Polymer–Wall Interactions Slow Infiltration Dynamics in Bicontinuous, Nanoporous Structures

IF 5.2 1区化学 Q1 POLYMER SCIENCE

Macromolecules Pub Date : 2025-04-15 DOI:10.1021/acs.macromol.4c02326

Weiwei Kong, Anastasia Neuman, Laetitia Moore, Daeyeon Lee, Robert A. Riggleman, Russell J. Composto

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Abstract

Polymer infiltration is studied in a bicontinuous nanoporous gold (NPG) scaffold. For poly(2-vinylpyridine) (P2VP) with molecular weights (M_w) ranging from 51k to 940k Da, infiltration is investigated in an NPG with a fixed pore radius (R_p = 34 nm) under moderate confinement (Γ = R_g/R_p) 0.18 to 0.78. The time for 80% infiltration (τ_80%) scales as M_w^1.43, similar to PS, but weaker than the bulk behavior. Infiltration of P2VP is slower than PS due to stronger P2VP–wall interactions resulting in a physisorbed P2VP layer. This interpretation is supported by the similar scaling of τ_80% for P2VP and PS, as well as molecular dynamics (MD) simulations. Simulations show that infiltration time scales as M_w^1.4 and that infiltration slows as the polymer–wall attraction increases. As M_w increases, the effective viscosity transitions from greater than to less than the bulk viscosity due to pore narrowing and a reduction in entanglement density. These studies provide new insight into polymer behavior under confinement and a new route for preparing nanocomposites at high filler loadings.

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聚合物-壁相互作用在双连续纳米多孔结构中的缓慢渗透动力学

研究了聚合物在双连续纳米孔金（NPG）支架中的渗透。对于分子量（Mw）在51k ~ 940k Da之间的聚（2-乙烯基吡啶）（P2VP），在中等约束（Γ = Rg/Rp） 0.18 ~ 0.78下，在固定孔径半径（Rp = 34 nm）的NPG中进行了渗透研究。80%入渗时间（τ80%）的尺度为Mw1.43，与PS相似，但弱于体行为。P2VP的渗透速度比PS慢，这是由于P2VP与壁的相互作用更强，导致P2VP层被物理吸附。这一解释得到了P2VP和PS相似的τ80%标度以及分子动力学（MD）模拟的支持。模拟结果表明，渗透时间尺度为Mw1.4，随着聚合物壁吸引力的增加，渗透速度减慢。随着Mw的增加，由于孔隙缩小和缠结密度的降低，有效粘度从大于小于体粘度转变为小于体粘度。这些研究为聚合物在约束条件下的行为提供了新的见解，并为制备高填料负载的纳米复合材料提供了新的途径。

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.