Rheological Scaling of Ionic-Liquid-Based Polyelectrolytes in Ionic Liquid Solutions

Matsumoto, Atsushi; Giudice, Francesco Del; Rotrattanadumrong, Rachapun; Shen, Amy Q.

doi:10.1021/acs.macromol.8b02544

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Rheological Scaling of Ionic-Liquid-Based Polyelectrolytes in Ionic Liquid Solutions

Atsushi Matsumoto, Francesco Del Giudice

, Rachapun Rotrattanadumrong, Amy Q. Shen

Macromolecules, Volume: 52, Issue: 7, Pages: 2759 - 2771

Swansea University Author: Francesco Del Giudice

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DOI (Published version): 10.1021/acs.macromol.8b02544

Abstract

Polymerized ionic liquids (PILs) are a special class of polyelectrolytes with ionic liquid (IL) species being covalently attached to the repeating unit. The rheological properties of PIL in IL solutions are strongly influenced by the electrostatic screening between IL and PIL chains. However, the ef...

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Published in:	Macromolecules
ISSN:	0024-9297 1520-5835
Published:	2019
Online Access:	Check full text
URI:	https://cronfa.swan.ac.uk/Record/cronfa49624
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spelling	2021-01-15T10:34:07.8367954 v2 49624 2019-03-19 Rheological Scaling of Ionic-Liquid-Based Polyelectrolytes in Ionic Liquid Solutions 742d483071479b44d7888e16166b1309 0000-0002-9414-6937 Francesco Del Giudice Francesco Del Giudice true false 2019-03-19 CHEG Polymerized ionic liquids (PILs) are a special class of polyelectrolytes with ionic liquid (IL) species being covalently attached to the repeating unit. The rheological properties of PIL in IL solutions are strongly influenced by the electrostatic screening between IL and PIL chains. However, the effect of IL electrostatic screening on the rheology of PIL in IL solutions remains elusive. To address this challenging yet important question, we conduct detailed rheological characterization of a model system containing a PIL [PC4-TFSI: poly(1-butyl-3-vinylimidazolium bis(trifluoromethanesulfonyl)imide)] in a mixture of a salt-free solvent (DMF: dimethylformamide) and an IL [Bmim-TFSI: 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide] solution, with low to high IL concentrations, while spanning dilute and semidilute polymer regimes. We compare the specific viscosity ηsp and the longest relaxation time λ of PILs measured at various Bmim-TFSI concentrations from 0 M (pure DMF) to 3.42 M (pure Bmim-TFSI) with the scaling predictions for ordinary polyelectrolyte solutions. We find good agreement at low IL concentrations but significant deviations at higher IL concentrations. We capture this discrepancy by proposing and validating a modified scaling law accounting for the modified screening length in concentrated solutions of ordinary salts. We propose that extended PIL chains initially shrink due to the charge screening effect at low IL concentrations but revert to expanded configuration at higher IL concentrations due to the charge underscreening effect when the screening length increases with increasing IL concentrations. Our results shed new insights on the conformation of PIL in IL solutions and, for the first time, provide a valid reference for the study of general polyelectrolyte solutions at high salt concentrations, where the Debye–Hückel theory is no longer valid. Journal Article Macromolecules 52 7 2759 2771 0024-9297 1520-5835 9 4 2019 2019-04-09 10.1021/acs.macromol.8b02544 COLLEGE NANME Chemical Engineering COLLEGE CODE CHEG Swansea University 2021-01-15T10:34:07.8367954 2019-03-19T12:02:17.7167350 Faculty of Science and Engineering School of Engineering and Applied Sciences - Chemical Engineering Atsushi Matsumoto 1 Francesco Del Giudice 0000-0002-9414-6937 2 Rachapun Rotrattanadumrong 3 Amy Q. Shen 4 49624__17782__b9ac33ac3c9d4f77a4a8bc8616f3bb33.pdf 49624.pdf 2020-07-24T11:35:50.5888606 Output 2906669 application/pdf Version of Record true This is an open access article published under an ACS AuthorChoice License. true eng http://pubs.acs.org/page/policy/authorchoice_termsofuse.html
title	Rheological Scaling of Ionic-Liquid-Based Polyelectrolytes in Ionic Liquid Solutions
spellingShingle	Rheological Scaling of Ionic-Liquid-Based Polyelectrolytes in Ionic Liquid Solutions Francesco Del Giudice
title_short	Rheological Scaling of Ionic-Liquid-Based Polyelectrolytes in Ionic Liquid Solutions
title_full	Rheological Scaling of Ionic-Liquid-Based Polyelectrolytes in Ionic Liquid Solutions
title_fullStr	Rheological Scaling of Ionic-Liquid-Based Polyelectrolytes in Ionic Liquid Solutions
title_full_unstemmed	Rheological Scaling of Ionic-Liquid-Based Polyelectrolytes in Ionic Liquid Solutions
title_sort	Rheological Scaling of Ionic-Liquid-Based Polyelectrolytes in Ionic Liquid Solutions
author_id_str_mv	742d483071479b44d7888e16166b1309
author_id_fullname_str_mv	742d483071479b44d7888e16166b1309_***_Francesco Del Giudice
author	Francesco Del Giudice
author2	Atsushi Matsumoto Francesco Del Giudice Rachapun Rotrattanadumrong Amy Q. Shen
format	Journal article
container_title	Macromolecules
container_volume	52
container_issue	7
container_start_page	2759
publishDate	2019
institution	Swansea University
issn	0024-9297 1520-5835
doi_str_mv	10.1021/acs.macromol.8b02544
college_str	Faculty of Science and Engineering
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department_str	School of Engineering and Applied Sciences - Chemical Engineering{{{_:::_}}}Faculty of Science and Engineering{{{_:::_}}}School of Engineering and Applied Sciences - Chemical Engineering
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description	Polymerized ionic liquids (PILs) are a special class of polyelectrolytes with ionic liquid (IL) species being covalently attached to the repeating unit. The rheological properties of PIL in IL solutions are strongly influenced by the electrostatic screening between IL and PIL chains. However, the effect of IL electrostatic screening on the rheology of PIL in IL solutions remains elusive. To address this challenging yet important question, we conduct detailed rheological characterization of a model system containing a PIL [PC4-TFSI: poly(1-butyl-3-vinylimidazolium bis(trifluoromethanesulfonyl)imide)] in a mixture of a salt-free solvent (DMF: dimethylformamide) and an IL [Bmim-TFSI: 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide] solution, with low to high IL concentrations, while spanning dilute and semidilute polymer regimes. We compare the specific viscosity ηsp and the longest relaxation time λ of PILs measured at various Bmim-TFSI concentrations from 0 M (pure DMF) to 3.42 M (pure Bmim-TFSI) with the scaling predictions for ordinary polyelectrolyte solutions. We find good agreement at low IL concentrations but significant deviations at higher IL concentrations. We capture this discrepancy by proposing and validating a modified scaling law accounting for the modified screening length in concentrated solutions of ordinary salts. We propose that extended PIL chains initially shrink due to the charge screening effect at low IL concentrations but revert to expanded configuration at higher IL concentrations due to the charge underscreening effect when the screening length increases with increasing IL concentrations. Our results shed new insights on the conformation of PIL in IL solutions and, for the first time, provide a valid reference for the study of general polyelectrolyte solutions at high salt concentrations, where the Debye–Hückel theory is no longer valid.
published_date	2019-04-09T04:00:47Z
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score	11.037253

Rheological Scaling of Ionic-Liquid-Based Polyelectrolytes in Ionic Liquid Solutions

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