Disentangling and Lamellar Thickening of Linear Polymers during Crystallization: Simulation of Bimodal and Unimodal Molecular Weight Distribution Systems

ZQ Zhaio and C Fusco and J Morthomas and M Perez and O Lame, ACS NANO, 13, 11310-11319 (2019).

DOI: 10.1021/acsnano.9b04459

We have performed coarse-grained molecular dynamics simulations to study the isothermal crystallization of bimodal and unimodal molecular weight distribution (MWD) polymers with equivalent average molecular weight (M-w). By using primitive path analysis, we can monitor the entanglement evolution during the process of crystallization. We have discovered a quantitative correlation between the degree of disentanglement and crystallinity, indicating that chain disentanglement permits the process of crystallization. In addition, the crystalline stem length also displays a linear relation with the degree of disentanglement at different temperatures. Based on the observation in our simulations, we can build a scenario of the whole process of chain disentangling and lamellar thickening on the basis of chain sliding diffusion. Furthermore, we have enough evidence to infer that the temperature dependence of crystalline stem length is basically a result of temperature dependence of chain sliding diffusion. Our observations are also in agreement with Hikosaka's sliding diffusion theory. Compared to the unimodal system, the disentanglement degree of the bimodal system is more delayed than its crystallinity due to the slower chain sliding of the long-chain component; the bimodal system reaches a larger crystalline stem length at all temperatures due to the promotion of higher chain sliding mobility of the short-chain component.

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