In-situ TiC particle reinforced Ti–Al matrix composites: Powder preparation by mechanical alloying and Selective Laser Melting behavior

Mechanical alloying of Ti–Al–graphite elemental powder mixture was performed to synthesize nanocomposite powder with Ti(Al) solid solution matrix reinforced by in-situ formed TiC particles. The evolutions in phases, microstructures, and compositions of milled powders with the applied milling times were investigated. It showed that with increasing the milling time, the starting irregularly shaped powder underwent a successive change in its morphology from a flattened shape (10 h) to a highly coarsened spherical one (15 h) and, eventually, to a fine, equiaxed and uniform one (above 25 h). The prepared TiC/Ti(Al) composite powder was nanocrystalline, with the estimated average crystallite size of 12 nm and of 7 nm for Ti(Al) and TiC, respectively. Formation mechanisms behind the microstructural development of powders were elucidated. The Ti(Al) solid solution is formed through a gradual and progressive solution of Al into Ti lattice. The formation of TiC is through an abrupt, exothermic, and self-sustaining reaction between Ti and C elements. Selective Laser Melting (SLM) of as-prepared TiC/Ti(Al) composite powder was performed. The TiC particle reinforced TiAl₃ (a major phase) and Ti₃AlC₂ (a minor phase) matrix composite part was obtained after SLM. Although a slight grain growth occurred as relative to as-milled powder, the SLM processed composites still exhibited a refined microstructure.     

Neutron polarization analysis on the multiferroic TbMn2O5

Polycrystalline TbMn₂O₅ was prepared by the standard solid-state reaction method and characterized by powder X-ray diffraction and magnetization to assure it is of single phase. Heat capacity measurements on the compound reveal an antiferromagnetic phase transition at 45 K. A broad peak below 6 K in the heat capacity measurements corresponds to the crossover transition of Tb³⁺ ordering. To confirm these magnetic orderings, neutron powder diffractions on TbMn₂O₅ with XYZ neutron polarization analysis were performed at the diffuse neutron scattering (DNS) spectrometer, FRJ-II, by using neutron wavelength of 4.8 Å in the temperature range of 1.8–250 K. Magnetic scattering was separated from nuclear coherent and spin incoherent scattering contributions. Long-range ordered magnetic peaks were observed below 39 K which is consistent with the heat capacity results. The drastic increasing intensities below 6 K indicate the ferromagnetic transition in Tb³⁺ orderings.     

The effect of stoichiometry on the combustion behavior of a nanoscale Al/MoO3 thermite

The effect of stoichiometry on the combustion behavior of the nanoscale aluminum molybdenum trioxide (nAl/MoO₃) thermite was studied in a burn tube experiment by characterizing the propagation velocity and pressure output of the reaction. Changing the stoichiometry affects the combustion through changes in the product temperature, phase, and composition. The mixture ratios of the composites were varied over an extremely wide range (5% nAl (95% MoO₃)–90% nAl (10% MoO₃)). Results revealed three separate combustion regimes: a steady high speed propagation (100 to 1000 m/s) from approximately 10% to 65% nAl, an oscillating and accelerating wave near 70% nAl, and a steady-slow speed propagation (0.1–1 m/s) from approximately 75% to 85% nAl. Propagation was observed to fail both <10% nAl and >85% nAl. This is the first known observation of such limits for a nanoscale thermite in a tube geometry. The instrumented tube tests revealed peak pressures over 8 MPa near stoichiometric conditions in the steady high speed propagation region, no measurable pressure rise at low speed propagation, and building pressures for accelerating waves. The results suggest the propagation mode to be a supersonic convective wave for near stoichiometric mixtures and a conductive deflagration for extremely fuel-rich mixtures. The implications of these results for microscale combustion applications are discussed.     

Effect of the synthesis route on the structural properties and shape of the indium oxide (In2O3) nano-particles

Nano-crystalline indium oxide (In₂O₃) particles have been synthesized by sol–gel and hydro-thermal techniques. A simple hydro-alcoholic solution consisting indium nitrate hydrate and citric acid (in sol–gel method) and 1, 4-butandiol (in hydro-thermal method) have been utilized. The structural properties of indium oxide nano-powders annealed at 450 °C (for both methods) have been characterized by the X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and specific surface area (SSA) analysis. Structural analysis of the samples shows cubic phase in sol–gel and cubic-hexagonal phase mixture in hydro-thermally prepared particles. The nano-particles prepared by sol–gel method have nearly spherical shape, whereas hydro-thermally-made ones display wire- and needle-like shape in addition to the spherical shape. The obtained In₂O₃ nano-particles surface areas were 23.2 and 55.3 in sol–gel and hydro-thermal methods, respectively. The optical direct band gap of In₂O₃ nano-particles were determined to be 4.32 and 4.24 eV for sol–gel and hydro-thermal methods, respectively. These values exhibit 0.5 eV blue shift from that the bulk In₂O₃ (3.75 eV), which is related to the particle size reduction and approaching the quantum confinement limit of nano-particles.     

Structure and reaction pathways of methyl lactate on Pd(1 1 1)

The adsorption and reaction of methyl lactate (CH₃CH(OH)COOCH₃) is studied in ultrahigh vacuum on a Pd(1 1 1) surface using temperature-programmed desorption (TPD) and reflection–absorption infrared spectroscopy (RAIRS). Methyl lactate reacts at relatively low temperatures (220 K) by O–H bond scission. This intermediate can either react with hydrogen to reform methyl lactate at 280–300 K or undergo β-hydride elimination to form flat-lying methyl pyruvate. This decomposes to form acetyl and methoxy carbonyl species as found previously following methyl pyruvate adsorption on Pd(1 1 1). These species predominantly react to form carbon monoxide, methane and hydrogen.     

Microstructure characterization of mechanosynthesized nanocrystalline NiFe2O4 by Rietveld's analysis

Nanocrystalline nickel ferrite (NiFe₂O₄) is synthesized at room temperature by high-energy ball milling the stoichiometric mixture of (1:1 mol%) of NiO and α-Fe₂O₃ powders. The structural and microstructural evolution of NiFe₂O₄ caused by milling is investigated by X-ray powder diffraction. The relative phase abundance, particle size, r.m.s. strain, lattice parameter changes of different phases have been estimated employing Rietveld structure refinement analysis of X-ray powder diffraction data. Particle size and content (wt%) of both NiO and α-Fe₂O₃ phases reduce rapidly with increasing milling time and a significant amount of nanocrystalline NiFe₂O₄ is formed within 1 h of ball milling. Particle sizes of all the phases reduce to ∼10 nm within 5 h of milling and remain almost unchanged with increasing milling time up to 20 h. Lattice parameter of cubic NiO decreases linearly with increasing milling time, following the Vegard's law of solid-solution alloy. A continuous decrease in lattice parameter of cubic NiFe₂O₄ phase clearly suggests that smaller Ni atoms have occupied some of the vacant oxygen sites of ferrite lattice. Cation distribution both in octahedral and tetrahedral sites changes continuously with milling time and the normal spinel lattice formed at early stage of milling, transforms to inverse spinel lattice in the course of milling. High-resolution transmission electron microscope (HRTEM) micrographs of 11 h milled sample corroborates the findings of X-ray profile analysis.     

Structure and properties of the one-dimensional cobalt oxide CaCo2O4

We have studied crystal structure and transport properties of the quasi one-dimensional cobalt oxide CaCo₂O₄. The CaCo₂O₄ phase crystallizes in calcium-ferrite type structure, which consists of a corner- and edge-shared CoO₆ octahedron network including one-dimensional double chains. Large thermoelectric power (S  150 μV/K at 390 K) with metallic temperature dependence of S, moderate resistivity (ρ  2.9 × 10⁻¹ Ω cm at 390 K) with carrier localization at low temperature, and normal thermal conductivity (κ  6.3 W/Km at 390 K) were observed. The phonon mean-free path was calculated from the observed data, as a function of temperature. The long phonon mean-free path (l  24 Å at 300 K) implies that the thermal conductivity could be suppressed by impurity scattering of phonons with partial element substitution.     

Chiral superconducting phase transition in 3-K phase of Sr2RuO4

We have investigated the transports of micro-fabricated sample of 3-K phase superconductivity (T_c  3 K) in Sr₂RuO₄–Ru eutectic system in order to clarify the pairing symmetry. Up to now, pure Sr₂RuO₄ (T_c = 1.5 K: 1.5-K phase) is widely recognized to be a spin-triplet odd-parity superconductor. However, the enhancement mechanism of T_c up to 3 K and the pairing symmetry of the 3-K phase have not been cleared yet. By using micro fabrication technique with focused ion beam, we have succeeded to extract individual superconducting channels for the 3-K phase in which only a few pieces of Ru inclusions are contained. Multiple kink structures observed in differential resistance–current (dV/dI − I) characteristics indicate serially connected superconducting filaments in the 3-K phase. We confirm that the 3-K phase is an odd-parity superconductor similar to pure Sr₂RuO₄ from the monotonous temperature dependence of the critical currents. In addition, we observed a quite unusual hysteresis in dV/dI − I below 2 K, which suggests the internal degrees of freedom in the superconducting state: the most probably the chiral p-wave state.     

Microstructure and optical characterizations of mechanosynthesized nanocrystalline semiconducting ZrTiO4 compound

A ZrO₂–TiO₂ solid solution is obtained by high energy ball milling of equimolar mixture of monoclinic (m) ZrO₂ and anatase (a) TiO₂. Nanocrystalline orthorhombic ZrTiO₄ compound is initiated from the nucleation of TiO₂–ZrO₂ solid solution with isostructural s-TiO₂ (srilankite) base after 30 min of milling. After 12 h of milling, 95 mol% non-stoichiometric ZrTiO₄ phase is formed. Post-annealing of 12 h ball-milled powder mixture at 1073 K for 1 h in open air results in complete formation of stoichiometric ZrTiO₄ compound. Microstructures of all powder mixtures milled for different durations have been characterized by Rietveld's structure and microstructure refinement method using X-ray powder diffraction data. HRTEM images of 12 h milled and annealed samples provide direct evidence of the results obtained from the Rietveld analysis. Optical bandgaps of ball milled and annealed ZrTiO₄ compounds lie within the semiconducting region (~2.0 eV) and increases with increase in milling time.     

Microwave dielectric properties of (1 − x)(Mg0.95Co0.05)TiO3–x(Na0.5La0.5)TiO3 ceramic system

The microstructures and the microwave dielectric properties of the (1 − x)(Mg_0.95Co_0.05)TiO₃–x(Na_0.5La_0.5)TiO₃ ceramic system were investigated. Two-phase system was confirmed by the XRD patterns and the EDX analysis. A co-existed second phase (Mg_0.95Co_0.05)Ti₂O₅ was also detected. The microwave dielectric properties are strongly related to the density and the matrix of the specimen. A new microwave dielectric material 0.88(Mg_0.95Co_0.05)TiO₃–0.12(Na_0.5La_0.5)TiO₃, possessing an excellent combination of dielectric properties: ε_r  22.36, Q × f  110,000 GHz (at 9 GHz), τ_f  2.9 ppm/°C), is proposed as a candidate dielectric for GPS patch antennas.     

Spontaneous ignition of ultra-fine magnesium powder without an original oxide coat at room temperature in O2/N2 mixture streams

To examine the pyrophoric characteristics of Mg powder, we generated ultra-fine Mg particles (average particle diameter: about 0.3 μm) without an original oxide coat in an Ar stream. The ignition of the powder was measured by using the impinging O₂/N₂ mixture streams over a wide range of the experimental parameters: pressure, oxygen concentration and velocity of the streams. The Mg powder was found to ignite even at room temperature. The spontaneous ignition temperatures in the range of 278  324 K were insensitive to all the experimental parameters. The ignition delay time had a tendency to decrease with increasing experimental parameters.The ignition process of the Mg powder was found to be controlled by the surface reaction rate without an oxide coat. We proposed a new ignition hypothesis considering a critical oxide thickness on the Mg powder particles at the transition temperature from protective to non-protective nature: that is, the ignition of the Mg powder occurs when the powder temperature rises above the transition temperature before surface reactions form a protective oxide coat with the critical thickness on the individual particle surfaces. According to this hypothesis, an ignition model of Mg powder cluster was developed, and the relation between the spontaneous critical ignition temperature and the ultra-fine powder size, depending on the critical thickness of the protective oxide coat, was clarified. The critical oxide thickness was estimated.     

Proton segregation on a growing ice interface

Hydronium segregates to the surface of H₂O (D₂O) ice films grown on Pt(1 1 1) above 151 K (158 K). This is observed via the voltage that develops across the films, utilizing work function measurements. The dependence of this voltage on the film’s thickness is explained by a simple equilibrium model: as the film grows, most of the surface ions migrate so as to remain at the ice–vacuum interface, while a fixed percentage (0.05%) take the thermodynamically–unfavored route, to become incorporated into the growing bulk ice. This model implies a ΔG of about +0.1 eV for the movement of ions from the ice surface into the bulk ice.     

Dimensional evolution of silicon nanowires synthesized by Au–Si island-catalyzed chemical vapor deposition

This study explores the nucleation and morphological evolution of silicon nanowires (Si-NWs) on Si (0 0 1) and (1 1 1) substrates synthesized using nanoscale Au–Si island-catalyzed rapid thermal chemical vapor deposition. The Au–Si islands are formed by Au thin film (1.2–3.0 nm) deposition at room temperature followed by annealing at 700 °C, which are employed as a liquid-droplet catalysis during the growth of the Si-NWs. The Si-NWs are grown by exposing the substrates with Au–Si islands to a mixture of gasses SiH₄ and H₂. The growth temperatures and the pressures are 500–600 °C and 0.1–1.0 Torr, respectively. We found a critical thickness of the Au film for Si-NWs nucleation at a given growth condition. Also, we observed that the dimensional evolution of the NWs significantly depends on the growth pressure and temperature. The resulting NWs are 30–100 nm in diameter and 0.4–12.0 μm in length. For Si (0 0 1) substrates 80% of the NWs are aligned along the 1 1 1 direction which are 30° and 60° with respect to the substrate surface while for Si (1 1 1) most of the NWs are aligned vertically along the 1 1 1 direction. In particular, we observed that there appears to be two types of NWs; one with a straight and another with a tapered shape. The morphological and dimensional evolution of the Si-NWs is significantly related to atomic diffusion kinetics and energetics in the vapor–liquid–solid processes.     

Gas-phase vibrational spectroscopy and ab initio calculations of Rb(H2O)n and Rb(H2O)nAr cluster ions

The competition between ion–water electrostatic interactions and water–water hydrogen bonding in cluster ions depends on several factors, including charge density of the ion and temperature of the system. Infrared photodissociation spectra of Rb⁺(H₂O)_n=2–5 and Rb⁺(H₂O)_n=1–5Ar are presented here and compared to previous experiments involving potassium and cesium. The temperature, or internal energy, of hydrated rubidium cluster ions is controlled by varying the evaporative path available for cluster formation. Warmer clusters (with effective temperatures of 250–500 K) are formed by the evaporation of water, while colder clusters (40–120 K) can be formed by argon evaporation. Colder cluster ions tend to favor conformers with more hydrogen bonds compared to those cluster ions at warmer temperatures. Previous work from this laboratory has shown significant and dramatic differences between the spectra of hydrated potassium and cesium ions. With a charge density intermediate between that of K⁺ and Cs⁺, Rb⁺ plays an important role in bridging the gap in our previous studies.     

Modification of photonic properties in porphyrin-infiltrated opal crystals

Structural, optical and magnetic properties of porphyrin-infiltrated opal hybrid structures were investigated. Bulk samples of synthetic opal were grown by sedimentation technique from colloidal solution of SiO₂ spheres of diameter 250 nm. The structure of the samples was examined by atomic force microscopy. The photonic properties of crystals were investigated by optical measurements in transmission and reflection modes. The stop band was observed in the region 510–550 nm. The photonic properties of synthetic opal crystals were modified by infiltration with aqueous basic solution of iron–porphyrin (FeTPPS) of concentration 1.0 mM. In hybrid samples the absorption bands typical of FeTPPS were observed in the vicinity of the opal stop band. Magnetic properties of FeTPPS-infiltrated opal samples have been studied at 5–300 K in magnetic fields up to 5 T. The FeTPPS-infiltrated opal crystals can be considered as the structures perspective for magnetophotonic devices.     

Electronic stopping power of polymers for heavy ions in the ion energy domain of LSS theory

LSS based computed electronic stopping power values have been compared with the corresponding measured values in polymers for heavy ions with Z = 5–29, in the reduced ion velocity region, v_red ≤ 1. Except for limited v_red  0.6–0.85, the formulation generally shows significantly large deviations with the measured values. The ζ factor, which was approximated to be Z₁^1/6, involved in LSS theory has been suitably modified in the light of the available experimental stopping power data. The calculated stopping power values after incorporating modified ζ in LSS formula have been found to be in close agreement with measured values in various polymers in the reduced ion velocity range 0.35 ≤ v_red ≤ 1.0.     

Localization and antilocalization in InSb and InAs antidot lattices

We report on the observation of localization, antilocalization and Altshuler–Aronov–Spivak (AAS) oscillations in antidot lattices patterned on high-mobility InSb/InAlSb and InAs/AlGaSb heterostructures. In addition, the antidot lattices display ballistic commensurability features. The strength of the localization peak in InSb antidot lattices decreases exponentially with temperature, with a high characteristic temperature of 25 K between 0.4 and 50 K. Analysis of the AAS oscillations enables the extraction of phase and spin coherence lengths in InAs.     

High-performance pyroelectric single crystals for uncooled infrared detection applications

Uncooled pyroelectric infrared detectors based on ferroelectric single crystals 0.74Pb(Mg_1/3Nb_2/3)O₃–0.26PbTiO₃ (PMN–0.26PT) were fabricated. The performances of pyroelectric detectors dependence on detector fabrication temperature, absorption layer, and element thickness were compared. The room-temperature voltage responsivity (R_v) of 200 V/W and specific detectivity (D^*) of 10⁸ cm Hz^1/2/W at 12.5 Hz have been achieved. The results reveal that the better pyroelectric response can be expected by controlling temperature below 70 °C during the fabrication of the pyroelectric detectors, selecting absorption layer with high absorption coefficient, and decreasing the thickness of the elements.     

High-resolution electron microscopy observations of continuous precipitates with Pitsch-Schrader orientation relationship in an Mg–Al based alloy and interpretation with the O-lattice theory

High-resolution electron microscopy was applied to analyze the continuous precipitated particles of the γ-Mg₁₇Al₁₂ phase with Pitsch-Schrader OR in the heat-treated AZ91 alloy at 473 K for 8 h. The existence of a continuous precipitated particle with the Pitsch-Schrader OR including the selection of the habit plane and the growth direction in Mg–Al system is rationalized by the constrained coincidence site lattice/constrained complete pattern shift lattice (CCSL/CDSCL) model and the O-lattice theory.     

Scanning tunneling microscopy/spectroscopy on multi-layered cuprate superconductor Ba2Ca5Cu6O12 (O1−x Fx)2

Scanning tunneling microscopy/spectroscopy (STM/STS) measurements on multi-layered cuprate superconductor Ba₂Ca₅Cu₆O₁₂ (O_1−x F_x)₂ are carried out. STM topographies show randomly distributed bright spot structures with a typical spot size of 0.8 nm. These bright spots are occupied about 28% per one unit cell of c-plane, which is comparable to the regular amount of apical oxygen of 20% obtained from element analysis. Tunneling spectra simultaneously show both the small and the large gap structures. These gap sizes at 4.9 K are about Δ 15 meV and 90 meV, respectively. The small gap structure disappears at the temperature close to T_C, while the large gap persists up to 200 K. Therefore, these features correspond to the superconducting gap and pseudogap, respectively. These facts give evidence for some ordered state with large energy scale even in the superconducting state. For the superconducting gap, the ratio of 2Δ/K_BT_C = 4.9 is obtained with T_C = 70 K, which is determined from temperature dependence of the tunneling spectra.