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基于蒸发控制的聚合物溶液在基底上滴落延伸流变学。

Evaporation-controlled dripping-onto-substrate (DoS) extensional rheology of viscoelastic polymer solutions.

机构信息

Department of Chemical Engineering and Materials Science, University of Minnesota, Minneapolis, 55455, USA.

出版信息

Sci Rep. 2022 Mar 18;12(1):4697. doi: 10.1038/s41598-022-08448-x.

DOI:10.1038/s41598-022-08448-x
PMID:35304499
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC8933544/
Abstract

Extensional flow properties of polymer solutions in volatile solvents govern many industrially-relevant coating processes, but existing instrumentation lacks the environment necessary to control evaporation. To mitigate evaporation during dripping-onto-substrate (DoS) extensional rheology measurements, we developed a chamber to enclose the sample in an environment saturated with solvent vapor. We validated the evaporation-controlled DoS device by measuring a model high molecular weight polyethylene oxide (PEO) in various organic solvents both inside and outside of the chamber. Evaporation substantially increased the extensional relaxation time [Formula: see text] for PEO in volatile solvents like dichloromethane and chloroform. PEO/chloroform solutions displayed an over 20-fold increase in [Formula: see text] due to the formation of an evaporation-induced surface film; evaporation studies confirmed surface features and skin formation reminiscent of buckling instabilities commonly observed in drying polymer solutions. Finally, the relaxation times of semi-dilute PEO/chloroform solutions were measured with environmental control, where [Formula: see text] scaled with concentration by the exponent [Formula: see text]. These measurements validate the evaporation-controlled DoS environment, and confirm that chloroform is a good solvent for PEO, with a Flory exponent of [Formula: see text]. Our results are the first to control evaporation during DoS extensional rheology, and provide guidelines establishing when environmental control is necessary to obtain accurate rheological parameters.

摘要

聚合物溶液在挥发性溶剂中的拉伸流动性质控制着许多工业相关的涂层工艺,但现有的仪器缺乏控制蒸发的必要环境。为了在滴涂到基底(DoS)拉伸流变学测量过程中减轻蒸发,我们开发了一个腔室,将样品封闭在溶剂蒸气饱和的环境中。我们通过在腔室内外测量各种有机溶液中的模型高分子量聚乙烯氧化物(PEO),验证了蒸发控制的 DoS 装置的有效性。蒸发显著增加了 PEO 在挥发性溶剂如二氯甲烷和氯仿中的拉伸松弛时间[Formula: see text]。PEO/氯仿溶液由于形成蒸发诱导的表面膜,[Formula: see text]增加了 20 多倍;蒸发研究证实了类似于在干燥聚合物溶液中常见的失稳现象的表面特征和表皮形成。最后,在环境控制下测量了半稀 PEO/氯仿溶液的松弛时间,其中[Formula: see text]按浓度以指数[Formula: see text]缩放。这些测量验证了蒸发控制的 DoS 环境,并证实氯仿是 PEO 的良溶剂,具有 Flory 指数[Formula: see text]。我们的结果是首次在 DoS 拉伸流变学中控制蒸发,为确定何时需要环境控制以获得准确的流变学参数提供了指导。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4c4e/8933544/8237a3570d72/41598_2022_8448_Fig4_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4c4e/8933544/121d073c23b3/41598_2022_8448_Fig1_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4c4e/8933544/3a4c2fbf1650/41598_2022_8448_Fig2_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4c4e/8933544/b2f3e36debd1/41598_2022_8448_Fig3_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4c4e/8933544/8237a3570d72/41598_2022_8448_Fig4_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4c4e/8933544/121d073c23b3/41598_2022_8448_Fig1_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4c4e/8933544/3a4c2fbf1650/41598_2022_8448_Fig2_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4c4e/8933544/b2f3e36debd1/41598_2022_8448_Fig3_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4c4e/8933544/8237a3570d72/41598_2022_8448_Fig4_HTML.jpg

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本文引用的文献

1
Solvent Effects on the Elasticity of Electrospinnable Polymer Solutions.溶剂对可静电纺丝聚合物溶液弹性的影响
ACS Polym Au. 2021 Dec 28;2(2):108-117. doi: 10.1021/acspolymersau.1c00041. eCollection 2022 Apr 13.
2
Extensional Relaxation Times of Dilute, Aqueous Polymer Solutions.稀的聚合物水溶液的拉伸松弛时间
ACS Macro Lett. 2015 Jul 21;4(7):804-808. doi: 10.1021/acsmacrolett.5b00393. Epub 2015 Jul 13.
3
Small-volume extensional rheology of concentrated protein and protein-excipient solutions.高浓度蛋白和蛋白-赋形剂溶液的小体积拉伸流变学。
Soft Matter. 2021 Nov 3;17(42):9624-9635. doi: 10.1039/d1sm01253c.
4
Liquid Transfer for Viscoelastic Solutions.粘弹性溶液的液体转移
Langmuir. 2021 Aug 31;37(34):10348-10353. doi: 10.1021/acs.langmuir.1c01462. Epub 2021 Aug 18.
5
Measurement of relaxation times in extensional flow of weakly viscoelastic polymer solutions.弱粘弹性聚合物溶液在拉伸流动中弛豫时间的测量。
Rheol Acta. 2017;56(1):11-20. doi: 10.1007/s00397-016-0980-1. Epub 2016 Nov 19.
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Macromolecular relaxation, strain, and extensibility determine elastocapillary thinning and extensional viscosity of polymer solutions.高分子弛豫、应变和伸展性决定了聚合物溶液的弹毛细管变薄和拉伸黏度。
Proc Natl Acad Sci U S A. 2019 Apr 30;116(18):8766-8774. doi: 10.1073/pnas.1820277116. Epub 2019 Apr 12.
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Pinch-off dynamics and dripping-onto-substrate (DoS) rheometry of complex fluids.复杂流体的夹断动力学和滴落在基底上(DoS)流变学
Lab Chip. 2017 Jan 31;17(3):460-473. doi: 10.1039/c6lc01155a.
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