IDATEN and G‐SITENNO: GUI‐assisted software for coherent X‐ray diffraction imaging experiments and data analyses at SACLA

Using our custom‐made diffraction apparatus KOTOBUKI‐1 and two multiport CCD detectors, cryogenic coherent X‐ray diffraction imaging experiments have been undertaken at the SPring‐8 Angstrom Compact free electron LAser (SACLA) facility. To efficiently perform experiments and data processing, two software suites with user‐friendly graphical user interfaces have been developed. The first is a program suite named IDATEN, which was developed to easily conduct four procedures during experiments: aligning KOTOBUKI‐1, loading a flash‐cooled sample into the cryogenic goniometer stage inside the vacuum chamber of KOTOBUKI‐1, adjusting the sample position with respect to the X‐ray beam using a pair of telescopes, and collecting diffraction data by raster scanning the sample with X‐ray pulses. Named G‐SITENNO, the other suite is an automated version of the original SITENNO suite, which was designed for processing diffraction data. These user‐friendly software suites are now indispensable for collecting a large number of diffraction patterns and for processing the diffraction patterns immediately after collecting data within a limited beam time.     

A scanning Kelvin probe for synchrotron investigations: the in situ detection of radiation‐induced potential changes

A wide range of high‐performance X‐ray surface/interface characterization techniques are implemented nowadays at every synchrotron radiation source. However, these techniques are not always `non‐destructive' because possible beam‐induced electronic or structural changes may occur during X‐ray irradiation. As these changes may be at least partially reversible, an in situ technique is required for assessing their extent. Here the integration of a scanning Kelvin probe (SKP) set‐up with a synchrotron hard X‐ray interface scattering instrument for the in situ detection of work function variations resulting from X‐ray irradiation is reported. First results, obtained on bare sapphire and sapphire covered by a room‐temperature ionic liquid, are presented. In both cases a potential change was detected, which decayed and vanished after switching off the X‐ray beam. This demonstrates the usefulness of a SKP for in situ monitoring of surface/interface potentials during X‐ray materials characterization experiments.     

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.     

Simultaneous X‐ray fluorescence and scanning X‐ray diffraction microscopy at the Australian Synchrotron XFM beamline

Owing to its extreme sensitivity, quantitative mapping of elemental distributions via X‐ray fluorescence microscopy (XFM) has become a key microanalytical technique. The recent realisation of scanning X‐ray diffraction microscopy (SXDM) meanwhile provides an avenue for quantitative super‐resolved ultra‐structural visualization. The similarity of their experimental geometries indicates excellent prospects for simultaneous acquisition. Here, in both step‐ and fly‐scanning modes, robust, simultaneous XFM‐SXDM is demonstrated.     

Elemental mapping of frozen‐hydrated cells with cryo‐scanning X‐ray fluorescence microscopy

Visualizing the elemental distributions of cells and tissues is of growing importance in biology and medical science because such data deepen our understanding of the behavior of metal‐binding proteins and ions. Elemental mapping by X‐ray fluorescence analysis with a hard X‐ray nanobeam is very well suited for this purpose owing to its high sensitivity and high resolution. Using this technique, samples must be prepared without artifacts that are caused by treatments such as chemical fixation and staining procedures. In many studies of elemental mapping, sample preparation is not explicitly considered. To overcome this deficiency, we developed a cryo‐scanning X‐ray fluorescence microscope and installed it in the second experimental hutch of BL29XUL of SPring‐8. We used it to observe frozen‐hydrated cells that had been fixed by a quick‐freezing technique to preserve elemental data of the living state at an X‐ray energy of 11.5 keV. The distributions of K, Ca, Fe, Cu and Zn were successfully visualized. The distributions of these elements (especially those of K, Ca and Fe) differed from those in cells fixed with paraformaldehyde. Copyright © 2010 John Wiley & Sons, Ltd.     

A video camera system for coaxial observation of a sample with an incident soft X‐ray beam

A video camera system for observing a sample from the direction of an incident soft X‐ray beam has been developed. The sample is seen via two reflecting mirrors. The first mirror, which has a hole to allow the soft X‐ray beam to pass through, is set on the beam axis in a vacuum. The second mirror is used to cancel out the mirror inversion of the image. This camera system is used for efficient positioning of samples in a soft X‐ray beam.     

X‐ray nanotomography and focused‐ion‐beam sectioning for quantitative three‐dimensional analysis of nanocomposites

Knowing the relationship between three‐dimensional structure and properties is paramount for complete understanding of material behavior. In this work, the internal nanostructure of micrometer‐size (～10 µm) composite Ni/Al particles was analyzed using two different approaches. The first technique, synchrotron‐based X‐ray nanotomography, is a nondestructive method that can attain resolutions of tens of nanometers. The second is a destructive technique with sub‐nanometer resolution utilizing scanning electron microscopy combined with an ion beam and `slice and view' analysis, where the sample is repeatedly milled and imaged. The obtained results suggest that both techniques allow for an accurate characterization of the larger‐scale structures, while differences exist in the characterization of the smallest features. Using the Monte Carlo method, the effective resolution of the X‐ray nanotomography technique was determined to be ～48 nm, while focused‐ion‐beam sectioning with `slice and view' analysis was ～5 nm.     

Application of kinoform lens for X‐ray reflectivity analysis

In this paper the first practical application of kinoform lenses for the X‐ray reflectivity characterization of thin layered materials is demonstrated. The focused X‐ray beam generated from a kinoform lens, a line of nominal size ～50 µm × 2 µm, provides a unique possibility to measure the X‐ray reflectivities of thin layered materials in sample scanning mode. Moreover, the small footprint of the X‐ray beam, generated on the sample surface at grazing incidence angles, enables one to measure the absolute X‐ray reflectivities. This approach has been tested by analyzing a few thin multilayer structures. The advantages achieved over the conventional X‐ray reflectivity technique are discussed and demonstrated by measurements.     

Analysis and interpretation of the first monochromatic X‐ray tomography data collected at the Australian Synchrotron Imaging and Medical beamline

The first monochromatic X‐ray tomography experiments conducted at the Imaging and Medical beamline of the Australian Synchrotron are reported. The sample was a phantom comprising nylon line, Al wire and finer Cu wire twisted together. Data sets were collected at four different X‐ray energies. In order to quantitatively account for the experimental values obtained for the Hounsfield (or CT) number, it was necessary to consider various issues including the point‐spread function for the X‐ray imaging system and harmonic contamination of the X‐ray beam. The analysis and interpretation of the data includes detailed considerations of the resolution and efficiency of the CCD detector, calculations of the X‐ray spectrum prior to monochromatization, allowance for the response of the double‐crystal Si monochromator used (via X‐ray dynamical theory), as well as a thorough assessment of the role of X‐ray phase‐contrast effects. Computer simulations relating to the tomography experiments also provide valuable insights into these important issues. It was found that a significant discrepancy between theory and experiment for the Cu wire could be largely resolved in terms of the effect of the point‐spread function. The findings of this study are important in respect of any attempts to extract quantitative information from X‐ray tomography data, across a wide range of disciplines, including materials and life sciences.     

Focused ion beam preparation of samples for X‐ray nanotomography

The preparation of hard material samples with the necessary size and shape is critical to successful material analysis. X‐ray nanotomography requires that samples are sufficiently thin for X‐rays to pass through the sample during rotation for tomography. One method for producing samples that fit the criteria for X‐ray nanotomography is focused ion beam/scanning electron microscopy (FIB/SEM) which uses a focused beam of ions to selectively mill around a region of interest and then utilizes a micromanipulator to remove the milled‐out sample from the bulk material and mount it on a sample holder. In this article the process for preparing X‐ray nanotomography samples in multiple shapes and sizes is discussed. Additionally, solid‐oxide fuel cell anode samples prepared through the FIB/SEM technique underwent volume‐independence studies for multiple properties such as volume fraction, average particle size, tortuosity and contiguity to observe the characteristics of FIB/SEM samples in X‐ray nanotomography.     

High‐energy transmission Laue micro‐beam X‐ray diffraction: a probe for intra‐granular lattice orientation and elastic strain in thicker samples

An understanding of the mechanical response of modern engineering alloys to complex loading conditions is essential for the design of load‐bearing components in high‐performance safety‐critical aerospace applications. A detailed knowledge of how material behaviour is modified by fatigue and the ability to predict failure reliably are vital for enhanced component performance. Unlike macroscopic bulk properties (e.g. stiffness, yield stress, etc.) that depend on the average behaviour of many grains, material failure is governed by `weakest link'‐type mechanisms. It is strongly dependent on the anisotropic single‐crystal elastic–plastic behaviour, local morphology and microstructure, and grain‐to‐grain interactions. For the development and validation of models that capture these complex phenomena, the ability to probe deformation behaviour at the micro‐scale is key. The diffraction of highly penetrating synchrotron X‐rays is well suited to this purpose and micro‐beam Laue diffraction is a particularly powerful tool that has emerged in recent years. Typically it uses photon energies of 5–25 keV, limiting penetration into the material, so that only thin samples or near‐surface regions can be studied. In this paper the development of high‐energy transmission Laue (HETL) micro‐beam X‐ray diffraction is described, extending the micro‐beam Laue technique to significantly higher photon energies (50–150 keV). It allows the probing of thicker sample sections, with the potential for grain‐level characterization of real engineering components. The new HETL technique is used to study the deformation behaviour of individual grains in a large‐grained polycrystalline nickel sample during in situ tensile loading. Refinement of the Laue diffraction patterns yields lattice orientations and qualitative information about elastic strains. After deformation, bands of high lattice misorientation can be identified in the sample. Orientation spread within individual scattering volumes is studied using a pattern‐matching approach. The results highlight the inability of a simple Schmid‐factor model to capture the behaviour of individual grains and illustrate the need for complementary mechanical modelling.     

Development of a two‐dimensional imaging system of X‐ray absorption fine structure

A two‐dimensional imaging system of X‐ray absorption fine structure (XAFS) has been developed at beamline BL‐4 of the Synchrotron Radiation Center of Ritsumeikan University. The system mainly consists of an ionization chamber for I₀ measurement, a sample stage, and a two‐dimensional complementary metal oxide semiconductor (CMOS) image sensor for measuring the transmitted X‐ray intensity. The X‐ray energy shift in the vertical direction, which originates from the vertical divergence of the X‐ray beam on the monochromator surface, is corrected by considering the geometrical configuration of the monochromator. This energy correction improves the energy resolution of the XAFS spectrum because each pixel in the CMOS detector has a very small vertical acceptance of ～0.5 µrad. A data analysis system has also been developed to automatically determine the energy of the absorption edge. This allows the chemical species to be mapped based on the XANES feature over a wide area of 4.8 mm (H) × 3.6 mm (V) with a resolution of 10 µm × 10 µm. The system has been applied to the chemical state mapping of the Mn species in a LiMn₂O₄ cathode. The heterogeneous distribution of the Mn oxidation state is demonstrated and is considered to relate to the slow delocalization of Li⁺‐defect sites in the spinel crystal structure. The two‐dimensional‐imaging XAFS system is expected to be a powerful tool for analyzing the spatial distributions of chemical species in many heterogeneous materials such as battery electrodes.     

Hard X‐ray‐induced damage on carbon–binder matrix for in situ synchrotron transmission X‐ray microscopy tomography of Li‐ion batteries

The electrode of Li‐ion batteries is required to be chemically and mechanically stable in the electrolyte environment for in situ monitoring by transmission X‐ray microscopy (TXM). Evidence has shown that continuous irradiation has an impact on the microstructure and the electrochemical performance of the electrode. To identify the root cause of the radiation damage, a wire‐shaped electrode is soaked in an electrolyte in a quartz capillary and monitored using TXM under hard X‐ray illumination. The results show that expansion of the carbon–binder matrix by the accumulated X‐ray dose is the key factor of radiation damage. For in situ TXM tomography, intermittent X‐ray exposure during image capturing can be used to avoid the morphology change caused by radiation damage on the carbon–binder matrix.     

The first microbeam synchrotron X‐ray fluorescence beamline at the Siam Photon Laboratory

The first microbeam synchrotron X‐ray fluorescence (µ‐SXRF) beamline using continuous synchrotron radiation from Siam Photon Source has been constructed and commissioned as of August 2011. Utilizing an X‐ray capillary half‐lens allows synchrotron radiation from a 1.4 T bending magnet of the 1.2 GeV electron storage ring to be focused from a few millimeters‐sized beam to a micrometer‐sized beam. This beamline was originally designed for deep X‐ray lithography (DXL) and was one of the first two operational beamlines at this facility. A modification has been carried out to the beamline in order to additionally enable µ‐SXRF and synchrotron X‐ray powder diffraction (SXPD). Modifications included the installation of a new chamber housing a Si(111) crystal to extract 8 keV synchrotron radiation from the white X‐ray beam (for SXPD), a fixed aperture and three gate valves. Two end‐stations incorporating optics and detectors for µ‐SXRF and SXPD have then been installed immediately upstream of the DXL station, with the three techniques sharing available beam time. The µ‐SXRF station utilizes a polycapillary half‐lens for X‐ray focusing. This optic focuses X‐ray white beam from 5 mm × 2 mm (H × V) at the entrance of the lens down to a diameter of 100 µm FWHM measured at a sample position 22 mm (lens focal point) downstream of the lens exit. The end‐station also incorporates an XYZ motorized sample holder with 25 mm travel per axis, a 5× ZEISS microscope objective with 5 mm × 5 mm field of view coupled to a CCD camera looking to the sample, and an AMPTEK single‐element Si (PIN) solid‐state detector for fluorescence detection. A graphic user interface data acquisition program using the LabVIEW platform has also been developed in‐house to generate a series of single‐column data which are compatible with available XRF data‐processing software. Finally, to test the performance of the µ‐SXRF beamline, an elemental surface profile has been obtained for a piece of ancient pottery from the Ban Chiang archaeological site, a UNESCO heritage site. It was found that the newly constructed µ‐SXRF technique was able to clearly distinguish the distribution of different elements on the specimen.     

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.     

Sample thickness and quantitative concentration measurements in Br K‐edge XANES spectroscopy of organic materials

While XANES spectroscopy is an established tool for quantitative information on chemical structure and speciation, elemental concentrations are generally quantified by other methods. The edge step in XANES spectra represents the absolute amount of the measured element in the sample, but matrix effects and sample thickness complicate the extraction of accurate concentrations from XANES measurements, particularly at hard X‐ray energies where the X‐ray beam penetrates deeply into the sample. The present study demonstrates a method of quantifying concentration with a detection limit approaching 1 mg kg^?1 using information routinely collected in the course of a hard X‐ray XANES experiment. The XANES normalization procedure unambiguously separates the signal of the absorber from any source of background. The effects of sample thickness on edge steps at the bromine K‐edge were assessed and an empirical correction factor for use with samples of variable mass developed.     

Non‐invasive measurement of X‐ray beam heating on a surrogate crystal sample

Cryocooling is a technique routinely used to mitigate the effects of secondary radiation damage on macromolecules during X‐ray data collection. Energy from the X‐ray beam absorbed by the sample raises the temperature of the sample. How large is the temperature increase and does this reduce the effectiveness of cryocooling? Sample heating by the X‐ray beam has been measured non‐invasively for the first time by means of thermal imaging. Specifically, the temperature rise of 1 mm and 2 mm glass spheres (sample surrogates) exposed to an intense synchrotron X‐ray beam and cooled in a laminar flow of nitrogen gas is experimentally measured. For the typical sample sizes, photon energies, fluxes, flux densities and exposure times used for macromolecular crystallographic data collection at third‐generation synchrotron radiation sources and with the sample accurately centered in the cryostream, the heating by the X‐ray beam is only a few degrees. This is not sufficient to raise the sample above the amorphous‐ice/crystalline‐ice transition temperature and, if the cryostream cools the sample to 100 K, not even enough to significantly enhance radiation damage from secondary effects.     

A feasibility study of dynamic stress analysis inside a running internal combustion engine using synchrotron X‐ray beams

The present investigation establishes the feasibility of using synchrotron‐generated X‐ray beams for time‐resolved in situ imaging and diffraction of the interior components of an internal combustion engine during its operation. The demonstration experiment was carried out on beamline I12 (JEEP) at Diamond Light Source, UK. The external hutch of the JEEP instrument is a large‐scale engineering test bed for complex in situ processing and simulation experiments. The hutch incorporates a large capacity translation and rotation table and a selection of detectors for monochromatic and white‐beam diffraction and imaging. These capabilities were used to record X‐ray movies of a motorcycle internal combustion engine running at 1850 r.p.m. and to measure strain inside the connecting rod via stroboscopic X‐ray diffraction measurement. The high penetrating ability and high flux of the X‐ray beam at JEEP allowed the observation of inlet and outlet valve motion, as well as that of the piston, connecting rod and the timing chain within the engine. Finally, the dynamic internal strain within the moving connecting rod was evaluated with an accuracy of ～50 × 10^?6.     

Imaging interfacial micro‐ and nano‐bubbles by scanning transmission soft X‐ray microscopy

Synchrotron‐based scanning transmission soft X‐ray microscopy (STXM) with nanometer resolution was used to investigate the existence and behavior of interfacial gas nanobubbles confined between two silicon nitride windows. The observed nanobubbles of SF₆ and Ne with diameters smaller than 2.5 µm were quite stable. However, larger bubbles became unstable and grew during the soft X‐ray imaging, indicating that stable nanobubbles may have a length scale, which is consistent with a previous report using atomic force microscopy [Zhang et al. (2010), Soft Matter, 6 , 4515–4519]. Here, it is shown that STXM is a promising technique for studying the aggregation of gases near the solid/water interfaces at the nanometer scale.     

Early commissioning results for spectroscopic X‐ray Nano‐Imaging Beamline BL 7C sXNI at PLS‐II

For spectral imaging of chemical distributions using X‐ray absorption near‐edge structure (XANES) spectra, a modified double‐crystal monochromator, a focusing plane mirrors system and a newly developed fluorescence‐type X‐ray beam‐position monitoring and feedback system have been implemented. This major hardware upgrade provides a sufficiently stable X‐ray source during energy scanning of more than hundreds of eV for acquisition of reliable XANES spectra in two‐dimensional and three‐dimensional images. In recent pilot studies discussed in this paper, heavy‐metal uptake by plant roots in vivo and iron's phase distribution in the lithium–iron–phosphate cathode of a lithium‐ion battery have been imaged. Also, the spatial resolution of computed tomography has been improved from 70 nm to 55 nm by means of run‐out correction and application of a reconstruction algorithm.