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ID15A is a newly refurbished beamline at the ESRF devoted to operando and time‐resolved diffraction and imaging, total scattering and diffraction computed tomography. The beamline is optimized for rapid alternation between the different techniques during a single operando experiment in order to collect complementary data on working systems. The high available energy (up to 120 keV) means that even bulky and highly absorbing systems may be studied. The beamline is equipped with optimized focusing optics and a photon‐counting CdTe pixel detector, allowing for both unprecedented data quality at high energy and for very rapid triggered experiments. A large choice of imaging detectors and ancillary probes and sample environments is also available. [ABSTRACT FROM AUTHOR]

To improve lithium and sodium ion battery technology, it is imperative to understand how the properties of the different components are controlled by their chemical structures. Operando structural studies give us some of the most useful information for understanding how batteries work, but it remains difficult to separate out the contributions of the various components of a battery stack (e.g., electrodes, current collectors, electrolyte, and binders) and examine specific materials. We have used operando X-ray diffraction computed tomography (XRD-CT) to study specific components of an essentially unmodified working cell and extract detailed, space-resolved structural information on both crystalline and amorphous phases that are present during cycling by Rietveld and pair distribution function (PDF) methods. We illustrate this method with the first detailed structural examination of the cycling of sodium in a phosphorus anode, revealing surprisingly different mechanisms for sodiation and desodiation in this promising, high-capacity anode system. [ABSTRACT FROM AUTHOR]

Linear parabolic diamond refractive lenses are presented, designed to withstand high thermal and radiation loads coming from upgraded accelerator X-ray sources. Lenses were manufactured by picosecond laser treatment of a high-quality single-crystal synthetic diamond. Twelve lenses with radius of curvature at parabola apex R = 200 µm, geometrical aperture A = 900 µm and length L = 1.5 mm were stacked as a compound refractive lens and tested at the ESRF ID06 beamline. A focal spot of size 2.2 µm and a gain of 20 were measured at 8 keV. The lens profile and surface quality were estimated by grating interferometry and X-ray radiography. In addition, the influence of X-ray glitches on the focusing properties of the compound refractive lens were studied. [ABSTRACT FROM AUTHOR]

Semiconducting indium sulfide (In2S3) has recently attracted considerable attention as a buffer material in the field of thin film photovoltaics. Compared with this growing interest, however, detailed characterizations of the crystal structure of this material are rather scarce and controversial. In order to close this gap, we have carried out a reinvestigation of the crystal structure of this material with an in situ X-ray diffraction study as a function of temperature using monochromatic synchrotron radiation. For the purpose of this study, high quality polycrystalline In2S3 material with nominally stoichiometric composition was synthesized at high temperatures. We found three modifications of In2S3 in the temperature range between 300 and 1300 K, with structural phase transitions at temperatures of 717 K and above 1049 K. By Rietveld refinement we extracted the crystal structure data and the temperature coefficients of the lattice constants for all three phases, including a high-temperature trigonal γ-In2S3 modification. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Tracking the dynamic morphology of active materials during operation of lithium batteries is essential for identifying causes of performance loss. Digital volume correlation (DVC) is applied to high‐speed operando synchrotron X‐ray computed tomography of a commercial Li/MnO2 primary battery during discharge. Real‐time electrode material displacement is captured in 3D allowing degradation mechanisms such as delamination of the electrode from the current collector and electrode crack formation to be identified. Continuum DVC of consecutive images during discharge is used to quantify local displacements and strains in 3D throughout discharge, facilitating tracking of the progression of swelling due to lithiation within the electrode material in a commercial, spiral‐wound battery during normal operation. Displacement of the rigid current collector and cell materials contribute to severe electrode detachment and crack formation during discharge, which is monitored by a separate DVC approach. Use of time‐lapse X‐ray computed tomography coupled with DVC is thus demonstrated as an effective diagnostic technique to identify causes of performance loss within commercial lithium batteries; this novel approach is expected to guide the development of more effective commercial cell designs. [ABSTRACT FROM AUTHOR]

This article reports the creation of tomographic reconstructions giving three-dimensional data on the distribution of various structural features for SAPO-34 zeolite catalyst beds used in the commercially important methanol to olefin conversion process. The data were processed using parametric Rietveld refinement to treat entire slices of the tomograph as single refined data sets, allowing extraction of real structural parameters from all voxels of the reconstruction. This has the advantage over more traditional methods of X-ray diffraction computed tomography using peak intensities, that the structural parameters are independent of the intensity, meaning that information can still be extracted from poor data sets: an example is shown where part of the sample was no longer in the beam during data collection. Reconstructions using several structural parameters are presented and the results compared. Analysis of the variation of the catalyst c axis (linked to the degree of deactivation in earlier work) shows small but significant three-dimensional variations in the degree of deactivation with patterns which depend on the silicon content of the catalyst. Average data for the tomographic slices compare well with the results of earlier operando two-dimensional reactor scanning experiments. [ABSTRACT FROM AUTHOR]

This paper reports a simple but effective filtering approach to deal with single-crystal artefacts in X-ray diffraction computed tomography (XRD-CT). In XRD-CT, large crystallites can produce spots on top of the powder diffraction rings, which, after azimuthal integration and tomographic reconstruction, lead to line/streak artefacts in the tomograms. In the simple approach presented here, the polar transform is taken of collected two-dimensional diffraction patterns followed by directional median/mean filtering prior to integration. Reconstruction of one-dimensional diffraction projection data sets treated in such a way leads to a very significant improvement in reconstructed image quality for systems that exhibit powder spottiness arising from large crystallites. This approach is not computationally heavy which is an important consideration with big data sets such as is the case with XRD-CT. The method should have application to two-dimensional X-ray diffraction data in general where such spottiness arises. [ABSTRACT FROM AUTHOR]

X-ray diffraction (XRD) is typically silent towards information on low loadings of precious metals on solid catalysts because of their finely dispersed nature. When combined with a concentration modulation approach, time-resolved high-energy XRD is able to provide the detailed redox dynamics of palladium nanoparticles with a diameter of 2 nm in 2 wt % Pd/CZ (CZ=ceria-zirconia), which is a difficult sample for extended X-ray absorption fine structure (EXAFS) measurements because of the cerium component. The temporal evolution of the Pd(111) and Ce(111) reflections together with surface information from synchronous diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) measurements reveals that Ce maintains Pd oxidized in the CO pulse, whereas reduction is detected at the beginning of the O2 pulse. Oxygen is likely transferred from Pd to Ce3+ before the onset of Pd re-oxidation. In this context, adsorbed carbonates appear to be the rate-limiting species for re-oxidation. [ABSTRACT FROM AUTHOR]

Different solutions have been proposed over the years to optimize control of the temperature and atmosphere over a catalyst in order to reach an ideal reactor behavior. Here, a new innovative solution which aims to minimize temperature gradients along the catalyst bed is demonstrated. This was attained by focusing the infrared radiation generated from the heating elements onto the catalyst bed with the aid of an aluminium shield. This method yields a ∼0.13 K mm−1 axial temperature gradient ranging from 960 to 1173 K. With the selection of appropriate capillaries, pressures of 20 bar (2 MPa) can be attained. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

The evolution of time-resolved experiments, covering a multipurpose surface and bulk characterization of catalytic solids, during their preparation process and under reaction conditions, is presented. Particular emphasis is given to recent studies that attempt to unveil contemporary unresolved questions concerning the control of physicochemical properties of nanosolids, as well as the evolution of such solid materials under reactive atmospheres. To reach this goal, representative in situ and in operando works, using either modern (mostly synchrotron radiation based) approaches or multi-technique methods (mainly, although not exclusively, X-ray-vibrational coupling), and considering experiments in liquid and gas phase, as well as with amorphous, nanocrystalline and surface-deposited materials, are reviewed. [ABSTRACT FROM AUTHOR]

Ultrafast synchrotron microtomography has been used to study in situ and in real time the initial stages of silicate glass melt formation from crystalline granular raw materials. Significant and unexpected rearrangements of grains occur below the nominal eutectic temperature, and several drastically different solid-state reactions are observed to take place at different types of intergranular contacts. These reactions have a profound influence on the formation and composition of the liquids produced, and control the formation of heterogeneities. [ABSTRACT FROM AUTHOR]

Collective particle behavior such as interparticle coordination and particle rearrangement plays a significant role in the sintering of heterogeneous powder systems. Those phenomena have been investigated by in situ X-ray microtomography and discrete element simulation (DEM). In situ 3D images of sintering copper-based systems have been obtained at the European Synchrotron Research Facilities. The sintered systems comprise a dense packing of atomized copper powder with a size range of 0–63 μm and the same powder including artificial pores. Quantitative analysis of these images provided valuable data on local strain, coordination number, and particle movement. The sintering of the same systems has been simulated with the discrete element code dp3D. From this set of information, the importance of collective behavior on densification and microstructural evolution is assessed and the relevance of DEM to describe it is discussed. [ABSTRACT FROM AUTHOR]

The anomalous scattering properties of innate sulfur for proteins and phosphorus for DNA and RNA can be used to solve the phase problem in macromolecular crystallography (MX) via the single-wavelength anomalous dispersion method (SAD). However, this method, which is carried out at longer X-ray wavelengths (1.5-2.5 Å), is still not a routine tool in MX. The increased absorption from both air and sample associated with the use of longer X-ray wavelengths presents a key difficulty. The absorption can be corrected for through empirical algorithms, provided truly redundant data are available. Unfortunately, weakly diffracting macromolecular crystals suffer from radiation damage, resulting in a dose-dependent non-isomorphism which violates the assumption upon which these empirical algorithms are based. In this report, X-ray microtomography is used to reconstruct the three-dimensional shapes of vitrified macromolecular crystals including the surrounding solvent and sample holder. The setup can be integrated within an MX beamline environment and exploits both absorption and phase contrast. The dose needed for the tomographic measurements could be low enough to allow the technique to be used for crystal integrity characterization and alignment. X-ray tomography has some major benefits compared with the optical-light-based crystal alignment protocols currently used. [ABSTRACT FROM AUTHOR]

Single-wavelength anomalous diffraction (SAD), multiwavelength anomalous diffraction (MAD) and single isomorphous replacement with anomalous scattering (SIRAS) phasing at ultra-high X-ray energy, 55 keV, are used successfully to determine a high-quality and high-resolution experimental electronic density map of hen egg-white lysozyme, a model protein. Several combinations, between single- and three-wavelength, with native data were exploited to demonstrate that standard phasing procedures with standard equipment and software can successfully be applied to three-dimensional crystal structure determination of a macromolecule, even at these very short wavelengths. For the first time, a high-quality three-dimensional molecular structure is reported from SAD phasing with ultra-high-energy X-rays. The quality of the crystallographic data and the experimental electron density maps meet current standards. The 2.7% anomalous signal from three Ho atoms, at the Ho K edge, was sufficient to obtain a remarkable electron density and build the first lanthanide structure for HEWL in its entirety. [ABSTRACT FROM AUTHOR]

Semiconducting indium sulfide (In2S3) has recently attracted considerable attention as a buffer material in the field of thin film photovoltaics. Compared with this growing interest, however, detailed characterizations of the crystal structure of this material are rather scarce and controversial. In order to close this gap, we have carried out a reinvestigation of the crystal structure of this material with an in situ X-ray diffraction study as a function of temperature using monochromatic synchrotron radiation. For the purpose of this study, high quality polycrystalline In2S3 material with nominally stoichiometric composition was synthesized at high temperatures. We found three modifications of In2S3 in the temperature range between 300 and 1300 K, with structural phase transitions at temperatures of 717 K and above 1049 K. By Rietveld refinement we extracted the crystal structure data and the temperature coefficients of the lattice constants for all three phases, including a high-temperature trigonal γ-In2S3 modification. [ABSTRACT FROM AUTHOR]

Semiconducting indium sulfide (In2S3) has recently attracted considerable attention as a buffer material in the field of thin film photovoltaics. Compared with this growing interest, however, detailed characterizations of the crystal structure of this material are rather scarce and controversial. In order to close this gap, we have carried out a reinvestigation of the crystal structure of this material with an in situ X-ray diffraction study as a function of temperature using monochromatic synchrotron radiation. For the purpose of this study, high quality polycrystalline In2S3 material with nominally stoichiometric composition was synthesized at high temperatures. We found three modifications of In2S3 in the temperature range between 300 and 1300 K, with structural phase transitions at temperatures of 717 K and above 1049 K. By Rietveld refinement we extracted the crystal structure data and the temperature coefficients of the lattice constants for all three phases, including a high-temperature trigonal γ-In2S3 modification.