Several ABO3 perovskite ferroelectric crystals, PbTiO3, Pb(Zr, Ti)O3, and BaTiO3 have been in situ grown from amorphous gels with glass elements, and the structural evolution has been systematically investigated using x-ray diffraction (XRD), infrared spectra (IR), differential thermal analysis (DTA), thermogravimetric analysis (TGA), and dielectric measurements. It is found that in the Si-contained glass-ceramic systems, Si and B glass elements are incorporated into the crystalline structures, resulting in the variation of the crystallization process, change of lattice constant, and dielectric properties. Some metastable phases expressed by a general formula AxByGzOw (A = Pb and Ba; B = Zr and Ti; G for glass elements, especially for Si) have been observed and discussed.

In this study, amorphous carbon coatings were deposited with thicknesses ranging from 20 nm to 100 nm on single-crystal silicon substrates by sputtering, ion beam, and cathodic arc deposition techniques. An indentation system with a three-plate transducer with electrostatic actuation and capacitive sensor has been used to make load displacement measurements and subsequently carry out in situ imaging of the indents. Indentation experiments were carried out using a three-sided pyramidal (Berkovich) diamond tip. Measurements include load-displacement curves and calculation of hardness and Young's modulus of elasticity at various indentation depths, studies of hysteresis behavior, creep behavior, and strain rate effect of various carbon coatings. The cathodic arc coating exhibited the highest hardness and elastic modulus followed by the sputtered and ion beam coatings.

The influence of organic binders on fiber/matrix bonding during the powder metallurgy fabrication of sapphire fiber-reinforced NiAl matrix composites (sapphire/NiAl) was investigated. One composite panel was fabricated using a poly(methyl methacrylate) (PMMA) fiber binder and a teflon matrix powder binder; another panel was fabricated by binderless powder metallurgy consolidation. The effect of the binders on fiber/matrix bonding was evaluated by fiber push-out testing from room temperature to 900 °C. Examination of mating fiber and matrix-trough fracture surfaces by scanning electron microscopy (SEM) and Auger electron spectroscopy (AES) revealed differences in interfacial morphology and chemistry, depending on the use of binders in fabrication. The primary difference between the two composites was the much higher concentration of carbon at the fiber/matrix interface in sapphire/NiAl fabricated with binders. This carbon residue from binder burnout prevented clean contact between the sapphire fiber and NiAl matrix surfaces, resulting in a weak, thermomechanically clamped fiber/matrix interface, in contrast to the stronger, less temperature dependent, interfacial bonding observed without binders.

New electrolytic systems were prepared by reacting K3Fe(CN)6 and K2PdCl4 in a mixture of water and poly(ethylene glycol) 600 (PEG). The reaction occurs in two steps: first a gel is formed, which then shrinks, releasing the solvent. The product thus obtained has the consistency of a smooth, solid plastic paste and is very stable. The influence of the reaction mixture on the structure, morphology, and conductivity of the products was investigated carrying out three preparations (I, II, III) at increasing ratio PEG 600/H2O. By FT-IR studies and analytical data it was concluded that these materials are inorganic-organic networks containing CN bridges between Fe and Pd atoms and PEG 600 bridges between Pd atoms. Scanning electron microscopy studies revealed that the morphology of polymers I, II, and III is significantly influenced by the conditions of the synthesis. Conductivity measurements made at different temperatures showed that polymers I, II, and III conduct ionically. The conductivity of polymer I, which was synthesized with the highest water/PEG 600 ratio, is on the order of 1.4 · 10−3 Sycm at 25 °C.

Single crystals with the structure of KTiOPO4 (KTP) were grown from mixtures containing equal concentrations of KSnOPO4 and KGeOPO4 (i), KTiOPO4 and KGeOPO4 (ii), and KTiOPO4 and KTiOAsO4 (iii), respectively. The comparison of the lattice parameters measured and calculated from Vegard's rule shows that structural stability of KTiOAsO4 is higher in comparison with KTiOPO4. It was found that addition of GeO2 to the KTP containing flux is accompanied by increasing all lattice parameters of KTP that correspond to substitution of As5+ by Ge4+.

Polyimides can be infused with silver complexes by the use of supercritical fluids. Highly reflective polyimide films were formed by infusing (1,5-cyclooctadiene-1,1,1,5,5,5-hexafluoroacetylacetonato)silver(I) [Ag(COD) (HFA)] into a number of polyimides and then thermally curing those films at 300 °C for time intervals between 30 min and 3 h. Reflectivities of the films exhibited strong dependence on the infusion and cure conditions as well as on the type of polyimide used. The highest reflectivity of 67.1% was achieved with a silvered film prepared from 3,3′,4,4′-benzophenonetetracarboxylic acid dianhydride (BTDA) and oxydianiline (ODA) infused at 5000 psi, 100 °C, for 30 min and cured for 1 h at 300 °C. Reflectivities of silvered surfaces of other polyimides investigated varied from 39% to 61%. A strong correlation between the presence of a ketonic group in the polyimide structure and the formation of mirror surfaces was detected.

X-ray Photoelectron Spectroscopy (XPS) and optical studies have been performed on P(EO)n –NaI–TCNQ (n = 1, 10) systems, obtained by means of a solid state reaction technique. The electron spectroscopy, the absorption in the ultraviolet visible near infrared range, and the infrared transmission findings allow us to conclude that the interaction among the polymer, the iodide, and the electron acceptor molecule results in the formation of the ion-radical salt Na–TCNQ and in the oxidation of I− to the metallic state. The presence within the examined specimens of crystalline and amorphous phases has been confirmed by the results of Differential Scanning Calorimetry (DSC) measurements. The optical, electronic, and thermal properties of the P(EO)n–NaI–TCNQ mixtures have then been correlated to the results of preliminary ac electrical transport investigations.

The synthesis and characterization of mesostructured zirconia and titanium oxides are presented. The samples were investigated by x-ray powder diffraction (XRD), transmission electron microscopy (TEM), and atomic force microscopy (AFM). XRD and TEM revealed only lamellar structures for both materials, whereas AFM could detect locally restricted initial stages of cubic or hexagonal phases in a globally lamellar Ti oxide.

180° domain boundaries in flux-grown lead titanate single crystals show intriguing domain boundary extreme fringe contrast using transmission electron microscopy. Symmetrically distributed domain boundaries with alternate contrast have been observed, indicating that opposite displacement vectors exist one by one at boundaries. If appropriate reflection vectors were employed, an inclined domain boundary shows reversed fringe contrast. An analysis based upon the two-beam dynamical theory and a rule similar to stacking-fault contrast analysis was employed to predict the geometric configuration of a 180° domain boundary using the extreme fringe contrast (EFC) behavior. Appropriately choosing reflection vectors and utilizing the EFC reversal, a displacement vector as well as the polarization vector arrangement across a 180° domain boundary can be unambiguously identified. Employing the information derived from diffraction patterns and a tilting experiment across a nearby 90° boundary, the whole polarization configuration can be uniquely determined.

The mechanism of ionic transport in the amorphous anodic film formed on Al–40 at.% Sm alloy has been examined by transmission electron microscopy and Rutherford backscattering spectroscopy. The film consists of an outer layer, about 6% of the total film thickness, composed of relatively pure Sm2O3 and an inner layer containing units of Al2O3 and Sm2O3 distributed homogeneously at the available resolution. The anodic film material is formed by migration of O2−/OH− ions inward and migration of cations outward, with a cation transport number about 0.29. The two-layered film develops as a consequence of faster migration of Sm3+ ions than Al3+ ions in the film.

We wrote two computer programs, 3D and BUMP, to interpret transmission electron microscope (TEM) micrographs made during a study of the initial stage sintering of ultrafine alumina particles (UFP's, 20–50 nm in diameter). The first simulated the 3D geometric relationships of particles, from which we concluded that surface diffusion was the predominant sintering mechanism because no shrinkage occurred. BUMP simulated random contact of two particles and showed that the particle chains that formed before sintering were not formed purely by chance. Instead the particles experienced a rearrangement process (rotation and sliding) which reduced the total surface energy.

To integrate irreconcilable material properties into a single component, a new class of engineered materials termed “surface composites” has been developed. In this engineered material, the second phase is spatially distributed in the near surface regions, such that the phase composition is linearly graded as a function of distance from the surface. Surface composites are different from existing engineered materials such as “bulk composites” and “functionally graded materials” (FGM). Unlike bulk composites, the surface phase in surface composites is present only at the near surface regions. In contrast to FGM, the graded properties of surface composites are achieved by unique morphological surface modification of the bulk phase. To fabricate surface composites, the initial surface of the bulk material is transformed using a novel multiple pulse irradiation technique into truncated cone-like structures. The laser induced micro-rough structures (LIMS) possess surface areas which are up to an order of magnitude higher than the original surface. The second phase is deposited on the surface using thin or thick film deposition methods. A key characteristic of surface composites is the formation of a three-dimensional, compositionally and thermally graded interface, which gives rise to improved adhesion of the surface phase. Examples of various types of surface composites such as W/Mo, silica/SiC, diamond/steel, etc. are presented in this paper. The unique properties of surface composites make them ideal engineered materials for applications involving adherent thick film coatings of thermally mismatched materials, compositional surface modification for controlled catalytic activity, and creating adherent metal-ceramic and ceramic-polymeric joints.

High refractive index composites of iron sulfides and poly(ethylene oxide) (PEO) have been prepared by co-precipitation from aqueous solution. Several reaction parameters were varied: inorganic reactants, reactant ratios, reaction temperatures, and reaction times. Selected samples were characterized with organic microelemental analysis, x-ray fluorescence spectroscopy, x-ray diffraction, DSC, and TEM. The nanocomposites with the highest refractive indices have been prepared using PEO, Mohr's salt, and H2S or NaHS. The analyses indicate that the iron sulfides in these materials consist of finely dispersed mackinawite and greigite (“amorphous” FeS) and, partially, also pyrite. The refractive indexes of the resulting composites are clearly above 2 at 632.8 and 1295 nm and can assume values between 2.5 and 2.8.

A high-resolution electron microscopy study of β–SiC nanoparticles formed by C+-implantation of single crystal silicon with subsequent annealing has been carried out. The as-implanted sample had a trilayered structure, in which the surface layer, A, and the bottom layer, C, were crystalline but damaged, and the middle layer, B, was amorphous. After annealing this structure, β–SiC particles were formed throughout the trilayered structure but with different forms: a few epitaxial β–SiC nanoparticles in layers A and C, and more random nanoparticles in layer B. The β–SiC nanoparticles, in the size range 2–8 nm, should be responsible for the blue-emitting effect of the silicon-based porous β–SiC.

Epitaxial BaTiO3 thin films were prepared on SrTiO3 (100) substrates by the dipping-pyrolysis process using metal naphthenates as starting materials. Highly oriented BaTiO3 thin films were crystallized by heat treatment at 800 °C and higher, from amorphous precursor films pyrolyzed at 470 °C. XRD pole-figure and reciprocal-space mapping analyses showed that the films were epitaxially grown on SrTiO3substrates and were pseudocubic phase with an a║/aτ ratio of 1.003, smaller than the c0/a0 ratio (=1.011) of bulk tetragonal BaTiO3.

Power ultrasound of 20 kHz was applied to the synthesis of silica spheres via the controlled hydrolysis of tetraethoxysilane (TEOS). Silica spheres of about 0.3 μm were agglomerated to form tolerably uniform, dense particles of about 2 μm through 90 min sonication. This agglomeration behavior was examined by laser diffraction particle size analysis and transmission electron microscopy. It was found that the agglomeration process involves (I) an incubation period in which no agglomeration occurs, (II) rapid formation of ramified particles, and (III) their densification. It was inferred that sonication enhances collision among silica spheres.

The preparation, by direct melt intercalation, and the properties of new hybrid organic-inorganic nanocomposites, consisting of a commercial sample of poly(styrene-b-butadiene) copolymer (SBS) and a commercial organophilic clay containing the dioctadecyl dimethyl ammonium salt are described. In addition, several mixtures between the same copolymer and an unfunctionalized clay were prepared and studied. XRD spectra showed a partial insertion of the SBS block copolymer segments in the interlayers of the organophilic clay, accompanied by a loss of correlation within the layers. The degree of insertion increased by annealing the nanocomposites at 120 °C for increasing time periods. No interaction between the polymer matrix and the unfunctionalized clay was found. The storage modulus value, in the plateau region between the glass transition processes of the polybutadiene and the polystyrene blocks, and the glass transition temperature of the polystyrene block domain increase as both the organophilic clay content and the annealing time increase. The glass transition process of the polybutadiene block domain is practically unaffected by the filler content and the annealing treatments. These data are most promising for upgrading the thermo-mechanical behavior and the application temperature window of the SBS thermoplastic elastomers through the preparation of nanocomposites employing suitably designed organophilic clays.

Except for atomistic models of individual carbon nanotube growth, there is still no precise understanding of the large scale deposition of carbon during the arc discharge. We study the microstructure of cathode deposits in detail using scanning electron microscopy, focusing on two distinct regimes found in the deposits having different large scale morphology. The shell grown circumferentially consists of extended graphite layers with preferred orientation, and the structure reveals close similarity to pyrolitic graphite. The core region is a porous assembly of nanotubes and nanoparticles. We conclude that closed nanostructures self-assemble from a dense carbon vapor, whereas pyrographitic shell grows by continuous deposition on exposed substrates.

Laser-driven synthesis of Al2O3 based ceramic powders from gaseous precursors has been accurately investigated. Different concentrations of the reactant gaseous precursors are shown to influence both the process yield and the synthesized powder composition. Depending on the relative concentration of TMA: Al(CH3)3 and N2O, the process leads either to the formation of nanocrystalline γ−Al2O3 with large free carbon contamination and traces of the Al3O3Nphase or to the formation of a mixed γ−Al2O3, Al2OC compound. The different reaction paths have been attributed to the intermediate formation of aluminum carbide. Particular attention has been paid to the gaseous reaction products to correctly interpret the source of carbon contamination observed in the formed powders. Calcining at moderate (900 °C) and high (1400 °C) temperatures induces nanosized γ−Al2O3 powder and the γ → α-Al2O3 transition with particle coalescence and growth.

Elastic modulus of thin homogeneous films can be determined by indenting the specimen to various depths and extrapolating the measured (apparent) E-values to zero penetration. The paper shows the application of five approximation functions for this purpose: linear, exponential, reciprocal exponential, Gao's, and the Doerner and Nix functions. Comparison of the results for 26 film/substrate combinations has shown that the indentation response of film/substrate composites can, in general, be described by the Gao analytical function. In determining the thin film modulus from experimental data, satisfactory results can also be obtained with the exponential function, while linear function may be used only for thick films where the relative depths of penetration are small. The article explains the pertinent procedures and gives practical recommendations for the testing.