Wessels Paul P F, Schmidt Matthias, Löwen Hartmut
Institut für Theoretische Physik II, Heinrich-Heine-Universität Düsseldorf, Germany.
Phys Rev E Stat Nonlin Soft Matter Phys. 2003 Dec;68(6 Pt 1):061404. doi: 10.1103/PhysRevE.68.061404. Epub 2003 Dec 17.
We consider the Asakura-Oosawa model of hard sphere colloids and ideal polymers in contact with a porous matrix modeled by immobilized configurations of hard spheres. For this ternary mixture a fundamental measure density functional theory is employed, where the matrix particles are quenched and the colloids and polymers are annealed, i.e., allowed to equilibrate. We study capillary condensation of the mixture in a small sample of matrix as well as demixing and the fluid-fluid interface inside a bulk matrix. Density profiles normal to the interface and surface tensions are calculated and compared to the case without matrix. Two kinds of matrices are considered: (i) colloid-sized matrix particles at low packing fractions and (ii) large matrix particles at high packing fractions. These two cases show fundamentally different behavior and should both be experimentally realizable. Furthermore, we argue that capillary condensation of a colloidal suspension could be experimentally accessible. We find that in case (ii), even at high packing fractions, the main effect of the matrix is to exclude volume and, to high accuracy, the results can be mapped onto those of the same system without matrix via a simple rescaling.
我们考虑硬球胶体和理想聚合物与由硬球固定构型模拟的多孔基质接触的朝仓-大泽模型。对于这种三元混合物,采用了一种基本度量密度泛函理论,其中基质颗粒被淬火,而胶体和聚合物被退火,即允许达到平衡。我们研究了混合物在基质小样本中的毛细凝聚以及在大块基质内部的相分离和流体-流体界面。计算了垂直于界面的密度分布和表面张力,并与无基质的情况进行了比较。考虑了两种基质:(i)低填充率下胶体尺寸的基质颗粒和(ii)高填充率下大尺寸的基质颗粒。这两种情况表现出根本不同的行为,并且在实验上都应该是可实现的。此外,我们认为胶体悬浮液的毛细凝聚在实验上是可以实现的。我们发现,在情况(ii)中,即使在高填充率下,基质的主要作用是排除体积,并且在高精度下,通过简单的重新缩放,结果可以映射到无基质的同一系统的结果上。