Coarse-grained molecular dynamics simulations on self-assembly of polystyrene-block-poly(2-vinylpyridine)

doi:10.1016/j.cjche.2025.02.032

中国化学工程学报 ›› 2025, Vol. 83 ›› Issue (7): 15-25.DOI: 10.1016/j.cjche.2025.02.032

Coarse-grained molecular dynamics simulations on self-assembly of polystyrene-block-poly(2-vinylpyridine)

Daiwen Li¹, Shoutian Qiu², Gan Liu¹, Ming Liu¹, Mingjie Wei¹, Shipeng Sun¹, Weihong Xing¹, Xiaohua Lu¹, Yong Wang^1,3

1 State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, Nanjing 211816, China;
2 College of Materials Science and Engineering, State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, Nanjing 211816, China;
3 School of Energy and Environment, Southeast University, Nanjing 210096, China

收稿日期:2024-11-02 修回日期:2025-01-01 接受日期:2025-02-19 出版日期:2025-07-28 发布日期:2025-07-28
通讯作者: Mingjie Wei,E-mail:mj.wei@njtech.edu.cn
基金资助:
This work was financially supported by the National Natural Science Foundation of China (22438005, 22108117). The authors also thank the High Performance Computing Centre of Nanjing Tech University for supporting the computational resources.

Coarse-grained molecular dynamics simulations on self-assembly of polystyrene-block-poly(2-vinylpyridine)

Daiwen Li¹, Shoutian Qiu², Gan Liu¹, Ming Liu¹, Mingjie Wei¹, Shipeng Sun¹, Weihong Xing¹, Xiaohua Lu¹, Yong Wang^1,3

1 State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, Nanjing 211816, China;
2 College of Materials Science and Engineering, State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, Nanjing 211816, China;
3 School of Energy and Environment, Southeast University, Nanjing 210096, China

Received:2024-11-02 Revised:2025-01-01 Accepted:2025-02-19 Online:2025-07-28 Published:2025-07-28
Contact: Mingjie Wei,E-mail:mj.wei@njtech.edu.cn
Supported by:
This work was financially supported by the National Natural Science Foundation of China (22438005, 22108117). The authors also thank the High Performance Computing Centre of Nanjing Tech University for supporting the computational resources.

摘要/Abstract

摘要： Self-assembly of block copolymers (BCPs) is highly intricate and is adsorbing extensive experimental and simulation efforts to reveal it for maximizing structural order and device performances. The coarse-grained (CG) molecular dynamics (MD) simulation offers a microscopic angle to view the self-assembly of BCPs. Although some molecular details are sacrificed during CG processes, this method exhibits remarkable computational efficiency. In this study, a comprehensive CG model for polystyrene-block-poly(2- vinylpyridine), PS-b-P2VP, one of the most extensively studied BCPs for its high Flory-Huggins interaction parameter, is constructed, with parameters optimized using target values derived from all-atom MD simulations. The CG model precisely coincides with various classical self-assembling morphologies observed in experimental studies, matching the theoretical phase diagrams. Moreover, the conformational asymmetry of the experimental phase diagram is also clearly revealed by our simulation results, and the phase boundaries obtained from simulations are highly consistent with experimental results. The CG model is expected to extend to simulate the self-assembly behaviors of other BCPs in addition to PS-b-P2VP, thus increasing understanding of the microphase separation of BCPs from the molecular level.

关键词: Block copolymers, Self-assembly, Martini force field, Polymers, Computer simulation, Molecular simulation

Abstract: Self-assembly of block copolymers (BCPs) is highly intricate and is adsorbing extensive experimental and simulation efforts to reveal it for maximizing structural order and device performances. The coarse-grained (CG) molecular dynamics (MD) simulation offers a microscopic angle to view the self-assembly of BCPs. Although some molecular details are sacrificed during CG processes, this method exhibits remarkable computational efficiency. In this study, a comprehensive CG model for polystyrene-block-poly(2- vinylpyridine), PS-b-P2VP, one of the most extensively studied BCPs for its high Flory-Huggins interaction parameter, is constructed, with parameters optimized using target values derived from all-atom MD simulations. The CG model precisely coincides with various classical self-assembling morphologies observed in experimental studies, matching the theoretical phase diagrams. Moreover, the conformational asymmetry of the experimental phase diagram is also clearly revealed by our simulation results, and the phase boundaries obtained from simulations are highly consistent with experimental results. The CG model is expected to extend to simulate the self-assembly behaviors of other BCPs in addition to PS-b-P2VP, thus increasing understanding of the microphase separation of BCPs from the molecular level.

Key words: Block copolymers, Self-assembly, Martini force field, Polymers, Computer simulation, Molecular simulation

Daiwen Li, Shoutian Qiu, Gan Liu, Ming Liu, Mingjie Wei, Shipeng Sun, Weihong Xing, Xiaohua Lu, Yong Wang. Coarse-grained molecular dynamics simulations on self-assembly of polystyrene-block-poly(2-vinylpyridine)[J]. 中国化学工程学报, 2025, 83(7): 15-25.

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Coarse-grained molecular dynamics simulations on self-assembly of polystyrene-block-poly(2-vinylpyridine)

Coarse-grained molecular dynamics simulations on self-assembly of polystyrene-block-poly(2-vinylpyridine)

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