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.

Design of temperature-compensated reference electrodes for non-isothermal galvanic sensors

The criterion for the design of a temperature-compensated reference electrode for non-isothermal galvanic sensors is deduced from the basic flux equations of irreversible thermodynamics. It is shown that when the Seebeck coefficient of the non-isothermal cell using a solid oxygen ion-conducting electrolyte under pure oxygen is equal to the relative partial molar entropy of oxygen in the reference electrode divided by 4F, then the EMF of the non-isothermal cell is the same as that of an isothermal cell with the same electrodes operating at the higher temperature. By measuring the temperature of the melt alone and the EMF of the non-isothermal galvanic sensor, one can derive the chemical potential or the concentration of oxygen in a corrosive medium. The theory is experimentally checked using sensors for oxygen in liquid copper constructed with various metal+oxide electrodes and fully stabilised (CaO)ZrO2 as the electrolyte. To satisfy the exact condition for temperature compensation it is often necessary to have the metal or oxide as a solid solution in the reference electrode.

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.

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.

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

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.

Carbon nanotube reinforced supramolecular gels with electrically conducting, viscoelastic and near-infrared sensitive properties

Pristine and long-chain functionalized single-walled carbon nanotubes (SWNTs) were incorporated successfully in supramolecular organogels formed by an all-trans tri(p-phenylenevinylene) bis-aldoxime to give rise to new nanocomposites with interesting mechanical, thermal and electrical properties. Variable-temperature UV-vis and fluorescence spectra reveal both pristine and functionalized SWNTs promote aggregation of the gelator molecules and result in quenching of the UV-vis and fluorescence intensity. Electron microscopy and confocal microscopy show the existence of a densely packed and directionally aligned fibrous network in the resulting nanocomposites. Differential scanning calorimetry (DSC) of the composites shows that incorporation of SWNTs increases the gel formation temperature. The DSC of the xerogels of 1-SWNT composites indicates formation of different thermotropic mesophases which is also evident from polarized optical microscopy. The reinforced aggregation of the gelators on SWNT doping was reflected in the mechanical properties of the composites. Rheology of the composites demonstrates the formation of a rigid and viscoelastic solid-like assembly on SWNT incorporation. The composites from gel-SWNTs were found to be semiconducting in nature and showed enhanced electrical conductivity compared to that of the native organogel. Upon irradiation with a near IR laser at 1064 nm for 5 min it was possible to selectively induce a gel-to-sol phase transition of the nanocomposites, while irradiation for even 30 min of the native organogel under identical conditions did not cause any gel-to-sol conversion.

Influence of lattice distortion on the Curie temperature and spin-phonon coupling in LaMn0.5Co0.5O3

Two distinct ferromagnetic phases of LaMn0.5Co0.5O3 having monoclinic structure with distinct physical properties have been studied. The ferromagnetic ordering temperature T-c is found to be different for both the phases. The origin of such contrasting characteristics is assigned to the changes in the distance(s) and angle(s) between Mn-O-Co resulting from distortions observed from neutron diffraction studies. Investigations on the temperature dependent Raman spectroscopy provide evidence for such structural characteristics, which affects the exchange interaction. The difference in B-site ordering which is evident from the neutron diffraction is also responsible for the difference in T-c. Raman scattering suggests the presence of spin-phonon coupling for both the phases around the T-c. Electrical transport properties of both the phases have been investigated based on the lattice distortion.

A Novel Synthetic Route For The Preparation Of Ammonium And Alkali-Metal Tetrafluoroborates And Alkyl Substituted Ammonium Tetrafluoroborates Using Pyridinium Tetrafluoroborate As The Precursor

Ammonium and alkali metal tetrafluoroborates have been prepared by the cation exchange reaction of pyridinium tetrafluoroborate with the corresponding hydroxides/halides. The reaction of pyridinium tetrafluoroborate with primary, secondary and tertiary alkyl amines at room temperature gives rise to mono-, di- and tri-alkylammonium tetrafluoroborates, respectively. The yields are good and the samples are of high purity. The products have been characterised by elemental analysis, IR and PMR spectroscopy. The spectral data for most of the compounds are reported for the first time.

A simple apparatus for the measurement of thermoelectric power in the temperature range 4·2–300K

A simple apparatus to measure the absolute thermoelectric power of solids in the temperature range 4·2–300K is described. The cryostat and the associated instrumentation is simple to operate. Representative data of measurements on metallic wire and pressed pellets are given. An accuracy of better than 10% in absolute thermopower can be obtained in this apparatus.