The microstructure and chemistry of (Ba,Sr)TiO3 thin films deposited on Pt/SiO2/Si substrates by metalorganic chemical vapor deposition were studied using highresolution transmission electron microscopy and quantitative spectrum imaging in electron energy loss spectroscopy. The grain boundaries in all films with overall Ti content ranging from 50.7% to 53.4% exhibit a significant increase in Ti/Ba ratio as compared to the grain interiors. The results suggest that the deviations of Ti/(Ba + Sr) ratio from the stoichiometric value of unity are accommodated by the creation of Ba/Sr vacancies, which segregate to the grain boundary regions. The films with Ti contents equal to or greater than 52% additionally contained an amorphous Ti-rich phase at some grain boundaries and multiple grain junctions; the amount of this phase increases with increasing overall Ti content. The analysis indicates that the amorphous phase can only partially account for the significant drop in dielectric permittivity accompanying increases in the Ti/(Ba + Sr) ratio.

The interlayer space of a thin film of layered titanate, Cs0.68Ti1.83‪0.17O4, was successfully expanded by SiO2 pillaring. Ion exchange of the Cs ions in the interlayer to alkylammoniuim cations, n-CnH2n+1NH3+ (n = 8, 12, 18), expanded the interlayer space, and enabled intercalation of tetraethylorthosilicate. X-ray diffraction and the cross section of transmission electron microscopy images revealed that tetraethylorthosilicate-treated thin film maintained the expansion of interlayer space by SiO2 pillaring after calcination at 773 K. X-ray photoelectron spectroscopy after etching the thin film about 100 nm from the surface further confirmed the existence of SiO2 in the interlayer space.

Small-angle x-ray scattering (SAXS) technique has been used to investigate nano-sized powders of Y2O3, Y1.8Er0.2O3, and Y1.8Nd0.2O3, obtained by means of combustion synthesis. The results show that the powders have a mass-fractal behavior, with fractal dimension, Df, in the 1.7–1.8 range, and average particle sizes in the 20–30-nm range. These results are supported by transmission electron microscope observations. Moreover, from SAXS data, it has been possible to establish a narrow particle size polydispersity, as well as the presence of particle-diffuse or “fuzzy” interfaces. These results show, for the first time, the fractal behavior of materials prepared by combustion synthesis and are in agreement with a recently developed model. The nanostructural features are discussed within the framework of the peculiar optical properties of the doped luminescent materials.

The role of elastic mismatch in determining critical conditions for indentation fracture in brittle coatings on substrates of unlike modulus was investigated. A model transparent trilayer system, consisting of a glass coating layer bonded to a thick substrate of different glass or polymer by a thin layer of epoxy adhesive, facilitated in situ observations of crack initiation and propagation. A tungsten carbide sphere was used to load the layer system. Abrasion flaws were introduced into the top and bottom glass coating surfaces to control the flaw populations and to predetermine the origins of fracture: cone cracks occurred at abraded top surfaces, radial cracks at abraded bottom surfaces. Analytical relations for the critical loads are presented for each crack system in terms of elastic modulus mismatch, indenter and coating dimensions, and material fracture parameters. Implications concerning materials selection for resistance to crack initiation are considered.

A new family of microporous semicrystalline silica materials (MSSMs) were developed at room temperature from acidic mixtures of alkyl-substituted silane and tetramethylalkoxysilane. Hydrolyzed alkyl-substituted silica precursors, having hydrophilic silanol groups and hydrophobic alkyl groups, presumably act not only as templates but also as sol stabilizers for continuous pore engineering of silica materials in the micropore region. Depending on the substituted alkyl (SUA) groups in initial sols, MSSMs have distinct broad x-ray diffraction peaks in low 2θ range of 2° to 12°, distinguishable thermal behavior of SUA groups, highly flexible processability, and discrete micropore size with good thermal stability of micropores after the removal of SUA groups. These designer microporous silicas are expected to be useful for molecular sieving applications.

Layered materials are susceptible to failure upon temperature cycling. This paper describes an intriguing mechanism: cracking in a brittle layer caused by ratcheting in an adjacent ductile layer. For example, on a silicon die directly attached to an organic substrate, cracking often occurs in the silicon nitride film over aluminum pads. The silicon die and the organic substrate have different thermal expansion coefficients, inducing shear stresses at the die corners. Aided by cycling temperature, the shear stresses cause ratcheting in the aluminum pads. Incrementally, the stress relaxes in the aluminum pads and builds up in the overlaying silicon nitride film, leading to cracks.

Mechanical properties of 2H–NbS2 and its intercalation derivative Nax(H2O)yNbS2 were measured by using nanoindentation techniques. The intercalation chemical process was conducted in solution and the cation–hydrated derivative produced was [Nax(H2O)yNbS2]. It was observed that the intercalation process occurs through the crystal edges producing a wave intercalation's front that moved as the reaction proceeded. The hardness and elastic modulus presented very low values in the intercalated region. The load × displacement curves from nanoindentation tests suggested that intercalation of hydrated sodium ions through the edges caused layer separation even in the nonintercalated region at the center of the crystal. It is important to emphasize that no similar studies were found in the literature about this theme. Intercalation process is very important in several areas, like solid-state batteries, and mechanical properties of these kinds of materials are not completely understood. This study is a new approach to understanding the mechanical behavior of layered materials submitted to an intercalation process.

A surface layer of metal carbides provides an excellent interface to achieve a highly adherent diamondlike carbon (DLC) coating. A plasma immersion ion implantation (PIII)-based procedure is described, which delivers a high retained dose of implanted carbon at the surface of aluminum alloys. A shallow implantation profile, followed by argon sputter cleaning and continued until a saturated carbon matrix is brought to the surface, provides an excellent interface for subsequent growth of DLC. At a carbon retained dose above 1018 atoms/cm2 the DLC adhesion exceeds the coating's cohesion strength. Regardless of the silicon content in the aluminum, the coating produced by this method required tensile strengths typically exceeding 140 MPa to separate an epoxy-coated stud from the coating in a standard pull test. Improved DLC adhesion was also observed on chromium and titanium. The reported tensile strength is believed to substantially exceed performance of DLC coatings produced by any other method.

Measurement of the electrical conductivity in high-resistance insulators is made difficult by previously unrecognized limits in the electric guarding technique. Electron irradiation experiments on single-crystalline Al2O3, performed for studying the effects of irradiation on the electrical conductivity, revealed that radiation-induced electrical degradation effects in ceramic insulators, previously reported to occur after electron, ion, and neutron irradiation, are an artifact.

Magnesium oxide (MgO) precursors were prepared by the sol-gel method using magnesium acetate. The reaction products and intermediates obtained during the sol-gel processing of magnesium acetate under various conditions were analyzed thermally and spectroscopically. No organic groups were detected by infrared spectroscopy after heat treating the reaction products at 400 °C. A large exothermic differential thermal analysis peak below 400 °C demonstrated the oxidation of organic moieties in each product. It was found that the presence of an acid catalyst was crucial during the sol-gel processing of magnesium acetate to produce sols suitable for depositing MgO films. The MgO films fabricated on Si(111) substrates using the precursor sol showed (200) orientation regardless of the presence of surface oxides on the substrates.

Two processing routes were explored to produce crack-free amorphous Si–N–C ceramics by pyrolysis of polyureasilazane ceramic precursor. Using a warm-pressing/ pyrolysis route, a ceramic body with certain amount of open porosity was produced; densification behavior during pyrolysis was examined. A prepyrolysis/binding/pyrolysis route was also developed. Ceramics formed using this route were characterized by higher density, lower volume shrinkage during consolidation, and larger viable material size. Open porosity was essentially absent in consolidated amorphous materials produced by this second route. Recrystallization of the consolidated amorphous ceramics resulted in a Si3N4/SiC nanocomposite with both silicon nitride and silicon carbide grains in the nanometric size range.

Solidification of FeSi2 alloy by single-roller rapid solidification technology was studied, and monophase α–FeSi2 ribbons were obtained. Phase evolution of the monophase and metastable α–FeSi2 ribbons during subsequent annealing was studied with in situ electric resistance measurements. The results show that the metastable α–FeSi2 phase transforms into the β–FeSi2 phase at about 620 °C and then transforms into the α–FeSi2 phase again at a higher temperature when heated. A new relatively simple method to prepare bulk β–FeSi2 alloy, that is, formation of bulk β–FeSi2 alloy by annealing monophase α–FeSi2 alloy, is presented.

A novel optical multilayer filter characterized by symmetrically stepwise graded refractive index profiles and high optical performance was designed. This 33-layer TiO2–SiO2 filter was fabricated by helicon plasma sputtering. The prepared filter exhibited a sharp cutoff reflection band around the central wavelength of 1340 nm and wide pass regions with high transmittance. These results correspond well with calculated estimations. Symmetrically stepwise graded refractive index profiles were demonstrated to effectively contribute to suppression of the sidelobes and to be potentially applicable in the design of other filters.

Ammonium hydrogen carbonate was used as the precipitant to synthesize yttrium aluminate garnet (YAG) precursors from a mixed solution of aluminum and yttrium nitrates via coprecipitation. The carbonate precursor, with an approximate composition of NH4AlY0.6(CO3)1.9(OH)2 · 0.8H2O, transformed to pure YAG at 900 °C without the formation of intermediate phases. Reactive YAG powder was produced by calcining the precursor at 1100 °C. The YAG powder densified to 99.8% of the theoretical density by vacuum sintering at 1500 °C for 2 h, and the sintered body showed transparency. Less agglomeration of the precursor and good dispersity of the resultant YAG powder were responsible for the excellent sinterability.

Multiwall open-end and closed carbon nanotubes with the wall thickness from several to more than 100 carbon layers were produced by a principally new method— hydrothermal synthesis—using polyethylene/water mixtures in the presence of nickel at 700–800 °C under 60–100 MPa pressure. An important feature of hydrothermal nanotubes is a small wall thickness, which is about 10% of the large inner diameter of 20–800 nm. Closed nanotubes were leak-tight by virtue of holding encapsulated water at high vacuum and can be used as test tubes for in situ experiments in transmission electron microscope (TEM). Raman microspectroscopy analysis of single nanotubes shows a well-ordered graphitic structure, in agreement with high-resolution TEM. The hydrothermal synthesis has the potential for producing multiwall nanotubes for a variety of applications. The fabrication of nanotubes under hydrothermal conditions may explain their presence in coals and carbonaceous rocks and suggests that they should be present in natural graphite deposits formed under hydrothermal conditions.

The average dislocation velocity in hydrogenated Ni3Al single crystals was directly measured as a function of resolved shear stress (RSS) at room temperature (293 K) by the etch-pit technique. It was found that the dislocation velocity with hydrogen is about 5–25 times faster than that without hydrogen for the same RSS, and hydrogen decreases activation energy for dislocation motion in Ni3Al single crystals. The reason hydrogen can enhance dislocation velocity in this compound is briefly discussed. These preliminary results quantitatively provide the first evidence of hydrogen-enhancing dislocation mobility in Ni3Al material.

Metal–intermetallic Ni/Ni3Al multilayered thin films were synthesized by the magnetron sputtering technique. The synthesized films possessed high hardness that could be compared with intermetallic Ni3Al films. The constituent layers of Ni and Ni3Al were fully adherent to one another at the multilayered boundaries. The fracture surface of the multilayered films on bending showed the characteristics of local ductile fracture. This novel type of multilayered thin films is expected to be used as hard coatings and miniaturized parts of apparatus in micro-electromechanical systems.

In the present work we studied the depth of damage layer in machined silicon wafers that was incorporated with chemical etching using micro-Raman spectroscopy. Subsurface damage causes changes in the shape and intensity for the shoulder (450–570 cm−1) of the most intense band (519 cm−1) and the second band (300 cm−1) regions of the Raman spectrum. Etching reduces the thickness of the damage layer and, hence, the intensities at the shoulder and the second band. The intensities at the shoulder and the second band become stable when the damage layer is completely etched out. The shoulder consists of two Gaussian profiles: the major and the minor. The band for the major profile is independent of etching depth, but the band for the minor profile shifts toward the longer wave numbers with increasing etching period until the damage layer is completely etched out. The depth of the damage layer is determined by the profiles of the shoulder and the second band and confirmed by the band shift of the minor profile. Transmission electron microscopy (TEM) further verified the results with respect to the depth of the damage layer. TEM observation showed that dislocations and stacking faults are responsible for the subsurface damage.

Due to its endurance to ferroelectric fatigue, SrBi2Ta2O9 (SBT) has been extensively investigated. We report here the synthesis of Sr1−xBaxBi2Ta2O9 (x = 0.0, 0.1, 0.5, 1.0) using a solution-based route. The precursors used in this work were the salts of strontium, barium, bismuth, and tantalum ethoxide. X-ray diffraction and Raman spectroscopic studies indicated the formation of complete solid solution system for Sr1−xBaxBi2Ta2O9. This material system may provide interesting properties relevant to microwave tuning and ferroelectric memory applications, which are under investigation.

We have demonstrated that an efficient energy transfer takes place from Yb3+ to Cr4+ in calcium aluminate glasses. Yb3+ improves excitation efficiency at around 980 nm, enhancing emission intensity of Cr4+ fluorescence at 1.2–1.6 μm. Nonradiative energy transfer via electric dipole–dipole interaction between ytterbium and chromium ions was found to be dominant over radiative Yb3+ → Cr4+ energy transfer. A diffusionlimited energy transfer mechanism well explains the decay behavior of Yb3+/Cr4+- codoped glasses. This codoping scheme may be applicable to other Cr4+-containing crystals and glasses.