Transition from confined to bulk dynamics in symmetric star-linear polymer mixtures

Abstract

We report on the linear viscoelastic properties of mixtures comprising multiarm star (as model soft colloids) and long linear chain homopolymers in a good solvent. In contrast to earlier works, we investigated symmetric mixtures (with a size ratio of 1) and showed that the polymeric and colloidal responses can be decoupled. The adopted experimental protocol involved probing the linear chain dynamics in different star environments. To this end, we studied mixtures with different star mass fraction, which was kept constant while linear chains were added and their entanglement plateau modulus ($G_p$) and terminal relaxation time ($\tau_d$) were measured as functions of their concentration. Two distinct scaling regimes were observed for both $G_p$ and $\tau_d$: at low linear polymer concentrations, a weak concentration dependence was observed, that became even weaker as the fraction of stars in the mixtures increased into the star glassy regime. On the other hand, at higher linear polymer concentrations, the classical entangled polymer scaling was recovered. Simple scaling arguments show that the threshold crossover concentration between the two regimes corresponds to the maximum osmotic star compression and signals the transition from confined to bulk dynamics. These results provide the needed ingredients to complete the state diagram of soft colloid-polymer mixtures and investigate their dynamics at large polymer-colloid size ratios. They also offer an alternative way to explore aspects of the colloidal glass transition and the polymer dynamics in confinement. Finally, they provide a new avenue to tailor the rheology of soft composites.Comment: 9 Figure