Disentanglement of Linear Polymer Chains Toward Unentangled Crystals

Large scale and long time molecular dynamics simulations and primitive path analysis are used to investigate the disentanglement of long linear polymer chains during their crystallization from the melt state. In general, two competitive processes, a slow decrease of average entanglement length during cooling caused by stiffening of chains and a strong increase during crystallization, can be observed. In both homogeneous and heterogeneous nucleation, disentanglement occurs via forming folds from locally unentangled segments and continues in postcrystallization processes (slow reorganization), in particular, during annealing. Re-entanglement processes after melting are slow and can lead to memory effects in heating-recooling protocols such as self-seeding.