Transmission electron microscopy characterization of spark plasma sintered ZrB2 ceramic

Microstructures of ZrB₂ ceramics consolidated by hot-pressing and spark plasma sintering were investigated by transmission electron microscopy (TEM), combining energy dispersive X-ray spectroscopy (EDX). The microstructures of both ceramics were compared. Amount of impurities was lower for ZrB₂ consolidated by spark plasma sintering than for hot-pressed ZrB₂. In particular, oxygen impurity was not detected even at the grain-boundaries in ZrB₂ consolidated by spark plasma sintering. The cleaning effect generated on the powder surfaces during spark plasma sintering cycle was displayed. In addition, dislocations were present only in the spark plasma sintered ZrB₂ ceramic, as a result of localized high stresses.     

Influence of TiN dopant on microstructure of TiB2 ceramic sintered by spark plasma

In this study, the impact of TiN as a sintering aid on the relative density and microstructure of TiB₂ ceramic was investigated. Monolithic TiB₂ and TiB₂ doped with 5?wt% TiN were sintered at 1900?°C for 7?min dwell time under the pressure of 40?MPa by spark plasma. The addition of TiN affected the microstructure of TiB₂-based sample considerably depicting the finer grains in the as-sintered ceramic. X-ray diffraction evaluation indicated that no interaction occurred between the initial materials. However, detail investigation by the map analysis and energy dispersive spectroscopy results revealed the formation of in-situ nano-sized hBN secondary phase in the TiN-doped TiB₂. In addition, TiN played a remarkable role on increasing the relative density of TiN-doped TiB₂ ceramic producing a nearly fully dense ceramic with relative density of 99.9% in comparison with the monolithic ceramic having 96.7% relative density.     

Transmission electron microscopy of supported molybdenum and vanadium oxides

Transmission electron microscopy has been used to characterize dispersions of molybdena and vanadia on titania and silica supports. When silica spheres of controlled morphology were used as support, the dispersed monolayer phase of both oxides could be imaged due to characteristic changes in contrast. In addition to the dispersed phase, we could detect three-dimensional crystallites of V₂O₅ but in the case of MoO₃ only two-dimensional islands were seen. On Degussa P-25 titania, there was no observable contrast change due to the presence of a monolayer of these dispersed oxides. However, exposure to the electron beam caused dramatic changes in the surface texture of the support. Such changes were not seen when blank TiO₂ was similarly irradiated. These e-beam induced changes were more pronounced in the vanadia/titania catalysts leading to formation of 1–3 nm clusters of reduced VO _x . However, on the MoO₃/TiO₂ sample, e-beam exposure caused only a pronounced change in texture but no well defined clusters could be detected.     

Growth of carbon nanofibers from the iron-copper catalyzed decomposition of CO/C2H4/H2 mixtures

The growth of carbon nanofibers from Fe-Cu catalyzed decomposition of CO/C₂H₄/H₂ mixtures at temperatures over the range 500-650 °C has been investigated. Based on analysis of the gas phase and solid products it is apparent that co-adsorption of CO and C₂H₄ induces major perturbations in the surfaces of the bimetallic catalyst particles. These features are reflected in an increase in the yield of solid carbon and subtle changes in the structural characteristics of the carbon nanofibers. Optimum performance with respect to the yield of carbon nanofibers is found for iron-rich particles treated in CO/C₂H₄/H₂ (1:3:1) at 600 °C. Deactivation of the catalyst is observed to occur with high Cu concentrations and at reaction temperatures in excess of 600 °C. It is suggested that under these conditions the surface of the particles in contact with the reactant gas mixture become enriched in Cu, which does not possess the ability to dissociatively chemisorb either CO or C₂H₄.     

Electrochemical behavior of C60 films and C60/lipid films in ionic liquids

Cyclic voltammograms (CVs) of C₆₀ films and C₆₀ embedded in cast films of triple-tailed cationic surfactant solutions and salt-free zero-charged cationic/anionic (catanionic) surfactant vesicles on glassy carbon electrode in a typical room-temperature ionic liquid (RT-IL), 1-n-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF₆]), were examined. CVs show typically electrochemical oxidation and reduction. The salt-free zero-charged catanionic surfactant bilayer vesicles were determined by freeze-fracture transmission electron microscopy (FF-TEM) images and small-angle X-ray scattering (SAXS) measurements. The cast films of the salt-free zero-charged catanionic surfactant vesicles incorporated C₆₀ molecules were employed to study the electrochemical properties in RT-ILs, which would open new fields for the bulk electronic properties of fullerenes or their derivatives in ionic liquids.     

Phase analysis and wear behavior of in-situ spark plasma sintered Ti3SiC2

In-situ synthesis of dense near-single phase Ti₃SiC₂ ceramics from 3Ti/SiC/C/0.15Al starting powder using spark plasma sintering (SPS) at 1250 °C is reported. Systematic analysis of the phase development over a range of sintering temperatures (1050–1450 °C) suggested that solid state reactions between intermediate TiC and Ti₅Si₃ phases lead to the formations of Ti₃SiC₂. The effect of starting powder composition on phase development after SPS at 1150 °C was also investigated using three distinct compositions (3Ti/SiC/C, 2Ti/SiC/TiC, and Ti/Si/2TiC). The results indicate that the starting powder compositions, with higher amounts of intermediate phase such as TiC, favor the formation of Ti₃SiC₂ at relatively lower sintering temperature. Detailed analysis of wear behavior indicated that samples with higher percentage of TiC, present either as an intermediate phase or a product of Ti₃SiC₂ decomposition, exhibited higher microhardness and better wear resistance compared to near single phase Ti₃SiC₂.     

Effects of TaSi2 addition on room temperature mechanical properties of ZrB2-20SiC composites

The effects of TaSi₂ addition on the room temperature mechanical properties of ZrB₂–20SiC (volume fraction, %) composite were investigated. Dense ZrB₂–20SiC-xTaSi₂ (x?=?3, 6, 10) composites were prepared by hot pressing the mixture of ZrB₂, SiC and TaSi₂ powders at 1850–1900?°C under 30?MPa in flowing Ar. In the as-prepared composites, apart from ZrB₂, SiC and TaSi₂, (Zr,Ta)B₂ solid solution also existed around ZrB₂ grains. It became a continuous layer and the thickness increased gradually with the increase of TaSi₂ content. When the addition of TaSi₂ was within the range of 3–10%, Vickers hardness of ZrB₂–20SiC reduced slightly by about 1–2?GPa, but the flexural strength and fracture toughness increased simultaneously by more than 35%. These phenomena could be attributed to the relatively low hardness of TaSi₂, and the decrease of ZrB₂ grain size as well as the presence of a continuous (Zr,Ta)B₂ solid solution layer around ZrB₂ grains.     

Characterizing herring bone structures in carbon nanofibers using selected area electron diffraction and dark field transmission electron microscopy

The use of selected area electron diffraction and centered dark field imaging using a transmission electron microscope is demonstrated for studying the herringbone structure of carbon nanofibers (CNFs). The experimental method is described and illustrated with CNFs that were grown via a chemical vapor deposition method with a nickel catalyst. It is demonstrated that this method gives the angle of the herringbone with great accuracy and gives insight into the uniformity of graphitic elements in the herringbone structure. It was found that the Ni catalyst could be removed from the fiber-tips by treatment in HNO₃, without affecting the carbon structure. These electron microscopy results were confirmed by XRD. The parameters that can be determined by application of this characterization method are expected to be useful to study and optimize growth conditions for carbon nanofibers grown by chemical vapor deposition.     

Formation, densification, and selected mechanical properties of hot pressed Al4SiC4, Al4SiC4 with 30 vol.% WC, and Al4SiC4 with 30 vol.% TiC

Powders of Al₄C₃ and SiC were combined by high-energy milling to produce Al₄SiC₄, Al₄SiC₄ + 30 vol.% TiC, and Al₄SiC₄ + 30 vol.% WC. Five different temperatures were used to hot press the constituents. XRD, SEM, relative density, and hardness measurements showed that formation of single-phase Al₄SiC₄ occurred at 1450 °C and full densification (99%) was achieved at 1500 °C. Both of these temperatures are lower than previously reported. Adding TiC and WC increases hardness, while WC improves densification (99.5%).     

Isothermal titration calorimetry, transmission electron microscopy, and field emission scanning electron microscopy of a main-chain viologen polymer containing bromide as counterions

The interaction of a main-chain viologen polymer containing bromide as counterions with water and aqueous potassium bromide over a broad range of concentrations was studied with isothermal titration calorimetry. The dilution process of this polymer was endothermic as opposed to flexible poly(sodium acrylate) and poly(sodium styrenesulfonate). This result may be related to the different mechanism of hydration of pyridinium and bromide groups in the main chain. It also exhibited aggregation phenomenon in both water and aqueous potassium bromide solutions as detected by transmission electron microscopy like other flexible and rigid-rod polyelectrolytes. As the polymer concentrations in aqueous solutions increase, the aggregated polymer exhibited more defined ordered structures than random structures observed at low polymer concentrations. Field emission scanning electron microscopy also revealed the effect of variation of concentration of aqueous potassium bromide on the morphology of the polymer matrix. At increasing concentrations of aqueous potassium bromide, the polymer structures became more ordered than those in low concentrations.     

Visualizing dispersion morphology via ultra-rapid freezing/transmission electron microscopy

Optical microscopy has been a useful technique for visualizing aqueous dispersions, but it lacks the high resolution available with transmission electron microscopy (TEM). In order to withstand the vacuum of the electron microscope, water-based systems must be either dried or frozen, but this distorts morphology. The ultra-rapid freezing technique can be used in such studies to preserve microstructure and also be compatible with the vacuum of the electron microscope. Also known as cryo-TEM, this technique has been used in coatings research to visualize the morphologies of a variety of aqueous dispersions. Besides being consistent with what we already know optically, these complementary techniques of ultra-rapid freezing and transmission electron microscopy now permit us a unique view of fluid microstructure far below the limit of optical microscopy.     

Transmission electron microscopy study of room temperature cured PMMA grafted natural rubber toughened epoxy/layered silicate nanocomposite

Abstract

A morphological study was conducted on ternary systems containing epoxy, poly(methyl methacrylate) grafted natural rubber and organic chemically modified montmorillonite (Cloisite 30B), using TEM. The following four materials were prepared at room temperature: cured unmodified epoxy, cured toughened epoxy, cured unmodified epoxy/Cloisite 30B nanocomposites and cured toughened epoxy/Cloisite 30B nanocomposites. Mixing process was performed by mechanical stirring. Poly(etheramine) was used as the curing agent. The detailed TEM images revealed cocontinuous and dispersed spherical rubber in the epoxy–rubber blend, suggesting a new proposed mechanism of phase separation. High magnification TEM analysis showed good interactions between rubber and Cloisite 30B in the ternary system. In addition, it was found that rubber particles could enhance the separation of silicate layers.     

Preparation and characterization of CNTs-TiO2 composites

Carbon nanotubes-based TiO₂ composites were fabricated by hydrolysis, and the transmission electron microscopy(TEM) results showed that carbon nanotubes were partly coated with TiO₂. X-ray photoelectron spectroscopy (XPS) results of purified carbon nanotubes indicated that there were some polar oxygenated groups such as C-O, C=O and O-C=O which might stimulate formation of the composites, and enhance the interfacial combination of TiO₂ with carbon nanotubes. The formation of TiO₂ and its compounding with CNTs happened almost simultaneously in this process. The method is a convenient route to fabricate CNTs-based TiO₂ composites with different ratios.     

Carbon nanotubes as a template for mild synthesis of magnetic CoFe2O4 nanowires

Hundred nanometers outer diameter multi-walled carbon nanotubes have been used as suitable host template for synthesizing CoFe₂O₄ nanowires encapsulated inside nanotubes under mild conditions, i.e. 100 °C and atmospheric pressure, with a high filling yield of the nanotubes, using an aqueous nitrate precursor solution and the confinement effect provided by the surrounding walls. The formation of caps near the tube tips at the beginning of the nitrate decomposition led to consider each nanotube as a closed nanoreactor, in which the reaction conditions could be far different from the macroscopic conditions outside the tube. The structure of the CoFe₂O₄ nanowires could be continuously changed from a disordered hair-like dendritic structure at 100 °C to highly crystallized domains when increasing the temperature. A material with high coercivity at room temperature for small particles of about 25 nm in diameter was obtained by submitting the nanowires to an Ar treatment at 550 °C for 2 h.     

TEM and electron tomography studies of carbon nanospheres for lithium secondary batteries

The structure of carbon nanospheres of 100-200 nm diameter, which showed superior high-speed charge-discharge behavior as the negative electrode in a lithium ion battery, was investigated with XRD, SEM and TEM with an electron tomography attachment. Observation of carbon 0 0 2 lattice images, as well as electron diffraction patterns, illustrated that heterogeneous microtexture was formed as the polyhedronization of the particle proceeded with heat-treatment. The outside region of the particle heat-treated at 2800 °C has stacking structure of aromatic layers with some distribution of d₀₀₂, while the center region consisted of non-graphitic. Structure defects seemed to be concentrated along the ridgelines of the polyhedronized particles after heat-treatment. The electron tomography technique clarified the morphology of the graphitized particles, although the images should be understood with other crystallographic measurements. A slice image computed in the 3D-reconstruction process showed the inner texture of the graphitized particles more clearly than the conventional TEM bright-field image.     

Synthesis and characterization of polycrystalline Mo2BC ceramic

Single-phase polycrystalline Mo₂BC ceramic bulks were synthesized successfully from molybdenum, boron, and graphite powders using the spark plasma sintering method. Herein, it was established that the synthesis temperature of the Mo₂BC ceramic could be as low as 1300 °C. Transmission electron microscopy (TEM) characterization confirmed that the crystal structure of the Mo₂BC ceramic was comparable to that of the MoAlB ceramic. The Vickers hardness of the Mo₂BC ceramic was measured to be 18.1 GPa. Additionally, the compressive strength, flexural strength, and fracture toughness were determined to be 1.74 GPa, 457.72 MPa, and 3.26 MPa· m^1/2, respectively. The Mo₂BC bulk exhibited typical brittle features, in which intergranular and transgranular fractures were the main failure modes.     

New acrylic monolithic carbon molecular sieves for O2/N2 and CO2/CH4 separations

The modification of activated carbon fibres prepared from a commercial textile acrylic fibre into materials with monolithic shape using phenolic resin as binder was studied. The molecular sieving properties for the gas separations CO₂/CH₄ and O₂/N₂ were evaluated from the gas uptake volume and selectivity at 100 s contact time taken from the kinetic adsorption curves of the individual gases. The pseudo-first order rate constant was also determined by the application of the LDF model. The samples produced show high CO₂ and O₂ rates of adsorption, in the range 3-35 × 10⁻³ s⁻¹, and in most cases null or very low adsorption of CH₄ and N₂ which make them very promising samples to use in PSA systems, or similar. Although the selectivity was very high, the adsorption capacity was low in certain cases. However, the gas uptake in two samples reached 23 cm³ g⁻¹ for CO₂ and 5 cm³ g⁻¹ for O₂, which can be considered very good. The materials were heat-treated using a microwave furnace, which is a novel and more economic method, when compared with conventional furnaces, to improve the molecular sieves properties.     

Influence of rare earth Tb4O7 addition on the densification,abrasion resistance and microstructure of alumina ceramics

This study aimed to improve the purity and performance of alumina ceramics used as ball milling media. High-alumina ceramics (>?96?wt% Al₂O₃), with high densification and excellent abrasion resistance, were fabricated by the cold isostatic pressing method. The effects of adding the rare earth Tb₄O₇ on the densification, abrasion resistance, crystalline phase, micro-morphology and grain size of the ceramics were studied. The experiment results showed that the densification and abrasion resistance of the samples increased with Tb₄O₇ addition. The sample with 0.8?wt% Tb₄O₇ sintered at 1625?°C exhibited the best performance, with a linear shrinkage, relative density and abrasion rate of 22.28%, 95.70% and 0.103‰^, respectively. The abrasion resistance improved by 27.5% compared with the sample without Tb₄O₇. X-ray diffraction analysis indicated that the primary phases of the samples were corundum, spinel, CaAl₁₂O₁₉ and α-quartz, and a small quantity of Tb₃Al₅O₁₂ was generated when more than 0.4?wt% Tb₄O₇ was added. Furthermore, some Mg²⁺ and Ca²⁺ ions in the liquid phases dissolved into Tb₃Al₅O₁₂ crystalline grains during the sintering process, which enhanced the grain boundary cohesion of the materials. Scanning electron microscopy indicated that the existence of Tb₃Al₅O₁₂ at grain boundaries reduced the average size of the corundum grains. This helped transform inter-granular fractures into trans-granular fractures, thereby improving the abrasion resistance of the ceramic materials.     

Discrimination of B–C–N nanotubes through energy-filtering electron microscopy

Various multi-walled nanotubes in the B–C–N system are thoroughly investigated using a JEOL-3100FEF high-resolution field emission transmission electron microscope operating at 300 kV and equipped with an in-column built Omega filter. Spatially-resolved B, C and N elemental maps of the nanotubes are constructed. It is realized that a wide variety of tubular arrays composed of B, C and N atoms may exist in the system. Sandwich-like BN-rich and C-rich alternating tubular shells, graphitic C layers inside and outside of pure BN shells induced either by surface contamination, or electron beam irradiation, separation of C-rich and BN-rich tubes and/or BN particles within tubular bunches may take place. One should carefully take these effects into account while analyzing nanotube physical properties, e.g., electrical or optical, rather than simply rely on electron energy loss spectra typically collected from B, C and N containing nanostructures as a whole. Striking dependence of an individual nanotube electrical conductivity on tubular shell chemistry is demonstrated using I–V curve recording in an atomic force microscope.     

Transmission Electron Microscopy Study on the Annealing of YBa2Cu3O7-δ

Annealing in oxygen-rich atmosphere at temperatures between 400° and 600°C is an important step in the manufacture of superconducting YBa₂Cu₃O_7-δ. The symmetry of the orthorhombic phase requires that if more than one type of twin plane is present within a grain, a distorted region should exist inside the multiple twinned grain. This distorted region hinders the tetragonal-to-orthorhombic transformation and may account for some retained tetragonal phase inside an otherwise orthorhombic grain. A physical model is presented describing the formation of such regions and their eventual transformation into low-angle grain boundaries after long annealing. Extended annealing at intermediate temperatures apparently leads to the formation of planar faults in off-stoichiometric samples. Transmission electron microscope image contrast and energy dispersive X-ray analyses of highly defective regions suggest these defects are CuO _x ( x = 1, 2) extra layers. These extra layers tend to form near grain boundaries or free surfaces, where oxygen is readily available.