)

    2014-02-13

    Feb 13, 2014 ... 800 nm and ∼2 ps laser pulses. Cu2O NPs exhibited two-photon absorption at lower peak intensities while three-photon absorption was observed at higher peak intensities. Other samples exhibited two-photon absorption at all peak intensities. Keywords. Picosecond; laser ablation; copper complex; ...

  18. Synthesis of Cu 2 O, CuCl, and Cu2OCl 2 nanoparticles by ultrafast ...

    Indian Academy of Sciences (India)

    2014-02-13

    Feb 13, 2014 ... We have also performed nonlinear optical studies of colloidal nanoparticles using Z-scan technique at 800 nm and ∼2 ps laser pulses. Cu2O NPs exhibited two-photon absorption at lower peak intensities while three-photon absorption was observed at higher peak intensities. Other samples exhibited ...

  19. Epitaxial growth of Cu on Cu(001): Experiments and simulations

    International Nuclear Information System (INIS)

    Furman, Itay; Biham, Ofer; Zuo, Jiang-Kai; Swan, Anna K.; Wendelken, John

    2000-01-01

    A quantitative comparison between experimental and Monte Carlo simulation results for the epitaxial growth of Cu/Cu(001) in the submonolayer regime is presented. The simulations take into account a complete set of hopping processes whose activation energies are derived from semiempirical calculations using the embedded-atom method. The island separation is measured as a function of the incoming flux and the temperature. A good quantitative agreement between the experiment and simulation is found for the island separation, the activation energies for the dominant processes, and the exponents that characterize the growth. The simulation results are then analyzed at lower coverages, which are not accessible experimentally, providing good agreement with theoretical predictions as well

  20. Preparation of conductive Cu patterns by directly writing using nano-Cu ink

    Energy Technology Data Exchange (ETDEWEB)

    Li, Wei [School of Materials Science and Engineering, Tianjin University, Tianjin 300072 (China); Li, Wenjiang; Wei, Jun [School of Materials Science and Engineering, Tianjin University of Technology, Tianjin 300384 (China); Tan, Junjun [School of Chemical and Materials and Engineering, Hubei University of Technology, Hubei 435003 (China); Chen, Minfang, E-mail: mfchentj@126.com [School of Materials Science and Engineering, Tianjin University of Technology, Tianjin 300384 (China)

    2014-07-01

    Conductive and air-stable Cu patterns were directly made on ordinary photo paper using a roller pen filled with nano-Cu ink, which was mainly composed of metallic Cu nanoparticles (NPs) capped with poly(N-vinylpyrrolidone) (PVP). The nano-Cu NPs were obtained via the reduction of Cu{sup 2+} ions by using an excess of hydrazine and PVP. The low sintering temperature (160 °C) in Ar atmosphere played an important role for the preparation of air-stable Cu patterns. The conductivity of a radio-frequency identification antenna made from nano-Cu ink was tested by a lamp, and its resistivity achieved 13.4 ± 0.4 μΩ cm. The Cu NPs were confirmed by means of X-ray powder diffraction and X-ray photoelectron spectra, and the Cu patterns were characterized by scanning electron microscopy and energy dispersive X-ray spectrometry. A mechanism for the high conductivity of the Cu pattern made from Cu NPs is proposed. - Highlights: • The synthesis of pure Cu is related to the reducing agent and capping agent. • The sintering under Ar atmosphere prevents Cu pattern's rapid oxidation. • The formation of the bulk Cu decreases the resistivity of the Cu pattern.

  1. Stability enhancement of Cu2S against Cu vacancy formation by Ag alloying

    Science.gov (United States)

    Barman, Sajib K.; Huda, Muhammad N.

    2018-04-01

    As a potential solar absorber material, Cu2S has proved its importance in the field of renewable energy. However, almost all the known minerals of Cu2S suffer from spontaneous Cu vacancy formation in the structure. The Cu vacancy formation causes the structure to possess very high p-type doping that leads the material to behave as a degenerate semiconductor. This vacancy formation tendency is a major obstacle for this material in this regard. A relatively new predicted phase of Cu2S which has an acanthite-like structure was found to be preferable than the well-known low chalcocite Cu2S. However, the Cu-vacancy formation tendency in this phase remained similar. We have found that alloying silver with this structure can help to reduce Cu vacancy formation tendency without altering its electronic property. The band gap of silver alloyed structure is higher than pristine acanthite Cu2S. In addition, Cu diffusion in the structure can be reduced with Ag doped in Cu sites. In this study, a systematic approach is presented within the density functional theory framework to study Cu vacancy formation tendency and diffusion in silver alloyed acanthite Cu2S, and proposed a possible route to stabilize Cu2S against Cu vacancy formations by alloying it with Ag.

  2. Highly charged swelling mica reduces Cu bioavailability in Cu-contaminated soils

    Energy Technology Data Exchange (ETDEWEB)

    Stuckey, Jason W. [Department of Crop and Soil Sciences, Pennsylvania State University, 116 ASI Building, University Park, PA 16802 (United States); Neaman, Alexander [Facultad de Agronomia, P. Universidad Catolica de Valparaiso, Centro Regional de Estudios en Alimentos Saludables (Chile); Ravella, Ramesh; Komarneni, Sridhar [Department of Crop and Soil Sciences, Pennsylvania State University, 116 ASI Building, University Park, PA 16802 (United States); Martinez, Carmen Enid [Department of Crop and Soil Sciences, Pennsylvania State University, 116 ASI Building, University Park, PA 16802 (United States)], E-mail: cem17@psu.edu

    2009-01-15

    This is the first test of a highly charged swelling mica's (Na-2-mica) ability to reduce the plant-absorbed Cu in Cu-contaminated soils from Chile. Perennial ryegrass (Lolium perenne L.) was grown in two acid soils (Sector 2: pH 4.2, total Cu = 172 mg Cu kg{sup -1} and Sector 3: pH 4.2, total Cu = 112 mg Cu kg{sup -1}) amended with 0.5% and 1% (w/w) mica, and 1% (w/w) montmorillonite. At 10 weeks of growth, both mica treatments decreased the shoot Cu of ryegrass grown in Sector 2 producing shoot Cu concentrations above 21-22 mg Cu kg{sup -1} (the phytotoxicity threshold for that species), yet the mica treatments did not reduce shoot Cu concentrations when grown in Sector 3, which were at a typical level. The mica treatments improved shoot growth in Sector 3 by reducing free and extractable Cu to low enough levels where other nutrients could compete for plant absorption and translocation. In addition, the mica treatments improved root growth in both soils, and the 1% mica treatment reduced root Cu in both soils. This swelling mica warrants further testing of its ability to assist re-vegetation and reduce Cu bioavailability in Cu-contaminated surface soils. - In situ remediation of Cu-contaminated soils with a synthetic mica (Na-2-mica) will aid in re-vegetative efforts.

  3. Copper interactions in TlCu7S4 and TlCu7Se4

    International Nuclear Information System (INIS)

    Noren, L.; Delaplane, R.G.; Berger, R.

    1999-01-01

    Complete text of publication follows. The copper chalcogenides ACu 7 S 4 (A=NH 4 + , Tl + , Rb + ) are quasi-one-dimensional metals at ambient and higher temperatures which is due to the high mobility of copper in these structures. TlCu 7 S 4 and TlCu 7 Se 4 are isostructural compounds, space group I4/m, which can be described on the basis of a TlX 8 cube with two different Cu sites, Cu(1) and Cu(2). Cu(2)-Cu(2) zigzag chains run along the c axis with only 3/4 occupation of the Cu(2) sites. However, these two compounds differ in behaviour on cooling. The sulphide shows a polymorphic first-order transition to the CsAg 7 S 4 type (P4/n) owing to ordering of the vacancies in the Cu(2)-Cu(2) chains. In order to study the nature of the Cu(2) order/disorder in the two title compounds, a series of neutron diffraction measurements (both Bragg and diffuse scattering) were made at several temperatures from 40 to 713 K on the instrument SLAD at Studsvik. The structure at each temperature was modelled using RMC techniques. The resulting configuration show that as the temperature increases, there is a marked increase in the mobility of the Cu atoms in the Cu(2)-Cu(2) chains for TlCu 7 S 4 but not for TlCu 7 Se 4 . This is due to the initial difference in the Cu(2)-Cu(2) distances, only 2.2A for the thiocuprate, but 2.7A in the selenocuprate which explains the relative ease for Cu(2) ordering in the latter case. (author)

  4. Determination of Cr(VI) in wood specimen: A XANES study at the Cr K edge

    International Nuclear Information System (INIS)

    Strub, E.; Plarre, R.; Radtke, M.; Reinholz, U.; Riesemeier, H.; Schoknecht, U.; Urban, K.; Juengel, P.

    2008-01-01

    The content of chromium in different oxidation states in chromium-treated wood was studied with XANES (X-ray absorption near-edge structure) measurements at the Cr K absorption edge. It could be shown that wood samples treated with Cr(VI) (pine and beech) did still contain a measurable content of Cr(VI) after four weeks conditioning. If such wood samples were heat exposed for 2 h with 135 deg. C prior conditioning, Cr(VI) was no longer detected by XANES, indicating a complete reduction to chromium (III)

  5. Electronic structure effects on B K-edge XANES of minerals

    Czech Academy of Sciences Publication Activity Database

    Šipr, Ondřej; Rocca, F.

    2010-01-01

    Roč. 17, č. 3 (2010), s. 367-373 ISSN 0909-0495 R&D Projects: GA ČR GA202/08/0106 Institutional research plan: CEZ:AV0Z10100521 Keywords : structure * potentials * boron Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.335, year: 2010

  6. Photoionization of the Fe lons: Structure of the K-Edge

    Science.gov (United States)

    Palmeri, P.; Mendoza, C.; Kallman, T.; Bautista, M.; White, Nicholas E. (Technical Monitor)

    2002-01-01

    X-ray absorption and emission features arising from the inner-shell transitions in iron are of practical importance in astrophysics due to the Fe cosmic abundance and to the absence of traits from other elements in the nearby spectrum. As a result, the strengths and energies of such features can constrain the ionization stage, elemental abundance, and column density of the gas in the vicinity of the exotic cosmic objects, e.g. active galactic nuclei (AGN) and galactic black hole candidates. Although the observational technology in X-ray astronomy is still evolving and currently lacks high spectroscopic resolution, the astrophysical models have been based on atomic calculations that predict a sudden and high step-like increase of the cross section at the K-shell threshold (see for instance. New Breit-Pauli R-matrix calculations of the photoionization cross section of the ground states of Fe XVII in the region near the K threshold are presented. They strongly support the view that the previously assumed sharp edge behaviour is not correct. The latter has been caused by the neglect of spectator Auger channels in the decay of the resonances converging to the K threshold. These decay channels include the dominant KLL channels and give rise to constant widths (independent of n). As a consequence, these series display damped Lorentzian components that rapidly blend to impose continuity at threshold, thus reformatting the previously held picture of the edge. Apparent broadened iron edges detected in the spectra of AGN and galactic black hole candidates seem to indicate that these quantum effects may be at least partially responsible for the observed broadening.

  7. X-Ray Absorption in Carbon Ions Near the K-Edge

    Science.gov (United States)

    Hasoglu, M. F.; Abdel-Naby, Sh. A.; Nikolic, D.; Gorczyca, T. W.; McLaughlin, B. M.

    2007-06-01

    K-shell photoabsorption calculations are important for determining the elemental abundances of the interstellar medium (ISM) from observed X-ray absorption spectra. Previously, we performed reliable K-shell photoabsorption calculations for oxygen [1-3] and neon [4,5] ions. We have executed detailed R-matrix calculations for carbon ions, including Auger broadening, by using an optical potential, and relaxation effects, by using pseudoorbitals with the necessary pseudoresonance elimination. This work was funded by NASA's Astronomy Physics Research and Analysis (APRA) and Solar and Heliospheric Physics (SHP) Supporting Research and Technology (SR&T) programs. References: [1] T. W. Gorczyca and B. M. McLaughlin. J Phys. B. 33 L859 (2000) [2] A. M. Juett, et al., Astrophys. J. 612, 308 (2004) [3] J. Garcia et al., Astrophys. J. Supp. S. 158, 68 (2005) [4] T. W. Gorczyca., Phys. Rev. A. 61, 024702 (2000) [5] A. M. Juett, et al., Astrophys. J. 648, 1066 (2006)

  8. Characterization of Boroaluminosilicate Glass Surface Structures by B k-edge NEXAFS

    Energy Technology Data Exchange (ETDEWEB)

    R Schaut; R Lobello; K Mueller; C Pantano

    2011-12-31

    Techniques traditionally used to characterize bulk glass structure (NMR, IR, etc.) have improved significantly, but none provide direct measurement of local atomic coordination of glass surface species. Here, we used Near-Edge X-ray Absorption Fine Structure (NEXAFS) as a direct measure of atomic structure at multicomponent glass surfaces. Focusing on the local chemical structure of boron, we address technique-related issues of calibration, quantification, and interactions of the beam with the material. We demonstrate that beam-induced adsorption and structural damage can occur within the timeframe of typical measurements. The technique is then applied to the study of various fracture surfaces where it is shown that adsorption and reaction of water with boroaluminosilicate glass surfaces induces structural changes in the local coordination of boron, favoring B{sup IV} species after reaction.

  9. Spatially resolved sulfur K-edge XANES spectroscopy of wheat leaves infected by Puccinia triticina

    International Nuclear Information System (INIS)

    Lichtenberg, H; Prange, A; Hormes, J; Steiner, U; Oerke, E-C

    2009-01-01

    In this study, wheat leaves infected with brown rust, a plant disease of serious economic concern caused by the fungus Puccinia triticina, were investigated using spatially resolved XANES (X-ray Absorption Near Edge Structure) spectroscopy at the sulfur K-absorption edge.

  10. Spatially resolved sulfur K-edge XANES spectroscopy of wheat leaves infected by Puccinia triticina

    Energy Technology Data Exchange (ETDEWEB)

    Lichtenberg, H; Prange, A; Hormes, J [CAMD, Louisiana State University, 6980 Jefferson Hwy, Baton Rouge, LA 70806 (United States); Steiner, U; Oerke, E-C, E-mail: lichtenberg@lsu.ed [INRES-Phytomedicine, University of Bonn, Nussallee 9, 53115 Bonn (Germany)

    2009-11-15

    In this study, wheat leaves infected with brown rust, a plant disease of serious economic concern caused by the fungus Puccinia triticina, were investigated using spatially resolved XANES (X-ray Absorption Near Edge Structure) spectroscopy at the sulfur K-absorption edge.

  11. Fe K-EDGE X-RAY ABSORPTION SPECTROSCOPY OF SILICATE MINERALS AND GLASSES

    OpenAIRE

    Binsted , N.; Greaves , G.; Henderson , C.

    1986-01-01

    Structural parameters determined for crystalline iron, fayalite and aegirine agree closely with X-ray crystallograhic data. A glass of NaFeSi2O6 composition has Fe predominantly present as Fe3+ in tetrahedral coordination i.e. as a network former. CaFeSiO4 and CaFeSi2O6 glasses have about 1/3 of the total Fe in octahedral coordination i.e. as a network modifier.

  12. K-edge x-ray fluorescence analysis for actinide and heavy elements solution concentration measurements

    International Nuclear Information System (INIS)

    Camp, D.C.

    1984-07-01

    Advantages of using Co-57 as an exciter for K XRFA include: a compact design that requires no x-ray tubes; the exciter-detector assembly locates remote from support electronics; on-line, at-line, or off-line configurations for monitor/measurements; systems that can be run by semi-skilled technicians, once programmed; and operated via remote terminals with results sent to control rooms; heavy element concentrations that are measurable thru industrial pipes; independent of minor changes in solution matrix or source half life with concentration results reported in near-real-time; a dynamic range of measurable concentrations that is greater than 10 4 ; measurement times that are reasonable even at 1 gram/liter; and for nuclear safeguards, it provides the <0.5% accuracy required by DOE for the accountability of U, Pu, or both, once the system is calibrated

  13. Site-selective photofragmentation of chlorinated polymeric films observed around the chlorine K-edge

    Energy Technology Data Exchange (ETDEWEB)

    Arantes, C., E-mail: csilva@inmetro.gov.br [Divisão de Metrologia de Materiais, Instituto Nacional de Metrologia, Qualidade e Tecnologia, Xerém 25250-020, Duque de Caxias, RJ (Brazil); Mendes, L.A.V. [Instituto de Física, Universidade Federal da Bahia, Ondina, 40210-340 Salvador, BA (Brazil); Pinho, R.R. [Departamento de Física-ICE, Universidade Federal de Juiz de Fora, Campus Universitário, 36036-330 Juiz de Fora, MG (Brazil); Ferreira, M. [PEMM/COPPE, Universidade Federal do Rio de Janeiro, Cidade Universitária, Ilha do Fundão, 21941-972 Rio de Janeiro, RJ (Brazil); Souza, G.G.B. de; Rocha, A.B.; Rocco, M.L.M. [Instituto de Química, Universidade Federal do Rio de Janeiro, Cidade Universitária, Ilha do Fundão, 21941-909 Rio de Janeiro, RJ (Brazil)

    2013-03-29

    Highlights: ► PVC and PVDC were studied by PSID and NEXAFS techniques at the Chlorine 1s-edge. ► PVC film presented isotope ratio of 3:1 in the PSID spectrum. ► Cl{sup +} ion yield curves reproduce the photoabsorption spectrum for both polymers. ► Site-selectivity of C–Cl bond breaking due to an efficient spectator Auger decay. - Abstract: Photon stimulated ion desorption (PSID) and Near-edge X-ray absorption fine structure (NEXAFS) studies have been performed on poly(vinyl chloride) (PVC) and poly(vinyl dichloride) (PVDC) around the chlorine 1s-edge. Experiments were performed using a synchrotron source operating in the single-bunch mode and a time-of-flight mass spectrometry for ion analysis. Cl{sup +} ion yields, as a function of the photon energy, reproduce the photoabsorption spectrum, showing significant increase at the 1s-resonance. Edge-jump ratios, defined as the ratio between edge-jumps (intensity ratio of the yields between above and below the absorption edge) of two different transitions, for Cl{sup +} ion yields were much higher than the equivalent electron yields, indicating site-selectivity in C–Cl bond breaking for both polymers, as a result of efficient spectator Auger decay. The expected isotope ratio of 3:1 for chlorine was measured for PVC. The interpretation of the NEXAFS spectrum was assisted by quantum mechanical calculations at a multireference perturbation theory level.

  14. The X-ray photoabsorption spectrum of potassium near the K-edge

    International Nuclear Information System (INIS)

    Azuma, Y.; Berry, H.G.; Cowan, P.L.; Gemmell, D.S.; LeBrun, T.

    1996-01-01

    The authors have used a heat-pipe target in an X-ray beam to obtain photoabsorption spectra of potassium at the K- and KM-edges, in the photon energy range 3,600 to 3,650 eV. Preliminary identifications of most of the peaks observed are made using Dirac Hartree-Fock calculations. They compare these results with those obtained previously in closed-shell rare gas absorption spectra

  15. Quantitative spectral K-edge imaging in preclinical photon-counting x-ray computed tomography.

    Science.gov (United States)

    de Vries, Anke; Roessl, Ewald; Kneepkens, Esther; Thran, Axel; Brendel, Bernhard; Martens, Gerhard; Proska, Roland; Nicolay, Klaas; Grüll, Holger

    2015-04-01

    The objective of this study was to investigate the feasibility and the accuracy of spectral computed tomography (spectral CT) to determine the tissue concentrations and localization of high-attenuation, iodine-based contrast agents in mice. Iodine tissue concentrations determined with spectral CT are compared with concentrations measured with single-photon emission computed tomography (SPECT) and inductively coupled plasma mass spectrometry (ICP-MS). All animal procedures were performed according to the US National Institutes of Health principles of laboratory animal care and were approved by the ethical review committee of Maastricht, The Netherlands. Healthy Swiss mice (n = 4) were injected with an iodinated emulsion radiolabeled with indium as multimodal contrast agent for CT and SPECT. The CT and SPECT scans were acquired using a dedicated small-animal SPECT/CT system. Subsequently, scans were performed with a preclinical spectral CT scanner equipped with a photon-counting detector and 6 energy threshold levels. Quantitative data analysis of SPECT and spectral CT scans were obtained using 3-dimensional volumes-of-interest drawing methods. The ICP-MS on dissected organs was performed to determine iodine uptake per organ and was compared with the amounts determined from spectral CT and SPECT. Iodine concentrations obtained with image-processed spectral CT data correlated well with data obtained either with noninvasive SPECT imaging (slope = 0.96, r = 0.75) or with ICP-MS (slope = 0.99, r = 0.89) in tissue samples. This preclinical proof-of-concept study shows the in vivo quantification of iodine concentrations in tissues using spectral CT. Our multimodal imaging approach with spectral CT and SPECT using radiolabeled iodinated emulsions together with ICP-based quantification allows a direct comparison of all methods. Benchmarked against ICP-MS data, spectral CT in the present implementation shows a slight underestimation of organ iodine concentrations compared with SPECT but with a more narrow distribution. This slight deviation is most likely caused by experimental rather than technical issues.

  16. Doping and bond length contributions to Mn K-edge shift in La1 ...

    Indian Academy of Sciences (India)

    ... corresponds to the shift in the center of gravity of the unoccupied Mn 4-band contributing to the Mn K-absorption edge region. This correspondence is then used to separate the doping and size contributions to the edge shift due to variation in the number of electrons in valence band and Mn-O bond lengths, respectively, ...

  17. Resonant X-ray Scattering of carbonyl sulfide at the sulfur K edge

    International Nuclear Information System (INIS)

    Journel, Loïc; Marchenko, Tatiana; Guillemin, Renaud; Kawerk, Elie; Simon, Marc; Kavčič, Matjaž; Žit-nik, Matjaž; Bučar, Klemen; Bohinc, Rok

    2015-01-01

    New results on free OCS molecules have been obtained using Resonant X-ray Inelastic Scattering spectroscopy. A deconvolution algorithm has been applied to improve the energy resolution spectra of which we can extract detailed information on nuclear dynamics in the system. (paper)

  18. Resonant X-ray Scattering of carbonyl sulfide at the sulfur K edge

    OpenAIRE

    Journel , Loïc; Marchenko , Tatiana; Guillemin , Renaud; Kawerk , Elie; Kavčič , Matjaž; Žit-nik , Matjaž; Bučar , Klemen; Bohinc , Rok; Simon , Marc

    2015-01-01

    International audience; New results on free OCS molecules have been obtained using Resonant X-ray Inelastic Scattering spectroscopy. A deconvolution algorithm has been applied to improve the energy resolution spectra of which we can extract detailed information on nuclear dynamics in the system.

  19. X-ray attenuation around K-edge of Zr, Nb, Mo and Pd: A ...

    Indian Academy of Sciences (India)

    of 155 eV at 5.9 keV and had a 0.025 mm thick berillium window. The measuring ... A Linux-based FREEDOM software. [28], developed ..... Base (1999). [27] C M Lederer and V S Shirly, Table of isotopes (Wiley Interscience, New York, 1978).

  20. The O2-Evolving Complex of Photosystem II: Recent Insights from Quantum Mechanics/Molecular Mechanics (QM/MM), Extended X-ray Absorption Fine Structure (EXAFS), and Femtosecond X-ray Crystallography Data.

    Science.gov (United States)

    Askerka, Mikhail; Brudvig, Gary W; Batista, Victor S

    2017-01-17

    Efficient photoelectrochemical water oxidation may open a way to produce energy from renewable solar power. In biology, generation of fuel due to water oxidation happens efficiently on an immense scale during the light reactions of photosynthesis. To oxidize water, photosynthetic organisms have evolved a highly conserved protein complex, Photosystem II. Within that complex, water oxidation happens at the CaMn 4 O 5 inorganic catalytic cluster, the so-called oxygen-evolving complex (OEC), which cycles through storage "S" states as it accumulates oxidizing equivalents and produces molecular oxygen. In recent years, there has been significant progress in understanding the OEC as it evolves through the catalytic cycle. Studies have combined conventional and femtosecond X-ray crystallography with extended X-ray absorption fine structure (EXAFS) and quantum mechanics/molecular mechanics (QM/MM) methods and have addressed changes in protonation states of μ-oxo bridges and the coordination of substrate water through the analysis of ammonia binding as a chemical analog of water. These advances are thought to be critical to understanding the catalytic cycle since protonation states regulate the relative stability of different redox states and the geometry of the OEC. Therefore, establishing the mechanism for substrate water binding and the nature of protonation/redox state transitions in the OEC is essential for understanding the catalytic cycle of O 2 evolution. The structure of the dark-stable S 1 state has been a target for X-ray crystallography for the past 15 years. However, traditional X-ray crystallography has been hampered by radiation-induced reduction of the OEC. Very recently, a revolutionary X-ray free electron laser (XFEL) technique was applied to PSII to reveal atomic positions at 1.95 Å without radiation damage, which brought us closer than ever to establishing the ultimate structure of the OEC in the S 1 state. However, the atom positions in this crystal

  1. Cyclotron production of Cu-61

    Czech Academy of Sciences Publication Activity Database

    Lebeda, Ondřej; Ráliš, Jan; Seifert, Daniel

    2013-01-01

    Roč. 40, 2 Supplement (2013), S323-S323 ISSN 1619-7070. [Annual Congress of the European Association of Nuclear Medicine (EANM). 19.10.2013-23.10.2013, Lyon] R&D Projects: GA TA ČR TA02010797 Institutional support: RVO:61389005 Keywords : cyclotron U-120M * PET * Cu-61 Subject RIV: BG - Nuclear, Atomic and Molecular Physics, Colliders

  2. Cu diffusion as an alternative method for nanopatterned CuTCNQ film growth

    International Nuclear Information System (INIS)

    Capitán, M J; Álvarez, J; Miranda, R; Navío, C

    2016-01-01

    In this paper we show by means of ‘in situ’ x-ray diffraction studies that CuTCNQ formation from Cu(solid)–TCNQ(solid tetracyanoquinodimethane) goes through Cu diffusion at room temperature. The film quality depends on the TCNQ evaporation rate. At low evaporation rate we get a single phase-I CuTCNQ film very well crystallized and well oriented. The film has a CuTCNQ(0 2 0) orientation. The film is formed by CuTCNQ nanorods of a very homogeneous size. The film homogeneity has also been seen by atomic force microscopy (AFM). The electronic properties of the film have been measured by x-ray photoelectron spectroscopy (XPS) and ultra-violet photoelectron spectroscopy (UPS). Thus, the Cu-diffusion method has arisen as a very simple, clean and efficient method to grow localized CuTCNQ nanorods on Cu, opening up new insights for technological applications. (paper)

  3. Growth and characterisation of potentiostatically electrodeposited Cu2O and Cu thin films

    International Nuclear Information System (INIS)

    Wijesundera, R.P.; Hidaka, M.; Koga, K.; Sakai, M.; Siripala, W.

    2006-01-01

    Cuprous oxide and copper thin films were potentiostatically electrodeposited in an acetate bath. Voltammetric curves were used to investigate the growth parameters; deposition potential, pH and temperature of the bath. Deposition potential dependency on the structural, morphological, optical and electronic properties of the films were investigated by the X-ray diffraction measurements, scanning electron micrographs, absorption measurements and dark and light current-voltage characterisations. It was observed that single phase polycrystalline Cu 2 O can be deposited from 0 to - 300 mV Vs saturated calomel electrode (SCE) and co-deposition of Cu and Cu 2 O starts at - 400 mV Vs SCE. Further increase in deposition potential from - 700 mV Vs SCE produces single phase Cu thin films. Single phase polycrystalline Cu 2 O thin films with cubic grains of 1-2 μm can be possible within the very narrow potential domain around - 200 mV Vs SCE. Enhanced photoresponse in a photoelectrochemical cell is produced by the Cu 2 O thin film prepared at - 400 mV Vs SCE, where Cu is co-deposited with Cu 2 O with random distribution of Cu spheres on the Cu 2 O surface. This study reveals that a single deposition bath can be used to deposit both Cu and Cu 2 O separately and an admixture of Cu-Cu 2 O by controlling the deposition parameters

  4. New Production Routes for Medical Isotopes 64Cu and 67Cu Using Accelerator Neutrons

    Science.gov (United States)

    Kin, Tadahiro; Nagai, Yasuki; Iwamoto, Nobuyuki; Minato, Futoshi; Iwamoto, Osamu; Hatsukawa, Yuichi; Segawa, Mariko; Harada, Hideo; Konno, Chikara; Ochiai, Kentaro; Takakura, Kosuke

    2013-03-01

    We have measured the activation cross sections producing 64Cu and 67Cu, promising medical radioisotopes for molecular imaging and radioimmunotherapy, by bombarding a natural zinc sample with 14 MeV neutrons. We estimated the production yields of 64Cu and 67Cu by fast neutrons from \\text{natC(d,n) with 40 MeV 5 mA deuterons. We used the present result together with the evaluated cross section of Zn isotopes. The calculated 64Cu yield is 1.8 TBq (175 g 64Zn) for 12 h of irradiation; the yields of 67Cu by 67Zn(n,p)67Cu and 68Zn(n,x)67Cu were 249 GBq (184 g 67Zn) and 287 GBq (186 g 68Zn) at the end of 2 days of irradiation, respectively. From the results, we proposed a new route to produce 67Cu with very little radionuclide impurity via the 68Zn(n,x)67Cu reaction, and showed the 64Zn(n,p)64Cu reaction to be a promising route to produce 64Cu. Both 67Cu and 64Cu are noted to be produced using fast neutrons.

  5. Bimetallic AgCu/Cu2O hybrid for the synergetic adsorption of iodide from solution.

    Science.gov (United States)

    Mao, Ping; Liu, Ying; Liu, Xiaodong; Wang, Yuechan; Liang, Jie; Zhou, Qihang; Dai, Yuexuan; Jiao, Yan; Chen, Shouwen; Yang, Yi

    2017-08-01

    To further improve the capacity of Cu 2 O to absorb I - anions from solution, and to understand the difference between the adsorption mechanisms of Ag/Cu 2 O and Cu/Cu 2 O adsorbents, bimetallic AgCu was doped into Cu 2 O through a facile solvothermal route. Samples were characterized and employed to adsorb I - anions under different experimental conditions. The results show that the Cu content can be tuned by adding different volumes of Ag sols. After doping bimetallic AgCu, the adsorption capacity of the samples can be increased from 0.02 mmol g -1 to 0.52 mmol g -1 . Moreover, the optimal adsorption is reached within only 240 min. Meanwhile, the difference between the adsorption mechanisms of Ag/Cu 2 O and Cu/Cu 2 O adsorbents was verified, and the cooperative adsorption mechanism of the AgCu/Cu 2 O hybrid was proposed and verified. In addition, the AgCu/Cu 2 O hybrid showed excellent selectivity, e.g., its adsorption efficiencies are 85.1%, 81.9%, 85.9% and 85.7% in the presence of the Cl - , CO 3 2- , SO 4 2- and NO 3 - competitive anions, respectively. Furthermore, the AgCu/Cu 2 O hybrid can worked well in other harsh environments (e.g., acidic, alkaline and seawater environments). Therefore, this study is expected to promote the development of Cu 2 O into a highly efficient adsorbent for the removal of iodide from solution. Copyright © 2017 Elsevier Ltd. All rights reserved.

  6. The role of the A ion in the Fe local structure of the AFe{sub 2}As{sub 2} systems (A=Sr, Eu, Ba): an EXAFS study

    Energy Technology Data Exchange (ETDEWEB)

    Tobia, Dina; Radaelli, Matheus; Piva, Mario Moda; Lesseux, Guilherme Gorgen; Jesus, Camilo Bruno Ramos; Urbano, Ricardo Rodrigues; Granado, Eduardo; Pagliuso, Pascoal G., E-mail: ifitobia@ifi.unicamp.br [Universidade Estadual de Campinas (UNICAMP), SP (Brazil). Instituto de Fisica Gleb Wataghin; Saleta, Martin Eduardo [Laboratorio Nacional de Luz Sincrotron (LNLS), Campinas, SP (Brazil)

    2016-07-01

    Full text: The recent discovery of high-T{sub C} superconductivity on Fe-based intermetallic materials has motivated an extensive research in this area due to the rich phase diagrams that they present. The non-doped AFe{sub 2}As{sub 2} compounds (named A122) are oxygen free iron arsenides (with A= Ba, Sr, Ca, Eu). At room temperature they are paramagnetic and crystallize in a tetragonal structure. At low temperature they exhibit a spin-density-wave (SDW) ordering transition (typically 100 K < T{sub SDW} < 200 K), connected with a structural phase transition to an orthorhombic structure. These transitions are reflected as anomalies in the electric resistivity, magnetic susceptibility and specific heat data. Although the pure A122 compounds are not superconductors, in these systems, it was observed that the SDW phase can be destabilized through chemical substitution or external applied pressure, leading to the emergence of superconductivity. In particular, the atomic substitution of the alkali atoms with different ionic radii in the A site results in a change of the cell parameters and, consequently, these systems experience effects of chemical pressure. In this context, it is of great interest to investigate the role of the local distortion on the Fe-As bonds for temperatures above and below T{sub SDW}, as the Fe-As bond distance controls directly the chemical pressure on Fe and ultimately the orbital differentiation of the Fe 3d bands on the Fermi Surface of these compounds. Extended X-ray absorption fine structure (EXAFS) measurements are ideal to obtain information about the relationship between local structural distortions and the system spin dynamics. In this work we present a study of the As local environment in AFe{sub 2}As{sub 2} (for A=Eu, Sr, Ba) as a function of temperature through EXAFS measurements in the As K absorption edge. We have investigated the effects of each particular A-site ion on the Fe-As bond from a local point of view. In all cases, high

  7. IR and TPD studies of the interaction of alkenes with Cu + sites in CuNaY and CuNaX zeolites of various Cu content. The heterogeneity of Cu + sites

    Science.gov (United States)

    Datka, J.; Kukulska-Zajaç, E.; Kozyra, P.

    2006-08-01

    Cu + ions in zeolites activate organic molecules containing π electrons by π back donation, which results in a distinct weakening of multiple bonds. In this study, we followed the activation of alkenes (ethene and propene) by Cu + ions in CuY and CuX zeolites of various Cu content. We also studied the strength of bonding of alkenes to Cu + ions. IR studies have shown that there are two kinds of Cu + sites of various electron donor properties. We suppose that they could be attributed to the presence of Cu + ions of various number of oxygen atoms surrounding the cation. IR studies have shown that Cu ions introduced into Y and X zeolites in the first-order (at low Cu content) form Cu + ions of stronger electron donor properties (i.e. activate alkenes to larger extend) than Cu ions introduced in the next order (at higher Cu content). IR and TPD studies of alkenes desorption evidenced that Cu + ions of stronger electron donor properties bond alkenes stronger than less electron donor ones. It suggests that π back donation has more important contribution to the strength of bonding alkenes to cation than π donation.

  8. Facile synthesis of dendritic Cu by electroless reaction of Cu-Al alloys in multiphase solution

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Ying; Liang, Shuhua, E-mail: liangxaut@gmail.com; Yang, Qing; Wang, Xianhui

    2016-11-30

    Highlights: • Nano- or micro-scale fractal dendritic copper (FDC) was synthesized by electroless immersing of Cu-Al alloys in CuCl{sub 2} + HCl. • FDC size increases with the increase of Al content in Cu-Al alloys immersed in CuCl{sub 2} + HCl solution. • Nanoscale Cu{sub 2}O was found at the edge of FDC. Nanoporous copper (NPC) can also be obtained by using Cu{sub 17}Al{sub 83} alloy. • The potential difference between CuAl{sub 2} and α-Al phase and the replacement reaction in multiphase solution are key factors. - Abstract: Two-dimensional nano- or micro-scale fractal dendritic coppers (FDCs) were synthesized by electroless immersing of Cu-Al alloys in hydrochloric acid solution containing copper chloride without any assistance of template or surfactant. The FDC size increases with the increase of Al content in Cu-Al alloys immersed in CuCl{sub 2} + HCl solution. Compared to Cu{sub 40}Al{sub 60} and Cu{sub 45}Al{sub 55} alloys, the FDC shows hierarchical distribution and homogeneous structures using Cu{sub 17}Al{sub 83} alloy as the starting alloy. The growth direction of the FDC is <110>, and all angles between the trunks and branches are 60°. Nanoscale Cu{sub 2}O was found at the edge of FDC. Interestingly, nanoporous copper (NPC) can also be obtained through Cu{sub 17}Al{sub 83} alloy. Studies showed that the formation of FDC depended on two key factors: the potential difference between CuAl{sub 2} intermetallic and α-Al phase of dual-phase Cu-Al alloys; a replacement reaction that usually occurs in multiphase solution. The electrochemical experiment further proved that the multi-branch dendritic structure is very beneficial to the proton transfer in the process of catalyzing methanol.

  9. Cu-Zr-Ag bulk metallic glasses based on Cu8Zr5 icosahedron

    International Nuclear Information System (INIS)

    Xia Junhai; Qiang Jianbing; Wang Yingmin; Wang Qing; Dong Chuang

    2007-01-01

    Based on the cluster line criterion, the Ag addition into the Cu 8 Zr 5 cluster composition is investigated for the search of ternary Cu-Zr-Ag bulk metallic glasses with high glass forming abilities. Two initial binary compositions Cu 0.618 Zr 0.382 and Cu 0.64 Zr 0.36 are selected. The former one corresponds to a deep eutectic point; it is also the composition of the Cu 8 Zr 5 icosahedron, which is derived from the Cu 8 Zr 3 structure. The latter one, which can be regarded as the Cu 8 Zr 5 cluster plus a glue atom Cu, is the best glass-forming composition in the Cu-Zr binary system. Two composition lines (Cu 0.618 Zr 0.382 ) 1-x Ag x and (Cu 0.64 Zr 0.36 ) 1-x Ag x are thus constructed in the Cu-Zr-Ag system by linking these two compositions with the third constitute Ag. A series of Cu-Zr-Ag bulk metallic glasses are found with 2-8 at.% Ag contents in both composition lines. The optimum composition (Cu 0.618 Zr 0.382 ) 0.92 Ag 0.08 within the searched region with the highest T g /T l = 0.633, is located along the cluster line (Cu 0.618 Zr 0.382 ) 1-x Ag x , where the deep eutectic Cu 0.618 Zr 0.382 exactly corresponds to the dense packing cluster Cu 8 Zr 5 . The alloying mechanism is discussed in the light of atomic size and electron concentration factors

  10. TPD IR studies of CO desorption from zeolites CuY and CuX

    Science.gov (United States)

    Datka, Jerzy; Kozyra, Paweł

    2005-06-01

    The desorption of CO from zeolites CuY and CuX was followed by TPD-IR method. This is a combination of temperature programmed desorption and IR spectroscopy. In this method, the status of activated zeolite (before adsorption), the process of adsorption, and the status of adsorbed molecules can be followed by IR spectroscopy, and the process of desorption (with linear temperature increase) can be followed both by IR spectroscopy and by mass spectrometry. IR spectra have shown two kinds of Cu + sites in both CuY and CuX. Low frequency (l.f.) band (2140 cm -1 in CuY and 2130 cm -1 in CuX) of adsorbed CO represents Cu + sites for which π back donation is stronger and σ donation is weaker whereas high frequency h.f. band (2160 cm -1 in CuY and 2155 cm -1 in CuX) represent Cu + sites for which π back donation is weaker and σ donation is stronger. The TPD-IR experiments evidenced that the Cu + sites represented by l.f. band bond CO more weakly than those represented by h.f. one, indicating that σ donation has more important impact to the strength of Cu +-CO bonding. On the contrary, π back donation has bigger contribution to the activation of adsorbed molecules.

  11. Purity of targets prepared on Cu substrates

    Science.gov (United States)

    Méens, A.; Rossini, I.; Sens, J. C.

    1993-09-01

    The purity of several elemental self-supporting targets usually prepared by evaporation onto soluble Cu substrates has been studied. The targets were analysed by Rutherford backscattering and instrumental neutron activation analysis. Because of the high percentage of Cu observed in some Si targets, further measurements, including transmission electron microscopy, have been performed on Si targets deposited by e-gun bombardment onto Cu and ion-beam sputtering onto betaine.

  12. Phase diagram and EXAFS study of La sub 0 sub . sub 7 Ca sub 0 sub . sub 3 sub - sub x Ba sub x MnO sub 3 manganites

    CERN Document Server

    Ulyanov, A N; Yang, D S

    2003-01-01

    The phase diagram and local structure of La sub 0 sub . sub 7 Ca sub 0 sub . sub 3 sub - sub x Ba sub x MnO sub 3 (x=0; 0.03; 0.06; ... 0.3) lanthanum manganites were studies. The Curie temperature, T sub c , of the compositions showed a sharp change near the concentrational structural orthorhombic-rhombohedral phase transition. Maximums of dispersion, sigma sub M sub n sub - sub O sup 2 , and asymmetry, sigma M sub n sub - sub O sup 3 , of pair distribution function for the Mn-O bond distances of MnO sub 6 octahedron on x-dependence were observed by extended X-ray absorption fine structure (EXAFS) analysis. The maximum of sigma sub M sub n sub - sub O sup 2 is caused by increase of dynamic rms displacements of Mn-O bond distances near the T sub c. The observed x dependence of sigma sub M sub n sub - sub O sup 3 reflects the reduction of charge carriers mobility at approaching to T sub c. (author)

  13. Bonding in [CuNRR′]4 type clusters

    Institute of Scientific and Technical Information of China (English)

    WANG Bingwu; XU Guangxian; CHEN Zhida

    2004-01-01

    Many polynuclear Cu(I) compounds have been synthesized, but the problem whether there is direct or no direct Cu-Cu bonding in these compounds is not clear. The electronic structure of [CuNRR′]4 type clusters was investigated by using density functional methods. The results of geometrical optimization are in good agreement with experiment, and the localization of MO's shows that there are four Cu-Cu ( bonds to form the square Cu4 ring in addition to the four bridging Cu-N-Cu bonds. A concept of the covalence of molecular fragments is proposed to describe the bonding in these clusters.

  14. Spatial part-set cuing facilitation.

    Science.gov (United States)

    Kelley, Matthew R; Parasiuk, Yuri; Salgado-Benz, Jennifer; Crocco, Megan

    2016-07-01

    Cole, Reysen, and Kelley [2013. Part-set cuing facilitation for spatial information. Journal of Experimental Psychology: Learning, Memory, & Cognition, 39, 1615-1620] reported robust part-set cuing facilitation for spatial information using snap circuits (a colour-coded electronics kit designed for children to create rudimentary circuit boards). In contrast, Drinkwater, Dagnall, and Parker [2006. Effects of part-set cuing on experienced and novice chess players' reconstruction of a typical chess midgame position. Perceptual and Motor Skills, 102(3), 645-653] and Watkins, Schwartz, and Lane [1984. Does part-set cuing test for memory organization? Evidence from reconstructions of chess positions. Canadian Journal of Psychology/Revue Canadienne de Psychologie, 38(3), 498-503] showed no influence of part-set cuing for spatial information when using chess boards. One key difference between the two procedures was that the snap circuit stimuli were explicitly connected to one another, whereas chess pieces were not. Two experiments examined the effects of connection type (connected vs. unconnected) and cue type (cued vs. uncued) on memory for spatial information. Using chess boards (Experiment 1) and snap circuits (Experiment 2), part-set cuing facilitation only occurred when the stimuli were explicitly connected; there was no influence of cuing with unconnected stimuli. These results are potentially consistent with the retrieval strategy disruption hypothesis, as well as the two- and three-mechanism accounts of part-set cuing.

  15. Synthesis, Characterization and Catalytic Activity of Cu/Cu2O Nanoparticles Prepared in Aqueous Medium

    Directory of Open Access Journals (Sweden)

    Sayed M. Badawy

    2015-07-01

    Full Text Available Copper/Copper oxide (Cu/Cu2O nanoparticles were synthesized by modified chemical reduction method in an aqueous medium using hydrazine as reducing agent and copper sulfate pentahydrate as precursor. The Cu/Cu2O nanoparticles were characterized by X-ray Diffraction (XRD, Energy Dispersive X-ray Fluorescence (EDXRF, Scanning Electron Microscope (SEM, and Transmission Electron Microscope (TEM. The analysis revealed the pattern of face-centered cubic (fcc crystal structure of copper Cu metal and cubic cuprites structure for Cu2O. The SEM result showed monodispersed and agglomerated particles with two micron sizes of about 180 nm and 800 nm, respectively. The TEM result showed few single crystal particles of face-centered cubic structures with average particle size about 11-14 nm. The catalytic activity of Cu/Cu2O nanoparticles for the decomposition of hydrogen peroxide was investigated and compared with manganese oxide MnO2. The results showed that the second-order equation provides the best correlation for the catalytic decomposition of H2O2 on Cu/Cu2O. The catalytic activity of hydrogen peroxide by Cu/Cu2O is less than the catalytic activity of MnO2 due to the presence of copper metal Cu with cuprous oxide Cu2O. © 2015 BCREC UNDIP. All rights reservedReceived: 6th January 2015; Revised: 14th March 2015; Accepted: 15th March 2015How to Cite: Badawy, S.M., El-Khashab, R.A., Nayl, A.A. (2015. Synthesis, Characterization and Catalytic Activity of Cu/Cu2O Nanoparticles Prepared in Aqueous Medium. Bulletin of Chemical Reaction Engineering & Catalysis, 10 (2: 169-174. (doi:10.9767/bcrec.10.2.7984.169-174 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.10.2.7984.169-174  

  16. In situ XAS study of the Mn(III)(salen)Br catalyzed synthesis of cyclic organic carbonates from epoxides and CO2

    DEFF Research Database (Denmark)

    Jutz, Fabian; Grunwaldt, Jan-Dierk; Baiker, Alfons

    2009-01-01

    In situ X-ray absorption spectroscopy at the Mn K- and Br K-edge was employed to study the cycloaddition of carbon dioxide to propylene oxide and styrene oxide, catalyzed by Mn(III) salen bromide complexes. Three homogeneous complexes with varying salen ligand structure and one complex immobilized...... coordination of the bromine neighbors to the Mn central atom was also evidenced by EXAFS spectra, e.g. loss of Br backscattering in the Mn K-EXAFS spectra and the Mn-backscattering in the Br K-edge spectra. In the catalytic studies it was observed that propylene oxide usually reacted much faster than styrene...

  17. Giant Cu 2p Resonances in CuO Valence-Band Photoemission

    NARCIS (Netherlands)

    Tjeng, L.H.; Chen, C.T.; Ghijsen, J.; Rudolf, P.; Sette, F.

    1991-01-01

    We report the observation of a giant resonance in the Cu 2p resonant-photoemission spectra of CuO. The study allows the unambiguous identification of the local Cu 3d8 configuration in the valence-band photoemission spectrum, providing conclusive evidence for the charge-transfer nature of the

  18. Phase relationships in Cu-rich corner of the Cu-Cr-Zr phase diagram

    International Nuclear Information System (INIS)

    Zeng, K.J.; Haemaelaeinen, M.; Lilius, K.

    1995-01-01

    In the available experimental information on the Cu-Cr-Zr ternary system, there exist different opinions concerning the phase relationships in the Cu-rich corner of Cu-Cr-Zr phase diagram. Glazov et al. and Zakharov et al. investigated the Cu-rich corner of the Cu-Cr-Zr phase diagram within the composition range up to 3.5 Cr and 3.5 Zr (wt. %). A quasi-eutectic reaction L → (Cu) + αCr 2 Zr was observed to occur at 1,020 C and several isothermal sections were constructed within the temperature range from 600 to 1,000 C to show the (Cu)-αCr 2 Zr two phase equilibrium. Therefore, a pseudobinary Cu-Cr 2 Zr system was supposed. Afterwards, Dawakatsu et al, Fedorov et al, and Kuznetsov et al studied the cu-rich corner of the phase diagram in a wider composition range up to 5 Cr and 20 Zr (at.%). Contrary to Glazov et al. and Zakharov et al., they found no Cr 2 Zr phase in their samples. Hence, the pseudobinary Cu-Cr 2 Zr system does not exist. In this study an experimental investigation is presented on the phase relationships in Cu-rich corner of the Cu-Cr-Zr phase diagram at 940 C in order to clear up the confusion

  19. Coupled growth of Al-Al2Cu eutectics in Al-Cu-Ag alloys

    International Nuclear Information System (INIS)

    Hecht, U; Witusiewicz, V; Drevermann, A

    2012-01-01

    Coupled eutectic growth of Al and Al 2 Cu was investigated in univariant Al-Cu-Ag alloys during solidification with planar and cellular morphology. Experiments reveal the dynamic selection of small spacings, below the minimum undercooling spacing and show that distinct morphological features pertain to nearly isotropic or anisotropic Al-Al 2 Cu interfaces.

  20. Cu uptake and turnover in both Cu-acclimated and non-acclimated rainbow trout (Oncorhynchus mykiss)

    DEFF Research Database (Denmark)

    Grosell, M.; Hogstrand, C.; Wood, C.M.

    1997-01-01

    -acclimation clearly involves changes in copper accumulation kinetics in the plasma. The acclimated fish showed a 65% reduced Cu-64 accumulation after 65 h and an increased turnover of Cu in the plasma compared to the non-acclimated fish. Total Cu in the plasma increased by 59% after 3 h of exposure in the non...... aortic catheter. By measuring both Cu-64 accumulation and total Cu concentrations, we were able to analyse the ongoing uptake and turnover of ambient Cu, independent of any Cu already present in the fish. Plasma accounted for at least 90% of the Cu-64 labelled Cu present in the blood and Cu...... h of exposure. Acclimation did not have an unambiguous effect on branchial Cu uptake and differences in branchial uptake could not explain the reduced accumulation in the plasma. The rapidly exchangeable Cu pools were 54% in the gills and 33% in the liver, suggesting a considerable hepatic Cu...