Nanostructured gold/titania and gold/silica particles with up to 4 wt% Au were made by a single-step process in a spray flame reactor. Gold(III)-chloride hydrate and titania- or silica-based metalorganic precursors were mixed in a liquid fuel solution, keeping concentrations in the flame and overall combustion enthalpy constant. The powders were characterized by x-ray diffraction, transmission electron microscopy, Brunauer–Emmett–Teller, and ultraviolet–visible analysis. The titania or silica specific surface area and the crystalline structure of titania were not affected by the presence of gold in the flame. Furthermore the size of the gold deposits was independent of the metal oxide support (TiO2 or SiO2) and its specific surface area (100 and 320 m2/g, respectively). The gold nanoparticles were nonagglomerated, spherical, mostly single crystalline, and well dispersed on the metal oxide support. Depending on the Au weight fraction (1, 2, and 4 wt%) the Au nanoparticles' mass mean diameter was 3, 7, and 15 nm, respectively, on both titania and silica. The particles showed surface plasmon absorption bands in the ultraviolet–visible region, which is typical for nano-sized gold. This absorption band was red shifted in the case of the titania support, while no shift occurred with the silica support.

Interfacial reactions and intermetallic compound formation of the eutectic Sn–0.7Cu and hypereutectic Sn–3Cu on thin film metallization of Al/Ni/Cu, Al/Cu, and Al/Ni were investigated. While the Ni layer of Al/Ni/Cu was almost consumed by Sn–0.7Cu after one reflow at 240 °C, most of it was preserved with Sn–3Cu even after ten reflows. Since the Cu content in Sn–0.7Cu is below the solubility limit of Cu in Sn at 240 °C, the Cu layer of Al/Ni/Cu was dissolved completely into Sn–0.7Cu, and the Ni was exposed to the molten solder to form intermetallics. As Cu content in Sn–3Cu is more than the solubility limit, intermetallics formed between the solder and the Cu layer, but not the Ni layer, of Al/Ni/Cu. The supersaturation of Cu in Sn–3Cu was found to be beneficial in reducing the interfacial intermetallic compound formation and in improving the interfacial stability.

We report on the exact shape of a propagating crack in a plate with a high width/thickness ratio and subjected to bending deformation. Fracture tests were carried out with brittle solids—single crystal, polycrystalline, and amorphous. The shape of the propagating crack was determined from direct temporal crack length measurements and from the surface perturbations generated during rapid crack propagation. The shape of the crack profile was shown to be quarter-elliptical with a straight, long tail; the governing parameter of the ellipse axes is the specimen's thickness at most length of crack propagation. Universality of the crack front shape is demonstrated. The continuum mechanics approach applicable to two-dimensional problems was used in this three-dimensional problem to calculate the quasistatic strain energy release rate of the propagating crack using the formulations of the dynamic energy release rate along the crack loci. Knowledge of the crack front shape in the current geometry and loading configuration is important for practical and scientific aspects.

The microstructural changes in the initial stage of a conversion process of α-tricalcium phosphate [α-Ca3(PO4)2] (α-TCP) to hydroxyapatite [Ca10(PO4)6(OH)2] (HAp) by the hydrolysis method were investigated by transmission electron microscopy (TEM). To investigate the microstructural changes that take place during the conversion process, we prepared two types of α-TCP specimens for TEM: α-TCP powder and sintered α-TCP thin film. According to our results, the microstructural changes can be summarized as follows. At first, the surface of the α-TCP was covered with an amorphous calcium phosphate layer, resulting from hydration or the dissolution of α-TCP. Subsequently, the nucleation of HAp occurred on the amorphous layer, and then dendritic structures appeared on the layer. Thereafter, the dendritic structures would grow into needlelike fine HAp crystals.

Monodispersed Sc2O3 precursor particles were synthesized by the urea-based homogeneous precipitation method, with an investigation into the effects of supporting anions (NO3−, Cl−, and SO4 2−) on powder properties. Characterizations of the powders were achieved by elemental analysis, x-ray diffractometry, Fourier transform infrared, differential thermal analysis/thermogravimetry, high-resolution scanning electron microscopy, and the Brunauer-Emmett-Teller method. Unlike other rare earths, Sc3+ does not precipitate as basic carbonate but instead forms hydrated γ-ScOOH from either nitrate or chloride solution. Particles of the hydrated γ-ScOOH are pumpkin-shaped (approximately 1.0 μm) and are made up of thin-platelike crystallites emanating from a common axis. The presence of complexing SO42− changes the reaction chemistry toward Sc2O3 powders, leading to basic sulfate [Sc(OH)1.6(SO4)0.7 η H2O] precursor particles having hexagonal morphology (approximately 10 μm in diameter and 0.5 μm in thickness). The hydrated γ-ScOOH directly converts to Sc2O3 by calcination at 400 °C or above, while the basic sulfate transforms to oxide at temperatures ≥ 900 °C via an amorphous state and a Sc2(SO4)3 intermediate. The effect of SO42− on powder morphologies and reaction chemistry is discussed. Nanocrystalline Sc2O3 powders comprising monodispersed particles were obtained via thermal decomposition of the precursors.

One-dimensional CdS nanocrystallites were used as precursors for preparation of mesoporous CdS nanorods through an ion-exchange process at room temperature. The results from x-ray photoelectron spectroscopy, transmission electron microscopy, energy-dispersive x-ray analysis, and x-ray powder diffraction techniques showed that Ag+ did not affect the electronic structure of CdS or cause the disorder of crystal structure although the product contained a considerable amount of Ag2S. The visible absorption of Ag2S nanoparticles in the mesoporous structure led to the result that the intensities of Raman scattering peaks of the mesoporous nanorods were weaker than those of CdS initial nanorods.

Glassy Fe65Co10Ga5P12C4B4 alloy powders with a large supercooled liquid region of 50 K before crystallization were synthesized in the particle size range below 125 μm by Ar gas atomization. With the aim of developing a large-size Fe-based glassy core with good soft magnetic properties, the consolidation method of spark plasma sintering was applied to the Fe65Co10Ga5P12C4B4 glassy powders. The existence of the supercooled liquid region enabled us to form a large-size glassy alloy disc 20 mm in diameter and 5 mm in thickness with a high relative density of 99.7% at the glass-transition temperature of 723 K and under the external applied pressure of 300 MPa. The resulting glassy core of 18 mm in outer diameter, 10 mm in inner diameter, and 4 mm in thickness exhibits good soft magnetic properties: 1.20 T for saturation magnetization, 6 A/m for coercive force, and 8900 for maximum permeability. The good soft magnetic properties of the Fe-based bulk glassy core are attributed to the combination of the high relative density and the maintenance of the single glassy structure.

Combustion of the thermite system is a promising approach for synthesis of alloys (e.g., Co-based) that are widely used in orthopedic applications. This process typically involves formation of two liquids (oxide and metal alloy), followed by their phase separation. The latter is generally believed to be controlled solely by gravity-driven buoyancy. To verify this hypothesis, a fundamental study of phase separation during alloy synthesis was conducted in both normal gravity and microgravity conditions. It was shown that a non-gravity-driven mechanism primarily controls the segregation process. Quenching experiments identified the reaction and phase separation mechanisms in the investigated systems.

The structure and composition of Cr-nitrides formed on an electroplated hard Cr layer during an ion-nitriding process were analyzed, and its growth kinetics was examined as a function of the ion-nitriding temperature and time to establish a computer simulation model for the prediction of growth behavior of the Cr-nitride layer. The Cr-nitrides formed during the ion-nitriding at 550–770 °C were composed of outer CrN and inner Cr2N layers. A nitrogen diffusion model in the multilayer, based on fixed-grid finite difference method, was applied to simulate the growth kinetics of Cr-nitride layers. By measuring the thickness of Cr-nitride layers as a function of ion-nitriding temperature and time, the activation energy (Q) and nitrogen diffusion constant (Do) were determined for growth of CrN and Cr2N; the result was applied to simulate the growth kinetics of Cr-nitride layers, and reasonable good agreement was obtained with the experimental results.

This work addresses the issues of coating of oxide fibers or laminates with debondable oxide interphases. It fabricates a model system for an alumina matrix reinforced with alumina fibers, wherein an enstatite interphase is transformation weakened, resulting in interphase debonding. A suitable multilayer coating sequence was chosen to act as a chemical bridge between the alumina fiber and matrix. The pulsed excimer laser ablation method (KrF excimer laser of λ = 248 nm) was used to deposit several oxide materials individually onto silicon wafers. Titania (TiO2 or T), aluminum titanate (Al2O3 · TiO2,Al2TiO5 or AT), and enstatite (MgO · SiO2, MgSiO3 or EN) layers were deposited from sintered target materials. X-ray photoelectron spectroscopy, scanning electron microscopy, and transmission electron microscopy investigations indicated that as-deposited coatings were amorphous or partially crystallized into nanosize grains, and their thicknesses were uniformly distributed over the Si-substrate, growing in columnar texture (although not as pronounced for enstatite). Transmission electron microscopy/energy dispersive spectroscopy analysis confirmed that the chemical composition of the coating materials was the same as that of the target materials and that the coatings were completely crystallized into nano- or submicrometer grain size after annealing at 1200 °C for 1 h. With these data, sapphire monofilaments were sequentially coated with five layers of Al2TiO5, TiO2, MgSiO3, TiO2, and Al2TiO5. This construction provided a chemical bridge between the alumina monofilament and the enstatite debondable interphase.

In this paper a novel buffer layer architecture consisting of LaMnO3/MgO/TiN is proposed as a suitable structural and chemical template for the epitaxial growth of high-transition temperature (Tc) superconductors on Cu metal surfaces. Using techniques such as high-energy electron diffraction and scanning transmission electron microscopy, we present in situ and ex situ analyses of the buffer-layer and superconductor growth with focus on structural properties of the interfaces formed. While MgO is a good barrier to oxygen diffusion, we find that MgO alone is not a suitable buffer layer due to rapid Cu diffusion. Further, growth of MgO with a single epitaxy can be hindered by the presence of impurities such as S, which form strongly bonded superstructures on the metal surface. With the addition of a TiN layer as a barrier to Cu diffusion, oxide formation is suppressed, interfaces are clean, and a single cube-on-cube epitaxy is observed. While the Cu/TiN and TiN/MgO interfaces are rough, the MgO and LaMnO3 layers planarize the material, leading to growth of smooth YBa2Cu3O7−δ (YBCO). Residual strain in the YBCO film is 0.25% or less and does not lead to apparent cracking. The superconducting properties of the samples were investigated by electrical transport and magnetization measurements. For the first time, high critical current density (Jc) values are reported for YBCO films grown on (001) single-crystal and 100‹100›?textured Cu surfaces without intervening metal coatings. Jc on single crystal-like substrates is as high as 3.5 MA/cm2. Reduced Jc of approximately 1 MA/cm2 on rolled Cu tapes is limited by damage to the tape surface during the rolling process.

Microalloying of MoSi2 to form Mo(1−x)MexSi2 (Me = Nb or V) was investigated by the self-propagating high-temperature synthesis method. With alloying element contents up to 5 at.%, a homogeneous C11b solid solution was obtained. For higher contents of alloying elements, the product contained both the C11b and the hexagonal C40 phases. The relative amount of the C40 phase increases with an increase in the content of alloying metals in the starting mixture. The alloying element content in the hexagonal C40 Mo(1−x)MexSi2 phase was nearly constant at a level of about 12 at.% for all starting compositions. In contrast, the content of the alloying elements in the tetragonal phase is considerably lower (around 4 at.%) and increases slightly as the Me content in the starting mixture is increased.

The effect of the layer-charge density of clay on the orientation and aggregation of a cationic dye, methylene blue (MB), in MB/clay films was investigated using a series of layer-charge-controlled montmorillonites as host materials. Polarized ultraviolet-visible spectroscopy and x-ray diffraction were used for the characterization of the arrangement and orientation of dye cations in host interlayer spaces. It was revealed that high charge densities of layers induced the formation of relatively ordered and homogeneous phases with dye dimers. The reduction of the charge led to the formation of disordered, mixed phases with large amounts of monomers (isolated dye cations). Dimers and monomers were slightly tilted against the plane of the clay surface, and their angles were not affected by the layer charge.

Sol-gel spin coating of lead-titanate films differs from most processing routes, such as metalorganic chemical vapor deposition and pulsed laser deposition, in that crystallization cannot occur without a postdeposition annealing step. This work focuses on the annealing of sol-gel-derived PbZrTiO3 films on LaAlO3 substrates in attempts to identify the precise conditions necessary to grow films of quality similar to that obtained through other techniques. In particular, the effects of Pb excess (in precursor solutions), annealing times, and temperature were investigated through transmission electron microscopy and four-circle x-ray diffraction. The significance of this work is in the direct observation of the correlation between Pb excess and film crystallization. It is shown that the effects of Pb excess on the completeness of film crystallization become more dramatic at lower annealing temperatures, even while epitaxial quality is maintained.

The load-transfer efficiency of reinforcement, in cylindrical forms in metal-matrix composite (MMC), was analyzed based on the shear-lag model. Both the geometric shape and alignment of reinforcement were considered. The stress transferred to a misaligned whisker was calculated from differential equations based on the force equilibrium in longitudinal and transverse directions. A new parameter, defined as effective aspect ratio, was used to indicate the load-transfer efficiency of misaligned reinforcement. The effective aspect ratio was formulated as a function of aspect ratio and misorientation angle of reinforcement in MMC. A probability density function of misorientation distribution was used to estimate the strengthening effect of all misaligned whiskers distributed in the matrix. Considering the contributions of both effective aspect ratio and misorientation distribution on load-transfer efficiency, a generalized shear-lag model was proposed to explain the mechanical anisotropy of discontinuous reinforced MMC.

Nano-TiO2 modified composites, including TiO2 + EP648 and M40/TiO2 + EP648, were fabricated, in which the nano-TiO2 particles were dispersed in an EP648 epoxy matrix using a high-speed shearing emulsification technique. A jet type of vacuum ultraviolet (VUV) source was used to simulate the VUV spectrum in space and acquire various doses of VUV irradiation. In terms of the changes in specific-area mass loss and surface morphology, the resistance to VUV irradiation of the TiO2 + EP648 and M40/TiO2 + EP648 nanocomposites was evaluated. Experimental results showed that compared to the EP648 epoxy and M40/EP648 composite, the specific-area mass loss of the TiO2 + EP648 was decreased by 44% and that of M40/TiO2 + EP648 composite by 38%, respectively. By increasing the dose of VUV irradiation, the internal layer shear strength of the M40/TiO2 + EP648 increased gradually, while that of the M40/EP648 showed a decreasing trend. After irradiation, the surface of the M40/TiO2 + EP648 changed a little, but that of the M40/EP648 was damaged severely. It was indicated by means of scanning electron microscopy and atomic force microscopy observations that the VUV damage occurred mainly in the epoxy matrix, while the carbon fibers showed good resistance to irradiation.

The light diffusion behavior in a glass particle-dispersed epoxy matrix composite was evaluated using a pico-second order light pulse. Change in pulse profile was detected, and this change in different detection areas is discussed. The light scattering behavior in the composite was directly observed, and the result was compared with the pulse profile change. This change appeared in the pulse shape, and depended on the particle volume fraction and the area of light detected. The maximum probable light path extension and the light transmittance were strongly correlated with the direct observation result of spatial spreading behavior of light in the composite. The combination use of (i) maximum probable light path extension and (ii) light transmittance was effective in evaluating the light-scattering behavior of the composite. The method is applicable to evaluation of the light-scattering process in light-transmitting materials.

The fracture toughness of small volumes of brittle materials may be investigated by using pyramidal indenters to initiate radial cracks. The length of these cracks, together with indenting load and the hardness to modulus ratio of the material, were combined to calculate the critical stress intensity factor Kc pertinent to fracture toughness. Modulus and hardness may be obtained from the literature or may be measured using nanoindentation techniques. If the material volume is very small, such as single grains in a conglomerate, a reduction of scale may be obtained by reducing the internal face angles of the indenter. This encourages crack initiation at lower loads, but cracks produced at very low loads are short and difficult to measure. Experiments on fused silica and glassy carbon suggested that radial cracks are initiated during loading and that when indenters with sufficiently small angles are used these cracks immediately pop-in, to become fully developed median/radial crack systems. Following pop-in, the rate of penetration of the indenter increases and at higher loads there is an extra increment of penetration over that which would otherwise have occurred. In this study a method is described whereby this extra penetration may be determined. Then for two dissimilar brittle materials, crack length is shown to be correlated with extra penetration leading to a relationship that may possibly avoid the necessity for crack-length measurement.

Strontium-modified lead titanate thin films with composition Pb1−xSrxTiO3 were grown on Pt/Ti/SiO2/Si substrates using the polymeric precursor method. The structural phase evolution as a function of the Sr contents was studied using micro-Raman scattering, specular reflectance infrared Fourier transform spectroscopy, and x-ray diffraction. The results showed a gradual change from tetragonal to cubic structure, the transition occurring at about x = 0.58. The infrared reflectance spectra showed that the frequency of several peaks decreases as the strontium concentration increases. These features are correlated with a decrease in the tetragonal distortion of the TiO6 octahedra as the strontium concentration increases.

It is confirmed on the basis of extensive test results for various ceramic and metallic materials that the indentation load P versus penetration depth h curves (P–h curves) both in loading and unloading processes are well approximated with the quadratic formulas of P = k1h2 and P = k2(h – hr)2, respectively, and unloading parameter k2 is quantitatively related to the elastic modulus E′ of the material indented, where hr is the residual penetration depth after a complete unload. The unloading/reloading indentation processes for a locally deformed conical/pyramidal impression are well represented by the equivalent mechanical process of a conical/pyramidal indenter with the effective face angle of βeff = (β – βr) on a flat elastic half-space, in terms of the inclined face angles β and βr of the indenter used and of the residual impression formed, respectively. With utilization of the unloading parameter k2 and the relative residual depth of penetration ξr, a novel method is proposed for estimating E′. Theoretical considerations for a nonquadratic P–h unloading behavior are also made.