Using Monte Carlo simulations, we studied the effect of bidispersity on the dynamics of polymer films capped between two neutral walls, where we chose three representative compositions for bidispersed polymer films. Our results demonstrate that the characteristic entanglement length is an important parameter to clarify the effect of the bidispersity on the dynamics of polymer films. For the short chains, shorter than the characteristic entanglement length, the average number of near-neighboring particles increases with the decrease of the film thickness and limits the diffusivity of the short chains, which is independent of the film compositions. However, the dynamics of the long chains, of which is above the characteristic entanglement length, is determined by the film’s composition. In our previous paper, we inferred from the structures and entanglements of the bidisperse system with short and long chains that the constraint release contributes significantly to the relaxation mechanism of long chains. By calculating the self-diffusion coefficient of long chains, we confirmed this prediction that, with a lower weight fraction of long chains, the self-diffusion coefficient of long chains decreases slowly with the decrease of the film thickness, which is similar to that of short chains. With a higher weight fraction of long chains, the competition between the disentanglement and the increased in the local degree of confinement which resulted in the self-diffusion coefficient of long chains varying non-monotonically with the film thickness. Furthermore, for the bidisperse system with long and long chains, the diffusivity of long chains was not affected by the constraint release, which varied nonmonotonically with the decrease of the film thickness due to the competition between the disentanglement and the enhanced confinement. Herein, compared with the previous work, we completely clarified the relationship between the structures and dynamics for three representative compositions of bidisperse polymer films, which contains all possible cases for bidisperse systems. Our work not only establishes a unified understanding of the dependency of dynamics on the bidispersity of polymer films, but also helps to understand the case of polydispersity, which can provide computational supports for various applications for polymer films.
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