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High entropy metal chalcogenides are materials containing five or more elements within a disordered sublattice. These materials exploit a high configurational entropy to stabilize their crystal structure and have recently become an area of significant interest for renewable energy applications such as electrocatalysis and thermoelectrics. Herein, we report the synthesis of bulk particulate HE zinc sulfide analogues containing four, five, and seven metals. This was achieved using a molecular precursor cocktail approach with both transition and main group metal dithiocarbamate complexes which are decomposed simultaneously in a rapid (1 h) and low-temperature (500 °C) thermolysis reaction to yield high entropy and entropy-stabilized metal sulfides. The resulting materials were characterized by powder XRD, SEM, and TEM, alongside EDX spectroscopy at both the micro- and nano-scales. The entropy-stabilized (CuAgZnCoMnInGa)S material was demonstrated to be an excellent electrocatalyst for the hydrogen evolution reaction when combined with conducting carbon black, achieving a low onset overpotential of (∼80 mV) and η 10 of (∼255 mV)., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Chemical staining of biological specimens is commonly utilised to boost contrast in soft tissue structures, but unambiguous identification of staining location and distribution is difficult without confirmation of the elemental signature, especially for chemicals of similar density contrast. Hyperspectral X-ray computed tomography (XCT) enables the non-destructive identification, segmentation and mapping of elemental composition within a sample. With the availability of hundreds of narrow, high resolution (~ 1 keV) energy channels, the technique allows the simultaneous detection of multiple contrast agents across different tissue structures. Here we describe a hyperspectral imaging routine for distinguishing multiple chemical agents, regardless of contrast similarity. Using a set of elemental calibration phantoms, we perform a first instance of direct stain concentration measurement using spectral absorption edge markers. Applied to a set of double- and triple-stained biological specimens, the study analyses the extent of stain overlap and uptake regions for commonly used contrast markers. An improved understanding of stain concentration as a function of position, and the interaction between multiple stains, would help inform future studies on multi-staining procedures, as well as enable future exploration of heavy metal uptake across medical, agricultural and ecological fields., (© 2022. The Author(s).)

Here we apply hyperspectral bright field imaging to collect computed tomographic images with excellent energy resolution (~ 1 keV), applying it for the first time to map the distribution of stain in a fixed biological sample through its characteristic K-edge. Conventionally, because the photons detected at each pixel are distributed across as many as 200 energy channels, energy-selective images are characterised by low count-rates and poor signal-to-noise ratio. This means high X-ray exposures, long scan times and high doses are required to image unique spectral markers. Here, we achieve high quality energy-dispersive tomograms from low dose, noisy datasets using a dedicated iterative reconstruction algorithm. This exploits the spatial smoothness and inter-channel structural correlation in the spectral domain using two carefully chosen regularisation terms. For a multi-phase phantom, a reduction in scan time of 36 times is demonstrated. Spectral analysis methods including K-edge subtraction and absorption step-size fitting are evaluated for an ex vivo, single (iodine)-stained biological sample, where low chemical concentration and inhomogeneous distribution can affect soft tissue segmentation and visualisation. The reconstruction algorithms are available through the open-source Core Imaging Library. Taken together, these tools offer new capabilities for visualisation and elemental mapping, with promising applications for multiply-stained biological specimens., (© 2021. The Author(s).)

In this study, we investigate the effect of thermal treatment/calcination on the stability and activity of a Na-Mn-W/SiO 2 catalyst for the oxidative coupling of methane. The catalyst performance and characterisation measurements suggest that the W species are directly involved in the catalyst active site responsible for CH 4 conversion. Under operating conditions, the active components, present in the form of a Na-W-O-Mn molten state, are highly mobile and volatile. By varying the parameters of the calcination protocol, it was shown that these molten components can be partially stabilised, resulting in a catalyst with lower activity (due to loss of surface area) but higher stability even for long duration OCM reaction experiments.

Metal sulfide and metal oxide alloys of the form Mo 1- x W x S 2 and Mo 1- x W x O 3 (0 ≤ x ≤ 1) are synthesized with varying nominal stoichiometries ( x = 0, 0.25, 0.50, 0.75, and 1.0) by thermolysis of the molecular precursors MoL 4 and WS(S 2 )L 2 (where L = S 2 CNEt 2 ) in tandem and in various ratios. Either transition-metal dichalcogenides or transition-metal oxides can be produced from the same pair of precursors by the choice of reaction conditions; metal sulfide alloys of the form Mo 1- x W x S 2 are produced in an argon atmosphere, while the corresponding metal oxide alloys Mo 1- x W x O 3 are produced in air, both under atmospheric pressure at 450 °C and for only 1 h. Changes in Raman spectra and in powder X-ray diffraction patterns are observed across the series of alloys, which confirm that alloying is successful in the bulk materials. For the oxide materials, we show that the relatively complicated diffraction patterns are a result of differences in the tilt angle of MO 6 octahedra within three closely related unit cell types. Alloying of Mo and W in the products is characterized at the microscale and nanoscale by scanning electron microscopy-energy-dispersive X-ray spectroscopy (EDX) and scanning transmission electron microscopy-EDX spectroscopy, respectively., Competing Interests: The authors declare no competing financial interest., (Copyright © 2020 American Chemical Society.)

In this study we present the results from two in situ X-ray diffraction computed tomography experiments of catalytic membrane reactors (CMRs) using Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF) hollow fibre membranes and Na-Mn-W/SiO2 catalyst during the oxidative coupling of methane (OCM) reaction. The negative impact of CO2, when added to the inlet gas stream, is seen to be mainly related to the C2+ yield, while no evidence of carbonate phase(s) formation is found during the OCM experiments. The main degradation mechanism of the CMR is suggested to be primarily associated with the solid-state evolution of the BSCF phase rather than the presence of CO2. Specifically, in situ XRD-CT and post-mortem SEM/EDX measurements revealed a collapse of the cubic BSCF phase and subsequent formation of secondary phases, which include needle-like structures and hexagonal Ba6Co4O12 and formation of a BaWO4 layer, the latter being a result of chemical interaction between the membrane and catalyst materials at high temperatures.

Contrast-enhanced digital mammography (CEDM) is an alternative to conventional X-ray mammography for imaging dense breasts. However, conventional approaches to CEDM require a double exposure of the patient, implying higher dose, and risk of incorrect image registration due to motion artifacts. A novel approach is presented, based on hyperspectral imaging, where a detector combining positional and high-resolution spectral information (in this case based on Cadmium Telluride) is used. This allows simultaneous acquisition of the two images required for CEDM. The approach was tested on a custom breast-equivalent phantom containing iodinated contrast agent (Niopam 150®). Two algorithms were used to obtain images of the contrast agent distribution: K-edge subtraction (KES), providing images of the distribution of the contrast agent with the background structures removed, and a dual-energy (DE) algorithm, providing an iodine-equivalent image and a water-equivalent image. The high energy resolution of the detector allowed the selection of two close-by energies, maximising the signal in KES images, and enhancing the visibility of details with the low surface concentration of contrast agent. DE performed consistently better than KES in terms of contrast-to-noise ratio of the details; moreover, it allowed a correct reconstruction of the surface concentration of the contrast agent in the iodine image. Comparison with CEDM with a conventional detector proved the superior performance of hyperspectral CEDM in terms of the image quality/dose tradeoff.

The average residual stress distribution as a function of depth in an air plasma-sprayed yttria stabilized zirconia top coat used in thermal barrier coating (TBC) systems was measured using synchrotron radiation X-ray diffraction in reflection geometry on station I15 at Diamond Light Source, UK, employing a series of incidence angles. The stress values were calculated from data deconvoluted from diffraction patterns collected at increasing depths. The stress was found to be compressive through the thickness of the TBC and a fluctuation in the trend of the stress profile was indicated in some samples. Typically this fluctuation was observed to increase from the surface to the middle of the coating, decrease a little and then increase again towards the interface. The stress at the interface region was observed to be around 300 MPa, which agrees well with the reported values. The trend of the observed residual stress was found to be related to the crack distribution in the samples, in particular a large crack propagating from the middle of the coating. The method shows promise for the development of a nondestructive test for as-manufactured samples.

Synchrotron X-rays on the Swiss Norwegian Beamline and BM28 (XMaS) at the ESRF have been used to record the diffraction response of the PMN-PT relaxor piezoelectric 67% Pb(Mg 1/3 Nb 2/3 )O 3 -33% PbTiO 3 as a function of externally applied electric field. A DC field in the range 0-18 kV cm -1 was applied along the [001] pseudo-cubic direction using a specially designed sample cell for in situ single-crystal diffraction experiments. The cell allowed data to be collected on a Pilatus 2M area detector in a large volume of reciprocal space using transmission geometry. The data showed good agreement with a twinned single-phase monoclinic structure model. The results from the area detector were compared with previous Bragg peak mapping using variable electric fields and a single detector where the structural model was ambiguous. The coverage of a significantly larger section of reciprocal space facilitated by the area detector allowed precise phase analysis.

We investigated the structure of the tungsten bronze barium neodymium titanates Ba(6-3n)Nd(8+2n)Ti(18)O(54), which are exploited as microwave dielectric ceramics. They form a complex nanostructure, which resembles a nanofilm with stacking layers of ∼12 Å thickness. The synthesized samples of Ba(6-3n)Nd(8+2n)Ti(18)O(54) (n = 0, 0.3, 0.4, 0.5) are characterized by pentagonal and tetragonal columns, where the A cations are distributed in three symmetrically inequivalent sites. Synchrotron X-ray diffraction and electron energy loss spectroscopy allowed for quantitative analysis of the site occupancy, which determines the defect distribution. This is corroborated by density functional theory calculations. Pentagonal columns are dominated by Ba, and tetragonal columns are dominated by Nd, although specific Nd sites exhibit significant concentrations of Ba. The data indicated significant elongation of the Ba columns in the pentagonal positions and of the Nd columns in tetragonal positions involving a zigzag arrangement of atoms along the b lattice direction. We found that the preferred Ba substitution occurs at Nd[3]/[4] followed by Nd[2] and Nd[1]/[5] sites, which is significantly different to that proposed in earlier studies. Our results on the Ba(6-3n)Nd(8+2n)Ti(18)O(54) "perovskite" superstructure and its defect distribution are particularly valuable in those applications where the optimization of material properties of oxides is imperative; these include not only microwave ceramics but also thermoelectric materials, where the nanostructure and the distribution of the dopants will reduce the thermal conductivity.

An X-ray diffraction computed tomography data-collection strategy that allows, post experiment, a choice between temporal and spatial resolution is reported. This strategy enables time-resolved studies on comparatively short timescales, or alternatively allows for improved spatial resolution if the system under study, or components within it, appear to be unchanging. The application of the method for studying an Mn-Na-W/SiO 2 fixed-bed reactor in situ is demonstrated. Additionally, the opportunities to improve the data-collection strategy further, enabling post-collection tuning between statistical, temporal and spatial resolutions, are discussed. In principle, the interlaced scanning approach can also be applied to other pencil-beam tomographic techniques, like X-ray fluorescence computed tomography, X-ray absorption fine structure computed tomography, pair distribution function computed tomography and tomographic scanning transmission X-ray microscopy.

We report the development of laboratory based hyperspectral X-ray computed tomography which allows the internal elemental chemistry of an object to be reconstructed and visualised in three dimensions. The method employs a spectroscopic X-ray imaging detector with sufficient energy resolution to distinguish individual elemental absorption edges. Elemental distributions can then be made by K-edge subtraction, or alternatively by voxel-wise spectral fitting to give relative atomic concentrations. We demonstrate its application to two material systems: studying the distribution of catalyst material on porous substrates for industrial scale chemical processing; and mapping of minerals and inclusion phases inside a mineralised ore sample. The method makes use of a standard laboratory X-ray source with measurement times similar to that required for conventional computed tomography.

We report the results from an operando XRD-CT study of a working catalytic membrane reactor for the oxidative coupling of methane. These results reveal the importance of the evolving solid state chemistry during catalytic reaction, particularly the chemical interaction between the catalyst and the oxygen transport membrane.

In recent times, there has been a drive to develop non-destructive X-ray imaging techniques that provide chemical or physical insight. To date, these methods have generally been limited; either requiring raster scanning of pencil beams, using narrow bandwidth radiation and/or limited to small samples. We have developed a novel full-field radiographic imaging technique that enables the entire physio-chemical state of an object to be imaged in a single snapshot. The method is sensitive to emitted and scattered radiation, using a spectral imaging detector and polychromatic hard X-radiation, making it particularly useful for studying large dense samples for materials science and engineering applications. The method and its extension to three-dimensional imaging is validated with a series of test objects and demonstrated to directly image the crystallographic preferred orientation and formed precipitates across an aluminium alloy friction stir weld section.

The internal crystalline structure of a human molar tooth has been non-destructively imaged in cross-section using X-ray diffraction computed tomography. Diffraction signals from high-energy X-rays which have large attenuation lengths for hard biomaterials have been collected in a transmission geometry. Coupling this with a computed tomography data acquisition and mathematically reconstructing their spatial origins, diffraction patterns from every voxel within the tooth can be obtained. Using this method we have observed the spatial variations of some key material parameters including nanocrystallite size, organic content, lattice parameters, crystallographic preferred orientation and degree of orientation. We have also made a link between the spatial variations of the unit cell lattice parameters and the chemical make-up of the tooth. In addition, we have determined how the onset of tooth decay occurs through clear amorphization of the hydroxyapatite crystal, and we have been able to map the extent of decay within the tooth. The described method has strong prospects for non-destructive probing of mineralized biomaterials., (Copyright © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.)

X-ray tomography is a ubiquitous tool used, for example, in medical diagnosis, explosives detection or to check structural integrity of complex engineered components. Conventional tomographic images are formed by measuring many transmitted X-rays and later mathematically reconstructing the object, however the structural and chemical information carried by scattered X-rays of different wavelengths is not utilised in any way. We show how a very simple; laboratory-based; high energy X-ray system can capture these scattered X-rays to deliver 3D images with structural or chemical information in each voxel. This type of imaging can be used to separate and identify chemical species in bulk objects with no special sample preparation. We demonstrate the capability of hyperspectral imaging by examining an electronic device where we can clearly distinguish the atomic composition of the circuit board components in both fluorescence and transmission geometries. We are not only able to obtain attenuation contrast but also to image chemical variations in the object, potentially opening up a very wide range of applications from security to medical diagnostics.

An emerging theme of modern composites and devices is the coupling of nanostructural properties of materials with their targeted arrangement at the microscale. Of the imaging techniques developed that provide insight into such designer materials and devices, those based on diffraction are particularly useful. However, to date, these have been heavily restrictive, providing information only on materials that exhibit high crystallographic ordering. Here we describe a method that uses a combination of X-ray atomic pair distribution function analysis and computed tomography to overcome this limitation. It allows the structure of nanocrystalline and amorphous materials to be identified, quantified and mapped. We demonstrate the method with a phantom object and subsequently apply it to resolving, in situ, the physicochemical states of a heterogeneous catalyst system. The method may have potential impact across a range of disciplines from materials science, biomaterials, geology, environmental science, palaeontology and cultural heritage to health.

A new data collection strategy for performing synchrotron energy-dispersive X-ray diffraction computed tomography has been devised. This method is analogous to angle-dispersive X-ray diffraction whose diffraction signal originates from a line formed by intersection of the incident X-ray beam and the sample. Energy resolution is preserved by using a collimator which defines a small sampling voxel. This voxel is translated in a series of parallel straight lines covering the whole sample and the operation is repeated at different rotation angles, thus generating one diffraction pattern per translation and rotation step. The method has been tested by imaging a specially designed phantom object, devised to be a demanding validator for X-ray diffraction imaging. The relative strengths and weaknesses of the method have been analysed with respect to the classic angle-dispersive technique. The reconstruction accuracy of the method is good, although an absorption correction is required for lower energy diffraction because of the large path lengths involved. The spatial resolution is only limited to the width of the scanning beam owing to the novel collection strategy. The current temporal resolution is poor, with a scan taking several hours. The method is best suited to studying large objects (e.g. for engineering and materials science applications) because it does not suffer from diffraction peak broadening effects irrespective of the sample size, in contrast to the angle-dispersive case.

We have developed a pixellated high energy X-ray detector instrument to be used in a variety of imaging applications. The instrument consists of either a Cadmium Zinc Telluride or Cadmium Telluride (Cd(Zn)Te) detector bump-bonded to a large area ASIC and packaged with a high performance data acquisition system. The 80 by 80 pixels each of 250 μm by 250 μm give better than 1 keV FWHM energy resolution at 59.5 keV and 1.5 keV FWHM at 141 keV, at the same time providing a high speed imaging performance. This system uses a relatively simple wire-bonded interconnection scheme but this is being upgraded to allow multiple modules to be used with very small dead space. The readout system and the novel interconnect technology is described and how the system is performing in several target applications.

A prototype X-ray colour imaging system has been assembled using the principle of tomographic energy-dispersive diffraction imaging (TEDDI). The new system has been tested using samples of nylon-6, aluminium powder and deer antler bone. Non-destructive three-dimensional images of the test objects have been reconstructed on a 300 microm scale with an associated diffraction pattern at each voxel. In addition, the lattice parameters of the polycrystalline material present in the sampled voxels have been determined using full pattern refinement methods. The use of multiple diffracted parallel colour X-ray beams has allowed simultaneous spatially resolved data collection across a plane of the sample. This has simplified the sample scan motion and has improved data collection times by a factor scaling with the number of detector pixels. The TEDDI method is currently limited to thin samples (approx. 1-2mm) with light atoms owing to the very low detection efficiency of the silicon detector at X-ray energies above 25 keV. We describe how these difficulties can be removed by using semiconductor detectors made from heavier atomic material.

An in-vacuum diffractometer has been modified to collect powder diffraction data from a sample of promazine hydrochloride. Strong anomalous contrast has been observed at, or close to, the sulphur edge. Based on the data collected, a bespoke diffractometer has been designed that, together with minor changes to the geometry of the experiment, will enable the routine collection of powder data at absorption edges below 5.5 keV.

A new beamline (MPW6.2) has been designed and built for the study of materials during processing where three synchrotron techniques, SAXS, WAXS and XAS, are available simultaneously. It has been demonstrated that Rietveld refinable data can be collected from silicon SRM 640b over a 60 degrees range in a time scale of 1 s. The data have been refined to a chi(2) of 2.4, the peaks fitting best to a Pearson VII function or with fundamental parameters. The peak halfwidths have been found to be approximately constant at 0.06 degrees over a 120 degrees angular range indicating that the instrumental resolution function has matched its design specification. A quantitative comparison of data sets collected on the same isotactic polypropylene system on MPW6.2 and DUBBLE at the ESRF shows a 17% improvement in angular resolution and a 1.8 improvement in peak-to-background ratio with the RAPID2 system; the ESRF data vary more smoothly across detector channels. The time-dependent wide-angle XRD was tested by comparing a hydration reaction of gypsum-bassanite-anhydrite with energy-dispersive data collected on the same system on the same time scale. Three sample data sets from the reaction were selected for analysis and gave an average chi(2) of 3.8. The Rietveld-refined lattice parameters are a good match with published values and the corresponding errors show a mean value of 3.3 x 10(-4). The data have also been analysed by the Pawley decomposition phase-modelling technique demonstrating the ability of the station to quickly and accurately identify new phases. The combined SAXS/WAXS capability of the station was tested with the crystallization and spinodal decomposition of a very dilute polymer system. Our measurements show that the crystallization of a high-density co-polymer (E76B38) as low as 0.5% by weight can be observed in solution in hexane. The WAXS and SAXS data sets were collected on the same time scale. The SAXS detector was calibrated using a collagen sample that gave 30 orders of diffraction in 1 s of data collection. The combined XRD and XAS measurement capability of the station was tested by observing the collapse and re-crystallization of zinc-exchanged zeolite A (zeolite Zn/Na-A). Previous studies of this material on station 9.3 at the SRS were compared with those from the new station. A time improvement of 38 was observed with better quality counting statistics. The improved angular resolution from the WAXS detector enabled new peaks to be identified.

Without any prior knowledge of the molecular structure, all 31 carbon and oxygen atoms of fluorescein diacetate were accurately located based on a high-resolution powder diffraction experiment. Direct methods and Fourier recycling were used. This represents a considerable advance with respect to the size of an organic molecule whose structure can be solved by ab initio methods from measurements on a powder., (© 1998 WILEY-VCH Verlag GmbH, Weinheim, Fed. Rep. of Germany.)

SRS station 16.3 is now a fully scheduled user facility for high-resolution and high-energy single-crystal X-ray diffraction. It is based on a large three-axis diffractometer, designed and constructed at Daresbury for a wide range of physics and materials science applications. Served by wiggler 16 (a 6 T superconducting wavelength-shifter), the station has access to a broad spectrum of photon energies, extending to over 50 keV, and is designed for simple polarization-state tuning by motorized height adjustment of all optical components. This paper outlines the key design features and some of the science projects carried out during the first year of operation.

A high-temperature furnace with an induction heater coil and a cryogenic system based on closed-cycle refrigeration have been assembled to enhance the non-ambient powder diffraction facilities at the Synchrotron Radiation Source, Daresbury Laboratory. The commissioning of the high- and low-temperature devices on the high-resolution powder diffractometer of Station 2.3 is described. The combined temperature range provided by the furnace/cryostat is 10-1500 K. Results from Fe and NH(4)Br powder samples are presented to demonstrate the operation of the apparatus. The developments presented in this paper are applicable to a wide range of other experiments and diffraction geometries.

A new single-crystal diffraction facility has been constructed on beamline 9 of the SRS at Daresbury Laboratory for the study of structural problems in chemistry and materials science. The station utilizes up to 3.8 mrad horizontally from the 5 T wiggler magnet which can be focused horizontally and vertically. The horizontal focusing is provided by a choice of gallium-cooled triangular bent Si (111) or Si (220) monochromators, giving a wavelength range from 0.3 to 1.5 A. Focusing in the vertical plane is achieved by a cylindrically bent zerodur mirror with a 300 mum-thick palladium coating. The station is equipped with a modified Enraf-Nonius CAD-4 four-circle diffractometer and a Siemens SMART CCD area-detector system. High- and low-temperature facilities are available to cover the temperature range from about 80 to 1000 K. Early results on test compounds without optimization of the beam optics demonstrate that excellent refined structures can be obtained from samples giving diffraction patterns too weak to be measured with conventional laboratory X-ray sources, fulfilling a major objective of the project.

A high-pressure low-temperature cell has been developed for in-situ diffraction studies of carbon dioxide and propane gas hydrate crystallization. The design and implementation of the cell, which can operate up to 3.5 MPa and down to 253 K, are described. Using synchrotron energy-dispersive X-ray diffraction, the first growth of the hydrate crystals from solution has been successfully observed. The lattice parameters of the hydrate crystals were found to be 11.927 (2) and 17.196 (2) A, respectively.