Phase behavior of hard spheres mixed with supramolecular polymers

We present a theory that predicts the phase behavior of hard spheres (HS) mixed with non-adsorbing supramolecular polymers in a common solvent. It combines Generalized Free Volume Theory with a mean-field model for equilibrium polymers in solution extended with scaling theory to incorporate excluded volume effects in a good solvent. The system displays similar phase stability as conventional HS-polymer mixtures, although there is a small preference for gas-liquid coexistence with respect to fluid-crystal equilibrium in the case of a HS-supramolecular polymer mixture. Phase transitions can be induced by external stimuli such as temperature or light due to the stimuli-responsive nature of the supramolecular polymer size.