Electrochemical reduction of oxygen on gold and boron-doped diamond electrodes in ambient temperature, molten acetamide-urea-ammonium nitrate eutectic melt

The electrochemical reduction of oxygen has been studied on gold, boron-doped diamond (BDD) and glassy carbon (GC) electrodes in a ternary eutectic mixture of acetamide (CH3CONH2), urea (NH2CONH2) and ammonium nitrate (NH4NO3). Cyclic voltammetry (CV), differential pulse voltammetry (DPV), chronoamperometry and rotating disk electrode (RDE) voltammetry techniques have been employed to follow oxygen reduction reaction (ORR). The mechanism for the electrochemical reduction of oxygen on polycrystalline gold involves 2-step. 2-electron pathways of O-2 to H2O2 and further reduction of H2O2 to H2O. The first 2-electron reduction of O-2 to H2O2 passes through superoxide intermediate by 1-electron reduction of oxygen. Kinetic results suggest that the initial 1-electron reduction of oxygen to HO2 is the rate-determining step of ORR on gold surfaces. The chronoamperometric and ROE studies show a potential dependent change in the number of electrons on gold electrode. The oxygen reduction reaction on boron-doped diamond (BOO) seems to proceed via a direct 4-electron process. The reduction of oxygen on the glassy carbon (GC) electrode is a single step, irreversible, diffusion limited 2-electron reduction process to peroxide. (C) 2010 Elsevier Ltd. All rights reserved.

Low Temperature Synthesis of Nano-Crystalline CaCu3Ti4O12 Through aFuel Mediated Auto-Combustion Pathway

A novel, cost effective,environment-friendly and energetically beneficial alternative method for the synthesis of giant dielectric pseudo-perovskite material CaCu3Ti4O12 (CCTO) is presented. The method involved auto-combustion of an aqueous precursor solution in oxygen atmosphere with the help of external fuels and is capable of producing high amount of CCTO at ultra-low temperature, in the combustion residue itself. The amount of phase generated was observed to be highly dependent on the combustion process i.e. on the nature and amount of external-fuels added for combustion. Two successful fuel combinations capable of producing reasonably higher amount of the desired compound were investigated. On a structural characterization grain size was observed to decrease drastically to nano-dimension compared to submicron-size that was obtained in a traditional sol-gel combustion and subsequent cacination method. Therefore, the method reported can produce nano-crystalline CaCu3Ti4O12 ceramic matrix at an ultra-low temperature and is expected to be applicable for other multifunctional perovskite oxide materials.

The hard-particle model for a dense granular flow down an inclined plane

Perfectly hard particles are those which experience an infinite repulsive force when they overlap, and no force when they do not overlap. In the hard-particle model, the only static state is the isostatic state where the forces between particles are statically determinate. In the flowing state, the interactions between particles are instantaneous because the time of contact approaches zero in the limit of infinite particle stiffness. Here, we discuss the development of a hard particle model for a realistic granular flow down an inclined plane, and examine its utility for predicting the salient features both qualitatively and quantitatively. We first discuss Discrete Element simulations, that even very dense flows of sand or glass beads with volume fraction between 0.5 and 0.58 are in the rapid flow regime, due to the very high particle stiffness. An important length scale in the shear flow of inelastic particles is the `conduction length' delta = (d/(1 - e(2))(1/2)), where d is the particle diameter and e is the coefficient of restitution. When the macroscopic scale h (height of the flowing layer) is larger than the conduction length, the rates of shear production and inelastic dissipation are nearly equal in the bulk of the flow, while the rate of conduction of energy is O((delta/h)(2)) smaller than the rate of dissipation of energy. Energy conduction is important in boundary layers of thickness delta at the top and bottom. The flow in the boundary layer at the top and bottom is examined using asymptotic analysis. We derive an exact relationship showing that the a boundary layer solution exists only if the volume fraction in the bulk decreases as the angle of inclination is increased. In the opposite case, where the volume fraction increases as the angle of inclination is increased, there is no boundary layer solution. The boundary layer theory also provides us with a way of understanding the cessation of flow when at a given angle of inclination when the height of the layer is decreased below a value h(stop), which is a function of the angle of inclination. There is dissipation of energy due to particle collisions in the flow as well as due to particle collisions with the base, and the fraction of energy dissipation in the base increases as the thickness decreases. When the shear production in the flow cannot compensate for the additional energy drawn out of the flow due to the wall collisions, the temperature decreases to zero and the flow stops. Scaling relations can be derived for h(stop) as a function of angle of inclination.

Influence of substrate temperature and post-deposition heat treatment on the optical properties of SiO2 films

Silicon dioxide films are extensively used as protective, barrier and also low index films in multilayer optical devices. In this paper, the optical properties of electron beam evaporated SiO2 films, including absorption in the UV, visible and IR regions, are reported as a function of substrate temperature and post-deposition heat treatment. A comparative study of the optical properties of SiO2 films deposited in neutral and ionized oxygen is also made.

A possible mechanism for high-temperature superconductivity: Application to Bi and Tl compounds

We applied our previous theory of high temperature superconductivity to Bi and Tl compounds in this paper. The theory involves the role of electron pairs in the spin singlet of species Xequal-or-greater, slanted (Bi3+ (6S2), Tl(6S2) etc.) and their virtual excited state X0 (Bi5+ (6s0), Tl3+ (6s0), etc.) in the pairing interaction of quasiholes. Bi and Tl species provide additional channels of kind (Xequal-or-greater, slanted left angle bracket X0) owing to the charge fluctuations. We treated the two states of these species like a two-level Bose system. We used the pseudospin formalism to calculate the expression for the critical temperature in this paper. We also calculated numerically the value of Tc for Bi and Tl compounds and found a good agreement between theory and experiment.

Purification and characterization of endo-1,4-β-xylanase from Paecilomyces varioti Bainier

An endo-xylanase (1,4-β-d-xylanxylanohydrolase EC 3.2.1.8) was isolated from the culture filtrate of Paecilomyces varioti Bainier. The enzyme was purified 3.2 fold with a 60% yield by gel filtration and ion exchange chromatography. The purified enzyme had a molecular weight of 25,000 with a sedimentation coefficient of 2.2 S. The isoelectric point of the enzyme was 3.9. The enzyme was obtained in crystalline form. The optimum pH range was 5.5–7.0 and the temperature, 65°C. The Michaelis constant was 2.5 mg larchwood xylan/ml. The enzyme was found to degrade xylan by an endo mechanism producing arabinose, xylobiose, xylo- and arabinosylxylo-oligosaccharides, during the initial stages of hydrolysis. On prolonged incubation, xylotriose, arabinosylxylotriose and xylobiose were the major products with traces of xylotetraose, xylose and arabinose.

Structural aspects of high-temperature cuprate superconductors

High-temperature superconductivity constitutes the most sensational discovery of recent times. Since these new superconductors are complex metal oxides, chemistry has had a big role to play in the investigations. For the first time, stoichiometry, structure, bonding, and such chemical factors have formed central themes in superconductivity, an area traditionally dominated by physicists. These oxide superconductors have given a big boost to solid-state chemistry.

Analysis of effects of ambients (temperature and light intensity) on the electrical breakdown in bipolar transistors

This paper presents an analysis of the effects of ambients-temperature and light intensity on the V-l characteristics of bipolar transistors under electrical breakdown. The analysis is based on the transportation and storage of majority carriers in the base region. It is shown that this analysis can explain the observed shift in the V-l characteristics to lower voltages with increase in either temperature or light intensity.

Low-voltage varistors from ZnO+CaMnO3 ceramics

: Varistors prepared from ZnO with CaMnO3 perovskite as the only forming additive, exhibit voltage-limiting current-voltage characteristics with nonlinearity coefficient alpha up to 380 at low voltages of 1.8-12 V/mm. High nonlinearity is observed only with a suitable combination of processing parameters. The most crucial of them are (i) initial formulation of ceramics and (ii) the sintering temperature and conditions of post-sinter annealing. An electrically active intergranular phase is formed between ZnO grains with the composition ranging from Ca4Mn6Zn4O17 to Ca4Mn8Zn3O19, which creates the n-p-n heterojunctions. The low-voltage nonlinearity originates as a result of higher concentration of Mn(III)/Mn(IV) present at the grain boundary layer regions, being charge compensated by zinc vacancies. Under the external electric field, the barrier height is lowered due to the uphill diffusion of holes mediated by the acceptor states. Above the turn-on voltages, the unhindered transport of charge carriers between grains generates high current density associated with large nonlinearity.

A simple classical approach for the melting temperature of inert-gas nanoparticles

Like the metal and semiconductor nanoparticles, the melting temperature of free inert-gas nanoparticles decreases with decreasing size. The variation is linear with the inverse of the particle size for large nanoparticles and deviates from the linearity for small nanoparticles. The decrease in the melting temperature is slower for free nanoparticles with non-wetting surfaces, while the decrease is faster for nanoparticles with wetting surfaces. Though the depression of the melting temperature has been reported for inert-gas nanoparticles in porous glasses, superheating has also been observed when the nanoparticles are embedded in some matrices. By using a simple classical approach, the influence of size, geometry and the matrix on the melting temperature of nanoparticles is understood quantitatively and shown to be applicable for other materials. It is also shown that the classical approach can be applied to understand the size-dependent freezing temperature of nanoparticles.

Design and fabrication of an automated temperature programmed reaction system to evaluate 3-way catalysts Ce1-x-y(La/Y)(x)PtyO2-delta

A completely automated temperature-programmed reaction (TPR) system for carrying out gas-solid catalytic reactions under atmospheric flow conditions is fabricated to study CO and hydrocarbon oxidation, and NO reduction. The system consists of an all-stainless steel UHV system, quadrupole mass spectrometer SX200 (VG Scientific), a tubular furnace and micro-reactor, a temperature controller, a versatile gas handling system, and a data acquisition and analysis system. The performance of the system has been tested under standard experimental conditions for CO oxidation over well-characterized Ce1-x-y(La/Y)(y)O2-delta catalysts. Testing of 3-way catalysis with CO, NO and C2H2 to convert to CO2, N-2 and H2O is done with this catalyst which shows complete removal of pollutants below 325 degrees C. Fixed oxide-ion defects in Pt substituted Ce1-y(La/Y)(y)O2-y/2 show higher catalytic activity than Pt ion-substituted CeO2

Al/SiC carriers for microwave integrated circuits by a new technique of pressureless infiltration

Materials with high thermal conductivity and thermal expansion coefficient matching with that of Si or GaAs are being used for packaging high density microcircuits due to their ability of faster heat dissipation. Al/SiC is gaining wide acceptance as electronic packaging material due to the fact that its thermal expansion coefficient can be tailored to match with that of Si or GaAs by varying the Al:SiC ratio while maintaining the thermal conductivity more or less the same. In the present work, Al/SiC microwave integrated circuit (MIC) carriers have been fabricated by pressureless infiltration of Al-alloy into porous SiC preforms in air. This new technique provides a cheaper alternative to pressure infiltration or pressureless infiltration in nitrogen in producing Al/SiC composites for electronic packaging applications. Al-alloy/65vol% SiC composite exhibited a coefficient of thermal expansion of 7 x 10(-6) K-1 (25 degrees C-100 degrees C) and a thermal conductivity of 147 Wm(-1) K-1 at 30 degrees C. The hysteresis observed in thermal expansion coefficient of the composite in the temperature range 100 degrees C-400 degrees C has been attributed to the presence of thermal residual stresses in the composite. Thermal diffusivity of the composite measured over the temperature range from 30 degrees C to 400 degrees C showed a 55% decrease in thermal diffusivity with temperature. Such a large decrease in thermal diffusivity with temperature could be due to the presence of micropores, microcracks, and decohesion of the Al/SiC interfaces in the microstructure (all formed during cooling from the processing temperature). The carrier showed satisfactory performance after integrating it into a MIC.

Low-temperature polymer precursor-based synthesis of nanocrystalline particles of lanthanum calcium manganese oxide (La0.67Ca0.33MnO3) with enhanced ferromagnetic transition temperature

We report a simple modified polymeric precursor route for the synthesis of highly crystalline and homogenous nanoparticles of lanthanum calcium manganese oxide (LCMO). The LCMO phase formation was studied by thermal analysis, x-ray powder diffraction, and infrared spectroscopy at different stages of heating. These nanocrystallites (average particle size of 30 nm) possess ferromagnetic-paramagnetic transition temperature (T-c) of 300 K, nearly 50 K higher than that of a single crystal. The Rietveld analysis of the powder x-ray diffraction data of the nanopowders reveals significant lattice contraction and reduction in unit cell anisotropy-these structural changes are correlated to the enhancement in T-c.