Diamond films have been grown by hot filament chemical vapor deposition (CVD) on mirror-polished positively biased Si substrates. Very smooth films a few micrometers thick were obtained in only 30 min. SEM, x-ray diffraction patterns, and Raman were used to characterize the films. Not only diamond but other carbon phases, were also detected. The initial structure showed a high density of defects and large stresses. Structural changes in time were found to occur with films apparently undergoing a phase transformation.

Data on phase relations in the system Na2ZnP2O7-Zn2P2O7 reported in the literature are scarce and contradictory. The system was first studied by Berul and Voskresenskaya [Russ. J. Inorg. Mater. (English transl.) 4 (12), 2129 (1968)], who established the existence of a congruently melting intermediate compound, Na8Zn6(P2O7)5. In the paper by Majling et al. [Chem. Zvesti. 28 (3), 294 (1974)], the system Na2ZnP2O7-Zn2P2O7 is considered to be eutectic. The subsolidus phase relations are represented by a mixture of two phases, terminal members of the system. The existence of the above-mentioned compound was not confirmed for this system. In the present work we studied the phase relations in the system Na2ZnP2O7-Zn2P2O7 on samples obtained by solid-state synthesis and glass crystallization. The sequence of crystallization of phases was investigated, and the equilibrium and metastable phase diagrams were constructed for the system.

Ultralow load indentation techniques can be used to obtain time-dependent mechanical properties, termed indentation creep, of materials. However, the comparison of indentation creep data to that obtained during conventional creep testing is difficult, mainly due to the determination of the strain rate experienced by the material during indentation. Using the power-law creep equation and the equation for Newtonian viscosity as a function of stress and strain rate, a relationship between indentation strain rate, , and the effective strain rate occurring during the indentation creep process is obtained. Indentation creep measurements on amorphous selenium in the Newtonian viscous flow regime above the glass transition temperature were obtained. The data were then used to determine that the coefficient relating indentation strain rate to the effective strain rate is equal to 0.09, or .

We examine the use of chemisorptive emission (electron emission accompanying the adsorption of a reactive gas on a metal surface) and atomic force microscopy as measures of plastic deformation during fracture along a metallic Mg/glass interface. Localized ductile deformation in the metallic phase enhances the fracture energy, exposes metallic Mg to the reactive O2 atmosphere, and produces intense emissions. The number of electrons emitted following fracture in low-pressure oxygen atmospheres is strongly correlated with the total energy expended during failure (peel energy). The presence of localized ductile deformation is verified by atomic force microscopy (AFM): voids are observed on surfaces yielding significant cmissions and enhanced fracture energies. These voids are not observed on samples yielding the lowest peel energies and emission intensities, i.e., where the contribution of deformation to the peel energy is negligible. Quantitative use of roughness data derived from the AFM images is, however, problematic. The potential for chemisorptive electron emission as a probe of deformation along interfaces involving Mg, Ti, Zr, and Al is promising.

The evolution of structure and chemical distribution in sol-gel derived Pb(Zr0.53T10.47)O3 thin layers was monitored by x-ray diffraction, analytical electron microscopy, and diffuse reflectance Fourier transform infrared spectroscopy. Electron microscopy confirmed the as-deposited coatings were amorphous with short-range order. Medium-range order developed on heat treatment, and chemical heterogeneity was observed at the nanoscale. The extent of compositional heterogeneity decreased with increasing temperature. Above 500 °C, the coatings crystallized into an intermediate phase which converted to the perovskite phase above 600 °C.

Using the nonconventional sintering technique, such as microwave sintering, it is observed to enhance the densification rate of SrTiO3 materials as effectively as employing the highly active powders prepared by the chemical route. Although the chemically derived powders demonstrate better sinterability than the mixed oxide powders, the thermal analysis indicates that the segregation of Ti4+-containing clusters during decomposition of precursors in the direct pyrolysis (DP) process induces the occurrence of TiO2 particles (anatase phase) prior to the formation of SrTiO3 phase. These particles retard the necking process required to sinter the materials. The spray pyrolysis (SP) process can circumvent the preferential nucleation of TiO2 phase and, therefore, produce powders exhibiting superior sintering behavior to the DP-derived powders. The microwave sintering technique, on the other hand, substantially enhances the rate of diffusion of the ions in the materials such that even the mixed oxide powders can be sintered at a temperature about 200 °C lower than that needed to achieve the same density in a conventional sintering process. Fine grain (∼4 μm) microstructure is obtained for the materials microwave sintered at 1220 °C for 10 min. The migration of grain boundaries requires higher temperature to initiate than the formation of neckings between the grains. The grain growth occurs only when the material was sintered at temperatures higher than 1250 °C.

This paper describes the effects of monomer and polymer properties on the competition between degradation of organic vehicle and transport of degradation products in ceramic moldings during pyrolysis. An experimentally tested model is studied systematically for ranges of material and process parameters characteristic of known polymers and their degradation products. The work highlights the properties having the greatest influence on the successful removal of organic vehicle from molded ceramics. The polymer properties controlling the diffusion constant are linked to the temperature dependence of viscosity of the molten suspension. Enthalpy of vaporization of the organic vehicle and the activation energy for the diffusion coefficient have a commanding influence on the critical heating rate for avoidance of defects. Preliminary guidelines emerge for the design of polymers for plastic forming of ceramic suspensions.

Nanophase powders of Si, C, and SiC with narrow size distributions are synthesized by dissociating reactants in a dc are plasma and quenching the hot gases in a subsonic nozzle expansion. The plasma is characterized by calorimetric energy balances and the powders by on-line aerosol measurcment techniques and conventional materials analysis. The measured nozzle quench rate is about 5 × 106 K/s. The generated particles have number mean diameters of about 10 nm or less, with Si forming relatively dense, coalesced particles, while SiC forms highly aggregated particles. Our data suggest that SiC particle formation is initiated by the nucleation of small silicon particles.

The microwave dielectric properties of (Zr0.8Sn0.2)TiO4 were investigated as a function of the amount of additives such as Nb2O5 Ta2O5 and Sb2O5 in the temperature range of 20 °C to 80 °C at 7 GHz. As the amount of additives increased up to 1.0 mol %, the unloaded Q increased due to the decrease of oxygen vacancies in the (Zr0.8Sn0.2)TiO4 lattice and then decreased with further addition of additives because the electron concentration was increased. The temperature coefficient of the resonant frequency turned more negative with increasing additives. Although the Nb+5, Ta+5, and Sb+5 ions have a similar ionic size and the same valence electronics, each resulted in different microwave dielectric properties.

Solid lubricant films produced by cosputtering metals with MoS2 and by forming metal/MoS2 multilayers are being planned for use in the next generation of solid lubricated devices on spacecraft, including gimbal and sensor bearings, actuators, and sliding electrical contacts. The films exhibit increased densities and wear lives compared to films without additives, but the mechanism of density enhancement is not well understood. The extended x-ray absorption fine structure (EXAFS) technique is ideal for elucidating the structure of these poorly crystalline films. We analyzed MoS2 films cosputtered with 0, 2, and 10% Ni, as well as Ni/MoS2 and Au(Pd)/MoS2 multilayer films. The results obtained at the Mo-K absorption edge showed that the metal-containing films comprised predominantly the same nanocrystalline phases present in similar films without added metals: pure MoS2 and a MoS2−xOx phase. MoS2−xOx is isostructural with MoS2, with O atoms substituting for S atoms in the MoS2 crystal lattice. For all Ni-containing films, EXAFS data obtained at the Ni-K absorption edge showed that the Ni had not chemically reacted with the MoS2−xOx and MoS2, but formed a disordered NiOx phase. However, Ni-cosputtered films showed decreasing Mo-Mo bond lengths in the MoS2−xOx phase with increasing Ni content, probably due to preferential oxidation of Ni compared to MoS2. EXAFS of these Ni-cosputtcred films showed only a small decrease in short-range order with Ni content, while x-ray diffraction showed a concurrent large decrease in long-range order. The results indicate that film densification in Ni-cosputtered films is caused by NiOx formation at the edges of nucleating MoS2−xOx/MoS2 crystallites, limiting the crystallite size attainable within the films.

Wide Angle X-ray Scattering (WAXS) and Small Angle X-ray Scattering (SAXS) were applied to elucidate the microstructure and morphology of two zwitterionic copolymers. The first system is a sulfobetaine derivative of poly(4-vinyl pyridine) with an ionic content of 10% (10% of the degree of quaternization). The copolymer is almost amorphous, with a small degree of crystallinity (10%). The second copolymer is a N-oxide derivative of the poly(N,N dimethyl aminoethyl methacrylate) highly crystalline (90%). The latter forms superstructures of globular shape with crystalline domains of coordinated polymer-salt systems. X-ray data are in accordance with those published by Castaño et al. [J. Mater. Res. 5, 654 (1990)]. These authors reported TEM micrographs of zwittcrionic systems, where clusters with grainy appearance were observed within the length of scale range found in this work. Models for the morphology of these copolymers are proposed for each use.

The observation of aerogels submitted to a pressure of mercury indicates that this porous material is compacted and not intruded by the mercury. Consequently, the classical Washburn equation cannot be applied. A relation is established between the pressure P of compaction and the size L of the largest pores. The size of pores is estimated by using the nitrogen adsorption-desorption isotherms analysis and SEM measurements. A relation is found in which P is proportional to L−4 The new relation is applied to mercury porosimetry. Finally, a mechanical model is proposed that reproduces successfully the behavior of aerogels under high pressure of mercury.

Surface chemical studies on zinc phosphate glasses were carried out with an ammonia probe using FTIR and XPS. Low softening point zinc phosphate glasses can be co-extruded with high softening point polymers to form polymer filled blends. NH3 reacts with P-OH groups (Br⊘nsted acid sites) to form bound NH4+ and with the zinc ions (Lewis acid sites) to form coordinately bound NH3. Bulk nitridation reactions, forming various P-N bonds to >100 nm, occur concurrently. The glass surfaces were depleted in Zn compared to the batch compositions. Exposure to ambient water vapor removed Lewis acid bound ammonia; aqueous washing removed both types. Di- and tri-methyl amines also reacted with surface Br⊘nsted and Lewis acid sites. These amine reactions have the potential for binding polymer chains to the glass surface.

Glass formation from the melt of organic monomers was studied for a variety of different organic molecular structures with Tg near ambient temperature. Crystallization is suppressed by one or more of the molecular properties, hydrogen bonding, interlocking, dipolar, and hydrogen bonding, combined with hindered rotational isomerism. Examples of materials in each category are presented for illustration. The viscosity of undercooled liquids was characterized by the Vogel-Tammon-Fulcher (VTF) equation, η = A cxp[DT0/(T - T0)], where A, D, and T0 are experimentally determined parameters. Our experimental D values are discussed in relation to the molecular structure and glass formation mechanism. The insight provided by our interpretation is intended to assist in the design of new molecular structures with controlled viscosity-temperature characteristics, as well as glass-forming ability by cooling from melts.

At the U.S. Department of Energy's Hanford Site, processes are being developed to vitrify waste generated during nuclear materials processing. One of the wastes slated for vitrification is known as neutralized current acid waste (NCAW). The batch chemistry of simulated NCAW was varied with oxidants and reductants. Untreated, formated, nitrated, or sugar-added samples were combined with frit to produce melter feed. Offgas measurements of the formated melter feed showed that formates decomposed at temperatures too low for participation in melt redox reactions. Sugar pyrolyzed and produced CO and H2 at temperatures exceeding 665 °C. For the sugar-added samples, the glass quenched from 1200 °C produced an Fe2+ /ΣFe of 0.79. The measured iron redox ratios from the glasses made from untreated, formated, and nitrated wastes were essentially indistinguishable (0.0024 at 1000 °C and 0.032 at 1200 °C). However, the batch chemistry affected volume expansion and the reaction paths.