A comparison of calculated and experimental HRTEM images of twinned boron carbide

High resolution TEM images of boron carbide (B13C2) have been recorded and compared with images calculated using the multislice method as implemented by M. A. O'Keefe in the SHRLI programs. Images calculated for the [010] zone, using machine parameters for the JEOL 2000FX AEM operating at 200 keV, indicate that for the structure model of Will et al., the optimum defocus image can be interpreted such that white spots correspond to B12 icosahedra for thin specimens and to low density channels through the structure adjacent to the direct inter-icosahedral bonds for specimens of intermediate thickness (-40 > t > -100 nm). With this information, and from the symmetry observed in the TEM images, it is likely that the (101) twin plane passes through the center of icosahedron located at the origin. This model was tested using the method of periodic continuation. Resulting images compare favorably with experimental images, thus supporting the structural model. The introduction of a (101) twin plane through the origin creates distortions to the icosahedral linkages as well as to the intra-icosahedral bonding. This increases the inequivalence of adjacent icosahedral sites along the twin plane, and thereby increases the likelihood of bipolaron hopping.

HRTEM assessment of Wurtzite and Zinc-Blende phases in GaAs nanowires for optoelectronic devices

Màster en Nanociència i Nanotecnologia. Curs 2007-2008. Directors: Francesca Peiró i Martínez and Jordi Arbiol i Cobos

Evidence of multiwall carbon nanotube deformation caused by poly(3-hexylthiophene) adhesion

We show that when a soft polymer like Poly(3-hexyl-thiophene) wraps multiwall nanotubes by coiling around the main axis, a localized deformation of the nanotube structure is observed. High resolution transmission electron microscopy shows that radial compressions of about 4% can take place, and could possibly lead to larger interlayer distance between the nanotube inner walls and reduce the innermost nanotube radius. The mechanical stress due to the polymer presence was confirmed by Raman spectroscopic observation of a gradual upshift of the carbon nanotube G-band when the polymer content in the composites was progressively increased. Vibrational spectroscopy also indicates that charge transfer from the polymer to the nanotubes is responsible for a peak frequency relative downshift for high P3HT-content samples. Continuously acquired transmission electron microscopy images at rising temperature show the MWCNT elastic compression and relaxation due to polymer rearrangement on the nanotube surface.

Integrated TEM, XRD and electron-microprobe investigation of mixed-layer chlorite smectite from the Point-Sal ophiolite, California

Five basalt samples from the Point Sal ophiolite, California, were examined using HRTEM and AEM in order to compare observations with interpretations of XRD patterns and microprobe analyses. XRD data from ethylene-glycol-saturated samples indicate the following percentages of chlorite in mixed-layer chlorite-smectite identified for each specimen: (i) L2036 almost-equal-to 50%, (ii) L2035 almost-equal-to 70 and 20%, (iii) 1A-13 almost-equal-to 70%, (iv) 1B-42 almost-equal-to 70%, and (v) 1B-55 = 100%. Detailed electron microprobe analyses show that 'chlorite' analyses with high Si, K, Na and Ca contents are the result of interlayering with smectite-like layers. The Fe/(Fe + Mg) ratios of mixed-layer phyllosilicates from Point Sal samples are influenced by the bulk rock composition, not by the percentage of chlorite nor the structure of the phyllosilicate. Measurements of lattice-fringe images indicate that both smectite and chlorite layers are present in the Point Sal samples in abundances similar to those predicted with XRD techniques and that regular alternation of chlorite and smectite occurs at the unit-cell scale. Both 10- and 14-angstrom layers were recorded with HRTEM and interpreted to be smectite and chlorite, respectively. Regular alternation of chlorite and smectite (24-angstrom periodicity) occurs in upper lava samples L2036 and 1A-13, and lower lava sample 1B-42 for as many as seven alternations per crystallite with local layer mistakes. Sample L2035 shows disordered alternation of chlorite and smectite, with juxtaposition of smectite-like layers, suggesting that randomly interlayered chlorite (< 0.5)-smectite exists. Images of lower lava sample 1B-55 show predominantly 14-angstrom layers. Units of 24 angstrom tend to cluster in what may otherwise appear to be disordered mixtures, suggesting the existence of a corrensite end-member having thermodynamic significance.

High-resolution imaging of ordered mixed-layer clays

HRTEM has been used to examine illite/smectite from the Mancos shale, rectorite from Garland County, Arkansas; illite from Silver Hill, Montana; Na-smectite from Crook County, Wyoming; corrensite from Packwood, Washington; and diagenetic chlorite from the Tuscaloosa formation. Thin specimens were prepared by ion milling, ultra-microtome sectioning and/or grain dispersal on a porous carbon substrate. Some smectite-bearing clays were also examined after intercalation with dodecylamine hydrochloride (DH). Intercalation of smectite with DH proved to be a reliable method of HRTEM imaging of expanded smectite, d(001) 16 A which could then be distinguished from unexpanded illite, d(001) 10 A. Lattice fringes of basal spacings of DH-intercalated rectorite and illite/smectite showed 26 A periodicity. These data support XRD studies which suggest that these samples are ordered, interstratified varieties of illite and smectite. The ion-thinned, unexpanded corrensite sample showed discrete crystallites containing 10 A and 14 A basal spacings corresponding with collapsed smectite and chlorite, respectively. Regions containing disordered layers of chlorite and smectite were also noted. Crystallites containing regular alternations of smectite and chlorite were not common. These HRTEM observations of corrensite did not corroborate XRD data. Particle sizes parallel to the c axis ranged widely for each sample studied, and many particles showed basal dimensions equivalent to > five layers. -J.M.H.

High resolution imaging of boron carbide microstructures

Two samples of boron carbide have been examined using high resolution transmission electron microscopy (HRTEM). A hot pressed B13C2 sample shows a high density of variable width twins normal to (10-11). Subtle shifts or offsets of lattice fringes along the twin plane and normal to (10 5) were also observed. A B4C powder showed little evidence of stacking disorder in crystalline regions.

High resolution transmission electron microscopy of the Murchison Carbonaceous Chondrite and the Kenna Ureilite

Fine-grained matrices in carbonaceous chondrites and small, micron-sized inclusions in achondrites can be characterized effectively using high resolution transmission electron micro­scopy (HRTEM).

Structural and textural variations in carbonaceous chondrite matrices

Recent studies of C2 carbonaceous chondrite matrices using high resolu­tion transmission electron microscopy (HRTEM)have shown that structural details of the matrix minerals can be imaged [1-4]. The Murchison and Mighei matrices contain minerals having ordered and disordered mixed-layer structures [1,3,4] in addition to chrysotile- and lizardite-type structures [2].

Characterization of precursors to methanol synthesis catalysts Cu/ZnO system

The composition of a series of hydroxycarbonate precursors to copper/zinc oxide methanol synthesis catalysts prepared under conditions reported as optimum for catalytic activity has been studied. Techniques employed included thermogravimetry (TG), temperature-programmed decomposition (TPD), X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), and Raman and FTIR spectroscopies. Evidence was obtained for various structural phases including hydrozincite, copper hydrozincite, aurichalcite, zincian malachite and malachite (the concentrations of which depended upon the exact Cu/Zn ratio used). Significantly, previously reported phases such as gerhardite and rosasite were not identified when catalysts were synthesized at optimum solution pH and temperature values, and after appropriate aging periods. Calcination of the hydroxycarbonate precursors resulted in the formation of catalysts containing an intimate mixture of copper and zinc oxides. Temperature-programmed reduction (TPR) revealed that a number of discrete copper oxide species were present in the catalyst, the precise concentrations of which were determined to be related to the structure of the catalyst precursor. Copper hydrozincite decomposed to give zinc oxide particles decorated by highly dispersed, small copper oxide species. Aurichalcite appeared to result ultimately in the most intimately mixed catalyst structure whereas zincian malachite decomposed to produce larger copper oxide and zinc oxide grains. The reason for the stabilization of small copper oxide and zinc oxide clusters by aurichalcite was investigated by using carefully selected calcination temperatures. It was concluded that the unique formation of an 'anion-modified' oxide resulting from the initial decomposition stage of aurichalcite was responsible for the 'binding' of copper species to zinc moieties.

A nanometre-scale non-periodic structural variation in high temperature superconducting ceramics and the implications for properties

Non-periodic structural variation has been found in the high Tc cuprates, YBa2Cu3O7-x and Hg0.67Pb0.33Ba2Ca2Cu 3O8+δ, by image analysis of high resolution transmission electron microscope (HRTEM) images. We use two methods for analysis of the HRTEM images. The first method is a means for measuring the bending of lattice fringes at twin planes. The second method is a low-pass filter technique which enhances information contained by diffuse-scattered electrons and reveals what appears to be an interference effect between domains of differing lattice parameter in the top and bottom of the thin foil. We believe that these methods of image analysis could be usefully applied to the many thousands of HRTEM images that have been collected by other workers in the high temperature superconductor field. This work provides direct structural evidence for phase separation in high Tc cuprates, and gives support to recent stripes models that have been proposed to explain various angle resolved photoelectron spectroscopy and nuclear magnetic resonance data. We believe that the structural variation is a response to an opening of an electronic solubility gap where holes are not uniformly distributed in the material but are confined to metallic stripes. Optimum doping may occur as a consequence of the diffuse boundaries between stripes which arise from spinodal decomposition. Theoretical ideas about the high Tc cuprates which treat the cuprates as homogeneous may need to be modified in order to take account of this type of structural variation.

Monoclinic β-MoO3 nanosheets produced by atmospheric microplasma : application to lithium-ion batteries

Porous high surface area thin films of nanosheet-shaped monoclinic MoO 3 were deposited onto platinized Si substrates using patch antenna-based atmospheric microplasma processing. The films were characterized by high resolution transmission electron microscopy (HRTEM), scanning electron microscopy (SEM) and electrochemical analysis. The electrochemical analysis shows original redox peaks and high charge capacity, and also indicates a reversible electrochemical behaviour particularly beneficial for applications in Li-ion batteries. SEM shows that the films are highly porous and consist of nanosheets 50-100 nm thick with surface dimensions in the micrometre range. HRTEM reveals that the MoO3 nanosheets consist of the monoclinic beta phase of MoO3. These intricate nanoarchitectures made of monoclinic MoO3 nanosheets have not been studied previously in the context of applications in Li-ion batteries and show superior structural and morphological features that enable effective insertion of Li ions.

Synthesis, characterization and activity of an immobilized photocatalyst : natural porous diatomite supported titania nanoparticles

Diatomite, a porous non-metal mineral, was used as support to prepare TiO2/diatomite composites by a modified sol–gel method. The as-prepared composites were calcined at temperatures ranging from 450 to 950 _C. The characterization tests included X-ray powder diffraction (XRD), scanning electron microscopy (SEM) with an energy-dispersive X-ray spectrometer (EDS), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and nitrogen adsorption/desorption measurements. The XRD analysis indicated that the binary mixtures of anatase and rutile exist in the composites. The morphology analysis confirmed the TiO2 particles were uniformly immobilized on the surface of diatom with a strong interfacial anchoring strength, which leads to few drain of photocatalytic components during practical applications. In further XPS studies of hybrid catalyst, we found the evidence of the presence of Ti–O–Si bond and increased percentage of surface hydroxyl. In addition, the adsorption capacity and photocatalytic activity of synthesized TiO2/diatomite composites were evaluated by studying the degradation kinetics of aqueous Rhodamine B under UV-light irradiation. The photocatalytic degradation was found to follow pseudo-first order kinetics according to the Langmuir–Hinshelwood model. The preferable removal efficiency was observed in composites by 750 _C calcination, which is attributed to a relatively appropriate anatase/rutile mixing ratio of 90/10.

Graphene-type sheets of Nb1-xWxS2 : synthesis and in situ functionalization

Enlightened by the discovery of graphenes, a variety of inorganic analogues have been synthesized and characterized in recent years. Solvated Nb1-xWxS2 analogues of graphene-type sheets were prepared by lithiation and exfoliation of multistacked Nb1-xWxS2 coin roll nanowires (CRNWs), followed by in situ functionalization with gold nanoparticles to synthesize gold-loaded Nb1-xWxS2/Au nanocomposites. The Nb1-xWxS2 nanosheets and the corresponding Nb1-xWxS2/Au nanocomposites were characterized by high resolution electron microscopy (HRTEM), energy-dispersive X-ray spectroscopy (EDX), scanning transmission electron microscopy (STEM), dynamic light scattering (DLS) and scanning force microscopy (AFM). The graphene-type sheets are stable in water and other solvents and can be functionalized similarly as chalcogen-terminated surfaces (e.g. with Au nanoparticles).

Synthesis, Structural Characterization and Formation Mechanism of Ferroelectric Bismuth Vanadate Nanotubes

We report the synthesis and structural characterization of ferroelectric bismuth vanadate (Bi2VO5.5) (BVO) nanotubes within the nanoporous anodic aluminum oxide (AAO) templates via sol-gel method. The as-prepared BVO nanotubes were characterized by X-ray powder diffraction (XRD), Scanning Electron Microscope (SEM), High-Resolution Transmission Electron Microscope (HRTEM) and the stoichiometry of the nanotubes was established by energy-dispersive X-ray spectroscopy (EDX). Postannealed (675 degrees C for 1 h), BVO nanotubes were a polycrystalline and the XRD studies confirmed the crystal structure to be orthorhombic. The uniformity in diameter and length of the nanotubes as reveled by the TEM and SEM suggested that these were influenced to a guest extent by the thickness and pore diameter of the nanoporous AAO template. EDX analysis demonstrated the formation of stoichiometric Bi2VO5.5 phase. HRTEM confirmed that the obtained BVO nanotubes were made up of nanoparticles of 5-9 nm range. The possible formation mechanism of nanotubes was elucidated.