An accelerated united-atom molecular dynamics simulation on the fast crystallization of ring polyethylene melts

K Hagita and S Fujiwara and N Iwaoka, JOURNAL OF CHEMICAL PHYSICS, 150, 074901 (2019).

DOI: 10.1063/1.5080332

To investigate crystallinities based on trans-structures, we determined the differences in the crystallization properties of ring and linear polymers by performing united-atom-model molecular dynamics (MD) simulations of homogeneous polyethylene melts of equal length, N, which refers to the number of monomers per chain. Modified parameters based on the DREIDING force field for the CH2 units were used in order to accelerate the crystallization process. To detect polymer crystallization, we introduced some local-order parameters that relate to trans-segments in addition to common crystallinities using neighboring bond orders. Through quenching MD simulations at 5 K/ns, we roughly determined temperature thresholds, T-th, at which crystallization is observed although it was hard to determine the precise T-th as observed in the laboratory time frame with the present computing resources. When N was relatively small (100 and 200), T-th was determined to be 320 and 350 K for the linear- and ring-polyethylene melts, respectively, while T-th was found to be 330 and 350 K, respectively, when N was 1000. Having confirmed that the crystallization of a ring-polyethylene melt occurs faster than that of the analogous linear melt, we conclude that the trans-segment-based crystallinities are effective for the analysis of local crystal behavior. Published under license by AIP Publishing.

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