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Surface fractionation effects on slip of polydisperse polymer melts
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The slip behavior of several high-density polyethylenes with broad range of molecular weight (MW) including bimodals is studied as a function of molecular weight (MW) and its distribution. A formulation similar to the double reptation theory is used to predict the slip velocity of the studied polymers as a function of MWD coupled with a model of surface molecular weight fractionation. 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 entropy driven migration of short chains toward the die wall has a profound effect and should be considered in order to calculate the effective MWD on the boundary layer and thus the correct magnitude of wall slip.
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