Bead‐releasing agents used in the preparation of solid samples as beads for WD‐XRF measurement

This paper carries the results of an evaluation of various materials, which may be used to aid in the release of a fused bead from its mould during a wavelength‐dispersive x‐ray fluorescence (WD‐XRF) measurement. The following bead‐releasing agents were studied: NaI, LiBr, NH₄I, and LiI. Each was incorporated in different quantities, as a solid and/or in an aqueous solution, together with a flux, into samples of ceramic raw materials. Release agent interference in the WD‐XRF measurement was analysed, and the optimum quantity of release agent needed to obtain suitable beads for WD‐XRF measurement was determined. The best results were obtained for LiI, which yielded reproducible beads without significant interference in the WD‐XRF measurement when a relatively small quantity (0.11 LiI g/bead) was used. Copyright © 2008 John Wiley & Sons, Ltd.     

Fatigue life prediction for high‐heat‐load components made of GlidCop by elastic‐plastic analysis

A procedure to predict the fatigue fracture life of high‐heat‐load components made of GlidCop has been successfully established. This method is based upon the Manson–Coffin equation with a cumulative linear damage law. This prediction was achieved by consolidating the results of experiments and analyses, and considered the effects of environment and creep. A low‐cycle‐fatigue test for GlidCop was conducted so that environment‐dependent Δ?_t–N_f diagrams for any temperature could be prepared. A special test piece was designed to concentrate the strain in a central area locally, resulting in the low‐cycle‐fatigue fracture. The experiments were carried out by repeatedly irradiating a test piece with an electron beam. The results of the experiment confirmed that the observed fatigue life was within a factor of two when compared with the predicted fatigue life, yet located on the safer side.     

Combination of HAADF‐STEM and ADF‐STEM Tomography for Core–Shell Hybrid Materials

Characterization of core–shell type nanoparticles in 3D by transmission electron microscopy (TEM) can be very challenging. Especially when both heavy and light elements coexist within the same nanostructure, artifacts in the 3D reconstruction are often present. A representative example would be a particle comprising an anisotropic metallic (Au) nanoparticle coated with a (mesoporous) silica shell. To obtain a reliable 3D characterization of such an object, a dose‐efficient strategy is proposed to simultaneously acquire high‐angle annular dark‐field scanning TEM and annular dark‐field tilt series for tomography. The 3D reconstruction is further improved by applying an advanced masking and interpolation approach to the acquired data. This new methodology enables us to obtain high‐quality reconstructions from which also quantitative information can be extracted. This approach is broadly applicable to investigate hybrid core–shell materials.     

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.     

Near‐IR surface‐enhanced Raman spectrum of lignin

Compacted powders of commercially available nano‐ and microparticles of silver were used to successfully induce the surface‐enhanced Raman scattering (SERS) effect in spruce milled‐wood lignin (MWL). For the two silver particle sizes used in this investigation, the spectra were mostly similar. Some general characteristics of the lignin SERS spectrum are described. The SERS technique was found to be sensitive for detecting lignin. Significant spectral changes were present between the SERS and normal Raman spectra of MWL. The SERS spectrum was assigned on the basis of literature‐reported vibrational assignments of lignin and its models. Based on significant changes in Raman features, we propose that the lignin is strongly adsorbed on silver. To determine whether SERS of lignin can be obtained directly from wood without its isolation, Wiley‐milled spruce wood (WMW) adsorbed on silver was studied. The results indicated that not only the surface‐enhancement effect was successfully induced in the WMW, but that its spectrum was similar to MWL SERS. Moreover, for WMW, no signals from the carbohydrate components were observed, and therefore, lignin was detected selectively. This nano‐ and microparticle‐based molecularly specific method is expected to make a significant contribution in identifying and investigating lignin in various lignin‐containing materials. Published in 2009 by John Wiley & Sons, Ltd.     

Optimization of extinction efficiency of gold‐coated polystyrene bead substrates improves surface‐enhanced Raman scattering effects by post‐growth microwave heating treatment

We report a novel post‐growth microwave treatment approach to selectively modify the surface morphologies of gold (Au) films coated on the polystyrene (PS) bead substrates for effectively improving the surface‐enhanced Raman scattering (SERS) effect on the analytes. The discrete dipole approximation (DDA) model was introduced to evaluate the enhancement effects by calculating the localized electromagnetic field distribution and extinction efficiency based on the sizes of the trenches and voids, and the surface roughness of the modified Au–PS bead substrates. The SERS performance of microwave‐modified Au–PS substrates on rhodamine 6G (Rh 6G) and saliva yields at least 10‐fold improvements in SERS intensities compared to the as‐grown substrates, which is also in agreement with theoretical predictions by DDA modeling. This work demonstrates both experimentally and theoretically the efficacy of the microwave heating treatment on modifying the Au–PS bead substrates for the realization of high SERS performance in biomedical applications. Copyright © 2009 John Wiley & Sons, Ltd.     

Synchrotron‐radiation‐based X‐ray micro‐computed tomography reveals dental bur debris under dental composite restorations

Dental burs are used extensively in dentistry to mechanically prepare tooth structures for restorations (fillings), yet little has been reported on the bur debris left behind in the teeth, and whether it poses potential health risks to patients. Here it is aimed to image dental bur debris under dental fillings, and allude to the potential health hazards that can be caused by this debris when left in direct contact with the biological surroundings, specifically when the debris is made of a non‐biocompatible material. Non‐destructive micro‐computed tomography using the BioMedical Imaging & Therapy facility 05ID‐2 beamline at the Canadian Light Source was pursued at 50 keV and at a pixel size of 4 µm to image dental bur fragments under a composite resin dental filling. The bur's cutting edges that produced the fragment were also chemically analyzed. The technique revealed dental bur fragments of different sizes in different locations on the floor of the prepared surface of the teeth and under the filling, which places them in direct contact with the dentinal tubules and the dentinal fluid circulating within them. Dispersive X‐ray spectroscopy elemental analysis of the dental bur edges revealed that the fragments are made of tungsten carbide–cobalt, which is bio‐incompatible.     

Real‐time image‐content‐based beamline control for smart 4D X‐ray imaging

Real‐time processing of X‐ray image data acquired at synchrotron radiation facilities allows for smart high‐speed experiments. This includes workflows covering parameterized and image‐based feedback‐driven control up to the final storage of raw and processed data. Nevertheless, there is presently no system that supports an efficient construction of such experiment workflows in a scalable way. Thus, here an architecture based on a high‐level control system that manages low‐level data acquisition, data processing and device changes is described. This system is suitable for routine as well as prototypical experiments, and provides specialized building blocks to conduct four‐dimensional in situ, in vivo and operando tomography and laminography.     

Evaluation of the improved three‐dimensional resolution of a synchrotron radiation computed tomograph using a micro‐fabricated test pattern

A micro test pattern prepared by focused ion beam milling was used to evaluate the three‐dimensional resolution of a microtomograph at the BL20B2 beamline of SPring‐8. The resolutions along the direction within the tomographic slice plane and perpendicular to it were determined from the modulation transfer functions. The through‐plane resolution perpendicular to the tomographic slice was evaluated to be 8 µm, which corresponds to the spatial resolution of two‐dimensional radiographs. In contrast, the in‐plane resolution within the slice was evaluated to be 12 µm. Real‐space interpolation was performed prior to the tomographic reconstruction, giving an improved in‐plane resolution of 8.5 µm. However, the 8 µm pitch pattern was resolved in the interpolated slice image. To reflect this result, another resolution measure from the peak‐to‐valley difference plot was introduced. This resolution measure gave resolution limits of 7.4 µm for the in‐plane direction and 6.1 µm for the through‐plane direction. The three‐dimensional test pattern along with the interpolated reconstruction enables the quantitative evaluation of the spatial resolution of microtomographs.     

Chemical analysis of very small‐sized samples by wavelength‐dispersive X‐ray fluorescence

The chemical characterisation of very small‐sized samples is often of major interest in forensic analysis, studies of artworks, particulate matter on filters, raw materials impurities, and so on, although it generally poses considerable problems owing to the difficulty of obtaining precise and accurate results. This study was undertaken to develop a set of methods for the chemical characterisation of very small‐sized samples by wavelength‐dispersive X‐ray fluorescence. To conduct the study, sample preparation (as beads and pellets) and measurement conditions were optimised to reach the necessary detection and quantification limits and to obtain the appropriate measurement uncertainty for characterising the types of materials involved. The measurements were validated by using reference materials. Three test methods were developed. In two methods, the samples were prepared in the form of beads (one method being for geological materials and the other for the analysis of nongeological materials such as particulate matter on filters, glasses, frits, and ceramic glazes and pigments). In the third method, the samples were prepared in the form of pellets for the analysis of volatile elements in geological materials. In the three methods, detection limits, quantification limits and measurement uncertainties were obtained similar to those found when a bead or pellet is prepared by the usual methods from 0.5 g sample. However, in this study, sample size was between 30 and 40 times smaller in the case of beads and 100 times smaller in the case of pellets, thus broadening the range of possible wavelength‐dispersive X‐ray fluorescence applications in the chemical characterisation of materials. Copyright © 2012 John Wiley & Sons, Ltd.     

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.     

Amorphous BeN as a new solid host for rare‐earth‐related luminescent materials

Beryllium‐nitride (BeN) thin films were prepared by sputtering a Be target in an atmosphere of pure nitrogen. The films were doped with samarium simply by placing a piece of Sm metal on the surface of the Be target. Under these deposition conditions the films present an amorphous structure and an optical bandgap of approx. 4 eV. They also exhibit visible light emission due to Sm³⁺ ions as a result of either photon or electron excitation. The present experimental results show that amorphous BeN films are suitable, and efficient, III‐nitride hosts for rare‐earth doping purposes. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Fast and accurate X‐ray fluorescence computed tomography imaging with the ordered‐subsets expectation maximization algorithm

The ordered‐subsets expectation maximization algorithm (OSEM) is introduced to X‐ray fluorescence computed tomography (XFCT) and studied; here, simulations and experimental results are presented. The simulation results indicate that OSEM is more accurate than the filtered back‐projection algorithm, and it can efficiently suppress the deterioration of image quality within a large range of angular sampling intervals. Experimental results of both an artificial phantom and cirrhotic liver show that with a satisfying image quality the angular sampling interval could be improved to save on the data‐acquisition time when OSEM is employed. In addition, with an optimum number of subsets, the image reconstruction time of OSEM could be reduced to about half of the time required for one subset. Accordingly, it can be concluded that OSEM is a potential method for fast and accurate XFCT imaging.     

Morphological,Structural, and Compositional Evolution of Pt–Ni Octahedral Electrocatalysts with Pt‐Rich Edges and Ni‐Rich Core: Toward the Rational Design of Electrocatalysts for the Oxygen Reduction Reaction

The progress in colloidal synthesis of Pt–Ni octahedra has been instrumental in rising the oxygen reduction reaction catalytic activity high above the benchmark of Pt catalysts. This impressive catalytic performance is believed to result from the exposure of the most active catalytic sites after an activation process, chemical or electrochemical, which leads to a Pt surface enrichment. A foremost importance is to understand the structure and the elemental distribution of Pt–Ni octahedral, which leads to an optimal catalytic activity and stability. However, the factors governing the synthesis of the Pt–Ni octahedra are not well understood. In this study, unprecedented surface atomic segregation of Pt atoms in a Ni‐rich Pt–Ni octahedral nanoparticle structure is established by advanced electron microscopy. The Pt atoms are almost exclusively located on the edges of the Pt–Ni octahedra. This structure is formed in a pristine form, i.e., prior to any chemical or electrochemical etching. A new growth mechanism is revealed, which involves the transformation from an octahedron with a Pt‐rich core to a Ni‐rich octahedron with Pt‐rich edges. This observation may pave the way for a deeper understanding of this class of Pt–Ni octahedral nanoparticles as an electrocatalyst.     

DNA‐Mediated Stabilization of Self‐Assembling Bead Monolayers for Microfluidic Applications

Forming ordered 2D or 3D arrays of colloidal particles on the micro‐ or nanometer scale in a bottom‐up process is a challenging task. In previous works by various groups, hybridization between DNA strands localized on the particle surface is used to create crystalline arrays. However, this method requires an annealing process with a duration of one day or more and usually yields agglomerates of only a few dozen particles. In this work, a method for the rapid formation of highly‐ordered 2D agglomerates of superparamagnetic microparticles (beads) is presented. Dipolar coupling between the beads under the influence of a rotating magnetic field leads to the formation of a dense monolayer. The monolayer is then stabilized through DNA hybridization between DNA strands immobilized on the bead surface and a linker strand in solution. The whole self‐assembly process requires less than an hour and is therefore significantly faster than comparable methods.     

Template‐Free Fabrication of Mesoporous Hollow ZnMn2O4 Sub‐microspheres with Enhanced Lithium Storage Capability towards High‐Performance Li‐Ion Batteries

In this work, we rationally designed an efficient template‐free synthetic strategy to fabricate hierarchical mesoporous hollow ZnMn₂O₄ sub‐microspheres (HZSMs) constructed entirely from nanoparticle (NP) building blocks of size ≈15 nm. The well‐known inside‐out Ostwald ripening process was tentatively proposed to shed light on the formation mechanism of the mesoporous hollow nano‐/microarchitecture. In favor of the intrinsic structural advantages, these resulting HZSMs exhibited superior electrochemical lithium‐storage performance with high specific capacity, excellent cyclability, and good rate capability when evaluated as an anode material for advanced Li‐ion batteries (LIBs). The excellent electrochemical performance should be reasonably ascribed to the porous and hollow structure of the unique HZSMs with nanoscale subunits, which reduced the diffusion length for Li⁺ ions, improved the kinetic process and enhanced the structural integrity with sufficient void space for tolerating the volume variation during the Li⁺ insertion/extraction. These results further revealed that the as‐prepared mesoporous HZSMs would be a promising anode for high‐performance LIBs.     

On the correlation between the X‐ray absorption chemical shift and the formal valence state in mixed‐valence manganites

Here the correlation between the chemical shift in X‐ray absorption spectroscopy, the geometrical structure and the formal valence state of the Mn atom in mixed‐valence manganites are discussed. It is shown that this empirical correlation can be reliably used to determine the formal valence of Mn, using either X‐ray absorption spectroscopy or resonant X‐ray scattering techniques. The difficulties in obtaining a reliable comparison between experimental XANES spectra and theoretical simulations on an absolute energy scale are revealed. It is concluded that the contributions from the electronic occupation and the local structure to the XANES spectra cannot be separated either experimentally or theoretically. In this way the geometrical and electronic structure of the Mn atom in mixed‐valence manganites cannot be described as a bimodal distribution of the formal integer Mn³⁺ and Mn⁴⁺ valence states corresponding to the undoped references.     

On aberrations in saw‐tooth refractive X‐ray lenses and on their removal

The X‐ray lens, which is composed of opposing canted saw‐tooth structures, originally assembled from cut‐out pieces from long‐playing records, is understood by recognizing that an incident plane X‐ray wave will traverse a varying number of triangular prisms in them. The refraction will deflect any beam towards the prism tips and the variation of the deflection angle, which grows linearly with the number of traversed prisms, can result in X‐ray focusing. The structure offers focusing flexibility by simply changing the taper angle. This report will discuss the aberrations arising in the saw‐tooth structure in its simplest form with identical prisms. It is found that the saw‐tooth structures in low‐Z materials with focal length below 1 m provide less flux density in the focal spot than stacks of one‐dimensionally focusing refractive lenses with identical transmission function. This is due to excessive aberrations in the regular structure, which are absent in stacks of concave lenses, and which limit the focusing to spot sizes of just submicrometre dimensions, as measured experimentally for some lenses. It will be shown that this limitation can be overcome by appropriately modifying the prism shape. Then the image size could be reduced by about an order of magnitude to the diffraction limit with competitive numbers even below 0.1 µm. Microfabrication techniques are identified as the appropriate means for producing the structures.     

Hybrid Comminution with High‐Pressure Roller and Stirred Bead Milling

This paper presents the experimental results on the wet grinding of a moist calcium carbonate material in a hybrid comminution system, which consists of a high pressure roller mill (HPRM) and a subsequent stirred bead mill. The results show that the pre‐treatment of the material with the HPRM could result in energy saving and efficient size reduction during the subsequent wet ultra‐fine grinding in the stirred bead mill. It was found that the level of fineness of the ground product is dramatically influenced by the number of repeat passes of pre‐grinding in the HRPM. The formation of micro‐cracks in the particles under compressive loads was discussed in order to elucidate the role of the HRPM as a pre‐grinder in the hybrid comminution system. The simulated breakage behaviors of various irregular shaped particles indicate that the tortuous micro‐crack propagation paths and the crack branching behavior are related to the heterogeneity of the particle and the stress distributions.     

Rapid atto‐molar level detection of surface‐enhanced Raman spectroscopy technique based on glycidyl methacrylate–ethylene dimethacrylate (GMA–EDMA) porous material

A novel miniature device for rapid ultra‐sensitive surface‐enhanced Raman scattering (SERS) detection was developed in the present study. The device was made of a syringe, a piece of filter, and a Teflon tube. Therefore, it was with advantages of simplicity, miniaturization, and easy operability. The tube was filled in advance with the glycidyl methacrylate‐ethylene dimethacrylate powder porous material which has been proved to increase the sensitivity of normal SERS dramatically, then the mixture solution containing the analyte, silver colloid, and NaCl solution passed through the porous material by the action of the syringe. SERS signals were collected from the surface of the material. Rhodamine 6G (R6G), p‐aminothiophenol (PATP), and thiabendazole (TBZ) were employed as the probe molecules in the present work. R6G at microlitre‐scale can be detected at an extremely low concentration of 10^–18 mol/l, and the relative standard deviation of spot to spot is 14.16% at the intensity of the band at 609 cm⁻¹. The concentrations of PATP and TBZ that can be detected with the method are 10⁻¹¹ mol/l and 1.3 × 10⁻⁶ mol/l, respectively. This method not only has achieved the ultra‐sensitive detection of dye and pesticide but also realized the simple, rapid, and small sample quantity requirement detection, and it is of great potential use for lots of analytes. Copyright © 2013 John Wiley & Sons, Ltd.