Lanthanum and neodymium titanates were prepared by a sol-gel route. Synthesis of La2Ti2O7 from pure alkoxide precursors yielded an intermediate perovskite type phase, La(1–x)TiO3, which partially transformed to La2Ti2O7 on heating to 1500 °C. Substitution of the lanthanum acetylacetonate for alkoxide precursor yielded La2Ti2O7 without any intermediate phase at a very low temperature of 700 °C. Sintering of the La2Ti2O7 gel powder yielded a highly dense ceramic with ∼97% theoretical density. Similar sintering treatment resulted in ∼92% theoretical density for Nd2Ti2O7.

Droplets of 1,6–di (N-carbazolyl)-2,4 hexadiyne (DCHD) polydiacetylene were prepared by room temperature evaporation of dilute (0.01 wt. %) solution of the monomer in chloroform onto amorphous carbon-coated mica substrates. High Resolution Electron Microscopy (HREM) and Selected Area Electron Diffraction (SAED) revealed small crystallographically textured droplets (∼1 μm diameter) with cracks parallel to the [001] chain direction. The droplet geometry allowed us to investigate the organization of the polymer near surfaces. It was found that the curvature of the droplet edge caused a local bending of the polymer crystal lattice. Direct imaging of the molecular structure near the droplet surface revealed that the mechanism of lattice bending was by the formation of edge dislocations. Dislocations were etched in some droplets to gain information about perturbations in structure and reactivity near the core.

The effects of heating rate on the sintering of BaTi5O11 ceramics from an alkoxide-derived powder were investigated, and the microwave properties were measured. Density and the crystalline phase of the sintered bodies varied with heating rate. Density increased with an increase in heating rate up to 30 °C/min and decreased at one exceeding 30 °C/min. BaTi5O11 ceramics with >99% theoretical density were obtained by sintering at 1120 °C for 48 h with a heating rate at 30 °C/min. The sintering with a heating rate at 100 °C/min resulted in a decomposition of BaTi5O11 to Ba2Ti9O20 and rutile that hindered sintering. The dielectric constant εr and Q volume, neither sensitive to microstructure or the crystalline phase, were 42 and ca. 6100 at 9.7 GHz, respectively. The temperature coefficient of resonant frequency τf was 39.3 ppm/°C at 7 GHz.

The effects of indentation on the electrical resistance of rectifying gold-chromium contacts on silicon and germanium have been studied using nanoindentation techniques. The DC resistance of circuits consisting of positively and negatively biased contacts with silicon and germanium in the intervening gap was measured while indenting either directly in the gap or on the contacts. Previous experiments showed that a large decrease in resistance occurs when an indentation bridges a gap, which was used to support the notion that a transformation from the semiconducting to the metallic state occurs beneath the indenter. The experimental results reported here, however, show that a large portion of the resistance drop is due to decreases in the resistance of the metal-to-semiconductor interface rather than the bulk semiconductor. Experimental evidence supporting this is presented, and a simple explanation for the physical processes involved is developed which still relies on the concept of an indentation-induced, semiconducting-to-metallic phase transformation.

Sulfur has been purified by a dynamic pyrolysis procedure that takes into account the unique viscosity-temperature relationship of the liquid. An apparatus is described that incorporates gas-bubbling and rocking to overcome diffusion-limited kinetics. For the first time, a mechanism is proposed for the pyrolytic purification of sulfur based upon Carsul formation and the H2S ↔ H2Sx equilibrium. Infrared methods are delineated for qualitative analysis and quantitative estimates of anion contaminants, including the omnipresent hydrocarbon impurities. Our purified sulfur has a total carbon, oxygen, and hydrogen impurity level of <10 μg/g.

Solid state interfacial reactions of Ti3Al with Si3N4 and SiC have been studied via both bulk and thin film diffusion couples at temperatures of 1000 and 1200 °C. The nature of reactions of Ti3Al with Si3N4 and SiC was found to be similar. Only limited reactions were detected in samples reacted at 1000 °C. In the Ti3Al/Si3N4, layered reaction products consisting of mainly titanium silicide(s), titanium-silicon-aluminide, and titanium-silicon-nitride were formed; in the Ti3Al/SiC, the reaction product was primarily titanium-silicon-carbide. In both cases, silicon was enriched near the surface region, and aluminum was depleted from the reacted region. Reactions at 1200 °C resulted in a drastic change of the Si distribution profiles; the enrichment of Si in near surface regions was no longer observed, and the depletion of Al became more extensive. Titanium nitride and titanium-silicon-carbide were the major reaction products in the Ti3Al/Si3N4 and Ti3Al/SiC reactions, respectively. Mechanisms of driving the variation of Si, N, and C diffusion behavior (as a function of temperature) and the depletion of Al from the diffusion zone are suggested. It is proposed that reactions of Ti3Al with Si3N4 and SiC lead to in situ formation of a diffusion barrier, which limits the diffusion kinetics and further reaction. The thermodynamic driving force for the Ti3Al/Si3N4 reactions is discussed on the basis of Gibbs free energy.

Titanium dioxide thin films were grown on sapphire (11$\overline 1$0) substrates in a low-pressure metal-organic chemical vapor deposition system at temperatures ranging from 400 to 800 °C. Raman scattering, x-ray diffraction, transmission electron microscopy, and high resolution electron microscopy techniques were employed to characterize the structural properties of the deposited films. The resultant phases and structures of the deposited films depended on both the growth temperature and the substrate surface properties (surface imperfections, steps, etc.). At the growth temperature of 800 °C, single-crystal rutile films were obtained reproducibly with two possible epitaxial relationships. At lower temperatures (400 to 775 °C), the deposited films can be epitaxial or polycrystalline with highly oriented grains. The similarity between the atomic arrangements of the substrate and the film is discussed in detail to explain the observed epitaxial relationships and abruptness of the interfaces.

PECVD reactors are increasingly used for the manufacturing of electronic components. This paper presents a reactor model for the deposition of amorphous hydrogenated silicon in a dc glow discharge of Ar–SiH4 The parallel-plate configuration is used in this study. Electron and positive ion densities have been calculated in a self-consistent way. A macroscopic description that is based on the Boltzmann equation with forwardscattering is used to calculate the ionization rate. The dissociation rate constant of SiH4 requires knowledge about the electron energy distribution function. Maxwell and Druyvesteyn distributions are compared and the numerical results show that the deposition rate is lower for the Druyvesteyn distribution. The plasma chemistry model includes silane, silyl, silylene, disilane, hydrogen, and atomic hydrogen. The sensitivity of the deposition rate toward the branching ratios SiH3 and SiH2 as well as H2 and H during silyl dissociation is examined. Further parameters that are considered in the sensitivity analysis include anode/cathode temperatures, pressure, applied voltage, gap distance, gap length, molar fraction of SiH4, and flow speed. This work offers insight into the effects of all design and control variables.

On heating a gel of composition 33.5SnO2−66.5SiO2 (wt. %) up to 1050 °C, SnO2 crystallization occurred with different mechanisms according to thermal treatments. Thermal analysis, SAXS (Small Angle X-Ray Scattering), WAXS (Wide Angle X-Ray Scattering), and TEM (Transmission Electron Microscopy) results obtained for samples treated at different temperatures demonstrated that the SnO2 load is divided into two moieties, one composed of isolated SnO2 particles suitable for primary crystallization yielding crystallites with 4.0 nm of average size; the other, being dissolved in SiO2, remains in the amorphous SiO2/SnO2 solid solution up to the highest temperature. The presence of these two phases accounts for SnO2 surface segregation at the expense of the SnO2 concentration of neighboring outer layers and the independence of apparent density on temperature.

Several copper vanadium oxide melts were tested for possible application as the active medium in phase-change optical data storage devices. These materials were melted in the bulk and then quenched. Their phase development was characterized to help determine their applicability to optical data storage. It was found that they satisfy many of the criteria necessary for successful phase-change data storage; further studies of their behavior in thin film geometry would be warranted.

The existence and imperfection of several types of epitaxial layers and films on the substrate crystals were successfully detected and characterized nondestructively using a new interference fringes method. It was found that the interference fringes generated by amorphous thin films showed many very tiny bright spots that became discontinuous, which was quite different from the case of fringes generated by a crystalline epitaxially grown layer (smooth fringes). Multiple layers on a substrate were also observed by the fringes that were not concentric, but interlacing.

This paper compares the luminescence spectra of Eu3+ in sol-gel derived silica samples heated at different temperatures, following the densification process from wet gel to compact silica glass. Lifetimes, linewidths, and Stark splittings of the transitions were used to study the structural evolution of the gel network.

Single crystals of mixed mercurous halides Hg2X2 (where X = Cl and Br) were grown by the physical vapor transport process. Structural parameters and optical properties were determined to examine the suitability of mixed crystals for acousto-optic devices. Mixed crystals grown in the low concentration region did not show striations or banding. Crystals grown in the high concentration region showed considerable inhomogeneity in the refractive index. Since we had used identical thermal conditions, inhomogeneity was attributed to the solutal convection caused by the difference in densities of mercurous chloride and bromide vapors. A low concentration of dopant did not change the acoustic velocity of the parent components.

Boehmite compacts and boehmite gels (seeded and unseeded) were annealed at various temperatures in nitrogen and 1 atm water vapor to determine the influence of water vapor on boehmite transformation to new phases, changes in porosity, and morphology. Water vapor was found to accelerate the phase transformations markedly compared to dry N2 treatment. The catalyzing effect of water vapor may be due to its interactions on grain surfaces and generation of fast diffusion paths, resulting in nucleation and growth of new phases. This result shows that control of the furnace atmosphere is a useful variable in thermally activated processes.

A number of nanocrystalline ceramics have been fabricated by the gas phase condensation technique. The mechanical properties of one of the first ceramics produced by this method, nanophase TiO2, have been discussed in an earlier study.1 This paper reports a similar study undertaken to examine the properties of nanocrystalline ZnO. Nanoindenter techniques are used to determine hardness, Young's modulus, and strain rate sensitivity in ultra-fine grained ZnO. Significant properties variations are experienced within a given sample, indicating a large degree of microstructural inhomogeneity. Nevertheless, a distinct evolution in properties can be observed as a function of sintering temperature. Young's modulus and hardness values increase almost linearly with increasing sintering temperature, and, in addition, there also appears to be a linear correlation between the development of the two materials properties. In contrast, strain rate sensitivity is shown to have an inverse dependence on sintering temperature. This dependence appears to be linked to the strong influence of grain size on strain rate sensitivity, so that the lower sintering temperatures, which provide the finer grain sizes, tend to promote strain rate sensitivity. The results of this study are strikingly similar to those obtained earlier for nanophase TiO2, and they indicate that the earlier results could probably be generalized to a much broader range of nanocrystalline ceramics.

A glass based on ZrF4 was synthesized by a combination of sol-gel and reactive atmosphere processing. Infrared spectroscopy and combustion analysis show that the fluorination process reduces the concentration of organic and hydroxide impurities. Chemical changes have occurred during fluorination; this is indicated by different x-ray diffraction traces and crystallization characteristics for the fluorinated sample compared to the oxide gel product. Chemical analysis from x-ray fluorescence indicates that the fluorinated gel is chemically similar to a melted glass of the same composition. Differential scanning calorimetry gives a glass transition temperature of 290 °C and a crystallization temperature of 390 °C. These values are consistent with those expected for a fluoride glass prepared by conventional methods.

Ceramic dielectrics in the PbO–MgO–Nb2O5 based system, doped with several dopants such as Ti, Co, and Zn, were characterized for their microstructure and composition by transmission electron microscopy (TEM) and energy dispersive x-ray microanalysis (EDS). The ceramics exhibited a microstructure comprised of the matrix and many crystalline inclusions. The inclusions are compositionally enriched with magnesium and a smaller concentration of cobalt. Based on the selected area electron diffraction pattern (SADP) of the inclusion, the calculated interplanar spacings match those of (Mg, Co)O while those of the matrix match those of Pb(Mg0.33Nb0.67)O3. X-ray spectrometry (EDS) does not reveal a PbO phase in the matrix grain boundaries. The matrix exhibits finer features upon prolonged irradiation by the 200 keV electron beam. This does not affect the composition or interplanar spacings even though they exhibit polycrystalline diffraction patterns, and the high resolution micrographs show moiré patterns.

A Zr-modified polycarbosilane has been obtained reacting a zirconium alkoxide with a polycarbosilane. This new preceramic polymer has been nitridated in flowing ammonia up to 1000 °C. The conversion process of the polymer precursor to the Si–N–Zr–O ceramic has been followed mainly by FT-IR, XRD, and TEM investigations. The formation of the Si–N–Si network starts at 600 °C. At 1000 °C the system can be described as an amorphous silicon nitride ceramic in which very fine zirconia-based particles are dispersed. Increasing the temperature to 1300 °C results in the crystallization of t-ZrO2 microcrystals (35 Å in size). At higher temperatures the crystallization of the silicon nitride matrix into β–Si3N4 has been observed.

High purity silicon nitride powders have been obtained by Chemical Vapor Deposition (CVD), through the reaction of SiH4 and NH3 gas mixtures at 1000 °C in a quartz reactor. The crystallization characteristics of the powder have been followed by infrared and x-ray diffraction analysis. The material shows a transition from amorphous to the α-phase after a thermal treatment at about 1300 °C for 1 h, while the β-phase starts to appear at 1725 °C. The sintering properties of the amorphous and crystalline phases were evaluated by measuring the dilatometric curves of compacted powders.