Synthesis of High Entropy and Entropy-Stabilized Metal Sulfides and Their Evaluation as Hydrogen Evolution Electrocatalysts.

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 η10 of (∼255 mV).

Quantifying multiple stain distributions in bioimaging by hyperspectral X-ray tomography.

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.

High-energy synchrotron X-ray tomography coupled with digital image correlation highlights likely failure points inside ITER toroidal field conductors.

Two sections of heat-treated (HT) and non-heat-treated (NHT) Cable-in-Conduit Conductor (CICC) of a design similar to the ITER tokomak have been imaged using very high energy X-ray tomography at the ESRF beamline ID19. The sample images were collected at four temperatures down to 77 K. These results showed a greater degree of movement, bundle distortion and touching strands in the NHT sample. The HT sample showed non-linear movements with temperature especially close to 77 K; increasing non-circularity of the superconducting fibre bundles towards the periphery of the CICC, and touching bundles throughout the CICC. The images have highlighted where future design might improve potential weakness, in particular at the outer perimeters of the conductor and the individual sub-cable, 'petal' wraps.

Enhanced hyperspectral tomography for bioimaging by spatiospectral reconstruction.

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.

Effect of thermal treatment on the stability of Na-Mn-W/SiO2 catalyst for the oxidative coupling of methane.

In this study, we investigate the effect of thermal treatment/calcination on the stability and activity of a Na-Mn-W/SiO2 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 CH4 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.

Rapid and Low-Temperature Molecular Precursor Approach toward Ternary Layered Metal Chalcogenides and Oxides: Mo1-x W x S2 and Mo1-x W x O3 Alloys (0 ≤ x ≤ 1).

Metal sulfide and metal oxide alloys of the form Mo1-x W x S2 and Mo1-x W x O3 (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 MoL4 and WS(S2)L2 (where L = S2CNEt2) 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 Mo1-x W x S2 are produced in an argon atmosphere, while the corresponding metal oxide alloys Mo1-x W x O3 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 MO6 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.

In situ X-ray diffraction computed tomography studies examining the thermal and chemical stabilities of working Ba0.5Sr0.5Co0.8Fe0.2O3-δ membranes during oxidative coupling of methane.

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.

The nondestructive measurement of strain distributions in air plasma sprayed thermal barrier coatings as a function of depth from entire Debye-Scherrer rings.

The residual strain distribution has been measured as a function of depth in both top coat and bond coat in as-received and heat-treated air plasma sprayed thermal barrier coating samples. High-energy synchrotron X-ray beams were used in transmission to produce full Debye-Scherrer rings whose non-circular aspect ratio gave the in-plane and out-of-plane strains far more efficiently than the sin2ψ method. The residual strain in the bond coat is found to be tensile and the strain in the ß phase of the as-received sample was measured. The residual strains observed in the top coat were generally compressive (increasing towards the interface), with two kinds of nonlinear trend. These was a 'jump' feature near the interface, and in some cases there was another 'jump' feature near the surface. It is shown how these trend differences can be correlated to cracks in the coating.

Residual stress distribution analysis of heat treated APS TBC using image based modelling.

We carried out a residual stress distribution analysis in a APS TBC throughout the depth of the coatings. The samples were heat treated at 1150 °C for 190 h and the data analysis used image based modelling based on the real 3D images measured by Computed Tomography (CT). The stress distribution in several 2D slices from the 3D model is included in this paper as well as the stress distribution along several paths shown on the slices. Our analysis can explain the occurrence of the "jump" features near the interface between the top coat and the bond coat. These features in the residual stress distribution trend were measured (as a function of depth) by high-energy synchrotron XRD (as shown in our related research article entitled 'Understanding the Residual Stress Distribution through the Thickness of Atmosphere Plasma Sprayed (APS) Thermal Barrier Coatings (TBCs) by high energy Synchrotron XRD; Digital Image Correlation (DIC) and Image Based Modelling') (Li et al., 2017) [1].

High Energy Resolution Hyperspectral X-Ray Imaging for Low-Dose Contrast-Enhanced Digital Mammography.

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.

A rapid two-dimensional data collection system for the study of ferroelectric materials under external applied electric fields.

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(Mg1/3Nb2/3)O3-33% PbTiO3 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.

Interlaced X-ray diffraction computed tomography.

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/SiO2 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.

Tungsten Bronze Barium Neodymium Titanate (Ba(6-3n)Nd(8+2n)Ti(18)O(54)): An Intrinsic Nanostructured Material and Its Defect Distribution.

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 Šthickness. 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.

Dark-field hyperspectral X-ray imaging.

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.

Pair distribution function computed tomography.

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.

Non-invasive imaging of the crystalline structure within a human tooth.

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.

A laboratory system for element specific hyperspectral X-ray imaging.

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.

Simultaneous measurement of X-ray diffraction and ferroelectric polarization data as a function of applied electric field and frequency.

The characteristics of a new ferroelectric measurement system at the European Synchrotron Radiation Facility are presented. The electric-field-induced phase transitions of Pb(Mg(1/3)Nb(2/3))O(3)-xPbTiO(3) are determined via in situ measurements of electric polarization within the synchrotron diffraction beamline. Real-time data collection methods on single-crystal samples are employed as a function of frequency to determine the microstructural origin of piezoelectric effects within these materials, probing the dynamic ferroelectric response.

A new approach to synchrotron energy-dispersive X-ray diffraction computed tomography.

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.

Solution of the Crystal and Molecular Structure of Complex Low-Symmetry Organic Compounds with Powder Diffraction Techniques: Fluorescein Diacetate.

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.