927 resultados para Deep eutectic solvent


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The coefficient of thermochromism of polyaniline solutions has been found to be solvent dependent and the solvent effect is not negligible. Hence, thermochromism of polyaniline solutions cannot be explained solely on the basis of conformational change induced by a change in temperature. Further, comparison of the solvatochromism of polyaniline and polytoluidine shows a higher solvatochromic shift for the former. It implies that the higher energy associated with the exciton peak of polytoluidine is not due to the higher ring torsional angle induced by the higher steric repulsion of the methyl group, as widely accepted, but is due to its less solvatochromic red-shift as compared to polyaniline.

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Influence of succinonitrile (SN) dynamics on ion transport in SN-lithium perchlorate (LiClO4) electrolytes is discussed here via dielectric relaxation spectroscopy. Dielectric relaxation spectroscopy (similar to 2 x 10(-3) Hz to 3 MHz) of SN and SN-LiClO4 was studied as a function of salt content (up to 7 mol % or 1 M) and temperature (-20 to +60 degrees C). Analyses of real and imaginary parts of permittivity convincingly reveal the influence Of trans gauche isomerism and solvent-salt association (solvation) effects on ion transport. The relaxation processes are highly dependent on the salt concentration and temperature. While pristine SN display only intrinsic dynamics (i.e., trans-gauche isomerism) which enhances with an increase in temperature, SN-LiClO4 electrolytes especially at high salt concentrations (similar to 0.04-1 M) show salt-induced relaxation processes. In the concentrated electrolytes, the intrinsic dynamics was observed to be a function of salt content, becoming faster with an increase in salt concentration. Deconvolution of the imaginary part of the permittivity spectra using Havriliak-Negami (HN) function show a relaxation process corresponding to the above phenomena. The permittivity data analyzed using HN and Kohlrausch-Williams-Watta (KWW) functions show non-Debye relaxation processes and enhancement in the trans phase (enhanced solvent dynamics) as a function of salt concentration and temperature.

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Studies on the low-humidity (88%) forms of tetragonal and monoclinic lysozyme, resulting from water-mediated transformations, have provided a wealth of information on the variability in protein hydration, its structural consequences and the water structure associated with proteins, in addition to facilitating the delineation of the rigid and the flexible regions in the protein molecule and the invariant features in its hydration shell. Surprisingly, monoclinic lysozyme continues to diffract even when the environmental humidity is drastically reduced, thus permitting the structural study of the enzyme at different levels of hydration. As part of a study in this direction, three very low humidity forms, two of them occuring at a nominal relative humidity of 38% and the other at 5% relative humidity, have been characterized. These have unprecedented low solvent contents of 16.9, 17.6 and 9.4%, respectively, as determined by the Matthews method.

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The convective available potential energy (CAFE) based on monthly mean sounding has been shown to be relevant to deep convection in the tropics. The variation of CAFE with SST has been found to be similar to the variation of the frequency of deep convection at one station each in the tropical Atlantic and W. Pacific oceans. This suggests a strong link between the frequency of tropical convection and CAFE. It has been shown that CAFE so derived can be interpreted as the work potential of the atmosphere above the boundary layer with ascent in the convective region and subsidence in the surrounding cloud-free region.

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Limiting ionic conductance (Lambda(0)) of rigid symmetrical unipositive ions in aqueous solution shows a strong temperature dependence. For example, Lambda(0) more than doubles when the temperature is increased from 283 to 318 K. A marked variation also occurs when the solvent is changed from ordinary water (H2O) to heavy water (D2O). In addition, Lambda(0) shows a nonmonotonic size dependence with a skewed maximum near Cs+. Although these important results have been known for a long time, no satisfactory theoretical explanation exists for these results. In this article we present a simple molecular theory which provides a nearly quantitative explanation in terms of microscopic structure and dynamics of the solvent. A notable feature of this theory is that it does not invoke any nonquantifiable models involving solvent-berg or clatherates. We find the strong temperature dependence of Lambda(0) to arise from a rather large number of microscopic factors, each providing a small but nontrivial contribution, but all acting surprisingly in the same direction. This work, we believe, provides, for the first time, a satisfactory explanation of both the anomalous size and temperature dependencies of Lambda(0) of unipositive ions in molecular terms. The marked change in Lambda(0) as the solvent is changed from H2O to D2O is found to arise partly from a change in the dielectric relaxation and partly from a change in the effective interaction of the ion with the solvent.

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A detailed investigation of viscosity dependence of the isomerization rate is carried out for continuous potentials by using a fully microscopic, self-consistent mode-coupling theory calculation of both the friction on the reactant and the viscosity of the medium. In this calculation we avoid approximating the short time response by the Enskog limit, which overestimates the friction at high frequencies. The isomerization rate is obtained by using the Grote-Hynes formula. The viscosity dependence of the rate has been investigated for a large number of thermodynamic state points. Since the activated barrier crossing dynamics probes the high-frequency frictional response of the liquid, the barrier crossing rate is found to be sensitive to the nature of the reactant-solvent interaction potential. When the solute-solvent interaction is modeled by a 6-12 Lennard-Jones potential, we find that over a large variation of viscosity (eta), the rate (k) can indeed be fitted very well to a fractional viscosity dependence: (k similar to eta(-alpha)), with the exponent alpha in the range 1 greater than or equal to alpha >0. The calculated values of the exponent appear to be in very good agreement with many experimental results. In particular, the theory, for the first time, explains the experimentally observed high value of alpha even at the barrier frequency, omega(b). similar or equal to 9 X 10(12) s(-1) for the isomerization reaction of 2-(2'-propenyl)anthracene in liquid eta-alkanes. The present study can also explain the reason for the very low value of vb observed in another study for the isomerization reaction of trans-stilbene in liquid n-alkanes. For omega(b) greater than or equal to 2.0 X 10(13) s(-1), we obtain alpha similar or equal to 0, which implies that the barrier crossing rate becomes identical to the transition-state theory predictions. A careful analysis of isomerization reaction dynamics involving large amplitude motion suggests that the barrier crossing dynamics itself may become irrelevant in highly viscous liquids and the rate might again be coupled directly to the viscosity. This crossover is predicted to be strongly temperature dependent and could be studied by changing the solvent viscosity by the application of pressure. (C) 1999 American Institute of Physics. [S0021-9606(9950514-X].

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ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

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An attempt was made to study the deep level impurities and defects introduced into thyristor grade silicon under different processing conditions. DLTS, C-V and I-V measurements were carried out. The ideality factors of the diodes is around 1-7. Activation energy, trap density and minority carrier lifetime were measured.

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Properties of cast aluminium matrix composites are greatly influenced by the nature of distribution of reinforcing phase in the matrix and matrix microstructural length scales, such as grain size, dendrite arm spacing, size and morphology of secondary matrix phases, etc. Earlier workers have shown that SIC reinforcements can act as heterogeneous nucleation sites for Si during solidification of Al-Si-SiC composites. The present study aims at a quantitative understanding of the effect of SiC reinforcements on secondary matrix phases, namely eutectic Si, during solidification of A356 Al-SiC composites. Effect of volume fraction of SiC particulate on size and shape of eutectic Si has been studied at different cooling rates. Results indicate that an increase in SiC volume fraction leads to a reduction in the size of eutectic Si and also changes its morphology from needle-like to equiaxed. This is attributed to the heterogeneous nucleation of eutectic Si on SiC particles. However, SiC particles are found to have negligible influence on DAS. Under all the solidification conditions studied in the present investigation, SiC particles are found to be rejected by the growing dendrites. (C) 1999 Elsevier Science Ltd. All rights reserved.

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Systematic ab initio molecular orbital studies of the conformational equilibria and vibrational spectra of dipropionamide using the basis sets 6-31g(d) and 6-31++G(d,p) have been carried out. The vibrational spectra of dipropionamide have been satisfactorily interpreted taking into account the agreement between the calculated frequencies, infrared and Raman band intensities and the shifts in the spectra of deuterated molecules with those observed. The previous assignments of most of the vibrational bands are well confirmed, a few bands need reassignment, however. The solvent effects were investigated by self-consistent reaction field theory using dipole and self-consistent isodensity polarized continuum model methods. The introduction of a dielectric medium has only a marginal effect on the conformational equilibria and vibrational spectra. However, the calculated changes in geometry and vibrational spectra on going from the gas phase to the solution phase are in accord with the increasing weight of the dipolar resonance structure in polar solvents. (C) 2002 Elsevier Science B.V. All rights reserved.

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The interaction between laminar Rayleigh-Benard convection and directional solidification is studied for the case of an eutectic solution kept in a rectangular cavity cooled from the top. Experiments and numerical simulations are carried out using an NH4Cl-H2O solution as the model fluid. The flow is visualized using a sheet of laser light scattered by neutrally buoyant, hollow-glass spheres seeded in the fluid. The numerical modeling is performed using a pressure-based finite-volume method according to the SIMPLER algorithm. The present configuration enables us to visualize flow vortices in the presence of a continuously evolving solid/liquid interface. Clear visualization of the Rayleigh-Benard convective cells and their interaction with the solidification front are obtained. It is observed that the convective cells are characterized by zones of up-flow and down-flow, resulting in the development of a nonplanar interface. Because of the continuous advancement of the solid/liquid interface, the effective liquid height of the cavity keeps decreasing. Once the height of the fluid layer falls below a critical value, the convective cells become weaker and eventually die out, leading to the growth of a planar solidification front. Results of flow visualization and temperature measurement are compared with those from the numerical simulation, and a good agreement is found.

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The ultrasonic degradation of poly(vinyl acetate) was carried out in six different solvents and two mixtures of solvents. The evolution of molecular weight distribution (MWD) with time was determined with gel permeation chromatography. The observed MWDs were analyzed by continuous distribution kinetics. A stoichiometric kernel that accounts for preferential mid-point breakage of the polymer chains was used. The degradation rate coefficient of the polymer in each solvent was determined from the model. The variations of rate coefficients were correlated with vapor pressure of the solvent, the Flory–Huggins polymer–solvent interaction parameter and the kinematic viscosity of the solution. A lower saturation vapor pressure resulted in higher degradation rates of the polymer. The degradation rate increased with increasing kinematic viscosity.

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The severe wear of a near eutectic aluminium silicon alloy is explored using a range of electron microscopic, spectroscopic and diffraction techniques to identify the residually strained and unstrained regions, microcracks and oxidized regions in the subsurface. In severe wear the contact pressure exceeds the elastic shakedown limit. Under this condition the primary and eutectic silicon particles fragment drastically. The fragments are transported by the matrix as it undergoes incremental straining with each cyclic contact at the asperity level. The grains are refined from similar to 2000 nm in the bulk to 30 nm in the near surface region. A large reduction in the interparticle distance compared with that for a milder stage of wear gives rise to high strain gradients which contribute to an enhancement of the dislocation density. The resulting regions of very high strain in the boundaries of the recrystallized grains as well as within the subgrains lead to the formation of microvoidskracks. This is accompanied by the formation of brittle oxides at these subsurface interfaces due to enhanced diffusion of oxygen. We believe that the abundance of such microcracks in the near surface region, primed by severe plastic deformation, is what distinguishes a severe wear regime from mild wear. (C) 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

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In this paper, we report a significant improvement in mechanical properties of near eutectic Nb-Si alloys by addition of Gallium (Ga) and control of microstructural length scale. A comparative study of two alloys Nb-18.79 at.%Si and Nb-20.2 at.%Si-2.7 at.%Ga were carried out. The microstructure refinements were carried out by vacuum suction casting in water cooled thick copper mold. It is shown that addition of Ga suppresses Nb(3)Si phase and promotes beta-Nb(5)Si(3) phase. The microstructural length scale and in particular eutectic spacing reduces significantly to 50-100 nm in suction cast ternary alloys. Compression test shows a strength of 2.8 +/- 0.1 GPa and plasticity of 4.3 +/- 0.03%. In comparison, the binary Nb-18.79 at.%Si alloy processed under identical conditions exhibit coarser length scale (300-400 nm) and brittle behavior. The fracture toughness of Ga containing suction cast alloy shows a value of 24.11 +/- 0.5 MPa root m representing a major improvement for bulk Nb-Si eutectic alloy. (C) 2011 Elsevier Ltd. All rights reserved.

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The chemical potentials of tin in its α-solid solutions with Cu, Au and Cu + Au alloys have been measured using a gas-solid equilibration technique. The variation of the excess chemical potential of tin with its composition in the alloy is related to the solute-solute repulsive interaction, while the excess chemical potential at infinite dilution of the solute is a measure of solvent-solute interaction energies. It is shown that solute-solute interaction is primarily determined by the concentration of (s + p) electrons in the conduction band, although the interaction energies are smaller than those predicted by either the rigid band model or calculation based on Friedel oscillations in the potential function. Finally, the variation of the solvent-solute interaction with solvent composition in the ternary system can be accounted for in terms of a quasi-chemical treatment which takes into account the clustering of the solvent atoms around the solute.