Gas-atomized Ni powders were mechanically milled under liquid nitrogen and subsequently sprayed using a high-velocity oxygen-fuel thermal spraying system. The resultant coatings were evaluated using various analytical methods, including scanning electron microscopy (SEM), transmission electron microscopy, and atom probe field ion microscopy (APFIM). The results indicated that the majority of the grains in nanocrystalline Ni coating were equiaxed with an average grain size of 50 ± 23 nm. SEM elemental dot mapping analysis suggested that oxide particles were distributed along the prior droplet boundaries and interpass boundaries in the coatings. The APFIM analysis indicated that the distribution of oxygen was very inhomogeneous in the nanocrystalline coating samples studied. Mostly small NiO precipitates with a size range of 1–7 nm were found throughout the grains, and the average size of these precipitates was approximately 4 nm. However, large oxide precipitates with a size up to 55 nm were also observed. In addition, increased amounts of oxygen were found at the grain boundaries and at structural defects.

Crystals of CaAl4O7 (space group C2/c) have been examined by high-temperature powder x-ray diffractometry to determine the change in unit-cell dimensions with temperature up to 1473 K. The lattice deformation induced by thermal expansion has been investigated by matrix algebra analysis to determine the directions and magnitudes of the principal distortions. During heating from 298 K, two of the three principal distortions, λ1 and λ2, invariably showed a positive thermal expansion, the magnitudes of which at 1473 K are respectively approximately 1.0% and approximately 0.8%. The direction of λ1 was nearly parallel to [304], and the λ2 axis invariably coincides with the crystallographic b axis. On the other hand, the distortion λ3 showed a negative thermal expansion below approximately 1173 K; the maximum contraction of approximately 0.2% occurred at approximately 673 K nearly along [207]. During further heating to 1473 K, λ3 showed, to the contrary, a positive expansion of approximately 0.2% nearly along [50, 16]. The negative thermal expansion along the λ3 axis substantially accounts for the mean linear thermal expansion being very low at temperatures below approximately 473 K.

The deposition mechanism that determines the microstructure of colloidal films was investigated using a constant-filtration-rate procedure. In particular, we studied the dependence of the grain size on the filtration rate and the volume fraction of the particles in liquid. We correlated the surface diffusion distance to the final grain size and identified a processing window for large-grain colloidal films. The necessary conditions for homoepitaxy of colloidal crystals were successfully identified. In particular, the surface diffusion distance of deposited particles before embedment emerged as an important parameter for film microstructural control. Sufficiently long the diffusion distances correlated well with the slow deposition rates often required for crystal growth. Low deposition rates allowed more time for depositing particles to sample surface sites for low-energy configurations. This surface diffusion model for microstructure control has universal application to other film deposition methods for mono-dispersed particles.

The development of denser and higher powered integrated circuits has led to a corresponding demand on the performance of dielectric substrates. This paper reports on the fabrication and properties of an AlN multilayered sandwich substrate comprising porous tape-cast layers sandwiched between nonporous layers. Tapes were produced by nonaqueous tape casting, with the porous tapes produced using polymer microspheres as sacrificial molds. Starting from initially Al2O3-rich tapes, the multilayered sandwich substrates were reaction sintered to produce AlN substrates. No interface cracking or delamination was observed in the substrates as a result of the processing. The added porosity resulted in a decrease in the substrate dielectric constant in correspondence to porosity volume. Mechanical strength of the sandwich substrates was improved over that of nonsandwich porous substrates, while substrates having noninterconnected pores showing higher mechanical strength than substrates with connected pores. Substrates with more than 2% porosity showed porosity-dependent thermal conductivity values, while thermal conductivity of substrates with less than 2% porosity was dependent on grain boundary effects. Thermal expansion coefficient of the substrates was unaffected by porosity levels.

Morphology and analysis of composition of inclusions were done by secondary electron microscopy and spatially resolved energy-dispersive analysis of x-ray on semiintrinsic CdTe:Cl and CdTe:Zn:Cl crystals grown from the vapor phase by the modified Markov technique and on undoped CdTe crystals grown from the melt by the Bridgman method. In CdTe:Cl and CdTe:Zn:Cl crystals nonstoichiometric inclusions of about 10–20 μm were found, which contain high concentrations of Cl and Na impurities. The Cl is concentrated in small precipitates of 1–2 μm inside these inclusions. After short-time low-temperature annealing (600 °C), the inclusions mostly disappeared.

The cathodic deposition of iron–cobalt alloys inside the pores of anodically formed nanoporous silicon (PS) from p-type Si substrate is investigated with respect to the electrolyte composition. The samples were characterized by scanning electron microscopy, energy dispersive spectrometry, Auger electron spectroscopy, and Fourier transform infrared spectroscopy. Results showed that the nucleation of pure cobalt started at the bottom of the pores and the nucleation of pure iron occurred all over the pore walls, leading to a preferential deposition on top surface of the porous layer. Nevertheless, a low concentration of Co2+ ions (5 at.%) in the electrolyte drastically improved the penetration of iron into the pores. As a result, a good filling of the pores with Co metal as well as with Fe–Co alloys was achieved. It was also shown that the deposition process oxidizes the structure mainly at the pore walls. The results of our investigation indicate that the mechanisms occurring during the electrodeposition of metals on porous p-type silicon substrates are completely different depending on the kind of electrolyte used: pure iron-based electrolyte or cobalt-based solutions. A complete understanding of the deposition process requires further analyses of the carrier transport in PS and of the charge exchange at the Si/electrolyte and PS/electrolyte interfaces. These new results involving the deposition of iron-group materials into porous p-type silicon are useful for future silicon technologies.

The morphotropic phase boundary (MPB) composition that is characterized by the coexistence of rhombohedral and tetragonal phases in the Pb(Zn1/3Nb2/3)O3–BaTiO3– PbTiO3 system was modified by W-doping at the B site of a perovskite structural block. To maintain the electrical neutrality, creation of A-site vacancies was intentionally introduced in the formulation of the examined compositions. Incorporation of W ions was revealed to stabilize the tetragonal phase against the rhombohedral one, shifting the MPB toward the PZN-rich end at room temperature. High-temperature x-ray diffraction examination in combination with dielectric measurements discloses two successive phase transitions as a sample is cooled from high temperature, namely, paraelectric cubic to ferroelectric rhombohedral followed by ferroelectric rhombohedral to ferroelectric tetragonal. W addition appears to suppress the first transition while promoting the second one.

Polycrystalline samples of Ca1-xBixMnO3 (0.02 ≤ x ≤ 0.20) were studied by means of x-ray diffraction, electrical resistivity (ρ), thermoelectric power (S), and thermal conductivity (κ) at high temperature. Bi doping leads to the lattice parameters a, b, and c increasing. And the ρ and the absolute value of S decrease rapidly with Bi doping. The largest power factor, S2/ρ, is obtained in the x = 0.04 sample, which is 3.6×10−4 Wm−1 K−2 at 400 K. The figures of merit (Z = S2/ρκ) for this sample and 1.0×10−4 and 0.86 × 10−4 K−1 at 600 and 1000 K, respectively.

Comparative investigations are carried out for spectral (Raman) electrical and structural properties of V2O5 single crystals and polycrystalline samples obtained by IR laser light illumination of pure metallic samples in an oxidizing atmosphere (air). It is shown that the structures grown on metallic plates in the field of laser light are predominantly V2O5 polycrystals. Raman measurements reveal that the main peaks, which are characteristic for single crystals, are also present in laser-driven samples but with different intensities. Some peaks are attributed to laser-grown thick films, which are not present in the single-crystalline phase. There are shifts in the peak positions indicating the existence of different force constants for films as compared with crystals. The activation energies obtained from the electrical properties (conductivity, impedance versus temperature) yield similar values except for the anisotropic characteristics of the single crystal where the values are a bit different along different crystallographic axes (unlike the polycrystalline oxide films made by the laser). The single-crystalline phase has a well-defined layered structure with well-defined shapes showing formed units of truncated oktaeders, while the film structure shows randomly distributed tubular micron-size structures with empty holes at the peripheral part of the irradiated area, and nanoscaled long and thin tubes well oriented along the direction of the incoming laser light in the central part of the irradiation spot.

Fracture and deformation in model brittle-outerlayer/metal-core/polymer-substrate trilayer systems in concentrated loading are studied. Model systems for experimental study are fabricated from glass microscope slides glued with epoxy adhesive onto steel and aluminum sheets, and the resulting laminates glued onto polycarbonate substrate bases. Critical loads to initiate two basic fracture modes in the glass layers—cone cracks at the top surfaces and radial cracks at the undersurfaces—are measured as a function of metal thickness by in situ observation through the glass side walls. Finite element modeling (FEM) is used to quantify these competing fracture modes. The more damaging radial fracture mode is attributed to flexure of the glass layers on soft underlayers. Although much of this flexure can be eliminated by removing the soft adhesive interlayer between glass and metal, yield in the metal limits the potential increases in critical load for radial cracking. Trilayer systems consisting of porcelain fused to Co-, Pd- and Au-alloy core support layers relevant to dental crowns are then analyzed by FEM. The hardness (especially) and elastic modulus of the metal are identified as the primary controlling material parameters, with modulus and strength of the brittle layer as supplemental parameters. Guidelines for improving metal-based crownlike layer structures are thereby developed via optimization of metal properties and relative layer thicknesses.

The crystal structure of microwave dielectric ceramics in the (1 − x)La(Mg0.5Ti0.5)O3 (LMT)–xBaTiO3 (BT) (0 ≤ x ≤ 0.9) system has been refined by Rietveld method using x-ray powder diffraction data. LMT and BT were found to form a solid solution in the whole compositional range. The increase of BaTiO3 content results in the following sequence of structure transformations of those solid solutions: P21/n (a−a−c+, B-site ordered) → Pbnm (a−a−c+) → I4/mcm (a0a0c−) → Pm3m (a0a0a0). These structural changes are related to the disappearance of B-site cation ordering (x > 0.1), in-phase tilting (x > 0.3), and antiphase tilting (x > 0.5), respectively.

A symmetrically layered SiC/TiC ceramic with a gradual structure was designed by the finite element method (FEM). After sintering, proper thermal residual stress was introduced into the ceramic due to the coefficients of thermal expansion mismatch between the different layers. After different SiC + C interlayers were inserted into the layers to weaken the interface, the effect of the composition of the SiC + C interlayers between the layers on the residual stress was evaluated. It was found that the weak SiC + C interlayer had little relaxation effect on the residual stress distribution. These ceramics were then fabricated by aqueous tape casting, stacking, and hot-press sintering. An x-ray stress analyzer was used to test the surface stress conditions of the sintered materials. The tested surface stress of the layered SiC/TiC ceramic without interlayer was very close to the FEM calculation. However, there were differences between the tested and calculated results of the layered SiC/TiC ceramics with interlayers; the reason for this was analyzed.

Nano-sized copper particles are loaded into the pores of monolithic mesoporous silica by soaking and drying, followed by thermal reduction of copper nitrate [Cu(NO3)2]in a hydrogen atmosphere at 973 K for 90 min. It has been shown that copper nanoparticles are isolated from each other and highly uniformly dispersed inside the pores of silica. It is found that the surface plasmon resonance peak of the copper particles shows a significant red-shift with decreasing the particle size, which is in contrast to the corresponding fully embedded system. The peak decreases with exposure time to air and exhibits a linear relation with logarithmic exposure time. This red-shift phenomenon and decrease are explained on the basis of the structural features of this new composite or coexistence of local porosity and the nanoparticle's free surface in contact with air.

Nanowires were produced by injection of molten Hg and Pb into chrysotile nanotubes. The breakdown of chrysotile and the surface tension of the molten metals are the limiting factors for the filling procedure. The thermal stability of chrysotile nanotubes was investigated by infrared spectrometry, thermogravimetry, differential thermal analysis, and x-ray diffraction analyses. For short-term thermal annealing (30 min) the tube morphology remains stable up to 700 °C. The high surface tension of both molten Pb and Hg (γLV > 200 mN/m) requires external pressure for the melts to penetrate into the tubes. Filling of the tubes was achieved under high pressure and high temperature conditions compatible with the stability range for chrysotile determined in the annealing experiments. Transmission electron microscopy observations confirmed high filling yields for both metals. Almost all nanotubes were partially filled with lead. The length of continuous wires ranged from tens to hundreds of nanometers. Additional experiments with tin were not successful.

In situ reinforced microstructures with well-dispersed elongated grains, up to 10 μm in length, embedded in matrices consisting of submicron equiaxed grains, were developed by hot pressing Y-, Yb-, and (Y + Yb)-doped a-sialon ceramics containing approximately 3 vol% extra liquid phase at a comparatively low sintering temperature, 1800 °C. The liquid phase, thermodynamically compatible with a-sialon, was introduced by raising the oxygen content of an already oxygen-rich α-sialon composition, e.g., by increasing the O/N ratio in RExSi12-(3x+n) Al3x+nOnN16−n. Two different α–Si3N4 precursor powders, one fine-grained and one coarse, and one coarse β–Si3N4 powder were used, and the influence of particle size and crystalline modification of the precursor Si3N4 powder on the formation of elongated a-sialon grains was investigated. The formation of elongated α-sialon grains was promoted by introducing an extra liquid phase and by using a fine-grained α–Si3N4 powder, whereas the coarse β–Si3N4 powder did not yield any elongated grains at all. The obtained in situ reinforced α-sialon ceramics were both hard and tough, with a Vickers hardness and a fracture toughness of 21 GPa and approximately 5 MPa m1/2, respectively.

A two-parameter “area function” characterizing the depth-dependent projected area of an indenter was introduced and applied to a Berkovich tip. The two parameters have physical meaning, corresponding to the effective tip radius and effective cone angle. The indenter tip was calibrated on a commercial load-controlled Nano Indentert® XP (MTS Systems Corp., Eden Prairie, MN). All calibrations were carried out using the procedure of Oliver and Pharr [J. Mater. Res. 7, 1564 (1992)] using several homogeneous materials. Plane-strain modulus and hardness values deconvoluted from indentation load–displacement traces using the calibrated two-parameter area function compared well with the values determined using the empirical eight-parameter area function of Oliver and Pharr.

Semiconductor selenides of MSe (M = Cd, Hg) nanocrystalline powders were synthesized through the reactions between metal chlorides and sodium selenosulfate in the ammoniacal aqueous solution at room temperature for 6–10 h. The samples were characterized by x-ray powder diffraction, transmission electron microscopy, electron diffraction, x-ray photoelectron spectroscopy, and elemental analysis. The average diameters of CdSe and HgSe nanocrystallites are 4 and 8 nm, respectively. The storage and an interesting phase transition under hydrothermal conditions have been presented. The absorption spectrum of the as-prepared samples exhibits obvious blue shift due to the size confinement.

The free volume of metallic glasses has a significant effect on atomic relaxation processes, although a detailed understanding of the nature and distribution of free volume sites is currently lacking. Positron annihilation spectroscopy was employed to study free volume in a Zr–Ti–Ni–Cu–Be bulk metallic glass following plastic straining and cathodic charging with atomic hydrogen. Multiple techniques were used to show that strained samples had more open volume, while moderate hydrogen charging resulted in a free volume decrease. It was also shown that the free volume is associated with zirconium and titanium at the expense of nickel, copper, and beryllium. Plastic straining led to a slight chemical reordering.

The effect of pore size and uniformity on the humidity response of nanoporous alumina, formed on aluminum thick films through an anodization process, is reported. Pore sizes examined range from approximately 13 to 45 nm, with a pore size standard deviations ranging from 2.6 to 7.8 nm. The response of the material to humidity is a strong function of pore size and operating frequency. At 5 kHz an alumina sensor with an average pore size of 13.6 nm (standard deviation 2.6 nm) exhibits a well-behaved change in impedance magnitude of 103 over 20% to 90% relative humidity. Increasing pore size decreases the humidity range over which the sensors have high sensitivity and shifts the operating range to higher humidity values. Cole–Cole plots of 5 to 13 MHz measured impedance spectra, modeled using equivalent circuits, are used to resolve the effects of water adsorption and ion migration within the adsorbed water layer. The presence of impurity ions within the highly ordered nano-dimensional pores, accumulated during the anodization process, appear highly beneficial for obtaining a substantial variation in measured impedance over a wide range of humidity values.

Superplastic deformation was studied in fine-grained (0.7–1.1 μm) YBa2Cu3O7–x/Ag composites containing 2.5–25 vol% Ag. The compression tests were conducted in the temperature range of 750–875 °C and at strain rates of 10−5 to 10−3/s. For the YBa2Cu3O7−x/25%Ag composites with grain size of 0.7–1.1 μm, deformed at 800–850 °C and 10−5 to 10−3/s, the stress exponent, grain size exponent, and the activation energy of deformation were 2.0 ± 0.1, 2.5 ± 0.7, and 760 ± 100 kJ/mol, respectively. These values were the same as those of the pure YBa2Cu3O7−x, indicating that the deformation of the composite was controlled by that of the rigid YBa2Cu3O7−x phase. However, the strain rate was increased by the addition of silver as explained by the soft inclusion model of Chen. The dependence of the flow stress on the silver content was in close agreement with the prediction of the model.