188 resultados para FREE-RADICALS


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The nonaxisymmetric unsteady motion produced by a buoyancy-induced cross-flow of an electrically conducting fluid over an infinite rotating disk in a vertical plane and in the presence of an applied magnetic field normal to the disk has been studied. Both constant wall and constant heat flux conditions have been considered. It has been found that if the angular velocity of the disk and the applied magnetic field squared vary inversely as a linear function of time (i.e. as (1??t*)?1, the governing Navier-Stokes equation and the energy equation admit a locally self-similar solution. The resulting set of ordinary differential equations has been solved using a shooting method with a generalized Newton's correction procedure for guessed boundary conditions. It is observed that in a certain region near the disk the buoyancy induced cross-flow dominates the primary von Karman flow. The shear stresses induced by the cross-flow are found to be more than these of the primary flow and they increase with magnetic parameter or the parameter ? characterizing the unsteadiness. The velocity profiles in the x- and y-directions for the primary flow at any two values of the unsteady parameter ? cross each other towards the edge of the boundary layer. The heat transfer increases with the Prandtl number but reduces with the magnetic parameter.

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A finite element method (FEM)-based study has been carried out for the design of flat microtensile samples to evaluate tensile properties of Pt-aluminide (PtAl) bond coats. The critical dimensions of the sample have been determined using a two-dimensional elastic stress analysis. In the present testing scheme, the ratio of the dimensions of the holding length to the fillet radius of the sample was found important to achieve failure within the gage length. The effect of gage length and grip head length also has been examined. The simulation predictions have been experimentally verified by conducting microtensile test of an actual PtAl bond coat at room temperature. The sample design and testing scheme suggested in this study have also been found suitable for evaluation of tensile properties at high temperature. (C) 2010 Elsevier Ltd. All rights reserved.

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A cross-linked polymer-gel soft matter electrolyte with superior electrochemical, thermal and mechanical properties obtained from free radical polymerization of vinyl monomers in a semi-solid organic nonionic plastic crystalline electrolyte for application in rechargeable lithium-ion batteries is discussed here.

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The geometries of alpha- and beta-silyl substituted vinyl radicals and of alpha,beta-disilylvinyl radical have been optimised with the STO-3G and the STO-3G* basis sets. The relative stabilities of various conformers have been determined at the UMP2/6-31G* level. The stabilisation of vinyl radicals through alpha-silyl substitution is larger than that due to corresponding alkyl groups. The presence of an alpha-silyl group also leads to a tendency towards linearisation of the vinyl radical centre and a corresponding reduction in the inversion barrier. In marked contrast, the beta-silyl effect is negligible. The geometric, conformational and energetic consequences are insignificant. Overall, the silyl substituent effect at vinyl radicals is very different from that computed earlier for the vinyl cations, but qualitatively similar to that found in carbanions.

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Numerical solutions are presented for the free convection boundary layers over cylinders of elliptic cross section embedded in a fluid-saturated porous medium. The transformed conservation equations of the nonsimilar boundary layers are solved numerically by an efficient finite-difference method. The theory was applied to a number of cylinders and the results compared very well with published analytical solutions. The results are of use in the design of underground electrical cables, power plant steam, and water distribution lines, among others.

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An improved flux draining technique for the extraction of grown YBCO crystals from its solvent is reported. This simple and efficient technique facilitates in-situ flux separation in the isothermal region of the furnace. Consequently, the crystals are spared from thermal shock and subsequent damage. Flux-free surfaces of these crystals were studied by optical microscopy. Transmission X-ray topographs of the crystals reveal the dislocations present in them as well as the stresses developed as a result of ferroelastic phase transition occurring during cooling.

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The low-T-c layered superconductor 2H-NbSe2 shows remarkable results for free flux-flow Hall effect. At low magnetic fields, the Nozieres-Vinen result of a field-independent Hall angle appears to hold. At larger fields, a marked departure occurs leading to an extremely sharp and pronounced minimum slightly below H-c2, unaccounted for in the standard theoretical models. The results suggest the existence of collective dynamics and phase transitions (such as melting) in a clean flux line lattice.

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Palladium substituted in cerium dioxide in the form of a solid solution, Ce-0.98 Pd-0.02 O-1.98 is a new heterogeneous catalyst which exhibits high activity and 100% trans-selectivity for the Heck reactions of aryl bromides including heteroaryls with olefins. The catalytic reactions work without any ligand. Nano-crystalline Ce-0.98 Pd-0.02 O-1.98 is prepared by solution combustion method and Pd is in +2 state. The catalyst can be separated, recovered and reused without significant loss in activity.

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The unsteady free convection boundary layer at the stagnation point of a two-dimensional body and an axisymmetric body with prescribed surface heat flux or temperature has been studied. The magnetic field is applied parallel to the surface and the effect of induced magnetic field has been considered. It is found that for certain powerlaw distribution of surface heat flux or temperature and magnetic field with time, the governing boundary layer equations admit a self-similar solution locally. The resulting nonlinear ordinary differential equations have been solved using a finite element method and a shooting method with Newton's corrections for missing initial conditions. The results show that the skin friction and heat transfer coefficients, and x-component of the induced magnetic field on the surface increase with the applied magnetic field. In general, the skin friction, heat transfer and x-component of the induced magnetic field for axisymmetric case are more than those of the two-dimensional case. Also they change more when the surface heat flux or temperature decreases with time than when it increases with time. The skin friction, heat transfer and x-component of the induced magnetic field are significantly affected by the magnetic Prandtl number and they increase as the magnetic Prandtl number decreases. The skin friction and x-component of the magnetic field increase with the dissipation parameter, but heat transfer decreases.

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A comprehensive exact treatment of free surface flows governed by shallow water equations (in sigma variables) is given. Several new families of exact solutions of the governing PDEs are found and are shown to embed the well-known self-similar or traveling wave solutions which themselves are governed by reduced ODEs. The classes of solutions found here are explicit in contrast to those found earlier in an implicit form. The height of the free surface for each family of solutions is found explicitly. For the traveling or simple wave, the free surface is governed by a nonlinear wave equation, but is arbitrary otherwise. For other types of solutions, the height of the free surface is constant either on lines of constant acceleration or on lines of constant speed; in another case, the free surface is a horizontal plane while the flow underneath is a sine wave. The existence of simple waves on shear flows is analytically proved. The interaction of large amplitude progressive waves with shear flow is also studied.

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The free vibration of strings with randomly varying mass and stiffness is considered. The joint probability density functions of the eigenvalues and eigenfunctions are characterized in terms of the solution of a pair of stochastic non-linear initial value problems. Analytical solutions of these equations based on the method of stochastic averaging are obtained. The effects of the mean and autocorrelation of the mass process are included in the analysis. Numerical results for the marginal probability density functions of eigenvalues and eigenfunctions are obtained and are found to compare well with Monte Carlo simulation results. The random eigenvalues, when normalized with respect to their corresponding deterministic values, are observed to tend to become first order stochastically stationary with respect to the mode count.

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A new method is described for measuring intracellular free calcium concentrations, [(Ca2+)(i)], in the cells of Dictyostelium discoideum transformed with apoaequorin cDNA of the jellyfish, Aequorea victoria. Aequorin, a calcium-specific indicator, was regenerated in vivo from apoaequorin produced in the cells by incubation with coelenterazine. The results showed that [(Ca2+)(i)] in developing cells markedly increases at the aggregation stage and again at the culmination stage after a temporary drop at the migration stage. Except for the vegetative stage, the cells al all stages of development exhibit a sharp transient increase in [(Ca2+)(i)] upon stimulation with a cAMP (50 nM) pulse, high responses being observed at the migration and culmination stages. Separated prestalk cells of migrating slugs contain more than twice as much [(Ca2+)(i)] and show three times as large a response to cAMP stimulation as prespore cells.

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Three independent studies have been reported on the free energy of formation of NiWO4. Results of these measurements are analyzed by the �third-law� method, using thermal functions for NiWO4 derived from both low and high temperature heat capacity measurements. Values for the standard molar enthalpy of formation of NiWO4 at 298·15 K obtained from �third-law� analysis are compared with direct calorimetric determinations. Only one set of free energy measurements is found to be compatible with calorimetric enthalpies of formation. The selected value for ?f H m 0 (NiWO4, cr, 298·15 K) is the average of the three calorimetric measurements, using both high temperature solution and combustion techniques, and the compatible free energy determination. A new set of evaluated data for NiWO4 is presented.