Continuous microindentation has been carried out on an iron–3% silicon single crystal in 1 M sulfuric acid. The ability of the material to support elastic loading is directly linked to the presence of thermally grown oxide films and passive films applied through potentiostatic control of the sample. When the passive film is removed, either by chemical or electrochemical means, the iron alloy can no longer sustain pressures on the order of the theoretical shear strength of iron. Instead, the metal behaves in a traditional elastic-plastic manner when no film is present. The oxide film at the edges of the indentation can sustain applied tensile stresses up to 1.2 GPa prior to failure. Indentation in materials undergoing dissolution must account for the rate of material removal over the remote surface and the resulting plastic deformation around the contact of the indentation.

The slip system of TiN at room temperature has been determined to be {110} 〈110〉 by Burgers vector analysis using transmission electron microscopy and slip trace analysis of indents made on a TiN(001) film deposited on a MgO(001) substrate. Both small indents (0.4 mN maximum load) and large indents (40 mN maximum load) were used to study the dislocation structure in TiN. The nucleation of dislocations was investigated using small indents. Further development of the plastic zone was studied using large indents and microhardness indents (1.6 N). The critical resolved shear stress evaluated at the load when pop-in occurs was estimated to be 3.7 GPa, assuming a Hertzian elastic contact. Indents made with a 0.4 mN maximum load show a complex dislocation pattern with loops and straight segments that belong to the same slip system. Dislocations of mixed screw and edge type are dominant. The cascade of dislocations generated during pop-in is likely to nucleate from loops. For larger indents, the plastic zone extends more than three times the diameter of the imprint. The straight dislocations outside the large imprint are arranged in arrays along the 〈100〉 and 〈110〉 directions. A scanning force microscopy study of the surface outside a microhardness indent revealed a raised surface along 〈110〉 and formation of troughs along 〈100〉.

In order to clarify the effect of bias treatments on the highly oriented growth of diamond, we investigated the relation between the silicon surface morphology changes after applying a bias voltage, and the orientation of the diamond crystallites after growth. We report two major findings. First, a textured structure on the Si surface after the bias pretreatment was found to be a necessary but insufficient indicator for the subsequent growth of highly oriented diamond. Second, although bias pretreatments effectively enhance nucleation, we did not find a clear relationship between the nucleation density and the percentage of oriented crystallites. The highest nucleation densities resulted in randomly oriented films. We conclude that bias pretreatments affect the nucleation enhancement and the diamond orientation through different mechanisms.

We present the epitaxial growth by rf reactive sputtering of aluminum nitride on Si(111) at high temperature. The grain size of the obtained films was sufficient to obtain a good low energy electron diffraction (LEED) pattern from which we determined a lattice parameter of 3.1 Å, indicative of fully relaxed films. The surface of the film was examined in situ by Auger electron spectroscopy (AES); no contamination was detected, with the exception of low levels of oxygen. The film and its interface were studied by high resolution electron energy loss spectroscopy (HREELS), x-ray photoelectron spectroscopy (XPS) depth profiling, and transmission electron microscopy (TEM). Again, a low concentration of oxygen and no carbon contamination were detected by XPS. Three different growth methods were applied to the deposition of aluminum nitride at high temperature. The obtained films were studied in order to determine the influence of the methods on the interface, on the ‘bulk structure’ of the film, and on its surface. Each has been shown to have particular characteristics. The first one, performed at a temperature of 1000 °C, and including a cleaning of the surface by exposure to Al flux, was characterized by an interfacial layer with no long-range order and increasing the interaction between the film and the substrate. The second growth consisting of deposition at the same high temperature has shown a good surface quality for very thin layers (<50 Å ) and the absence of an interfacial layer. The last method, based on a first step of growth at low temperature (700 °C), resulted in good quality thick layers which allowed us to determine the infrared dielectric constants of aluminum nitride by HREELS.

The adhesion strength between a low-firing substrate consisting of an alumina/glass composite and a copper thick film was affected by the addition of cupric oxide and glass frit to the copper paste in a new co-firing process. An interlayer, 3–4 μm in thickness, was produced in the metal-ceramic interface during the new co-firing process due to the diffusion of copper. At the same time, the adhesion strength was improved by controlling the cupric oxide content. The addition of about 3 wt.% glass frit (softening point = 670 °C, based on the calcium-barium borosilicate glass composition) to the metal paste resulted in highest adhesion strength of 3 kg/mm2 with a shift of the debonding site toward the ceramic substrate within the interlayer. The shift of the debonding site could be observed by comparing the ratios of Al2O3/Cu and Ca concentration at the test pad areas on the substrate after debonding. The shift of the debonding site is attributed to the migration of glass frit into the interfacial region. The migration of glass frit occurred easily when the softening point of the glass frit was compatible with the new co-firing process, regardless of how much frit was used.

Pb(Zr0.52Ti0.48)O3 (PZT) thin film on Pt/RuO2 double electrode was successfully prepared by using a new alkoxide-alkanolamine, sol-gel method. It was observed that the use of Pt/RuO2 double electrode reduced leakage current, resulting in a marked improvement in the leakage characteristics and more reliable capacitors. Typical P-E hysteresis behavior was observed even at low applied voltage of 5 V, manifesting greatly improved remanence and coercivity. Fatigue and breakdown characteristics, measured at 5 V, showed stable behavior, and no degradation in polarization was observed up to 1011 cycles.

A physical percolating composite model is presented for description of the changes in the transport-type properties with grain size in nanocrystalline materials. The model is based on hierarchial percolation through the different microstructural components such as grain boundaries, triple lines, and quadruple nodes at grain sizes when their respective percolation thresholds are reached. The model yields critical grain sizes at which the properties may change significantly. These grain sizes depend on the grain boundary thickness. Master curves were calculated for the elastic modulus and compared to the experimental data from the literature. Better fit was found with the experimental data in comparison to Hill's approximation model. The critical grain size at grain boundary percolation threshold is suggested as a criterion for definition of materials to exhibit nanocrystalline properties.

A BN film containing comparable amounts of sp2 and sp3 phases was subjected to a gas-phase chemical etch in a hot-filament environment containing 1% CH4 in H2. After a partial etch, examination by FTIR shows that the sp2 was preferentially etched, leaving a larger sp3 fraction than in the unetched film. The possibility that preferential etching could be used to increase the purity of cBN films is discussed.

The ion-assisted nucleation of diamond was studied in a microwave plasma chemical vapor deposition system to gain insights into the processes controlling this phenomenon. The dependence of the nucleation density on bias voltage and temperature, as well as experiments with an electrically isolated substrate, are consistent with an ion bombardment mechanism for diamond nucleation. However, the growth of these nuclei is dominated by neutral species rather than ions. Measurements of the bias current under various conditions also provide details on the roles of the incident ion flux and substrate electron emission during this process. Furthermore, Monte Carlo simulations of the ion energy distribution at the substrate are compared to experimental measurements. Preferential sputtering, thermal spike, and carbon subplantation nucleation mechanisms are assessed based on the experimental and modeling results.

A discrete-sectional model accounting for particle formation by chemical reaction and growth by coagulation and condensation is developed to predict the evolution of the nanocomposite aerosol size distribution in a multicomponent iron-silicon system in a flame. Particle formation by nucleation of the vapor is represented by an Arrhenius-type rate expression, with the rate constant being obtained from experiments and simulation results reported in the literature. Precursor vapor concentrations and the second aerosol volume moment predictions are compared to laser-induced fluorescence (LIF) and light scattering intensity measurements from experiments described in Part I20 of the paper. The results elucidate the important formation and growth mechanisms of nanocomposite ferric oxide-silica particles in flame reactors. The role of operating parameters such as precursor characteristics and temperature profiles on the final product characteristics is established.

Graphitically encapsulated ferromagnetic Ni nanocrystals have been synthesized via a modified tungsten arc-discharge method. By virtue of the protective graphitic coating, these nanocrystals are stable against environmental degradation, including extended exposure to strong acids. The magnetic properties of the encapsulated particles are characterized with regard to the nanoscale nature of the particles and the influence of the graphitic coating which is believed to be benign insofar as the intrinsic magnetic properties of the encapsulated nanocrystals are concerned. The Curie temperature of graphitically encapsulated Ni nanocrystals is the same as that of microcrystalline Ni. However, saturation magnetization, remanent magnetization, and coercivity of these particles are reduced, for a range of temperatures. The unique features are compared with those of unencapsulated nanocrystalline and coarse microcrystalline nickel particles.

Tantalum carbide whiskers have been synthesized via a vapor-liquid-solid (VLS) growth mechanism in the temperature region 1200–1300 °C in nitrogen or argon. The starting materials consisted of Ta2O5, C, Ni, and NaCl. Carbon was added to reduce tantalum pentoxide, via a carbothermal reduction process, and Ni was used to catalyze the whisker growth. Thermodynamic calculations showed that tantalum is transported in the vapor phase as an oxochloride rather than as a chloride. An alkali metal chloride such as NaCl can be used as a source of Cl. The formation of TaC whiskers was found to be strongly dependent on the processing conditions used, on the choice of precursor materials, e.g., their particle sizes, and on the mixing procedure. So far we have obtained TaC whisker in a yield of 75–90 vol %. These whiskers are 0.1–0.6 μm in diameter and 10–30 μm in length, and they are straight and exhibit smooth surfaces. The main impurities are TaC particles, minor amounts of unreacted carbon, and remnants of the Ni catalyst.

AC susceptibility of ac has been measured simultaneously in three different ranges of Y–Ba–Cu –O ceramic samples in the presence of a large and variable temperature gradient. The results obtained for normal-superconducting or superconducting-normal transitions under the effect of the one-dimensional nonequilibrium temperature distribution reveal the vortex motion to consist of not only conventional flux expulsion (or flux penetration), but flux exchange too, appearing between different ranges of samples and between samples and their close physical environment. The thermal cycles are shown to represent a supplementary heat treatment, increasing the homogeneity of the sample and decreasing the pinning, which accelerate the process of vortex motion.

Vanadium dioxide thin films (VO2) have been deposited by laser ablation. The temperature dependence of resistivity and temperature coefficient of resistance (TCR) for each deposition condition were investigated. It was clarified that the TCR at room temperature (RT) can be optimized by controlling the oxygen pressure introduced during deposition as the deposition parameter. In the result, larger TCR's at RT were observed for the oxygen deficient condition of VO2 than for oxygen-richer samples. Obtained TCR values were 0.072/K and 0.045/K at 25°C for VO2 thin films deposited onto R-cut sapphire and SiO2/Si, respectively.

Organic modification of aerogel chemical formulations is known to transfer desirable hydrophobicity to lightweight solids. However, the effects of chemical modification on other material constants such as elasticity, compliance, and sound dampening present a difficult optimization problem. Here a statistical treatment of a 9-variable optimization is accomplished with multiple regression and an artificial neural network (ANN). The ANN shows 95% prediction success for the entire data set of elasticity, compared to a multidimensional linear regression which shows a maximum correlation coefficient, R = 0.782. In this case, using the Number of Categories Criterion for the standard multiple regression, traditional statistical methods can distinguish fewer than 1.83 categories (high and low elasticity) and cannot group or cluster the data to give more refined partitions. A nonlinear surface requires at least three categories (high, low, and medium elasticities) to define its curvature. To predict best and worst gellation conditions, organic modification is most consistent with changed elasticity for sterically large groups and high hydroxyl concentrations per unit surface area. The isocontours for best silica and hydroxyl concentration have a complex saddle, the geometrical structure of which would elude a simple experimental design based on usual gradient descent methods for finding optimum.

Transmission electron energy loss spectroscopy was used to obtain local dielectric properties in barium titanate. The high frequency dielectric function of the material was studied dynamically during the cubic-to-tetragonal (c → t) phase transformation in conjunction with the effect of a small amount (0.9%) of donor dopant (niobium). In order to obtain the local dielectric function during the phase transformation, Kramers–Kronig relations were applied to the energy loss measurements. The optical excitations in the energy loss spectra were consistent with band structure results from the literature. The Re (1/∈), real part of the inverse dielectric function, obtained from the energy loss data indicated a change at the phase transformation. Specifically, a broadening of the valence plasmon excitation is observed which is attributed to the order-disorder nature of the t → c transformation. A 0.4 eV shift in the volume plasmon was observed in the Nb-doped sample in all regions (within grains as well as at grain boundaries), indicating a uniform incorporation of the dopant in the lattice. In this paper, the changes in the dielectric function, such as shifts in collective excitations, are attributed to a large contribution from loosely bound Nb electrons. Furthermore, it is demonstrated that it is possible to obtain local (≈10 nm) physical property of a complex material dynamically at relatively high temperature.

Decomposition behavior of Ln2Mn4/3W2/3O7 (Ln = Eu and Er) in reducing atmosphere at 1273 K was determined. These compounds decomposed to LnMnO3 and Ln2MnWO7 at PO2 = 10−8.46 atm for Ln = Eu and 10−7.46 atmosphere for Ln = Er, respectively. Decomposition product Eu2MnWO7 decomposed to Eu2MnWO6 at PO2 = 10−15.67 atm, while Er2MnWO7 decomposed to Er2O3, MnO, and W less than 10−17 atm. The standard Gibbs free energy changes of decomposition for Eu2Mn4/3W2/3O7, Eu2MnWO7, and Er2Mn4/3W2/3O7 at 1273 K were determined to be 34.4 kJ · mol−1, 191.9 kJ · mol−1, and 44.8 kJ · mol−1, respectively. The standard Gibbs free energy changes of formation of Er2Mn4/3W2/3O7 and Er2MnWO7 were also determined to be −2429.5 and −2463.2 kJ · mol−1 at 1273 K, respectively.

It is established that nitridation of aluminum (Al) 6061-T4 by plasma source ion implantation (PSII) can dramatically enhance the pitting corrosion resistance of this alloy in marine environments (i.e., chlorine-ion-bearing aqueous solutions or humid atmospheres). Corrosion tests and microstructure analyses establish that the mechanism for successful passivation against chloride-induced pitting corrosion involves the formation of a multilayered microstructure, including the presence of a continuous layer of aluminum-nitride (AlN). Important process variables are the implantation voltage and the nitrogen dose (or total implantation time), as these two variables establish the implanted nitrogen concentration. Too high or too low an implanted nitrogen concentration will not yield the continuous AlN layer required for good corrosion resistance. PSII is attractive for this application as it provides for uniform, conformal implantation of irregularly shaped objects without masking, beam rastering, or object rotation.

Alkoxide-based hydrothermal powder synthesis of lead titanate was investigated. The objective of this work was to lower the synthesis temperature. By modifying titanium isopropoxide with acetylacetone during solution mixing, the phase-pure lead titanate with perovskite structure was synthesized at temperatures as low as 150 °C. It was determined that the pH of the hydrothermal reaction medium and the initial Pb/Ti ratio are critical factors in forming stoichiometric PbTiO3. When the pH of the initial feedstock is above 14 and the Pb/Ti ratio is greater than 1.5, a phase-pure PbTiO3 can be obtained. The modification of titanium alkoxide gave rise to the formation of a stable complex against hydrolysis and eventually reduced the synthesis temperature significantly. A possible formation mechanism for PbTiO3 is the dissolution-recrystallization from an amorphous precursor to a well-crystalline product as originally proposed by Rossetti et al. Hall–Williamson analysis was also performed on the hydrothermally derived PbTiO3 to interpret the systematic peak broadening and asymmetry for {001} reflections, unlike the commercial PbTiO3. It was observed that the strain in the c-axis direction is much higher than that in the a-axis direction while the domain sizes for both directions are similar. This strain anisotropy exerted in the particles may indicate a unique domain structure in the hydrothermally synthesized particles in which either only 180° domains exist or possibly only a single domain.

Superlattices of Fe3O4–NiO layers have been studied by high-resolution transmission electron microscopy (HRTEM). These superlattices are grown by oxygen-plasma-assisted molecular-beam epitaxy (MBE) on (001) oriented MgO substrates, and exhibit a high degree of ordering at the interfaces between the interlayers. The lack of misfit dislocations at the Fe3O4–NiO interfaces suggeststhat lattice strain is largely accommodated by changes in the lattice spacing. By quantitative HRTEM analysis of Fe3O4–NiO interfaces, possible atomic models are discussed, having implications in magnetic ordering and spin exchange mechanisms for such interlayer systems.