X‐ray fluorescence determination of sulfur chemical state in sulfide ores

This paper describes the X‐ray fluorescence technique for estimation of the ratio between sulfide and total sulfur in sulfide ores using the influence of sulfur chemical state on positions and intensities of lines (SKα_1,2, SKβ_1,3) and satellites (SKβ′, SKα_3,4) of the sulfur X‐ray emission spectra measured by the wavelength‐dispersive X‐ray fluorescence spectrometer. The samples to be analyzed were prepared as pressed powder pellets on boric acid substrate. The SKα_1,2 line chemical shift is the most appropriate parameter for sulfur chemical state estimation because spectral lines in this field are intensive and are almost not affected by spectral overlap of lead spectrum lines. The ratios of line intensities SKβ′/SKβ_1,3, SKα_3,4/SKα_1,2 and SKβ_1,3/SKα_1,2 were also used as analytical parameters. Forty‐one samples of sulfide ores collected in the Russian Far East and Southern Ural deposits have been analyzed. The results of estimation of sulfur chemical state by gravimetric and proposed X‐ray fluorescence techniques agree fairly well. Copyright © 2016 John Wiley & Sons, Ltd.     

Study of chemical shift in Ll and Lƞ X‐ray emission lines in different chemical forms of 48Cd and 50Sn compounds using WDXRF technique

Chemical shift in Ll and L? X‐ray emission lines of ₄₈Cd and ₅₀Sn elements in various chemical compounds was determined with high resolution wavelength dispersive X‐ray fluorescence (WDXRF) spectrometer. The positive and negative shifts were measured in ₄₈Cd compounds viz, CdS, CdB₄O₇, CdCl₂, Cd₃(PO₄)₂, CdCO₃, CdI₂ and CdO with reference to pure Cd foil and ₅₀Sn compounds viz, Sn(CrO₄)₂, SnO, SnO₂, SnCl₂, SnF₂, SnF₄ with reference to pure Sn foil. The measured energy shifts in Ll X‐ray emission lines range from ?0.47 to 1.82 eV and L? emission lines range from ?2.67 to 1 eV for both compounds. The effective charges (q, q ^/ , q ^// , and q ^/// ) were calculated from four models (Pauling method, Suchet method, Levine method and Batsonav method) and found to be linear dependence with chemical shift. The measured chemical shifts were correlated with effective charge, number of ligands and electronegativity of the central metal atom in the given compounds.     

X‐ray fluorescence determination of the manganese valence state and speciation in manganese ores

This work concerns determination of the manganese valence state and speciation by wavelength‐dispersive X‐ray fluorescence analysis. The authors investigated the effect of the manganese valence state and speciation on the intensity of some К‐series lines of the X‐ray emission spectrum for the samples of manganese compounds. The intensities of MnKβ₅ line and MnKβ′ satellite are least influenced by speciation, and they may be used for evaluating the manganese valence state for the samples containing low iron. The intensities of MnKβ″ and MnKβ^x satellites may be employed for assessing the manganese speciation. The results of X‐ray fluorescence determination of the manganese valence state and speciation in the manganese ores of the South Ural deposits agree with the X‐ray diffraction data. The X‐ray fluorescence method is definitely advantageous, because it does not require a complicated process of sample preparation and allows to receive fast information on the manganese valence state and speciation with the purpose to assess the quality of manganese ores. Copyright © 2015 John Wiley & Sons, Ltd.     

Vanadium K‐edge XANES in vanadium‐bearing model compounds: a full multiple scattering study

A systematic study is presented on a set of vanadium‐bearing model compounds, representative of the most common V coordination geometries and oxidation states, analysed by means of vanadium K‐edge X‐ray absorption near‐edge spectroscopy calculations in the full multiple scattering (FMS) framework. Analysis and calibration of the free parameters of the theory under the muffin‐tin approximation (muffin‐tin overlap and interstitial potential) have been carried out by fitting the experimental spectra using the MXAN program. The analysis shows a correlation of the fit parameters with the V coordination geometry and oxidation state. By making use of this correlation it is possible to approach the study of unknown V‐bearing compounds with useful preliminary information.     

Sample thickness and quantitative concentration measurements in Br K‐edge XANES spectroscopy of organic materials

While XANES spectroscopy is an established tool for quantitative information on chemical structure and speciation, elemental concentrations are generally quantified by other methods. The edge step in XANES spectra represents the absolute amount of the measured element in the sample, but matrix effects and sample thickness complicate the extraction of accurate concentrations from XANES measurements, particularly at hard X‐ray energies where the X‐ray beam penetrates deeply into the sample. The present study demonstrates a method of quantifying concentration with a detection limit approaching 1 mg kg^?1 using information routinely collected in the course of a hard X‐ray XANES experiment. The XANES normalization procedure unambiguously separates the signal of the absorber from any source of background. The effects of sample thickness on edge steps at the bromine K‐edge were assessed and an empirical correction factor for use with samples of variable mass developed.     

A miniature X‐ray emission spectrometer (miniXES) for high‐pressure studies in a diamond anvil cell

Core–shell X‐ray emission spectroscopy (XES) is a valuable complement to X‐ray absorption spectroscopy (XAS) techniques. However, XES in the hard X‐ray regime is much less frequently employed than XAS, often as a consequence of the relative scarcity of XES instrumentation having energy resolutions comparable with the relevant core‐hole lifetimes. To address this, a family of inexpensive and easily operated short‐working‐distance X‐ray emission spectrometers has been developed. The use of computer‐aided design and rapid prototype machining of plastics allows customization for various emission lines having energies from ～3 keV to ～10 keV. The specific instrument described here, based on a coarsely diced approximant of the Johansson optic, is intended to study volume collapse in Pr metal and compounds by observing the pressure dependence of the Pr Lα emission spectrum. The collection solid angle is ～50 msr, roughly equivalent to that of six traditional spherically bent crystal analyzers. The miniature X‐ray emission spectrometer (miniXES) methodology will help encourage the adoption and broad application of high‐resolution XES capabilities at hard X‐ray synchrotron facilities.     

Finite lifetime broadening of calculated X‐ray absorption spectra: possible artefacts close to the edge

X‐ray absorption spectra calculated within an effective one‐electron approach have to be broadened to account for the finite lifetime of the core hole. For methods based on Green's function this can be achieved either by adding a small imaginary part to the energy or by convoluting the spectra on the real axis with a Lorentzian. By analyzing the Fe K‐ and L_2,3‐edge spectra it is demonstrated that these procedures lead to identical results only for energies higher than a few core‐level widths above the absorption edge. For energies close to the edge, spurious spectral features may appear if too much weight is put on broadening via the imaginary energy component. Special care should be taken for dichroic spectra at edges which comprise several exchange‐split core levels, such as the L₃‐edge of 3d transition metals.     

X‐ray K absorption spectral studies of copper (II) hydroxamic acid mixed ligand complexes

X‐ray absorption spectra at the K‐edge of copper have been studied in copper mixed ligand complexes having hydroxamic acid as one of the ligands. The X‐ray absorption spectra have been recorded at BL‐8 Dispersive Extended X‐ray Absorption Fine Structure (EXAFS) beamline at the 2.5‐GeV INDUS‐2 Synchrotron Source, RRCAT, Indore, India. The data obtained has been processed using EXAFS data analysis program Athena. The energies of the K absorption edge, chemical shifts, edge‐widths and shifts of the principal absorption maximum in the complexes have been determined and discussed. The chemical shift data have been utilized to estimate effective nuclear charge on the absorbing atom. The normalized EXAFS spectra have been Fourier transformed. The position of the first peak in the Fourier transform gives the value of first shell bond length, which is shorter than the actual bond length as a result of energy dependence of the phase factors in the sine function of the EXAFS equation. This distance is thus the phase‐uncorrected bond length and has also been determined by Lytle, Sayers and Stern's (LSS) graphical method. The results obtained from LSS and the Fourier transformation methods are comparable with each other. The first shell bond length has also been estimated by Lytle's and Levy's methods from the EXAFS data. Copyright © 2014 John Wiley & Sons, Ltd.     

An attempt at kidney stone analysis with the application of synchrotron radiation

X‐ray absorption near‐edge spectroscopy (XANES) is a spectroscopic technique using synchrotron light to determine the valence state of excited atoms as well as the electronegativity of their neighbouring atoms. XANES spectra can provide information about the chemical bond in the second coordination shell of the excited atom. In this study, XANES spectra of unknown compounds from human kidney stones were recorded around the K‐edges of sulfur, phosphorus and calcium. The XANES results agree well with the diffractogram data of the same stones obtained through an X‐ray powder diffraction (XRPD) technique. By comparing the measurement techniques presented here, it is shown that XANES requires a smaller amount of each sample than XRPD for analysis.     

Characterization of X‐ray gas attenuator plasmas by optical emission and tunable laser absorption spectroscopies

X‐ray gas attenuators are used in high‐energy synchrotron beamlines as high‐pass filters to reduce the incident power on downstream optical elements. The absorption of the X‐ray beam ionizes and heats up the gas, creating plasma around the beam path and hence temperature and density gradients between the center and the walls of the attenuator vessel. The objective of this work is to demonstrate experimentally the generation of plasma by the X‐ray beam and to investigate its spatial distribution by measuring some of its parameters, simultaneously with the X‐ray power absorption. The gases used in this study were argon and krypton between 13 and 530 mbar. The distribution of the 2p excited states of both gases was measured using optical emission spectroscopy, and the density of argon metastable atoms in the 1s₅ state was deduced using tunable laser absorption spectroscopy. The amount of power absorbed was measured using calorimetry and X‐ray transmission. The results showed a plasma confined around the X‐ray beam path, its size determined mainly by the spatial dimensions of the X‐ray beam and not by the absorbed power or the gas pressure. In addition, the X‐ray absorption showed a hot central region at a temperature varying between 400 and 1100 K, depending on the incident beam power and on the gas used. The results show that the plasma generated by the X‐ray beam plays an essential role in the X‐ray absorption. Therefore, plasma processes must be taken into account in the design and modeling of gas attenuators.     

Characterization of EUV periodic multilayers

Nanometric Co/Mg, Co/Mg/B₄C, Al/SiC and Al/Mo/SiC periodic multilayers deposited by magnetron sputtering are studied in order to correlate their optical performances in the extreme ultraviolet (EUV) range to their structural quality. To that purpose, our recently developed methodology based on high‐resolution X‐ray emission spectroscopy (XES) and X‐ray and EUV reflectometry is now extended to nuclear magnetic resonance (NMR) spectroscopy and time‐of‐flight secondary ions mass spectrometry (ToF‐SIMS). The analysis of the Co Lαβ and Mg Kβ emission spectra shows that the Co and Mg atoms within the multilayers are in a chemical state equivalent to that of the atoms in the pure Co and Mg references, respectively. But NMR spectra give evidence for a reaction between Co atoms and B and/or C atoms from B₄C. The Al and Si Kβ emission spectra do not reveal the formation of an interfacial compound in Al/SiC and Al/Mo/SiC. Only the roughness limits the optical quality of Al/SiC. The comparative analysis of the ToF‐SIMS spectra of Al/SiC and Al/Mo/SiC indicates that the structural quality is enhanced when Mo is introduced within the stack. Copyright © 2011 John Wiley & Sons, Ltd.     

Characterization of surface carbon films on weathered Japanese roof tiles by soft x‐ray spectroscopy

The effects of weathering on carbon films deposited on Japanese smoked roof tiles were investigated by soft x‐ray absorption and emission spectroscopy using synchrotron radiation. X‐ray absorption measurements revealed that weathering oxidizes the carbon films and that partial carboxy chemical bonding occurs. Incident angle‐dependent x‐ray absorption spectra in the C K region confirmed that the degree of the orientation at the surface of the oxidized carbon films decreases with weathering. However, the take‐off angle‐dependent C K x‐ray emission spectra showed that the orientation of the layered carbon structure is maintained in the bulk portion when weathered. Therefore, it is confirmed that oxidation proceeds from the surface of the carbon films. Weathering degrades and oxidizes the surface carbon films, which causes the metallic silver color to change to darker gray. Copyright © 2005 John Wiley & Sons, Ltd.     

Development of a two‐dimensional imaging system of X‐ray absorption fine structure

A two‐dimensional imaging system of X‐ray absorption fine structure (XAFS) has been developed at beamline BL‐4 of the Synchrotron Radiation Center of Ritsumeikan University. The system mainly consists of an ionization chamber for I₀ measurement, a sample stage, and a two‐dimensional complementary metal oxide semiconductor (CMOS) image sensor for measuring the transmitted X‐ray intensity. The X‐ray energy shift in the vertical direction, which originates from the vertical divergence of the X‐ray beam on the monochromator surface, is corrected by considering the geometrical configuration of the monochromator. This energy correction improves the energy resolution of the XAFS spectrum because each pixel in the CMOS detector has a very small vertical acceptance of ～0.5 µrad. A data analysis system has also been developed to automatically determine the energy of the absorption edge. This allows the chemical species to be mapped based on the XANES feature over a wide area of 4.8 mm (H) × 3.6 mm (V) with a resolution of 10 µm × 10 µm. The system has been applied to the chemical state mapping of the Mn species in a LiMn₂O₄ cathode. The heterogeneous distribution of the Mn oxidation state is demonstrated and is considered to relate to the slow delocalization of Li⁺‐defect sites in the spinel crystal structure. The two‐dimensional‐imaging XAFS system is expected to be a powerful tool for analyzing the spatial distributions of chemical species in many heterogeneous materials such as battery electrodes.     

H+ and He2 + induced W L X‐rays intensity ratios: part I,Si(Li) data and EDS high resolution insight

Recently, the authors have presented experimental evidences that for some energy windows, proton‐induced W L shell X‐rays intensity ratios of transitions to L₁ subshell depend on the ion beam energy and on the chemical species even after known matrix effects are subtracted. These results, which put in question the assumption of the invariance of the relative intensity of X‐ray transitions to the same atomic subshells, are further exploited in this work, where more data for three different W compounds (W, Li₂WO₄ and P₂O₅.24WO₃.xH₂O) are presented followed by a detailed study using an ultra‐pure (99.995%) W thick foil, used to avoid any possible target contamination interference on the results. Samples were irradiated by H⁺ beams in various conditions in the energy range between 0.25 and 2.38 MeV and by He^{2 +} beams having energies between 3.5 and 5.0 MeV. Spectra were collected using the Si(Li) detector at CTN 2.5 MV Van de Graaff standard Proton‐Induced X‐ray Emission (PIXE) set‐up as well as using the Energy Dispersive Spectrometry (EDS) high resolution X‐ray microcalorimeter spectrometer (XMS) at CTN 3.0 MV Tandetron accelerator high resolution high energy (HRHE) PIXE end station. Results were normalized to the theoretical intensity ratios and plotted as function of the ratio of collision characteristic times allowing the comparison of H⁺ and He^{2 +} results. W L X‐rays intensity ratio variations are presented and compared with theoretical expected results. Radiative Auger emission transitions observed in an EDS high resolution XMS spectra are shown to probably play a crucial role in the highly unexpected results obtained for intensity ratios of transitions to the same subshell. Copyright © 2013 John Wiley & Sons, Ltd.     

Fensterbierscheiben in the Pena National Palace collection – chemical and iconographic relations

The stained‐glass collection from the Pena National Palace (Sintra, Portugal) includes around 130 ‘rural panels’, also known as Fensterbierscheiben, that were produced between the 16th and 19th centuries. The aim of this investigation is to characterise the glass composition of this collection of Fensterbierscheiben and relate it with the iconographic research made on these panels, in order to establish possible provenance of production. This is the first study on Fensterbierscheiben, where the chemical information of the glass is considered and related with historical information. The micro‐energy dispersive X‐ray fluorescence allowed performing non‐invasive analysis, mostly performed in situ. Micro‐particle‐induced X‐ray emission analysis was performed on the cross section of a small group of fragmented panels for obtaining quantitative chemical composition of the glass. Through the analysis of the colourless glass, and the comparison of micro‐energy dispersive X‐ray fluorescence and micro‐particle‐induced X‐ray emission data, it was concluded that the majority of the panes have a high lime low alkali glass composition. Furthermore, the Fensterbierscheiben panes form a cohesive group in terms of composition, suggesting that they were all manufactured with raw materials from the same region. This study also allowed one to observe the chronological evolution in terms of treatments applied to the used raw materials. Copyright © 2016 John Wiley & Sons, Ltd.     

Insight into growth of Au–Pt bimetallic nanoparticles: an in situ XAS study

Au–Pt bimetallic nanoparticles have been synthesized through a one‐pot synthesis route from their respective chloride precursors using block copolymer as a stabilizer. Growth of the nanoparticles has been studied by simultaneous in situ measurement of X‐ray absorption spectroscopy (XAS) and UV–Vis spectroscopy at the energy‐dispersive EXAFS beamline (BL‐08) at Indus‐2 SRS at RRCAT, Indore, India. In situ XAS spectra, comprising both X‐ray near‐edge structure (XANES) and extended X‐ray absorption fine‐structure (EXAFS) parts, have been measured simultaneously at the Au and Pt L₃‐edges. While the XANES spectra of the precursors provide real‐time information on the reduction process, the EXAFS spectra reveal the structure of the clusters formed in the intermediate stages of growth. This insight into the formation process throws light on how the difference in the reduction potential of the two precursors could be used to obtain the core–shell‐type configuration of a bimetallic alloy in a one‐pot synthesis method. The core–shell‐type structure of the nanoparticles has also been confirmed by ex situ energy‐dispersive spectroscopy line‐scan and X‐ray photoelectron spectroscopy measurements with in situ ion etching on fully formed nanoparticles.     

Chemical shifts of Cr Kα and Kβ1, 3 lines by WDXRF spectrometry

Chemical shift and full widths at half maximum (FWHM) intensity of chromium Kα and Kβ_{1, 3} lines were examined for 12 kinds of materials containing chromium (CH₃CO₂)₇Cr₃(OH)₂, CrK(SO₄)₂.12H₂O, Cr(NO3)₃.9H₂O, Cr₂O₃, CrF₂, CrF₃.4H₂O, CrCl₂, CrCl₃, CrCl₃.6H₂O, [CrCl₂(H₂O)₄]Cl.2H₂O, Cr₂(SO₄)₃.15H₂O, CrO and Cr metal by wavelength‐dispersive X‐ray fluorescence (WDXRF) spectrometry. The chemical shifts, asymmetry index and the half‐widths of both the X‐ray emission lines show interesting trends with the oxidation state of chromium. It was observed that the chemical shifts for F compounds are higher than Cl compounds. It was also found larger chemical shifts and FWHM for Kβ_{1, 3} lines than Kα ones. It should be noted that the magnitude of chemical shifts increases with increase in the number of ligand atoms. Copyright © 2009 John Wiley & Sons, Ltd.     

Measurement of relative line intensities for L‐shell X‐rays from selected elements between Z = 68 (Er) and Z = 79 (Au)

Relative line intensities of L1, L2 and L3 sub‐shell X‐rays were measured for Er, Tm, Yb, Hf, Ta, W, Pt and Au. The L‐shell X‐ray spectra were recorded by exciting pure element samples (eight cases) and oxide samples (two cases) with approximately 17‐keV exciting radiation from a filtered X‐ray tube source, and measuring the fluorescence spectra with a silicon drift detector. The spectra were carefully fitted to determine line energies and intensities, accounting for Lorentzian line broadening, incomplete charge collection and escape effects. A Monte Carlo approach was used to calculate attenuation and detector efficiency corrections. We report up to 15 line intensity ratios for each element and compare these to Scofield's theoretical predictions and Elam's extrapolated experimental database. Our measured relative line intensities agree best with Elam's data, but overall we find significant discrepancies with previously reported results. For the element Ta, we also find significant errors in the accepted L‐shell line energies in the widely used National Institute of Standard and Technology (NIST) database. Our results highlight the need for an experimental and theoretical re‐evaluation of L‐shell intensity databases to support high‐accuracy X‐ray analysis methods such as X‐ray fluorescence and particle‐induced X‐ray emission. Copyright © 2016 John Wiley & Sons, Ltd.     

Real‐space multiple‐scattering Hubbard model calculations for d‐ and f‐state materials

Calculations are presented of the electronic structure and X‐ray spectra of materials with correlated d‐ and f‐electron states based on the Hubbard model, a real‐space multiple‐scattering formalism and a rotationally invariant local density approximation. Values of the Hubbard parameter are calculated ab initio using the constrained random‐phase approximation. The combination of the real‐space Green's function with Hubbard model corrections provides an efficient approach to describe localized correlated electron states in these systems, and their effect on core‐level X‐ray spectra. Results are presented for the projected density of states and X‐ray absorption spectra for transition metal‐ and lanthanide‐oxides. Results are found to be in good agreement with experiment.     

Measuring partial fluorescence yield using filtered detectors

Typically, X‐ray absorption near‐edge structure measurements aim to probe the linear attenuation coefficient. These measurements are often carried out using partial fluorescence yield techniques that rely on detectors having photon energy discrimination improving the sensitivity and the signal‐to‐background ratio of the measured spectra. However, measuring the partial fluorescence yield in the soft X‐ray regime with reasonable efficiency requires solid‐state detectors, which have limitations due to the inherent dead‐time while measuring. Alternatively, many of the available detectors that are not energy dispersive do not suffer from photon count rate limitations. A filter placed in front of one of these detectors will make the energy‐dependent efficiency non‐linear, thereby changing the responsivity of the detector. It is shown that using an array of filtered X‐ray detectors is a viable method for measuring soft X‐ray partial fluorescence yield spectra without dead‐time. The feasibility of this technique is further demonstrated using α‐Fe₂O₃ as an example and it is shown that this detector technology could vastly improve the photon collection efficiency at synchrotrons and that these detectors will allow experiments to be completed with a much lower photon flux reducing X‐ray‐induced damage.