Nonmonotonic Impact of Statistical Copolymer Composition on the Kinetics of Capillary Rise Infiltration

IF 5.1 1区化学 Q1 POLYMER SCIENCE Macromolecules Pub Date : 2024-10-24 DOI:10.1021/acs.macromol.4c01708

Tae-Young Heo, Théophile Ienn, Julien Bernard, Robert A. Riggleman, Daeyeon Lee

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Abstract

Infiltration dynamics of poly(styrene-stat-2-vinylpyridine) (PS-stat-P2VP) statistical copolymers (StCPs) undergoing capillary rise infiltration into the interstices of silica nanoparticle (SiO₂ NP) packings are investigated by in situ spectroscopic ellipsometry with varying ratios of strongly interacting 2-vinylpyridine (2VP) and weakly interacting styrene (S) repeat units. As the fraction of 2VP (f_P2VP) increases, a nonmonotonic dependence is observed in the time required to fully fill the interstices of the SiO₂ NP packings (t_inf) and the effective viscosity (η_eff). To understand the mechanism behind the nonmonotonic trend in infiltration dynamics, polymer properties such as zero-shear viscosity (η₀) and glass transition temperature (T_g) are considered; however, these factors fail to explain the trend. When the strong interactions between 2VP and SiO₂ are suppressed by modifying the surface of SiO₂ NPs with the epoxide group, the infiltration dynamics no longer show strong dependence on f_P2VP. This result indicates the important role played by the 2VP unit in the anomalous slowdown observed in StCPs, possibly by controlling its conformation on the pore surface and the interactions between the surface-adsorbed chains and chains that are translated through the pores.

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统计共聚物成分对毛细管上升渗透动力学的非单调影响

通过原位光谱椭偏仪研究了聚苯乙烯-苯乙烯-2-吡啶（PS-stat-P2VP）统计共聚物（StCPs）在二氧化硅纳米粒子（SiO2 NP）填料的间隙中进行毛细管上升渗透时的渗透动力学，2-乙烯基吡啶（2VP）强相互作用和苯乙烯（S）弱相互作用重复单元的比例各不相同。随着 2VP 部分（fP2VP）的增加，完全填充 SiO2 NP 填料间隙所需的时间（tinf）和有效粘度（ηeff）出现了非单调依赖性。为了了解渗透动力学非单调趋势背后的机制，我们考虑了零剪切粘度 (η0) 和玻璃化转变温度 (Tg) 等聚合物特性；然而，这些因素无法解释这一趋势。当通过环氧基团修饰 SiO2 NPs 表面来抑制 2VP 与 SiO2 之间的强相互作用时，渗透动力学不再显示出对 fP2VP 的强烈依赖性。这一结果表明，2VP 单元在 StCPs 中观察到的异常减速中发挥了重要作用，可能是通过控制其在孔隙表面的构象以及表面吸附链与通过孔隙平移的链之间的相互作用。

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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.