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251.
Current fuel cell proton exchange membranes rely on a random network of conducting hydrophilic domains to transport protons across the membrane. Despite extensive investigation, details of the structure of the hydrophilic domains in these membranes remain unresolved. In this study a dynamic self-consistent mean field theory has been applied to obtain the morphologies of hydrated perfluorosulfonic acid membranes (equivalent weight of 1100) as a model system for Nafion at several water contents. A coarse-grained mesoscale model was developed by dividing the system into three components: backbone, side chain, and water. The interaction parameters for this model were generated using classical molecular dynamics. The simulated morphology shows phase separated micelles filled with water, surrounded by side chains containing sulfonic groups, and embedded in the fluorocarbon matrix. The size distribution and connectivity of the hydrophilic domains were analyzed and the small angle neutron scattering (SANS) pattern was calculated. At low water content (lambda<6, where lambda is the number of water molecules per sulfonic group) the isolated domains obtained from simulation are nearly spherical with a domain size smaller than that fitted to experimental SANS data. At higher water content (lambda>8), the domains deform into elliptical and barbell shapes as they merge. The simulated morphology, hydrophilic domain size and shape are generally consistent with some experimental observations. 相似文献
252.
C. S. Lalitha 《Optimization Letters》2010,4(1):57-66
The main aim of this note is to extend the dual (in the form of an optimization problem) given for equilibrium problem by
Martinez-Legaz and Sosa (in J Glob Optim 35:311–319, 2006) for a generalized equilibrium problem in finite dimensional setting
and to establish its equivalence with the dual derived by Bigi et al. (in J Math Anal Appl 342:17–26, 2008) (in the form of
inclusion conditions) under a mild condition. 相似文献
253.
Verevkin SP Zaitsau DH Emel'yanenko VN Schick C Jayaraman S Maginn EJ 《Chemical communications (Cambridge, England)》2012,48(55):6915-6917
We used DSC for determination of the reaction enthalpy of the synthesis of the ionic liquid [C(4)mim][Cl]. A combination of DSC and quantum chemical calculations presents a new, indirect way to study thermodynamics of ionic liquids. The new procedure was validated with two direct experimental measurements and MD simulations. 相似文献
254.
Karthik Jayaraman Raghuram Shivkumar Chandrasekaran Joseph Moffitt Ming Gu Hrushikesh Mhaskar 《Journal of Computational and Applied Mathematics》2012
A higher order numerical discretization technique based on Minimum Sobolev Norm (MSN) interpolation was introduced in our previous work. In this article, the discretization technique is presented as a tool to solve two hard classes of PDEs, namely, the exterior Laplace problem and the biharmonic problem. The exterior Laplace problem is compactified and the resultant near singular PDE is solved using this technique. This finite difference type method is then used to discretize and solve biharmonic type PDEs. A simple book keeping trick of using Ghost points is used to obtain a perfectly constrained discrete system. Numerical results such as discretization error, condition number estimate, and solution error are presented. For both classes of PDEs, variable coefficient examples on complicated geometries and irregular grids are considered. The method is seen to have high order of convergence in all these cases through numerical evidence. Perhaps for the first time, such a systematic higher order procedure for irregular grids and variable coefficient cases is now available. Though not discussed in the paper, the idea seems to be easily generalizable to finite element type techniques as well. 相似文献
255.
A new metal ion-responsive azo-based fluorescent probes have been synthesized and characterized by NMR spectral techniques.
Steady-state fluorometric study has been used to analyze the spectroscopic and photophysical characteristics of dye derivatives
in various solvents. The fluorescence properties of these dyes are strongly solvent dependent, the wavelength of maximum fluorescence
emission shifts to the red. The Kamlet-Taft and Catalan’s solvent scales were found to be the most suitable for describing
the solvatochromic shifts of the absorption and fluorescence emission. The hydroxy substituted azo dye formed complexes with
several metal ions (Co2+, Hg2+, Ni2+ and Cu2+) and fluorescence quenching with metal ions reveal that it can be used as a new fluorescence sensor to detect the Cu2+ ion. 相似文献
256.
A coordinate transformation method is proposed for modelling unsteady, depth-averaged shallow water equations for a open channel flow with moving lateral boundaries. The transformation technique which maps the changing domain onto a fixed domain and solves the governing equations in the mapped domain, facilitates the numerical treatment of an irregular boundary configuration. The transformed equations are solved on a staggered grid with a conditionally stable, explicit finite difference scheme. Several numerical experiments are carried out corresponding to different situations, viz., flow with constant discharge, flow with constant discharge and a closed boundary at the downstream, flow in a converging channel with constant discharge and finally flow with varying discharge. The experiments are used to verify the model ability to predict free surface elevation, circulatory pattern and displacement of the boundaries. The simulated results such as displaced area, depth, displacement–time and flow-field are used to evaluate the effects of excess discharge at the upstream on the movement of lateral boundaries. 相似文献
257.
Jayaraman S May EL Hillier AC 《Langmuir : the ACS journal of surfaces and colloids》2006,22(25):10322-10328
The influence of a surface potential gradient on the location and extent of electrochemical reactions was examined using a scanning electrochemical microscope. A linear potential gradient was imposed on the surface of a platinum-coated indium tin oxide electrode by applying two different potential values at the edges of the electrode. The applied potentials were used to control the location and extent of several electrochemical reactions, including the oxidation of Ru(NH3)6(2+), the oxidation of H2, and the oxidation of H2 in the presence of adsorbed CO. Scanning electrochemical mapping of these reactions was achieved by probing the feedback current associated with the oxidation products. The oxidation of Ru(NH3)6(2+) occurred at locations where the applied potential was positive of the formal potential of the Ru(NH3)6(2+/3+) redox couple. The position of this reaction on the surface could be spatially translated by manipulating the terminal potentials. The rate of hydrogen oxidation on the platinum-coated electrode varied spatially in the presence of a potential gradient and correlated with the nature of the electrode surface. High oxidation rates occurred at low potentials, with decreasing rates observed as the potential increased to values where platinum oxides formed. The extent of oxide formation versus position was confirmed with in-situ ellipsometry mapping. In the presence of adsorbed carbon monoxide, a potential gradient created a localized region of high activity for hydrogen oxidation at potentials between where carbon monoxide was adsorbed and platinum oxides formed. The position of this localized region of activity could be readily translated along the surface by changing the terminal potential values. The ability to manipulate electrochemical reactions spatially on a surface has potential application in microscale analytical devices as well as in the discovery and analysis of electrocatalytic systems. 相似文献
258.
259.