Electronic structure of early transition metal oxides, Ca1−xSrxVO3 and La1−xCaxVO3: What can we learn from photoelectron spectroscopy

Photoemission spectroscopy offers the unique possibility of mapping out the electronic structure of the occupied electron states. However, the extreme surface sensitivity of this technique ensures that only the surface and the near-surface regions of any sample are probed. An important question arises in this context—Is the electronic structure of the surface region the same as that of the bulk? We address this issue using two different series of vanadium oxides, Ca1−xSrxVO3 and La1−xCaxVO3. Our results clearly establish that the electronic structure of the surface region is drastically different from that of the bulk in both these cases. We provide a method to separate the two contributions: one arising from the near-surface region and the other representative of the bulk. This separation allows us to deduce some very unusual behaviors of the electronic structures in these systems.

Towards sustainability: a new, solid-state synthetic route for supported metal nanocatalysts

Noble metal ions like Pt(IV) and Pd(II) were impregnated on gamma-alumina and aerosol 300 silica surfaces. Reduction of these ions using ammonia borane in the solid state resulted in the formation of the respective metal nanoparticles embedded in BNHx polymer which is dispersed on the oxide support. Removal of the BNH polymer was accomplished by washing the samples repeatedly with methanol. In this process the polymer undergoes solvolysis to release H-2 accompanied by the formation of ammonium methoxy borate salt, which has been removed by repeated methanol washings. As a result, metal nanoparticles well dispersed on gamma-alumina and aerosol 300 silica were obtained. These samples have been characterized by a combination of techniques, including electron microscopy, powder X-ray diffraction, NMR spectroscopy and surface area analyser.

A k-epsilon model for turbulent weld pool convection in gas metal arc welding process

In this paper, we present a modified k - epsilon model capable of addressing turbulent weld-pool convection in a GMAW process, taking into account the morphology of the phase change interface during a Gas Metal Arc Welding (GMAW) process. A three-dimensional turbulence mathematical model has been developed to study the heat transfer and fluid flow within the weld pool by considering the combined effect of three driving forces, viz., buoyancy, Lorentz force and surface tension (Marangoni convection). Mass and energy transports by the droplets are considered through the thermal analysis of the electrode. The falling droplet's heat addition to the molten pool is considered to be a volumetric heat source distributed in an imaginary cylindrical cavity ("cavity model") within the weld pool. This nature of heat source distribution takes into account the momentum and the thermal, energy of the falling droplets. The numerically predicted weld pool dimensions both from turbulence and laminar models are then compared with the experimental post-weld results sectioned across the weld axis. The above comparison enables us to analyze the overall effects of turbulent convection on the nature of heat and fluid flow and hence on the weld pool shape/size during the arc welding processes.

Efficiency enhancement in DSSC using metal nanoparticles: A size dependent study

The photoelectrode of Eosin-Y sensitised DSSC was modified by incorporating Au-nanoparticles to enhance the power conversion efficiency via scattering from surface plasmon polaritons. Size dependence of Au nanoparticle on conversion efficiency was performed in DSSC for the first time by varying the particle size from 20 to 94 nm. It was found that, the conversion efficiency is highly dependent on the size of the Au nanoparticles. For larger particles (>50 nm), the efficiency was found to be increased due to constructive interference between the transmitted and scattered waves from the Au nanoparticle while for smaller particles, the efficiency decreases due to destructive interference. Also a reduction in the V-oc was observed in general, due to the negative shifting of the TiO2 Fermi level on the adsorption of Au nanoparticle. This shift was negligible for larger particles. When 94 nm size particles were employed the conversion efficiency was doubled from 0.74% to 1.52%. This study points towards the application of the scattering effect of metal nanoparticle to enhance the conversion efficiency in DSSCs. (C) 2011 Elsevier Ltd. All rights reserved.

High-Performance Metal-Insulator-Metal Capacitors Using Europium Oxide as Dielectric

We report the first demonstration of metal-insulator-metal (MIM) capacitors with Eu2O3 dielectric for analog and DRAM applications. The influence of different anneal conditions on the electrical characteristics of the fabricated MIM capacitors is studied. FG anneal results in high capacitance density (7 fF/mu m(2)), whereas oxygen anneal results in low quadratic voltage coefficient of capacitance (VCC) (194 ppm/V-2 at 100 kHz), and argon anneal results in low leakage current density (3.2 x 10(-8) A/cm(2) at -1 V). We correlate these electrical results with the surface chemical states of the films through X-ray photoelectron spectroscopy measurements. In particular, FG anneal and argon anneal result in sub-oxides, which modulate the electrical properties.

Improvements in Efficiency of Surface Potential Computation for Independent DG MOSFET

A robust numerical solution of the input voltage equations (IVEs) for the independent-double-gate metal-oxide-semiconductor field-effect transistor requires root bracketing methods (RBMs) instead of the commonly used Newton-Raphson (NR) technique due to the presence of nonremovable discontinuity and singularity. In this brief, we do an exhaustive study of the different RBMs available in the literature and propose a single derivative-free RBM that could be applied to both trigonometric and hyperbolic IVEs and offers faster convergence than the earlier proposed hybrid NR-Ridders algorithm. We also propose some adjustments to the solution space for the trigonometric IVE that leads to a further reduction of the computation time. The improvement of computational efficiency is demonstrated to be about 60% for trigonometric IVE and about 15% for hyperbolic IVE, by implementing the proposed algorithm in a commercial circuit simulator through the Verilog-A interface and simulating a variety of circuit blocks such as ring oscillator, ripple adder, and twisted ring counter.

Monodispersity and stability: case of ultrafine aluminium nanoparticles (< 5 nm) synthesized by the solvated metal atom dispersion approach

The synthesis of THF coordinated aluminium nanoparticles by the solvated metal atom dispersion (SMAD) method is described. These colloids are not stable with respect to precipitation of aluminium nanoparticles. The precipitated aluminium nanopowder is highly pyrophoric. Highly monodisperse colloidal aluminium nanoparticles (3.1 +/- 0.6 nm) stabilized by a capping agent, hexadecyl amine (HDA), have also been prepared by the SMAD method. They are stable towards precipitation of particles for more than a week. The Al-HDA nanoparticles are not as pyrophoric as the Al-THF samples. Particles synthesized in this manner were characterized by high-resolution electron microscopy and powder X-ray diffraction. Annealing of the Al-HDA nanoparticles resulted in carbonization of the capping agent on the surface of the particles which imparts air stability to them. Carbonization of the capping agent was established using Raman spectroscopy and TEM. The annealed aluminium nanoparticles were found to be stable even upon their exposure to air for over a month which was evident from the powder XRD, TGA/DSC, and TEM studies. The successful passivation was further confirmed with the determination of high active aluminium content (95 wt%) upon exposure and storage under air.

Transition metal oxide loaded MCM catalysts for photocatalytic degradation of dyes

Transition metal oxide (TiO2, Pe(2)O(3), CoO) loaded MCM-41 and MCM-48 were synthesized by a two-step surfactant-based process. Nanoporous, high surface area compounds were obtained after calcination of the compounds. The catalysts were characterized by SEM, XRD, XPS, UV-vis and BET surface area analysis. The catalysts showed high activity for the photocatalytic degradation of both anionic and cationic dyes. The degradation of the dyes was described using Langmuir-Hinshelwood kinetics and the associated rate parameters were determined.

Transition metal oxide loaded MCM catalysts for photocatalytic degradation of dyes

Transition metal oxide (TiO2, Pe(2)O(3), CoO) loaded MCM-41 and MCM-48 were synthesized by a two-step surfactant-based process. Nanoporous, high surface area compounds were obtained after calcination of the compounds. The catalysts were characterized by SEM, XRD, XPS, UV-vis and BET surface area analysis. The catalysts showed high activity for the photocatalytic degradation of both anionic and cationic dyes. The degradation of the dyes was described using Langmuir-Hinshelwood kinetics and the associated rate parameters were determined.

Layer-by-Layer Self-Assembled Metal-Ion- (Ag-, Co-, Ni-, and Pd-) Doped TiO2 Nanoparticles: Synthesis, Characterisation, and Visible Light Degradation of Rhodamine B

Metal-ion- (Ag, Co, Ni and Pd) doped titania nanocatalysts were successfully deposited on glass slides by layer-by-layer (LbL) self-assembly technique using a poly(styrene sulfonate sodium salt) (PSS) and poly(allylamine hydrochloride) (PAH) polyelectrolyte system. Solid diffuse reflectance (SDR) studies showed a linear increase in absorbance at 416 nm with increase in the number of m-TiO2 thin films. The LbL assembled thin films were tested for their photocatalytic activity through the degradation of Rhodamine B under visible-light illumination. From the scanning electron microscope (SEM), the thin films had a porous morphology and the atomic force microscope (AFM) studies showed ``rough'' surfaces. The porous and rough surface morphology resulted in high surface areas hence the high photocatalytic degradation (up to 97% over a 6.5 h irradiation period) using visible-light observed. Increasing the number of multilayers deposited on the glass slides resulted in increased film thickness and an increased rate of photodegradation due to increase in the availability of more nanocatalysts (more sites for photodegradation). The LbL assembled thin films had strong adhesion properties which made them highly stable thus displaying the same efficiencies after five (5) reusability cycles.

Influence of Bottom Bubbling Rate on Formation of Metal Emulsion in Al-Cu Alloy and Molten Salt System

In steel refining process, an increase of interfacial area between the metal and slag through the metal droplets emulsified into the slag, so-called ``metal emulsion'', is one prevailing view for improving the reaction rate. The formation of metal emulsion was experimentally evaluated using Al-Cu alloy as metal phase and chloride salt as slag phase under the bottom bubbling condition. Samples were collected from the center of the salt phase in the container. Large number of metal droplets were separated from the salt by dissolving it into water. The number, surface area, and weight of the droplets increased with the gas flow rate and have local maximum values. The formation and sedimentation rates of metal droplets were estimated using a mathematical model. The formation rate increased with the gas flow rate and has a local maximum value as a function of gas flow rate, while the sedimentation rate is independent of the gas flow rate under the bottom bubbling condition. Three types of formation mode of metal emulsion, which occurred by the rupture of metal film around the bubble, were observed using high speed camera. During the process, an elongated column covered with metal film was observed with the increasing gas flow rate. This elongated column sometimes reached to the top surface of the salt phase. In this case, it is considered that fine droplets were not formed and in consequence, the weight of metal emulsion decreased at higher gas flow rate.

Metal-Ion Metathesis in Metal-Organic Frameworks: A Synthetic Route to New Metal-Organic Frameworks

A porous metalorganic framework, Mn(H3O)(Mn4Cl)(3)(hmtt)(8)] (POST-65), was prepared by the reaction of 5,5',10,10',15,15'-hexamethyltruxene-2,7,12-tricarboxylic acid (H(3)hmtt) with MnCl2 under solvothermal conditions. POST-65(Mn) was subjected to post-synthetic modification with Fe, Co, Ni, and Cu according to an ion-exchange method that resulted in the formation of three isomorphous frameworks, POST-65(Co/Ni/Cu), as well as a new framework, POST-65(Fe). The ion-exchanged samples could not be prepared by regular solvothermal reactions. The complete exchange of the metal ions and retention of the framework structure were verified by inductively coupled plasmaatomic emission spectrometry (ICP-AES), powder X-ray diffraction (PXRD), and BrunauerEmmettTeller (BET) surface-area analysis. Single-crystal X-ray diffractions studies revealed a single-crystal-to-single-crystal (SCSC)-transformation nature of the ion-exchange process. Hydrogen-sorption and magnetization measurements showed metal-specific properties of POST-65.

Effect of substrate surface roughness on electric current induced flow of liquid metals

Electric current can induce long-range flow of liquid metals over a conducting substrate. This work reports on the effect of the substrate surface roughness on the liquid metal-front velocity during such a flow. Experiments were conducted by passing electric current through liquid gallium placed over similar to 170 nm thick, 500 mu m wide gold and platinum films of varying roughness. The ensuing flow, thus, resembles micro-fluidics behavior in an open-channel. The liquid-front velocity decreased linearly with the substrate surface roughness; this is attributed to the reduction in the effective electric field along the liquid metal-substrate interface with the substrate surface roughness. (C) 2013 American Institute of Physics. http://dx.doi.org/10.1063/1.4790182]

Effect of Metal Ions (Ag, Co, Ni, and Pd) on the Visible Light Degradation of Rhodamine B by Carbon-Covered Alumina-Supported TiO2 in Aqueous Solutions

Metal-ion (Ag, Co, Ni, and Pd) doped TiO2 nanocatalysts were successfully embedded on carbon-covered alumina supports. The CCA-embedded catalysts were crystalline and had a high surface area compared to the free metal-ion doped titania nanocatalysts while they still retained the anatase phase of the core TiO2. These catalysts were photocatalytically active under solar light irradiation. Rhodamine B was used as a model pollutant and the reactivity followed a pseudo-first-order reaction kinetics. The reaction rate of the CCA-supported catalysts was Pd > Ag > Co > Ni. Among the ratios of the CCA:catalyst used, it was found that the 1:1 ratio had the fastest reaction rate, followed by the 1:2 ratio, while the 2:1 ratio exhibited the lowest reaction rate. The CCA/metal-ion doped titania were found to have photocatalytic activities comparable with those of CCA-supported titania.

Effect of substrate surface on electromigration-induced sliding at hetero-interfaces

Electromigration (EM)-induced interfacial sliding between a metal film and Si substrate occurs when (i) only few grains exist across the width of the film and (ii) diffusivity through the interfacial region is significantly greater than diffusivity through the film. Here, the effect of the substrate surface layer on the kinetics of EM-induced interfacial sliding is assessed using Si substrates coated with various thin film interlayers. The kinetics of interfacial sliding, and therefore the EM-driven mass flow rate, strongly depends on the type of the interlayer (and hence the substrate surface composition), such that strongly bonded interfaces with slower interfacial diffusivity produce slower sliding.