The size distribution and morphology of particles (dense or hollow) produced from polydispersed droplets in spray pyrolysis were studied both experimentally and theoretically. Zirconia, generated from a zirconyl hydroxychloride precursor, was selected as a model material. The simulation method that was previously developed by our group [J. Mater. Res., 15, 733 (2000)], in which droplets were assumed to be uniform, was improved to evaluate the effect of polydispersity in droplets on the size and morphology of the resulting particles. Simultaneous equations for heat and mass transfer of solvent evaporation and solute mass transfer inside droplets were solved numerically for a number of discrete classes of droplet size distribution. The role of the decomposition reaction was also included after the evaporation stage of polydispersed droplets in an attempt to explain the densification of particles. In hollow particle generation, this simulation was used to evaluate the thickness of a particle shell. The experimental results were in good agreement with the simulation data, suggesting that the model provides a more realistic prediction.

The surface nanodeformation of a discontinuously reinforced Ti–6Al–4V composite during tensile loading was investigated by in situ atomic force microscope (AFM) observation. The material used was a TiB whisker and TiC particle reinforced Ti–6Al–4V composite. The evolution of surface roughness and slip band spacing was quantified as a function of applied strain. The microstructural damage during tensile loading was also studied. The formation of slip bands within a grain of the Ti–6Al–4V matrix was clearly observed when the applied strain above was 1.3%. The amount of slip bands and surface roughness increase with increasing applied strain. The rupture of TiC particle and multiple cracking of TiB whiskers were also observed at the applied strain above 1.3%. The interaction of slip bands with the reinforcements and mechanisms of deformation and fracture of the composite were elucidated.

The stress-life fatigue behavior and fracture morphology of a (Cu60Zr30Ti10)99Sn1 bulk-metallic glass alloy was investigated under both three-point and four-point bending conditions. For all stress levels tested, the fatigue lifetimes tended to be higher for the three-point loading condition. The fatigue endurance limits (defined as 107 cycles without failure), based on the applied stress range, for three-point and four-point loading conditions were approximately 475 MPa and 350 MPa, respectively. All fracture surfaces were found to be composed of four main regions: a crack-initiation site, a stable crack-growth region, an unstable fast-fracture region, and a melting region. Finely spaced parallel marks, similar to fatigue striations found in crystalline alloys, oriented somewhat perpendicular to the direction of crack propagation were observed in the stable crack-growth region. Analyses of these marks found that their spacing increased with increasing stress-intensity-factor range. Damage was found to initiate from preexisting defects present on or near the surface.

A novel polymeric composite material, polystyrene (PS)-grafted carbon nanocapsules (CNCs), has been prepared. sec-butyllithium was first used to introduce negative charges on CNCs, and these CNC carbanions acted then as initiators for anionic polymerization of styrene. Based on a weight loss at the decomposition temperature of the butyl groups, the quantity of the butyls attached to the CNC surface was determined as 1.18 wt%, corresponding to 0.25 mol% initiator per mol of carbon atom on the CNC surface. Furthermore, the decomposition temperature of butylated CNCs was lower than that of the pristine CNCs by nearly 200 °C. The polystyrene content in our PS-grafted CNC sample was approximately 20%, and the molecular weight of the grafted PS on the surface of CNCs was calculated as 1200 gmol−1. Compared with the molecular weight of the ungrafted PS, the molecular weight of grafted PS was lower, thus indicating rates of initiation and/or propagation for CNC-bound carbanions lower than those of the free sec-butyllithium. The PS-grafted CNCs had good dispersion in toluene, tetrahydrofuran, cyclohexane, and other common organic solvents in which polystyrene was dissolvable and thus indicated good compatibility when further blended with other styrenic polymers. The PS-grafted CNCs were characterized and examined by Fourier transform infrared, thermogravimetric analysis, atomic force microscopy, differential scanning calorimetry, ultraviolet-visible spectroscopy, Raman spectroscopy, scanning electron microscopy, and transmission electron microscopy. The electron microscopy images indicated that the PS-grafted CNCs were homogeneous composites containing uniform polymer/CNC ratios.

We report on ultrabroad infrared (IR) luminescences covering the 1000–1700-nm wavelength region, from Bi-doped 75GeO2–20RO–5Al2O3–1Bi2O3(R = Sr, Ca, and Mg) glasses. The full width at half-maximum of the IR luminescences excited at 980 nm increases (315 → 440 → 510 nm) with the change of alkaline earth metal (Mg2+→ Ca2+→ Sr2+). The fluorescence lifetime of the glass samples is 1725, 157, and 264 μs when R is Sr, Ca, and Mg, respectively. These materials may be promising candidates for broad-band fiber amplifiers and tunable laser resources.

Two different morphologies of MoS2 (short and long sheets) were utilized to elucidate the intercalation mechanism of 1,2,3,4 tetrahydroquinoline (THQ). MoS2 (short sheets) and molybdenite (MB) (long sheets) were exfoliated and restacked in the presence of THQ. The x-ray diffraction patterns of both samples show a new reflection in the 001 plane, which implies a lowering of symmetry and corresponds to an expansion of the layers by approximately 12.3 Å. In the MoS2-THQ sample, 80% of the MoS2 was intercalated and 20% remained stacked. In the MB-THQ sample, 30% of MB was intercalated while 70% remained stacked. X-ray absorption structure (XAS) studies showed changes in atomic geometry and coordination. The x-ray absorption near-edge spectra showed shifts in the geometry of the intercalated MoS2 and MB sample compared to the unintercalated samples. Extended x-ray absorption fine structure studies showed lower coordination numbers compared to the untreated samples. Infrared spectroscopy characterization of these same samples suggests intercalation and partial dehydrogenation of the THQ.

Bis(2,2,6,6-tetramethyl-3,5-heptanedionato)zinc [Zn(TMHD)2] is a relatively uninvestigated precursor that was used in this work to grow highly c-axis-oriented ZnO films on Si(100). X-ray photoelectron spectroscopy studies before and after Ar ion sputtering indicated that surface carbon on several samples was reduced from as much as 34 at.% to much less than 1 at.% within the first 5 nm, indicating very clean Zn(TMHD)2 precursor decomposition. Microstructural and compositional analysis revealed columnar ZnO grains with domain widths of approximately half the total film thickness and a Zn-to-O atomic percent ratio indicative of stoichometric ZnO.

ZnO nanostructures were grown directly on sapphire substrates and GaN epilayers by thermal evaporation. Their morphologies and densities were found to be strongly dependent on the synthesis position and the kinds of substrate loaded into the reactor due to the different oxygen densities and the lattice mismatch, respectively. Scanning electron microscopy and transmission electron microscopy studies revealed that ZnO nanorods on sapphire substrates grew in four directions, one 〈0001〉Sapphire and three (1014)Sapphire directions. It was found that the in-plane lattice mismatch of inclined ZnO nanorods was remarkably reduced by forming the planar relationship of (0002)ZnO//(1014)Sapphire, compared to that of (1120)ZnO//(1010)Sapphire in the ZnO film. On the other hand, for the GaN epilayers, vertically well-aligned ZnO nanorods were grown after growing an epitaxial ZnO film due to reduced lattice mismatch. Electron energy-loss spectroscopy data showed that Zn-rich stoichiometry was responsible for the formation of ZnO nanostructures.

High-resolution transmission electron microscopy, x-ray photoelectron spectroscopy (XPS), and Raman spectroscopy were used to study phase configuration and nanostructure evolutions of Ti–Cx–Ny thin films with different amounts of C incorporation. It was found that the atomic ratio of (C + N)/Ti played a crucial role in phase configuration and nanostructure evolutions as well as mechanical behaviors. When the ratio was less than one unit, a nanocrystalline (nc-) Ti(C, N) solid solution was formed by way of dissolution of C into TiN lattice. When this dissolution reached saturation, precipitation of a small amount of amorphous (a-) C phase along nc-Ti(C, N) grains was followed with more C incorporation. Further increase of C content (up to ∼19 at.% C) made the amorphous phase fully wet nanocrystallites, which resulted in the formation of two-phase nanocomposite thin films with microstructures comprising of ∼5 nm nc-Ti(C,N) crystallites separated by ∼0.5 nm a-(C, CNx) phase. Thicker amorphous walls and smaller sized grains were followed when the C content was further increased, accompanying with the formation of some disorders and defects in nc-grains and amorphous matrices. When the C content was increased to ∼48 at.%, 1–3 nm nanocrystallites with an average size of ∼2 nm were embedded into amorphous matrices. Both microhardness and residual compressive stress values were increased with increase of the atomic ratio in solid solution thin films when the atomic ratio value was less than one unit. Their maximums were obtained at stiochiometry nc-Ti(C,N) solid solution. Enhancement of hardness values was attributed to solid solution effect.

Polychromatic synchrotron x-ray microdiffraction is used to determine the epitaxy of YBa2Cu3Ox (YBCO) films grown on polycrystalline Y.15Zr.85O1.925/CeO2/Y2O3/Ni95W5(Ni) rolling-assisted, biaxially textured substrates (RABiTS). A novel analysis technique is introduced in which the orientation of mosaic films is measured by using a Hough transform to recognize arcs in Laue microdiffraction patterns that correspond to low-index zone axes. While the overall epitaxy is cube-on-cube, grain-by-grain analysis reveals a systematic misorientation of YBCO with respect to Ni: the YBCO [001] rotates toward the direction of the surface normal. The crystal mosaic (for rotation about the rolling direction) measured by a single diffraction pattern sampling a 0.5-μm2 surface area is 0.7° full width at half-maximum for YBCO grown on Ni grains with a low tilt; for more highly tilted grains, the YBCO patterns can no longer be measured, presumably due to the large mosaic. The YBCO mosaic over the entire area of a Ni grain is ∼2.5° and varies with grain size; the mosaic is smaller for larger grains.

CoSn3 phase is formed in Sn/Co couples reacted at 200 °C. The reaction phase shows a unique cruciform pattern that is observed for the first time in the solid/solid reaction. The reaction phase layers are thick and uniform along the edges of the Co substrate, and there are no reaction phases at the corners. A continuous reaction layer is formed in Sn/Co couples reacted at 180 °C. A metastable CoSn4 phase is formed at the corner, and the reaction phase along the edge of the Co substrate is the CoSn3 phase. The reaction CoSn3 phase region shows a cruciform pattern if the CoSn4 phase region is ignored. It is concluded that the Sn flux is much faster than the Co flux, and the cruciform pattern of the reaction CoSn3 phase layer is formed either by cracking or transformation to the CoSn4 phase at the corners where stresses are most intensified.

TbMnO3 exists in an orthorhombic phase in nature. Recently, we successfully grew TbMnO3 thin films in the hexagonal phase using epitaxial stabilization techniques. In this article, we will show the details of the deposition conditions that allow us to fabricate the hexagonal TbMnO3 films on Pt–Al2O3(0001) substrates. The artificial hexagonal phase can be easily formed above 850 °C, irrespective of the oxygen partial pressure. The hexagonal TbMnO3 films showed ferroelectric properties, which are significantly enhanced compared to those of the orthorhombic TbMnO3 bulk phase. We find interesting anomalies in the magnetic and magnetodielectric properties of the TbMnO3 films at around 45 K, which should be related with the Mn3+ spin reorientation. We also find spin-glass-like behaviors in the magnetic susceptibility, which could be attributed to the geometric frustration of antiferromagnetically coupled Mn spins with an edge-sharing triangular lattice. This work shows details of the growth and properties of hexagonal TbMnO3 films.

A bulk nanocrystalline (nc) Ni–Fe alloy was subjected to tensile deformation, which leads to grain growth. The nanoindentation study indicates that the hardness, H, and Young’s modulus, E, of the nc alloy before and after tensile deformation did not show a clear indentation-rate effect. However, the tensile deformation results in a decrease in the E values of about 15%, which might be attributed to the grain rotation, leading to texture development during the stress-induced grain growth.

Epitaxial ZnO thin films were grown on (111) MgAl2O4 with a pre-seeded, two-step chemical solution deposition process. Isolated, epitaxial ZnO islands (seeds) were formed on the substrate in the first step by spin coating a very thin layer of the precursor solution and heat-treating to 950 °C/3 h. In the second step, the seeded substrate was coated with another layer of precursor to produce an epitaxial film. The result was compared with the case in which a MgAl2O4 substrate was not seeded. Both the seeded and unseeded ZnO films have out-of-plane and in-plane orientation relationships of , respectively. However, only the seeded ZnO films have very faceted surface morphology without grain boundaries, indicating epitaxy, whereas the unseeded ZnO films have deep grain boundaries indicative of polycrystalline nature. This result shows that the formation of seeds in the first step plays an instrumental role in the formation of an epitaxial ZnO film.

The hardness and elastic modulus of ultra thin amorphous carbon overcoat (COC) films were measured using a recently developed sub-nm nanoindentation system. The carbon overcoat film thickness was varied to be 2.5 nm, 5 nm, and 10 nm on a glass substrate with a 2 nm titanium interlayer. A very sharp indenting tip, which was a cube corner tip with a radius of 44 nm, was used for the experiments. It was found that the mechanical properties of sub-10 nm film thicknesses can be reliably measured using the sub-nm indentation system and a sharp indenting tip. As the thickness of the carbon overcoat increased, so too did the surface roughness. For all three film thickness samples, the trends of hardness and elastic modulus values with the contact depth are very similar. When the contact depth is smaller than the film thickness, the measured values of hardness and elastic modulus are higher than those of the glass substrate, and gradually decrease and then approach the values of glass substrate. When the contact depth is larger than the film thickness, the measured values approximate those of the glass substrate. The thinner film shows higher values of hardness and elastic modulus near the surface, which indicates that mechanical properties do change with film thickness and that measurements made on thicker films and extrapolated to thinner films may lead to incorrect conclusions.

In this work, we performed nanoindentation studies on polymers with different moduli in the range of several millipascals up to several gigapascals. The focus was on the initial contact identification during indentation testing. Surface-detection methods using quasi-static loading as well as methods employing the dynamic forces associated with the continuous stiffness measurement technique were compared regarding their practicability and accuracy for the testing of polymeric materials. For the most compliant material with a modulus of 1 MPa, where contact identification is most critical, we used load-displacement curves obtained from finite element modeling analysis as a reference for the evaluation of experimental techniques. The results show how crucial the precise surface detection is for achieving accurate indentation results, especially for compliant materials. Further, we found that surface detection by means of dynamic testing provides mechanical-property values of higher accuracy for all polymers used in this study. This was due to smaller errors in surface detection, thus avoiding a significant underestimation of the contact area.

In this work, instrumented nanoindentation experiments with two spherical tips with radii of 13.5 and 1 μm were used to explore the deformation behavior of ZnO single crystals with two orientations, C (basal) and A (prism). By converting the nanoindentation load–displacement data to stress–strain curves, we show that the main reason the hardening rates are higher for the C plane than they are for the A plane is the activation of dislocations—with widely different flow stresses—on different sets of slip planes. For the former, glide occurs on basal planes as well as pyramidal planes; for the latter, glide occurs predominantly on basal planes. The C plane is roughly twice as hard as the A plane, probably due to the orientation of basal planes with respect to the indentation axis. A Weibull statistical analysis of the pop-in stresses indicates that the inherent defect concentration at or near the surface is the main factor for the initiation of plastic deformation. The strain energy released when the pop-ins occur determines their extent. The elastic moduli values, determined by Berkovich nanoindentation, are 135 ± 3 GPa and 144 ± 4 GPa for the C and A planes, respectively. In the C orientation repeated indentations to the same stress result in fully reversible hysteretic loops that are attributed to the formation of incipient kink bands.

The growth of HfO2 thin films on a HF-dipped p-Si(100) substrate at 200 °C by atomic-layer deposition (ALD) using Hf[N(C2H5)(CH3)]4 and H2O vapor as precursors is demonstrated. Uniform HfO2 thin films are obtained on a 4-in. silicon wafer, and the energy-band gap and band offset are determined by x-ray photoelectron spectroscopy analysis. The as-deposited HfO2 thin film is amorphous and able to crystallize at 500 ∼ 600 °C with only the monoclinic phase. As for the electrical performance of Au–Ti–HfO2–Si metal oxide semiconductor capacitors, a dielectric constant of ∼17.8 and an equivalent oxide thickness value of ∼1.39 nm are obtained from the 40-cycle ALD film after annealing at 500 °C. In addition, the breakdown field is in the range of 5 ∼ 5.5 MV/cm, and the fixed charge density is on the order of 1012 cm−2, depending on the annealing temperatures. The interface quality of HfO2 thin films on silicon is satisfactory with an interface-trap charge density of ∼3.7 × 1011 cm−2 eV−1.

Broadband near-infrared (IR) luminescence in transparent alkali gallium silicate glass-ceramics containing Ni2+-doped β-Ga2O3 nanocrystals was observed. This broadband emission could be attributed to the 3T2g (3F) → 3A2g (3F) transition of octahedral Ni2+ ions in glass-ceramics. The full width at half-maximum (FWHM) of the near-IR luminescence and fluorescent lifetime of the glass-ceramic doped with 0.10 mol% NiO were 260 nm and ∼1220 μs, respectively. It is expected that transparent Ni2+-doped β-Ga2O3 glass-ceramics with this broad near-IR emission and long fluorescent lifetime have potential applications as super-broadband optical amplification media.

Fundamental to investigating the coexistence of superconductivity and magnetic ordering in GdSr2RuCu2Oy(Gd1212) is the fabrication of macroscopic crystallographically oriented samples. To achieve this, we need to identify the conditions in which Gd1212 incongruent melting reaction, producing solid GdSr2RuO6(Gd1210) in Cu-rich liquid, dominates over decomposition due to RuO2sublimation. Only in these conditions is it possible, indeed, to grow oriented samples by any melting and resolidifying technique. Moreover, the optimal mixture of Gd1212 and its melting products has to be identified to perform melt-textured or flux-flow growth. By means of thermogravimetric and differential thermal analysis (TG–DTA) we analyzed, up to 1200 °C in air, several mixtures of Gd1212 with Gd1210 or CuO, performing a scan of the entire CuO–Gd1212–Gd1210 coexistence line of the Gd–Sr–Ru–Cu–O phase diagram. Gd1212 melting temperatures have shown a certain dependence on composition, decreasing about 30 °C for high Gd1210 content samples and about 20 °C for high CuO content samples with respect to pure Gd1212. A huge undercooling was observed for resolidification processes that were revealed to start at temperatures around 990 °C. Measurements proved that in this range of temperatures in air, no mass is lost at the end of each melting process, so that they are not affected by RuO2sublimation. A strong dependence on the atmosphere has also been observed for pure Gd1212, melting temperature decreasing by more than 80 °C from 100% O2atmosphere to He atmosphere (less than 10−2% O2). Measurements revealed that high O2partial pressures favor RuO2sublimation, whereas low oxygen atmospheres prevent resolidification.