In situ synchrotron X‐ray diffraction analysis of deformation behaviour in Ti–Ni‐based thin films

Deformation mechanisms of as‐deposited and post‐annealed Ti_50.2Ni_49.6, Ti_50.3Ni_46.2Cu_3.5 and Ti_48.5Ni_40.8Cu_7.5 thin films were investigated using the in situ synchrotron X‐ray diffraction technique. Results showed that initial crystalline phases determined the deformation mechanisms of all the films during tensile loading. For the films dominated by monoclinic martensites (B19′), tensile stress induced the detwinning of 〈011〉 type‐II twins and resulted in the preferred orientations of (002)_B19′ parallel to the loading direction (∥ LD) and (020)_B19′ perpendicular to the LD (⊥ LD). For the films dominated by austenite (B2), the austenite directly transformed into martensitic variants (B19′) with preferred orientations of (002)_B19′ ∥ LD and (020)_B19′ ⊥ LD. For the Ti_50.3Ni_46.2Cu_3.5 and Ti_48.1Ni_40.8Cu_7.5 films, martensitic transformation temperatures decreased apparently after post‐annealing because of the large thermal stress generated in the films due to the large differences in thermal expansion coefficients between the film and substrate.     

Grazing‐incidence X‐ray diffraction study of rubrene epitaxial thin films

The growth of organic semiconductors as thin films with good and controlled electrical performances is nowadays one of the main tasks in the field of organic semiconductor‐based electronic devices. In particular it is often required to grow highly crystalline and precisely oriented thin films. Here, thanks to grazing‐incidence X‐ray diffraction measurements carried out at the ELETTRA synchrotron facility, it is shown that rubrene thin films deposited by organic molecular beam epitaxy on the surface of tetracene single crystals have the structure of the known orthorhombic polymorph, with the (2 0 0) plane parallel to the substrate surface. Moreover, the exact epitaxial relationship between the film and the substrate crystalline structures is determined, demonstrating the presence of a unique in‐plane orientation of the overlayer.     

Analysis and localization of metal‐ and metalloid‐containing proteins by synchrotron radiation x‐ray fluorescence spectrometry

Synchrotron radiation x‐ray fluorescence (SRXRF) spectrometry has been applied for the determination of metals and metalloids in electrophoretically separated proteins and histological samples. The method was tested by the analysis of trace element‐containing proteins in rat testis homogenate and the determination of the spatial distribution of some metals in brain sections of scrapie‐infected hamsters. After sodium dodecyl sulfate—polyacrylamide gel electrophoresis (SDS‐PAGE) and transfer on to a blotting membrane, the distribution of selenium among the proteins of testis homogenate was determined. The comparison with the autoradiogram of ⁷⁵Se‐labeled testicular proteins separated in the same way showed that of nine selenium‐containing proteins found by autoradiography, four could be detected by SRXRF. The distribution of several metals and metalloids in cryo‐sections of 10 µm thin brain sections of three Syrian hamsters intracerebrally infected with the scrapie strain ME7‐H and of three control animals was investigated at the HASYLAB beamline L by scanning with a synchrotron radiation beam focused by a polycapillary lens. The copper‐binding prion protein (PrP) in its pathological form PrP^Sc, determined by immunohistochemistry on cryo‐sections, was found to be diffusely dispersed in the scrapie‐infected brains, and the copper distribution differed from that in the control animals. The question whether, and to what extent, PrP^Sc and copper hot‐spots are related, remains to be investigated. The method was shown to be suitable for the determination of trace element distribution patterns in electrophoretically separated proteins and histological tissue preparations. Copyright © 2004 John Wiley & Sons, Ltd.     

Bone‐nanohydroxyapatite spheres interface evaluation by synchrotron radiation X‐ray microfluorescence

Hydroxyapatite (HA) is largely used as bone graft; it seems to be the most promising synthetic implant material, mainly because of its excellent biocompatibility. The crystallinity, particle and pore size of HA are important characteristics and can be modified by decreasing basic structural form below 100 nm and have evoked a great amount of attention for improving prevention, diagnosis, and disease treatment, besides improving bone repair through the biodegradation of the material. The aim of this study was to investigate bone mineral content in bone samples with nanohydroxyapatite and HA spheres, specially its spatial distribution on bone microarchitecture. Circular bone defects were made in both tibiae of 12 White New Zeland adult rabbits (Oryctolagus cuniculus) and were divided randomly into five groups – blood clot (control group), sintered HA, non‐sintered HA, sintered nanoHA and non‐sintered nanoHA – all materials in spherical shape, to smooth handling and accommodation of the surgical bed, and to minimize inflammatory response. The rabbits were euthanatized according to the experimental period of 1 and 4 weeks after surgery. The samples were evaluated by polarized microscopy as well as X‐ray microfluorescence in order to account the bone mineral content bone‐implant interfaces, through synchrotron radiation. Our results revealed greater newly formed bone area in the non‐sintered materials and control groups, and the used technique showed that the amount of calcium of new bone was consistent with both mature bone and HA spheres. In conclusion, the present findings suggest that HA‐based biomaterials are biocompatible, promote osteoconduction and favored bone repair. Copyright © 2011 John Wiley & Sons, Ltd.     

High‐resolution stress mapping of polycrystalline alumina compression using synchrotron X‐ray diffraction

The ability to achieve uniform stress in uniaxial compression tests of polycrystalline alumina is of significance for the calibration of piezospectroscopic coefficients as well as strength studies in ceramics. In this study high‐energy X‐rays were used to capture powder diffraction profiles over a half‐section of a polycrystalline alumina parallelepiped sample under an increasing uniaxial compressive load. The data were converted to strain and results were used for stress mapping of the sample. Stress maps from the study quantify the higher stresses at the sample–platen contact interface and reveal the evolution of the stress distribution in these specimens with load. For the geometry of the samples used, at the center section of the specimen the overall magnitudes of the compressive stresses were found to be 20% higher compared with the average expected theoretical stress based on the applied load and cross‐sectional area. The observed compressive stresses at the corners of the parallelepiped specimen were 62% higher and shear stresses were observed at the specimen interface to the load mechanism. The effects, seen at the interface, can lead to premature failure at these locations and can affect the accuracy of calibration of spectral peaks with stress as well as compression strength measurements. The results provide important information that can be used to establish guidelines on material and geometry considerations in developing compression tests on high‐strength ceramics.     

Portable x‐ray fluorescence spectrometer with a pyroelectric x‐ray generator

A portable x‐ray fluorescence spectrometer was assembled with an x‐ray generator that was driven by a 9 V dry electric battery. Several possible optimum geometries of the x‐ray generator and detector were evaluated, and the results showed that the intensity of fluorescent x‐rays was strong enough when the angle between the x‐ray generator and detector was as small as 30°. The geometrically optimized x‐ray spectrometer was applied to the analysis of paints, plastics and aluminum foils. Pigments in paint and toxic elements in plastic could be easily detected with on‐site analysis. Fe in aluminum foil was quantitatively determined down to the sub‐% level. The detection limit of Fe was 180 ppm for 100 s of measurement. Copyright © 2005 John Wiley & Sons, Ltd.     

Guiding synchrotron X‐ray diffraction by multimodal video‐rate protein crystal imaging

Synchronous digitization, in which an optical sensor is probed synchronously with the firing of an ultrafast laser, was integrated into an optical imaging station for macromolecular crystal positioning prior to synchrotron X‐ray diffraction. Using the synchronous digitization instrument, second‐harmonic generation, two‐photon‐excited fluorescence and bright field by laser transmittance were all acquired simultaneously with perfect image registry at up to video‐rate (15 frames s^?1). A simple change in the incident wavelength enabled simultaneous imaging by two‐photon‐excited ultraviolet fluorescence, one‐photon‐excited visible fluorescence and laser transmittance. Development of an analytical model for the signal‐to‐noise enhancement afforded by synchronous digitization suggests a 15.6‐fold improvement over previous photon‐counting techniques. This improvement in turn allowed acquisition on nearly an order of magnitude more pixels than the preceding generation of instrumentation and reductions of well over an order of magnitude in image acquisition times. These improvements have allowed detection of protein crystals on the order of 1 µm in thickness under cryogenic conditions in the beamline. These capabilities are well suited to support serial crystallography of crystals approaching 1 µm or less in dimension.     

Calculation of attenuation and x‐ray fluorescence intensities for non‐parallel x‐ray beams

With the nowadays widespreaded use of x‐ray optics in x‐ray fluorescence analysis, large convergence or divergence angles can occur. This experimental situation violates a basic assumption of the usual fundamental parameter quantification procedure. In order to take beam divergences in micro x‐ray fluorescence analysis into account, a way of calculating fluorescence intensities numerically by Monte Carlo integration is described. For three examples of typical micro‐XRF set‐ups the fluorescence intensities and their deviation from the parallel beam geometry are calculated. Furthermore, we propose a new approach with ‘equivalent angles’ which correct for the beam divergences in fundamental parameter methods. Copyright © 2003 John Wiley & Sons, Ltd.     

High‐throughput synchrotron X‐ray diffraction for combinatorial phase mapping

Discovery of new materials drives the deployment of new technologies. Complex technological requirements demand precisely tailored material functionalities, and materials scientists are driven to search for these new materials in compositionally complex and often non‐equilibrium spaces containing three, four or more elements. The phase behavior of these high‐order composition spaces is mostly unknown and unexplored. High‐throughput methods can offer strategies for efficiently searching complex and multi‐dimensional material genomes for these much needed new materials and can also suggest a processing pathway for synthesizing them. However, high‐throughput structural characterization is still relatively under‐developed for rapid material discovery. Here, a synchrotron X‐ray diffraction and fluorescence experiment for rapid measurement of both X‐ray powder patterns and compositions for an array of samples in a material library is presented. The experiment is capable of measuring more than 5000 samples per day, as demonstrated by the acquisition of high‐quality powder patterns in a bismuth–vanadium–iron oxide composition library. A detailed discussion of the scattering geometry and its ability to be tailored for different material systems is provided, with specific attention given to the characterization of fiber textured thin films. The described prototype facility is capable of meeting the structural characterization needs for the first generation of high‐throughput material genomic searches.     

Background of x‐ray nanophotonics based on the planar air waveguide resonator

The work elucidates some model details of x‐ray flux waveguide resonance propagation through a planar, narrow, extended slit. The phenomenological substantiation of the correctness of the introduction of the waveguide resonance model is confirmed on the basis of the concept of flux spatial coherence. The peculiarities of the model realization in various designs of planar x‐ray waveguide resonators (PXWR) are discussed. The main fields of practical application of PXWRs are characterized by experimental results. Nanophotonics perspectives using waveguide resonance structures are outlined. Copyright © 2007 John Wiley & Sons, Ltd.     

Local study of fissure caries by Fourier transform infrared microscopy and X‐ray diffraction using synchrotron radiation

Investigations of intact dental enamel as well as carious‐affected human dental enamel were performed using infrared spectromicroscopy and X‐ray diffraction applying synchrotron radiation. Caries of enamel was shown to be characterized by an increase in the number of deformation and valence vibrations for N—C—O, N—H and C=O bonds, a decrease of the crystallinity index, and by the absence of the preferable orientation of hydroxyapatite crystals within the affected enamel. This indicates the presence of destructive processes in the organic matrix of hard tooth tissues.     

Stability of thermoresponsive methylcellulose thin film: x‐ray reflectivity study

Methylcellulose (MC), a thermoreversible polymer, was fabricated as thin films into silicon substrates and characterized by x‐ray reflectivity (XRR) measurements for its stability with time and heating. XRR data from the as‐is thin films showed good agreement with the single‐layer model on top of a substrate from Parratt's formalism. Data fitting showed that the density of the thin films is slightly higher than the reported value by manufacturers. Interface roughness values indicate good wetting of the polymer onto the substrate. Heating the thin films at the phase transition temperatures and quenching them to room temperature showed no significant changes in the thin film parameters before and after heating. This showed the thermal stability and/or thermoreversibility of the film. Diffuse scattering measurements also showed no significant changes in the lateral structure of the film with heating and quenching. XRR measurements done on fabricated thin films stored for a month showed a slight increase in the film thickness which could be due to the hygroscopic nature of the polymer. Vacuum heating of the stored thin films at 100 °C for 1 h slightly decreased the thickness, but it has been found that other parameters such as density and surface/interface roughness show good thermal stability. Copyright © 2009 John Wiley & Sons, Ltd.     

In situ rheological measurements at extreme pressure and temperature using synchrotron X‐ray diffraction and radiography

Dramatic technical progress seen over the past decade now allows the plastic properties of materials to be investigated under extreme pressure and temperature conditions. Coupling of high‐pressure apparatuses with synchrotron radiation significantly improves the quantification of differential stress and specimen textures from X‐ray diffraction data, as well as specimen strains and strain rates by radiography. This contribution briefly reviews the recent developments in the field and describes state‐of‐the‐art extreme‐pressure deformation devices and analytical techniques available today. The focus here is on apparatuses promoting deformation at pressures largely in excess of 3 GPa, namely the diamond anvil cell, the deformation‐DIA apparatus and the rotational Drickamer apparatus, as well as on the methods used to carry out controlled deformation experiments while quantifying X‐ray data in terms of materials rheological parameters. It is shown that these new techniques open the new field of in situ investigation of materials rheology at extreme conditions, which already finds multiple fundamental applications in the understanding of the dynamics of Earth‐like planet interior.     

Rietveld and pair distribution function study of Hägg carbide using synchrotron X‐ray diffraction

Fischer–Tropsch (FT) synthesis is an important process in the manufacturing of hydrocarbons and oxygenated hydrocarbons from mixtures of carbon monoxide and hydrogen (syngas). The reduced iron catalyst reacts with carbon monoxide and hydrogen to form bulk Fe₅C₂ Hägg carbide (χ‐HC) during FT synthesis. Arguably, χ‐HC is the predominant catalyst phase present in the working iron catalyst. Deactivation of the working catalyst can be due to oxidation of χ‐HC to iron oxide, a step‐wise decarburization to cementite (θ‐Fe₃C), carbon formation or sintering with accompanying loss of catalytic performance. It is therefore critical to determine the precise crystal structure of χ‐HC for the understanding of the synthesis process and for comparison with the first‐principles ab initio modelling. Here the results of high‐resolution synchrotron X‐ray powder diffraction data are reported. The atomic arrangement of χ‐HC was confirmed by Rietveld refinement and subsequent real‐space modelling of the pair distribution function (PDF) obtained from direct Fourier transformation. The Rietveld and PDF results of χ‐HC correspond well with that of a pseudo‐monoclinic phase of space group Pī [a = 11.5661 (6) Å, b = 4.5709 (1) Å, c = 5.0611 (2) Å, α = 89.990 (5)°, β = 97.753 (4)°, γ = 90.195 (4)°], where the Fe atoms are located in three distorted prismatic trigonal and one octahedral arrangement around the central C atoms. The Fe atoms are distorted from the prismatic trigonal arrangement in the monoclinic structure by the change in C atom location in the structure.     

Quantitative determination of major systematics in synchrotron x‐ray experiments: seeing through harmonic components

In line with an ongoing programme to determine accurately x‐ray attenuation coefficients, we have developed a method for the quantitative determination of the effect on experimental results of monochromator harmonic components in a synchrotron beam. The technique can be adapted to suit a wide variety of experiments, and is of particular interest because it determines the effect of the harmonic components directly. This avoids the necessity for modelling and is therefore robust. Results of a direct determination of the effect of harmonic components illustrate the power of the technique. We extended the technique to quantify the effects of dark current‐induced errors. Copyright © 2003 John Wiley & Sons, Ltd.     

Multi‐element analysis of sea water from Sepetiba Bay,Brazil, by total reflection x‐ray fluorescence spectrometry using synchrotron radiation

Trace elements in the surface waters of Sepetiba Bay were studied by total reflection x‐ray fluorescence spectrometry using synchrotron radiation (SRTXRF). The bay is located in the south of Rio de Janeiro State, Brazil. The water samples were collected at 21 sampling stations, prepared in order to preconcentrate the metallic elements with ammonium pyrrolidinedithiocarbamate and to remove the salt matrix. Samples were spiked with an internal standard (Se) and the precipitated dithiocarbamates of trace elements were separated by filtration through a Millipore filter, then transferred to a Perspex reflector and digested with HNO₃ for SRTXRF measurement. Elemental concentrations of Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo and Pb were determined and a comparison was made between the results obtained and the values given in the literature for sea water. Copyright © 2005 John Wiley & Sons, Ltd.     

Fish otolith trace element maps: new approaches with synchrotron microbeam x‐ray fluorescence

Otoliths, the carbonate earstones of fishes, take up minor and trace amounts of elements as they accrete through a fish's life. We apply synchrotron microbeam x‐ray fluorescence methods to establish a breakthrough in high‐resolution, simultaneous area mapping of multiple trace elements in otoliths, with spatial resolution down to 20 µm and trace element detection down into the part per million range for multiple elements. Concentration maps of Ca, Sr, Zn and, for the first time, Ba, Mn, and Se are obtained simultaneously. Combinations of these elemental maps provide new insights into the environmental history of fishes and their lifetime movements, illustrated by several case studies. This method helps pave the way toward improved spatial analysis of otolith microchemistry. Copyright © 2007 John Wiley & Sons, Ltd.     

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.     

Nondestructive discrimination of small glass fragments for forensic examination using high energy synchrotron radiation x‐ray fluorescence spectrometry

This paper demonstrates that high‐energy SR‐XRF (synchrotron radiation x‐ray fluorescence spectrometry) utilizing 116 keV x‐rays is a powerful technique for nondestructive discrimination of small glass fragments. An XRF spectrum of glass fragments of a standard material SRM612 gave well‐resolved K‐line peaks of 34 elements, including the rare‐earth elements. The relative standard deviations (RSD) of the ratios of the intensities of heavy elements normalized by that of Ba were less than 8.2% for the analyses of 10 fragments (<1 mg) in the energy region above 20 keV. A comparison of glass fragments (<1 mg) obtained from 26 figured glass sheet was performed using elemental intensity ratios that were defined as the intensities of detected elements divided by that of Ba. Analyses of glass fragments revealed the existence of Mo, Pd, Sb, Cs and Bi, and these trace elements could be useful as important indexes to discriminate glass samples. The Ce:Ba ratios could be measured for all the samples with precision of 1.9% and were found to be quite effective parameters for identification of glass fragments, even though these fragments would contain no other characteristic heavy elements. All glass fragments in this study that could not be distinguished on the basis of refractive index (RI) values could be discriminated by this method. Copyright © 2006 John Wiley & Sons, Ltd.