Electron microscopy of carbon nanotubes

High-resolution electron microscopy was used to study multiwall carbon nanotubes obtained by the arc-discharge technique and double-and single-wall nanotubes produced by the arc-discharge catalytic synthesis. The structure of conical layer nanotubes obtained by the CVD technique is characterized in detail. It is established that heat treatment of nanotubes gives rise to their structural changes. The structure of nanotubes obtained by carbon evaporation in the N₂-Ar atmosphere under high pressure is determined. A new type of nano-and microtubes with surface-modulated walls is revealed. Possible applications of carbon nanotubes are reviewed.     

Electron microscopy of bismuth oxychloride crystallites

Investigations on the crystal structure and morphology of bismuth oxychloride crystallites as a function of the growth conditions are described. A decrease in the concentration of the reactant or an increase in the temperatur during the reaction improves the crystallinity of the bismuth oxychloride precipitate. The crystallites are usually platelets with the c-axis normal to the crystallite plane.     

Electron microscopy of bulk metallic glass machining chips

Machined Zr_52.5Ti₅Cu_17.9Ni_14.6Al₁₀ bulk metallic glass (BMG) chips were characterized using high resolution electron microscopy. Compared to conventional processing techniques, machining produces very high heating/cooling, and deformation rates. It is therefore of interest to compare structural changes in machining chips with those produced by conventional processing. Large (～1 μm) crystalline grain, residual amorphous region, and phase separation in the amorphous–crystalline transition region were detected in bright field TEM images. Three equilibrium phases, Zr₂Cu, ZrAl₂, and Zr₂Ni, which have been identified in samples undergoing conventional annealing, were revealed from selected area electron diffraction patterns of the chips. High magnification TEM micrographs showed nanocrystallites, about 10 nm in size, in the amorphous–crystalline transition region.     

Electron microscopy methods in studies of cultural heritage sites

The history of the development and application of scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy-dispersive X-ray microanalysis (EDXMA) in studies of cultural heritage sites is considered. In fact, investigations based on these methods began when electron microscopes became a commercial product. Currently, these methods, being developed and improved, help solve many historical enigmas. To date, electron microscopy combined with microanalysis makes it possible to investigate any object, from parchment and wooden articles to pigments, tools, and objects of art. Studies by these methods have revealed that some articles were made by ancient masters using ancient “nanotechnologies”; hence, their comprehensive analysis calls for the latest achievements in the corresponding instrumental methods and sample preparation techniques.     

Thermal transformations of the mineral component of composite biomaterials based on chitosan and apatite

Composite biomaterials based on chitosan and calcium apatite with different chitosan/apatite ratio were prepared by chemical synthesis of apatite in chitosan solution using one‐step co‐precipitation method. Initial and annealed samples were characterized by X‐ray diffraction, FTIR spectroscopy and scanning electron microscopy coupled to energy‐dispersive electron X‐ray spectroscopy. The data obtained suggest that the formation of the calcium‐phosphate mineral in chitosan solution is substantially modulated by the chemical interaction of the components; apparently, a part of calcium is captured by chitosan and does not participate in the formation of the main mineral phase. The apatite in the composite is calcium‐deficient, carbonate‐substituted and is composed of dispersed nano‐sized crystallites, i.e. has properties that closely resemble those of bone mineral. Varying synthesis, drying and lyophilization conditions, the composite materials can be produced with the desirable chitosan/apatite ratio, both in the dense and porous form. The structural analysis of composite samples after annealing at certain temperatures is examined as an approach to elucidate the mechanism of co‐precipitation by one‐step method. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Electron and optical microscopy studies of extraterrestrial minerals in NWA4047 meteorite

Analytical electron microscopy and optical microscopy were used to determine the elemental and mineral composition of NWA4047 meteorite. The meteorite was found in 2005 in Morocco, and in 2006 was preliminary classified as H4‐5 ordinary chondrite. The main crystalline meteorite minerals: olivines, pyroxenes, kamacite and taenite, feldspars, as well as troilite identified in our sample represent extraterrestrial minerals typical of the ordinary chondrite of high iron content. Low‐Ca orthopyroxene called bronzite has been revealed. Single enstatite and clinopyroxene crystals have also been identified. Olivines in the meteorite contain 18 mol% of fayalite. The meteorite is a monomict breccia, in which fragments of petrographic types 4, 5, and 6 are present, with the groundmass being type 4. Some of clasts contain large grains of feldspars and high content of feldspars, which is typical of petrologic type 6. Chemical and mineral composition, petrologic types of chondrules, their abundance and sizes, the presence of troilite‐kamacite veins, and nonoxidised iron phases prove that the chondrite belong to H group, i.e. to the olivine‐bronzite group. Our results show that the NWA4047 meteorite is H4‐6 ordinary chondrite. The weathering grade of the meteorite W0/1 is the same as previously established, but the shock grade S3 seems to be higher in comparison with the previous classification. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Electron microscopy of phase and structural transformations in soft magnetic nanocrystalline Fe-Zr-N films

The effect of deposition conditions (film thickness) on the structure of soft magnetic Fe_80–78Zr₁₀N_10–12 films formed by reactive magnetron deposition on a heat-resistant glass substrate has been investigated by analytical transmission electron microscopy, high-resolution electron microscopy, and diffraction analysis. The processes of evolution of the phase and structural state of films and the film-substrate interface upon annealing in the temperature range of 200–650°C have been analyzed taking into account the thermodynamic, kinetic, and structural factors and the specific features of the nanocrystalline state.     

Study of synthetic hydroxyapatite by the method of high-resolution transmission electron microscopy: Morphology and growth direction

Hydroxyapatite crystals grown from aqueous solutions have been studied by the methods of high-resolution electron microscopy and transmission electron diffraction. Processing of the experimental electron micrographs with the use of the Digital Micrograph program and the study of the corresponding Fourier trans-forms showed that the submicron microcrystals grow mainly along the [0001] direction. The (0001) and the $(01\bar 10)$ planes are perpendicular and parallel to the long edge of the crystals, respectively. The good accord between the experimental electron-microscopy images and the electron microscopy images calculated by the EMS program was attained only for crystals with the thicknesses ranging from one to five lattice periods. This allows us to state that hydroxyapatite grows from aqueous solutions in the form of very thin (with the thickness of the order of several lattice parameters) platelike crystals.     

Three-dimensional reconstruction of a surface based on scanning electron microscopy images

Modern methods of three-dimensional reconstruction of sample surfaces based on scanning electron microscopy images allow one to quantitatively estimate morphological surface characteristics (specifically, parameters of irregularities, volumes of convexities and concavities, etc.). The accuracy of the method is analyzed by an example of commercial and specially prepared test samples. Examples of application to various objects are given.     

Electron microscopy study of an Old Russian (XII century) encolpion cross with black inlay

The phase compositions of the basic material (alloy) of a pre-Mongolian Old Russian encolpion cross found near Suzdal and its black inlay have been investigated by methods of scanning and transmission electron microscopy and energy-dispersive X-ray microanalysis. The cross material is lead–zinc–tin α-bronze, and the black is copper sulfide with lead inclusions. As a result of the corrosion, tin and copper oxides and zinc sulfides, which made the cross dark gray, were formed on its surface. It is shown that the corrosion depth is as large as 50 μm; thus, laps must be prepared to accurately determine the morphology and phase composition of the corrosion layer. Decoration with black was apparently performed by pouring with copper sulfide melt or melting a powder preliminarily placed in grooves forming an image on the surface.     

Electron microscopy study of the microstructure of nanosize MoO<Subscript>3</Subscript> powders

Linear double-chain aggregates and orthogonal superlattices of nanoparticles are observed in nanosize MoO₃ powders treated by vibrationally excited hydrogen molecules. Coiled aggregates of MoO₃ nanoparticles are revealed which, under the action of intense electron irradiation, uncoil and form branched chains.     

Inhibitory effect of polyelectrolytes on crystallization kinetics of hydroxyapatite

Modelling of the biologic materials, well-organized multifunctional structures and systems found in nature has attracted the interest of scientists working in many scientific disciplines. A new and rapidly growing field of biomimetics has stimulated an increased focus on biological materials as the researchers attempt to mimic the features, characteristics and growth of these naturally-occurring materials. This review discusses the principal features of biomineralization in relation to the controlled crystallization of inorganic materials and biomimetic routes to the formation of nanometer hydroxyapatite particles. This approach can be compared with biologic mineralization and has the potential for providing much greater control of particle size and distribution than would conventional methods. The constant-composition method has been used to study the influence of polyelectrolytes on the kinetics of crystal growth of hydroxyapatite (HAP), the thermodynamically most stable calcium phosphate phase, on HAP seed crystals at pH 7.4 and 37 °C. The results indicate that polyelectrolyte concentration and the larger number of negatively charged functional groups markedly affect the growth rate. The fit of the Langmuir adsorption model to the experimental data supports a mechanism of inhibition through molecular adsorption of polymers on the surface of growing crystals. This system may allow insights into biomineralization processes.     

Size distribution of nanoparticle aggregates in an aqueous magnetic fluid based on atomic-force microscopy data

Atomic-force microscopy (AFM) has been applied in a fluid environment to determine the size distribution function of nanoparticle aggregates in an aqueous magnetic fluid with magnetite particles coated by polyacrylic acid for stabilization. It is proposed to use an external magnetic field to anchor aggregates on the substrate. The data are compared with the AFM data for dried precipitates of the system under consideration, formed during evaporation of the liquid carrier under different conditions, as well as with the particle size distribution in the initial system obtained from small-angle X-ray scattering data.     

Nanostructure of plasma-sprayed hydroxyapatite coating

Calcium phosphate coatings were studied by high-resolution transmission microscopy, microdiffraction, and X-ray energy-dispersive spectroscopy. Coatings were prepared by spraying hydroxyapatite targets onto copper, nickel, and chromium substrates and onto NaCl and BaF₂ single crystals in an argon plasma at a gas pressure of ～1 Pa; the sputter power was about 200 W; and the RF-generator frequency was 13.56 MHz. Under the conditions used, thin layers of nanocrystalline hydroxyapatite were formed regardless of the nature of the substrate.     

Electron microscopy studies of epitaxial MgB2 superconducting thin films grown by in situ reactive evaporation

The morphology and chemistry of epitaxial MgB₂ thin films grown using reactive Mg evaporation on different substrates have been characterized by transmission electron microscopy methods. For polycrystalline alumina and sapphire substrates with different surface planes, an MgO transition layer was found at the interface region. No such layer was present for films grown on MgO and 4-H SiC substrates, and none of the MgB₂ films had any detectable oxygen incorporation nor MgO inclusions. High-resolution electron microscopy revealed that the growth orientation of the MgB₂ thin films was closely related to the substrate orientation and the nature of the intermediary layer. Electrical measurements showed that very low resistivities (several μΩ cm at 300 K) and high superconducting transition temperatures (38 to 40 K) could be achieved. The correlation of electrical properties with film microstructure is briefly discussed.     

Electron microscopy of epitaxial structures of pseudobinary A III B V solid solutions and the model of nonequilibrium ordering in epitaxial growth

The results of the electron microscopy studies of self-modulated GaAlAs, GaAsP, and InGaP layers have been generalized, and the laws governing the self-oscillatory growth of these materials have been formulated. The growth characteristics under the autocatalysis conditions were established from a computer simulation of the epitaxial process. It is demonstrated that the autocatalytic model of crystallization corresponds to the experimental characteristics of self-modulation. The anomalies in electron microscopy images of the boundaries were revealed, which can be interpreted only with the invocation of the autocatalytic model. The reliabilities of various theoretical self-modulation models are also discussed.     

Microstructural characterization of CPPD and hydroxyapatite crystal depositions on human menisci

Meniscus is a fibrocartilaginous tissue composed mainly of water and a dense elaborate collagen network with a predominantly circumferential alignment. Crystal formation and accumulation on meniscal tissue is frequently observed especially in elderly. In this study, we used X‐ray diffraction (XRD), FTIR and FT‐Raman for the structural identification of the depositions and Optical microscopy, Scanning Electron microscopy (SEM/EDX) and Atomic Force microscopy (AFM), in order to investigate the structural relationship between the crystal deposits and the collagen fibers of human meniscal tissues. We are reporting on the formation of intercalary “colonies” of Calcium Pyrophosphate Dihydrate (CPPD) crystals with two distinct morphologies corresponding to the monoclinic and the triclinic phase, as well as the formation of micro‐aggregations composed of nano‐crystalline HAP aggregations which are developed along the longitudinal axis of collagen fibers without extensively disturbing the collagens arrangement.     

Electron microscopy investigations on structures of ZrO2‐rich phases in the quasibinary system ZrO2‐Zr3N4

Slowly cooled nitrided zirconia samples were investigated and characterized by means of transmission electron microscopy (TEM). Besides the well‐known different modifications of ZrO₂ some ZrO₂‐rich oxynitride phases could be further found, called β‐type phases. An overview regarding the formation of such different structural modifications could be gained, supported by previously performed measurements using powder X‐ray diffractometry (XRD). Similar to fast cooled nitrided zirconia samples Zr(N,O), the slowly cooled ones also contain different kinds of ZrO₂ precipitates, which can be obviously emphasized by using the methods of diffraction contrast. A super cell was successively built, derived from the unit cells of the β and β′ phase, in order to explain the structure of the observed modulated β″ phase. Agreements from the comparisons between experimental high resolution images and the simulated ones of such modulated structures confirm the suggested starting points. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)