Anomalous Structural Changes and Gas Transport Properties in Ultrathin Films of Polymers of Intrinsic Microporosity

IF 5.1 1区化学 Q1 POLYMER SCIENCE

Macromolecules Pub Date : 2024-11-26 DOI:10.1021/acs.macromol.4c01712

Tae Hoon Lee, Jun Kyu Jang, Byung Kwan Lee, Wan-Ni Wu, Zachary P. Smith, Ho Bum Park

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Abstract

Solution-processable polymers of intrinsic microporosity (PIMs) have been explored as a next-generation material for the synthesis of CO₂ capture membranes. Herein, we highlight the critical need for understanding the transition from bulk PIM materials (50–150 μm) to their thin films (<3 μm). 6FDA-DAM and PIM-1 were chosen as archetypal PIMs, and their thin-film composite (TFC) membranes were prepared via a spin-coating method. Interestingly, the PIM-based TFC membranes always exhibited lower gas permeabilities compared to the model predictions based on their bulk films. Moreover, such deviations became more pronounced by reducing the selective layer thickness to several tens of nanometers. Two-dimensional grazing-incidence wide-angle X-ray scattering (2D GIWAXS) analyses reveal that the PIM thin films significantly differ from those of bulk films by showing thickness-dependent anisotropic microstructures potentially due to fast solvent evaporation and confinement effects during film preparation. Also, physical aging significantly affects the microstructures and the CO₂ capture performance of the aged PIM films, which should be decoupled from the effects of film thickness.

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具有内在微孔的聚合物超薄薄膜的异常结构变化和气体传输特性

具有固有微孔的可溶液加工聚合物（PIMs）已被视为合成二氧化碳捕集膜的下一代材料。在此，我们强调了解从块状 PIM 材料（50-150 μm）到薄膜（3 μm）过渡的关键需求。我们选择了 6FDA-DAM 和 PIM-1 作为 PIM 的原型，并通过旋涂法制备了它们的薄膜复合膜 (TFC)。有趣的是，与基于其体膜的模型预测相比，基于 PIM 的 TFC 膜总是表现出较低的气体渗透率。此外，当选择层厚度减小到几十纳米时，这种偏差会变得更加明显。二维掠入射广角 X 射线散射（2D GIWAXS）分析表明，PIM 薄膜与块状薄膜存在显著差异，可能是由于制备薄膜过程中溶剂的快速蒸发和限制效应，薄膜呈现出与厚度相关的各向异性微结构。此外，物理老化也会对老化 PIM 薄膜的微观结构和二氧化碳捕获性能产生重大影响，这种影响应与薄膜厚度的影响相分离。

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.