Competition of Composition Fluctuation Modes in Weakly Segregated Salt-doped Symmetric Diblock Copolymers

Yuan-Xin Zhou; Xian Kong

doi:10.1007/s10118-024-3145-1

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Competition of Composition Fluctuation Modes in Weakly Segregated Salt-doped Symmetric Diblock Copolymers

RESEARCH ARTICLE | Updated：2024-08-27

- Competition of Composition Fluctuation Modes in Weakly Segregated Salt-doped Symmetric Diblock Copolymers
- Competition of Composition Fluctuation Modes in Weakly Segregated Salt-doped Symmetric Diblock Copolymers
- 高分子科学（英文版） 2024年42卷第9期页码：1375-1385
- Affiliations：
  
  a.South China Advanced Institute for Soft Matter Science and Technology, School of Emergent Soft Matter, South China University of Technology, Guangzhou 510640, China
  b.Guangdong Provincial Key Laboratory of Functional and Intelligent Hybrid Materials and Devices, South China University of Technology, Guangzhou 510640, China
- Author bio：
  
  xk@scut.edu.cn
- Funds：
  
  This work was financially supported by the Major Research Plan of the National Natural Science Foundation of China (No. 92372104), Guangdong Basic and Applied Basic Research Foundation (No. 2022A1515110016), the Recruitment Program of Guangdong (No. 2016ZT06C322), and TCL Science and Technology Innovation Fund.;Electronic supplementary information (ESI) is available free of charge in the online version of this article at http://doi.org/10.1007/s10118-024-3145-1.
- DOI：10.1007/s10118-024-3145-1
  中图分类号：
- 收稿：2024-03-07，
  
  修回：2024-04-11，
  
  录用：2024-04-12，
  
  网络首发：2024-06-06，
  
  纸质出版：2024-09-01
- Accepted：
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Zhou, Y. X.; Kong, X. Competition of composition fluctuation modes in weakly segregated salt-doped symmetric diblock copolymers. Chinese J. Polym. Sci. 2024, 42, 1375–1385

Yuan-Xin Zhou, Xian Kong. Competition of Composition Fluctuation Modes in Weakly Segregated Salt-doped Symmetric Diblock Copolymers[J]. Chinese Journal of Polymer Science, 2024, 42(9): 1375-1385.
Zhou, Y. X.; Kong, X. Competition of composition fluctuation modes in weakly segregated salt-doped symmetric diblock copolymers. Chinese J. Polym. Sci. 2024, 42, 1375–1385 DOI： 10.1007/s10118-024-3145-1.

Yuan-Xin Zhou, Xian Kong. Competition of Composition Fluctuation Modes in Weakly Segregated Salt-doped Symmetric Diblock Copolymers[J]. Chinese Journal of Polymer Science, 2024, 42(9): 1375-1385. DOI： 10.1007/s10118-024-3145-1.

摘要

Investigating the phase separation of salt-doped diblock copolymers

this study reveals the significant role of charged species in modulating phase behavior. Across various wave numbers

the phase separation exhibits a transition between the polymer-modulated and salt-out-modulated modes. These findings provide substantial guidance for precise nanostructure fabrication.

Abstract

Salt-doped block copolymers have widespread applications in batteries

fuel cells

semiconductors

and various industries

where their properties crucially depend on phase separation behavior. Traditionally

investigations into salt-doped diblock copolymers have predominantly focused on microphase separation

overlooking the segregation between ionic and polymeric species. This study employs weak segregation theory to explore the interplay between phase separation dominated by the polymer-modulated mode and the salt-out-modulated mode

corresponding to microscopic and macroscopic phase separations

respectively. By comparing diblock copolymers doped with salts to those doped with neutral solvents

we elucidate the significant role of charged species in modulating phase behavior. The phase separation mode exhibits a transition between the polymer-modulated and salt-out-modulated modes at different wavenumbers. In systems doped with neutral solvents

this transition is stepwise

while in salt-ion-doped systems

it is continuous. With a sufficiently large Flory-Huggins parameter between ions and polymers

the salt-out-modulated mode becomes dominant

promoting macrophase separation. Due to the solvation effect of salt ions

salt-doped systems are more inclined to undergo microphase separation. Furthermore

we explore factors influencing the critical wavenumber of phase separation

including doping level and the Flory-Huggins parameters between two blocks and between ions and polymeric species. Our findings reveal that in a neutral solvent environment

these factors alter only the boundary between micro- and macro-phase separations

leaving the critical wavenumber unchanged in microphase separation cases. However

in a salt-doped environment

the critical wavenumber of microphase separation varies with these parameters. This provides valuable insights into the pivotal role of electrostatics in the phase separation of salt-doped block copolymers.

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