Quantitative Insights into Pressure-Responsive Phase Behavior in Diblock Copolymers

IF 5.1 1区化学 Q1 POLYMER SCIENCE

Macromolecules Pub Date : 2025-03-02 DOI:10.1021/acs.macromol.4c02253

Hiroki Degaki, Ikuo Taniguchi, Shigeru Deguchi, Tsuyoshi Koga

引用次数: 0

Abstract

The pressure-responsive phase behavior of block copolymers, which is crucial for energy-efficient processing of certain polymeric materials, is systematically studied using a compressible self-consistent field theory based on a simple lattice vacancy model. To date, predictions of the phase behavior have been based mainly on qualitative assessments. In this study, we quantitatively show that large differences in the self-interaction energy between blocks lead to disordering with increasing pressure, while small differences lead to ordering. We discuss the molecular mechanisms underlying the phase behavior with a focus on voids, which account for the compressibility. The results from our theory agrees with the effective Flory–Huggins interaction parameter calculated by the compressible random phase approximation theory. Additionally, extending the theory to multicomponent systems, we investigate the effect of gas absorption on phase behavior, focusing on the balance of interaction parameters. Our results predict that gas absorption enhances pressure-induced ordering.

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利用基于简单晶格空位模型的可压缩自洽场理论，系统地研究了嵌段共聚物的压力响应相行为，这对于某些聚合物材料的节能加工至关重要。迄今为止，对相行为的预测主要基于定性评估。在本研究中，我们定量地表明，随着压力的增加，块体间自相互作用能的巨大差异会导致无序化，而微小差异则会导致有序化。我们讨论了相行为的分子机制，重点是空隙，空隙是可压缩性的原因。我们的理论结果与可压缩随机相近似理论计算出的有效 Flory-Huggins 相互作用参数一致。此外，我们将理论扩展到多组分系统，研究了气体吸收对相行为的影响，重点是相互作用参数的平衡。我们的结果预测，气体吸收会增强压力诱导的有序性。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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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.