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.     

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.     

Performances of a metallic magnetic calorimeter for the measurement of hard X‐ray emission intensities

The energy spectrum analysis of X‐ray intensities with semiconductor detectors is often difficult because their energy resolution is usually not good enough to separate the different X‐ray lines. Metallic magnetic calorimeters (MMCs) can be an alternative; they can offer both high energy resolution and high intrinsic detection efficiency from 0 to 100 keV. MMCs are thermal detectors; that is to say, the energy of each absorbed photon is measured as a temperature elevation. At very low temperature, typically few tens of mK, a very large pulse height‐to‐noise ratio can be obtained that is an essential condition for high energy resolution. We are involved in the development of MMCs for metrology applications such as the determination of hard X‐ray emission intensities. For that purpose, we conceived an MMC with an energy resolution of 57 eV around 30 keV. The absorber is made of gold providing high intrinsic detection efficiency even for a small volume, greater than 90% below 60 keV. We will describe the physical principle and the practical realisation of this detector and discuss its performances by analysing the energy spectrum obtained from a ¹³³Ba source. Preliminary outcomes of relative emission intensities of the K X‐ray of cesium are presented and compared with other experimental data and theoretical calculations. Copyright © 2012 John Wiley & Sons, Ltd.     

Speciation of inclusions and precipitates in steel by means of XRF and LEEIXS

Fundamentals of x‐ray fluorescence spectrometry and X‐ray emission spectrometry in the case of electron probe x‐ray microanalysis and low‐energy electron induced x‐ray spectrometry are compared. The different aluminum and titanium compounds occurring in steel can be investigated by examining soft x‐ray spectra, arising from valence shell orbitals. The non‐metallic inclusions were isolated by galvanometric electrolysis. In the case of the speciation of titanium, direct electron bombardment of the sample is used to generate soft x‐rays. By investigating the Ti L lines, titanium carbide, nitride and sulfide can be distinguished. To specify aluminum compounds, the Kβ transition in the x‐ray fluorescence spectrum was examined. The concentration of aluminum oxide and nitride in precipitates of special steel qualities can be determined with a satisfactory determination limit. Finally, pre‐operational studies for the determination of different silicon inclusions using electron excitation were carried out. Copyright © 2003 John Wiley & Sons, Ltd.     

Discrepancies in atomic shell and fluorescent X‐ray energies in the Evaluated Photon Data Library EPDL97

There are significant differences between the atomic orbital energies listed in the evaluated photon data library EPDL97 and values published elsewhere. In particular, comparisons with the values adopted by the National Institute of Standards and Technology (NIST) show discrepancies up to several hundred electron volts. Although the uncertainties in the EPDL97 atomic orbital energies were recognised by the original authors, the library has subsequently been widely adopted as a primary source of photon transport and atomic relaxation data. We compare experimentally measured X‐ray fluorescence spectra with fits using the EPDL97 and NIST line energies. Our results strongly favour the NIST energies for K‐shell and L‐shell fluorescent X‐rays and show that the EPDL97 atomic orbital energy values should not be used for applications, such as X‐ray fluorescence, where atomic relaxation phenomena are important. Copyright © 2012 John Wiley & Sons, Ltd.     

Chemical speciation via X‐ray emission spectra

Since the early days of X‐ray spectrometry, X‐ray emission and fluorescence spectra have been used to investigate chemical speciation, e.g. the dependence on the formal oxidation state. Laboratory wavelength‐dispersive spectrometers have adequate resolution for these measurements. However, almost all studies have employed empirical methods to interpret the spectra. We aim to place such methods on a quantitative basis by means of efficient ab initio calculations of the X‐ray emission line shapes based on a self‐consistent, real‐space Green's function approach, as implemented in the X‐ray spectroscopy code FEFF8.2. Calculations are presented for the phosphorus K‐M_{2, 3}, and the chromium L‐series emission lines for a selection of simple compounds. These lines exhibit changes depending on the oxidation state and on the neighboring atoms in the compounds that can be observed with instruments available in many XRF laboratories. The calculated spectra, as modified by convolution with a model monochromator response function, are compared with measured spectra. Simulated and measured spectra are found to be in reasonable agreement, and show that the approach has the potential to yield quantitative information about the chemical state. Copyright © 2006 John Wiley & Sons, Ltd.     

A three‐crystal spectrometer for high‐energy resolution fluorescence‐detected X‐ray absorption spectroscopy and X‐ray emission spectroscopy at SSRF

A Johann‐type spectrometer for the study of high‐energy resolution fluorescence‐detected X‐ray absorption spectroscopy, X‐ray emission spectroscopy and resonant inelastic X‐ray scattering has been developed at BL14W1 X‐ray absorption fine structure spectroscopy beamline of Shanghai Synchrotron Radiation Facility. The spectrometer consists of three crystal analyzers mounted on a vertical motion stage. The instrument is scanned vertically and covers the Bragg angle range of 71.5–88°. The energy resolution of the spectrometer ranges from sub‐eV to a few eV. The spectrometer has a solid angle of about 1.87 × 0^?3 of 4π sr, and the overall photons acquired by the detector could be 10⁵ counts per second for the standard sample. The performances of the spectrometer are illustrated by the three experiments that are difficult to perform with the conventional absorption or emission spectroscopy. Copyright © 2016 John Wiley & Sons, Ltd.     

X‐ray fluorescence determination of Cs,Ba, La,Ce, Nd,and Ta concentrations in rocks of various composition

The technique has been developed for the quantification of small tantalum, cesium, barium, lanthanum, cerium, and neodymium concentration in rocks with X‐ray wavelength dispersive spectrometer S8 TIGER (Bruker AXS, Germany). The optimum conditions have been chosen for registration of the analyzed elements characteristic radiation and background positions. To determine the concentrations of analyzed elements accurately, the contribution of overlapping lines to the experimental intensities of the analytical lines has been taken into account. The sample of mass about 1.2 g has been pressed into pellet by the hydraulic press. Metrological studies showed that the accuracy in the determination of the concentration of analyzed elements for the developed technique meets the requirements for methods of III accuracy class. The Ta detection limits calculated for TaL_β1‐analytical and CsL_α1‐analytical lines were 2.6 and 3.4 ppm, respectively. The detection limit of Ba, La, Ce, and Nd was (in ppm), respectively, 4.3, 2.7, 5.8, and 4.7. The metrological characteristics of the previously developed and adapted techniques were compared. Ta concentration in granite pegmatite samples has been quantified. The samples of the highest tantalum content have been investigated additionally by powder diffraction and X‐ray microprobe analysis. The X‐ray diffraction method turned out to be insensitive to the detection of mineral phase of tantalum niobates, while micro‐XRF allowed detecting its presence in tourmaline grains. Copyright © 2017 John Wiley & Sons, Ltd.     

Measurement of L subshell fluorescence yield ratios of some high Z elements by selective excitation method

The L₁, L₂ and L₃ subshells of Hf, Ta and Re atoms have been excited selectively by using microprobe XRF beam line, Indus‐2, RRCAT, India. The consequent characteristic L X‐ray photons, emitted from the targets due to creations of vacancies in L subshells, are measured using silicon drift detector (X‐123) spectrometer. As the energy of synchrotron radiation increases, the contribution of characteristic L X‐ray intensity increases. The advantage of the increase in the intensity of the characteristic L X‐ray photons with an increase in the energy of synchrotron radiation has been used to determine the L subshell fluorescence yield ratios of Hf, Ta and Re atoms by adopting the selective excitation method. The measured ratios of L subshell fluorescence yield have been compared with theoretical and other experimental values.     

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.     

Confocal full‐field X‐ray microscope for novel three‐dimensional X‐ray imaging

A confocal full‐field X‐ray microscope has been developed for use as a novel three‐dimensional X‐ray imaging method. The system consists of an X‐ray illuminating `sheet‐beam' whose beam shape is micrified only in one dimension, and an X‐ray full‐field microscope whose optical axis is normal to the illuminating sheet beam. An arbitral cross‐sectional region of the object is irradiated by the sheet‐beam, and secondary X‐ray emission such as fluorescent X‐rays from this region is imaged simultaneously using the full‐field microscope. This system enables a virtual sliced image of a specimen to be obtained as a two‐dimensional magnified image, and three‐dimensional observation is available only by a linear translation of the object along the optical axis of the full‐field microscope. A feasibility test has been carried out at beamline 37XU of SPring‐8. Observation of the three‐dimensional distribution of metallic inclusions in an artificial diamond was performed.     

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.     

Preconcentration of mercury on polyaniline expands the horizon for energy dispersive X‐ray fluorescence determination

Hg(II) was sorbed on polyaniline from aqueous solutions, followed by determination using energy dispersive X‐ray fluorescence spectrometry. Distribution coefficient of Hg(II) on polyaniline was about 4 × 10³ in water, whereas distribution coefficient was 1.2 × 10⁴ at 0.1 M HCl and decreased drastically with increase in HCl concentration. Rapid kinetics of sorption was evinced by the 80% uptake within the initial 1 min and quantitative sorption within 5 min of equilibration. The sorption was found to follow Langmuir isotherm model, and the Langmuir capacity was calculated as 19.7 mg g^?1. The ability of polyaniline to form stable and homogeneous pellets facilitated the energy dispersive X‐ray fluorescence determination without recourse to elution. Detection limit of Hg was found to be 22 ng, considering 100 mg pellet of polyaniline. The apparent detection limit was 6 pg, as the preconcentration factor of Hg(II) on polyaniline was 4 × 10³. The developed method is at par with the established method for mercury determination, namely, cold vapor atomic absorption spectrometry. Accuracy of the method was established by the analysis of the International Atomic Energy Agency reference materials, namely, hair and lichen, for Hg(II). Copyright © 2016 John Wiley & Sons, Ltd.     

X‐ray tube spectral measurement method for quantitative analysis of X‐ray fluorescence analysis

Lα and Lβ X‐ray fluorescence spectra of a lead metallic sheet were measured using an energy dispersive X‐ray spectrometer by changing the X‐ray tube voltage and the material of the primary filter. The Lα to Lβ intensity ratio changed from Lα: Lβ = 3: 1 at 15 kV to Lα: Lβ = 1: 1 at 50 kV depending on the X‐ray tube voltage and the filter. The scattered X‐ray spectra of an acrylic slab instead of the sample in the sample holder were measured by changing the applied voltage and the material of the primary filter. The calculated values of the Pb Lα/Lβ intensity ratio of the metallic sheet using the Shiraiwa–Fujino formula by inserting the scattered X‐ray spectra of an acrylic plate as incident X‐ray spectra and the fundamental parameters taken from the Elam database were in good agreement with the experimental ones. We conclude that we can obtain an incident X‐ray spectrum approximately by measuring the scattered X‐ray spectrum without measuring the direct incident beam. Copyright © 2010 John Wiley & Sons, Ltd.     

A high‐resolution X‐ray fluorescence spectrometer and its application at SSRF

A high‐resolution X‐ray fluorescence spectrometer based on Rowland circle geometry was developed and installed at BL14W1 XAFS beamline of Shanghai Synchrotron Radiation Facility. The spectrometer mainly consists of three parts: a sample holder, a spherically curved Si crystal, and an avalanche photodiode detector. The simplicity of the spectrometer makes it easily assembled on the general purpose X‐ray absorption beamline. X‐ray emission spectroscopy and high‐resolution X‐ray absorption near edge spectroscopy can be carried out by using this spectrometer. X‐ray emission preliminary results with high‐resolution about 3 eV of Mn compounds were obtained, which confirmed the feasibility of the spectrometer. The application about Eu (III) retention on manganese dioxide was also studied using this spectrometer. Compared with conventional X‐ray absorption fine structure spectroscopy technique, the fluorescence peak of probed element [Eu (III) Lα] and matrix constituents (Mn Kα) were discriminated using this technique, indicating its superiority in fluorescence detection. Copyright © 2013 John Wiley & Sons, Ltd.     

A portable spectrometer for simultaneous PIXE and XRF analysis

A new portable system that performs simultaneous particle induced x‐ray emission and x‐ray fluorescence analysis is described. It is based on the use of a ²⁴⁴Cm radioactive source as α‐particle and x‐ray emitter, coupled to a Si drift detector. Particular care has been devoted to the choice of the materials surrounding the source. X‐ray fluorescence spectra are presented, showing high detection efficiency for elements from Na (K lines) to Pb (L and M lines). The system can be used as a qualitative tool for ‘fingerprint’ analysis and, in some cases, as a quantitative one. Examples are presented and discussed. Copyright © 2007 John Wiley & Sons, Ltd.     

Nondestructive rare earth element imaging of fish teeth from deep‐sea sediments

X‐ray fluorescence computed tomography is an emerging imaging modality that allows for the nondestructive reconstruction of the internal distribution of elements within a sample. The common use of X‐ray excitation energy (up to approximately 20 keV) has necessitated the use of l ‐shell fluorescence for heavy elements. In this study, based on high energy X‐ray at BL13W1 of the Shanghai Synchrotron Radiation Facility, we employed high‐energy excitation for tomographic imaging of the heavy metals (rare earth elements) in fish teeth from deep‐sea sediments on the micrometer scale using K‐shell X‐ray fluorescence. The virtual cross‐sectional distribution of La, Ce, Pm, Pr, Nd, and Sm were obtained, thereby providing a feasible approach for analyzing the enrichment mechanism of rare earth elements. Copyright © 2015 John Wiley & Sons, Ltd.     

X‐ray spectra by means of Monte Carlo simulations for imaging applications

X‐ray tubes have a broad range of applications worldwide, including several techniques for atomic physics, like X‐ray fluorescence, as well as for medical imaging, like computed tomography. The performances of X‐ray imaging detectors have shown to be significantly sensitive to the incident beam spectrum. Therefore, an accurate knowledge of the X‐ray beam becomes necessary for the emission source characterization and the whole imaging process comprehension. Direct measurements and suitable Monte Carlo simulations may be used to establish the X‐ray spectra. Dedicated Monte Carlo simulation routines, based on the PENELOPE code, have been developed to determine the Bremsstrahlung X‐ray spectra generated by conventional X‐ray tubes. The simulated spectra have been validated by comparison with the corresponding experimental data showing an overall good agreement. The incorporation of a suitably designed virtual grid allowed to assess the angular distribution of Bremsstrahlung yield, showing a remarkable anisotropy. In addition, a dedicated program has been developed for virtual imaging, which enables to perform suitable X‐ray absorption contrast images. Also, the developed program includes a user‐friendly graphic interface to allow the upload of required input parameters, which include setup arrangement, beam characteristics, sample properties and image simulation parameters (spatial resolution, tracks per run, etc.). The software includes dedicated subroutines which handle the physical process from X‐ray generation up to detector signal acquisition. The aim of the developed program is to perform virtual imaging by means of absorption contrast and using conventional X‐ray sources, which may be a useful tool for the study the X‐ray imaging techniques in several research fields as well as for educational purposes. The performed comparisons with experimental data have shown good agreement. The obtained results for X‐ray imaging may constitute useful information for the comprehension and improvement of X‐ray image quality, like absorption contrast optimization, detail visualization, definition and detectability. Copyright © 2010 John Wiley & Sons, Ltd.     

A New Method for Determining the Composition of Core–Shell Nanoparticles via Dual‐EDX+EELS Spectrum Imaging

Simultaneously acquired microanalytical X‐ray and electron energy loss signals are obtained from a bimetallic core–shell nanoparticle system (FePt@Fe₃O₄). The signals are decomposed using independent component analysis and the extracted components are used to separately quantify the composition of the spatially overlapping core and shell phases in the nanoheterostructure. The utilization of the complementary strengths of energy dispersive X‐ray and electron energy‐loss spectroscopy microanalysis has enabled the quantification of both light and heavy elements in a single spectrum image acquisition.