Temperature and concentration dependence of adsorption properties of methane in NaY: a molecular dynamics study

Molecular dynamics calculations on methane sorbed in NaY (Si/Al = 3.0) employing realistic methane-methane and methane-zeolite intermolecular potential functions at different temperatures (50, 150, 220, and 300 K) and concentrations (2, 4, 6, and 8 molecules/cage) are reported. The thermodynamic results are in agreement with the available experimental data. Guest-guest and guest-host radial distribution functions (rdfs), energy distribution functions, distribution of cage occupancy, center-of-cage-center-of-mass (coc-com) rdfs, velocity autocorrelation functions for com and angular motion and the Fourier transformed power spectra, and diffusion coefficients are presented as a function of temperature and concentration. At 50 K, methane is localized near the adsorption site. Site-site migration and essentially free rotational motion are observed at 150 K. Molecules preferentially occupy the region near the inner surface of the alpha-cage. The vibrational frequencies for the com of methane shift toward higher values with decreasing temperature and increasing adsorbate concentration. The observed frequencies for com motion are 36, 53, and 85 cm-1 and for rotational motion at 50 K, 95 and 150 cm-1 in agreement with neutron scattering data. The diffusion coefficients show a type I behavior as a function of loading in agreement with NMR measurements. Cage-to-cage diffusion is found to be always mediated by the surface.

Temperature and pressure dependence of 35Cl NQR in NaClO3 and Ba(ClO3)2·H2O

Pressure and temperature dependence of 35Cl nuclear quadrupole resonance (NQR) has been investigated in NaClO3 and Ba(ClO3)2·H2O. NQR frequencies are measured in the temperature range 77–300 K and up to 5 kbar pressure. The torsional frequency of the ClO3 pyramid and its variation with both pressure and temperature are evaluated from the NQR frequencies under the harmonic approximation. In general, the pressure effect on the internal motions is found to be less in Ba (ClO3)2·H2O compared to NaClO3. When the samples are cooled to 77 K the pressure coeffecient of NQR frequency becomes nearly zero in sodium chlorate, whereas it retains a value of 6 kHz kbar−1 in barium chlorate. This behaviour follows from the fact that at 77K, the torsional frequency in NaClO3 is unaffected by the application of pressure while it increases at the rate 12 cm−1 kbar−1 in Ba(ClO3)2·H2O.

The Blackett Memorial Lecture, 1991: Chemical Insights into High-Temperature Superconductors

The high-temperature superconductors are complex oxides, generally containing two-dimensional CuO2 sheets. Various families of the cuprate superconductors are described, paying special attention to aspects related to oxygen stoichiometry, phase stability, synthesis and chemical manipulation of charge carriers. Other aspects discussed are chemical applications of cuprates, possibly as gas sensors and copper-free oxide superconductors. All but the substituted Nd and Pr cuprates are hole-superconductors. Several families of cuprates show a nearly constant n(h) at maximum T(c). Besides this universality, the cuprates exhibit a number of striking common features. Based on Cu(2p) photoemission studies, it is found that the Cu-O charge-transfer energy, DELTA, and the Cu(3d)-O(2p) hybridization strength, t(pd), are key factors in the superconductivity of cuprates. The relative intensity of the satellite in the Cu(2p) core-level spectra, the polarizability of the CuO2 sheets as well as the hole concentration are related to DELTA/t(pd). These chemical bonding factors have to be explicitly taken into account in any model for superconductivity of the cuprates.

The contribution of polarons, bipolarons and intersite tunneling to low temperature conductivity in doped polypyrrole

The conductivity of highly doped polypyrrole is less than that of intermediately doped samples, by two orders of magnitude, at 4.2 K. This may be due to more number of bipolarons in highly doped samples. Bipolarons require four times more activation energy than single polarons to hop by thermally induced virtual transitions to intermediate dissociated polaron states than by the nondissociated process. The conduction process in these polyconjugated systems involve ionization from deep trapped states, having a View the MathML source dependence, hopping from localised states, having View the MathML source dependence, and intersite tunnel percolation, having T−1 dependence. The interplay of these factors leads to a better fit by View the MathML source. The mechanism for this exponential behaviour need not be same as that of Motts variable range hopping. Conduction by percolation is possible, if an infinite cluster of chains can be connected by impurity centers created by dopant ions. The tendency for the saturation of conductivity at very low temperatures is due to the possibility of intersite tunnel percolation is disordered polaronic systems.

Rapid synthesis of room temperature ferromagnetic Ag-doped LaMnO3 perovskite phases by the solution combustion method

We report the rapid solution combustion synthesis and characterization of Ag-substituted LaMnO3 phases at relatively low temperature using oxalyl dihydrazide, as fuel. Structural parameters were refined by the Rietveld method using powder X-ray diffraction data. While the parent LaMnO3 crystallizes in the orthorhombic structure, the Ag-substituted compounds crystallize in the rhombohedral symmetry. On increasing Ag-content, unit cell volume and Mn-O-Mn bond angle decreases. The Fourier transform infra red spectrum shows two absorption bands corresponding to Mn-O stretching vibration (v(s) mode) and Mn-O-Mn deformation vibration (v(b) mode) around 600 cm(-1) and 400 cm(-1) for the compositions x = 0.0, 0.05 and 0.10, respectively. Electrical resistivity measurements reveal that composition-controlled metal to insulator transition, with the maximum metal to insulator being 280 K for the composition La0.75Ag0.25MnO3. Increase in magnetic moment was observed with increase in Ag-content. The maximum magnetic moment of 35 emu/g was observed for the composition La0.80Ag0.20MnO3. (C) 2010 Elsevier Ltd. All rights reserved.

Sensitive high-resolution ion microprobe U-Pb dating of prograde and retrograde ultrahigh-temperature metamorphism as exemplified by Sri Lankan granulites

Ultrahigh-temperature (UHT) granulites of the central Highland Complex, Sri Lanka, underwent some of the highest known peak temperatures of crustal metamorphism. Zircon and monazite U-Pb systems in granulites near Kandy, the highest grade region (similar to 1050 degrees C; 0.9 GPa), preserve both a record of the timing of prograde and retrograde phases of UHT metamorphism and evidence for the ages of older protolith components. Zircon grains from a quartz-saturated granulite containing relics of the peak UHT assemblage have remnant detrital cores with dates of ca. 2.5-0.83 Ga. Date clusters of ca. 1.7 and 1.04-0.83 Ga record episodes of zircon growth in the source region of the protolith sediment. Two generations of overgrowths with contrasting Th/U record metamorphic zircon growth at 569 +/- 5 and 551 +/- 7 Ma, probably in the absence and presence of monazite, respectively. The age of coexisting metamorphic monazite (547 +/- 7 Ma) is indistinguishable from that of the younger, low-Th/U zircon overgrowths. Zircon from a quartz-undersaturated monazite-absent UHT granulite with a mainly retrograde assemblage is mostly metamorphic (551 +/- 5 Ma). The ca. 570 Ma zircon overgrowths in the quartz-saturated granulite probably record partial melting just before or at the metamorphic peak. The ca. 550 Ma zircon in both rocks, and the ca. 550 Ma monazite in the quartz-saturated sample, record post-peak isothermal decompression. A possible model for this pressure-temperature-time evolution is ultrahot collisional orogeny during the assembly of Gondwana, locally superheated by basaltic underplating, followed by fast extensional exhumation.

Varistors based on mixed‐phase ceramics containing ZnO and negative temperature coefficient spinels

High nonlinearity coefficients of 60–150 are observed in the current‐voltage (I‐V) curves of the mixed phase ceramics formed by cosintering ZnO with spinel phases having large negative temperature coefficients (NTCs) in resistivity. The region of negative slope in the I‐V curves of the NTC ceramics is progressively made positive with ZnO phase content, wherein ZnO grains function as a built‐in resistor in series to the resistance of the NTC phase. High α depends on the optimum phase content of ZnO as much as its intrinsic conductivity. The studies indicate that the predominent contribution to power dissipation is by way of joule heating from the resistive component of the current.

Room-temperature synthesis of gold nanoparticles - Size-control by slow addition

We report a simple and rapid process for the room-temperature synthesis of gold nanoparticles using tannic acid, a green reagent, as both the reducing and stabilising agent. We systematically investigated the effect of pH on the size distribution of nanoparticles synthesized. Based on induction time and zeta- potential measurements, we show that particle size distribution is controlled by a fine balance between the rates of reduction (determined by the initial pH of reactants) and coalescence (determined by the pH of the reaction mixture) in the initial period of growth. This insight led to the optimal batch process for size-controlled synthesis of 2-10 nm gold nanoparticles - slow addition (within 10 minutes) of chloroauric acid into tannic acid.

Temperature dependent transport behavior of n-InN nanodot/p-Si heterojunction structures

The present work explores the temperature dependent transport behavior of n-InN nanodot/p-Si(100) heterojunction diodes. InN nanodot (ND) structures were grown on a 20 nm InN buffer layer on p-Si(100) substrates. These dots were found to be single crystalline and grown along 001] direction. The junction between these two materials exhibits a strong rectifying behavior at low temperatures. The average barrier height (BH) was determined to be 0.7 eV from current-voltage-temperature, capacitance-voltage, and flat band considerations. The band offsets derived from built-in potential were found to be Delta E-C=1.8 eV and Delta E-V=1.3 eV and are in close agreement with Anderson's model. (C) 2010 American Institute of Physics. doi:10.1063/1.3517489]

Temperature dependent free energy surface of polymer folding from equilibrium and quench studies

Langevin dynamics simulation studies have been employed to calculate the temperature dependent free energy surface and folding characteristics of a 500 monomer long linear alkane (polyethylene) chain with a realistic interaction potential. Both equilibrium and temperature quench simulation studies have been carried out. Using the shape anisotropy parameter (S) of the folded molecule as the order parameter, we find a weakly first order phase transition between the high-temperature molten globule and low-temperature rodlike crystalline states separated by a small barrier of the order of k(B)T. Near the melting temperature (580 K), we observe an intriguing intermittent fluctuation with pronounced ``1/f noise characteristics'' between these two states with large difference in shape and structure. We have also studied the possibilities of different pathways of folding to states much below the melting point. At 300 K starting from the all-trans linear configuration, the chain folds stepwise into a very regular fourfold crystallite with very high shape anisotropy. Whereas, when quenched from a high temperature (900 K) random coil regime, we identify a two step transition from the random coiled state to a molten globulelike state and, further, to a anisotropic rodlike state. The trajectory reveals an interesting coupling between the two order parameters, namely, radius of gyration (R-g) and the shape anisotropy parameter (S). The rodlike final state of the quench trajectory is characterized by lower shape anisotropy parameter and significantly larger number of gauche defects as compared to the final state obtained through equilibrium simulation starting from all-trans linear chain. The quench study shows indication of a nucleationlike pathway from the molten globule to the rodlike state involving an underlying rugged energy landscape. (C) 2010 American Institute of Physics. doi:10.1063/1.3509398]

An automated thermal relaxation calorimeter for operation at low temperature (0.5 K

We describe an automated calorimeter for measurement of specific heat in the temperature range 10 K>T>0.5 K. It uses sample of moderate size (100–1000 mg), has a moderate precision and accuracy (2%–5%), is easy to operate and the measurements can be done quickly with He4 economy. The accuracy of this calorimeter was checked by measurement of specific heat of copper and that of aluminium near its superconducting transition temperature.

A Novel Method for the Uniform Incorporation of Grain-Boundary Layer Modifiers in Positive Temperature Coefficient of Resistivity Barium Titanate

The presently developed two-stage process involves diping the prefired porous disks of n-BaTiO3 in nonaqueous solutions containing Al-buty rate, Ti-isopropoxide, and tetraethyl silicate and subsequent sintering. This leads to uniform distribution of the grain-boundary layer (GBL) modifiers (Al2O3+ TiO2+ SiO2) and better control of the grain size as well as the positive temperature coefficient of resistivity characteristics. The technique is particularly suited for GBL modifiers in low concentrations (< 1%).