Molecular dynamics simulation for polyethylene crystallization: Effect of long chain branches

Abstract

The influence of long branches on crystallization behavior has been studied by means of molecular dynamics simulations. Using two systems: polyethylene (PE) with long branches (LCB-PE) and PE without long branches (linear-PE) with the same molecular weight, we have examined the crystallization behavior of the two systems by molecular dynamics simulation. This paper explains the influence of long branches on the isothermal crystallization process and the non-isothermal crystallization process with similar initial interchain contact fraction (ICF) in terms of final ICF, crystal regions, crystallinity, concentration of tie chains and energy. It is found that the crystallization process is classified as two stages: the nucleation stage and the crystal growth stage. The existence of long branches is favorable for the first stage while unfavorable for the second stage. Knots that act as crystalline defects are excluded from the lamella, resulting in decreasing in regularity and crystallinity of molecular chains. From the perspective of potential energy and non-bond energy, LCB-PE has lower energy than linear-PE in the nucleation stage while the energy of linear-PE is lower than that of LCB-PE in the second stage. In short, the long branched chains inhibit the crystallization process.

Keywords

• molecular dynamics
• crystallization
• long branches
• nucleation
• tie chains