Atomistic simulation of crystallization of a polyethylene melt in steady uniaxial extension

We present simulation results of flow-induced crystallization of a dense polymeric liquid subjected to a strong uniaxial elongational flow using a rigorous nonequilibrium Monte Carlo method. A distinct transition between the liquid and the crystalline phases occurred at critical values of flow strength, with an abrupt, discontinuous transition of the overall chain conformation. The flow-induced crystalline phase matched quantitatively the experimental X-ray diffraction data of the real crystals remarkably well, including the sharp Bragg peaks at small wavenumbers, k < 1.5 Å−1, indicating the existence of a global long-range ordering. We also found that the enthalpy change (ΔH = 225 J/g) during the phase transition was quantitatively very similar to the experimental heat of fusion (276 J/g) of polyethylene crystals under quiescent conditions. Furthermore, a detailed analysis of the configuration-based temperature provided a sound microscopic physical origin for the effective enhancement of the crystallization (or melting) temperature that has been observed in experiments. Simulation results also allow for the deduction of potential nonequilibrium expressions for thermodynamic quantities, such as temperature and heat capacity.