The excitation and emission spectra of polymeric matrices—poly(ethylene oxide), PEO, and poly(propylene oxide), PPO—containing different concentrations of EuBr3 were recorded and most of the observed transitions identified. The Stark components of the 7F0−4, 5D0 levels and the corresponding barycenters were calculated based on the emission lines assignment to the 5D0,1 → 7F0−4 transitions. The spectra were discussed in terms of a C2v local Eu3+ coordination. The relative intensity of the 5D0 → 7F2 hypersensitive transition was related to the electrolyte morphological changes due to increasing europium concentration.

Epitaxial thin films of LiNbO3 were prepared by the sol-gel method on (0001)-sapphire, (0001)-LiTaO3 and (0001)-5% MgO-doped LiNbO3, substrates. The precursor films crystallized with the highly preferred orientation on all substrates. When sapphire substrates, which have large discrepancies in the lattice constant and thermal expansion percentage with the film were used, the resulting films showed a low crystallinity after heat treatment at 500 °C and grain growth at 650 °C. On the other hand, when using LiTaO3 and 5% MgO-doped LiNbO3 substrates, with smaller discrepancies, the formed films, after heat treatment at 500 °C, showed better crystallinity with the smooth surface.

This paper describes the effects of monomer and polymer properties on the competition between degradation of organic vehicle and transport of degradation products in ceramic moldings during pyrolysis. An experimentally tested model is studied systematically for ranges of material and process parameters characteristic of known polymers and their degradation products. The work highlights the properties having the greatest influence on the successful removal of organic vehicle from molded ceramics. The polymer properties controlling the diffusion constant are linked to the temperature dependence of viscosity of the molten suspension. Enthalpy of vaporization of the organic vehicle and the activation energy for the diffusion coefficient have a commanding influence on the critical heating rate for avoidance of defects. Preliminary guidelines emerge for the design of polymers for plastic forming of ceramic suspensions.

Three distinct morphologies of curved (curved, facetted, and corrugated) inversion domain boundaries (IDB's), observed in aluminum nitride, have been investigated using conventional transmission electron microscopy, convergent beam electron diffraction, high-resolution transmission electron microscopy, analytical electron microscopy, and atomistic computer simulations. The interfacial structure and chemistry of the curved and facetted defects have been studied, and based upon the experimental evidence, a single model has been proposed for the curved IDB which is consistent with all three observed morphologies. The interface model comprises a continuous nitrogen sublattice, with the aluminum sublattice being displaced across a {1011} plane, and having a displacement vector R = 0.23〈0001〉. This displacement translates the aluminum sublattice from upwardly pointing to downwardly pointing tetrahedral sites, or vice versa, in the wurtzite structure. The measured value of the displacement vector is between 0.05〈0001〉 and 0.43〈0001〉; the variation is believed to be due to local changes in chemistry. This is supported by atomistic calculations which indicate that the interface is most stable when both aluminum vacancies and oxygen ions are present at the interface, and that the interface energy is independent of displacement vector in the range of 0.05〈0001〉 to 0.35〈0001〉. The curved IDB's form as a result of nonstoichiometry within the crystal. The choice of curved IDB morphology is believed to be controlled by local changes in chemistry, nonstoichiometry at the interface, and proximity to other planar IDB's (the last reason is explained in Part III). A number of possible formation mechanisms are discussed for both planar and curved IDB's. The Burgers vector for the dislocation present at the intersection of the planar and curved IDB's was determined to be b = 1/3〈1010〉 + t〈0001〉, where tmeas = 0.157 and tcalc = 0.164.

The fracture behavior of the silicon/Pyrex glass anodic bond was investigated using the methods of linear elastic bimaterial fracture mechanics. Due to the high bond strength, interfacial cracks were invariably observed to kink away from the interface into the more compliant glass under approximately mode I remote tensile loading. Kink angles measured by profilometry increased from 14 to 28°as bonding temperature increased from 300 to 450 °C. A regime of stable cracking accompanied penetration of cracks into the glass, with maximum load and corresponding fracture toughness measurement occurring at a location significantly removed from the interface. Approximately mode I, near-interface, plane-strain fracture toughness values (KIC) measured by rising load testing of chevron-notched and straight-thru-cracked compact-tension specimens increased from 0.63 to 0.68 MPa-m1/2 and 0.66 to 0.75 MPa-m1/2, respectively, as bonding temperature increased from 300 to 450 °C. In addition, XPS measurements revealed a sodium depletion zone of decreasing size and depletion magnitude with increasing bonding temperature over the same range. The near-interface region of the glass also experiences compressive residual stresses which decrease linearly with distance from the interface according to linear elastic computations. These stresses increase in magnitude with increasing bonding temperature due to enhanced differential thermal contraction upon cooling to room temperature. It is proposed that the trends in toughness and in kink angle with bonding temperature can be at least partially accounted for by variation of crack-tip shielding with compressive residual stress magnitude, the effects of interfacial. crack-tip shear stresses induced by the thermal mismatch, and by an increase in Young's modulus of the near-interface glass accompanying sodium depletion.

Compositions in the (Pb1−xBix (Ti1−xFex)O3 solid solution system for x ⋚ 0.7 show unusually large tetragonal distortion. High-temperature x-ray diffraction was used to study the tetragonal distortion as a function of temperature (25–700 °C) for compositions (x = 0–0.7) using powders prepared by solid-state reaction in the above system. Large changes in the lattice parameters were observed over a narrow temperature range near Curie temperature (TC) for compositions near the morphotropic phase boundary (MPB) (x ≃ 0.7). Compositions near MPB showed a c/a ratio of 1.18 at room temperature. Polar plots of lattice constants at different temperatures indicated strong anisotropic thermal expansion with zero thermal expansion along the [201] direction.

This work presents an analysis on the main microstructural parameters that affect the dielectric and piezoelectric behavior of ceramics of calcium-modified lead titanate with Ca/Pb = 26/74. To this aim, ceramics were prepared under different sintering conditions to get a series of materials with different microstructures. Compositional and microstructural characterization was achieved by x-ray diffraction, energy dispersion spectroscopy, and optical microscopy. Computerized image analysis was carried out on the micrographs to determine grain and pore size distributions. These distributions were thoroughly analyzed using probability plots. Electromechanical coupling factors and piezoelectric coefficients were measured by the resonance method on thickness poled thin disks and rectangular bars. A similar combined effect of the grain size and the percentage of porosity on the inverse of the permittivity, the coupling factors at room temperature, and the temperature behavior of the electromechanical coupling factor k31 is found.

Auger Electron Spectroscopy (AES) has been used to examine as-received and oxidized silicon carbide whiskers and their respective whisker/matrix interfaces after fabrication into SiC-whisker-reinforced alumina composites. As-received whisker surfaces exhibited a 2–3 nm-thick near-surface region that was C-rich. Oxygen was detected at the outer surface, but diminished to near zero within 25 nm of the surface. Oxidized whiskers had 60 nm-thick SiO2 surface layers, which was in agreement with the transmission electron microscopy observations. The whisker/matrix interfaces in both composites consisted of thin (<0.5 nm) layers of a C-Si-O noncrystalline material. The thick SiO2 layers on the oxidized whiskers were ejected from the interfaces during hot-pressing. It was concluded that (i) the higher toughness of the composite fabricated with as-received SiC whiskers may be related to the higher C and lower O in its SiCw/Al2O3 interfaces, and (ii) interface composition cannot be reliably predicted using the surface composition of free whiskers prior to fabrication.

CO2 laser pyrolysis has been used to synthesize carbon black (particle diameter ∼30 nm) via a catalytically driven pyrolysis of benzene vapor. The H : C ratio is found to be ∼1 : 10, which is unusually high for carbon blacks. Subsequent heat treatment of the “laser black” to temperatures up to ∼2800 °C produces well-graphitized faceted particles with central polygonal cavities. High resolution TEM lattice imaging, Raman scattering, and x-ray diffraction have been used to characterize the morphological structure of these carbon particles in their as-synthesized and heat-treated forms. Furthermore, KOH treatment at ∼800 °C has been employed to activate the as-synthesized particles, producing a tenfold increase in the surface area from 50 to 700 m2/g. Possible pore structures generated during this activation process have been identified by high resolution TEM imaging.

Sol-gel Sr2Nb2O7 thin films were deposited on Si(100) and Pt-coated Si substrates for the first time by spin-coating. The Sr2Nb2O7 precursor solution was prepared from strontium metal dissolved in 2-methoxyethanol, acetylacetone, and niobium ethoxide. The formation of phase pure Sr2Nb2O7 occurred via an intermediate perovskite phase of composition close to Sr0.82NbO3. Crack-free Sr2Nb2O7 films of ∼0.4 μm thickness were deposited on these substrates using a single-coating followed by heat treatment at 850 °C for 12 h. SEM microstructure and thin film XRD results indicated the deposition of a grain-oriented film on the Pt-coated Si substrate. The room temperature dielectric constant and the loss values of the film measured at 10 kHz are 45 and 0.045, respectively.

Highly stable bilayer thin film resistors, which consist of an underlying layer of tantalum nitride and of a capping layer of ruthenium oxide, were developed by taking advantage of the desired characteristics of two different materials in a single system. The resistors fabricated in such a way were highly stable under power loading or thermal cycling. Resistors with one digit temperature coefficient of resistance (TCR) could be easily controlled by the layer thickness ratio of the tantalum nitride to the ruthenium oxide and the ex situ annealing temperature or duration. Auger electron spectroscopy depth profile on the thin films indicates that the ruthenium oxide layer is well defined for the as-deposited form. Nevertheless, interdiffusion takes place after thermal treatment of the bilayer which is used to tune the temperature coefficient of resistance and to stabilize the resistance of the resistors.

This paper extends the concepts that were developed to explain the structural rearrangement of the wurtzite AlN lattice due to incorporation of small amounts of oxygen, and to directly use them to assist in understanding the polytypoid structures. Conventional and high-resolution transmission electron microscopy, specific electron diffraction experiments, and atomistic computer simulations have been used to investigate the structural nature of the polytypoids. The experimental observations provide compelling evidence that polytypoid structures are not arrays of stacking faults, but are rather arrays of inversion domain boundaries (IDB's). A new model for the polytypoid structure is proposed with the basic repeat structural unit consisting of a planar IDB-P and a corrugated IDB. This model shares common structural elements with the model proposed by Thompson, even though in his model the polytypoids were described as consisting of stacking faults. Small additions (≃ 1000 ppm) of silicon were observed to have a dramatic effect on the polytypoid structure. First, it appears that the addition of Si causes the creation of a new variant of the planar IDB (termed IDB-P'), different from the IDB-P defect observed in the AlN-Al2O3 polytypoids; second, the addition of Si influences the structure of the corrugated IDB, such that it appears to become planar.

The effect of modifying the host composition on the photoluminescent properties of the ir stimulable phosphor system SrBaS : (Eu, Sm) was investigated. Spectral measurements (stimulated emission, fluorescent emission, excitation, and IR stimulation) were made on nine separate host compositions. The lattice constant, ionicity, and lattice strain affect Stark splitting of the rare earth excited states. While large shifts in the ir stimulated emission and fluorescence wavelengths were observed, no shift was observed for the peak excitation and ir stimulation wavelengths.

The interfacial fracture energy of Ti/Al2O3 composites was measured with and without a diffusion barrier at different bonding temperatures by using four-point bending tests. It was found that the interfacial fracture energy increases with increasing bonding temperature up to 950 °C. When the bonding temperature was further raised to 1000 °C, the interfacial fracture energy drops. The decrease of the interfacial fracture energy is due to the formation of the continuous intermetallic compound, Ti3Al, at the interface between Ti and Al2O3. By using a diffusion barrier, the interfacial fracture energy decreases from 25.4 to near O J/m2 and 32.9 to 8.7 J/m2 for applied bonding temperatures of 800 and 900 °C, respectively. This is because the diffusion barrier reduced the diffusion of Al across the interface and into the Ti, thereby preventing a strong chemical bond at the interface. For the composite bonded at 900 °C, the crack propagation was found to occur at the interface between the Ti and Al2O3. The interfacial failure was found to be in the Ti3Al reaction layer for the composite processed at 1000 °C. With a diffusion barrier, the crack propagation path follows several interfaces. Evaluation of the processing temperature on the mechanical properties of the Ti was also obtained by using a nanoindentation technique.

Barium titanate powder and heteroepitaxial thin films were successfully produced by hydrothermal routes at ambient pressure and temperatures less than 100 °C. This processing method provides a simple low temperature route for producing epitaxied barium titanate thin films on single-crystal SrTiO3 substrates and powders which could also be extended to other systems. A dissolution/reprecipitation growth mechanism also was proposed for the formation of barium titanate by this route using previously published aqueous stability diagrams. Repeated hydrothermal treatments improved film thickness and surface coverage at the expense of increased surface roughness.

Nanophase powders of Si, C, and SiC with narrow size distributions are synthesized by dissociating reactants in a dc are plasma and quenching the hot gases in a subsonic nozzle expansion. The plasma is characterized by calorimetric energy balances and the powders by on-line aerosol measurcment techniques and conventional materials analysis. The measured nozzle quench rate is about 5 × 106 K/s. The generated particles have number mean diameters of about 10 nm or less, with Si forming relatively dense, coalesced particles, while SiC forms highly aggregated particles. Our data suggest that SiC particle formation is initiated by the nucleation of small silicon particles.

27Al and 31P NMR spectroscopic data are presented for the tridymite polymorph of AlPO4 (AlPO4−1) through its structural phase transition at about 80 °C. The RT 27Al and 31P spectra of AlPO4−t both contain doublets of broad peaks, indicating two well-separated groups of sites in the RT structure with mean Al-O-P bond angles per tetrahedron of ∼ 147.8°and 153.1°(±1). With increasing temperature, the doublets remain the same up to about 74 °C, where the relative intensities of the two peaks start to change. The peak corresponding to smaller Al-O-P bond angles disappears, and above ∼88 °C the 27Al and 31P spectra contain single symmetrical peaks, corresponding to a mean Al-O-P bond angle of 153.4°. This bond angle increases gradually with increasing temperature to 153.7°at ∼150 °C and remains constant to about 500 °C. 27Al quadrupole echo experiments suggests that the 27Al nuclear quadrupole coupling constant (QCC) is small and decreases with increasing temperature. QCC remains nonzero in the high temperature phase of AlPO4−t, consistent with the previously proposed 3m local symmetry of Al in the high-temperature structure.

The model of capillary transport of liquid metals driven by shear stress resulting from the displacement of menisci [J.W. Nowok, Scripta Metal]. Mater. 29, 931 (1993); Acta Metall. Mater. 42, 4025 (1994)] is applicable to liquid-phase sintering of silicate/aluminosilicate glasses. The movement of a liquid phase between adjacent particles is compared with that in capillaries. It appears that the transport property of intergranular melt may be expressed by the viscosity (η) and volume diffusion (D) parameters if mean displacement of menisci is compared with the mean diffusive jump lengths of atoms/molecules (L). This leads to the following relation: (γ/η)Lα = Dcap, where α and Dcap are a specific permeability and volume diffusion coefficient. The use of this model requires the assumption that the diffusing species are also the viscous flow units, and they can be either atoms or structural units. This assumption seems to be applicable for depolymerized silicate melts if the dominant mass transport is initiated by the diffusion of both nonbridging oxygen and silicon atoms.

The microwave dielectric properties of (Zr0.8Sn0.2)TiO4 were investigated as a function of the amount of additives such as Nb2O5 Ta2O5 and Sb2O5 in the temperature range of 20 °C to 80 °C at 7 GHz. As the amount of additives increased up to 1.0 mol %, the unloaded Q increased due to the decrease of oxygen vacancies in the (Zr0.8Sn0.2)TiO4 lattice and then decreased with further addition of additives because the electron concentration was increased. The temperature coefficient of the resonant frequency turned more negative with increasing additives. Although the Nb+5, Ta+5, and Sb+5 ions have a similar ionic size and the same valence electronics, each resulted in different microwave dielectric properties.

The properties of four kinds of Type II carbon fibers, which had been precarbonized at 300 °C, 400 °C, 500 °C, and 600 °C, respectively, during two-stage continuous carbonization, were measured after being air oxidized for periods of 1 to 6 min at 550 °C. The effects of precarbonization temperature on mechanical properties, density, morphology, elemental composition, and microstructure of the carbon fibers during the air oxidation are discussed in this article. The precarbonization process strongly affected the surface properties and mechanical properties of the final oxidized carbon fibers. The carbon fibers developed from the different precarbonization temperatures all had different structures. The carbon fibers that had been precarbonized at 300 °C had a more ordered structure than other fibers after air oxidation. These carbon fibers also had a higher performance than the other fibers. Carbon fibers also showed different oxidation behaviors caused by differences in surface morphology resulting from each different precarbonization temperature. Optimum conditions not only improved the tensile strength and modulus, but also increased the density and oxygen content. Experimental results showed that the tensile strength of the carbon fibers precarbonized at 300 °C increased from 2.4 GPa to 4.3 GPa (80%) after 6 min oxidation at 550 °C.