We report the first observation of large graphitic capped clusters with threefold symmetry (tripods). They were generated under the diamond growth conditions by the chemical vapor deposition process activated by hot filaments on a Cu(111) surface while conditions of very poor diamond nucleation (104–105 cm-2) are fullfilled. They were characterized by direct high resolution imaging and selected area diffraction. Furthermore, a lot of them are connected. The behavior of hydrogen radicals to curl and to close limited-size graphitic planes is emphasized to explain their formation. These tripods appear to be readily stable carbon as they form only after other limited-size graphitic clusters such as graphite lumps or bucky onions. It is thus expected that the chemical vapor deposition process is a quite relevant preparation method to grow in a controlled way new forms of carbon with a narrow size distribution.

Calcium phosphate coatings, obtained at different deposition rates by pulsed laser deposition with a Nd:YAG laser beam of 355 nm wavelength, were studied. The deposition rate was changed from 0.043 to 1.16 Å/shot by modification of only the ablated area, maintaining the local fluence constant to perform the ablation process in similar local conditions. Characterization of the coatings was performed by scanning electron microscopy, x-ray diffractometry, and infrared, micro-Raman, and x-ray photoelectron spectroscopy. The coatings showed a compact surface morphology formed by glassy grains with some droplets on them. Only hydroxyapatite (HA) and alpha-tricalcium phosphate (α–TCP) peaks were found in the x-ray diffractograms. The relative content of (α–TCP diminished with decreasing deposition rates, and only HA peaks were found for the lowest rate. The origin of (α–TCP is discussed.

The mechanism for combustion synthesis (CS) of AlN was investigated in the present paper. A novel quenching technique was developed to retain the high-temperature structure formed in the sample during the combustion process. Based on the microstructural observation of the quenched specimen and thermodynamic analysis, a two-step reaction mechanism for CS AlN, i.e., vaporization of Al and subsequent reaction with N2, is proposed.

Thin films of poly(ethylene 2,6-naphthalate) (PEN) were isothermally crystallized at 190 °C after being melted at 300 °C. Morphological observation by transmission electron microscopy (TEM) showed the spherulitic texture in the films. Selected-area electron diffraction (SAED) indicated that the crystals in the films are the a form, as expected from our thermal condition for crystallization. The SAED pattern from the untilted specimen was characterized by the fairly intense reflection ring accompanied by other weak rings, and this intense ring was indexed as 010. A series of SAED patterns, which were obtained from the same specimen area tilted at various angles in the TEM column, suggested that the crystallites are oriented with their (001) planes being preferentially parallel to the film surface. Subsequently, a set of the dark-field images of the two-dimensional spherulite taken by using two different parts of the 010 reflection ring revealed that most of the crystallites in such a spherulite are oriented with their (010) planes being parallel in its radial direction. In addition, the spherulites in small pieces (0.05–0.08 mm thick) of PEN, which had been crystallized under the same thermal condition as above, were determined to be negatively birefringent by polarizing light microscopy.

Mixed composition layered lead zirconate titanate (PZT) films sZr/Ti ratio = 30/70 + 65/35d with stoichiometric lead containing PZT thin layer at the film/electrode interface were successfully fabricated by a modified chemical solution deposition method. These modified PZT thin films are highly (111) textured, and have square-shaped P-E hysteresis loops with large remanent polarization and low coercive field, as well as low saturation voltage. In addition, these films show good fatigue and imprint behavior with Pt electrodes; the retained polarization of the modified film was above 50% after fatigue testing to 109 cycles, and the thermally induced voltage shifts (ΔV) were 0.51 V after heating at 150 °C for 4410 s, two times lower than for films without a stoichiometric thin layer.

A low-temperature method was used to synthesize a nickel–chromium–zinc ferrite from stainless steel pickling liquor, a waste product of the steel industry, which is listed in most industrialized countries as a toxic and hazardous waste. This article reports the recovery (as a valuable ferric product) of the total metal content of this waste (namely, iron, chromium, nickel, and minor manganese), by coprecipitation of the multi-ionic solution and Zn2+ (provided by ZnO) with 1 M n-butylamine at room temperature. The spinel-type ferrite produced was characterized by x-ray diffraction, thermogravimetric analysis and differential scanning calorimetry, and scanning electron microscopy. Its recorded magnetization of 2600 emu cm−3 allows its use in different magnetic applications. Furthermore, the synthesis method is a low-cost technology that yields a more environmentally friendly final effluent.

Sodium silicate intergranular films (IGF) in contact with the [0001] basal plane of α-alumina were studied using the molecular dynamics computer simulation technique. The results were compared to previous simulations of calcium silicate and sol-gel silica IGF's in contact with alumina. An ordered, cagelike structure was observed at the interface. Sodium ions segregated to the cages at the interfaces. Calcium and hydrogen ions were also observed to segregate to the cages in the previous simulations. The modifier ions were surrounded by more oxygen ions in the cages at the interface than in the bulk of the IGF. This explains the segregation of modifiers at the interface. Interface energy decreased as the sodium content of the IGF increased. Interface energy decreased faster as a function of Na2O content than as a function of CaO content. However, interface energy decreased slower as a function of Na+ content than as a function of Ca2+content.

Persistent spectral hole burning was observed in Eu3+-doped BaO–PbO–P2O5 glasses, and the dependence of hole properties on the glass composition was investigated in relation to the local structure surrounding the Eu3+ ions. The hole was burned on the 7F0 → 5D0 transition of the Eu3+ ions, the depth of which decreased with increasing PbO content, whereas the hole width increased. The hole was burned at 6 K, filled on increase in temperature, and erased above 120 K. Judd–Ofelt parameters and fluorescence line-narrowing spectra indicated that the symmetry of the Eu3+ site increases and the covalency of the Eu–O bond decreases with increasing PbO content.

It has been observed that diamond deposition by flat flame chemical vapor deposition is achieved over a very narrow range of reactant composition. We demonstrate that this diamond deposition window is strongly determined by the nature of the substrate material. Furthermore, once a continuous diamond film is formed, the window appears to be independent of the original material. Substrates examined include silicon, glass, titanium, tungsten, nickel, and molybdenum. The dependence of growth rate, morphology, and quality on reactant composition has been quantified using scanning electron microscopy, Raman spectroscopy, and secondary ion mass spectroscopy (SIMS). It was found that the highest quality diamond was grown at conditions where diamond does not nucleate on ultrasonically scratched silicon. Thus, the production of high quality diamond on silicon by combustion synthesis requires different conditions for nucleation and growth.

Silicide formation in implanted channels and interfacial reactions of Ni, Co, Ti, and Cu contacts under high current density have been investigated. Silicide lines, forming in the implanted channels, were observed in Ni and Cu/p+–Si samples but not in Ti and Co samples. The silicide line formation is correlated to the high diffusivity of metals in Si. For the Ni/p+–Si sambles, silicode line was found to initiate form the cathode contact. Network structures at the cathode were found in both Co and Ni samples. The depth of silicide formation was found to extend to the junction depth. The relationships between the silicide length and contact size, the applied current, and the method of the applied current are discussed.

The role of the electrical conductivity of the product and of the thermal conductivities of the reactants on self-propagating combustion synthesis was investigated through modeling studies. Similar studies were made to investigate the role of the relative density of the reactants. The effect of an imposed electric field on the results of the modeling analysis was considered. For any given imposed field, the wave velocity exhibited a maximum at a given normalized thermal conductivity, electrical conductivity, and relative density. The results are discussed in terms of the Joule heat contribution of the field and are compared with experimental observations.

A proper powder preparation technique was used to develop elongated β–Si3N4 particles as seeds from raw materials. The phase transformation and development of microstructure in Si3N4 ceramics containing β–Si3N4 seeds were investigated. The specimens of seeded silicon nitride had higher phase transformation rates than the specimens without seed. A core/shell structure was observed by transmission electron microscopy in seeded specimens owing to the difference in aluminum concentration in Si3N4 grains. The misfit between the core and the shell was accommodated by interfacial dislocation that has a rotation character. The growth mode was epitaxial, although there was some compositional difference between the core and the shell. A relatively larger grain size and wider grain size distribution in seeded Si3N4 specimens was due to the amount of β-phase seeds that could act as the nuclei, and the final modification of the microstructure was due to the coalescence process. The crack wake process characterized the mechanism of toughening.

Ln3+-stabilized Na2SO4 (phase I) single crystals were grown by the Czochralski method. Differential thermal analysis revealed the influence of the ionic radius of Ln3+ on the stabilization of Na2SO4(I). Distribution coefficients (∼0.8–1.1) were measured by the inductively coupled plasma optical emission spectroscopy method and x-ray fluorescence spectroscopy. Spectroscopic investigations yielded absorption cross sections of 0.6 × 10−20 cm2 (π-polarized, 928.5 nm) and 1.5 × 10−20 cm2 (π-polarized, 797.3 nm) for Yb3+, La3+:Na2SO4 and Nd3+:Na2SO4, respectively. Crystal growth of Gd3+-stabilized Na2SO4(I) provides an interesting new material for stimulated Raman scattering experiments.

In order to make the surface of chemically vapor deposited diamond (CVDD) substrates amenable to metallization by both thin and thick film approaches currently utilized in electronic packaging, a thin, adherent, insulating aluminum oxide film was grown on diamond at low temperatures (<675 K). The film was produced by reactive thermal evaporation of Al and O in an oxygen atmosphere, followed by low-temperature annealing in oxygen. A Cr intermediate layer was deposited on diamond prior to the deposition of aluminum oxide in order to enhance adhesion between the oxide and diamond. The chemistry, crystal structure, and microstructure of the film were characterized in detail via scanning and transmission electron microscopy, as well as Auger electron spectroscopy. Particular attention was given to the mechanisms of bonding across the CVDD-Cr and Cr-alumina interfaces, as well as the stability of the surface treatment following metallization by fritted pastes requiring firing at elevated temperatures. The Cr was found to be bonded with CVDD by Cr23C6 formation, while the bonding between the Cr and alumina layers was provided by the formation of a compositionally modulated solid solution with Al2O3-rich and Cr2O3-rich regions.

Mullite-zirconia composites were synthesized by reaction-sintering powder mixtures of α-alumina, amorphous silica, and 3 mol% yttria-stabilized zirconia. It is found that the addition of 3 mol% yttria-zirconia improves sintering and lowers the mullitization temperature. It also suppresses the cristobalite formation and enhances zircon formation between 1300 and 1400 °C. Results further suggest that these effects are consequences of modification of the silicate glass by yttria. Samples containing ≥20 vol% of 3 mol% yttria-zirconia could be sintered at 1500 °C for 2 h to obtain dense composites consisting of mullite and tetragonal zirconia. The microstructural investigations of the sintered samples support the viewpoint that mullite formation is via nucleation and growth from aluminosilicate glass. They also reveal that zirconia can hinder the grain growth of mullite and that the coalescence of zirconia grains is accomplished by grain boundary diffusion.

The resistivity of SrRuO3 thin films on (001) SrTiO3 substrates grown at different temperatures by pulsed laser deposition is correlated to the microstructure. Films grown at 775 °C are of an orthorhombic structure, contain very few defects, and exhibit a low resistivity of 150 μΩ cm. Films grown at other temperatures contain a cubic phase and show higher resistivities. The defects present in the films, particularly twins and antiphase boundaries, are analyzed by high-resolution transmission electron microscopy, and their origin, as well as influence on film resistivity, is discussed.

A 13.56 MHz low pressure inductively coupled plasma (ICP) has been applied to prepare diamond films. The Faraday shield drastically suppressed the electrostatic coupling, which frequently causes contamination due to the etching of the quartz tube. The characterizations of the obtained deposits by scanning electron microscopy (SEM), transmission electron diffraction (TED), and reflection high energy electron diffraction (RHEED) revealed that the deposits are composed of microcrystalline diamond and disordered microcrystalline graphite. The CO additive to a CH4/H2 plasma brought about the morphological change from a scale-like deposit to a particle one. Besides, the number of encountered particles was increased with an increase of CO additive. The TED and RHEED observations showed that non-diamond carbon was effectively removed with an increase of CO additive. These results indicate that oxygen-contained radicals produced by the addition of CO play an effective role in the removal of non-diamond carbon in the diamond growth conditions and that the CO additive makes the supersaturation degree of carbon large.

High-temperature oxidative drop solution calorimetry was used to measure the enthalpy of formation of α− and β−Si3N4. Two different solvents, molten alkali borate (48 wt% LiBO2 · 52 wt% NaBO2) at 1043 and 1073 K and potassium vanadate (K2O · 3V2O5) at 973 K, were used, giving the same results. Pure α− and β−Si3N4 polymorphs have the same molar enthalpy of formation at 298 K of −850.9 ± 22.4 and −852.0 ± 8.7 kJ/mol, respectively. The unit cell dimensions of impure α−Si3N4 samples depend linearly on the O and C impurity contents, and so does the molar enthalpy of formation. The energetic stability of the α−Si3N4phase decreases when the sample contains O and C impurities. The experimental evidence strongly suggests that the impurities dissolve into the α−Si3N4 structure to form a (limited) isostructural solid solution series but that this solid solution series is energetically less stable than a mechanical mixture of pure (α or β) Si3N4, SiO2, and SiC. Thus, the α-phase is not stabilized by impurities and is probably always metastable.

The effect of mechanical deformation via high-energy ball milling on the structure of the Fe40Ni40P14B6 metallic glass was studied by means of x-ray diffactometry, transmission electron microscopy (TEM), and differential scanning calorimetry (DSC). After 5 h of milling, TEM observations indicated that some nanocrystallites with a diameter of about 6 nm precipitated from surface layers of the amorphous ribbons, whereas the bulk remained amorphous. When milling time was increased to 11 h, bulk crystallization occurred. The amorphous Fe40Ni40P14B6 alloy crystallized into a mixture of γ–(Fe, Ni) and (Fe, Ni)3(P, B). To understand the microstructural changes occurring in the amorphous ribbons before the onset of bulk crystallization, the isothermal crystallization behavior of as-deformed amorphous ribbons was studied. Compared with as-quenched amorphous ribbons, the local value of the Avrami exponent, derived from isothermal DSC data, increased from 3.5 to 4.1 for bulk crystallization. The thermal crystallization mechanism of deformed amorphous Fe40Ni40P14B6 ribbons changed from an eutectic-type reaction with simultaneous precipitation of γ–(Fe, Ni) and (Fe, Ni)3(P,B) from the amorphous matrix to a primary-type reaction with precipitation of α–Fe(P,B) preceding the formation of γ–(Fe,Ni) and (Fe,Ni)3(P,B). Our results suggest that several hours of mechanical milling cause surface crystallization and some atomic rearrangements in the amorphous alloy. The latter effect may be responsible for the observed primary-type reaction for crystallization of the deformed amorphous alloy

Ferroelectric SrBi2Ta2O9 (SBT) thin films on Pt/ZrO2/SiO2/Si were successfully prepared by using an alkanolamine-modified chemical solution deposition method. It was observed that alkanolamine provided stability to the SBT solution by retarding the hydrolysis and condensation rates. The crystallinity and the microstructure of the SBT thin films improved with increasing annealing temperature and were strongly correlated with the ferroelectric properties of the SBT thin films. The films annealed at 800 °C exhibited low leakage current density, low voltage saturation, high remanent polarization, and good fatigue characteristics at least up to 1010 switching cycles, indicating favorable behavior for memory applications.