Abstract: It is not straightforward to determine resolution for a 3D reconstruction when performing an electron tomography experiment. Different contributions such as missing wedge and misalignment add up and often influence the final resolution in an anisotropic manner. The conventional resolution measures can not be used for all of the reconstruction techniques, especially for iterative techniques which are more commonly used for electron tomography in materials science. Here we define a quantitative resolution measure that determines the resolution in three orthogonal directions of the reconstruction. As an application we use this measure to determine the optimum number of simultaneous iterative reconstruction technique (SIRT) iterations to reconstruct the gold nanoparticles, based on a high angle annular dark field STEM (HAADF-STEM) tilt series.

Abstract: We report on magnetisation of individual superconducting particles with size down to 0.1 micron. The non-invasive access to properties of such small objects has become possible using submicron Hall probes which detect a local magnetic field and work effectively as micro-fluxmeters similar to, e.g., SQUIDs but with an effective detection loop of only about a square micron. We have found that the spatial confinement of superconductivity in a small volume gives rise to dramatic changes in thermodynamic properties of mesoscopic superconductors. (C) 1998 Academic Press Limited.

Abstract: We measured the electrical resistivity R(T) and specific heat C-p(T) between room temperature (RT) and 4.2 K as well as the microstructure by transmission electron microscopy (TEM) of a Ni-52 Ti-48 SMA quenched from 1000degreesC (B2-Phase range) to RT and then annealed for 1h at T=380degreesC, 550degreesC and 650degreesC. In the “as quenched” and the “650degreesC annealed” state no martensitic transformations (MT's) occur. The diffraction patterns show faint reflections originating from coherent Ni4Ti3 precipitates in an early state of formation. Additional reflections of the type 1/2 <110>, 1/2 <111> and 1/3 <110> result from various lattice displacement waves, which are precursors of the MT's to the B19' and R-phase, respectively. Indeed, high resolution TEM micrographs of the [001] zone of the “as quenched” sample reveal transverse 1/2 <110> <110> lattice displacement waves, precursors of the B19' martensite. The coherent Ni4Ti3 precipitates, homogeneously distributed on a small length scale, binder the MT's in the “as quenched” and the “650degreesC annealed” state, and thus only the precursors appear. When annealed at T=380degreesC, however, coherent Ni4Ti3 precipitates with a length of 10nm are clearly visible in TEM. These precipitates trigger the NIT from the B2 to the R-phase on cooling, as evidenced also by anomalies in R(T) and C-p(T). Annealing at T-550degreesC leads to the well known two step MT's from the B2 to the R-phase and then into the B19'-phase. These martensitic transitions are clearly seen as additional peaks in the specific heat and anomalies in the resistance, while the “as quenched” and 650degreesC annealed samples show weak features in R(T) and C-p(T).

Abstract: Structure, morphology and composition of different tin oxide and germanium oxide thin film catalysts for the methanol steam reforming (MSR) reaction have been studied by a combination of (high-resolution) transmission electron microscopy, selected area electron diffraction, dark-field imaging and electron energy-loss spectroscopy. Deposition of the thin films on NaCl(0 0 1) cleavage faces has been carried out by thermal evaporation of the respective SnO2 and GeO2 powders in varying oxygen partial pressures and at different substrate temperatures. Preparation of tin oxide films in high oxygen pressures (10−1 Pa) exclusively resulted in SnO phases, at and above 473 K substrate temperature epitaxial growth of SnO on NaCl(0 0 1) leads to well-ordered films. For lower oxygen partial pressures (10−3 to 10−2 Pa), mixtures of SnO and β-Sn are obtained. Well-ordered SnO2 films, as verified by electron diffraction patterns and energy-loss spectra, are only obtained after post-oxidation of SnO films at temperatures T ≥ 673 K in 105 Pa O2. Preparation of GeOx films inevitably results in amorphous films with a composition close to GeO2, which cannot be crystallized by annealing treatments in oxygen or hydrogen at temperatures comparable to SnO/SnO2. Similarities and differences to neighbouring oxides relevant for selective MSR in the third group of the periodic system (In2O3 and Ga2O3) are also discussed with the aim of cross-correlation in formation of nanomaterials, and ultimately, also catalytic properties.

Abstract: Exfoliated graphite samples (EG) with different bulk densities were prepared by the exfoliation of expandable graphite under a thermal shock regime. As a conductive filler, EG has been incorporated successfully into the coal tar pitch matrix by mechanical mixing. The conducting behavior of the composite was interpreted based on the percolation theory. The percolation threshold of the EG/pitch conducting composites at room temperature was as low as 1.5 wt% and did not depend on the bulk density of the EG used. By means of thermogravimetry the improvement of thermal stability of the composites in comparison with pure pitches was detected. The phenomenon was ascribed to heat shielding effect of the EG particles evidenced by matrix-assisted laser desorption/ionization mass spectrometry.

Abstract: Hollow silica spheres were quickly synthesized by an octylamine (OA) templating method using tetraethyl orthosilicate (TEOS) as the silica source. N2-sorption results indicate that the hollow spheres have high surface areas and pore volumes. XRD and TEM measurements reveal that the structure of the hollow spheres depends on the amount of TEOS used in the synthesis. When low amount of TEOS is added, the template-containing precursor spheres depict an XRD pattern with two peaks, which can be indexed to a lamellar phase. After the removal of the template, the obtained hollow spheres show no diffraction peaks in the XRD pattern, suggesting that the nanopores in the silica shells are disordered. If increasing the amount of TEOS, either the uncalcined or the calcined sample gives an XRD pattern with a single diffraction peak. The mesostructure of these hollow silica spheres is typically as HMS materials. TGA analyses suggest that the interaction between the silica species and surfactant is stronger in the latter case.

Abstract: Nanocrystalline titanium dioxide was prepared via aerosol pyrolysis of titanium alkoxide precursor at 200-580 degrees C in air and in nitrogen atmospheres. Powders were characterized by x-ray diffraction, thermogravimetric analysis, Brunauer-Emmett-Teller analysis, scanning electron microscopy, transmission electron microscopy, energy dispersive spectroscopy, x-ray fluorescence, Raman and infrared spectroscopy, and Berner-type low-pressure impactor. The anatase phase transition was initiated at 500 degrees C in nitrogen and at 580 degrees C in air. Under other conditions amorphous powders were observed and transformed to nanocrystalline TiO2 via thermal postannealing. In air, smooth and spherical particles with 2-4-mu m diameter were formed with an as-expected tendency to convert to rutile in the thermal postannealings. In nitrogen, a fraction of the titanium tetrabutoxide precursor evaporated and formed ultrafine particles via the gas-to-particle conversion. At 500 degrees C thermally stable anatase phase was formed in nitrogen. A specific surface area as high as 280 m(2) g(-1) was observed for an as-prepared powder.

Abstract: The Li-ion rechargeable battery, due to its high energy density, has driven remarkable advances in portable electronics. Moving toward more sustainable electrodes could make this technology even more attractive to large-volume applications. We present here a new family of 3d-metal hydroxysulfates of general formula LiMSO4OH (M = Fe, Co, and Mn) among which (i) LiFeSO4OH reversibly releases 0.7 Li+ at an average potential of 3.6 V vs Li+/Li-0, slightly higher than the potential of currently lauded LiFePO4 (3.45 V) electrode material, and (ii) LiCoSO4OH shows a redox activity at 4.7 V vs Li+/Li-0. Besides, these compounds can be easily made at temperatures near 200 degrees C via a synthesis process that enlists a new intermediate phase of composition M-3(SO4)(2)(OH)(2) (M = Fe, Co, Mn, and Ni), related to the mineral caminite. Structurally, we found that LiFeSO4OH is a layered phase unlike the previously reported 3.2 V tavorite LiFeSO4OH. This work should provide an impetus to experimentalists for designing better electrolytes to fully tap the capacity of high-voltage Co-based hydroxysulfates, and to theorists for providing a means to predict the electrochemical redox activity of two polymorphs.

Abstract: Hydrogen-storage properties of complex hydrides depend of their form, such as a polymorphic form or an eutectic mixture. This Paper reports on an easy and reproducible way to synthesize a new stable form of magnesium borohydride by pressure-induced collapse of the porous gamma-Mg(BH4)(2). This amorphous complex hydride was investigated by temperature-programmed synchrotron X-ray diffraction (SXRD), transmission electron microscopy (TEM), thermogravimetric analysis, differential scanning calorimetry analysis, and Raman spectroscopy, and the dynamics of the BH4 reorientation was studied by spinlattice relaxation NMR spectroscopy. No long-range order is observed in the lattice region by Raman spectroscopy, while the internal vibration modes of the BH4 groups are the same as in the crystalline state. A hump at 4.9 angstrom in the SXRD pattern suggests the presence of nearly linear MgBH4 Mg fragments constituting all the known crystalline polymorphs of Mg(BH4)(2), which are essentially frameworks built of tetrahedral Mg nodes and linear BH4 linkers. TEM shows that the pressure-collapsed phase is amorphous down to the nanoscale, but surprisingly, SXRD reveals a transition at similar to 90 degrees C from the dense amorphous state (density of 0.98 g/cm(3)) back to the porous ? phase having only 0.55 g/cm(3) crystal density. The crystallization is slightly exothermic, with the enthalpy of -4.3 kJ/mol. The volumetric hydrogen density of the amorphous form is 145 g/L, one of the highest among hydrides. Remarkably, this form of Mg(BH4)2 has different reactivity compared to the crystalline forms. The parameters of the reorientational motion of BH4 groups in the amorphous Mg(BH4)(2) found from NMR measurements differ significantly from those in the known crystalline forms. The behavior of the nuclear spinlattice relaxation rates can be described in terms of a Gaussian distribution of the activation energies centered on 234 +/- 9 meV with the dispersion of 100 +/- 10 meV.

Abstract: The dynamics of the pinned vortex, antivortex and interstitial vortex have been studied in superconducting/magnetic hybrids consisting of arrays of Co/Pd multilayer nanodots embedded in Nb films. The magnetic nanodots show out-of-plane magnetization at the remanent state. This magnetic state allows for superconducting vortex lattices of different types in an applied homogeneous magnetic field. We experimentally and theoretically show three such lattices: (i) a lattice containing only antivortices; (ii) a vortex lattice entirely pinned on the dots; and (iii) a vortex lattice with pinned and interstitial vortices. Between the flux creep (low vortex velocity) and the free flux flow (high vortex velocity) regimes the interaction between the magnetic array and the vortex lattice governs the vortex dynamics, which in turn enables distinguishing experimentally the type of vortex lattice which governs the dissipation. We show that the vortex lattice with interstitial vortices has the highest onset velocity where the lattice becomes ordered, whereas the pinned vortex lattice has the smallest onset velocity. Further, for this system, we directly estimate that the external force needed to depin vortices is 60% larger than the one needed to depin antivortices; therefore we are able to decouple the antivortex-vortex motion.

Abstract: The treatment of sp2 carbon materials, including micrographite, nanographite, HOPG, onion-like-carbon, and single-walled carbon nanotubes, in a 3:1 sulfuric to nitric acid mixture produced photoluminescent reaction solutions. These colloidal, aqueous solutions appeared photoluminescently stable under a UV lamp and ranged in color from red to blue. The photoluminescent wavelength shifted to shorter wavelength with increasing reaction time or increasing reaction temperature. Raman spectroscopy showed evidence of defect structures in graphitic residue, and transmission electron microscopy showed unusual structures present in the supernatant including graphitic balls.

Abstract: Exfoliated graphite/coke composites modified by ZrO2 nanoparticles were produced using two different techniques and characterized by means of X-ray diffraction, scanning and transmission electron microscopy. In the first, low-density exfoliated graphite/coke blocks were dipped repeatedly and alternately in ZrO(NO3)2 and NH4OH solutions and subsequently heat treated at 1200°C in nitrogen to deposit thin layers of ZrO2 nanoparticles on the free surfaces of the carbon matrix. In the second, a mixture of expandable graphite, phenol-formaldehyde resin powder, and ZrOC2O4-modified fibrous cellulose in a sealed container was submitted to thermal shock at 900 °C followed by heat treatment at 1 200 °C in nitrogen to obtain the modified composites. The ZrO2 nanoparticles formed in the second technique were incorporated into the composites in three length scales: 6-30 nm-isolated nanoparticles and small blobs, 200-1000 nm-lengthy dendrite-like structures, and thin layer adhering to the surface of the 1-40 μm long cellulose carbon fibers.

Abstract: Catalytic synthesis and transmission electron microscopy (TEM) of multi-wall carbon nanotubes are presented. Silica, zeolite and alumina supported cobalt catalysts were prepared by different methods (impregnation and ion-adsorption precipitation) and were used to produce nanotubes. The synthesis was carried out in a fixed bed flow reactor and the process was optimized in order to produce carbon nanotubes on a gram scale. The influence of various parameters such as the method of catalyst preparation, the nature of the support, cobalt concentration and reaction conditions on the formation of nanotubes was investigated. The carbon deposits were measured and the quality of nanotubes was determined by low and high resolution TEM. Multi-wall straight and coiled nanotubes were found to be fairly regular with an average inner (outer) diameter of 4-7 nm (8-23 nm) and with lengths up to 0.1 mm.