Flow-induced fractionation effects on slip of polydisperse polymer melts

The slip behavior of several high-density polyethylenes with a broad range of molecular weights (MWs) including bimodal is studied as a function of MW and its distribution (MWD). A formulation inspired by the reptation theory is used to predict the slip velocity of the studied polymers as a function of MWD coupled with a model of surface MW fractionation that includes (i) the entropy driven migration of short chains toward the die wall due to the concentration gradient and (ii) the flow (stress)-induced migration effects. While surface fractionation has a minor effect on slip of narrow to moderate MWD polymers (particularly unimodal), its role is significant for broad bimodal MWD polymers. The inclusion of both effects (concentration and flow gradients) accurately captures the slip velocity of broad MWD polymers.