Magnetically tunable nonlinear current-voltage characteristics in oxygen deficient manganite perovskites

(La0.667Ca0.333Mn1-xMO3-delta)-O-x (M = Mg, Li or Re) exhibit insulating behaviour and nonlinear current-voltage (J-E) relationship with voltage-limiting characteristics at temperatures below the ferromagnetic transition (T-c). The high current region is set in at field strengths <60 V/cm. Nonlinearity exponent, alpha in the relation J = kE(alpha) increases inversely with temperature. In presence of an external magnetic field, the J-E curves show higher current density at lower field strengths. Microstructural studies indicate that there is no segregation of secondary phases in the grain boundary regions. There is remarkable changes in p(T) as well as J-E curves with the grain size. Annealing studies in lower p(O2) atmospheres indicate that there is significant out-diffusion of oxygen ions through the grain boundary layer (GBL) regions creating oxygen vacancies in the GBL regions. The concentration of Mn4+ ions is lowered at the GBL due to oxygen vacancies, reducing the probability of hopping and resulting in insulating behaviour. Therefore an insulating barrier is introduced between two conducting grains and the carrier motion between the grains is inhibited. Thus below T-c, where sufficient increase in resistivity is observed the conduction may be arising as a result of spin dependent tunneling across the barrier. External electric field lowers the barrier height and establishes carrier transport across the barrier. Above certain field strength, barrier height diminishes significantly and thereby allowing large number of carriers for conduction, giving rise to highly nonlinear conductivity. (C) 2002 Elsevier Science B.V. All rights reserved.

An XPS study on oxidation states of Pt and its alloys with Co and Cr and its relevance to electroreduction of oxygen

Cathodic reduction of oxygen in fuel cells is known to be enhanced on platinum alloys in relation to the platinum metal. The higher performance of the platinum alloys is as a result of the improved oxygen-reduction kinetics on the alloys but there is hardly any increase in the electrode platinum-surface-areas for the platinum alloys as compared to the platinum metal, and thus the higher performance is solely due to the enhanced electrocatalytic activity of the alloys as compared to the platinum metal. The present X-ray photoelectron spectroscopic (XPS) study on carbon-supported Pt, Pt–Co and Pt–Co–Cr electrocatalysts suggests the presence of a relatively lower Pt-oxide content on the alloys. The X-ray powder diffraction patterns for these electrocatalysts show that while the carbon-supported platinum electrocatalyst has a face-centered cubic (fcc) phase, carbon-supported Pt–Co and Pt–Co–Cr electrocatalysts exhibit a face-centered tetragonal (fct) phase. But, Pt electrocatalyst has a lower particle-size and, hence, a higher dispersion. Previous studies have shown higher activities on the Pt-alloys than on Pt, and have attributed it to changes in the electronic and structural characteristics of Pt. These changes can be correlated with the lower oxidation-state of Pt sites, as found in this study.

The influence of oxygen impurities on the formation of AlN-Al composites by infiltration of molten Al-Mg

The influence of residual oxygen in nitrogen on the formation of AlN-Al matrix by reactive infiltration has been investigated. Increasing the oxygen content from 10 ppm upwards decreased the nitride content in the matrix from 64 to 6%, Based on the analysis of the availability of oxygen at the Al-melt/gas interface, three distinct scenarios have been proposed (i) at lowest values, oxygen does not interfere with either infiltration or nitridation reaction; (ii) at intermediate values, nitridation is suppressed, however infiltration continues; and (iii) at a critical upper value, the melt passivates without any infiltration. This phenomenon offers control of the AlN/Al ratio in the matrix and the possibility of creation of microstructural gradierits by the appropriate choice of gas mixtures. (C) 2002 Elsevier Science B.V. All rights reserved.

The production of AlN-rich matrix composites by the reactive infiltration of Al alloys in nitrogen

Aluminium nitride (AlN)-Al matrices reinforced with Al2O3 particulate have been fabricated by reactive infiltration of Al-2% Mg alloy into Al2O3 preforms in N-2 in the temperature range of 900-1075 degreesC. The growth of composites of useful thickness was facilitated by the presence of a Mg-rich external getter, in the absence of which composite growth is self-limiting and terminates prematurely. Successful growth of composites has been attributed to the reduction in residual oxygen partial pressure brought about by the reaction with oxygen of highly volatile Mg in the getter alloy. The microstructure of the matrix consists of AlN-rich regions contiguous with the particulate with metal-rich channels in-between, thereby suggesting that nitridation initiates by preferential wicking of alloy along the particle surfaces. The increase in nitride content of the matrix with temperature is consistent with hardness values that vary between similar to3 and 10 GPa. (C) 2002 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved.

Remarkable photocytotoxicity in hypoxic HeLa cells by a dipyridophenazine copper(II) Schiff base thiolate

Copper(II) complexes Cu(satp)(L)] (1-3) of a Schiff base thiolate (salicylidene-2-aminothiophenol, H(2)satP) and phenanthroline bases (L), viz. 1,10-phenanthroline (phen in 1), dipyrido3,2-d:2',3'-f]quinoxaline (dpq in 2) and dipyrido3,2-a:2',3'-c]phenazine (dppz in 3), were prepared, characterized and their anaerobic DNA photocleavage activity and hypoxic photocytotoxicity studied. The redox active complexes show the Cu(II)-Cu(I) couple near -0.5 V for 1 and near 0.0 V vs. SCE (saturated calomel electrode) for 2 and 3. The one-electron paramagnetic complexes (similar to 1.85 mu(B)) are avid DNA binders giving K(b) values within 1.0 x 10(5) - 8.0 x 10(5) M(-1). Thermal melting and viscosity data along with molecular docking calculations suggest DNA groove and/or partial intercalative binding of the complexes. The complexes show anaerobic DNA cleavage activity in red light under argon via type-I pathway, while DNA photocleavage in air proceeds via hydroxyl radical pathway. The DFT (density functional theory) calculations reveal a thyil radical pathway for the anaerobic DNA photocleavage activity and suggest the possibility of generation of a transient copper(I) species due to bond breakage between the copper and sulfur to generate the thyil radical. An oxidation of the copper(I) species is likely by oxygen in an aerobic medium or by the buffer medium in an anaerobic condition. Complex 3 exhibits significant photocytotoxicity in HeLa cells (IC(50) = 8.3(+/- 1.0) mu M) in visible light, while showing lower dark toxicity (IC(50) = 17.2(+/- 1.0) mu M). A significant reduction in the dark toxicity is observed under hypoxic cellular conditions (IC(50) = 30.0(+/- 1.0) mu M in dark), while retaining its photocytotoxicity (IC(50) = 8.0(+/- 1.0) mu M). (C) 2011 Elsevier Inc. All rights reserved.

Study of pulsed laser ablated CaBi2Ta2O9 thin films

Polycrystalline CaBi2Ta2O9 thin films were grown on Pt/TiO2/SiO2/Si (100) substrates using a pulsed laser deposition technique. The influence of substrate temperature and oxygen pressure on crystallization and orientation of the films was studied. In-situ films deposited under a combination of higher substrate temperature and lower oxygen pressure exhibited a preferred c-axis orientation. Micro-Raman spectroscopy was used for complete understanding of phase evolution of CBT films. Thin films deposited at higher substrate temperatures showed larger grain size and higher surface roughness, observed by atomic force microscopy. The values of maximum polarization (2Pmnot, vert, similar13.4 μC/cm2), remanent polarization (2Prnot, vert, similar4.6 μC/cm2) and the coercive field Ec was about 112 kV/cm obtained for the film deposited at 650°C and annealed at 750°C. The room temperature, dielectric data revealed a dependence on the grain size.

Synthesis, crystal structure and catalytic properties of (p-cymene)ruthenium(II) azophenol complexes: azophenyl to azophenol conversion by oxygen insertion to a ruthenium---carbon bond

Azophenol complexes of formulation [(η6-p-cymene)RuCl(Ln)] (1–6, n=1–6) were prepared by two synthetic methods involving either an oxygen insertion to the Ru---C bond in cycloruthenated precursors forming complexes 1 and 2 or from the reaction of [{(η6-p-cymene)RuCl}2(μ-Cl)2] with azophenol ligands (HL3–HL6) in the presence of sodium carbonate in CH2Cl2. The molecular structure of the 1-(phenylazo)-2-naphthol complex has been determined by X-ray crystallography. The complex has a η6-p-cymene group, a chloride and a bidentate N,O-donor azophenol ligand. The complexes have been characterized from NMR spectral data. The catalytic activity of the complexes has been studied for the conversion of acetophenone to the corresponding alcohol in the presence of KOH and isopropanol. Complexes 4 and 6 having a methoxy group attached to the ortho-position of the phenylazo moiety and 2 with a methyl group in the meta-position of the phenolic moiety show high percentage conversion (>84%).

Kinetic decomposition of Ni2SiO4 in oxygen potential gradients

Nickel orthosilicate (Ni2SiO4) has been found to decompose into its component binary oxides in oxygen potential gradients at 1373 K. Nickel oxide was formed at the high oxygen potential boundary, while silica was detected at the low oxygen potential side. Significant porosity and fissures were observed near the Ni2SiO4/SiO2 interface and the SiO2 layer. The critical oxygen partial pressure ratio required for decomposition varied from 1.63 to 2.15 as the oxygen pressures were altered from 1.01 ⊠ 105 to 2.7X 10−4 Pa, well above the dissociation pressure of Ni2SiO4. Platinum markers placed at the boundaries of the Ni2SiO4 sample indicated growth of NiO at the higher oxygen potential boundary, without any apparent transport of material to the low oxygen potential side. However, significant movement of the bulk Ni2SiO4 crystal with respect to the marker was not observed. The decomposition of the silicate occurs due to the unequal rates of transport of Ni and Si. The critical oxygen partial pressure ratio required for decomposition is related both to the thermodynamic stability of Ni2SiO4 with respect to component oxides and the ratio of diffusivities of nickel and silicon. Kinetic decomposition of multicomponent oxides, first discovered by Schmalzried, Laqua, and co-workers [H. Schmalzried, W. Laqua, and P. L. Lin, Z. Natur Forsch. Teil A 34, 192 (1979); H. Schmalzried and W. Laqua, Oxid. Met. 15, 339 (1981); W. Laqua and H. Schmalzried, Chemical Metallurgy—A Tribute to Carl Wagner (Metallurgical Society of the AIME, New York, 1981), p. 29] has important consequences for their use at high temperatures and in geochemistry.

Electrical properties of ferroelectric YMnO3 films deposited on n-type Si(111) substrates

YMnO3 thin films were grown on an n-type Si substrate by nebulized spray pyrolysis in the metal-ferroelectric-semiconductor (MFS) configuration. The capacitance-voltage characteristics of the film in the MFS structure exhibit hysteretic behaviour consistent with the polarization charge switching direction, with the memory window decreasing with increase in temperature. The density of the interface states decreases with increasing annealing temperature. Mapping of the silicon energy band gap with the interface states has been carried out. The leakage current, measured in the accumulation region, is lower in well-crystallized thin films and obeys a space-charge limited conduction mechanism. The calculated activation energy from the dc leakage current characteristics of the Arrhenius plot reveals that the activation energy corresponds to oxygen vacancy motion.

Reduction of oxygen impurity at GaN/beta-Si(3)N(4)/Si interface via SiO(2) to Ga(2)O conversion by exposing of Si surface under Ga flux

The removal of native oxide from Si (1 1 1) surfaces was investigated by X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectra (SIMS) depth profiles. Two different oxide removal methods, performed under ultrahigh-vacuum (UHV) conditions, were carried out and compared. The first cleaning method is thermal desorption of oxide at 900 degrees C. The second method is the deposition of metallic gallium followed by redesorption. A significant decrease in oxygen was achieved by thermal desorption at 900 degrees C under UHV conditions. By applying a subsequent Ga deposition/redesorption, a further reduction in oxygen could be achieved. We examine the merits of an alternative oxide desorption method via conversion of the stable SiO(2) surface oxide into a volatile Ca(2)O oxide by a supply of Ga metals. Furthermore, ultra thin films of pure silicon nitride buffer layer were grown on a Si (1 1 1) surface by exposing the surface to radio-frequency (RF) nitrogen plasma followed by GaN growth. The SIMS depth profile shows that the oxygen impurity can be reduced at GaN/beta-Si(3)N(4)/Si interfaces by applying a subsequent Ga deposition/redesorption. (C) 2011 Elsevier B.V. All rights reserved.

Studies on the structural and ionic transport properties at elevated temperatures of La1-xMnO3 +/-delta synthesized by a wet chemical method

Structural transformation and ionic transport properties are investigated on wet-chemically synthesized La1-xMnO3 (X=0.0-0.18) compositions. Powders annealed in oxygen/air at 1000-1080 K exhibit cubic symmetry and transform to rhombohedral on annealing at 1173-1573 K in air/oxygen. Annealing above 1773 K in air or in argon/helium at 1473 K stabilized distorted rhombohedral or orthorhombic symmetry. Structural transformations are confirmed from XRD and TEM studies. The total conductivity of sintered disks, measured by four-probe technique, ranges from 5 S cm(-1) at 298 K to 105 S cm(-1) at 1273 K. The ionic conductivity measured by blocking electrode technique ranges from 1.0X10(-6) S cm(-1) at 700 K to 2.0X10(-3) S cm(-1) at 1273 K. The ionic transference number of these compositions ranges from 3.0X10(-5) to 5.0X10(-5) at 1273 K. The activation energy deduced from experimental data for ionic conduction and ionic migration is 1.03-1.10 and 0.80-1.00 eV, respectively. The activation energy of formation, association and migration of vacancies ranges from 1.07 to 1.44 eV. (C) 2002 Elsevier Science B.V. All rights reserved.

Pt-Au/C cathode with enhanced oxygen-reduction activity in PEFCs

Carbon-supported Pt-Au (Pt-Au/C) catalyst is prepared separately by impregnation, colloidal and micro-emulsion methods, and characterized by physical and electrochemical methods. Highest catalytic activity towards oxygen-reduction reaction (ORR) is exhibited by Pt-Au/C catalyst prepared by colloidal method. The optimum atomic ratio of Pt to Au in Pt-Au/C catalyst prepared by colloidal method is determined using linear-sweep and cyclic voltammetry in conjunction with cell-polarization studies. Among 3:1, 2:1 and 1:1 Pt-Au/C catalysts, (3:1) Pt-Au/C exhibits maximum electrochemical activity towards ORR. Powder X-ray diffraction pattern and transmission electron micrograph suggest Pt-Au alloy nanoparticles to be well dispersed onto the carbon-support. Energy dispersive X-ray analysis and inductively coupled plasma-optical emission spectroscopy data suggest that the atomic ratios of the alloying elements match well with the expected values. A polymer electrolyte fuel cell (PEFC) operating at 0 center dot 6 V with (3:1) Pt-Au/C cathode delivers a maximum power-density of 0 center dot 65 W/cm (2) in relation to 0 center dot 53 W/cm (2) delivered by the PEFC with pristine carbon-supported Pt cathode.

(1S*,3S*,8S*,10S*)-10-Fluoro-15-oxatetracyclo[6.6.1.0(1,10).0( 3,8)]pentadeca-5,12-dien-3-ol

The title compound, C(14)H(17)FO(2), was obtained from anti-4a, 9a:8a,10a-diepoxy-1,4,4a,5,8,8a, 9,9a, 10,10a-decahydroanthracene via tandem hydrogen-fluoride-mediated epoxide ring-opening and transannular oxacyclization. With the two cyclohexene rings folded towards the oxygen bridge, the title tetracyclic fluoroalcohol molecule displays a conformation reminiscent of a pagoda. The crystal packing is effected via intermolecular O-H center dot center dot center dot O hydrogen bonds, which link the molecules into a zigzag chain along the b axis.

Effect of oxygen pressure on the grain and domain structure of polycrystalline 0.85PbMg(1/3)Nb(2/3)O(3)-0.15PbTiO(3) thin films studied by scanning probe microscopy

0.85PbMg(1/3)Nb(2/3)O(3)-0.15PbTiO(3) ferroelectric-relaxor thin films have been deposited on La(0.5)nSr(0.5)CoO(3)/(1 1 1) Pt/TiO(2)/SiO(2)/Si by pulsed laser ablation at various oxygen partial pressures in the range 0.05 to 0.4 Torr. All the films have a rhombohedral perovskite structure. The grain morphology and orientation are drastically affected by the oxygen pressure, studied by x-ray diffraction and scanning electron microscopy. The domain structure investigations by dynamic contact electrostatic force microscopy have revealed that the distribution of polar nanoregions and their dynamics is influenced by the grain morphology, orientation and more importantly, oxygen vacancies. The correlation length extracted from autocorrelation function images has shown that the polarization disorder decreases with oxygen pressure up to 0.3 Torr. The presence of polarized domains and their electric field induced switching is discussed in terms of internal bias field and domain wall pinning. Film deposited at 0.4 Torr presents a curious case with unique triangular grain morphology and large polarization disorder.

Explorations en route to synthesis of tashironins: singlet oxygen cycloaddition to 1,3-cyclopentadienes embedded within allo-cedrane framework

In an approach directed toward a tashironin based complex natural product, efficacy of the singlet oxygen mediated [4+2]-cycloaddition to a tetracyclic cyclopentadiene has been evaluated to install the key cis-1,4-dihydroxy functionality. (C) 2011 Elsevier Ltd. All rights reserved.