Entropic phase separation of linked beads

Abstract

We study theoretically a model system of a transient network of microemulsion droplets connected by telechelic polymers and explain recent experimental findings. Despite the absence of any specific interactions between either the droplets or polymer chains, we predict that as the number of polymers per drop is increased, the system undergoes a first order phase separation into a dense, highly connected phase, in equilibrium with dilute droplets, decorated by polymer loops. The phase transition is purely entropic and is driven by the interplay between the translational entropy of the drops and the configurational entropy of the polymer connections between them. Because it is dominated by entropic effects, the phase separation mechanism of the system is extremely robust and does not depend on the particlular physical realization of the network. The discussed model applies as well to other polymer linked particle aggregates, such as nano-particles connected with short DNA linkers.