Molten nitrates in the system (1 − x)NaNO3−xBa(NO3)2 were solidified in the presence of a power ultrasound of 20 kHz. Their microstructures were compared with those of controlled samples which were solidified normally. Grain size in the controlled sample of monolithic NaNO3 (x = 0) was reduced by sonication. In the hypo- (x = 8 wt. %) and the hypereutectic (x = 28 wt. %) binary samples, the sonication completely eliminated the dendritic structure of the primary crystals and induced equiaxed particles of the primary phase. At eutectic (x = 18 wt. %), the sonication removed oriented structures of the eutectic lamellae. Several mechanisms of the microstructural modification were mentioned.

The activated chemical vapor deposition (CVD) diamond process became one of the worldwide interesting projects in the 1980s. The basic question is why diamond can grow under activated low pressure conditions. The driving force of the transformation from graphite to diamond under low pressure is coming from a coupled reaction of the association of superequilibrium atomic hydrogen. The thermodynamic coupling effect in the activated CVD process is different from the catalyst effect in the high pressure, catalyst-assisted process for the artificial diamond growth.

The present study involved the fabrication of three-layered composites consisting of outer layers that contained Si3N4 and an inner layer that contained TiN in a Si3N4 matrix. Surface compressive stresses were developed upon cooling due to the relatively higher thermal expansion coefficient (CTE) in the inner layer. The flexural strength of layered Si3N4 composites was substantially greater than that of monolithic Si3N4. This was attributed to the surface compressive stress. The effects of TiN composition and inner layer thickness on the mechanical properties were investigated. Layered samples containing 20 vol.% TiN had lower flexural strength than Si3N4–10% TiN/Si3N4–Si3N4 due to the formation of microcracks in the inner layer. Crack behaviors in layered samples were affected by the residual stress, interface, and free sample surface. Both theoretical and experimental results indicated that the strength and toughness of layered composites were substantially greater than those of monolithic materials. The determination of fracture toughness in three-layered materials by the surface indentation technique should be done carefully due to the influence of residual stress.

A porous and discontinuous Si3N4-based fiber coating was evaluated in SiC/Si3N4 minicomposites by fiber push-out and fractography for debond capabilities following high temperature exposures. The exposures consisted of 500 h annealing at 1350 °C, and 25–100 h oxidation in wafer form at 1200–1400 °C. In spite of considerable microstructural coarsening and/or oxidation of the coating, fiber debond and sliding were achieved in all cases, and at stress levels comparable to those reported for tough, as-fabricated SiC/Si3N4 composites with a carbon or boron nitride interphase. Therefore, the porous coating is expected to perform better than C or BN in applications where oxidation is inevitable. The role of porosity in accommodating and mitigating the effects of oxidation is thought to be important.

The results of high resolution transmission electron microscope (HRTEM) observation and image simulation show that Zr4Co4Si7 possesses the same structure type of Zr4Co4Ge7. Addition of Fe or Ni into the Zr4Co4Si7 compound, except that the dimensions changed slightly, does not change the lattice type and coordination in the crystal structure, maintaining the V-phase structure. Also, twins with coherent boundaries and partially coherent interfaces are observed. The image conditions of Zr4Co4Si7 and the structure differences between Zr4Co4Si7 and tetrahedral close-packed phases are also discussed.

The “aging” characteristics of an acetic acid/methanol solvent-based lead zirconate titanate (PZT) precursor solution, prepared by the Inverted Mixing Order (IMO) process, have been studied for an extended period of time. The changes in film properties were characterized using optical microscopy, optical scattering, and ferroelectric testing. Films generated from the IMO process exhibit an increase in thickness as a function of solution age due to chemical “aging” (esterification) of the precursor solution. This increased thickness results in a decrease in the microstructural uniformity, which affects the electrical and optical properties. In order to understand and eventually control this phenomenon, we have quantified the “aging” of this solution using a variety of analytical methods, including 1H NMR spectroscopy, pH measurements, and Fourier transform infrared (FTIR) spectroscopy. It is of note that we have discovered a method that circumvents this “aging” problem by removal of the volatile material, forming an IMO powder which can be redissolved to produce high quality PZT thin films whenever desired.

The influence of starting carbon material on the generation of carbon nanotubes is investigated. Comparisons are made between oriented graphite, randomly oriented graphite, carbon black, and a polycyclic aromatic hydrocarbon as carbon sources in helium and hydrogen arcs. Transmission electron microscopy investigation of the redeposited rod formed on the cathode and the soot from the chamber walls provides evidence for the building blocks that lead to the nanostructures formed. It is postulated that polycyclic aromatic hydrocarbons are precursors for carbon nanotube growth in a hydrogen arc. While, in the case of helium, low molecular weight carbon ions and molecules have been previously hypothesized by others to be the building blocks for nanotube growth.

Hydrogen uptake and discharge by thin metallic films under potentiostatic control was studied using x-ray diffraction at the National Synchroton Light Source (NSLS). The formation of metal-hydrogen phases in Pd, Pd-capped Nb, and Pd/Nb multilayer electrode structures was deduced from x-ray diffraction data and correlated with the cyclic voltammetry (CV) peaks. The x-ray data were also used to construct a plot of the hydrogen concentration as a function of cell potential for a multilayered thin film.

Magnesium titanate and MgTiO3–CaTiO3 ceramics were prepared by a chemical (Pechini) route and classical mixed oxide route. Selected specimens were doped with Cr or La. Specimens were sintered at 1350 °C and 1400 °C. Microstructures were examined by optical microscopy, scanning electron microscopy, and transmission electron microscopy. Dielectric properties were determined at 8 GHz by the Hakki and Coleman method. The highest Q values were obtained for undoped, chemically prepared MgTiO3 (20800); any dopants caused the Q value to be degraded. Additions of small amounts of Cr (≤1 mol %) to mixed oxide magnesium titanate increased the density to 97.1% theoretical, and increased the Q value (from 7000) to 13,000. Additions of La led to the formation of La2Ti2O7 second phase and reduction in the Q value for both materials. Both Cr and La acted as effective sintering aids, increasing density (to a maximum of 99% theoretical for 1% mol La in chemically prepared samples) and relative permittivity (to 18.1 for the same specimens). The relative permittivity of MgTiO3–CaTiO3 ceramics increased with calcium content, but the corresponding Q values decreased (∈r = 19.9, Q = 8500 for Mg:Ca = 94: 6). Small additions of La to Mg–Ca titanates enhanced the dielectric Q values but decreased the relative permittivities.

Ceramics were prepared by hot pressing of chemical mixtures of turbostratic boron nitride with copper. A positive effect of copper on boron nitride crystallization and densification has been found. Preferred orientation of boron nitride grains has been revealed in such ceramics, being opposite to general experience: the c-axis of boron nitride crystallites was arranged preferably within a plane perpendicular to the direction of uniaxial pressure. Such an arrangement is interpreted as a result of the uniaxial compression of the boron nitride grains extensively growing within the c crystallographic axis.

Epitaxial PbTiO3 films have been grown on vicinal (001) SrTiO3 substrates by pulsed laser deposition. Vicinal SrTiO3 substrates with misorientations up to 9° from (001) were used, and the influence of the direction of misorientation on the resulting domain structure was studied. 4-circle x-ray diffraction analysis indicates that thin (40 nm) PbTiO3 films are completely c-axis oriented [rocking curve full-width-at-half-maximum (FWHM) of 0.25° for the 002 reflection] and that thicker films (∼ 200 nm) contain mixed a-axis and c-axis PbTiO3 domains due to twinning along {011} planes. The [100] axis of the a-axis domains is misoriented by 2.1° to 3.3° toward 〈100〉 substrate directions with respect to the substrate normal. In contrast to growth on well-oriented (001) SrTiO3 surfaces where the four equivalent tilts of the [100] axis of the a-axis domains are equally likely, on vicinal SrTiO3 the a-axis domains are preferentially oriented in an uphill direction with respect to the crystallographic miscut.

A model of lead phosphate, which describes the rhombohedral-monoclinic phase transition, is used to form domain patterns in the annealing process. The obtained domain structures show W and W′ types of domain walls in agreement with the stress-free laws proposed in Sapriel's theory. The observed W domain walls are parallel to the ternary symmetry axis, while the W′ ones are tilted with respect to the same axis. The antiphase domain walls take no preferential orientations, and remain parallel to the ternary axis. The calculated density of the potential energy of the domain wall of type W is estimated to be Edw = 49 K/Å2 at T = 300 K.

The microstructure of Pb(Zr, Ti)O3 (PZT) and PbTiO3 (PT) thin films deposited by the sol-gel method and chemical vapor deposition, respectively, were examined by transmission electron microscopy (TEM). Domains with ∼7 and ∼20 nm widths were found for the PZT and PT thin films, respectively. The traditional parallel twin or wedge-type structures found in bulk ceramics have been observed in thin films. Differences between observed grain sizes and previous studies of similar compounds (in bulk form) are accounted for by geometrical considerations related to crystallographic factors. Finally, a classification scheme for domains in PZT and PT thin films based on these and other published results of several researchers is presented. Domain sizes varied according to three categories: mono-domains (2–50 nm in diameter), domains in spherulite lamellae (28–130 nm wide), and twins in conventional large grains (5–150 nm wide). The mono-domains are related to small grain sizes, while the lamellae are a function of the nucleation and growth associated with sol-gel processing.

The abnormal aging behavior, i.e., severe aging in the electric field induced piezoelectric coefficient while very weak dielectric aging, observed in the relaxor ferroelectric lead magnesium niobate-lead titanate (PMN-PT) ceramics under a dc electric bias field, can be significantly reduced by hot isostatic pressing (HIP) treatment on presintered samples. The aging can also be reduced by doping suitable amounts of either La (donor) or Mn (acceptor). We suggest that the reduction in the aging is due to the introduction of additional random fields into the material, which reduces the probability of the growth of micropolar regions into metastable and/or stable macropolar domains. The abnormal aging behavior and the effectiveness of HIP in reducing it indicate the importance of the elastic energy in controlling the aging and relaxor behavior in PMN-PT relaxor ferroelectrics.

Two kinds of characteristic grain boundaries were observed in textured Bi2Sr2Can−1CunOx (n = 2 and 3) bulk material: one (P-type) is nearly parallel to the (001) plane, and the other (N-type) is approximately normal to the (001) plane. Low-angle tilt N-type boundaries are composed of arrays of dislocations. However, for a small c-axis misorientation, the regions between the dislocation cores are still well connected, providing “pathways” for supercurrents crossing the boundary plane. The P-type boundaries exhibit compositionally and structurally modulated faceting. Although we see local regions of the low Tc (2201) phase at low-angle tilt (<10°) P-type boundaries, there are also “pathways” crossing the boundary plane made up of the high Tc (2212) and (2223) phases. The characteristics of such low-angle tilt grain boundary structures can therefore be modeled to provide general insight into the correlation between high critical current densities and low-texture breadths. On the other hand, a weak link could be formed at high-angle (> 10°) boundaries where there are the low Tc (2201) or insulating phases.

Formation of the ternary compound Cu3BiS3 during annealing of chemically deposited CuS (∼0.3 μm) films on Bi2S3 film (∼0.1 μm on glass substrate) is reported. The interfacial atomic diffusion leading to the formation of the compound during the annealing is indicated in x-ray photoelectron depth profile spectra of the films. The formation of Cu3BiS3 (Wittichenite, JCPDS 9-488) is confirmed by the x-ray diffraction (XRD) patterns. The films are optically absorbing in the entire visible region (absorption coefficient 4 × 104 cm−1 at 2.48 eV or 0.50 μm) and are p-type with electrical conductivity of 102−103 Ω−1 cm−1. Potential applications of these films as optical coatings in the control of solar energy transmittance through glazings and as a p-type absorber film in solar cell structures are indicated.

Effects of interlayers on diamond nucleation were investigated for the Si substrates. Interlayers were deposited on the diamond-abraded Si substrates by rf sputtering prior to diamond growth using microwave plasma chemical vapor deposition (CVD). Compared with 1 × 108/cm2 for the just abraded substrate, the nucleation density was greatly enhanced to 1 ∼ 2 × 109/cm2 by 50 nm thick interlayer, irrespective of the kind of interlayer material used in this study (Si, Mo, Ti, Pt, Ag, TiN, or SiO2). As the thickness of the Si interlayer increased from 20 to 500 nm, the nucleation density reached a maximum value, 3 × 109/cm2 at 100 nm. However, the growth rate was monotonically reduced from ∼300 nm/h to ∼100 nm/h. For the 700 nm thick Si interlayer, no diamond growth was observed. These results indicate that there is an optimum interlayer thickness around 100 nm for the higher nucleation density. The role of the interlayer in enhancing the nucleation density is believed to protect the nucleation sites generated by the diamond abrasion, otherwise they could be considerably etched away by atomic hydrogen during the initial diamond deposition.

In this paper we demonstrate a novel liquid-exchange process to replace a secondary silicon phase in reaction-bonded siliconized silicon carbides (RBSC's) with a ductile metal reinforcement phase. When RBSC is exchanged with pure Al or Al–Si liquid, secondary phase silicon is dissolved and is substituted by Al or Al–Si alloy. The resulting composites show improvements in fracture toughness (single-edge precracked beam technique), with KIC value up to 8.6 Mpa · m1/2, compared to 3–4 MPa · m1/2 in otherwise similar siliconized silicon carbide. Increased fracture strength (four point flexure) was also observed after the liquid exchange process. The processing furthermore allows the coefficient of thermal expansion to be adjusted, and the thermal conductivity increased, for electronic packaging applications.

Epitaxial lanthanum aluminate (LaAlO3) thin films were deposited on single-crystal substrates by pyrolysis of spin-on mixed nitrate precursors. The films are epitaxial without any second phase. TEM micrographs show that all of these films have pores with sizes ranging from 5 to 30 nm. Grain boundaries are not observed. Selected area diffraction shows that the films are single-crystal-like, despite the porosity. All the films are smooth and crack-free. The precursors first decompose into an amorphous mixture. Heterogeneous nucleation occurs on the lattice-matched, single-crystal substrate surface. The epitaxial films grow upward and consume the amorphous regions. The crystallization temperature of LaAlO3 is lower for thin films than for bulk samples due to nucleation on the substrate. The crystallization of LaAlO3 does not exhibit linear growth kinetics. The Johnson–Mehl–Avrami exponent of growth is between 1.4 and 1.5. This deviation from the linear growth model (n = 1) can be attributed to continuous nucleation on the substrate/film interface.

The uniformity and reaction kinetics of ion-beam deposited Al/Ni multilayer samples with the same composition, Al81.8Ni18.2, and modulation wavelength, Λ = 20 nm, but with different total film thicknesses were investigated by x-ray diffraction and differential scanning calorimetry measurements. The total film thicknesses varied between approximately 0.5 and 2.0 μm. It was found that the interface widths were approximately 1 nm and the Ni layers are much more disordered than the Al layers. The thicker samples show an increase in disorder on a length scale comparable to Λ. In other experiments, a change was observed with increasing modulation wavelength from semicoherent interfaces with a low density of misfit dislocations to semicoherent interfaces with a high density of misfit dislocations. The reaction kinetics for forming the Al9Ni2 phase is independent of the sample thickness.