Abstract
Despite their wide range of applications, fundamental understanding of how micelles respond to other components in solution is scarce. Here, the colloidal stability of micelle solutions in presence of (homo)polymers is investigated following a theoretical bottom-up approach. A simple, yet insightful, polymer mediated micelle–micelle interaction is extracted via the changes in the micelle–unimer equilibrium with varying the inter-micelle distance in presence of homopolymer. For different polymer-to-micelle size ratios, model crew-cut and starlike micelles are studied, for both homopolymer depletion and adsorption from/into the corona. The fluffy nature of the corona may prevent depletion-induced destabilization of the micellar suspension. Adsorption of polymers into the corona induces bridging attraction between micelles. Crew-cut micelles have a narrower yet denser corona, hence penetration of guest compounds into the coronal domain is less pronounced than for starlike micelles. This makes crew-cut micelles more suitable for applications in crowded environments, such as drug delivery. The trends observed for the colloidal stability of crew-cut micelles qualitatively match with experimental observations on aqueous dispersions of polycaprolactone–polyethylene glycol (PCL-PEO) micellar suspensions with added PEO chains.
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