151 resultados para Low-temperature
Resumo:
We report the electrical conductivity between 2 and 300 K for LaNi1-xFexO3 across the composition-controlled metal-insulator (m-i) transition. Using a method first suggested by Mobius, we identify the critical concentration x(c) to be 0.3 for the m-i transition. The negative temperature coefficient of resistivity observed at low temperatures in the metallic phase follows a temperature dependence characteristic of disorder effects. The semiconducting compositions (x greater than or equal to 0.3) do not show a simple activation energy but exhibit variable-range hopping at high temperatures confirming that the m-i transition in this system is driven by increasing disorder effects.
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D.C. electrical conductivity of polyaniline (33%,40%) blended with PMMA was measured from 5K to 300mK. The conductivity behaviour is consistent with fluctuation induced tunneling. Magneto-resistance (MR) was measured between 300K and 2K. From 20K to 2K, a large positive MR was observed. At 2K, for low magnetic fields (<1 Tesla), a deviation from the normal H-2 behaviour was observed.
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At low temperature (below its freezing/melting temperature), liquid water under confinement is known to exhibit anomalous dynamical features. Here we study structure and dynamics of water in the grooves of a long DNA duplex using molecular dynamics simulations with TIP5P potential at low temperature. We find signatures of a dynamical transition in both translational and orientational dynamics of water molecules in both the major and the minor grooves of a DNA duplex. The transition occurs at a slightly higher temperature (TGL ≈ 255 K) than the temperature at which the bulk water is found to undergo a dynamical transition, which for the TIP5P potential is at 247 K. Groove water, however, exhibits markedly different temperature dependence of its properties from the bulk. Entropy calculations reveal that the minor groove water is ordered even at room temperature, and the transition at T ≈ 255 K can be characterized as a strong-to-strong dynamical transition. Confinement of water in the grooves of DNA favors the formation of a low density four-coordinated state (as a consequence of enthalpy−entropy balance) that makes the liquid−liquid transition stronger. The low temperature water is characterized by pronounced tetrahedral order, as manifested in the sharp rise near 109° in the O−O−O angle distribution. We find that the Adams−Gibbs relation between configurational entropy and translational diffusion holds quite well when the two quantities are plotted together in a master plot for different region of aqueous DNA duplex (bulk, major, and minor grooves) at different temperatures. The activation energy for the transfer of water molecules between different regions of DNA is found to be weakly dependent on temperature.
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A locked high-pressure cell with working pressure range up to 10 kbars suitable for low-temperature studies to 77 K has been described. It can be used for both EPR and NMR studies of single crystals (and other solid samples). The high-pressure seal and all other aspects of the cell remain the same for either application. Only a change of the bottom plug is required for a switch from a nuclear-magnetic-resonance (NMR) to an electron-paramagnetic-resonance (EPR) experiment. Details of the procedure for the calibration of pressure inside the cell at various temperatures are discussed. The performance of the cell in EPR (Cr3+ion) and NMR (27Al nucleus) studies is reported.
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We report the evolution of diffuse intensity during the low-temperature ageing of Al-Mn quasicrystals. This is taken as evidence of short-range order in the icosahedral phase prior to its decomposition. The implication of these diffuse intensities is discussed.
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Low temperature fluorination technique is adopted for fluorination of the following sulphur compounds in freon-11 medium (1) Sulphur dioxide (2) Thionyl chloride (3) Sulphuryl chloride (4) Tetrasulphur tetra nitride and (5) Sulphur bromide. All the compounds undergo oxidative fluorination to give rise to sulphur-fluorine compounds except sulphuryl chloride which resists fluorination. Sulphuryl chloride thus behaves as a good solvent medium for fluorination of other reactive compounds like elemental sulphur. Details of the experimental procedures adopted and the identification of the products will be presented.
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We have carried out temperature- and pressure-dependent Raman and x-ray measurements on single crystals of Tb2Ti2O7. We attribute the observed anomalous temperature dependence of phonons to phonon-phonon anharmonic interactions. The quasiharmonic and anharmonic contributions to the temperature-dependent changes in phonon frequencies are estimated quantitatively using mode Grüneisen parameters derived from pressure-dependent Raman experiments and bulk modulus from high-pressure x-ray measurements. Further, our Raman and x-ray data suggest a subtle structural deformation of the pyrochlore lattice at ~9 GPa. We discuss possible implications of our results on the spin-liquid behavior of Tb2Ti2O7.
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Discharge periods of lead-acid batteries are significantly reduced at subzero centigrade temperatures. The reduction is more than what can he expected due to decreased rates of various processes caused by a lowering of temperature and occurs despite the fact that active materials are available for discharge. It is proposed that the major cause for this is the freezing of the electrolyte. The concentration of acid decreases during battery discharge with a consequent increase in the freezing temperature. A battery freezes when the discharge temperature falls below the freezing temperature. A mathematical model is developed for conditions where charge-transfer reaction is the rate-limiting step. and Tafel kinetics are applicable. It is argued that freezing begins from the midplanes of electrodes and proceeds toward the reservoir in-between. Ionic conduction stops when one of the electrodes freezes fully and the time taken to reach that point, namely the discharge period, is calculated. The predictions of the model compare well to observations made at low current density (C/5) and at -20 and -40 degrees C. At higher current densities, however, diffusional resistances become important and a more complicated moving boundary problem needs to be solved to predict the discharge periods. (C) 2009 The Electrochemical Society.
Resumo:
1H NMR spin-lattice relaxation time (T1) studies have been carried out in the temperature range 100 K to 4 K, at two Larmor frequencies 11.4 and 23.3 MHz, in the mixed system of betaine phosphate and glycine phosphite (BPxGPI(1-x)), to study the effects of disorder on the proton group dynamics. Analysis of T1 data indicates the presence of a number of inequivalent methyl groups and a gradual transition from classical reorientations to quantum tunneling rotations. At lower temperatures, microstructural disorder in the local environments of the methyl groups, result in a distribution in the activation energy (Ea) and the torsional energy gap (E01). For certain values of x, the magnetisation recovery shows biexponential behaviour at lower temperatures.
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Ordinary nickel (II) oxide prepared by any of the usual methods is always contaminated with some higher valency states of nickel. Such nickel oxide however can be converted to pure nickel (II) oxide by soaking for some hours at 800–850°C in a closed system under a static inert atmosphere and in the presence of pure MnO as oxygen-getter. The resulting Ni(IT)O is highly resistant to oxidation.
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We present a comparative study of the low temperature electrical transport properties of the carbon matrix containing iron nanoparticles and the films. The conductivity of the nanoparticles located just below the metal-insulator transition exhibits metallic behavior with a logarithmic temperature dependence over a large temperature interval. The zero-field conductivity and the negative magnetoresistance, showing a characteristic upturn at liquid helium temperature, are consistently explained by incorporating the Kondo relation and the two dimensional electron-electron interaction. The films, in contrast, exhibit a crossover of the conductivity from power-law dependence at high temperatures to an activated hopping law dependence in the low temperature region. The transition is attributed to changes in the energy dependence of the density of states near the Fermi level. The observed magnetoresistance is discussed in terms of quantum interference effect on a three-dimensional variable range hopping mechanism.
Resumo:
An electric field (100 V/cm at 230°C and 150°C) has been applied to ammonium perchlorate (AP)/polystyrene (PS) propellant mixtures in order to understand the low temperature decomposition behavior of the propellant. The charge-carrying species is anionic in nature at 230°C, which could be ClO4−, but is cationic at 150°C, which could be either NH4+ or H+. These results are parallel to that observed for pure ammonium perchlorate (AP) pellets [1]. The burning rate (r' ) of the propellant was found to follow the same trend as that for the thermal decomposition of the propellant on application of an electric field. At 150°C Image was higher at the −ve electrode than at the +ve electrode, but at 230°C just the opposite was observed. Kinetic studies have confirmed that the decomposition of the orthorhombic AP follows two mechanism corresponding to E = 30 kcal mol−1 (180–230°C) and E = 15 kcal mol−1 (150–180°C).
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A novel solid-solution precursor method for the preparation of fine-particle cobaltites at low temperatures has been described. The precursors, hydrazinium metal hydrazine carboxylate hydrates, N2H5M1/3Co2/3(N2H3COO)3 · H2O, where M = Mg, Mn, Fe, Co, Ni, and Zn, decompose in air <250°C to yield corresponding metal cobaltites, MCo2O4. Formation of cobaltites has been confirmed by thermogravimetry (TG) weight loss, IR, and X-ray diffraction. Combustion of the precursor in air yields fine-particle cobaltites with surface areas in the range of 12–115 m2g−1 and particle sizes of 1–40 μm. Low decomposition temperatures of the precursors accompanied by the evolution of large amounts of gases appear to control the particle size of the cobaltites.
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Glasses show very interesting behavior well below the glass transition temperature. Inspite of various experimental observations, even simple quantitative explanations relating these relaxation phenomena to structural properties are absent. In this paper we have tried to point out a phenomenological approach to this problem by identifying certain parameters which we think can be used to characterize these relaxations.
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A novel low-temperature method of preparing bronzes of tungsten and vanadium and other reduced phases is reported.