解缠效应和界面效应之间的竞争决定了缠结超薄聚苯乙烯薄膜的链松弛动力学

IF 5.1 1区化学 Q1 POLYMER SCIENCE

Macromolecules Pub Date : 2024-10-10 DOI:10.1021/acs.macromol.4c01788

Fengliang Wang, Sijia Li, Hongkai Guo, Jiaxiang Li, Jianquan Xu, Tongfei Shi, Xinping Wang

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引用次数: 0

摘要

聚合物-基底界面可改变封闭聚合物薄膜的动力学。然而，由于难以测量，界面相互作用对链动力学的影响尚不明确。在此，我们研究了基底-聚合物相互作用对封闭缠结聚苯乙烯（PS）薄膜链弛豫动力学的影响。在界面能（γs-p）分别为 44.9 和 2.3 mJ m-2 的基底上，聚苯乙烯薄膜的链松弛时间分别随着薄膜厚度的减小而单调减少和增加。基底上 PS 薄膜的链松弛时间（γs-p 为 33.5 至 10.6 mJ m-2）随着薄膜厚度的减小而先减小后增大，并且这种趋势随着 γs-p 的减小而单调增加。我们提出了一个描述这种特殊弛豫行为的新模型，并用它来阐明 PS 链的非单调链弛豫动力学的起源，这归因于解缠效应和基底效应之间的竞争。前者加速了 PS 薄膜的链松弛动力学，而后者则延缓了链松弛动力学。PS 自由表面对弛豫动力学的影响随着 γs-p 的减小而迅速减弱。蒙特卡罗模拟进一步证实了这一现象。这些结果为阐明界面相互作用影响密闭聚合物薄膜链松弛的机理提供了新的视角。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Competition between Disentanglement Effect and Interfacial Effect Determines the Chain Relaxation Dynamics of Entangled Ultrathin Polystyrene Films

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Competition between Disentanglement Effect and Interfacial Effect Determines the Chain Relaxation Dynamics of Entangled Ultrathin Polystyrene Films

Polymer–substrate interfaces can alter the dynamics of a confined polymer film. However, the influence of interfacial interactions on chain dynamics is unclear owing to difficulty in measurement. Herein, the effects of substrate–polymer interactions on the chain relaxation dynamics of confined-entangled polystyrene (PS) thin films were investigated. The chain relaxation time of a PS film on substrates with interfacial energies (γ_s–p) of 44.9 and 2.3 mJ m^–2 monotonically decreased and increased, respectively, with a decrease in film thickness. The chain relaxation time of the PS film on substrates with γ_s–p ranging from 33.5 to 10.6 mJ m^–2 decreased and then increased with decreasing film thickness, and this trend become monotonically increasing with the decrease of γ_s–p. A new model describing this particular relaxation behavior is proposed and was used to elucidate the origin of the nonmonotonic chain relaxation dynamics of PS chains, which is attributed to the competition between disentanglement and substrate effects. The former accelerates while the latter retards the chain relaxation dynamics of the PS films. The impact of the PS free surface on relaxation dynamics decreases rapidly with the decrease of γ_s–p. This phenomenon was further confirmed via Monte Carlo simulations. These results provide a new perspective for elucidating the mechanism of interface interactions affecting chain relaxation in the confined polymer film.

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来源期刊

Macromolecules 工程技术-高分子科学

CiteScore

9.30

自引率

16.40%

发文量

942

审稿时长

2 months

期刊介绍： Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.