Thermodynamics and structure of self-assembled networks

We study a generic model of self-assembling chains that can branch and form networks with branching points (junctions) of arbitrary functionality. The physical realizations include physical gels, wormlike micelles, dipolar fluids, and microemulsions. The model maps the partition function of a solution of branched, self-assembling, mutually avoiding clusters onto that of a Heisenberg magnet in the mathematical limit of zero spin components. As for the calculation of thermodynamic properties as well as the scattering structure factor, the mapping rigorously accounts for all possible cluster configurations, except for closed rings. The model is solved in the mean-field approximation. It is found that despite the absence of any specific interaction between the chains, the presence of the junctions induces an effective attraction between the monomers, which in the case of threefold junctions leads to a first-order reentrant phase separation between a dilute phase consisting mainly of single chains, and a dense network, or two network phases. The model is then modified to predict the structural properties at the mean-field level. Independent of the phase separation, we predict a percolation (connectivity) transition at which an infinite network is formed. The percolation transition partially overlaps with the first-order transition, and is a continuous, nonthermodynamic transition that describes a change in the topology of the system. Our treatment that predicts both the thermodynamic phase equilibria as well as the spatial correlations in the system allows us to treat both the phase separation and the percolation threshold within the same framework. The density-density correlation has the usual Ornstein-Zernicke form at low monomer densities. At higher densities, a peak emerges in the structure factor, signifying the onset of medium-range order in the system. Implications of the results for different physical systems are discussed.