Frozen topology: entanglements control nucleation and crystallization in polymers.

Abstract

Polymer chains form lamellar structures during crystallization which display a memory of thermal history. Using molecular dynamics simulations and primitive path analysis, we show a direct dependence of both density and crystalline stem length on the local entanglement length. The slow relaxation of the entanglement state after a change of external conditions can directly explain the role of thermal history for polymer crystallization, in particular memory effects. The analysis of the local entanglement state can be used to predict the occurrence of nucleation events. Our results present a fresh insight of the nonequilibrium properties of polymer crystals which might be identified as "frozen topology" of polymer melts.