Characterization of a Co-CoO obliquely evaporated magnetic tape by analytical electron microscopy and electron holography.

The microstructure and magnetic domain structure of a Co-CoO obliquely evaporated tape for magnetic recording are studied by analytical electron microscopy and electron holography, respectively. While the existence of Co and CoO crystallites is confirmed by energy-filtered electron diffraction, columnar structure of the Co crystallites surrounded by the densely packed CoO crystallites is visualized by an elemental mapping method with electron energy loss spectroscopy, and the crystal orientation relation among the Co crystallites is clarified by high-resolution electron microscopy. It is found that the neighboring Co crystallites have close crystal orientations. On the other hand, electron holography reveals the magnetic flux distribution in a thin section of the tape. Although there exists the background resulting from the effect of inner potential with thickness variation, the distribution of lines of magnetic flux is found to correspond well to the recorded pattern.     

Localization and chemical forms of cadmium in plant samples by combining analytical electron microscopy and X-ray spectromicroscopy

Cadmium (Cd) is a metal of high toxicity for plants. Resolving its distribution and speciation in plants is essential for understanding the mechanisms involved in Cd tolerance, trafficking and accumulation. The model plant Arabidopsis thaliana was exposed to cadmium under controlled conditions. Elemental distributions in the roots and in the leaves were determined using scanning electron microscopy coupled with energy dispersive X-ray microanalysis (SEM-EDX), and synchrotron-based micro X-ray fluorescence (μ-XRF), which offers a better sensitivity. The chemical form(s) of cadmium was investigated using Cd L_III-edge (3538 eV) micro X-ray absorption near edge structure (μ-XANES) spectroscopy. Plant μ-XANES spectra were fitted by linear combination of Cd reference spectra. Biological sample preparation and conditioning is a critical point because of possible artifacts. In this work we compared freeze-dried samples analyzed at ambient temperature and frozen hydrated samples analyzed at −170 °C. Our results suggest that in the roots Cd is localized in vascular bundles, and coordinated to S ligands. In the leaves, trichomes (epidermal hairs) represent the main compartment of Cd accumulation. In these specialized cells, μ-XANES results show that the majority of Cd is bound to O/N ligands likely provided by the cell wall, and a minor fraction could be bound to S-containing ligands. No significant difference in Cd speciation was observed between freeze-dried and frozen hydrated samples. This work illustrates the interest and the sensitivity of Cd L_III-edge XANES spectroscopy, which is applied here for the first time to plant samples. Combining μ-XRF and Cd L_III-edge μ-XANES spectroscopy offers promising tools to study Cd storage and trafficking mechanisms in plants and other biological samples.     

Thin dielectric film thickness determination by advanced transmission electron microscopy.

High-resolution transmission electron microscopy (HR-TEM) has been used as the ultimate method of thickness measurement for thin films. The appearance of phase contrast interference patterns in HR-TEM images has long been confused as the appearance of a crystal lattice by nonspecialists. Relatively easy to interpret crystal lattice images are now directly observed with the introduction of annular dark-field detectors for scanning TEM (STEM). With the recent development of reliable lattice image processing software that creates crystal structure images from phase contrast data, HR-TEM can also provide crystal lattice images. The resolution of both methods has been steadily improved reaching now into the sub-Angstrom region. Improvements in electron lens and image analysis software are increasing the spatial resolution of both methods. Optimum resolution for STEM requires that the probe beam be highly localized. In STEM, beam localization is enhanced by selection of the correct aperture. When STEM measurement is done using a highly localized probe beam, HR-TEM and STEM measurement of the thickness of silicon oxynitride films agree within experimental error. In this article, the optimum conditions for HR-TEM and STEM measurement are discussed along with a method for repeatable film thickness determination. The impact of sample thickness is also discussed. The key result in this article is the proposal of a reproducible method for film thickness determination.     

Ultrasoft magnetic films investigated with Lorentz tranmission electron microscopy and electron holography.

As a tribute to the scientific work of Professor Gareth Thomas in the field of structure-property relationships this paper delineates a new possibility of Lorentz transmission electron microscopy (LTEM) to study the magnetic properties of soft magnetic films. We show that in contrast to the traditional point of view, not only does the direction of the magnetization vector in nano-crystalline films make a correlated small-angle wiggling, but also the magnitude of the magnetization modulus fluctuates. This fluctuation produces a rapid modulation in the LTEM image. A novel analysis of the ripple structure in nano-crystalline Fe-Zr-N film corresponds to an amplitude of the transversal component of the magnetization deltaMy of 23 mT and a longitudinal fluctuation of the magnetization of the order of deltaMx = 30 mT. The nano-crystalline (Fe99Zr1)1-xNx films have been prepared by DC magnetron reactive sputtering with a thickness between 50 and 1000 nm. The grain size decreased monotonically with N content from typically 100 nm in the case of N-free films to less than 10 nm for films containing 8 at%. The specimens were examined with a JEOL 2010F 200 kV transmission electron microscope equipped with a post column energy filter (GIF 2000 Gatan Imaging Filter). For holography, the microscope is mounted with a biprism (JEOL biprism with a 0.6 microm diameter platinum wire).     

Metallo‐supramolecular micelles: Studies by analytical ultracentrifugation and electron microscopy

In aqueous solutions, amphiphilic block copolymers in which a polystyrene (PS) segment is connected to a poly(ethylene oxide) (PEO) block via a bis(2,2′:6′,2″‐ terpyridine ruthenium) complex can form micelles. Such micelles of the protomer type PS₂₀‐[Ru]‐PEO₇₀, according to the preparation procedure representing frozen micelles, were studied by sedimentation velocity and sedimentation equilibrium analysis in an analytical ultracentrifuge and by transmission electron microscopy, with different techniques applied for the sample preparation. The particles obtained were surprisingly multifarious in size. In ultracentrifugation experiments performed at relatively low salt concentrations, the distributions of the sedimentation coefficient s_20,w showed a pronounced peak at 9.6 S and a broad, only partly separated second peak around 14 S. The molar mass of the particles at the peak was around 430,000 g/mol, corresponding to an aggregation number of approximately 85. The average hydrodynamic diameter of the particles in the peak fraction was approximately 13 nm. In electron micrographs of negatively stained samples, spheres of diameters between 10 and 25 nm were the most abundant particles, but larger ones with a wide size range were also visible. The latter particles apparently were composed of smaller ones. The data from both sedimentation analysis and electron microscopy showed that (1) the studied compound formed primary micelles of diameters around 20 nm and (2) the primary micelles had a tendency toward aggregation. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3159–3168, 2003     

Elucidating a particulate matter deposition episode by combining scanning electron microscopy and X-ray fluorescence spectrometry.

Multielemental composition and morphology of particulate matter samples were examined to detect the presence of two potential responsible pollutant emitters at four sites impacted during a pollution episode in the City of Campana, Argentina. Coke and smoke black are the main constituents associated to the industrial plants that were considered, a priori, as responsible pollutant emitters. Wavelength dispersive X-ray fluorescence (WDXRF) was employed for the analysis of metals in samples coming from both, suspected sources and four sites. On the basis of multielemental composition profiles, a screening analysis was undertaken for exploring similarities among sources and sample sites adopting the average concentration profile of the crustal rock as soil surrogate. Particle morphology was studied by scanning electron microscopy (SEM) in source samples and in those environmental samples selected through the screening analysis. Two types of collected samples were analyzed: 1) those with composition profiles closer to the potential sources and 2) those closer to the cluster rock. This strategy was adequate to identify the responsible source of the contamination episode.     

Characterization of palladium nanoparticles by using X-ray reflectivity, EXAFS, and electron microscopy

We compared the characteristics of dodecanethiolate palladium nanoparticles synthesized by two different techniques, a one-phase method and a two-phase method. From transmission electron microscopy (TEM), we determined that the particle sizes were 46 +/- 10 angstroms and 20 +/- 5 angstroms for the one- and two-phase particles, respectively. Electron diffraction confirmed that their structure was face-centered cubic (fcc). The lattice constant a0 was 3.98 +/- 0.01 angstroms and 3.90 +/- 0.01 angstroms for the one- and two-phase particles, respectively. High-resolution TEM (HRTEM) showed that the one-phase particles had an ordered core surrounded by a disordered shell structure, while the two-phase particles appeared to be crystalline throughout. The particles were also analyzed with extended X-ray absorption fine structure (EXAFS). A cuboctahedral fcc model was used to fit the data, which implied particle sizes of less than 10 angstroms for both the one- and two-phase particles. The discrepancy between the two techniques was attributed to the presence of a disordered phase, which we presumed was composed of Pd-S compounds. Compared with the bulk palladium, lattice expansion was observed in both one- and two-phase particles by electron diffraction, HRTEM, and EXAFS. At the air/water interface, a uniform film that produced surface pressure/area isotherms could only be obtained from the two-phase particles. The one-phase particles did not wet the water surface. X-ray reflectivity data indicated that the Langmuir monolayer of the two-phase particles was only 13 angstroms thick. TEM revealed the diameter of the particles in this layer to be 23 angstroms; hence the particles assumed an oblate structure after spreading. EXAFS examination of a stack of 750 Langmuir monolayers indicated far fewer Pd-S compounds, which may have dissolved in the water. The data were consistent with a model of a monolayer of truncated cuboctahedron Pd particles that were 7 angstroms thick and 19 angstroms in diameter.     

Structure of low-density nanoporous dielectrics revealed by low-vacuum electron microscopy and small-angle X-ray scattering

Aerogels (AGs) are ultralow-density nanoporous solids that have numerous potential applications. However, as most AGs are strong insulators with poor mechanical properties, direct studies of the complex nanoporous structure of AGs by methods such as atomic force and conventional scanning electron microscopy (SEM) have not proven feasible. Here, we use low-vacuum SEM to image directly the ligament and pore size and shape distributions of representative AGs over a wide range of length scales (approximately 100-105 nm). The structural information obtained is used for unambiguous, real-space interpretation of small-angle X-ray scattering curves for these complex nanoporous systems. Low-vacuum SEM permits imaging of both cross-sections and skin layers of AG monoliths. Images of skin layers reveal the presence of microcracks, which alter the properties of cast monolithic AGs.     

Polymer electrostatics: detection and speciation of trapped electric charges by electric probe and analytical electron microscopy

This work reviews new probe and electron microscopy approaches for the detection of charged domains in insulating polymers, as well as for the identification of the charge-bearing species: scanning electric potential microscopy (SEPM), electric force microscopy (EFM) and energy-loss spectroscopy imaging in the transmission electron microscope (ESI-TEM). The SEPM and EFM micrographs show patterned domains bearing excess electric charges and extending for tens of nanometers, in polymer latex particles and films. The charged species are identified by ESI-TEM as emulsion polymerization initiator and surfactant residues, as well as the associated counter-ions. Charged domains are also observed in common thermoplastic polymers, producing unexpectedly large electric potential gradients.     

Bio-functionalization of monodisperse magnetic nanoparticles and their use as biomolecular labels in a magnetic tunnel junction based sensor

Monodisperse magnetic nanoparticles (NPs) could enable the ultra-sensitive magnetic detection of biological analytes. However, rendering these particles biocompatible has remained a challenge. We report the bio-functionalization and detection of 12-nm manganese ferrite NPs. We have achieved the site-specific binding of biotin-functionalized NPs onto avidin-patterned silicon oxide substrates and DNA-functionalized NPs onto complementary DNA-patterned silicon oxide substrates. Utilizing scanning SQUID microscopy, we show that these substrate-bound NPs retain their magnetic properties. Finally, we demonstrate a novel method of detecting either protein binding or DNA hybridization at room temperature using the NPs and a magnetic tunnel-junction-based biosensor situated in orthogonal magnetic fields.     

Crystalline properties and morphological changes in plastically deformed isotatic polypropylene evaluated by X-ray diffraction and transmission electron microscopy

The isotatic polypropylene (i-PP) plastically deformed by uniaxial plane strain compression was investigated using X-ray diffraction and transmission electron microscopy. The apparent crystallinity was evaluated by means of X-ray diffraction with a profile matching using a FULLPROF code. Two crystalline phases, α and β, were identified in the non-deformed polymer as well as with an amorphous halo. The deformation with 3, 10 and 100 MPa, induces an increase of the amorphous halo. The microstructural orientation of the i-PP, before and after deformation was evaluated using the “Quantikov” image analysis of transmission electron microscopy (TEM) data. The non-deformed material presents spherulitic structure, without any preferential orientation. The high resolution, in the nanometer scale, shows two preferential orientation axes. The deformation at 3, 10 and 100 MPa, affects the spherulitic, as well as, the lamellae structure, introducing fiber orientation, a break up of the lamellae in to small blocks and consequently amorphization of the system.     

扫描电镜-能谱法测定生活饮用水中石棉

建立了扫描电镜-能谱法(SEM-EDS)测定生活饮用水中石棉(≥10μm)的方法,使用场发射扫描电镜可对宽度大于0.050~0.124μm的石棉纤维进行定性和计数。若生活饮用水中存在以藻类为主的有机质干扰,使用紫外-过硫酸钾消解可消除相应干扰。配置低、中、高3个浓度的石棉悬浊液模拟水样交由国内不同地区的6家实验室进行方法学验证,结果表明,方法实验室内RSD为10%~37%,实验室间RSD为10%~39%,蓝藻干扰消除实验回收率平均值为98.1%,RSD为11%。方法检出限为5.0×10^4~11.6×10^4个/L,低于GB 5749限量规定的700×10^4个/L。     

Characterization of chromodulin by X-ray absorption and electron paramagnetic resonance spectroscopies and magnetic susceptibility measurements

The biologically active form of the essential trace element chromium is believed to be the oligopeptide chromodulin. Chromodulin binds four chromic ions before binding at or near the active site of activating insulin receptor and subsequently potentiating the tyrosine kinase activity of the receptor. Charge balance arguments and preliminary spectroscopic studies suggested that the chromic centers might be part of a multinuclear assembly. Using a combination of X-ray absorption and electron paramagnetic resonance spectroscopies and variable-temperature magnetic susceptibility measurements, we found that holochromodulin is shown to possess an antiferromagnetically coupled trinuclear assembly which probably weakly interacts with a fourth chromium center. The chromium centers possess octahedron coordination comprised of oxygen-based ligation, presumably derived primarily from oligopeptide-supplied carboxylate groups. X-ray absorption data cannot be reproduced with the presence of sulfur atom(s), indicating that the cysteine thiolate group does not coordinate to the chromium centers. Thus, chromodulin possesses a unique type of multinuclear assembly, distinct from those known in other bioinorganic systems.     

Morphological and crystalline studies of isotactic polypropylene plastically deformed and evaluated by small-angle X-ray scattering, scanning electron microscopy and X-ray diffraction

Morphological and structural properties of isotactic polypropylene (i-PP) submitted to uniaxial plane strain deformation at ambient temperature with compression pressures of 3, 10 and 20 MPa, were investigated using wide angle X-ray diffraction (WAXD), small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM) and scanning electron microscopy (SEM). Two kinds of samples were studied, namely: sample A: Mw = 117,400 g/mol Mn = 17,300, Mw/Mn = 6.8 and sample B: Mw = 271,000 g/mol Mn = 43,700 Mw/Mn = 6.2, both with isotactic content = 95%. Crystalline α- and β-phases are clearly identified by WAXD. The lamellar long period, as well as, the crystalline and amorphous lamellar thickness for the non-deformed samples measured by SAXS indicates the presence of a more symmetric spherulitic structure for sample A, while the sample B displays anisotropic scattering. The WAXD study of the apparent relative crystallinity and the orientation of crystallites, revealed that plastic deformation of i-PP by plane-strain compression, leads to preferred orientation of main axis of crystallites at relatively early stage of the deformation process induced a monocrystal texture and an excellent molecular alignment along the FD, in both samples. The SEM evaluation shows that a gradual change occurs in the spherulitic structure and seems to transform gradually and disappear almost for the 37% deformations. The sample with highest deformation shows thin shear bands oriented along the FD-view which originate an appearance of a layered structure. Concomitantly the crystalline lamellae were detected by TEM technique.     

Three-dimensional morphological characterization of optic nerve fibers by atomic force microscopy and by scanning electron microscopy.

A comparative study of scanning electron microscopy (SEM) and atomic force microscopy (AFM) imaging of the healthy human optic nerve was carried out to determine the similarities and the differences. In this study we compared the fine optic nerve structures as observed by SEM and AFM. The fibers of the right optic nerve of a 61-year-old man show different arrangements in transverse sections taken from the same individual 5 mm central to the optic canal and 5 mm peripheral to the optic chiasma; this difference can be recognized by light microscopy (LM), SEM, and AFM. AFM revealed such typical optic nerve fibers (taken from a point 5 mm central to the optic canal) with annular and longitudinal orientations, which were not visible by SEM in this form. By contrast, LM and SEM visualized other structures, such as pia mater and optic nerve fibers loosely arranged in bundles, none of which was visualized by AFM. The images, however, taken 5 mm peripheral from the optic chiasma show shapeless nerve fibers having a wavy course. Our results reveal that more detailed information on optic nerve morphology is obtained by exploiting the advantages of both SEM and AFM. These are the first SEM and AFM images of healthy human optic nerve fibers, containing clear representations of the three dimensions of the optic nerve.     

First critical steps for understanding complex advanced materials: Synergy between X-ray diffraction and electron microscopy

Attaining novel structures in compounds displaying remarkable properties is the goal of numerous solid-state chemists and physicists. Several approaches for predicting new structures exist but, whatever they are, one of the essential steps is to understand their architecture. It needs to collect the maximum information for deciphering the building code. In this paper, we give a personal account and focus on the powerful synergy of transmission electron microscopy and X-ray diffraction techniques for achieving it. We have chosen the example of the misfit-layered cobaltites, which appear more and more complex as we attain each new level in the hierarchy of their structures. We have limited our illustration to the first period of the misfit cobaltites “research story”, from the discovery of highly complex oxides to the understanding of the architecture building, without reporting on the numerous further papers devoted to iso-structural compounds and to their remarkable properties of thermoelectric power.     

Decomposition of tetraalkylammonium thiotungstates characterized by thermoanalysis, mass spectrometry, X-ray diffractometry and scanning electron microscopy

Thermal decomposition reactions of tetraalkylammonium thiotungstates, (R₄N)₂WS₄ (R = methyl to heptyl), were investigated with DSC and DTA-TG coupled with mass spectroscopy (MS). The results demonstrate that the complexity of thermal decomposition reactions is significantly influenced by the alkyl group, i.e., more complex steps are observed for the materials with longer alkyl chain lengths. Tetraethyl and tetrapropyl complexes show reversible and irreversible phase transitions detected by DSC experiments combined with thermodiffractometry. The tetrapentyl compound undergoes an irreversible phase transition while the tetraheptyl sample exhibits a glass-like transition and melting prior to decomposition. The whole series of compounds decompose without forming sulfur rich WS_n (n = 3 or 4) intermediates. The final WS₂ products are nearly stoichiometric for R = methyl to pentyl but for hexyl and heptyl samples the sulfur content is significantly reduced with a W/S ratio of about 1.5. The residual carbon and hydrogen contents increase in the final decomposition products in the same order as the number of C atoms in R₄N increase. For the N content no clear trend is obvious. A general thermal decomposition mechanism is suggested which follows a bimolecular nucleophilic substitution reaction. In the SEM images only for R = heptyl the formation of macro-pores with a sponge-like morphology is seen, but for the other precursors compact materials are formed which in part display a well developed morphology. X-ray diffraction analysis of the final products shows the formation of amorphous WS₂ up to the tetrapentyl precursor. But for the tetrahexyl and tetraheptyl materials the W:S ratio is significantly smaller than 1:2 and large amounts of C and H are determined by chemical analyses. In accordance with previously reported results it can be assumed that a carbosulfide phase is formed by a mixed C-W-S sandwich layered structure.     

Evolution of Cu-Zn-Si oxide catalysts in the course of reduction and reoxidation as studied by in situ X-ray diffraction analysis, transmission electron microscopy, and magnetic susceptibility methods

The reduced and reoxidized Cu-Zn-Si oxide catalysts as layered copper-zinc hydroxo silicates with the zincsilite structure were studied using in situ and ex situ X-ray diffraction analysis, transmission electron microscopy, and the temperature dependence of magnetic susceptibility. The catalysts were prepared by homogeneous deposition-precipitation. It was found that Cu⁰ particles were formed on the surface of a layered hydrosilicate with the zincsilite structure upon reduction with hydrogen. The reoxidation of the reduced samples with a mixture of oxygen and an inert gas, which contained no more than 0.05 vol % O₂, resulted in the formation of individual Cu₂O and CuO phases; copper ions did not return to the hydrosilicate structure. Catalytic tests of Cu-Zn-Si catalysts in methanol synthesis indicate that the specific catalytic activity of copper metal particles grows linearly with increasing zinc loading. This fact suggests that copper metal particles, which were obtained by the reduction of Cu²⁺ ions from the copper-zinc hydroxo silicate with the zincsilite structure, were responsible for activity in methanol synthesis. Consequently, the ability to return copper ions to a precursor compound in reoxidation with oxygen at low concentrations, which is known for reduced Cu/ZnO catalysts (these catalysts are highly active in methanol synthesis), is not related to the catalytic activity in methanol synthesis.     

Intact and fragmented triosmium clusters on MgO: characterization by X-ray absorption spectroscopy and high-resolution transmission electron microscopy

Oxidative fragmentation of the clusters Os(3)(CO)(12) adsorbed on MgO powder was investigated by X-ray absorption spectroscopy and scanning transmission electron microscopy (STEM). Exposure of the clusters to air leads to their fragmentation, oxidation of the osmium, and formation of ensembles consisting of three Os atoms. X-ray absorption near-edge spectra demonstrate the oxidative nature of the fragmentation process. Extended X-ray absorption fine structure (EXAFS) spectra indicate an average Os-Os distance of 3.33 Angstrom and an Os-Os coordination number of 2, consistent with the formation of ensembles of three Os atoms on the support. STEM images confirm the presence of such trinuclear ensembles, and the diameters of the observed scattering centers (6.0 Angstrom) match that indicated by the EXAFS results.