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二元点Yukawa流体的界面与润湿特性

Interfacial and wetting properties of a binary point Yukawa fluid.

作者信息

Hopkins Paul, Archer Andrew J, Evans Robert

机构信息

H.H. Wills Physics Laboratory, University of Bristol, Tyndall Avenue, Bristol BS8 1TL, United Kingdom.

出版信息

J Chem Phys. 2008 Dec 7;129(21):214709. doi: 10.1063/1.3027515.

Abstract

We investigate the interfacial phase behavior of a binary fluid mixture composed of repulsive point Yukawa particles. Using a simple approximation for the Helmholtz free energy functional, which yields the random phase approximation for the pair direct correlation functions, we calculate the equilibrium fluid density profiles of the two species of particles adsorbed at a planar wall. We show that for a particular choice (repulsive exponential) of the wall potentials and the fluid pair-potential parameters, the Euler-Lagrange equations for the equilibrium fluid density profiles may be transformed into a single ordinary differential equation and the profiles obtained by a simple quadrature. For certain other choices of the fluid pair-potential parameters fluid-fluid phase separation of the bulk fluid is observed. We find that when such a mixture is exposed to a planar hard wall, the fluid exhibits complete wetting on the species 2 poor side of the binodal, i.e., we observe a thick film of fluid rich in species 2 adsorbed at the hard wall. The thickness of the wetting film grows logarithmically with the concentration difference between the fluid state point and the binodal and is proportional to the bulk correlation length of the intruding (wetting) fluid phase. However, for state points on the binodal that are further from the critical point, we find there is no thick wetting film. We determine the accompanying line of first-order (prewetting) surface phase transitions which separate a thin and thick adsorbed film. We show that for some other choices of repulsive wall potentials the prewetting line is still present, but its location and extent in the phase diagram is strongly dependent on the wall-fluid interaction parameters.

摘要

我们研究了由排斥性点Yukawa粒子组成的二元流体混合物的界面相行为。通过对亥姆霍兹自由能泛函采用一种简单近似,该近似给出了对关联函数的随机相近似,我们计算了吸附在平面壁上的两种粒子的平衡流体密度分布。我们表明,对于壁势和流体对势参数的特定选择(排斥指数),平衡流体密度分布的欧拉 - 拉格朗日方程可以转化为一个单一的常微分方程,并通过简单的求积得到分布。对于流体对势参数的某些其他选择,观察到体相流体的流体 - 流体相分离。我们发现,当这样的混合物暴露于平面硬壁时,流体在双节线物种2贫侧表现出完全润湿,即我们观察到在硬壁上吸附有富含物种2的厚流体膜。润湿膜的厚度随着流体状态点与双节线之间的浓度差呈对数增长,并且与侵入(润湿)流体相的体相关长度成正比。然而,对于双节线上离临界点更远的状态点,我们发现没有厚的润湿膜。我们确定了伴随的一阶(预润湿)表面相变线,它将薄吸附膜和厚吸附膜分开。我们表明,对于排斥壁势的某些其他选择,预润湿线仍然存在,但其在相图中的位置和范围强烈依赖于壁 - 流体相互作用参数。

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