The three single-crystal elastic constants of the cubic materials Al and TiN were calculated by an ab initio method within the local-density approximation of density-functional theory. The values were compared with experiment and averaged by the Kroner method to give polycrystalline results. The results agree well with experiment.

Joining of melt-textured YBa2Cu3O7-δ (Y123) grains has been achieved without use of an external agent. The technique uses barium-cuprate liquid phase released from platelet boundaries to mediate the growth of Y123 at the interface between two grains. The epitaxial nature and high quality of the growth was determined by optical and transmission electron microscopy. The composition of Ba–Cu–O phases found in some parts of the joins was determined by electron probe microanalysis. A clean low-angle join was found to consist of a grain boundary with dislocation networks and facets. Transport critical current measurements on this type of join revealed strongly coupled behavior. The technique shows promise for the joining of melt-textured material for power engineering applications.

Preferred domain orientation of a piezoelectric ceramic develops through domain switching under electric poling. In previous investigations the critical free energy required for domain switching has been assumed as a constant. This assumption leads to overestimation of the poling-induced texture and provides no explanation for the switching reversal in ferroelectric ceramics after the poling field is removed. In this paper, the contribution of intergranular stress to critical energy for 90° domain switching is investigated. A criterion including intrinsic threshold energy and an interaction energy, which is related to the intergranular stress and the intergranular depolarization field, is proposed. The texture evolution during poling process is simulated using a computational model starting from an initial random domain orientation distribution. The resulted domain orientation distributions under and after poling are predicted. The remanent domain switching after poling is the result of the balance between the interaction energy and intrinsic threshold energy. The final texture is much weaker than that under the electric field. Pole figures of poled Navy VI lead zirconate titanate measured by x-ray diffraction are consistent with the predicted textures.

A method for the determination of site preference of substitutional elements in intermetallic compounds is proposed. It is demonstrated in Ni3Al–X alloys that the ridge direction in thermal conductivity contours in the ternary γ′ phase agrees with that of the solubility lobe of the γ′ phase in ternary phase diagrams. The ridge direction is a reliable indication of site preference of substitutional elements in intermetallic compounds. The present method is conveniently applied to a normal polycrystalline specimen with small size, and therefore, a versatile class of brittle compounds can be studied.

The variation of mechanical properties (hardness, indentation modulus) within a carbon-implanted region of a Ti–6Al–4V alloy—about 350-nm thick—was, for the first time, related with the microstructure and the chemical composition with a depth accuracy as small as ±20 nm. Microstructure, chemical composition, and mechanical properties of the implanted alloy were determined using transmission electron microscopy, Auger electron spectroscopy, and nanoindentation, respectively. The microstructure within the implanted region contains TiC precipitates, the density of which changes with depth in accordance with the carbon content. The hardness depends on the precipitate density: the maximum hardness occurs at the depth where an almost continuous TiC layer had formed. The depth profiles of hardness and indentation modulus were measured using three different methods: the cross-section method (CSM); the constant-load method (CLM); and the load-variation method (LVM). Only the hardness– depth profile obtained using the CSM, in which the indentations are performed perpendicular to the hardness gradient on a cross section of the specimen, reflects the microstructural variations present in the implanted region.

Highly conductive iridium dioxide (IrO2) thin films have been deposited onto in situ oxidized Si(100) substrates by means of a reactive pulsed laser deposition (PLD) process. The polycrystalline IrO2 films were obtained by ablating a metal iridium target under an optimal oxygen background pressure of 200 mtorr and at different substrate deposition temperatures (Td ) ranging from 350 to 550 °C. Conventional and high-resolution transmission electron microscopy (HRTEM) techniques were used to investigate the micro- and nanostructural changes of the PLD IrO2 films as a function of their deposition temperatures. The microstructure and the morphology of the PLD IrO2 films was found to change drastically from an irregular and loosely packed columnar structure at Td = 300 °C to a uniform and densely packed columnar structure for higher Td (≥350 °C). For IrO2 films deposited in the 350 ≤ Td ≤ 550 °C range, HRTEM have revealed the presence of highly textured arrangements of almost spherical IrO2 nanograins (of 3–5 nm diameter, regardless of Td) in the columns (of which diameter was found to increase from 85 ± 15 to 180 ± 20 nm as Td increases from 350 to 550 °C). Lattice resolution and dark-field imaging have pointed out the presence of large IrO2 crystallites made of many similarly oriented nanograins (i.e., under the same Bragg diffraction conditions). Moreover, a high continuity of the lattice planes across the entire crystallite was clearly observed. This latter aspect together with the highly textured nanostructure of the IrO2 films correlate well with their high conductivity (42 ± 6 μω cm for Td ≥ 400), which was found to be comparable with that of bulk single-crystal IrO2.

Experimental evidence of transient self-dewetting of metallic surfaces is presented. Steel surfaces are melted by a pulsed electron gun, and the subsequent fast cooling against its substrate gives rise to the formation of characteristic patterns that we attribute to the dewetting of the liquid film. The patterns formed are similar to those obtained by spinodal dewetting, that is, when the dewetting action develops from a nonlinear instability on the liquid surface, and not from holes nucleation. High-purity iron does not show a similar behavior, indicating that the origin of the instability is due to the influence of the sulfur in the temperature dependence of the surface tension of the melt, which gives rise to a Be’nard-Marangoni instability.

A solid-state reaction mechanism for the formation of Ba6−xLn8+2x /3Ti18O54 (Ln = Nd, Sm) solid solutions has been studied using x-ray powder diffraction, thermal analyses, and transmission electron microscopy (TEM). During the interaction of the starting reagents, Ln2Ti2O7, BaTi4O9, and BaTiO3 are formed. In the next sequence, these three phases react together to form a high-x end member of the Ba6−xLn8+2x /3Ti18O54 homogeneity region (Ba3.9Nd9.4Ti18O54 and Ba3.9Sm9.4Ti18O54). Subsequently, the reaction of Ba3.9Nd9.4Ti18O54 and Ba3.9Sm9.4Ti18O54 with the residual BaTiO3 takes place. TEM investigations revealed that compositional inhomogeneities and structural defects existed in the Ba4Sm9.33Ti18O54 sample heated at 1370 °C for 1 h. Sintering times, prolonged to ≥3 h, eliminated the structural defects and increased the homogeneity of the sample.

Electrolyte electroreflectance (EER) has been used as an in situ probe for determining the distribution of energy states at the surface of naked and metal-modified TiO2 film in contact with aqueous solution. The surface modification of polycrystalline TiO2films by electrodeposition of fine (a few nanometers in size) metal particles has been shown to result in the appearance of surface states with an energy of approximately 2.15 eV for Cu, 2.40 eV for Pd, 2.50 and 2.30 eV (two peaks in the EER spectrum) for Pt, and 2.65 eV for Ag (the energy values are measured versus valence band edge of TiO2). The important role of metal-induced surface states in the enhancement of charge exchange between conduction band of semiconductor oxide and metal islets has been demonstrated using the electrocatalytic oxidation of boron hydride as a model reaction.

Tracer oxygen diffusion coefficients, D*, in polycrystalline yttria doped with Ca have been determined by a gas–solid exchange technique and secondary ion mass spectrometry. Samples containing few pores were used to avoid their influences on diffusion profiles. The resulting profiles were assigned only to volume diffusion; no grain boundary diffusion was observed. According to the effects of Ca doping on D*, the Ca contents are divided into three regions. In a Ca content region of 0–0.17 mol%, D* changed a little with Ca doping and took a minimum experimentally at 0.02 mol%. D* increased significantly within a range of 0.17–0.54 mol% and saturated at 0.54 mol% or above because of a solubility limit. The activation energies of oxygen diffusion were estimated at 249–282 kJ/mol.

The sol-gel synthesis and structural characterization of SiO2–TiO2 powders are reported. Samples with titania concentrations in the range of 0 to 30 mol%, calcined at temperatures between 120 and 1300 °C, were characterized by 29Si magic-angle-spinning nuclear-magnetic-resonance (MAS NMR) and cross polarization MAS NMR, Raman and Fourier transform infrared spectroscopies, and powder x-ray diffraction. Tetrahedrally coordinated Ti (IV) ions were found in the titanosilicate matrix. When the titania content increases beyond approximately 10 mol% and upon calcination at temperatures over approximately 700 °C, the segregation of an amorphous silica-rich phase occurs, together with the precipitation of anatase nanocrystallites with average sizes between 3 and 17 nm, depending on the temperature. An increase in the heat treatment temperature, or the titania content, leads to an increase in the degree of homocondensation (Si–O–Si and Ti–O–Ti bonds) and a simultaneous reduction in the degree of heterocondensation (Si–O–Ti bonds).

The influence that trace concentrations of SiO2 have on improving grain-boundary conduction via precursor scavenging using additional heat treatment at 1200 °C for 40 h before sintering was investigated. At a SiO2-impurity level (SIL) ≤160 ppm by weight, the grain-boundary resistivity (ρgb) decreased to 20% of its value, while no improvement in grain-boundary conduction was found at a SIL ≥ 310 ppm. The correlation between the resistance per unit grain-boundary area, rgb, and average grain size indicated that the inhomogeneous distribution of the siliceous phase in the sample with a SIL ≥ 310 ppm hampered the scavenging reaction.

Continuous high-quality fibers of yttria-doped zirconia with 4 and 8 mol% yttria were blow spun using an inorganic sol precursor. The fibers were heated and analyzed using scanning electron microscopy, x-ray diffraction, differential thermal/thermogravimetric analysis, and surface area/porosity by nitrogen adsorption. The fibers were of a single-phase cubic structure after crystallization at 529 °C and typically 3.3–5.5 or 7.5–11.5 μm in diameter depending on the composition. Samples of fibers were heated to various temperatures and their friability index and creep properties analyzed using the bend stress relaxation technique and compared to other fibers of similar composition prepared by different solution techniques and commercially available fibers.

We describe a method for controlled preparation of sol-gel ceramic multilayer coatings obtained by dip-coating. The proposed fabrication routine guarantees obtaining crack-free multilayer coatings with control of the thickness and porosity of individual layers. The procedure is applied to obtain a 10-layer ZrO2–3 mol% Y2O3 coating deposited on AISI 310 stainless steel. The microstructure of this coating was investigated by using x-ray powder diffractometry and atomic force microscopy, and special consideration was given to the mechanical characterization of this thin film using ultramicrohardness indentation tests. Our results suggest that these zirconia coatings have good properties for use as protection barriers. Implications concerning general tailoring design of sol-gel dip-coatings are also considered.

We have studied the glass transition behavior of vitreous As2Se3 by carrying out temperature-modulated differential scanning calorimetry (TMDSC) and conventional differential scanning calorimetry (DSC) experiments to measure the glass transition temperature Tg. In TMDSC experiments we have examined the reversing heat flow (RHF), that is the complex heat capacity CP in the glass transition region as the glass is cooled from a temperature above the glass transition temperature (from a liquidlike state) and also as the glass is heated starting from room temperature (from a solidlike state). The RHF, or CP versus T, in TMDSC changes sigmoidally through the glass transition region without evincing an enthalpic peak which is one of its distinct advantages for studying the glass transformations. The Tg measurements by TMDSC were unaffected by the amplitude of the temperature modulation. We have determined apparent activation energies by using Tg-shift methods based on the Tg-shift with the frequency (ω) of temperature modulation in the TMDSC mode and Tg-shift with heating and cooling rates, r and q, respectively, in the DSC mode. It is shown that the apparent activation energies ∆h* obtained from ln ω versus 1/Tg and ln q versus 1/Tg plots are not the same, but nonetheless, they are approximately the same as the apparent activation energy ∆hn of the viscosity over the same temperature range where the empirical Vogel expression of Henderson and Ast, η = 12.9 exp[2940/(T - 335)], was used for the viscosity. The latter observation is in agreement with the assertion that the structural relaxation time Ʈ is proportional to the viscosity h. The apparent activation energy ∆hr obtained from the ln r versus 1/Tg plot during heating DSC scans is lower than ∆h* observed during cooling scans. The results are discussed in terms of a phenomenological Narayanaswamy type relaxation time. It was observed that Tg obtained from TMDSC cooling experiments did not depend on the underlying cooling rate for q ≤ 1 °C min-1; and for temperature amplitudes 0.5–5 °C. The transition due to the temperature modulation was well separated from the transition due to the underlying cooling rate. Further, the apparent activation energies obtained from ln ω versus 1/Tg during cooling and heating scans for q and r ≤ 1 °C min−1 are approximately the same as expected from Hutchison's calculations using a single relaxation time model of TMDSC experiments.

Cuprous oxide (Cu2O) films have been grown on single-crystal MgO(110) substrates by a chemical vapor deposition process in the temperature range 690–790 °C. X-ray diffraction measurements show that phase-pure, highly oriented Cu2O films form at these temperatures. The Cu2O films are observed to grow by an island-formation mechanism on this substrate. Films grown at 690 °C uniformly coat the substrate except for micropores between grains. However, at a growth temperature of 790 °C, an isolated, three-dimensional island morphology develops. Using a transmission electron microscopy and atomic force microscope, both dome- and hut-shaped islands are observed and are shown to be coherent and epitaxial. The isolated, coherent islands form under high mobility growth conditions where geometric strain relaxation occurs before misfit dislocation can be introduced. This rare observation for oxides is attributed to the relatively weak bonding of Cu2O, which also has a relatively low melting temperature.

Controlled crystallization of BaF2 under two different kinds of monolayers, octadecylamine [CH3(CH2)17NH2] and hexadecanol [CH3(CH2)14CH2OH], has been studied by using x-ray diffraction (XRD) and scanning electron microscope. It was found that the monolayer headgroup, the degree of ionization of the headgroup, etc., had a complicated effect on the selectivity of monolayers for crystal and on the morphology and orientation of crystals grown under the compressed monolayers. At pH = 7.0, XRD analysis showed that (100)-oriented BaF2 crystals were formed under the octadecylamine monolayer, while several kinds of crystals were found under the hexadecanol monolayer. In comparison, at pH = 8.5, both (100)-oriented BaF2 and (111)-oriented Ba(NO3)2 crystals were obtained under the monolayer of octadecylamine. However, crystals formed under hexadecanol monolayer consist of BaF2, Ba(NO3)2, etc. The detailed mechanism for crystallization was discussed in terms of the specific interaction and lattice matching between the monolayer headgroup and the nucleating species.

Pulsed heating experiments that measure high-temperature thermophysical properties using pyrometric measurement of the temperature–time history of metal specimens rapidly heated by passage of electric current have a 30-year history at the National Institute of Standards and Technology. In recent years, efforts have been made to move beyond the limitations of the standard technique of using costly, black-body geometry specimens. Specifically, simultaneous polarimetry measurement of the spectral emissivity has permitted study of sheet and wire specimens. This paper presents the results of two efforts to expand beyond the macroscopically monolithic, single-phase materials of all previous studies. In the first study the melting temperatures of coatings, including Ti and Ti(Al) alloys, deposited on higher melting Mo substrates are measured. In the second study the melting temperatures of substrates, Ti and Cr, covered by higher melting W and Mo coatings are measured.

Interface structure and solute-segregation behavior in the high-strain-rate superplastic SiCp/2124 and SiCp/6061 Al composites were investigated. Evidence for interfacial reaction between reinforcement and Al matrix, which was evident in the superplastic Si3N4p,w/2124 Al and Si3N4p,w/6061 Al composites, could not be detected in the current SiC-reinforced Al composites. Instead, strong solute segregation was observed at SiC/Al interfaces. Extensive formation of whiskerlike fibers was observed at the fractured surface of tensile samples above the critical temperature where particle weakening began to be seen. These results suggest that partial melting occurs at the solute-enriched region near SiC interfaces and is responsible for the particle weakening. The absence of reaction phase in the SiC-reinforced composite may explain why no endothermic peak for partial melting appears in its differential scanning calorimetry curve and why its optimum temperature for superplasticity is generally higher than that of the Si3N4-reinforced composite.

Two-dimensional simulation of thermal debinding in powder injection molding based on mass and heat transfer in deformable porous media is proposed. The primary mechanisms of mass transport, i.e., liquid flow, gas flow, vapor diffusion, and convection, as well as the pyrolysis of polymers, and their interactions, are included in the model. The simulated results revealed that polymer removal process is primarily affected by liquid flow, which is mainly dominated by pressure-forced flow rather than capillary-driven flow. A significant phenomenon, enrichment with liquid polymer in the outer surface regions of the compact, is explained.