X-ray diffraction with micrometre spatial resolution for highly absorbing samples.

X-ray diffraction with high spatial resolution is commonly used to characterize (poly)crystalline samples with, for example, respect to local strain, residual stress, grain boundaries and texture. However, the investigation of highly absorbing samples or the simultaneous assessment of high-Z materials by X-ray fluorescence have been limited due to the utilization of low photon energies. Here, a goniometer-based setup implemented at the P06 beamline of PETRA III that allows for micrometre spatial resolution with a photon energy of 35 keV and above is reported. A highly focused beam was achieved by using compound refractive lenses, and high-precision sample manipulation was enabled by a goniometer that allows up to 5D scans (three rotations and two translations). As experimental examples, the determination of local strain variations in martensitic steel samples with micrometre spatial resolution, as well as the simultaneous elemental distribution for high-Z materials in a thin-film solar cell, are demonstrated. The proposed approach allows users from the materials-science community to determine micro-structural properties even in highly absorbing samples.

Rapid aberration correction for diffractive X-ray optics by additive manufacturing.

Diffraction-limited hard X-ray optics are key components for high-resolution microscopy, in particular for upcoming synchrotron radiation sources with ultra-low emittance. Diffractive optics like multilayer Laue lenses (MLL) have the potential to reach unprecedented numerical apertures (NA) when used in a crossed geometry of two one-dimensionally focusing lenses. However, minuscule fluctuations in the manufacturing process and technical limitations for high NA X-ray lenses can prevent a diffraction-limited performance. We present a method to overcome these challenges with a tailor-made refractive phase plate. With at-wavelength metrology and a rapid prototyping approach we demonstrate aberration correction for a crossed pair of MLL, improving the Strehl ratio from 0.41(2) to 0.81(4) at a numerical aperture of 3.3 × 10-3. This highly adaptable aberration-correction scheme provides an important tool for diffraction-limited hard X-ray focusing.

Determination of the through-plane profile of vanadium species in hydrated Nafion studied with micro X-ray absorption near-edge structure spectroscopy - proof of concept.

Vanadium-ion transport through the polymer membrane results in a significant decrease in the capacity of vanadium redox flow batteries. It is assumed that five vanadium species are involved in this process. Micro X-ray absorption near-edge structure spectroscopy (micro-XANES) is a potent method to study chemical reactions during vanadium transport inside the membrane. In this work, protocols for micro-XANES measurements were developed to enable through-plane characterization of the vanadium species in Nafion 117 on beamline P06 of the PETRA III synchrotron radiation facility (DESY, Hamburg, Germany). A Kapton tube diffusion cell with a diameter of 3 mm was constructed. The tube diameter was chosen in order to accommodate laminar flow for cryogenic cooling while allowing easy handling of the cell components by hand. A vertical step size of 2.5 µm and a horizontal step size of 5 µm provided sufficient resolution to resolve the profile and good statistics after summing up horizontal rows of scan points. The beam was confined in the horizontal plane to account for the waviness of the membrane. The diffusion of vanadium ions during measurement was inhibited by the cryogenic cooling. Vanadium oxidation, e.g. by water radiolysis (water percentage in the hydrated membrane ∼23 wt%), was mitigated by the cryogenic cooling and by minimizing the dwell time per pixel to 5 ms. Thus, the photo-induced oxidation of V3+ in the focused beam could be limited to 10%. In diffusion experiments, Nafion inside the diffusion cell was exposed on one side to V3+ electrolyte and on the other side to VO2+. The ions were allowed to diffuse across the through-plane orientation of the membrane during one of two short defrost times (200 s and 600 s). Subsequent micro-XANES measurements showed the formation of VO2+ from V3+ and VO2+ inside the water body of Nafion. This result proves the suitability of the experimental setup as a powerful tool for the determination of the profile of vanadium species in Nafion and other ionomeric membranes.

Nanofocusing with aberration-corrected rotationally parabolic refractive X-ray lenses. Corrigendum.

A correction in the paper by Seiboth et al. [(2018). J. Synchrotron Rad. 25, 108-115] is made.

Tracking dynamic structural changes in catalysis by rapid 2D-XANES microscopy.

Many processes and materials in heterogeneous catalysis undergo dynamic structural changes depending on their chemical environment. Monitoring such dynamic changes can be challenging using conventional spectroscopic characterization tools, due to the high time resolution required. Here, a high-resolution 2D X-ray camera operating at 50 Hz full-frame rate was synchronized with a QEXAFS monochromator, enabling rapid spectro-microscopic imaging with chemical contrast over individual pixels. This was used to monitor chemical gradients within a model Pt/Al2O3 catalyst during catalytic partial oxidation of methane to synthesis gas. The transition from methane combustion (partly oxidized Pt) to combustion-reforming and partial oxidation (fully reduced Pt) was observed by a characteristic reduction front, which progressed from the end of the catalyst bed towards its beginning on the second time scale. The full-field QEXAFS imaging method applied here allows acquisition of entire XANES spectra `on the fly' in a rapid and spatially resolved manner. The combination of high spatial and temporal resolution with spectroscopic data offers new opportunities for observing dynamic processes in catalysts and other functional materials at work. The methodology is flexible and can be applied at beamlines equipped with a QEXAFS or other fast-scanning monochromators and a suitable sample environment for gas phase analytics to allow for catalytic studies at the same time.

Chemical Imaging of Hierarchical Porosity Formation within a Zeolite Crystal Visualized by Small-Angle X-Ray Scattering and In-Situ Fluorescence Microscopy.

Introducing hierarchical porosity to zeolites is vital for providing molecular access to microporous domains. Yet, the dynamics of meso- and macropore formation has remained elusive and pore space ill-characterized by a lack of (in situ) microscopic tools sensitive to nanoporosity. Here, we probe hierarchical porosity formation within a zeolite ZSM-5 crystal in real-time by in situ fluorescence microscopy during desilication. In addition, we introduce small-angle X-ray scattering microscopy as novel characterization tool to map intracrystal meso- and macropore properties. It is shown that hierarchical porosity formation initiates at the crystal surface and propagates to the crystal core via a pore front with decreasing rate. Also, hierarchical porosity only establishes in specific (segments of) subunits which constitute ZSM-5. Such space-dependent meso- and macroporosity implies local discrepancies in diffusion, performance and deactivation behaviors even within a zeolite crystal.

Correlated X-ray Ptychography and Fluorescence Nano-Tomography on the Fragmentation Behavior of an Individual Catalyst Particle during the Early Stages of Olefin Polymerization.

A combination of X-ray ptychography and X-ray fluorescence tomography (XRF) has been used to study the fragmentation behavior of an individual Ziegler-Natta catalyst particle, ∼40 µm in diameter, in the early stages of propylene polymerization with submicron spatial resolution. The electron density signal obtained from X-ray ptychography gives the composite phases of the Ziegler-Natta catalyst particle fragments and isotactic polypropylene, while 3-D XRF visualizes multiple isolated clusters, rich in Ti, of several microns in size. The radial distribution of Ti species throughout the polymer-catalyst composite particle shows that the continuous bisection fragmentation model is the main contributor to the fragmentation pathway of the catalyst particle as a whole. Furthermore, within the largest Ti clusters the fragmentation pathway was found to occur through both the continuous bisection and layer-by-layer models. The fragmentation behavior of polyolefin catalysts was for the first time visualized in 3-D by directly imaging and correlating the distribution of the Ti species to the polymer-catalyst composite phase.

Highly Sensitive Nondestructive Rare Earth Element Detection by Means of Wavelength-Dispersive X-ray Fluorescence Spectroscopy Enabled by an Energy Dispersive pn-Charge-Coupled-Device Detector.

Detection of rare earth elements (REE) is commonly performed with destructive techniques such as (LA)-ICPMS or coupled to a destructive sample preparation. When investigating unique geological samples, such as cometary, asteroidal, or interstellar material from sample return missions or inclusions in deep Earth diamonds, a nondestructive method is preferred. The presented nondestructive highly sensitive wavelength-dispersive X-ray fluorescence spectroscopy (WD-XRF) technique is designed to measure the L-lines of REE between 4.5 and 7 keV with a sensitivity down to the ppm level. REE fluorescence L-lines are often only separated by a few eV from neighboring XRF-lines and cannot be resolved by an energy dispersive approach especially in the presence of transition metal K-lines. In our spectrometer the characteristic X-rays emitted by the sample are dispersed by a fixed Ge(111) analyzer crystal over the active area of an energy dispersive pn-charge-coupled-device (pnCCD) detector, enabling high energy resolution detection of X-rays differentiated by their corresponding Bragg angles. The use of an energy-dispersive 2D detector enables the simultaneous acquiring of XRF-lines while eliminating any ambiguities due to potential contribution from higher order diffraction effects or other diffraction planes and thereby increases the sensitivity by reducing the (scatter) background. This detection method shows an energy resolution of 12 eV for the Ti-Kα fluorescence line and has a sensitivity down to 0.50 ppm for REE L-lines. The method was optimized specifically for the nondestructive analysis of inclusions in deep Earth diamonds, yielding in situ quantitative information about up-to-now inaccessible elemental (REE) composition patterns together with the more abundant transition metals like Ti, Cr, Mn, and Fe. This information is of great importance to decipher the role that deep Earth plays in the global carbon and fluid cycle.

Damages Induced by Synchrotron Radiation-Based X-ray Microanalysis in Chrome Yellow Paints and Related Cr-Compounds: Assessment, Quantification, and Mitigation Strategies.

Synchrotron radiation (SR)-based X-ray methods are powerful analytical tools for several purposes. They are widely used to probe the degradation mechanisms of inorganic artists' pigments in paintings, including chrome yellows (PbCr1-xSxO4; 0 ≤ x ≤ 0.8), a class of compounds often found in Van Gogh masterpieces. However, the high intensity and brightness of SR beams raise important issues regarding the potential damage inflicted on the analyzed samples. A thorough knowledge of the SR X-ray sensitivity of each class of pigment in the painting matrix is therefore required to find analytical strategies that seek to minimize the damage for preserving the integrity of the analyzed samples and to avoid data misinterpretation. Here, we employ a combination of Cr K-edge X-ray absorption near-edge structure spectroscopy, Cr-Kß X-ray emission spectroscopy, and X-ray diffraction to monitor and quantify the effects of SR X-rays on the stability of chrome yellows and related Cr compounds and to define mitigation strategies. We found that the SR X-ray beam exposure induces changes in the oxidation state and local coordination environment of Cr ions and leads to a loss of the compound's crystalline structure. The extent of X-ray damage depends on some intrinsic properties of the samples (chemical composition of the pigment and the presence/absence and nature of the binder). It can be minimized by optimizing the overall fluence/dose released to the samples and by working in vacuum and under cryogenic conditions.

Hard X-ray wavefront correction via refractive phase plates made by additive and subtractive fabrication techniques.

Modern subtractive and additive manufacturing techniques present new avenues for X-ray optics with complex shapes and patterns. Refractive phase plates acting as glasses for X-ray optics have been fabricated, and spherical aberration in refractive X-ray lenses made from beryllium has been successfully corrected. A diamond phase plate made by femtosecond laser ablation was found to improve the Strehl ratio of a lens stack with a numerical aperture (NA) of 0.88 × 10-3 at 8.2 keV from 0.1 to 0.7. A polymer phase plate made by additive printing achieved an increase in the Strehl ratio of a lens stack at 35 keV with NA of 0.18 × 10-3 from 0.15 to 0.89, demonstrating diffraction-limited nanofocusing at high X-ray energies.

Fast XANES fluorescence imaging using a Maia detector.

A new fast X-ray absorption spectroscopy scanning method was recently implemented at the Hard X-ray Microprobe endstation P06, PETRA III, DESY, utilizing a Maia detector. Spectromicroscopy maps were acquired with spectra for X-ray absorption near-edge structure (XANES) acquisition in the sub-second regime. The method combines XANES measurements with raster-scanning of the sample through the focused beam. The order of the scanning sequence of the axes, one beam energy axis and two (or more) spatial axes, is a variable experimental parameter and, depending on it, the dwell at each location can be either single and continuous (if the energy axis is the inner loop) or in shorter discontinuous intervals (if a spatial axis is innermost). The combination of improved spatial and temporal resolution may be necessary for rapidly changing samples, e.g. for following in operando chemical reactions or samples highly susceptible to beam damage where the rapid collection of single XANES spectra avoids issues with the emergence of chemical changes developing from latent damage. This paper compares data sets collected on a specially designed test pattern and a geological thin-section scanning the energy as inner, middle and outer axis in the sequence. The XANES data of all three scanning schemes is found to show excellent agreement down to the single-pixel level.

Nanofocusing with aberration-corrected rotationally parabolic refractive X-ray lenses.

Wavefront errors of rotationally parabolic refractive X-ray lenses made of beryllium (Be CRLs) have been recovered for various lens sets and X-ray beam configurations. Due to manufacturing via an embossing process, aberrations of individual lenses within the investigated ensemble are very similar. By deriving a mean single-lens deformation for the ensemble, aberrations of any arbitrary lens stack can be predicted from the ensemble with \bar{\sigma} = 0.034λ. Using these findings the expected focusing performance of current Be CRLs are modeled for relevant X-ray energies and bandwidths and it is shown that a correction of aberrations can be realised without prior lens characterization but simply based on the derived lens deformation. The performance of aberration-corrected Be CRLs is discussed and the applicability of aberration-correction demonstrated over wide X-ray energy ranges.

Application toward Confocal Full-Field Microscopic X-ray Absorption Near Edge Structure Spectroscopy.

Using X-ray absorption near edge structure (XANES) spectroscopy, information on the local chemical structure and oxidation state of an element of interest can be acquired. Conventionally, this information can be obtained in a spatially resolved manner by scanning a sample through a focused X-ray beam. Recently, full-field methods have been developed to obtain direct 2D chemical state information by imaging a large sample area. These methods are usually in transmission mode, thus restricting the use to thin and transmitting samples. Here, a fluorescence method is displayed using an energy-dispersive pnCCD detector, the SLcam, characterized by measurement times far superior to what is generally applicable. Additionally, this method operates in confocal mode, thus providing direct 3D spatially resolved chemical state information from a selected subvolume of a sample, without the need of rotating a sample. The method is applied to two samples: a gold-supported magnesia catalyst (Au/MgO) and a natural diamond containing Fe-rich inclusions. Both samples provide XANES spectra that can be overlapped with reference XANES spectra, allowing this method to be used for fingerprinting and linear combination analysis of known XANES reference compounds.

Spiral scanning X-ray fluorescence computed tomography.

Scanning X-ray fluorescence tomography was once considered impractical due to prohibitive measurement time requirements but is now common for investigating metal distributions within small systems. A recent look-ahead to the possibilities of 4th-generation synchrotron light sources [J. Synchrotron. Radiat. 21, 1031 (2014)] raised the possibility of a spiral-scanning measurement scheme where motion overheads are almost completely eliminated. Here we demonstrate the spiral scanning measurement and use Fourier ring correlation analysis to interrogate sources of resolution degradation. We develop an extension to the Fourier ring correlation formalism that enables direct determination of resolution from the measured sinogram data, greatly enhancing its power as a diagnostic tool for computed tomography.

Laboratory Scale X-ray Fluorescence Tomography: Instrument Characterization and Application in Earth and Environmental Science.

A new laboratory scale X-ray fluorescence (XRF) imaging instrument, based on an X-ray microfocus tube equipped with a monocapillary optic, has been developed to perform XRF computed tomography experiments with both higher spatial resolution (20 µm) and a better energy resolution (130 eV @Mn-K(α)) than has been achieved up-to-now. This instrument opens a new range of possible applications for XRF-CT. Next to the analytical characterization of the setup by using well-defined model/reference samples, demonstrating its capabilities for tomographic imaging, the XRF-CT microprobe has been used to image the interior of an ecotoxicological model organism, Americamysis bahia. This had been exposed to elevated metal (Cu and Ni) concentrations. The technique allowed the visualization of the accumulation sites of copper, clearly indicating the affected organs, i.e. either the gastric system or the hepatopancreas. As another illustrative application, the scanner has been employed to investigate goethite spherules from the Cretaceous-Paleogene boundary, revealing the internal elemental distribution of these valuable distal ejecta layer particles.

Fast X-ray microfluorescence imaging with submicrometer-resolution integrating a Maia detector at beamline P06 at PETRA†III.

The high brilliance of third-generation synchrotron sources increases the demand for faster detectors to utilize the available flux. The Maia detector is an advanced imaging scheme for energy-dispersive detection realising dwell times per image-pixel as low as 50 µs and count rates higher than 10 × 106 s-1. In this article the integration of such a Maia detector in the Microprobe setup of beamline P06 at the storage ring PETRA III at the Deutsches Elektronen-Synchrotron (DESY) in Hamburg, Germany, is described. The analytical performance of the complete system in terms of rate-dependent energy resolution, scanning-speed-dependent spatial resolution and lower limits of detection is characterized. The potential of the Maia-based setup is demonstrated by key applications from materials science and chemistry, as well as environmental science with geological applications and biological questions that have been investigated at the P06 beamline.

Photon Energy Becomes the Third Dimension in Crystallographic Texture Analysis.

Conventional analysis of the preferred orientation of crystallites (crystallographic texture) involves X-ray diffraction with area detectors and 2D data output. True 3D, spatially resolved information requires sample rotation in the beam, thus changing the probed volume, which introduces signal smearing and precludes the scanning of complex structures. This obstacle has been overcome by energy-dispersive Laue diffraction. A method has been devised to reach a large portion of reciprocal space and translate the X-ray photon energy into the missing third dimension of space. Carbon fibers and lobster exoskeleton as examples of biomineralized tissue have been analyzed. The major potential of this method lies in its "one-shot" nature and the direct 3D information requiring no previous knowledge of the sample. It allows the texture of large samples with complex substructures to be scanned and opens up the conceptual possibility of following texture changes in situ, for example, during crystallization.

Development and Applications of a Laboratory Micro X-ray Fluorescence (µXRF) Spectrometer Using Monochromatic Excitation for Quantitative Elemental Analysis.

The analytical characterization and an application example of a novel laboratory X-ray fluorescence (µXRF) microprobe is presented, which combines monochromatic, focused X-ray beam excitation with a high-performance silicon drift detector (SDD) and two-dimensional/three-dimensional (2D/3D) scanning capability. Because of the monochromatic excitation, below the (multiple) Compton/Rayleigh scattering peak region, the XRF spectra obtained by this laboratory spectrometer has similarly high peak-to-background ratios as those which can be obtained at synchrotron sources. However, the flux density difference between the proposed laboratory instrument and current synchrotron end stations is on the order of several orders of magnitude. As a result, sub-ppm minimum detection limits (MDL) for transition metals are obtained for a variety of sample matrices. The monochromatic excitation also allows for the efficient use of an iterative Monte Carlo simulation algorithm to obtain quantitative information on the analyzed samples. The analytical characteristics of this instrument and quantitative results, in combination with an iterative reverse Monte Carlo simulation algorithm, will be demonstrated using measurements conducted on an iron-containing meteorite.

Methodological challenges of optical tweezers-based X-ray fluorescence imaging of biological model organisms at synchrotron facilities.

Recently, a radically new synchrotron radiation-based elemental imaging approach for the analysis of biological model organisms and single cells in their natural in vivo state was introduced. The methodology combines optical tweezers (OT) technology for non-contact laser-based sample manipulation with synchrotron radiation confocal X-ray fluorescence (XRF) microimaging for the first time at ESRF-ID13. The optical manipulation possibilities and limitations of biological model organisms, the OT setup developments for XRF imaging and the confocal XRF-related challenges are reported. In general, the applicability of the OT-based setup is extended with the aim of introducing the OT XRF methodology in all research fields where highly sensitive in vivo multi-elemental analysis is of relevance at the (sub)micrometre spatial resolution level.

Micro-distribution of uranium in bone after contamination: new insight into its mechanism of accumulation into bone tissue.

After internal contamination, uranium rapidly distributes in the body; up to 20 % of the initial dose is retained in the skeleton, where it remains for years. Several studies suggest that uranium has a deleterious effect on the bone cell system, but little is known regarding the mechanisms leading to accumulation of uranium in bone tissue. We have performed synchrotron radiation-based micro-X-ray fluorescence (SR µ-XRF) studies to assess the initial distribution of uranium within cortical and trabecular bones in contaminated rats' femurs at the micrometer scale. This sensitive technique with high spatial resolution is the only method available that can be successfully applied, given the small amount of uranium in bone tissue. Uranium was found preferentially located in calcifying zones in exposed rats and rapidly accumulates in the endosteal and periosteal area of femoral metaphyses, in calcifying cartilage and in recently formed bone tissue along trabecular bone. Furthermore, specific localized areas with high accumulation of uranium were observed in regions identified as micro-vessels and on bone trabeculae. These observations are of high importance in the study of the accumulation of uranium in bone tissue, as the generally proposed passive chemical sorption on the surface of the inorganic part (apatite) of bone tissue cannot account for these results. Our study opens original perspectives in the field of exogenous metal bio-mineralization.