Barrier hopping, viscous flow, and kinetic gelation in particle-polymer suspensions

The naive mode coupling-polymer reference interaction site model (MCT-PRISM) theory of gelation and elasticity of suspensions of hard sphere colloids or nanoparticles mixed with nonadsorbing polymers has been extended to treat the emergence of barriers, activated transport, and viscous flow. The barrier makes the dominant contribution to the single particle relaxation time and shear viscosity, and is a rich function of the depletion attraction strength via the polymer concentration, polymer-particle size asymmetry ratio, and particle volume fraction. The dependences of the barrier on these three system parameters can be accurately collapsed onto a single scaling variable, and the resultant master curve is well described by a power law. Nearly universal master curves are also constructed for the hopping or alpha relaxation time for system conditions not too close to the ideal MCT transition. Based on the calculated barrier hopping time, a theory for kinetic gel boundaries is proposed. The form and dependence on system parameters of the kinetic gel lines are qualitatively the same as obtained from prior ideal MCT-PRISM studies. The possible relevance of our results to the phenomenon of gravity-driven gel collapse is studied. The general approach can be extended to treat nonlinear viscoelasticity and rheology of polymer-colloid suspensions and gels.