Origin of the insulating state in NaCuO2

We study the electronic structure of NaCuO2 by analysing experimental core level photoemission and X-ray absorption spectra using a cluster as well as an Anderson impurity Hamiltonian including the band structure of the oxygen sublattice. We show that the X-ray absorption results unambiguously establish a negative value of the charge transfer energy, A. Further, mean-field calculations for the edge-shared one-dimensional CuO2 lattice of NaCuO2 within the multiband Hubbard Hamiltonian show that the origin of the insulating nature lies in the band structure rather than in the correlation effects. LMTO-ASA band structure calculations suggest that NaCuO2 is an insulator with a gap of around 1 eV.

Diffusion path during internal displacement reactions in multi-component oxides: Reaction between Fe and (Co,Mg)TiO3 solid solution at 1273 K

The reaction between Fe foil and a disc of ilmenite solid solution (Co-0.48 Ni-0.52) TiO3 was studied at 1273 K. At the metal/oxide interface, the displacement reaction, Fe + (Co,Mg)TiO3 = Co + (Fe,Mg)TiO3 occurs, resulting in an ilmenite solid solution containing three divalent cations. Ferrous ions diffuse into the oxide solid solution and cause the precipitation of Co-Fe alloy as discrete particles inside the oxide matrix. The morphology of the product layer was characterized by SEM. Only two phases, alloy and ilmenite, were detected in the reaction zone. This suggests that the local flux condition imposed by ilmenite stoichiometry (Co + Fe + Mg):Ti = 1:1] was satisfied during the reactive diffusion: (J(Co) + J(Fe) + J(Mg)) = J(Ti). The composition of the alloy and the oxide was determined using EPMA as a function of distance in the direction of diffusion. Although Mg does not participate in the displacement reaction, its composition in the ilmenite phase was found to be position dependent inside the reaction zone. The up-hill diffusion of inert Mg is caused by the development of chemical potential gradients as a result of displacement reaction. The evolution of composition gradients inside the reaction zone and the diffusion path in a ternary composition diagram of the system CoTiO3-FeTiO3-MgTiO3 are discussed. (C) 2010 Elsevier B.V. All rights reserved.

Reaction of normal and pseudo 2-formylbenzenesulfonyl chlorides with amines:experimental and theoretical studies on the structure of 2-formyl benzenesulfonamides in solid, solution and gas phases

The reaction of 2-formylbenzenesulfonyl chloride 1 and its pseudo isomer 2 with primary amines give either the corresponding sulfonamido Schiff bases or the corresponding 2-formylbenzenesulfonamide depending on the concentration of the amine used. The derivatives exist as an equilibrium mixture of the corresponding sulfonamide and 2-alkyl-3-hydroxy(or 3-aminoalkyl)-benzisothiazole-1,1-dioxide. Spectroscopic studies suggest that 2-formylbenzenesulfonamides exist as benzisothiazole-1,1-dioxides in the solid state, as a mixture of 2-formylbenzenesulfonamide and the corresponding benzisothiazole-1,1-dioxide in solution and as 2-formyl-benzenesulfonamides in the gas phase.

Soft-chemical routes to synthesis of solid oxide materials

We describe three different families of metal oxides, viz., (i) protonated layered perovskites, (ii) framework phosphates of NASICON and KTiOPO4 (KTP) structures and (iii) layered and three-dimensional oxides in the H-V-W-O system, synthesized by 'soft-chemical' routes involving respectively ion-exchange, redox deinteracalation and acid-leaching from appropriate parent oxides. Oxides of the first family, HyA2B3O10(A = La/Ca; B = Ti/Nb), exhibit variable Bronsted acidity and intercalation behaviour that depend on the interlayer structure. V2(PO4)3 prepared by oxidative deintercalation from Na3V2(PO4)3 is a new host material exhibiting reductive insertion of lithium/hydrogen, while K0.5Nb0.5 M0.5OPO4(M = Ti, V) are novel KTP-like materials exhibiting second harmonic generation of 1064 nm radiation. HxVxW1-xO3 for x = 0.125 and 0.33 possessing alpha-MoO3 and hexagonal WO3 structures, prepared by acid-leaching of LiVWO6, represent functionalized oxide materials exhibiting redox and acid-base intercalation reactivity.

An investigation of the first-order spin-state transition in Fe(Phen)(2)(NCS)(2) EXAFS and infrared spectroscopy

The structure of Fe(Phen)(2)(NCS)(2) has been examined across the first-order spin-state transition by EXAFS with full multiple scattering analysis. The EXAFS data at 298 K can be satisfactorily assigned to the high-spin state, but the analysis of the low-temperature data at 90 K is not entirely unequivocal, although consistent with the predominant presence of the low-spin state. That some proportion of the high-spin state remains at low temperatures, well below the first-order transition, is clearly evidenced in the infrared spectra, suggesting possible sublattice ordering.

Photophysical properties of the fullerenes, C60 and C70

Photophysical properties of the singlet and triplet states of the fullerenes, C60 and C70, have been investigated in toluene, benzene, hexane and ethanol solutions by pico- and nano-second laser flash photolysis techniques. Lifetimes, extinction coefficients, quantum efficiencies of the formation of the excited states and such properties have been determined. True triplet�triplet absorption spectra of C60 and C70 are reported. C60, unlike C70, is found to undergo photoionization in ethanol solution giving solvated electrons.

New uniform solid catalyst for the low-temperature oxidation of carbon monoxide: A triple-layered rare earth perovskite containing Co and Cu ions

Oxygen reactivity and catalytic activity of the cobalt-containing layered defect perovskites, YBa2Cu2CoO7+delta and LaBa2Cu2CoO7+delta, in comparison with LaBa2Cu3O7-delta have been investigated employing temperature-programmed desorption (TPD) and temperature-programmed surface reactions (TPSR) in the stoichiometric and catalytic mode using carbon monoxide as a probe molecule. TPD studies showed evidence for the presence of two distinct labile oxygen species, one at (0 0 1/2) sites and the other at (0 1/2 0) sites in LaBa2Cu2CoO7+delta against a single labile species at (0 1/2 0) in the case of two other oxides. The activation energies for the catalytic oxidation of carbon monoxide by oxygen over LaBa2Cu3O7-delta, YBa2Cu2CoO7+delta, and LaBa2Cu2CoO7+delta have been estimated to be 24.2, 15.9, and 13.6 kcal/mol, respectively. The reactivity and catalytic activity of the oxide systems have been interpreted in terms of the structural changes brought about by substituents, guided by a directing effect of the larger rare earth cation. TPSR profiles, structural analysis, and infrared spectroscopic investigations suggest that the oxygen present at (0 0 1/2) sites in the case of LaBa2Cu2CoO7+delta is accessible to catalytic oxidation of CO through a Mars-Van Krevelen pathway. Catalytic conversion of CO to CO2 over LaBa2Cu2CoO7+delta occurs at 200 degrees C. The enhanced reactivity is explained in terms of changes brought about in the coordination polyhedra around transition metals, enhanced basal plane oxygen diffusivity, and redox potentials of the different transition metal cations.

Enhanced magnetoresistance in as?deposited oxygen?deficient La0.6Pb0.4MnO3-y thin films

The La0.6Pb0.4MnO3(LPMO) thin films were in situ deposited at different oxygen partial pressure and at a substrate temperature of 630 degrees C by pulsed laser deposition. The films grown at lower oxygen partial pressures showed an increase in lattice parameter and resistivity and a decrease in the insulator-metal transition temperature as compared to the stoichiometric LPMO thin film grown at 400 mTorr. Further, these oxygen-deficient thin films showed over 70% giant magnetoresistance (GMR) near the insulator-metal transition temperature against the 40% GMR in the case of stoichiometric thin films. (C) 1995 American Institute of Physics.

Ferroelectric properties of Bi2VO5.5 thin films on LaAlO3 and SiO2/Si substrates with LaNiO3 base electrode

Ferroelectric bismuth vanadate Bi2VO5.5 (BVO) thin films have been grown on LaAlO3 (LAO) and SiO2/Si substrates with LaNiO3 (LNO) base electrodes by the pulsed laser deposition technique. The effect of substrate temperature on the ferroelectric properties of BVO thin films, has been studied by depositing the thin films at different temperatures. The BVO thin films grown on LNO/LAO were textured whereas the thin films grown on LNO/SiO2/Si were polycrystalline. The BVO thin films grown at 450?°C exhibited good ferroelectric properties indicating that LNO acts as a good electrode material. The remanent polarization Pr and coercive field Ec obtained for the BVO thin films grown at 450?°C on LNO/LAO and LNO/SiO2/Si were 2.5 ?C/cm2, 37 kV/cm and 4.6?C/cm2, 93 kV/cm, respectively. © 1995 American Institute of Physics.

Solid Oxide-Ion Electrolytes

Solid oxide-ion electrolytes find application in oxygen sensors, oxygen pumps and in high-temperature electrolyser-fuel-cell hybrid systems. All the solid electrolytes known so Qr, however, exhibit: tow oxide-ion conductivities below 973 K. Therefore, there is a need for fast oxide-ion conductors operative at temperatures around 673 K, Recently, efforts have been directed towards developing such materials. This article summarizes various type of oxide-ton electrolytes reported in literature and outlines a strategy for the identificatiom/synthesis of improved materials.

Structural and Dielectric-Properties Of A Novel BI2O3-(1-X)WO3-XCUO Solid-Solution

A novel solid solution in the system Bi-W-Cu-O has been synthesized and its structural and dielectric properties studied. The solid solution Bi2O3-(1-x)WO3-xCuO exists up to x = 0.7; the solid solutions up to x = 0.65 are orthorhombic but stabilize in tetragonal structure in a narrow range around x = 0.7. The solid solutions are non-centrosymmetric and exhibit ferroelectric behaviour similar to their parent phase Bi2WO6. The Curie point of the solid solution is found to decrease with increase in x.

Theoretical Analysis of the Electromotive Force of a Cell Incorporating a Composition Gradient Solid Electrolyte

New composition gradient solid electrolytes have been designed for application in high temperature solid-state galvanic sensors and in thermodynamic measurements. The functionally gradient electrolyte consists of a solid solution between two or more ionic conductors with a common ion and gradual variation in composition of the other ionic species. Unequal rates of migration of the ions, caused by the presence of the concentration gradient, may result in the development of space charge, manifesting as diffusion potential. Presented is a theoretical analysis of the EMF of cells incorporating gradient solid electrolytes. An analytical expression is derived for diffusion potential, using the thermodynamics of irreversible processes, for different types of concentration gradients and boundary conditions at the electrode/electrolyte interfaces. The diffusion potential of an isothermal cell incorporating these gradient electrolytes becomes negligible if there is only one mobile ion and the transport numbers of the relatively immobile polyionic species and electrons approach zero. The analysis of the EMF of a nonisothermal cell incorporating a composition gradient solid electrolyte indicates that the cell EMF can be expressed in terms of the thermodynamic parameters at the electrodes and the Seebeck coefficient of the gradient electrolyte under standard conditions when the transport number of one of the ions approaches unity.

Activities in the spinel solid solution FeXMg1−XAl2O4

Abstract: Activities in the spinel solid solution FexMg1-xAl2O4 saturated with alpha-Al2O3 have been measured for the compositional range 0 < X < 1 between 1100 and 1350 K using a bielectrolyte solid-state galvanic cell, which may be represented as Pt, Fe + FexMg1-xAl2O4 + alpha-Al2O3//(Y2O3)ThO2/ (CaO)ZrO2//Fe + FeAl2O4 + alpha-Al2O3, Pt Activities of ferrous and magnesium aluminates exhibit small negative deviations from Raoult's law. The excess free energy of mixing of the solid solution is a symmetric function of composition and is independent of temperature: Delta G(E) = -1990 X(1 - X J/mol. Theoretical analysis of cation distribution in spinel solid solution also suggests mild negative deviations from ideality. The lattice parameter varies linearly with composition in samples quenched from 1300 K. Phase relations in the FeO-MgO-Al2O3 system at 1300 K are deduced from the results of this study and auxiliary thermodynamic data from the literature. The calculation demonstrates the influence of intracrystalline ion exchange equilibrium between nonequivalent crystallographic sites in the spinel structure on intercrystalline ion exchange equilibrium between the monoxide and spinel solid solutions (tie-lines). The composition dependence of oxygen partial pressure at 1300 K is evaluated for three-phase equilibria involving the solid solutions Fe + FexMg1-xAl2O4 + alpha-Al2O3 and Fe + FeyMg1-yO + FexMg1-xAl2O4. Dependence of X, denoting the composition of the spinel solid solution, on parameter Y, characterizing the composition of the monoxide solid solution with rock salt structure, in phase fields involving the two solid solutions is elucidated. The tie-lines are slightly skewed toward the MgAl2O4 corner.

LaNiO3: a promising material for contact with YBa2 Cu3O7-x thin films

Epitaxial LaNiO3 metallic oxide thin films have been grown on c-axis oriented YBa2Cu3O7-delta thin films on LaAlO3 substrates by pulsed laser deposition technique and the interface formed between the two films has been examined by measuring the contact conductance of the same. The specific contact conductance of the interface measured using a modified four probe method was found to be 1.4 to 6 x 10(4) ohm(-1) cm(-2) at 77 K, There are indications that contact conductance can be brought closer to that obtained for noble metal-YBCO interface.

Nonresonant microwave absorption studies of surface passivation of superconducting YBa2Cu3O7−δ thin films

The surfaces of laser ablated thin films of YBa2Cu3O7?? have been passivated with about 100 Å thick textured layer of Ca0.95Sr0.025Ba0.025Zr0.98Ta0.01Ti0.01O3. It is shown that this low loss dielectric material preserves the quality of the surface and also prolongs the aging process. The films (both passivated and as?deposited) have been studied for degradation on exposure to atmosphere and also on dipping directly in water. The technique of nonresonant microwave absorption is used to study the effects and extent of degradation in these films. © 1995 American Institute of Physics.