990 resultados para Mixed oxides


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Chlorine has been substituted at the 2- and 4-positions in the pyridine and quinoline rings of the corresponding N-oxides and 35Cl n.q.r. spectra have been studied in the temperature range 77–300 K. The change in the n.q.r. frequencies in N-oxides as compared to their parent compounds are interpreted in terms of the conjugative effect and the inductive effect of the N+—O– group. The negative temperature coefficients of the resonance frequencies in chloropyridine-N-oxides have been analysed using the Bayer, Kushida and Brown equations. The calculated torsional frequencies, which are in the range 52–78 cm–1, are found to be only slightly temperature dependent.

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The combined effects of the permeability of the medium, magnetic field, buoyancy forces and dissipation on the unsteady mixed convection flow over a horizontal cylinder and a sphere embedded in a porous medium have been studied. The nonlinear coupled partial differential equations with three independent variables have been solved numerically using an implicit finite-difference scheme in combination with the quasilinearization technique. The skin friction, heat transfer and mass transfer increase with the permeability of the medium, magnetic field and buoyancy parameter. The heat and mass transfer continuously decrease with the stream-wise distance, whereas the skin friction increases from zero, attains a maximum and then decreases to zero. The skin friction, heat transfer and mass transfer are significantly affected by the free stream velocity distribution. The effect of dissipation parameter is found to be more pronounced on the heat transfer than on the skin friction and mass transfer

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Likely presence of superconductivity in layered nickelates of K2NiF4 structure is pointed out.

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An analysis is performed to study the flow and heat transfer characteristics for the case of laminar mixed convection along a vertical circular cone. A mixed-convection parameter is introduced in the formulation of the problem such that smooth transition from one convective limit to the other is possible. The transformed conservation equations of the nonsimilar boundary layers are solved by an efficient finite-difference method.

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Oxides of the formula La3LnBaCu5O13+δ (Ln = Nd, Sm, Gd, Dy, or Y) exhibiting metallic resistivity have been prepared and characterized. In the case of yttrium, a composition close to La2Y2BaCu5O13+δ, which is also metallic, could be prepared.

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Electrical and magnetic properties of several oxide systems of K2NiF4 structure have been compared to those of the corresponding perovskites. Members of the La1−xSr1+xCoO4 system are all semiconductors with a high activation energy for conduction unlike La1−xSrxCoO3 (x ≥ 0.3) which is metallic; the latter oxides are ferromagnetic. La0.5Sr1.5CoO4 shows a magnetization of 0.5 μB at 0 K (compared to 1.5 μB of La0.5Sr0.5CoO3), but the high-temperature susceptibilities of the two systems are comparable. In SrO · (La0.5Sr0.5MnO3)n, both magnetization and electrical conductivity increase with the increase in n approaching the value of the perovskite La0.5Sr0.5MnO3. LaSrMn0.5Ni0.5(Co0.5)O4 shows no evidence of long-range ferromagnetic ordering unlike the perovskite LaMn0.5Ni0.5(Co0.5)O3; high-temperature susceptibility behavior of these two insulating systems is, however, similar. LaSr1−xBaxNiO4 exhibits high electrical resistivity with the resistivity increasing proportionately with the magnetic susceptibility (note that LaNiO3 is a Pauli-paramagnetic metal). High-temperature susceptibility of LaSrNiO4 and LaNiO3 are comparable. Susceptibility measurements show no evidence for long-range ordering in LaSrFe1−xNixO4 unlike in LaFe1−xNixO3 (x ≤ 0.35) and the electrical resistivity of the former is considerably higher. Electrical resistivity of Sr2RuO4 is more than an order of magnitude higher than that of SrRuO3. Some generalizations of the properties of two- and three-dimensional oxide systems have emerged from these experimental observations.

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Double perovskite oxides Sr2FeMoO6 have attracted a great interest for their peculiar magneto-transport properties, and, ill particular, for the large values of low-field magneto-resistance (MR) which remains elevated even at room temperature, thanks to their high Curie temperature (T-c > 400 K). These properties are strongly influenced by chemical cation disorder, that is by the relative arrangement of Fe and Mo on their sublattices: the regular alternation of Fe and Mo enhances the M R and saturation magnetization. On the contrary the disorder generally depresses the magnetization and worsen the MR response. In this work the X-ray absorption fine structure (XAFS) technique has been employed in order to probe the cation order from a local point of view. XAFS spectra were collected at the Fe and Mo K edges on Sr2FeMoO6 samples with different degree of long-range chemical order. The XAFS results prove that a high degree of short-range cation order is preserved, despite the different long-range order: the Fe-Mo correlations are always preferred over the Fe-Fe and Mo-Mo ones in the perfectly ordered as well as in highly disordered samples.

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The mixed convection flow due to a line thermal source embedded at the leading edge of an adiabatic vertical plane surface immersed in a saturated porous medium has been studied. Both weakly and strongly buoyant plume regimes have been considered. The cases of buoyancy assisting and buoyancy opposing flow conditions have been incorporated in the analysis. The results are presented for the entire range of buoyancy parameter from the pure forced convection (xgr=0) to the pure free convection (xgr rarr infin@#@) regimes. For buoyancy-assisting flow, the wall temperature and the velocity at the wall increase as the plume strength increases. However, they all decrease as the free-stream velocity increases. For buoyancyopposing flow, the temperature at the wall increases as the strength of the plume increases but velocity at the wall decreases.

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Recent experimental investigations of phase equilibria and thermodynamic properties of the systems M-Pb-O, where M = Ca, Sr or Ba, indicate a regular increase in thermodynamic stability of ternary oxides, MPbO3 and M2PbO4, with increasing basicity of the oxide of the alkaline-earth metal. Number of stable interoxide compounds at 1100 K in the systems M-Pb-O (M = Mg, Ca, Sr, Ba) increases in unit increments from Mg to Ba. In this paper, experimentally determined standard Gibbs energies of formation of M2PbO4 (M = Ca, Sr, Ba) and MPbO3 (M = Sr, Ba) from their component binary monoxides and oxygen gas are combined with an estimated value for CaPbO3 to delineate systematic trends in thermodynamic stability of the ternary oxides. The trends are interpreted using concepts of tolerance factor and acid-base interactions. All the ternary oxides in these systems contain lead in the tetravalent state. The small Pb4+ ions polarize the surrounding oxygen ions and cause the formation of oxyanions which are acidic in character. Hence, the higher oxidation state of lead is stabilized in the presence of basic oxides of alkaline-earth group. A schematic subsolidus temperature-composition phase diagram is presented for the system BaO-PbO-O-2 to illustrate the change in oxidation states in binary and ternary oxides with temperature.

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Stabilized forms of heteropolyacids (HPAs), namely phosphomolybdic acid (PMA), phosphotungstic acid (PTA), and silicotungstic acid (STA), are incorporated into poly (vinyl alcohol) (PVA) cross-linked with sulfosuccinic acid (SSA) to form mixed-matrix membranes for application in direct methanol fuel cells (DMFCs). Bridging SSA between PVA molecules not only strengthens the network but also facilitates proton conduction in HPAs. The mixed-matrix membranes are characterized for their mechanical stability, sorption capability, ion-exchange capacity, and wetting in conjunction with their proton conductivity, methanol permeability, and DMFC performance. Methanol-release kinetics is studied ex situ by volume-localized NMR spectroscopy (employing point-resolved spectroscopy'') with the results clearly demonstrating that the incorporation of certain inorganic fillers in PVA-SSA viz., STA and PTA, retards the methanol-release kinetics under osmotic drag compared to Nafion, although PVA-SSA itself exhibits a still lower methanol permeability. The methanol crossover rate for PVA-SSA-HPA-bridged-mixed-matrix membranes decreases dramatically with increasing current density rendering higher DMFC performance in relation to a DMFC using a pristine PVA-SSA membrane. A peak power density of 150 mW/cm(2) at a load current density of 500 mA/cm(2) is achieved for the DMFC using a PVA-SSA-STA-bridged-mixed-matrix-membrane electrolyte. (C) 2010 The Electrochemical Society. [DOI: 10.1149/1.3465653] All rights reserved.

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Several oxides of the Bi m M n Cu p O x family (m=2, 3;n=2, 3, 4;p=1, 2, 3 and M=alkaline earth or Bi), possessing structures similar to the Aurivillius family of oxides, show highT c superconductivity.

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New protonated layered oxides, HMWO6·1.5H2O (M=Nb or Ta), have been synthesized by topotactic exchange of lithium in trirutile LiMWO6 with protons by treatment with dilute HNO3. The tetragonal cell constants are a=4.71 (2) and c=25.70 (8)Å for HNbWO6·1.5H2O and a=4.70 (2) and c=25.75 (9) Å for HTaWO6·1.5H2O. Partially hydrated compounds, HMWO6·0.5H2O and anhydrous compounds, HMWO6 retain the layered structure. The structure of these oxides consists of MWO6 sheets built up of M/W-oxygen octahedra with rutile type corner- and edge-sharing. Interlayer protons in HMWO6 are exchanged with Li+, Na+, K+ and Tl+. HMWO6 exhibit Brønsted acidity intercalating n-alkylamines and pyridine.

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A novel chelate exchange reaction, leading to the formation of a series of N-alkyl substituent dependent mixed ligand isomeric complexes of the type Ni(R-AB)(AC') and Ni(R-AC)(AB') (Figure 1) are discussed. Here, AB and AC denote two different N-bonded isonitroso-β-keto-imino ligand moieties, while AB' and AC' are the corresponding O-bonded ligand moieties and R is an N-alkyl substituent. The isomeric complexes are suggested to be monomeric, neutral and diamagnetic with an asymmetric square planar geometry. The bonding isomerism of the isonitroso group in these complexes is discussed on the basis of the infrared and proton magnetic resonance spectral studies. A probable mechanism for the preparative route is also proposed.

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Semiconductor-Metal transitions in Ti2O3, VO2, V2O3 and Ti3O5 have been investigated employing X-ray and UV Photoelectron spectroscopy. The transitions are accompanied by significant changes in the 3d band of the transition metals as well as some of the core levels.

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With a view to understand the oxidation states of metal ions involved in oxide superconductors, oxidation behavior of Cu, Pb, and Bi metals have been studiedi employing x-ray-photoemission and ultraviolet-photoemission spectroscopy. Pb and Bi have distinct 6p (0 to 4 eV) and 6s (7.5 to 10 eV) bands and upon oxidation, only the 6p electrons are ionized forming PbO and Bi2O3 with the simultaneous development of the O2-(2p) band (3 to 7 eV). We show that the 6s band of metals lies below the O2-(2p) band, and hence 6s electrons cannot be ionized to form Pb4+ and Bi4+ as expected in PbO2, BaPbO3, BaBiO3, and BaPb0.75Bi0.25O3. Instead these oxides are stabilized with lower valent O22- along with O2- ions with metals remaining in +2 and +3 states. Similarly, it is shown that the Cu2+(3d) band overlaps with the O2-(2p) band in the YBa2Cu3O6.95 completely and the excess oxygen can be stabilized through lower valent oxide ions instead of Cu3+.