It is suggested that the “supermodulus effect” observed for composition-modulated strained-layer superlattices may arise from the presence of the structurally disordered solid interfaces and not necessarily from electronic-structure effects. The latter are excluded by investigating the elastic properties of a so-called grain-boundary superlattice in which chemically identical materials are joined to form a three-dimensional superlattice. Both an embedded-atom-method and Lennard-Jones potential are employed in our zero-temperature atomistic calculations of the elastic constants and moduli of such a superlattice. They yield qualitatively similar results which, for large modulation wavelengths, can be represented by a mean-field model in which the interfacial regions are characterized by a set of effective elastic constants which are different from those of the bulk regions. The appearance of a maximum in the biaxial modulus and a minimum in the shear modulus is shown to arise from the interaction between interfaces. It is also shown that such extreme anomalies appear only in the moduli but not in the elastic constants of the grain-boundary superlattice.

Inert-gas markers, Rutherford backscattering, and x-ray diffraction were used to investigate solid-state interdiffusion in Ni/Zr and Au/Zr bilayer films as a function of temperature; microstructural studies during annealing were performed in situ, in a high-voltage electron microscope. Au, in contrast to Ni, is not an anomalously fast diffuser in crystalline Zr. Nevertheless, an amorphous product phase was found in both alloy systems for reaction temperatures  550 K; heterogeneous nucleation of the amorphous phase was observed in Au/Zr. The interdiffusion data reveal two distinct Arrhenius regimes, 330–∼470 K and ∼480–550 K, with quite different apparent activation enthalpies. These thermal interdiffusion results are compared with temperature dependent studies of ion-beam mixing in similar bilayer specimens. This comparison indicates that the enhanced efficiencies observed for ion-beam mixing above ∼480 K result from the as-prepared metastable microstructurc, and are not due to radiation-enhanced diffusion.

Mössbauer spectrometry and x-ray diffractometry were used to characterize the microstructural changes that occurred during the mechanical alloying of Fe and V powders, After 3 h of essentially no interatomic intermixing, an Fe–V alloy began to form. At first the chemical composition of this alloy was highly inhomogeneous, having large variations over distance scales of less than 100 Å. After about 24 h of ball milling, the alloy homogenized and then became at least partly amorphous.

In the interfacial reaction zone between AlN and a Ag Cu–Ti braze alloy, a previously unreported phase belonging to the η family (M6X) has been found by transmission electron microscopy. The compound has an approximate stoichiometry of (Ti3−x Cu3−xAl2x)N and space group symmetry of Fd3m, with a cubic lattice parameter of a0 = 1.13 ± 0.02 nm. Large (>1 μm diameter), defect-free grains are present with occasional {111} twinning. Grain boundaries are free of second phases and amorphous interlayers. The formation of continuous layers that grow with reaction time indicate possible stability of the η nitride at 900 °C. The presence of this phase is integral to the chemical and structural development of the ceramic-metal interface.

Solid-state reactions between niobium and gallium arsenide in both thin film and bulk forms were studied in the temperature range 400 to 1000 °C using transmission electron microscopy (TEM), metallography, scanning electron microscopy (SEM), and electron probe microanalysis (EPMA). Initially Nb4As3 and Nb5Ga3 formed at the interface and grew very slowly. Following an incubation period, NbAs and NbGa, nucleated and grew at rates several orders of magnitude faster than the initial phases. The resulting metastable diffusion path, Nb/NbGa3/NbAs/GaAs, was observed even after relatively long-term annealing and is believed to be kinetically stabilized. Formation of the other Nb–Ga binary compounds as predicted by the phase diagram was inhibited by nucleation and kinetic barriers. The observed reaction sequence is discussed considering the thermodynamics, kinetics, and possible growth mechanisms involved in the reaction.

Using the double pulse technique with two synchronized lasers, we studied the conditions of ignition and evolution of explosive crystallization. The structure of the resulting crystallized layers is analyzed by TEM. Results of calculations are reported describing the development of the two phase fronts: amorphous/molten and molten/crystalline. It is shown that the system takes more than 500 ns to reach the steady state. The experimental results support the model of creating first a melt nucleus in the amorphous layer followed by the formation of the crystalline nucleus in the molten sphere. Competitive solid phase nucleation and growth in the amorphous layer limit the temperature-time interval of melt nucleation. Defined explosively crystallized areas in laterally structured SOI layers are presented.

The effects of ArF excimer laser irradiation on β–SiC in UHV were examined for a variety of laser intensities and pulse densities. The samples were analyzed in situ with Auger and electron loss spectroscopies, and ex situ with x-ray photoelectron spectroscopy. With progressively higher laser intensities, the SiC surface was initially cleaned of carbon and oxygen surface contaminants, and the Si–LVV Auger lineshape changed from the oxide to the carbide. Still higher laser intensities then partially reordered the surface. A carbon surface layer developed, and the C-KLL lineshape transformed from carbidic to graphitic. Finally, the surface segregated into an almost pure Si layer and an underlying carbon-rich layer, followed by ablation and pitting. Bulk heating during laser exposure may enhance reordering of sputtered or implanted material.

The passivation characteristics of various insulators are evaluated for the β–SiC surface. It is found that wet thermal oxides yield minimum electrical defects at the oxide-SiC interface. Dry thermal oxide results in too much charge either at the oxide-SiC interface or in the bulk. It is also shown that anodic aluminum oxide seems to possess suitable electrical properties for the fabrication of MOS structures on SiC, whereas the CVD silicon nitride proved to be the worst.

Electrodeposition from molten-salt systems has been studied extensively as a method of producing both polycrystalline and single-crystalline materials. In this work, the thermodynamic aspects of the electrodeposition process are examined in a number of cases in which the molten-salt system behaves effectively as an oxygen-transporting medium, with particular reference to the thermodynamic properties of the melt. It is demonstrated how information gained from the construction of the appropriate isothermal phase diagram may be used to control and/or rationalize the behavior found in a given melt system on electrolysis.

Iridium oxide films deposited on Ti-alloy stimulation electrode wires by rf sputtering exhibit markedly different surface morphologies and redox capacities in response to variations in applied substrate bias potential. Films deposited with a −20 volt bias were relatively smooth and featureless whereas those sputtered with a +20 volt bias were comprised of closely packed 1 micron long platelets. Intermediate substrate biases revealed a gradual progression from the smooth surface to one sparsely populated with particles to a morphology comprised of tightly packed platelets. The electrochemical properties of the films are strongly dependent on the substrate bias employed during deposition. As the DC bias was increased from −20 volts to +20 volts the anodic and cathodic charge capacities determined by cyclic voltammetry decreased linearly from 36 to 12 mC/cm2.

A periodically inhomogeneous medium is constructed by stacking up unit cells made of (identical) structurally chiral slabs. Each structurally chiral slab is comprised of a certain number of identical biaxially anisotropic plates, the consecutive optic axes describing either a right- or a left-handed spiral. The characteristic matrix of the unit cell is obtained and used with the Floquet-Lyapunov theorem to obtain the electromagnetic fields in the periodic medium. When the unit cell thickness is very small compared to the principal wavelengths in the biaxial plates, the periodically inhomogeneous biaxial medium is shown to be equivalent to a homogeneous biaxial medium, the two optic axes of the equivalent medium being dependent on the handedness of the periodic medium.

The classical model of Chemical Vapor Infiltration (CVI) treats diffusion and surface reaction in a representative cylindrical pore. Two significant modifications to that approach are presented herein. One accounts for more complex chemistry by allowing for both gas-phase and surface reactions which lead to film growth. The other couples the pore model to a reactor model for the region external to the porous preform. The results demonstrate that it is possible to select chemical schemes that yield densification from the interior to the exterior of the preform, thus avoiding premature trapping of interior voids.

The compound La2Ti2O7 was prepared by a liquid mix technique and examined at room temperature by x-ray diffraction, infrared absorption, and Raman spectroscopy. The examinations confirm and supplement the earlier observation by x-ray diffraction that La2Ti2O7 crystallizes in the monoclinic structure without an inversion symmetry. The energy-shifts (cm−1) that were observed in the vibrational spectra may be explained by a sixfold coordination for the titanium and a ninefold coordination for the lanthanum in the structure. This type of coordination satisfies Pauling's electrostatic valence rule regarding the electrostatic bond strengths at the shared anions.

The stress-displacement relation of the fiber is analyzed for fiber-reinforced ceramic composites during axial compressive loading (indentation) and unloading on the exposed end of an embedded fiber. An unbonded fiber/matrix interface subject to Coulomb friction and residual radial clamping stresses is considered in the present study. The results show that the stress-displacement curves during loading and unloading can be used to evaluate the magnitude of the clamping stress, the coefficient of friction, and the frictional stress distribution at the interface. Specifically, in the absence of Poisson's effect (i.e., when Poisson's ratio of the fiber is zero), the interfacial shear stress is constant, the loading curve is parabolic, and, after complete unloading, the residual fiber displacement equals half of the maximum fiber displacement at the peak loading stress. In the presence of Poisson's effect, the interfacial shear stress is not constant, and, after complete unloading, the residual fiber displacement is less than half of the maximum fiber displacement at the peak loading stress.

Laser-driven synthesis of refractory powders from the organosilicon compounds ((CH3)3Si)2NH and ((CH3)3Si)2O has been studied as prototypical of powder syntheses from large molecules. A cw CO2 laser is used for powder syntheses and pulsed TEA CO2 laser-driven homogeneous pyrolysis is used to study the initiation chemistry. Initial decomposition of the organosilanes by Si–C bond cleavage initiates free radical chain reactions which produce organosilicon polymers and subsequent refractory phases. A qualitative model is proposed which provides a framework for understanding the parameters influencing powder synthesis from large molecules.

Our recent applications of the atom-probe field ion microscope to the study of physics and chemistry of materials at the atomic level are summarized. The materials applicability of field ion microscopy has recently been extended to silicon, silicide, graphite, high Tc superconductors, and other materials. Atom-probe field ion microscopy has been used for atomic layer by atomic layer chemical analysis of surfaces in alloy and impurity segregations, for analyzing the compositional changes across metal-semiconductor interfaces, and for studying formation of cluster ions in laser stimulated field desorption. The energetics of atoms in solids and on surfaces can be studied by a direct kinetic energy analysis of field desorbed ions using a high resolution pulsed-laser time-of-flight atom-probe and by other field ion microscope measurements. The site specific binding energy of surface atoms can be measured at low temperature, where the atomic structure of the surface is still perfectly defined, to an accuracy of about 0.1 to 0.3 eV.

The properties of graphite intercalation compounds (GIC's) are discussed with respect to possible applications. Five families of intercalates give high electrical conductivity to GIC's: pentafluorides leading to high conductivity, 108 S/m (higher than metallic copper); metal chlorides; fluorine and alkali metals with bismuth giving relatively high conductivity of the order of 107 S/m plus stability in air; and residual halogens showing extremely high stability under severe conditions, though the conductivity is only of the order of 106 S/m. Electrodes of different GIC's have been tried in primary and secondary batteries, where their characteristics are high electrical conductivity and easy diffusion of electrochemically active species between the graphite layers. Primary lithium batteries of a covalent graphite fluoride are now widely used commercially. Secondary batteries using different host graphites and intercalates give interesting results. Large amounts of hydrogen can be stored in the functional space in alkali metal-GIC's. The same GIC's show high coefficients of isotope separation of hydrogen at liquid nitrogen temperature. The structure and texture of the host graphite play a decisive role in the absorption and separation behaviors of GIC's. Exfoliated graphite prepared by rapid heating of GIC's or their residue compounds leads to flexible graphite sheets which have great industrial applications. Some problems connected with the production and use of these sheets are discussed.