409 resultados para Bivalent transition metals


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We have synthesized specimens of nanometric lead dispersion in a glassy Al-Cu-V matrix by rapid solidification of the corresponding melt. The microstructure has been designed to avoid superconducting percolation due to coupling of the neighboring particles by the proximity effect. Using these specimens, we have determined quantitatively the effect of size of the ultrafine lead particles on the superconducting transition. (C) 1999 American Institute of Physics. [S0003-6951(99)02037-9].

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We have performed density functional calculations on tetragonal SnO and PbO (litharge) in the space group P4/nmm with the specific intention of examining the role played by Sn 5s and Pb 6s lone pairs in stabilizing the structure, and in giving rise to semi-metallic behavior (of SnO at ambient pressure and of PbO in the gamma phase). Use of the electron localization function has permitted real-space visualization of the lone pair in these structures. We also discuss the electronic structure of the orthorhombic PbO (massicot, space group Pbma) which again has localized lone pairs, contrary to some earlier expectation. (C) 2002 Editions scientifiques et medicales Elsevier SAS. All rights reserved.

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The ability of a metal to resist strain localisation and hence reduction in local thickness, is a most important forming property upon stretching. The uniform strain represents in this regard a critical factor to describe stretching ability - especially when the material under consideration exhibits negative strain rate sensitivity and dynamic strain ageing (DSA). A newly developed Laser Speckle Technique (LST), e.g. see [1], was used in-situ during tensile testing with two extensometers. The applied technique facilitates quantitative information on the propagating plasticity (i.e. the so-called PLC bands) known to take place during deformation where DSA is active. The band velocity (V-band), and the bandwidth (W-band) were monitored upon increasing accumulated strain. The knowledge obtained with the LST was useful for understanding the underlying mechanisms for the formability limit when DSA and negative strain rate sensitivity operate. The goal was to understand the relationship between PLC/DSA phenomena and the formability limit physically manifested as shear band formation. Two principally different alloys were used to discover alloying effects.

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In this paper, electroleaching and electrobioleaching of ocean manganese nodules are discussed along with the role of galvanic interactions in bioleaching. Polarization studies using a manganese nodule slurry electrode system indicated that the maximum dissolution of iron and manganese due to electrochemical reduction occurred at negative DC potentials of -600 and -1,400 mV(SCE). Electroleaching and electrobioleaching of ocean manganese nodules in the presence of Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans at the above negative applied DC potentials resulted insignificant dissolution of copper, nickel and cobalt in 1 M H2SO4 and in sulfuric acid solution at pH 0.5 and 2.0. Mechanisms involved in electrobioleaching of ocean manganese nodules are discussed. Galvanic leaching of ocean manganese nodules in the presence of externally added pyrite and pyrolusite for enhancement of dissolution was also studied. Various electrochemical and biochemical parameters were optimized, and the electroleaching and galvanic processes thus developed are shown to yield almost complete dissolution of all metal values. This electrobioleaching process developed in the laboratory may be cost effective, energy efficient and environmentally friendly.

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Experimental realization of quantum information processing in the field of nuclear magnetic resonance (NMR) has been well established. Implementation of conditional phase-shift gate has been a significant step, which has lead to realization of important algorithms such as Grover's search algorithm and quantum Fourier transform. This gate has so far been implemented in NMR by using coupling evolution method. We demonstrate here the implementation of the conditional phase-shift gate using transition selective pulses. As an application of the gate, we demonstrate Grover's search algorithm and quantum Fourier transform by simulations and experiments using transition selective pulses. (C) 2002 Elsevier Science (USA). All rights reserved.

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The oxygen content of La0.5Ca0.5MnOy was tuned by annealing the samples at high temperatures in flowing nitrogen with graphite powder nearby. The reduction of oxygen content has dramatic effect on the electrical transport and magnetic properties. The samples with y=2.983, 2.83, and 2.803 show an insulator-metal transition, and an unusual temperature and magnetic-field dependence of the magnetoresistance. The paramagnetic-ferromagnetic transition also shifts to lower temperatures and the antiferromagnetic transition at lower temperature is suppressed. The results are discussed in terms of the effect of oxygen vacancies on the various properties of La0.5Ca0.5MnOy. (C) 2002 American Institute of Physics.

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The layered chalcogenides, having structures analogous to graphite, are known to be unstable toward bending and show high propensity to form curved structures, thus eliminating dangling bonds at the edges. Since the discovery of fullerene and nanotube structures of WS2 and MoS2 by Tenne et al. [1-3], there have been attempts to prepare and characterize nanotubes of other layered dichalcogenides with structures analogous to MoS2. Nanotubes of MoS2 and WS2 were prepared by Tenne et al. by reducing the corresponding oxides to the suboxides followed by heating in an atmosphere of forming gas (5 % H-2 + 95 % N-2) and H2S at 700-900 degreesC [1-3]. Alternative methods of synthesis of MoS2 and WS2 nanotubes have since been proposed by employing the decomposition of the ammonium thiometallates or the corresponding trisulfide precursors. This alternative procedure was based on the observation that the trisulfide seems to be formed as an intermediate in the synthesis of the MoS2 and WS2 nanotubes [4]. Accordingly, the decomposition of the trisulfides of MoS2 and W in a reducing atmosphere directly yielded nanotubes of the disulfides MoS2 and WS2 [5]. In this article, we describe the synthesis, structure, and characterization of a few novel nanotubes of the disulfides of groups 4 and 5 metals. These include nanotubes of NbS2, TaS2, ZrS2, and HfS2. The study enlarges the scope of the inorganic nanotubes significantly and promises other interesting possibilities, including the synthesis of the diselenide nanotubes of these metals.

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Thin films of the semiconducting, monoclinic vanadium dioxide, VO2(M) have been prepared on ordinary glass by two methods: directly by low-pressure metalorganic chemical vapor deposition (MOCVD), and by argon-annealing films of the VO2(B) phase deposited by MOCVD. The composition and microstructure of the films have been examined by x-ray diffraction, scanning electron microscopy, and transmission electron microscopy. Films made predominantly of either the B or the M phase, as deposited, can only be obtained over a narrow range of deposition temperatures. At the lower end of this temperature range, the as-deposited films are strongly oriented, although the substrate is glass. This can be understood from the drive to minimize surface energy. Films of the B phase have a platelet morphology, which leads to an unusual microstructure at the lower-deposition temperatures. Those grown at similar to370 degreesC convert to the metallic, rutile (R) phase when annealed at 550 degreesC, whereas those deposited at 420 degreesC transform to the R phase only at 580 degreesC. (When cooled to room temperature, the annealed films convert reversibly from the R phase to the M phase.) Electron microscopy shows that annealing leads to disintegration of the single crystalline VO2(B) platelets into small crystallites of VO2(R), although the platelet morphology is retained. When the annealing temperature is relatively low, these crystallites are nanometer sized. At a higher-annealing temperature, the transformation leads to well-connected and similarly oriented large grains of VO2(R), enveloped in the original platelet. The semiconductor-metal transition near 68 degreesC leads to a large jump in resistivity in all the VO2(M) films, nearly as large as in epitaxial films on single-crystal substrates. When the annealed films contain well-connected large grains, the transition is very sharp. Even when preferred orientation is present, the transition is not as sharp in as-deposited VO2(M), because the crystallites are not densely packed as in annealed VO2(B). However, the high degree of orientation in these films leads to a narrow temperature hysteresis. (C) 2002 American Institute of Physics.

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We examine the symmetry-breaking transitions in equilibrium shapes of coherent precipitates in two-dimensional (2-D) systems under a plane-strain condition with the principal misfit strain components epsilon(xx)*. and epsilon(yy)*. For systems with cubic elastic moduli, we first show all the shape transitions associated with different values of t = epsilon(yy)*/epsilon(xx)*. We also characterize each of these transitions, by studying its dependence on elastic anisotropy and inhomogeneity. For systems with dilatational misfit (t = 1) and those with pure shear misfit (t = -1), the transition is from an equiaxed shape to an elongated shape, resulting in a break in rotational symmetry. For systems with nondilatational misfit (-1 < t < 1; t not equal 0), the transition involves a break in mirror symmetries normal to the x- and y-axes. The transition is continuous in all cases, except when 0 < t < 1. For systems which allow an invariant line (-1 less than or equal to t < 0), the critical size increases with an increase in the particle stiffness. However, for systems which do not allow an invariant line (0 < t less than or equal to 1), the critical size first decreases, reaches a minimum, and then starts increasing with increasing particle stiffness; moreover, the transition is also forbidden when the particle stiffness is greater than a critical value.

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Low-spin (LS) to intermediate-spin (IS) state transitions in crystals of LnCoO3 (Ln=La, Pr and Nd) have been investigated by variable temperature infrared spectroscopy. The spectra reveal the occurrence of the transition around 120, 220 and 275 K, respectively, in LaCoO3,PrCoO3 and NdCoO3, at which temperatures the intensities of the stretching and the bending modes associated with the LS state decrease, accompanied by an increase in the intensities of the bands due to IS state. The characteristic frequencies of both the spin states decrease with increase in temperature, showing anomalies around the transition.

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Low-spin (LS) to intermediate-spin (IS) state transitions in crystals of LnCoO(3) (Ln = La, Pr and Nd) have been investigated by variable temperature infrared spectroscopy. The spectra reveal the occurrence of the transition around 120, 220 and 275 K, respectively, in LaCoO3,PrCoo(3) and NdCoO3, at which temperatures the intensities of the stretching and the bending modes associated with the LS state decrease, accompanied by an increase in the intensities of the bands due to IS state. The characteristic frequencies of both the spin states decrease with increase in temperature, showing anomalies around the transition. (C) 2001 Published by Elsevier Science B.V.

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We have studied the insulator-superconductor transition (IST) by tuning the thickness in quench-condensed Bi films. The resistive transitions of the superconducting films are smooth and can be considered to represent ''homogeneous'' films. The observation of an IST very close to the quantum resistance for pairs R-square(N) similar to h/4e(2) on several substrates supports this idea. The relevant length scales here are the localization length, and the coherence length. However, at the transition, the localization length is much higher than the superconducting coherence length, contrary to expectation for a "homogeneous" transition. This suggests the invalidity of a purely fermionic model for the transition. Furthermore, the current-voltage characteristics of the superconducting films are hysteretic, and show the films to be granular. The relevant energy scales here are the Josephson coupling energy and the charging energy. However, Josephson coupling energies (E-J) and the charging energies (E-c) at the IST, they are found to obey the relation E-j < E-c. This is again contrary to expectation, for the IST in a granular or inhomogeneous system. Hence, a purely bosonic picture of the transition is also inconsistent with our observations. We conclude that the IST observed in our experiments may be either an intermediate case between the fermioinc and bosonic mechanisms, or in a regime of charge and vortex dynamics for which a quantitative analysis has not yet been done.