The effect of local chain stiffness on oligomer crystallization from a melt

20 May 2024, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


While the process by which a polymer crystal nucleates from the melt has been extensively studied via molecular simulation, differences in polymer models and simulated crystallization conditions have led to seemingly contradictory results. We make steps to resolve this controversy by computing low-temperature phase diagrams of oligomer melts using Wang-Landau Monte Carlo simulations. Two qualitatively different crystallization mechanisms are possible depending on the local bending stiffness potential. Polymers with a discrete bending potential crystallize via a single-step mechanism, whereas polymers with a continuous bending potential can crystallize via a two-step mechanism that includes an intermediate nematic phase. Other model differences can be quantitatively accounted for using an effective volume fraction and a temperature scaled by the bending stiffness. These results suggest that at least two universality classes of nucleation exist for melts and that local chain stiffness is a key determining factor in the mechanism of nucleation.


Polymer crystallization
Free energy methods
Wang Landau Monte Carlo
Primary nucleation
Phase behavior

Supplementary materials

Supplemental Material for “The effect of local chain stiffness on oligomer crystallization from a melt”
Parameterization of Soft Pair Potential Model, Effective Hard Bead Sizes at Finite Temperatures, Details of Persistence Length Calculations, Multiple Walker Scheme for WLMC Simulations, Thermal Profiles and Phase Diagrams of Model A and Finite Size Effects, Thermal Profiles and Phase Diagrams for Model B, Thermal Profiles for Model C, Effect of Softness of Beads on Phase Behavior


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