Polymer-mediated colloidal stability: on the transition between adsorption and depletion

Addition of polymers to a colloidal dispersion modulates the interactions between the colloids. We briefly review the effects of positive and negative adsorption (also termed depletion). The effective colloid-polymer interactions sensitively affect the colloidal phase behavior. We present a theoretical framework to predict the phase behavior of colloid-polymer mixtures for varying affinities between colloid and polymer, leading to either positive or negative adsorption of polymer segments. For certain conditions, polymers are neither depleted nor adsorbed: the polymer concentration is essentially constant up to the colloidal surface, a condition which we term neutral adsorption. Near this condition, the calculated phase diagrams reveal a stable-unstable-restabilisation transition with increasing polymer concentration. Similar effects have been reported experimentally, for instance as a function of temperature [Feng et al., Nat. Mat., 2015, 14, 61-65], which may modulate the effective polymer-colloid affinity. Understanding how to achieve neutral adsorption opens up the possibility of preparing highly dense, yet stable, colloid-polymer mixtures.