Scaling Behavior of Entanglement Dynamics in Polyelectrolyte Solutions: Insights from High-Frequency Rheometry

IF 5.2 Q1 POLYMER SCIENCE

ACS Macro Letters Pub Date : 2025-02-13 DOI:10.1021/acsmacrolett.4c0072210.1021/acsmacrolett.4c00722

Yahya Rharbi*,

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引用次数: 0

Abstract

Entanglement dynamics in polyelectrolyte solutions remain a challenging topic, particularly in capturing the entire dynamic spectrum, from single entanglement relaxation (τ_e) to reptation time (τ_rep), and aligning these observations with scaling predictions in the semidilute entangled (SE) and fully entangled (FE) neutral regimes. Using piezo compressional and classic rotational rheometry, we investigate the scaling behaviors of key viscoelastic properties over several decades of time scales in ten million Mw cationic polyacrylamide solutions. Specific viscosity (η_sp) and τ_rep scale as predicted within Fuoss, SE, and FE regimes, defining crossover concentrations between these regimes (C_e and C_D). More importantly, τ_e, the rubbery plateau width (τ_rep/τ_e), and the high-frequency modulus (G_e) scale as C^{–1.14±0.02}, C^1.25±0.07, and C^1.32±0.05, aligning with SE prediction in the early SE regime before transitioning to neutral scaling of C^–2.7±0.14, C^3.1±0.15, and C^2.35±0.07 at an intermediate concentration between C_e and C_D labeled C_D^e. These results indicate that electrostatic interactions affect single entanglements and reptation differently, leading to a transition to neutral behavior at C_D^e for the former and at C_D for the latter.

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聚电解质溶液中缠结动力学的标度行为：来自高频流变学的见解

多电解质溶液中的纠缠动力学仍然是一个具有挑战性的话题，特别是在捕获整个动态谱方面，从单纠缠弛豫（τe）到重复时间（τrep），并将这些观察结果与半稀释纠缠（SE）和完全纠缠（FE）中性状态下的标度预测相一致。利用压电压缩流变学和经典旋转流变学，我们研究了1000万Mw阳离子聚丙烯酰胺溶液中关键粘弹性性能在几十年时间尺度上的标度行为。比粘度（ηsp）和τrep标度在Fuoss， SE和FE体系中预测，定义了这些体系（Ce和CD）之间的交叉浓度。更重要的是，τe、弹性平台宽度（τrep/τe）和高频模量（Ge）尺度分别为C-1.14±0.02、C1.25±0.07和C1.32±0.05，与早期SE预测一致，然后在Ce和CD标记的CDe中间浓度过渡到C-2.7±0.14、C3.1±0.15和C2.35±0.07的中性尺度。这些结果表明，静电相互作用对单纠缠和重复的影响不同，导致前者在CDe和后者在CD中向中性行为过渡。

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来源期刊

ACS Macro Letters 化学-

CiteScore

10.40

自引率

3.40%

发文量

209

审稿时长

1 months

期刊介绍： ACS Macro Letters publishes research in all areas of contemporary soft matter science in which macromolecules play a key role, including nanotechnology, self-assembly, supramolecular chemistry, biomaterials, energy generation and storage, and renewable/sustainable materials. Submissions to ACS Macro Letters should justify clearly the rapid disclosure of the key elements of the study. The scope of the journal includes high-impact research of broad interest in all areas of polymer science and engineering, including cross-disciplinary research that interfaces with polymer science. With the launch of ACS Macro Letters, all Communications that were formerly published in Macromolecules and Biomacromolecules will be published as Letters in ACS Macro Letters.