TY - JOUR
T1 - Rheological Scaling of Ionic-Liquid-Based Polyelectrolytes in Ionic Liquid Solutions
AU - Matsumoto, Atsushi
AU - Del Giudice, Francesco
AU - Rotrattanadumrong, Rachapun
AU - Shen, Amy Q.
N1 - Funding Information:
The authors thank the anonymous reviewers for their careful review of our manuscript and their insightful comments and suggestions. The authors thank Prof. John de Bruyn from the Department of Physics and Astronomy at the University of Western Ontario, Canada, for helpful suggestions and careful proofreading. The authors also thank Kang-Yu Chu and Ting-Chun Chou from Micro/Bio/Nanofluidics Unit at OIST for their help with developing a custom-made video tracking MATLAB code for our gravity-driven capillary viscometer analysis. The authors gratefully acknowledge the support of the Okinawa Institute of Science and Technology Graduate University with subsidy funding from the Cabinet Office, Government of Japan. A.Q.S. also acknowledges funding from the Japanese Society for the Promotion of Science [Grants-in-Aid for Scientific Research (C) Grant JP17K06173 and Grants-in-Aid for Scientific Research (B) Grant JP18H01135]. The authors also thank Dr Yoshiteru Iinuma from OIST for his help with the use of the inductively coupled plasma mass spectrometer.
Publisher Copyright:
© 2019 American Chemical Society.
PY - 2019/4/9
Y1 - 2019/4/9
N2 - 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 sp and the longest relaxation time 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.
AB - 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 sp and the longest relaxation time 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.
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U2 - 10.1021/acs.macromol.8b02544
DO - 10.1021/acs.macromol.8b02544
M3 - Article
AN - SCOPUS:85064226172
VL - 52
SP - 2759
EP - 2771
JO - Macromolecules
JF - Macromolecules
SN - 0024-9297
IS - 7
ER -