Concentration Regimes for Extensional Relaxation Times of Unentangled Polymer Solutions

Concentration Regimes for Extensional Relaxation Times of Unentangled Polymer Solutions
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非缠结聚合物溶液的拉伸弛豫时间的浓度范围

DOI:
10.1021/acs.macromol.3c00097
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发表时间:
2023
期刊:
影响因子:
5.5
通讯作者:
Conrad, Jacinta C.
Conrad, Jacinta C.
中科院分区:
化学1区
文献类型:
--
作者:
Soetrisno, Diego D.;Martínez Narváez, Carina D.;Sharma, Vivek;Conrad, Jacinta C.

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研究了不同分子量和分散度的聚丙烯酰胺(PAM)溶液的拉伸流动特性。最近的一项研究[Dinic和Sharma, macromolecular, 2020,53, 4821-4835]表明,当拉伸和卷曲聚合物链的阻力系数比为s/ c> 4.5时,线圈-拉伸迟滞控制了拉伸弛豫时间λ e随浓度的标度指数。在这里,我们通过改变PAM分子量分布来检验这一假设。浓度依赖性的标度指数λEism = 0.34 PAM解决方案与ςs / cς< 4.5 andm > 0.5 PAMςs / cς> 4.5解决方案。标度指数的增加归因于线圈拉伸滞后的存在,它屏蔽了拉伸流动下排除的体积相互作用。对于高度分散的溶液withĐ≈21,指数从0.67到1的转变发生在由重量平均分子量而不是粘度平均分子量得出的重叠浓度*上,突出了长链的作用。这些结果深入了解了聚合物尺寸分布在稀溶液和未纠缠的半稀溶液中随浓度变化的拉伸材料响应中的作用。
We study the extensional flow properties of polyacrylamide (PAM) solutions with various molecular weights and dispersities using a dripping-onto-substrate (DoS) protocol. A recent study [Dinic and Sharma,Macromolecules2020,53, 4821–4835] suggested that coil–stretch hysteresis, which occurs when the drag coefficient ratio of stretched and coiled polymer chains ςs/ςc> 4.5, controls the scaling exponent of the extensional relaxation time λEwith concentration. Here, we test this hypothesis by varying ςs/ςcthrough the PAM molecular weight distribution. The scaling exponent of the concentration dependence of λEism= 0.34 for PAM solutions with ςs/ςc< 4.5 andm> 0.5 for PAM solutions with ςs/ςc> 4.5. The increase in the scaling exponent is attributed to the presence of coil–stretch hysteresis, which screens the excluded volume interactions under extensional flow. For highly disperse solutions withĐ≈ 21, the transition from an exponent of 0.67 to 1 occurs at overlap concentrationc* derived from the weight-averaged molecular weight instead of viscosity-averaged molecular weight, highlighting the role of long chains. These results provide insight into the role of the polymer size distribution in the concentration-dependent extensional material response in dilute and unentangled semidilute solutions.
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