The effect of matrix structure on the diffusion of fluids in porous media

Abstract

The effect of matrix structure on the transport properties of adsorbed fluids is studied using computer simulations and percolation theory. The model system consists of a fluid of hard spheres diffusing in a matrix of hard spheres fixed in space. Three different arrangements of the fixed spheres, random, templated, and polymeric, are investigated. For a given matrix volume fraction the diffusion coefficient of the fluid, D, is sensitive to the manner in which the matrix is constructed, with large differences between the three types of matrices. The matrix is mapped onto an effective lattice composed of vertices and bonds using a Voronoi tessellation method where the connectivity of bonds is determined using a geometric criterion, i.e., a bond is connected if a fluid particle can pass directly between the two pores the bond connects, and disconnected otherwise. The percolation threshold is then determined from the connectivity of the bonds. D displays universal scaling behavior in the reduced volume fraction, i.e., D approximately (1-phi(m)phi(c))(gamma), where phi(m) is the matrix volume fraction and phi(c) is the matrix volume fraction at the percolation threshold. We find that gamma approximately 2.2, independent of matrix type, which is different from the result gamma approximately 1.53 for diffusion in lattice models, but similar to that for conduction in Swiss cheese models. Lattice simulations with biased hopping probabilities are consistent with the continuous-space simulations, and this shows that the universal behavior of diffusion is sensitive to details of local dynamics.