The local structure of iron and uranium ions in a series of iron phosphate glasses with the general composition (40 – x)Fe2O3–xUO2–60P2O5 and (1–x–y)(40Fe2O3–60P2O5)– xUO2–y(Na2O or CaO) was investigated using Fe K-edge and U LIII-edge x-ray absorption fine structure spectroscopy. Replacing Fe2O3 by UO2 in the glass caused more distortion in the coordination environment of Fe(III) ions. Extended x-ray absorption fine structure fits revealed that the Fe–P bonds observed in the base glass also existed in all the waste-loaded glasses. X-ray absorption near-edge structure showed that the uranium ions were predominantly present as U(IV) in the glasses. Uranium ions were coordinated to approximately 8 ± 1 oxygen atoms and 2.5 ± 0.6 phosphorus atoms at an average distance of 2.47 ± 0.02 and 3.8 ± 0.02 Å, respectively. There were no Fe–U or U–Fe neighbors observed, indicating that uranium ions occupied voids in the glass away from the PO4 units. These conclusions were supported by Mössbauer, x-ray photoelectron, and Raman spectroscopic data.

The 1 MHz dielectric properties for mixed-phase polycrystalline ceramics in the system Bi4Ti3O12–Bi(InxSb1x)O3 were reported. In the vicinity of ambient temperature, the dielectric constants for the Sb and In end-members were approximately 430 and 160, respectively, and the temperature coefficients of dielectric constant (TCKs) were approximately -7600 and +430 ppm/deg. At an overall composition of Bi4Ti3O12:Bi(In0.37Sb0.63)O3 a dielectric constant of 144 and a low TCK were found. Powder x-ray diffraction and electron microscopy analyses indicated that the optimal composition contained three major phases. Deviation of any of the elements from the above ratio leads to degradation of the properties.

The thickness distribution of grain-boundary films during the superplastic deformation of fine-grained β–silicon nitride was investigated by high-resolution electron microscopy. In particular, grain-boundary thickness was considered with respect to the stress axis in two orientations; namely, parallel and perpendicular to the direction of applied stress. The results showed that the thickness distribution in boundaries perpendicular to the direction of applied stress was unimodal, whereas in parallel boundaries it was bimodal. Moreover, it was found that the majority of film-free boundaries were parallel to the direction of applied stress in the extremely deformed sample. The variation in spacing reflects distribution of stresses within the material due to irregular shape of the grains and the existence of percolating load-bearing paths through the microstructure.

Carbon tubes were successfully produced using microwave plasma-enhanced chemical vapor deposition on silicon, quartz, and ceramic substrates. The carbon tubes, about 80–100 nm in diameter and a few tens of microns in length, were formed under methane and hydrogen plasma at 720 °C with the aid of iron oxide particles. In this approach, an average tube density of about 109 cm−2 was obtained. The crooked and nonuniform diameters of some tubes suggested that they were composed of incompletely crystallized graphitic shells due to existing defects. The characteristic of the tubes grown upward on the silicon substrate accounted for a remarkably large electron field emission current of 0.1 mA/cm2 from the surface of the tube sample at a low turn-on field of 3 V/μm.

Plasma-enhanced chemical vapor deposition of SiOx coatings on thermoplastics provides a viable route for production of transparent composite materials with high fracture toughness and high gas barrier properties, which are important considerations in the food packaging and biomedical device industries. By examining several series of systematically varied SiOx/polycarbonate composites, we have identified design correlations between coating characteristics (thickness, density, surface roughness, and O2 transmission) and deposition conditions (time, power, pressure, and flow rates). Of particular interest is the observation that the thermal activation energy for O2 permeation through these composites increases (by up to 17 kJ/mol) as their barrier efficacy increases.

The quasi binary systems LaMnO3–SrMnO3 and LaMnO3–CaMnO3 were studied. Both systems show a miscibility gap at intermediate La:Sr and La:Ca ratios below about 1400 °C in air. This phenomenon causes the decomposition of single-phase (La,Sr)MnO3−x and (La,Ca)MnO3−x solid solution into La-rich SrMnO3−x + Sr-rich LaMnO3−x and La-rich CaMnO3−x + Ca-rich LaMnO3−x at lower temperatures, respectively. At 1400 °C in the system LaMnO3–SrMnO3, a structure transformation of (La,Sr)MnO3 from orthorhombic to rhombohedral with increasing Sr content was not observed, and the structure of La0.7Sr0.3MnO3 was determined to be orthorhombic with a = 0.54927 ± 0.0009 nm, b = 0.54582 ± 0.0009 nm, and c 4 0.76772 ± 0.0034 nm.

Cobalt-chloride- and dextrose-containing silica gels were reduced in situ under nitrogen atmosphere in the temperature range of 600 to 950 °C. Analysis of kinetic data on the in situ reduction shows that, in the temperature range of 600 to 750 °C, the contracting geometry type and, in the temperature range of 800 to 950 °C, the nucleation and growth type of mechanisms remain operative. The shape and size of the reduced cobalt nanoparticles in the silica matrix was studied by examining the transmission electron micrographs of the reduced Co/SiO2 samples. The morphology of the reduced metallic particles was found to be influenced by the change in reduction mechanism.

Glass-ceramics containing the LiNbO3 phase were used to grow nanometer-sized silver metal particles with median diameters in the range 10.5–17.3 nm. These nanocomposites showed large values of dielectric constant of the order of 103–104. Bergman's space charge model of a two-component composite gave results that differed from the experimental data. The polarization mechanism was concluded to be electronic in origin. An interrupted metallic strand model developed earlier by Rice and Bernasconi was used to explain the results obtained in the present specimen system.

Oxidative hydrolysis of elemental iron nanoclusters on hydroxylated surfaces such as silica or alumina is known to be influenced by the degree of hydration of the surface. The understanding and control of this process is crucial in the synthesis of iron oxide coated silica microspheres with a desired magnetic property. The hydrolysis of iron nanoparticles followed by heat treatment in the case of a hydrated microspherical silica surface results in the formation of maghemite (γ–Fe2O3), whereas a dehydrated surface yielded hematite (α–Fe2O3) nanoparticles. The influence of adsorbed water on the formation of intermediate iron oxides/oxidehydroxides and the mechanistic aspects of their subsequent thermal dehydration iron oxide phases were investigated by thermogravimetric analysis, Fourier transform infrared, and Mössbauer spectroscopies. The reactions on both the hydrated and the dehydrated surfaces were found to proceed through the formation of an x-ray amorphous lepidocrocite [γ–FeO(OH)] intermediate and its subsequent dehydration to maghemite (γ–Fe2O3). Maghemite to hematite transformation was readily facilitated only on a dry silica surface. The retardation of the lepidocrocite →maghemite →hematite transformation in the case of a hydrated silica surface is suggested to arise from strong hydrogen-bonded interactions between the substrate silica and the adsorbed nanoparticles.

The influence of Co addition on the glass-forming ability of slowly cooled Nd70-xFe20Al10Cox alloys (0 ≤ x ≤ 10) was studied by x-ray diffraction, constant-rate heating calorimetry, and magnetic measurements. Without addition of Co, the as-cast Nd70Fe20Al10 cylinders of 3-mm diameter show a mixture of amorphous and crystalline phases after copper mold casting. Increasing the Co content promotes amorphization, and bulk amorphous specimens can be obtained for Nd60Fe20Al10Co10. No glass transition or supercooled liquid region before crystallization was observed for the bulk Nd60Fe20Al10Co10 alloy. The bulk amorphous alloy exhibits hard magnetic behavior with a remanence (Jr) of 0.09 T, a magnetization (J1500) of 0.13 T, and a coercivity (Hc) of 298 kAm−1. The Curie temperature for the as-cast Nd70-xFe20Al10Cox cylinders increases from 480 K for x =0 to 487 K for x = 10. The enhanced glass-forming ability for the Nd–Fe–Al-based alloys upon Co addition will be critically discussed with respect to classical nucleation theory and the formation of metastable ordered clusters upon solidification.

The effective planar elastic moduli and planar conductivity (or dielectric constant) of regular hexagonal and triangular honeycombs were investigated for the entire range of volume fractions. Only the extreme limits of the volume fraction have been studied in the past. We studied the effective properties both numerically, via finite elements, and analytically, via rigorous three-point bounds, three-point approximations, and cross-property bounds. We show here that the three-point bounds and approximations are generally in excellent agreement with the simulation data and are superior to the two-point Hashin–Shtrikman bounds. Therefore, the three-point estimates provide accurate analytical predictions of the effective properties for all densities. Both the effective bulk modulus and effective conductivity are nearly extremal in the case of hexagonal honeycombs for the entire volume-fraction range, in contrast to the effective shear modulus. In the case of triangular honeycombs, all of the property values are relatively close to being optimal. Thus, the triangular honeycomb has desirable multifunctional performance for all densities in so far as the elastic moduli, conductivity, and dielectric constant are concerned.

Using a unique combination of in situ electrical and acoustical measurements and ex situ transmission electron microscopy, the phase transformations of silicon during point loading were shown to exhibit a strong dependence on the size of the deformed volume. For nanometer-size volumes of silicon, the final phase was the body centered cubic structure BC8, but for larger volumes it was amorphous. The size dependence was explained by considering how shear stress fields vary with contact size and how interfacial effects between the silicon substrate and the BC8 phase determine its stability. For both small and large contacts the presence of a nonmetallic phase (assumed to be the Rhombohedral structure R8) was observed.

A method was presented for the formation and metallization of cylindrical tubules from a diacetylenic lipid. This improved technique allowed for the production of metal microcylinders without the need for preliminary lipid purification and in large quantities. The physical and electrical properties of the material were investigated, and composites were used to form parallel plate capacitors. A comparison of the conductivity of the bulk material with the derived conductivity of a composite showing electromagnetic percolation showed the proportionality of the specific packing density and the critical volume fraction characteristic of percolating systems.

Boron nitride films were synthesized on silicon substrates by radio frequency-bias- assisted direct current jet chemical vapor deposition in Ar–N2–BF3–H2 system. The formation and content of cBN phase were investigated by means of Fourier transform infrared spectroscopy, glancing-angle x-ray diffraction, and scanning electron microscopy. The influences of the experimental parameters, i.e., bias voltage, substrate temperature, and gas composition, on the cBN content in the deposited films were systematically studied, and an experimentally optimum window for the deposition of cBN films was observed. Under optimized conditions, a boron nitride film with cBN content higher than 85% was deposited and a growth rate of about 70 nm/min was achieved.

The roles of NH3 · H2O and NH4HCO3 in the preparation of Ni particles from NiCl2 · 6H2O aqueous solution by ultrasonic spray pyrolysis were investigated. The results showed that both ammonia and ammonium bicarbonate had a remarkable influence on the solution chemistry and the resulting particles, and could significantly modify the reaction pathway. After the addition of these additives to the precursor solution, intermediate NiO was formed initially, followed by reduction to metallic Ni in the presence of a reductive gas. H2 is a powerful reducing agent; however, metallic Ni could also be obtained in the absence of H2 in the carrier gas. In the latter case, it was shown that NH3 was primarily responsible for Ni formation. A description of the mechanisms and processes of Ni formation during spray pyrolysis is proposed.

We have found that both tetragonal and monoclinic zirconia annealed at temperaturess in the range of 1100 to 1300 °C in atmospheres of low oxygen partial pressures (down to 10−26 Pa) transform slowly to an apparently cubic phase. The transformation can be reversed by increasing the oxygen partial pressure sufficiently, i.e., exposing the sample to air again. These observations were made by 111In/Cd perturbed angular correlation (PAC) measurements of undoped zirconia samples. Upon annealing under various reducing atmospheres PAC spectra show a steadily increasing fraction of Cd probe atoms in a locally cubic environment with the fraction of probe atoms in tetragonal or monoclinic sites decreasing accordingly.

A series of rhombohedral alkaline-earth-doped manganites, La1−x (Ca,Sr)x MnO3, were studied, with x = 0.28 to 0.375, a constant tolerance factor of 0.927 ± 0.002, a very small variation of the Mn–O bond angle (<0.3°), and constant ion size variance (ς2) of 0.0020 ± 0.0010. Compositional uniformity and crystallinity were excellent, and porosity low. The temperature of the maximum in the resistivity, Tm, for x 4 0.28 was higher (by more than 20 K) than previously reported. With increasing x (and at the same time increasing Ca for Sr substitution), the Mn–O bond length shortened, Tm decreased, and the polaron hopping activation energy increased, indicative of increased carrier localization. The behavior is opposite to the La1−xSrxMnO3 series and can be explained by a strong dependence of the electron–phonon interaction on Mn–O bond length. In order to maximize Tm, Mn–O bond length must be controlled to a precise degree.

Nanometer-sized particles of W are of interest in semiconductor device research, where such particles may store electrons inside heteroepitaxially defined structures. In this paper, we present results concerning W particles produced by thermal decomposition of tungsten hexacarbonyl. By the described method, it was possible to produce size-selected, single-crystalline W particles in the size range between 15 and 60 nm. The sintering behavior of the particles was studied between ambient temperatures and 1900 °C. The particle morphology and structure were examined with high-resolution transmission electron microscopy and electron diffraction techniques. Particles sintered at the highest temperatures typically were single crystals, with well-developed facets. Some problems concerning a yield reducing charging mechanism are discussed.

The formation energies and electronic structure of zinc vacancies and oxygen interstitials at a tilt boundary of ZnO were investigated by a combination of static lattice and first-principles molecular orbital methods. For both of the defect species, the formation energies were lower than those of the bulk defects at certain sites in the grain boundary. The defects with low formation energies formed electronic states close to the top of the valence band. The interfacial electronic states observed experimentally in ZnO varistors cannot be explained solely by the point defects associated with the oxygen excess: the effects of impurities should be significant for the states.

In this paper, we describe a new method for creating nanostructures, and demonstrate its use by depositing Au, Ni, and Zn on a SiO2 passivated Si substrate. The method combined the spatial control of electron-beam lithography with the ease of fabrication of self-assembled arrays. The technique enabled the selective electrochemical deposition of nanostructures by creating specific nucleation sites by nanoindentation. This offered the possibility of accurately creating nanostructures ranging in size from one to hundreds of nanometers. We showed that it is possible to electrically isolate the nanostructures from the substrate and each other by a thermal oxidation process. In principle, this technique allowed fabrication of quantum devices of any geometry.