Geometric percolation of hard nanorods: The interplay of spontaneous and externally induced uniaxial particle alignment.

Abstract

We present a numerical study on geometric percolation in liquid dispersions of hard slender colloidal particles subject to an external orienting field. In the formulation and liquid-state processing of nanocomposite materials, particle alignment by external fields such as electric, magnetic, or flow fields is practically inevitable and often works against the emergence of large nanoparticle networks. Using continuum percolation theory in conjunction with Onsager theory, we investigate how the interplay between externally induced alignment and the spontaneous symmetry breaking of the uniaxial nematic phase affects cluster formation in nanoparticle dispersions. It is known that particle alignment by means of a density increase or by an external field may result in a breakdown of an already percolating network. As a result, percolation can be limited to a small region of the phase diagram only. Here, we demonstrate that the existence and shape of such a "percolation island" in the phase diagram crucially depends on the connectivity length-a critical distance defining direct connections between neighboring particles. For some values of the connectivity range, we observe unusual re-entrance effects, in which a system-spanning network forms and breaks down multiple times with increasing particle density.