Electron and light microscopy studies on the domain structures of Zn3B7O13Cl, Zn3B7O13Br and Zn3B7O13I ferroic boracites

The domain structures of Zn₃B₇O₁₃Cl, Zn₃B₇O₁₃Br and Zn₃B₇O₁₃I boracite single crystals were studied by means of polarized light in conjunction with electron microscopy. Single crystals of the three compositions were grown by chemical transport reactions in closed quartz ampoules, at a temperature of 900 °C and were examined by polarizing optical microscopy (PLM), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). For both PLM and SEM, the same as‐grown samples were used without having to resort to metallization of the crystal faces. For TEM the single crystals were crushed and mounted on holey carbon films. Comparative electron microscope images were useful for revealing the domain structure of these ferroelectric/ferroelastic materials previously observed between the crossed polars of an optical microscope. X‐ray diffraction analysis of the pulverized crystals was performed for this triad of halogen boracites containing zinc as a common metal.     

结晶釉的研究进展

简述了结晶釉在国内外的发展状况,着重介绍了硅锌矿结晶釉。特别介绍了一些硅锌矿结晶釉的氧化物添加剂及其对硅锌矿结晶釉影响机理的研究,并用几张结晶釉的偏光显微照片展示了硅锌矿结晶釉在显微分析方面的研究进展。     

Structural analyses of Nd-doped CeO2 thin films deposited by pulsed laser deposition

CeO₂ thin films doped with neodymium oxides for application to gas sensors have been elaborated by the pulsed laser deposition technique. The films were deposited on orientated Si (100) substrates with variable deposition times (t = 90, 180 and 360 s) and molar fractions of Nd₂O₃ (0, 6.5, 15, 21.5 and 27 at.%). The resulting Nd–CeO₂ thin films were characterized by means of X‐ray diffraction analysis, scanning electron microscopy and transmission electron microscopy equipped with EDS (Energy Dispersive Spectrometer) microanalysis. From X‐ray diffraction analyses, it is clearly established that the texture is modified by Nd additions. The preferred (111) orientations of the CeO₂ crystals change into the (200) orientation. The morphology of the CeO₂ grains changes from triangles, for pure CeO₂ thin films, to spherical grains for Nd‐doped films. In addition, cell parameter analyses from X‐ray diffraction data show that a partial chemical substitution of Ce by Nd should occur in the face‐centred cubic lattice of ceria: this should give rise to Ce_1‐xNd_xO_2?z phases with oxygen non‐stoichiometry.     

Comparative study on the Ru ware,Ru-type ware of Qingliangsi kiln and celadon of Zhanggongxiang kiln

Thirty-three porcelain shards (28 Ru ware and 5 Ru-type ware) unearthed from Qinglingsi kiln and 31 celadon fragments from Zhanggongxiang kiln were studied systematically for tracing their correlation and difference in glaze and body characteristics through a variety of characterisation methods. Samples without HF corrosion were applied to achieve the microstructure and composition details by SEM and TEM. Results exhibited that there were certain similarities between Ru ware, Ru-type ware and Zhanggongxiang kiln celadon in glaze colour and thickness, body features, fracture structure; however, they showed obvious differences in body thickness, chemical composition of glaze and body, phase constituents and microstructure of glaze. Plentiful needle-like diopside were widely distributed in Zhanggongxiang kiln celadon glazes, while this type of crystals was only existed in few Ru and Ru-type ware glazes with small content. Besides, a large amount of residual quartz was present over the Ru ware glazes, which could have relation to the incorporation of agate. The liquid-liquid phase separation structure (Ca-rich droplets and Si-rich matrix) was generated within the interspaces of anorthite clusters or around the brims of anorthite needles or columns. The occurrence of phase separation was generally accompanied by Al₂O₃ consumption, but suppressed in the areas far from anorthite due to the rise of Al₂O₃ content, indicating that Al₂O₃ was the most sensitive constituent for this glaze behaviour. The distinguished size, shape and distribution of phase-separated droplets or interconnected structures were closely associated with the scale and crowding level of anorthite crystallisation.     

A vacuum-compatible wet-specimen chamber for compact X-ray microscopy

Soft X‐ray microscopy is a powerful tool for investigations of, for example, polymers or soils in their natural liquid environment. This requires a wet‐specimen chamber. Compact X‐ray microscopy allows the horizontal mounting of such samples, thereby reducing the influence of gravitational forces. We have developed a wet‐specimen chamber for such compact X‐ray microscope. The chamber is vacuum compatible, which reduces the exposure time. The vacuum sealing is achieved by a combination of mechanical sealing and sealing by bio‐compatible glue. With the wet‐specimen chamber the specimens can be kept in an aqueous environment in a vacuum of 10⁻⁴ mbar for several hours. Imaging of lipid droplets in water demonstrates the function of the wet‐specimen chamber.     

Influence of Ca content and oxygen partial pressure on microstructural evolution of (Co,Ca)O at elevated temperatures

Ca‐doped (1, 1.7, 5 and 10 mol% CaO) cobalt oxide single‐crystal samples, with an [001] orientation, were annealed at elevated temperatures of 1000–1200 °C for different times and at different oxygen partial pressures. The microstructure was examined by means of transmission light and electron microscopy. High‐temperature X‐ray diffractometry was used, with the aim of determining the temperature of the CoO ? Co₃O₄ transition in these materials. Extensive precipitation of Ca‐free Co₃O₄ spinel crystals was observed with increasing Ca content and oxygen activity. It is suggested that the electrical conductivity changes in this material may be related to this precipitation, because it changes the electronic state of cobalt cations.     

Structural investigations on green culms and charcoal of Bambusa multiplex

Green culms of Bambusa multiplex and the bamboo charcoal carbonized from the green culms at 700°C have been studied by means of X‐ray diffraction, X‐ray fluorescent element analysis, analytical scanning electron microscopy, and analytical scanning transmission electron microscopy (STEM), aiming at industrial applications as raw materials for functional devices and substances. It is revealed that the green culms and the charcoal contain a significant amount of Si, in particular, ～18 wt % in the skin. The green culms comprise amorphous and crystalline celluloses. The charcoal has a so‐called amorphous structure which is composed of randomly distributed carbon nanotubes and fibers. The growth of Ag‐doped activated charcoal powders that were produced by two different methods using this charcoal powder has also been studied.     

Simultaneous phase and amplitude extraction from a single defocused image of a homogeneous object

We demonstrate simultaneous phase and amplitude extraction from a single defocused image of a homogeneous object. Subject to the assumptions explicitly stated in the derivation, the algorithm solves the twin‐image problem of in‐line holography and is capable of analysing data obtained using X‐ray microscopy, electron microscopy, neutron microscopy or visible‐light microscopy, especially as they relate to defocus and point projection methods. Our simple, robust, non‐iterative and computationally efficient method is applied to data obtained using an X‐ray phase contrast ultramicroscope.     

Microstructural characterization of Ti‐6Al‐4V alloy subjected to the duplex SMAT/plasma nitriding

In this study, microstructural characterization of Ti‐6Al‐4V alloy, subjected to the duplex surface mechanical attrition treatment (SMAT)/nitriding treatment, leading to improve its mechanical properties, was carried out through novel and original samples preparation methods. Instead of acid etching which is limited for morphological characterization by scanning electron microscopy (SEM), an original ion polishing method was developed. Moreover, for structural characterization by transmission electron microscopy (TEM), an ion milling method based with the use of two ions guns was also carried out for cross‐section preparation. To demonstrate the efficiency of the two developed methods, morphological investigations were done by traditional SEM and field emission gun SEM. This was followed by structural investigations through selected area electron diffraction (SAED) coupled with TEM and X‐ray diffraction techniques. The results demonstrated that ionic polishing allowed to reveal a variation of the microstructure according to the surface treatment that could not be observed by acid etching preparation. TEM associated to SAED and X‐ray diffraction provided information regarding the nanostructure compositional changes induced by the duplex SMAT/nitriding process. Microsc. Res. Tech. 76:897–903, 2013. © 2013 Wiley Periodicals, Inc.     

Morphological studies of pseudowollastonite for biomedical application

Pseudowollastonite ceramic (psW) composed of CaO·SiO₂ was found to be bioactive in a simulated body fluid environment. The chemical reaction initiated at the material surface resulted in hydroxyapatite (HA)formation. These bone-bonding properties are essential for securing the necessary physico-chemical integration of the material with living bone. Materials behaving in this way can be considered for potential biomedical application as bone tissue substitute for a natural bone repair or replacement as implant. A mechanism of hydroxyapatite formation on pseudowollastonite ceramics surface was investigated during exposure to a simulated body fluid (SBF) for a period of 3 weeks. Morphology and structure of the surface product and its original substrate was examined by thin-film X-ray diffraction, scanning electron microscopy and high-resolution transmission electron microscopy. HA crystals were found to form on an amorphous silica intermediate layer. (100) lattice planes of HA were resolved and identified. Concentration of ions in the SBF and pH of the SBF were monitored throughout the exposure. Additional pH measurements were made at the interface of psW with SBF. The HA formation occurred when there was a sudden increase of pH from 7·25 to 10·5 at the interface of psW with SBF as a result of ionic exchange between 2H⁺ and Ca²⁺ within the psW network. This ionic exchange transformed the psW crystals into an amorphous silica phase. The appropriate pH and the ion concentrations were essential for partial dissolution of the amorphous silica phase and subsequent precipitation of a Ca-P rich phase which then transformed to HA.     

A method for determining void arrangements in inverse opals

The periodic arrangement of voids in ceramic materials templated by colloidal crystal arrays (inverse opals) has been analysed by transmission electron microscopy. Individual particles consisting of an approximately spherical array of at least 100 voids were tilted through 90° along a single axis within the transmission electron microscope. The bright‐field images of these particles at high‐symmetry points, their diffractograms calculated by fast Fourier transforms, and the transmission electron microscope goniometer angles were compared with model face‐centred cubic, body‐centred cubic, hexagonal close‐packed, and simple cubic lattices in real and reciprocal space. The spatial periodicities were calculated for two‐dimensional projections. The systematic absences in these diffractograms differed from those found in diffraction patterns from three‐dimensional objects. The experimental data matched only the model face‐centred cubic lattice, so it was concluded that the packing of the voids (and, thus, the polymer spheres that composed the original colloidal crystals) was face‐centred cubic. In face‐centred cubic structures, the stacking‐fault displacementvector is . No stacking faults were observed when viewingthe inverse opal structure along the orthogonal <110>‐type directions, eliminating the possibility of a random hexagonally close‐packed structure for the particles observed. This technique complements synchrotron X‐ray scattering work on colloidal crystals by allowing both real‐space and reciprocal‐space analysis to be carried out on a smaller cross‐sectional area.     

Reductive performance of ZVI/Cu polyscale particle to decolorize reactive black 5

Based on direct reducing of copper ions by commercially available zero valent iron (ZVI), ZVI/Cu polyscale particles with high activation are synthesized and exhibit significant removal efficiency for reactive black (RB) dye. The ZVI/Cu polyscale particles could maintain a good performance for RB removal at a wide pH range of 3.0–9.0. Different from the mineralization process of other organic pollutants in ZVI/Cu system, the degradation kinetics of RB could be described well by novel pseudo‐second kinetic models. Results of scanning electron microscopy (SEM), X‐ray fluorescence elemental analysis (EDX), and X‐ray diffraction (XRD) show the planting Cu has deposited on the surface of Fe⁰. The characterization of ZVI/Cu particles and RB solution before and after degradation reveals that decolorization of RB is not only resulted from the reduction process including direct reduction by accepting electrons from Fe⁰ oxidation and indirect reduction by atomic hydrogen generated on the ZVI/Cu surface, but also the oxidation of hydroxyl radicals in the mineralization procedure of RB dye.     

Is Scanning Electron Microscopy/Energy Dispersive X‐ray Spectrometry (SEM/EDS) Quantitative?

Scanning electron microscopy/energy dispersive X‐ray spectrometry (SEM/EDS) is a widely applied elemental microanalysis method capable of identifying and quantifying all elements in the periodic table except H, He, and Li. By following the “k‐ratio” (unknown/standard) measurement protocol development for electron‐excited wavelength dispersive spectrometry (WDS), SEM/EDS can achieve accuracy and precision equivalent to WDS and at substantially lower electron dose, even when severe X‐ray peak overlaps occur, provided sufficient counts are recorded. Achieving this level of performance is now much more practical with the advent of the high‐throughput silicon drift detector energy dispersive X‐ray spectrometer (SDD‐EDS). However, three measurement issues continue to diminish the impact of SEM/EDS: (1) In the qualitative analysis (i.e., element identification) that must precede quantitative analysis, at least some current and many legacy software systems are vulnerable to occasional misidentification of major constituent peaks, with the frequency of misidentifications rising significantly for minor and trace constituents. (2) The use of standardless analysis, which is subject to much broader systematic errors, leads to quantitative results that, while useful, do not have sufficient accuracy to solve critical problems, e.g. determining the formula of a compound. (3) EDS spectrometers have such a large volume of acceptance that apparently credible spectra can be obtained from specimens with complex topography that introduce uncontrolled geometric factors that modify X‐ray generation and propagation, resulting in very large systematic errors, often a factor of ten or more. SCANNING 35: 141‐168, 2013. ¹ Published 2012 Wiley Periodicals, Inc.     

Study of two tungstates Ca0.5Cd0.5WO4 and Ca0.2Cd0.8WO4 by transmission electron microscopy

To better understand the role of crystal structures and local disorder in the photonic properties of the system (1 ? x)CaWO₄ ? xCdWO₄ with 0 < x < 1, two specific phases with compositions x = 0.5 (scheelite phase) and 0.8 (wolframite phase) have been studied by scanning and transmission electron microscopies. High‐resolution electron microscopy images and image simulations, associated with X‐ray diffraction data, allowed confirming the lattices and space groups I4₁/a and P2/c of the two scheelite and wolframite phases, at the local scale. The electron microscopy data show the existence of a high degree of crystallization associated with statistical distribution of Ca or Cd atoms on a Ca_1?xCd_x site in each lattice.     

Size-selective colloidal-gold localization in transmission X-ray microscopy

Colloidal gold is a useful marker for functional‐imaging experiments in transmission X‐ray microscopy. Due to the low contrast of gold particles with small diameters it is necessary to develop a powerful algorithm to localize the single gold particles. The presented image‐analysis algorithm for identifying colloidal gold particles is based on the combination of a threshold with respect to the local absorption and shape discrimination, realized by fitting a Gaussian profile to the identified regions of interest. The shape discrimination provides the possibility of size‐selective identification and localization of single colloidal gold particles down to a diameter of 50 nm. The image‐analysis algorithm, therefore, has potential for localization studies of several proteins simultaneously and for localization of fiducial markers in X‐ray tomography.     

Wavelet-based image restoration for compact X-ray microscopy

Compact water‐window X‐ray microscopy with short exposure times will always be limited on photons owing to sources of limited power in combination with low‐efficency X‐ray optics. Thus, it is important to investigate methods for improving the signal‐to‐noise ratio in the images. We show that a wavelet‐based denoising procedure significantly improves the quality and contrast in compact X‐ray microscopy images. A non‐decimated, discrete wavelet transform (DWT) is applied to original, noisy images. After applying a thresholding procedure to the finest scales of the DWT, by setting to zero all wavelet coefficients of magnitude below a prescribed value, the inverse DWT to the thresholded DWT produces denoised images. It is concluded that the denoising procedure has potential to reduce the exposure time by a factor of 2 without loss of relevant image information.     

Comparative analysis of isolated cellular organelles by means of soft X-ray contact microscopy with laser-plasma source and transmission electron microscopy

Soft X‐ray contact microscopy (SXCM) is, at present, a useful tool for the examination at submicrometre resolution of biological systems maintained in their natural hydrated conditions. Among current X‐ray‐generating devices, laser‐plasma sources are now easily available and, owing to their pulse nature, offer the opportunity to observe living biological samples before radiation damage occurs, even if the resolution achievable is not as high as with synchrotron‐produced X‐rays. To assess the potential of laser‐plasma source SXCM in the study of cellular organelles, we applied it for the analysis of chloroplasts extracted from spinach leaves and mitochondria isolated from bovine heart and liver. X‐ray radiation was generated by a nanosecond laser‐plasma source, produced by a single shot excimer XeCl laser focused onto an yttrium target. The images obtained with SXCM were then compared with those produced by transmission electron microscopy observation of the same samples prepared with negative staining, a technique requiring no chemical fixation, in order to facilitate their interpretation and test the applicability of SXCM imaging.     

The effect of an Ni–Cr protective layer on cyclic oxidation of Ti3Al

The effect of an 80Ni?20Cr (at.%) metallic coating on the cyclic oxidation behaviour of a Ti₃Al‐based alloy with the composition Ti?25Al?11Nb (at.%) was investigated in this study. Cyclic oxidation tests were carried out in air at 600 °C and 900 °C for 120 h. For one cycle test, the specimens were held for 24 h at test temperature and then furnace‐cooled to room temperature. The oxidation rate was determined by plotting the mass gain per unit surface area of the specimen vs. exposure time. The morphology and composition of the oxidation products were characterized on the cross‐section of the specimens by scanning electron microscopy, energy‐dispersive X‐ray spectroscopy and atomic force microscopy. The oxidation scale forms during exposure at both 600 °C and 900 °C. TiO₂ is the main oxide component, whereas the Al₂O₃ layer appears only discontinuously. The remarkable improvement in oxidation resistance at 900 °C was attributed to the chemical composition and structure of the scale formed on the 80Ni?20Cr coating.     

Use of EBSD to study electropulsing induced reverse phase transformations in a Zn-Al alloy (ZA22)

Multi‐phase identification and phase transformations in electropulsing treated Zn–Al based alloy wire specimens were studied using electron back‐scattered diffraction, back‐scattered scanning electron microscopy and X‐ray diffraction techniques. By using electron back‐scattered diffraction, two phases: η′_S and η′_T with a small difference of about 1% in lattice parameters (c₀/a₀) were identified, based on the determined lattice parameters of the phases, and the reverse eutectoid phase transformations: η′_T+?′_T+α′_T→η′_S and ?+α→T′+η were successfully detected. Electron back‐scattered diffraction appeared to be an effective technique for studying complex electropulsing induced phase transformations.     

Crystal orientation mapping of NiO grown on cube textured Ni tapes

Samples of cube textured Ni tapes were oxidized in flowing oxygen at different temperatures. Crystal orientation maps (COMs) of the resulting oxide layers were produced by electron backscatter diffraction. The oxide layers were also analysed by X‐ray diffraction (XRD), scanning electron microscopy and atomic force microscopy (AFM). The oxide grain size of a sample oxidized at 600 °C was similar to that of the substrate and the oxide was highly textured, both indicating epitaxial growth. The orientation relationship between the substrate and the oxide was directly observed from XRD to be (111)_NiO//(001)_Ni, [01]_NiO//[110]_Ni with four, equivalent, in‐plane variants. In each variant, the oxide has both <110>‐ and <211>‐type directions parallel to the Ni <110> directions. Differences in oxide thickness and surface roughness on neighbouring grains were revealed by AFM and these were attributed to the existence of a range of oxide growth conditions resulting from small differences in the orientation of each substrate grain. Similar macrotexture and microstructure were observed on a sample oxidized at 1300 °C, but additional, facetted oxide crystals had formed at the oxide grain boundaries. COMs showed that these crystals were either cube or 45° rotated cube orientated, a texture different to that of the large oxide grains. The grain boundary crystals were thought to form by inward diffusion of oxygen at defects in the growing oxide scale.