弱分离盐掺杂对称二嵌段共聚物中成分波动模式的竞争

IF 4.1 2区 化学 Q2 POLYMER SCIENCE Chinese Journal of Polymer Science Pub Date : 2024-06-06 DOI:10.1007/s10118-024-3145-1
Yuan-Xin Zhou, Xian Kong
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引用次数: 0

摘要

掺盐嵌段共聚物广泛应用于电池、燃料电池、半导体和各行各业,其特性主要取决于相分离行为。传统上,对掺盐嵌段共聚物的研究主要集中在微相分离方面,忽略了离子和聚合物之间的偏析。本研究采用弱偏析理论来探讨聚合物调制模式和盐出调制模式主导的相分离之间的相互作用,这两种模式分别对应于微观和宏观相分离。通过比较掺盐和掺中性溶剂的二嵌段共聚物,我们阐明了带电物种在调制相行为中的重要作用。相分离模式表现出聚合物调制模式和盐出调制模式之间在不同波数的过渡。在掺杂了中性溶剂的体系中,这种转变是阶梯式的,而在掺杂了盐离子的体系中,这种转变是连续的。当离子和聚合物之间的 Flory-Huggins 参数足够大时,盐出调制模式将成为主导模式,从而促进大相分离。由于盐离子的溶解效应,掺盐体系更倾向于发生微相分离。此外,我们还探讨了影响相分离临界波数的因素,包括掺杂水平和两个嵌段之间以及离子与聚合物之间的 Flory-Huggins 参数。我们的研究结果表明,在中性溶剂环境中,这些因素只改变了微相分离和大相分离之间的边界,使微相分离情况下的临界波数保持不变。然而,在掺盐环境中,微相分离的临界波数会随着这些参数的变化而变化。这为了解静电在掺盐嵌段共聚物相分离中的关键作用提供了宝贵的见解。
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Competition of Composition Fluctuation Modes in Weakly Segregated Salt-doped Symmetric Diblock Copolymers

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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来源期刊
Chinese Journal of Polymer Science
Chinese Journal of Polymer Science 化学-高分子科学
CiteScore
7.10
自引率
11.60%
发文量
218
审稿时长
6.0 months
期刊介绍: Chinese Journal of Polymer Science (CJPS) is a monthly journal published in English and sponsored by the Chinese Chemical Society and the Institute of Chemistry, Chinese Academy of Sciences. CJPS is edited by a distinguished Editorial Board headed by Professor Qi-Feng Zhou and supported by an International Advisory Board in which many famous active polymer scientists all over the world are included. The journal was first published in 1983 under the title Polymer Communications and has the current name since 1985. CJPS is a peer-reviewed journal dedicated to the timely publication of original research ideas and results in the field of polymer science. The issues may carry regular papers, rapid communications and notes as well as feature articles. As a leading polymer journal in China published in English, CJPS reflects the new achievements obtained in various laboratories of China, CJPS also includes papers submitted by scientists of different countries and regions outside of China, reflecting the international nature of the journal.
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