Bilayer diamond films were deposited on Si substrates by microwave-plasma chemical-vapor deposition (CVD) using a methane-hydrogen gas mixture. The first layer was deposited for 3 h using a reaction gas which was composed of 2.5 vol. % methane and 97.5 vol.% hydrogen. The deposited film consisted of very weakly (110)-oriented microcrystalline diamonds as well as amorphous carbon and graphite. In order to remove non-diamond carbons from the film surface, the specimen was treated in hydrogen plasma for 1 h. Finally, a second layer was deposited on the first layer for 14 h using a methane concentration of between 0.2 and 1.6 vol.%. It was found that the x-ray intensity of the (220) diffraction of the bilayer films was much greater than that of the (111) diffraction, indicating that the diamond grains in the second layer were strongly oriented with their crystallographic (110) planes parallel to the substrate surface. X-ray diffraction spectra of bilayer films in which the second layer was deposited for 7, 14, 21, and 35 h using two different methane concentrations, 0.3 and 1.2 vol.%, showed that within periods of up to 21 h, the (220) intensity increased with the deposition time much more quickly than the (111) intensity, indicating that the degree of (110) orientation was further enhanced as the second layer thickness increased. However, the (220) intensity decreased after 21 h, presumably due to thermal randomization. Results of scanning electron microscopy, electron diffraction, and Raman spectroscopy of the bilayer films are also presented.

Dilatometry, high-temperature x-ray diffraction, differential thermal analysis, and differential scanning calorirmetry have been performed on LaGaO3, NdGaO3, PrGaO3, SmAlO3, and LaAlO3 single crystals grown by the Czochralski technique. First order phase transitions have been located at 145°C for LaGaO3 and 785°C for SmAlO3, and ΔH has been measured for the LaGaO3 transition. Second order transitions have been identified for LaGaO3, PrGaO3, NdGaO3, and LaAlO3. The usefulness of these compounds as substrates for high temperature superconducting films is discussed in terms of thermal expansion matching.

Chemical reaction can occur at the fiber/matrix interface of intermetallic matrix composites, leading to a degradation of mechanical properties. Fe–40Al matrix composites were fabricated using SiC, B, W, Mo-base, and Al2O3 fibers. Composite samples were heat treated up to 1500 K to study the reaction kinetics, and reaction rates were determined from reaction zone thickness measurements. The Al2O3 and W fibers were found to be compatible with the Fe–40Al matrix, while the Mo-based fibers reacted moderately and the B and SiC fibers reacted severely. Experimental results are compared to theoretical thermodynamic predictions.

Densification arising from chemical vapor deposition within a porous preform is modeled as a problem in diffusion and reaction. The effect of reaction rate on the nonuniformity of the final densified composite is explored. The possibility of achieving uniform densification by starting with an initially nonuniform porosity distribution is demonstrated with a simulation model. This model permits one to design a densification process from first principles using a simulation tool that yields results on a timescale far less than that of the processing laboratory.

Constant pressure molecular dynamics (MD) simulations have been used to simulate amorphous and crystalline forms of BaTiO3 and TiO2. Simulation results for pure RaTiO3 and TiO2 glasses show fourfold titanium coordination with a Ti–O bond distance of 1.8 Å, consistent with experimental evidence for the structure of titania doped glasses for all optical switching and ultra low expansivity (ULE) TiO2–SiO2 glasses. Radial distribution function data for crystalline, liquid, and amorphous forms of BaTiO3 were also obtained. The displacement polarization and its contribution to susceptibilities have been calculated by application of an electric field to the simulation cell. The calculated ionic dielectric constants (Ki) for simulated NaCI (crystal), TiO2 glass, and TiO2 (crystal) were 3.34, 5.96, and 19.4 as compared to the experimental values of ≍3.34, 3–10, and 78, respectively. The calculated cubic nonlinear susceptibility (ξ3) values for NaCI (crystal), TiO2 (glass), and TiO2 (crystal) were, respectively, 0.194, 2.175, and 4.68 (x 10−18m2V−2). The increase in ξ3 values is consistent with experimentally observed trends of the linear refractive indices. Improved agreement between experimental and calculated values of susceptibilities and dielectric constant was obtained for materials with higher ionicity.

The effect of 647 nm Kr-ion laser irradiation on small, 1 μm diameter regions of (In0.43Sb0.57)0.87Ge0.13 and In0.43Sb0.57 amorphous as-deposited thin alloy films was determined. Laser irradiation times of 50 ns-20 μs produced three distinct reflectivity states which differed from the original as-deposited values for both alloys. Both alloys exhibited an amorphous state of increased reflectivity after short pulse (∼100 ns to ∼500 ns) laser irradiation which has not been previously observed. Slightly longer pulses caused surface corrugations to form in these high reflectivity regions. The formation of corrugations was consistent with stress relaxation. Further laser annealing caused crystallization and decreased reflectivity. The addition of Ge increased the minimum time to crystallize by one order of magnitude, inhibited the precipitation of pure Sb crystals, and caused crystallites to nucleate at the spot edge rather than from the center of the spot. Optical, microstructure, and electrical changes were correlated. SEM and TEM showed that regions of similar reflectivity could result from significantly different microstructures.

Solid state reactions between SiC and Ni3Al were studied at 1000°C for different times. Multi-reaction-layers were generated in the interdiffusion zone. Cross-sectional views of the reaction zones show the presence of three distinguishable layers. The Ni3Al terminal component is followed by NiAl, Ni5.4Al1Si2, Ni(5.4−x)Al1Si2 + C layers, and the SiC terminal component. The Ni5.4Al1Si2 layer shows carbon precipitation free, while modulated carbon bands were formed in the Ni(5.4−x)Al1Si2 + C layer. The NiAl layer shows dramatic contrast difference with respect to the Ni3Al and Ni5.4Al1Si2 layers, and is bounded by the Ni3Al/NiAl and Ni5.4Al1Si2/NiAl phase boundaries. The kinetics of the NiAl formation is limited by diffusion, and the growth rate constant is measured to be 2 ⊠ 10−10 cm2/s. The thickness of the reaction zone on the SiC side is always thinner than that on the Ni3Al side and no parabolic growth rate is obeyed, suggesting that the decomposition of the SiC may be a rate limiting step for the SiC/Ni3Al reactions. The carbon precipitates were found to exist in either a disordered or partially ordered (graphitic) state, depending upon their locations from the SiC interface. The formation of NiAl phase is discussed based on an Al-rejection model, as a result of a prior formation of Ni–Al–Si ternary phase. A thermodynamic driving force for the SiC/Ni3Al reactions is suggested.

The interfacial adhesive shear strengths of four commercial polymer coatings on soda-lime glass were measured by the microindentation and single lap shear tests. The indentation interfacial shear strengths were over an order of magnitude greater and exhibited significantly less variability than those measured by lap shear. It is believed that the indentation test measures the “intrinsic” interfacial shear strength of the bonded coatings, whereas the lap shear strengths are controlled by large processing flaws (pores in this study) in the region of stress concentration near the overlap edge.

Oxidation of polycrystalline diamond films on (111) Si wafers in air at temperatures up to 1073 K was investigated by thermogravimetry. The diamond films before and after partial oxidation were characterized by optical and scanning electron microscopy, x-ray, infrared, and Raman spectroscopy. The oxidation of synthetic diamond films started at a lower temperature than that for natural diamond. The rates of oxidation of the diamond films synthesized by the hot filament and the microwave plasma methods were intermediate between the rates of oxidation of the 111 and 100 planes of natural diamond crystals. The apparent activation energy for the oxidation of the synthetic diamond films agreed well with that for the oxidation of natural diamond via diamond to graphite transition at low oxygen pressures.

Chemical vapor infiltration (CVI) is a relatively new fabrication method for forming ceramic composites. The vapor deposition mechanism is determined by the reaction pressure and temperature, as well as the concentration and composition of the reactants. This commentary discusses two mechanisms for the deposition of alumina from AlCl3–H2–CO2 gas mixtures, and it explains that the reaction of the gas reactants on the substrate surface is a highly feasible deposition mechanism of the CVI process for forming alumina matrix composites. Comments are also made regarding a recent publication of Middleman in the Journal of Materials Research.

A simple analytic theory to quantify the extent of “trapping” of cracks by a crystal lattice and its dependence on the range of the interatomic force law is presented. The theory requires a priori knowledge of only one or two lattice-dependent, but force law independent, parameters and can then reproduce nearly all previous (numerically demanding) theoretical results. Moreover, the extent of lattice trapping does not decrease monotonically with increasing range of the force law. For realistic interatomic potentials, however, lattice trapping is quite small. The analysis is then extended to the case of chemical corrosion by direct chemical attack of the crack tip bond. It is shown that similar slow crack growth thresholds can be predicted by the thermodynamic Griffith approach and a fracture criterion based on a local bond instability.

Niobium aluminide-based intermetallic matrix composites are currently being considered as potential high-temperature structural materials. One of the key factors in the selection of a reinforcement material is its chemical stability in the matrix. In this study, chemical interactions between two niobium aluminides, Nb3Al and Nb2Al, and several potential ceramic reinforcement materials, which include carbides, borides, nitrides, and oxides, were analyzed from thermodynamic considerations. Several thermodynamically stable reinforcement materials have been identified for these two matrices.

The atomic structures of heterophase interfaces with large misfits (>14% in Ag/Ni and Au/Ni) and with small misfits (∼2% in Ag/NiO and Au/NiO) have been studied by high-resolution electron microscopy (HREM). It is found that all interfaces are strongly faceted on (111) planes. This indicates that (111) interfaces have the lowest interfacial energy in both metal/metal and metal/metal-oxide systems. For the metal interfaces, this also agrees with determinations of interfacial energies by lattice statics calculations. The large misfit of Ag/Ni and Au/Ni interfaces is accommodated by misfit dislocations. Observations of misfit localization by HREM are in good agreement with images derived from computer simulation, based on relaxed structures, obtained in embedded atom calculations. All misfit dislocations at the Ag/Ni and Au/Ni interfaces lie exactly in the plane of the interfaces, while the dislocations at Ag/NiO and Au/NiO interfaces reside at a stand-off distance, 3 to 4 (111)Ag or (111)Au interplanar spacings from the interfaces.

It is shown that a phenomenological relation exists between the Debye temperature θ (in degree Kelvin) and the surface energy Γ (in ergs/cm2) of cubic solids: , where M is the atomic weight. This relation is derived theoretically in the Debye isotropic approximation by assuming that the interatomic potential is central. No restrictions are imposed on the range of the potential. The relation is obeyed very well by the observed values of θ and Γ in the case of many solids.

Thin C:N films were prepared by rf diode sputtering of a graphite target in a mixed argon/nitrogen plasma. We have observed a systematic variation of the properties of these C:N films with an increase in the nitrogen partial pressure. XPS, AES, and TEM studies show that nitrogen will stabilize the diamond sp3 bonding. From XPS studies, we found that the density of our C:N films is increased from 1.37 × 1023 atoms/cm3 to 1.63 × 1023 atoms/cm3 using a 100% nitrogen plasma. The energy gap of our nitrogen carbon also shows an increase from 1.1 eV to 1.4 eV using a 100% nitrogen plasma. The mechanical properties also are shown to be enhanced for certain applications. By using the same method, we can also show that it can produce 100% amorphous C:N films which are more diamond-like as compared with other methods.

The refractive index of the surface of a zirconium fluoride glass was increased by exchanging fluorine in the glass with gaseous chlorine. The chlorine profile in the glass surface, as measured by Rutherford backscattering, was that expected for diffusion. The refractive index change was measured with ellipsometry, and compared to models of the concentration profile of chlorine.

Schottky diodes were formed with free-standing polycrystalline thin film diamond base as well as with polycrystalline diamond films grown on crystalline silicon. Current-voltage and internal photoemission measurements were used to characterize the Schottky diodes and the diamond film. Internal photoemission measurements yielded a barrier height of 1.15 eV. A comparison of experimental data for metal contacts to free-standing diamond films and those on silicon substrates indicates that both rectification and internal photoemission originate at the metal/diamond interface.

X-ray tomographic microscopy (XTM), utilizing intense, highly collimated synchrotron radiation, has been used to nondestructively image materials structures in three dimensions. The spatial resolution of the technique approaches that of conventional optical microscopy, but XTM does not require polished surfaces or serial sections. We present the results of an XTM investigation of a composite material composed of silicon-carbide fibers in an aluminum matrix. The results reveal the aluminum/silicon-carbide interfaces and show microcracks running along many of the interfaces as well as in the matrix. Excellent contrast is observed between the silicon-carbide sheath of the fiber surrounding the graphite core and the coating at the fiber-matrix interface. The sensitivity to small changes in the linear absorption coefficient allows nondestructive imaging of variations in chemistry between graphite and silicon carbide and between silicon carbide and aluminum. The experimentally determined values of the absorption coefficients of these phases are identical to values published in the literature. For the first time, XTM will allow observation of damage accumulation and crack growth during deformation testing. The availability of such data will greatly improve our understanding of failure in advanced materials.