The optical band gap of ZnO films on fused silica in the carrier concentration regime of 1018−1020/cm3 is reported. Contrary to theoretical predictions there is an anomalous increase in the band gap of ZnO films at a carrier concentration of 5 × 1018/cm3, followed by an abrupt decrease at a critical concentration of 3−4 × 1019/cm3 before the optical band gap rises again. Similar observations have been made before, but an explanation of these observations was lacking. We propose a model based on the existence of potential barriers at the grain boundaries, causing quantum confinement of the electrons in the small grains realized in these films. Quantum confinement leads to the initial rise in the optical band gap. On increasing the carrier concentration to the critical value, the potentials at the grain boundaries collapse, leading to the abrupt decrease in the optical band gap. Above this carrier concentration the films behave according to existing many-body theories.

Formation of nanocrystalline Fe–4 wt.% Al solid solution has been achieved through SPEX ball milling of blended elemental Fe and Al powders. Differential scanning calorimetry (DSC) and x-ray diffraction (XRD) have been employed to follow the structural evolution during the ball-milling process. Exothermic peaks exhibited in DSC diagrams of the powders milled for 10 to 60 min yielded thermal enthalpies corresponding to the formation of Fe–4 wt.% Al solid solution, from which the kinetics of formation were found to follow the Johnson–Mehl–Avrami equation. Assessment of the kinetic parameter n reveals a diffusion controlled mechanism, in which grain and interphase boundaries may play a crucial role, during the solid solution formation of Fe–4 wt.% Al.

RuO2 thin films have been produced on silicon-based substrates by in situ pulsed laser deposition for the first time. The electrical properties, the surface characteristics, the crystalline structure, and the film-substrate interface of deposited samples have been investigated by 4-probe resistance versus temperature technique, scanning electron microscopy, x-ray photoelectron spectroscopy, x-ray diffraction, and transmission electron microscopy, respectively. The films show good electrical properties. The RuO2-substrate interface is very thin (≈3 nm), since it is not degraded by any annealing process. These two characteristics render our films suitable to be used as electrodes in PZT-based capacitors.

The microwave dielectric characteristics and crystal structure of the Zn(NbxTa1−x)2O6 and Mg(NbxTa1−x)2O6 systems have been investigated. It was found that both systems exhibited a morphotropic phase transition. Based on the results it was suggested that permittivity and temperature coefficient of resonant frequency depend more on crystal structure rather than on chemical composition. It was also suggested that a two-phase mixture is better than a solid solution for achieving both high quality factor and good temperature stability.

The microstructure of Fe2O3 sol-gel thin films, obtained from Fe(OCH2CH3)3, was investigated by x-ray diffraction (XRD), transmission electron microscopy (TEM), and Raman spectroscopy. Samples were nanocrystalline from 400 °C to 1000 °C, and the crystallized phase was haematite. In the coatings, the α–Fe2O3 clusters were dispersed as single particles in a network of amorphous ferric oxide.

We have investigated the stability of the (Bi, Pb)2Sr2Ca2Cu3Ox phase for the stoichiometry (Bi: Pb: Sr:Ca: Cu = 1.72: 0.34: 1.83: 1.97: 3.13), subjecting it to temperatures between 700 and 850 °C under various oxygen partial pressures. A narrow region was found in which Bi, Pb(2223) was the only superconducting phase. This region follows closely the thermal decomposition line. X-ray pure Bi, Pb(2223) will partially decompose if treated outside of the stability region. For a given oxygen partial pressure, the Bi, Pb(2223) phase tends to coexist with the 2201 phase for temperatures above, and the 2212 phase for temperatures below this region. At even lower temperatures an additional lead-rich phase appears. Critical temperatures Tc vary little with treatment and range between 108.5 K and 110.8 K. If 10% silver is added to the starting powder, the phase coexistence regions shift. Silver does not seem to have a significant effect on the absolute values of the critical temperature. The Bi, Pb(2223) thermal decomposition temperature for a given oxygen pressure is lowered by at least 10 K by the presence of Ag.

Natural degradation of YBa2Cu3O7−δ powders leads to trapping of CO2 by the powder. The presence of residual carbon in ceramics or textured materials can strongly affect the superconducting properties. Optimal conditions for carbon elimination during thermal treatment are defined. Amounts of carbon lower than 500 ppm are easily obtained when thermal treatment is performed in temperature, gas flowing rate, and heating ramp conditions allowing CO2 departure before pore closure. Liquid phase formation and the presence of BaCuO2 are limiting factors. An oxycarbonate formed by reaction between this latter compound and evolved CO2 is implied in the last step of the decarbonation process.

A Cu-rich CuInSe2 (CIS) thin film with an atomic ratio of Cu/In = 3.6 was characterized using high-resolution and analytical transmission electron microscopy (TEM). The film was deposited on a Mo coated soda-lime glass substrate by physical vapor deposition. Rutherford backscattering spectroscopy (RBS) and Auger electron spectroscopy (AES) showed that a secondary impurity phase such as Cu2Se segregated on the CIS surface. The three-dimensional crystallographic relationship between the Cu2Se and CIS was found to be (111)Cu2Se (111)CIS and [011]Cu2Se || [011]CIS where the Cu2Se and CIS had pseudocubic structures with a = 5.8 Å and a = 11.6 Å, respectively. CuPt type CIS could be observed near the interface between the Cu2Se and CIS. A growth model of CIS crystals under Cu and Se excess condition is proposed based on the results of TEM. The characteristics of the CIS growth model in Cu-rich CIS film are summarized as follows: (i) CIS crystals are produced from Cu2Se crystals by a “topotactic reaction,” and (ii) sphalerite and/or CuPt type CIS are produced first after the reaction, and (iii) the metastable sphalerite and/or CuPt type CIS is then transformed to the stable chalcopyrite CIS phase.

The quantitative description of highly nonequilibrium processes for the preparation of metastable and unstable phases requires the determination of the thermodynamic functions of the system under investigation. However, in systems such as Cu–Cr which are immiscible in the equilibrium states, the determination of the thermodynamic functions over the entire concentration range is often difficult if not impossible because reliable experimental data are not available for the metastable or unstable regime. The present paper demonstrates that such data can be obtained by a combination of thin film deposition techniques and differential scanning calorimetry. It is concluded that the phase formation in such thin films can be described in terms of the thermodynamics of the system, even when the heats of mixing are highly positive. The results indicate that models of the regular solution type still provide a reasonable description of the thermodynamic functions of such alloys.

Stoichiometric composition and formation process of the icosahedral phase in the Zn–Mg–Y system have been studied. The icosahedral phase exhibit a stoichiometric composition in the vicinity of Zn60Mg30Y10. During cooling, (Zn, Mg)5Y phase primarily crystallizes from the melt at ∼960 K and then undergoes a peritectic reaction with the residual Mg-enriched melt (∼820 K) to form the icosahedral phase. The melt with a constant composition close to Mg7Zn3 is in equilibrium with the (Zn, Mg)5Y phase above the peritectic temperature in a wide compositional range.

Microstructures of two-phase Ti–Cr alloys (Ti-rich bcc + TiCr2 and Cr-rich bcc + TiCr2) are analyzed. A variety of TiCr2 precipitate morphologies is encountered with different nominal alloy compositions and annealing temperatures. Lattice constants and crystal structures are determined by x-ray diffraction (XRD) and transmission electron microscopy (TEM). Orientation relationships between the beta bcc solid solution and C15 TiCr2 Laves phase are understood in terms of geometrical packing, and are consistent with a Laves phase growth mechanism involving twinning.

Micropyretic synthesis technique employs self-sustaining exothermic (combustion) reactions for the preparation of various ceramic, intermetallic, and composite materials. In the present work, the combustion reactions of Mo and Si with Al additions have been systematically studied. The atomic mixtures of the reactant powders are chosen to be Mo + (2 − x)Si + xAl with x = 0−0.4. In comparison with the Mo + 2Si reaction which leads to the formation of MoSi2, the substitution of Al for Si decreases the sample ignition temperature, but increases the intensity of the combustion reactions. In addition, the substitution of Al for Si results in the formation of a ternary intermetallic phase, called molybdenum alumino-silicide Mo(Si, Al)2, in the synthesized product. When the content of Al in the reactant mixtures reaches 0.4, nearly single phase Mo(Si, Al)2 is obtained and no MoSi2 is detected in the reaction product. These influences are analyzed by using x-ray diffraction (XRD), scanning electron microscopy (SEM), and differential thermal analysis (DTA). The effect of Al additions on the reaction mechanism is also discussed.

The high energy mechanical alloying of a Ti–Ru–Fe powder mixture (atomic ratio 2 : 1: 1) has been performed by extensive ball-milling in a steel crucible. The structural evolution of the resulting materials has been studied by x-ray powder diffraction analysis. The identification of the various phases present in the materials, as well as the crystallite size and strain, has been performed by Rietveld refinement analysis. In the first stage of the material transformation, Ru or Fe atoms dissolved into Ti to yield to the formation of β–Ti. Upon further ball-milling, almost all the original constituents of the powder mixture have disappeared and a new simple cubic Ti2RuFe phase is formed, with a crystallite size as small as 8 nm. The electrochemical properties of these materials have been tested in a typical chlorate electrolyte by cold-pressing the powders into disk electrodes. At 20 h of ball-milling, where the phase concentration of Ti2RuFe reaches 96%, a reduction of the activation overpotential at 250 mA cm−2 of nearly 250 mV is observed when compared to that of a pure iron electrode.

We examine quantitatively the impact of boundary nucleation on the size distribution of product grains in a computer simulation of a two-dimensional phase transformation. This is accomplished by determining the probability distribution of product grain areas under different nucleation conditions. Specifically, a comparison of the moments of normalized area distributions of product grains arising from site-biased nuclei with the corresponding moments of the area distribution of Voronoi grains reveals those spatial features of the collection of catalytic sites which most affect product microstructure. The impact of other relevant length scales, including the square root of the inverse nucleation site density, the lattice parameter, and the system size, on microstructure is also discussed.

A new design for solid oxide fuel cells (SOFC's) was developed aiming at the reduction of the total electrical resistance of the cell. The thickness of the electrolyte was decreased, while the anode took on the role of the substrate. The pore structure with respect to gas permeability of this component has to be optimized for the proper operation of this design. Anode substrates, consisting of a cermet (yttrium-stabilized ZrO2 and metallic Ni) and produced by two different processes, coat mix and tape casting, were characterized with respect to pore structure (shape and mean radius), porosity (total, open and permeable), pore size distribution and air permeability. The following methods were used: (i) optical and electron scanning microscopy in combination with image analysis, (ii) mercury porosity, and (iii) air permeability. Correlations between air permeability and porosity and also the percentage of permeable pores in anodes show the superiority of coat mix samples to tape-cast ones. It has been observed that the coat mix process can produce anode substrates with interconnecting porosity, while tape casting, as used in this study, needs some modifications in order to be appropriate for this purpose.

As-synthesized, low iron content, ferrisilicates of ZSM-5-type contain well-separated Fe(III) ions in a tetrahedral environment and display paramagnetic behavior. After hydrothermal treatment, the iron ions are partially extracted from the framework, generating nanosize iron oxide or oxyhydroxide ferrimagnetic particles. This process has been studied by transmission electron microscopy (TEM), Mössbauer spectroscopy, magnetic ac susceptibility (χac), and field dependent magnetization, on samples containing up to 6.7 wt.% Fe. The experiments evidence the growth of nonaggregated particles, with a typical size around 3 nm, presumably located at the surface of the ferrisilicate crystallites. From a thorough granulometric analysis involving TEM and χac data, it is concluded that, in the range from 1.5 to 4.6 wt.% Fe, the particle size distributions are significantly independent of the iron content.

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 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.

The growth of the shells of C60 crystals was carried out under various conditions. The detailed structures of the grown shells were investigated by transmission electron microscopy and Raman spectroscopy. The shells were formed during thermal sublimation of the C60 crystals, which were irradiated with white light in air. The shells were mainly composed of a kind of amorphous carbon. From these results, it is suggested that the oxygen-induced disintegration of C60 cages is responsible for the shell formation.

Carbon fibrous deposits grown in carbon dc electric arc at various buffer gas pressures and arc currents were investigated by transmission and scanning electron microscopy. The fibers contained in the deposits consisted of bundles of carbon tubes. It was found that yield and morphology were very sensitive to both parameters; sintering of the tubes could be prevented by adjusting buffer gas pressure for a given current. It is argued that these parameters control expansion of carbon gas and condensation rate, and therefore energy flow to the cathode. To purify samples by oxidation and to observe differences in resistance against oxidation of samples obtained at various conditions, the thermogravimetry method was used.