Results of ab initio Hartree–Fock calculations for the electronic structure of aluminum nitride in the (high-pressure) rocksalt phase are reported. In the rocksalt phase, the calculated lattice constant is 3.982 Å with the bulk modulus of 329 GPa. The band structure is predicted to be indirect at the X point with a gap of 8.9 eV. In this phase, the bonding is shown to be essentially ionic between Al and N. The direct gap shows a stronger linear dependence on pressure with a pressure derivative of 68 meV/GPa compared to that of the indirect gap with a pressure derivative of 31.7 meV/GPa.

Bombardment of a growing thin film by negative ions can lead to changes in the film through the process of resputtering. Macro-effects of resputtering (effects on the film thickness) include a slowing of the film growth rate and, in some cases, a complete suppression of the film growth as well as an etching of the substrate materials. To study this result of resputtering, rf-diode sputtering was used to deposit BaTiO3 films under a variety of conditions, varying deposition time, rf-power level, substrate-to-target distance, total gas pressure, and argon, oxygen, and hydrogen partial pressures. The effect resputtering had on the thickness was seen to be a result of the competition between deposition and etching of the thin film material. The relative influence of the various sputtering parameters and the effect each of these has on the thickness distribution were examined. It was found that the greatest influence was system geometry, followed by rf-power level. Various methods of controlling resputtering are discussed.

Negative ion bombardment of an evolving thin film can cause changes in the film's surface due to resputtering of the already deposited material. Through the study of rf-sputtered perovskite (BaTiO3) thin films, we have found that surface micro-effects, i.e., changes in the surface morphology of the films at the μm-scale level, are dependent on the deposition conditions. Ripples, cones, ridges, and etch pits of various shapes and sizes were all observed on growing films. A transformation of the morphology of the top surface of the film as a function of both deposition time and location on the substrate has been observed. The type of surface morphology found at any point was found to be dependent on a number of factors, including deposition rates, flux and energy of bombarding ions, and the average angle of incidence of the bombarding ions. We have developed a qualitative model for the formation of these surface features, based on the resputtering yield as a function of the average angle of incidence of the bombarding ions. The model suggests that surface nonuniformities, often ripples, initiate the development of etch pits. Other mechanisms of the surface morphology development (such as clustering) are used to explain the formation of surface features other than etch pits.

We have studied the influence of ion bombardment on the surfaces of MgO and Al2O3 single crystals. The two oxides were sputtered with low energy Ar+ ions, and x-ray photoelectron spectroscopy was used to analyze surface compositions and chemical interactions with metallic adsorbates. Expected changes in surface compositions have been calculated mathematically using first principle formulation from existing literature. The resulting effects on XPS spectra have been predicted based on concentration profile models and agree with experimental observations. Changes in surface oxygen activity were studied by evaporating Ni on these surfaces at an extremely slow rate and analyzing what fraction of the first monolayer was oxidized on adsorption. This fraction, used as a measure of surface oxygen activity, was substantially reduced in Al2O3 on sputtering, but remained practically unchanged for MgO. The amount of these changes matches reasonably well with calculated changes in surface oxygen fraction. Based on these results, the relation between ion bombardment and interfacial bonding has been discussed.

The hot corrosion of single crystal and polycrystalline aluminas has been investigated in SO2–SO3–O2 environments and in the presence of molten Na2SO4-based deposits at temperatures of 700 and 1000 °C. The effect of microstructure and impurities on the corrosion has been emphasized. Weight changes and wetting angles were determined, and the evolution of the morphology of the exposed substrates and the reaction products was investigated in detail. The corrosion was small under the conditions of this study and generally increased with the impurity content of the polycrystalline aluminas. Based on the experimental results, particularly those obtained by electron microscopy and microanalysis using the SEM/EPMA (scanning electron microscope–electron probe microanalyzer), mechanisms are proposed for the corrosion of polycrystalline aluminas which emphasize the role of the silicate impurities and the synergy of their corrosion with that of the alumina grains. As a result, the alumina grains were dissolved by acidic fluxing under the acidic and the basic experimental conditions.

Powders of calcium carbonate with strontium carbonate were solidified by mechanical compression under hydrothermal conditions. The effects of hydrothermal conditions such as temperature, pressure, and ratio of Ca/Sr on the reaction process and microstructure of the solidified bodies were examined. Solidification of every powder easily proceeded with shrinkage above 200 °C to 300 °C. The compacts of strontium carbonate were more easily solidified, and compressive strength was 190 MPa and its density was 93.5%. The solidification with shrinkage of compacts consisting of mixed powders of calcium and strontium carbonates was accelerated with an increase in strontium carbonate content. It was revealed that the small amount of strontium carbonate powder acts as a bonding material among large calcium carbonate particles.

Nanophase (n-) ZrO2 was produced in its pure and partially stabilized form by the gas-phase condensation method. The material was examined by x-ray diffraction and Raman scattering to obtain information on the structural evolution of the material during sintering. Two types of Y2O3-doped ZrO2 nanophase material were made: one by co-deposition of n-Y2O3 and n-ZrO2 in a consecutive manner and the second by mechanically mixing n-Y2O3 and n-ZrO2. We have determined that the co-deposition process is the most effective means of doping the n-ZrO2.

The structural environments of Zr, Th, and U in aperiodic (metamict) (Ca, Th)ZrTi2O7 were examined using Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. Samples are aperiodic due to a radiation-induced transformation caused by alpha-decay event damage. In the aperiodic samples, Zr is mainly 7-coordinated [d(Zr−O) ≍ 2.14–2.17 ≍ 0.02 Å]; whereas, Th is mainly 8-coordinated [d(Th–O) ≍ 2.40−2.41 ≍ 0.03 Å]. Nearly identical bond lengths and coordination numbers for these elements were determined for an annealed, crystalline sample. The radiation-induced transition from the periodic to the aperiodic state is characterized by a significant broadening of the distribution of (Zr, Th)–O distances. In one metamict sample with ≍1.9 wt.% U3O8, U is essentially tetravalent. The absence of higher oxidation states (U6+) is consistent with the lack of evidence for alteration (samples are over 500 million years old). The reduced medium-range order around Zr, Th, and U is related to the increase of alpha-decay event damage and precludes decomposition of zirconolite into simple oxides of Zr, Th, or U. Comparison with other metamict (Zr, Th, U)-bearing phases (e.g., ZrSiO4 and ThSiO4) suggests that Zr4+, Th4+, and U4+ prefer 7-, 8-, and 6-coordinated sites, respectively, in aperiodic phases at ambient temperatures and pressures. Examination of the structure of crystalline (Ca, Th)ZrTi2O7 demonstrates that M–O–M angles (M = Ca, Ti, Zr, and Th) are relatively small (≍100–120° for edge-sharing polyhedra). A limited relaxation of the constraints of periodicity around M cations caused by radiation damage (e.g., tilting of polyhedra) dramatically affects the distribution of these angles. This type of structural relaxation may be the mechanism by which long-range periodicity is lost and medium-range order is reduced with increasing radiation damage, while the major cations retain their nearest-neighbor environments. This relaxation may also help explain the lattice expansion observed in zirkelites when they undergo radiation damage.

Silicon-based ceramic whiskers, such as silicon carbide and silicon nitride, were produced in a plasma arc reactor. Silicon monoxide gas was generated by reacting briquettes of silica and carbon according to the following reaction: SiO2(s or l) + C(s) = SiO(g) + CO(g). The effects of operating variables on the production of silicon monoxide are discussed. The silicon monoxide gas was then back-reacted with carbon monoxide to produce silicon carbide whiskers according to the following reaction: SiO(g) + 3CO(g) = SiC(s) + 2CO2(g). In the presence of nitrogen, the product contained some silicon nitride and silicon oxynitride whiskers. The effects of gas composition and flow rate, crucible mass, and alkali additions on the amount and morphology of the whiskers were determined. It is concluded that the whiskers grew by a vapor-liquid-solid mechanism.

A modified sedimentation process was used in the production of a functionally gradient material (FGM), NiAl/Al2O3. A simple finite element model was used to guide our design and fabrication efforts by estimating residual stress states as a function of composite structure. This approach could lead to tailored designs that enhance or avoid specific residual stress states. Thermal cycling tests were factored into the model to predict time dependent or steady-state internal temperature and stress profiles. Four-point bend tests were conducted to establish the mechanical load-displacement behavior of a single interlayer FGM at room temperature, 800 and 1000 K. Room temperature bend strength of the FGM was 3–4 times that of the base NiAl. At elevated temperatures, composite fracture occurred in a gradual, noncatastrophic mode involving NiAl retardation of a succession of cracks originating in the alumina face.

Spherical silica particles, dispersed in ethanol/water solutions, were first coated with titania by hydrolysis of added titanium isopropoxide. The coating thickness could be readily adjusted by the ratio of titanium alkoxide concentration to the amount of silica. The coated cores prepared as above were then treated with ammonia in a temperature-programmed reaction to produce a shell of titanium nitride. After nitridation, the powders of the high specific surface area showed electrical conductivity, which depended on the thickness of the coatings.

Tungsta-titania samples with different W loadings up to 15 wt.% and calcined at different temperatures have been prepared and characterized by surface area measurements, mercury porosimetry, x-ray diffraction, microstructural analysis, and laser Raman spectroscopy. It has been found that W inhibits the initial sintering of TiO2 (anatase) and the anatase → rutile transformation. The morphological and structural properties of the samples (surface area, porosity, and phase composition) have been related to the microscopic properties of the materials such as crystallite dimensions and defects concentration. A model for the sintering of TiO2 is discussed. This model is based on the diffusion of surface hydroxyls, formed upon adsorption of water on surface oxygen vacancies. A role for W is proposed in terms of stabilization of both material defects and surface hydroxyls.

Functionally Gradient Materials (FGM's) are soon to be used in a variety of important commercial applications; joining and thermal barrier coatings are two of the most widely studied. FGM's of the TiC/NiAl and the TiC/Ni3Al systems were fabricated using a one-step, self-propagating high-temperature synthesis (SHS) and densification method. It was observed that ignition of the starting mixture for these two systems was affected by the initial sample temperature and the external pressure that was applied to the sample during the ignition stage. Quality of the final product (e.g., porosity, grain size, cracking and microcracking, etc.) depends on a number of factors during this one-step operation. Reaction temperature control is important and is necessary to minimize residual porosity of the final product. Particle size of reactant powders, as well as applied pressure, also has an effect on the resulting microstructure. If careful reaction temperature control is achieved, along with optimum reactant powder size and applied pressure, an FGM of minimal porosity is obtained without residual macrocracks. Further, this method can easily be used to fabricate an FGM with a highly precise composition and material properties gradient. Finally, this process results in FGM's of similar quality when compared to those prepared by existing fabrication methods at only a fraction of the cost. Most importantly, it is expected that this process can be scaled up with relative ease.

In situ formation of chromium carbide in mullite matrix through the reaction of Cr2O3, SiC, and Al2O3 has been studied. Three different chromium compounds, Cr3Si, Cr3C2, Cr7C3, and mullite were formed. The Cr3Si particles formed first and the Cr7C3 phase was only dominant above 1600 °C. The Cr3C2 phase was the main product chromium carbide at temperatures ranging from 1450–1550 °C. The mullite phase formed concurrently through the reaction of SiO2 with Al2O3. SiO2 is the product of the reaction between Cr2O3 and SiC. The composite hot-pressed at 1450 °C in argon gives a flexural strength and fracture toughness up to 407 MPa and 3.8 MPa m1/2, respectively.

The effectiveness of several coating systems which were used as a diffusion barrier for the SiC fiber-reinforced titanium aluminide composites was investigated. TaC, TiC, TiB2, B, C/graded TiB2, and Ag/Ta were applied to the SiC fiber via chemical vapor deposition and physical vapor deposition. The interfacial compatibility, interfacial stability, thermal residual stress, interfacial bond strength, and the transverse fracture behavior of the composites with coated fibers were characterized and determined. The results show that none of the above coating systems can satisfy the requirements for a strong, tough, and damage-tolerant SiC fiber-reinforced titanium aluminide composite. Several multilayer, multifunctional coating systems are proposed.

A review of the structure and properties of fullerenes is presented. Emphasis is given to their behavior as molecular solids. The structure and property modifications produced by alkali-metal doping are summarized, including modification to the electronic structure, lattice modes, transport, and optical properties. Particular emphasis is given to the alkali-metal-doped fullerenes because of their importance as superconductors. A review of the structure and properties of fullerene-based graphene tubules is also given, including a model for their one-dimensional electronic band structure. Potential applications for fullerene-based materials are suggested.