R. Theissmann

Nanodomains in morphotropic lead zirconate titanate ceramics : On the origin of the strong piezoelectric effect

The outstanding piezoelectric properties of lead zirconate titanate (PZT) ceramics with compositions close to the morphotropic phase boundary of the quasibinary phase diagram of lead zirconate and lead titanate are still under debate. A combination of ex situ and in situ transmission electron microscopy and high resolution x-ray diffraction revealed that the extrinsic piezoelectric effect in morphotropic PZT is closely connected to the existence of nanodomains. The in situ transmission electron microscopy investigations with applied electric field show that mainly the nanodomains respond to the electric field while the microdomain structure does not change noticeably in our experiments.

Plasma synthesis of nanostructures for improved thermoelectric properties

The utilization of silicon-based materials for thermoelectrics is studied with respect to the synthesis and processing of doped silicon nanoparticles from gas phase plasma synthesis. It is found that plasma synthesis enables the formation of spherical, highly crystalline and soft-agglomerated materials. We discuss the requirements for the formation of dense sintered bodies, while keeping the crystallite size small. Small particles a few tens of nanometres and below that are easily achievable from plasma synthesis, and a weak surface oxidation, both lead to a pronounced sinter activity about 350 K below the temperature usually needed for the successful densification of silicon. The thermoelectric properties of our sintered materials are comparable to the best results found for nanocrystalline silicon prepared by methods other than plasma synthesis.

Composition dependence of the domain configuration and size in Pb(Zr1−xTix)O3 ceramics

The composition dependent variation of domain configuration and size in Pb(Zr1−xTix)O3 (PZT) has been investigated in a detailed transmission electron microscopy study in the range of 0.40⩽x⩽0.55. Single phase composition, Pb(Zr0.45Ti0.55)O3 and Pb(Zr0.60Ti0.40)O3, the former belonging to the tetragonal, the latter to the rhombohedral phase, feature small microdomain widths coupled with a pronounced bimodal domain distribution. Samples with compositions around the morphotropic phase boundary exhibit a decrease of bimodal distribution and an increase in microdomain width associated with nanodomain formation. The investigation of micro- and nanodomains, as well as the bimodal distribution of microdomains in undoped PZT ceramics, with respect to composition, is reported. We define nanodomains as “domains arranged within microdomains possessing a width of a few nanometers.” The strict alternation of the two orientation variants of microdomains is denoted as “bimodal domain distribution,” and is characterized ...

Subsurface changes of a MoM hip implant below different contact zones

Metal-on-metal hip arthroplasties undergo distinct release of toxic metal particles and ions. Thus, it is necessary to minimize this. In order to evaluate the wear behaviour of metal-on-metal hip replacements it is essential to understand the micro-structural changes in the sub-surface region. Previous studies revealed that cobalt chromium metal-on-metal implants are able to alter their mechanical behaviour by adjusting the microstructure to load. The reason for this is the so-called mechanical mixing. This means that a nano-crystal layer is formed by rotating clusters of atoms that incorporate denatured proteins from the interfacial medium. This is followed by a layer of rhombic shaped nano-crystals in between sheared epsilon-martensite lathes, twins, and stacking faults. Although the primary wear zone has been well characterized, the sub-surface structure of the stripe wear and the non-contact zone of the hip ball have yet to be analysed. For this study a 28-mm cobalt base alloy femoral head and acetabular cup were analysed. The implant was simulator tested for 5 million cycles with the application of micro-separation resulting in a clearly visible stripe wear appearance. The TEM micrograph of the primary wear zone of the ball confirmed the presence of a sub-surface layer of nano-crystals. The thickness of this layer was approximately 200 nm and the average grain diameter ranged from 35 to 40 nm. Within the stripe wear zone the micrographs also revealed a nano-crystal layer but with a thickness of only 50 nm and an average grain diameter from 15 to 20 nm. The carbon and oxygen content was highest closest to the surface which proves the occurrence of mechanical mixing. The non-contact zone of the ball was analysed as well. When compared to the primary wear zone a nano-crystal layer with similar thickness but with an average grain diameter smaller than 15 nm was observed.

Role of oxygen on microstructure and thermoelectric properties of silicon nanocomposites

Phosphorus-doped silicon nanopowder from a gas phase process was compacted by DC-current sintering in order to obtain thermoelectrically active, nanocrystalline bulk silicon. A density between 95% and 96% compared to the density of single crystalline silicon was achieved, while preserving the nanocrystalline character with an average crystallite size of best 25 nm. As a native surface oxidation of the nanopowder usually occurs during nanopowder handling, a focus of this work is on the role of oxygen on microstructure and transport properties of the nanocomposite. A characterization with transmission electron microscopy (TEM) showed that the original core/shell structure of the nanoparticles was not found within the sintered nanocomposites. Two different types of oxide precipitates could be identified by energy filtered imaging technique. For a detailed analysis, 3-dimensional tomography with reconstruction was done using a needle-shaped sample prepared by focused ion beam (FIB). The 3-dimensional distribu...

Bifunctional electrocatalysis in Pt-Ru nanoparticle systems

Pt-Ru alloys are prominent electrocatalysts in fuel cell anodes as they feature a very high activity for the oxidation of reformate and methanol. The improved CO tolerance of these alloys has been discussed in relation to the so-called ligand and bifunctional mechanisms. Although these effects have been known for many years, they are still not completely understood. A new approach that bridges the gap between single crystals and practical catalysts is presented in this paper. Nanoparticulate model systems attached to an oxidized glassy carbon electrode were prepared by combining both ligand-stabilized and spontaneously deposited Pt and Ru nanoparticles. These electrodes showed very different voltammetric responses for CO and methanol oxidation. The cyclic voltammograms were deconvoluted into contributions attributed to Pt, Ru, and Pt-Ru contact regions to quantify the contribution of the latter to the bifunctional mechanism. Scanning transmission electron microscopy confirmed the proximity of Pt and Ru nanoparticles in the different samples.

Microcrystalline silicon formation by silicon nanoparticles

Thin silicon films are of great importance for large-area electronic applications, for example, as the basis for switching electronics in flat-panel display devices or as the active layer of solar cells. In this paper, we show that silicon nanoparticles have the potential to be used as raw material for further processing toward a microcrystalline silicon film. This can be done by thermal treatment with a reduced thermal budget because the melting point of the nanoparticles is much lower with only 60% of the equilibrium melting temperature of silicon. Coagulation processes of liquid droplets then lead to the growth of microcrystalline silicon in agglomerated nanoparticles. We demonstrate by in situ transmission electron microscopy (TEM) and differential thermal analysis that silicon nanoparticles with a size of approximately 20nm start melting at around 1000K; furthermore, the TEM observations directly demonstrate the details of the coagulation process leading to microcrystalline silicon.

Paired twins and [112] morphology in GaP nanowires.

Formation of random as well as periodic planar defects can occur during vapor-liquid-solid growth of nanowires with the zinc-blende crystal structure. Here we investigate the formation of pairs of twin planes in GaP nanowires. In such pairs, the first twin plane is formed at a random position, rapidly followed by the formation of a second twin plane of which the position is directly related to that of the first one. We show that the triangular [112] morphology of the nanowire is a key element in the formation of these twin pairs. We have extended our previous kinetic nucleation model and show that this describes the development of the nanowire morphology and its relation with the formation of single and paired twin planes.

Formation of metallic indium-tin phase from indium-tin-oxide nanoparticles under reducing conditions and its influence on the electrical properties

The correlation between defect structure, metal segregation, and electrical resistivity of indium-tin-oxide nanopowder upon treatment in reducing atmosphere was investigated. Morphology and defect structure have been investigated by in situ synchrotron x-ray diffraction and transmission electron microscopy, while traces of metallic indium have been detected by susceptibility measurements utilizing the superconducting properties of indium. With increasing treatment temperature under reforming gas the film resistivity decreases down to ρ=1.6×10−2 Ω cm at 330 °C annealing temperature. For even higher treatment temperatures, the resistivity increases further. This is accompanied by extractions of metallic indium. Under forming gas, grain growth could be observed at 350 °C, while in air grain growth starts at 650 °C. Furthermore forming gas causes a lattice expansion of ITO which persists in oxygen, at least for several hours. The results are discussed with respect to results published in the literature.

Characterization of individual aerosol particles in workroom air of aluminium smelter potrooms

Aerosol particles with aerodynamic diameters between 0.18 and 10 microm were collected in the workroom air of two aluminium smelter potrooms with different production processes (Soderberg and Prebake processes). Size, morphology and chemical composition of more than 2000 individual particles were determined by high resolution scanning electron microscopy and energy-dispersive X-ray microanalysis. Based on chemical composition and morphology, particles were classified into different groups. Particle groups with a relative abundance above 1%(by number) include aluminium oxides, cryolite, aluminium oxides-cryolite mixtures, soot, silicates and sea salt. In both production halls, mixtures of aluminium oxides and cryolite are the dominant particle group. Many particles have fluoride-containing surface coatings or show agglomerations of nanometer-sized fluoride-containing particles on their surface. The phase composition of approximately 100 particles was studied by transmission electron microscopy. According to selected area electron diffraction, sodium beta-alumina (NaAl(11)O(17)) is the dominant aluminium oxide and cryolite (Na(3)AlF(6)) the only sodium aluminium fluoride present. Implications of our findings for assessment of adverse health effects are discussed.