Nearest-neighbor connectedness theory: A general approach to continuum percolation.

We introduce a method to estimate continuum percolation thresholds and illustrate its usefulness by investigating geometric percolation of noninteracting line segments and disks in two spatial dimensions. These examples serve as models for electrical percolation of elongated and flat nanofillers in thin film composites. While the standard contact volume argument and extensions thereof in connectedness percolation theory yield accurate predictions for slender nanofillers in three dimensions, they fail to do so in two dimensions, making our test a stringent one. In fact, neither a systematic order-by-order correction to the standard argument nor invoking the connectedness version of the Percus-Yevick approximation yield significant improvements for either type of particle. Making use of simple geometric considerations, our new method predicts a percolation threshold of ρ_{c}l^{2}≈5.83 for segments of length l, which is close to the ρ_{c}l^{2}≈5.64 found in Monte Carlo simulations. For disks of area a we find ρ_{c}a≈1.00, close to the Monte Carlo result of ρ_{c}a≈1.13. We discuss the shortcomings of the conventional approaches and explain how usage of the nearest-neighbor distribution in our method bypasses those complications.

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

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.

Connectivity, Not Density, Dictates Percolation in Nematic Liquid Crystals of Slender Nanoparticles.

We show by means of continuum theory and simulations that geometric percolation in uniaxial nematics of hard slender particles is fundamentally different from that in isotropic dispersions. In the nematic, percolation depends only very weakly on the density and is, in essence, determined by a distance criterion that defines connectivity. This unexpected finding has its roots in the nontrivial coupling between the density and the degree of orientational order that dictate the mean number of particle contacts. Clusters in the nematic are much longer than wide, suggesting the use of nematics for nanocomposites with strongly anisotropic transport properties.

Unusual geometric percolation of hard nanorods in the uniaxial nematic liquid crystalline phase.

We investigate by means of continuum percolation theory and Monte Carlo simulations how spontaneous uniaxial symmetry breaking affects geometric percolation in dispersions of hard rodlike particles. If the particle aspect ratio exceeds about 20, percolation in the nematic phase can be lost upon adding particles to the dispersion. This contrasts with percolation in the isotropic phase, where a minimum particle loading is always required to obtain system-spanning clusters. For sufficiently short rods, percolation in the uniaxial nematic mimics that of the isotropic phase, where the addition of particles always aids percolation. For aspect ratios between 20 and infinity, but not including infinity, we find reentrance behavior: percolation in the low-density nematic may be lost upon increasing the amount of nanofillers but can be regained by the addition of even more particles to the suspension. Our simulation results for aspect ratios of 5, 10, 20, 50, and 100 strongly support our theoretical predictions, with almost quantitative agreement. We show that a different closure of the connectedness Ornstein-Zernike equation, inspired by scaled particle theory, is as least as accurate in predicting the percolation threshold as the Parsons-Lee closure, which effectively describes the impact of many-body direct contacts.

Continuum percolation of polydisperse rods in quadrupole fields: Theory and simulations.

We investigate percolation in mixtures of nanorods in the presence of external fields that align or disalign the particles with the field axis. Such conditions are found in the formulation and processing of nanocomposites, where the field may be electric, magnetic, or due to elongational flow. Our focus is on the effect of length polydispersity, which-in the absence of a field-is known to produce a percolation threshold that scales with the inverse weight average of the particle length. Using a model of non-interacting spherocylinders in conjunction with connectedness percolation theory, we show that a quadrupolar field always increases the percolation threshold and that the universal scaling with the inverse weight average no longer holds if the field couples to the particle length. Instead, the percolation threshold becomes a function of higher moments of the length distribution, where the order of the relevant moments crucially depends on the strength and type of field applied. The theoretical predictions compare well with the results of our Monte Carlo simulations, which eliminate finite size effects by exploiting the fact that the universal scaling of the wrapping probability function holds even in anisotropic systems. Theory and simulation demonstrate that the percolation threshold of a polydisperse mixture can be lower than that of the individual components, confirming recent work based on a mapping onto a Bethe lattice as well as earlier computer simulations involving dipole fields. Our work shows how the formulation of nanocomposites may be used to compensate for the adverse effects of aligning fields that are inevitable under practical manufacturing conditions.