Surface energy gradient driven convection for generating nanoscale and microscale patterned polymer films using photosensitizers

The Marangoni effect describes how fluid flows in response to gradients in surface energy. This phenomenon could be broadly harnessed to pattern the surface topography of polymer films if generalizable techniques for programming surface energy gradients existed. Here, a near UV–visible light (NUV–vis) photosensitizer, 9,10‐dibromo‐anthracene (DBA), was doped into thin films of a model polymer, poly(isobutyl methacrylate). After exposure to light through a photomask and heating above the glass transition, thermolysis of photo‐oxidized DBA and grafting to the polymer promoted flow of the film material into the exposed regions. This mechanism did not significantly alter the molecular weight of PiBMA or the film's glass transition temperature, but resulted in an increase in film surface energy as indicated by a decrease in water contact angle. Film height variations of 580 nm were produced using a mask with 12.5 μm features; a mask with 800 nm features was also employed to generate topographic features of corresponding width without expensive contacting equipment. Due to the broad absorbance spectra of DBA, highly accessible and/or unconventional light sources may be employed in this process; this advantage was demonstrated by patterning with sunlight. The nonspecific radical‐mediated nature of the DBA grafting reaction makes this a promising approach for many classes of polymers. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1195–1202     

Generic applications of 13C‐detected NMR diffusion to formulated systems with suppression of thermal convection induced by proton decoupling

Fast and effective structural/compositional analysis on formulated systems represents one of the major challenges encountered in analytical science. ¹³C‐detected diffusion represents a promising tool to tackle the aforementioned challenges, particularly in industry. Toward exploring the generic applications of ¹³C‐detected diffusion, thermal convection induced by ¹H decoupling has been identified as a key factor that resulted in significantly reduced resolution in the diffusion dimension. Optimization of experimental parameters and utilization of double‐stimulated echo‐based pulse sequence both can effectively suppress the thermal convection caused by the ¹H decoupling, the success of which allows robust and generic applications of ¹³C‐detected diffusion to systems from mixtures of small molecules, polymer blends, and copolymers to actual complex formulated systems. The method is particularly powerful in differentiating small molecules from polymers, polymer blends from copolymers, and end‐group analysis. Copyright © 2016 John Wiley & Sons, Ltd.     

Coupled convection of solution near the surface of ion-exchange membranes in intensive current regimes

Mechanisms responsible for the overlimiting ion transfer in membranes systems are discussed. The overlimiting transfer is shown to be due largely to the action of four effects coupled with the concentration polarization of the system. Two of these are connected with the water dissociation near the membrane/solution interface: the emergence of additional charge carriers (ions H⁺ or OH^?) in the depleted solution layer and the exaltation of transfer of salt counterions. The latter effect is connected with the perturbation of electric field caused by the water dissociation products. The other two effects are two versions of coupled convection, which leads to partial destruction of the depleted diffusion layer. These include gravitational convection and electroconvection. The former is caused by the emergence of the solution’s density gradient. The latter develops via a mechanism of electroosmotic slip. In this work, methods of voltammetry and chronopotentiometry and pH measurements are used to study the transfer of ions through homogeneous membranes Nafion-117 and AMX as a function of the concentration of sodium chloride solutions in the underlimiting and overlimiting current regimes. In a 0.1 M NaCl solution, gravitational convection makes a considerable contribution to the transfer of salt ions near the membrane surface in intensive current regimes. The influence of this effect on the electrochemical behavior of membrane systems weakens with the solution dilution and with increasing relative transfer of the H⁺ and OH^? ions that are generated at the membrane/solution interface. In conditions where gravitational convection is suppressed and the water dissociation near the membrane/solution interface is not great, the major contribution to the overlimiting growth of current is made by electroconvection. Topics for discussion in the paper include the mutual influence of effects on one another, in particular, the effect the rate of generation of the H⁺ and OH^? ions exerts on the gravitational convection and electroconvection and the reasons for the different behavior of cation-and anion-exchange membranes in intensive current regimes.     

Radiation effects in the transient hot-wire technique

The transient hot-wire technique is widely used for absolute measurements of the thermal conductivity and thermal diffusivity of fluids. It is well established that fluid radiation effects significantly influence these measurements, especially those for the thermal diffusivity. Corrections for radiation effects are based on the models developed and deviations of the measured data from the ideal line source model. In this paper, the effect of fluid radiation on the measurements of the thermal conductivity of n-pentane is presented. For comparison, the influence of thermal radiation effect on measurement of transparent fluids, such as argon is also shown. The difference between the influence of natural convection and thermal radiation is also demonstrated.     

Time-dependent natural convection in a square cavity: Application of a new finite volume method

A new finite volume (FV) approach with adaptive upwind convection is used to predict the two-dimensional unsteady flow in a square cavity. The fluid is air and natural convection is induced by differentially heated vertical walls. The formulation is made in terms of the vorticity and the integral velocity (induction) law. Biquadratic interpolation formulae are used to approximate the temperature and vorticity fields over the finite volumes, to which the conservation laws are applied in integral form. Image vorticity is used to enforce the zero-penetration condition at the cavity walls. Unsteady predictions are carried sufficiently forward in time to reach a steady state. Results are presented for a Prandtl number (Pr) of 0-71 and Rayleigh numbers equal to 10³, 10⁴ and 10⁵. Both 11 × 11 and 21 × 21 meshes are used. The steady state predictions are compared with published results obtained using a finite difference (FD) scheme for the same values of Pr and Ra and the same meshes, as well as a numerical bench-mark solution. For the most part the FV predictions are closer to the bench-mark solution than are the FD predictions.     

A characteristic nonoverlapping domain decomposition method for multidimensional convection‐diffusion equations

We develop a quasi‐two‐level, coarse‐mesh‐free characteristic nonoverlapping domain decomposition method for unsteady‐state convection‐diffusion partial differential equations in multidimensional spaces. The development of the domain decomposition method is carried out by utilizing an additive Schwarz domain decomposition preconditioner, by using an Eulerian‐Lagrangian method for convection‐diffusion equations and by delicately choosing appropriate interface conditions that fully respect and utilize the hyperbolic nature of the governing equations. Numerical experiments are presented to illustrate the method. © 2004 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq, 2005     

Solution to transient Navier–Stokes equations by the coupling of differential quadrature time integration scheme with dual reciprocity boundary element method

The two‐dimensional time‐dependent Navier–Stokes equations in terms of the vorticity and the stream function are solved numerically by using the coupling of the dual reciprocity boundary element method (DRBEM) in space with the differential quadrature method (DQM) in time. In DRBEM application, the convective and the time derivative terms in the vorticity transport equation are considered as the nonhomogeneity in the equation and are approximated by radial basis functions. The solution to the Poisson equation, which links stream function and vorticity with an initial vorticity guess, produces velocity components in turn for the solution to vorticity transport equation. The DRBEM formulation of the vorticity transport equation results in an initial value problem represented by a system of first‐order ordinary differential equations in time. When the DQM discretizes this system in time direction, we obtain a system of linear algebraic equations, which gives the solution vector for vorticity at any required time level. The procedure outlined here is also applied to solve the problem of two‐dimensional natural convection in a cavity by utilizing an iteration among the stream function, the vorticity transport and the energy equations as well. The test problems include two‐dimensional flow in a cavity when a force is present, the lid‐driven cavity and the natural convection in a square cavity. The numerical results are visualized in terms of stream function, vorticity and temperature contours for several values of Reynolds (Re) and Rayleigh (Ra) numbers. Copyright © 2008 John Wiley & Sons, Ltd.     

A convective weakly viscoelastic rotating flow with pressure Neumann condition

The objective of this work is to investigate through the numeric simulation, the effects of the weakly viscoelastic flow within a rotating rectangular duct subject to a buoyancy force due to the heating of one of the walls of the duct. A direct velocity–pressure algorithm in primitive variables with a Neumann condition for the pressure is employed. The spatial discretization is made with finite central differences on a staggered grid. The pressure field is directly updated without any iteration. Numerical simulations were done for several Weissemberg numbers (We) and Grashof numbers (Gr) . The numerical results show that for high Weissemberg numbers (We>7.4 × 10^?5) and for ducts with aspect ratio 2:1 and 8:1, the secondary flow is restabilized with a stretched double vortex configuration. It is also observed that when the Grashof number is increased (Gr>17 × 10^?4) , the buoyancy force neutralizes the effects of the Coriolis force for ducts with aspect ratio 8:1. Copyright © 2008 John Wiley & Sons, Ltd.     

Topology optimization of microfluidic mixers

This paper demonstrates the application of the topology optimization method as a general and systematic approach for microfluidic mixer design. The mixing process is modeled as convection dominated transport in low Reynolds number incompressible flow. The mixer performance is maximized by altering the layout of flow/non‐flow regions subject to a constraint on the pressure drop between inlet and outlet. For a square cross‐sectioned pipe the mixing is increased by 70% compared with a straight pipe at the cost of a 2.5 fold increase in pressure drop. Another example where only the bottom profile of the channel is a design domain results in intricate herring bone patterns that confirm findings from the literature. Copyright © 2008 John Wiley & Sons, Ltd.     

用有限解析差分格式数值求解化学输运方程

本文用有限解析差分格式研究在多孔介质中化学输运问题的数值模型,系统地计算结果表明:1.有限解析差分格式能够消除数值弥散和伪振荡; 2.随着弥散数(Peclct数)的减小(增加),浓度突破曲线将延迟到达和形状变陡,最终趋近浓度对流曲线;3.当流速数增加后,非稳态吸附对浓度分布的影响趋近稳态吸附的影响。