Effects of ion valency on polyelectrolyte brushes: a unified theory
Ion valency has strong effects on the conformation of polyelectrolyte brushes, which is important for designing the adhesive and lubrication properties of the surface. But a unified theory applicable to both monovalent and multivalent ions is still lacking. Using a consistent description of ion a...
| Main Authors: | , , |
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| Other Authors: | |
| Format: | Journal Article |
| Language: | English |
| Published: |
2023
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| Subjects: | |
| Online Access: | https://hdl.handle.net/10356/165256 |
| _version_ | 1811690211812311040 |
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| author | Li, Minglun Zhuang, Biln Yu, Jing |
| author2 | School of Materials Science and Engineering |
| author_facet | School of Materials Science and Engineering Li, Minglun Zhuang, Biln Yu, Jing |
| author_sort | Li, Minglun |
| collection | NTU |
| description | Ion valency has strong effects on the conformation of polyelectrolyte brushes, which
is important for designing the adhesive and lubrication properties of the surface. But a
unified theory applicable to both monovalent and multivalent ions is still lacking. Using
a consistent description of ion adsorption, we demonstrate the significant effect of ion
valency on the brush conformation and the distribution of ions in the system. Our
theoretical predictions are consistent with experimental and simulation results. When
the system involves only monovalent ions in the solution, our theory predicts that the
brush height vs. the added salt concentration undergoes the osmotic and salted brush
regimes, consistent with the previous studies. Interestingly, when multivalent ions are
present in the solution, the brush height undergoes an adsorption regime — which has
not been reported before—in addition to the osmotic and salted regimes. Furthermore,
at low salt concentrations, the ion valency of added ions can cause a phase transition in
the brush. Our study provides a unified theory for the effects of ions on polyelectrolyte
brushes. It reveals that the collapse behavior of the multivalent cation system is mainly
caused by adsorption, which originates from the strong electrostatic interaction between
monomers and multivalent cations under specific adsorption configurations. |
| first_indexed | 2024-10-01T06:00:24Z |
| format | Journal Article |
| id | ntu-10356/165256 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T06:00:24Z |
| publishDate | 2023 |
| record_format | dspace |
| spelling | ntu-10356/1652562023-07-14T15:48:16Z Effects of ion valency on polyelectrolyte brushes: a unified theory Li, Minglun Zhuang, Biln Yu, Jing School of Materials Science and Engineering Engineering::Materials Positive Ions Osmosis Ion valency has strong effects on the conformation of polyelectrolyte brushes, which is important for designing the adhesive and lubrication properties of the surface. But a unified theory applicable to both monovalent and multivalent ions is still lacking. Using a consistent description of ion adsorption, we demonstrate the significant effect of ion valency on the brush conformation and the distribution of ions in the system. Our theoretical predictions are consistent with experimental and simulation results. When the system involves only monovalent ions in the solution, our theory predicts that the brush height vs. the added salt concentration undergoes the osmotic and salted brush regimes, consistent with the previous studies. Interestingly, when multivalent ions are present in the solution, the brush height undergoes an adsorption regime — which has not been reported before—in addition to the osmotic and salted regimes. Furthermore, at low salt concentrations, the ion valency of added ions can cause a phase transition in the brush. Our study provides a unified theory for the effects of ions on polyelectrolyte brushes. It reveals that the collapse behavior of the multivalent cation system is mainly caused by adsorption, which originates from the strong electrostatic interaction between monomers and multivalent cations under specific adsorption configurations. Agency for Science, Technology and Research (A*STAR) National Research Foundation (NRF) Submitted/Accepted version M.L. and J.Y. thank the Singapore National Research Fellowship (NRF-NRFF11-2019-0004). B.Z. acknowledges support by A*STAR under its AME YIRG Grant (Project No. A20E6c0100). M.L. thanks members of M. Muthukumar’s group (University of Massachusetts Amherst) for helpful discussions. 2023-03-27T01:55:07Z 2023-03-27T01:55:07Z 2022 Journal Article Li, M., Zhuang, B. & Yu, J. (2022). Effects of ion valency on polyelectrolyte brushes: a unified theory. Macromolecules, 55(23), 10450-10456. https://dx.doi.org/10.1021/acs.macromol.2c01464 0024-9297 https://hdl.handle.net/10356/165256 10.1021/acs.macromol.2c01464 2-s2.0-85142643861 23 55 10450 10456 en NRF-NRFF11-2019-0004 A20E6c0100 Macromolecules © 2022 American Chemical Society. This document is the Accepted Manuscript version of a published work that appeared in final form in Macromolecules, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.macromol.2c01464. application/pdf |
| spellingShingle | Engineering::Materials Positive Ions Osmosis Li, Minglun Zhuang, Biln Yu, Jing Effects of ion valency on polyelectrolyte brushes: a unified theory |
| title | Effects of ion valency on polyelectrolyte brushes: a unified theory |
| title_full | Effects of ion valency on polyelectrolyte brushes: a unified theory |
| title_fullStr | Effects of ion valency on polyelectrolyte brushes: a unified theory |
| title_full_unstemmed | Effects of ion valency on polyelectrolyte brushes: a unified theory |
| title_short | Effects of ion valency on polyelectrolyte brushes: a unified theory |
| title_sort | effects of ion valency on polyelectrolyte brushes a unified theory |
| topic | Engineering::Materials Positive Ions Osmosis |
| url | https://hdl.handle.net/10356/165256 |
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