Underscreening in concentrated electrolytes: re-entrant swelling in polyelectrolyte brushes

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dc.contributor.authorRobertson, Hen_AU
dc.contributor.authorElliott, GRen_AU
dc.contributor.authorNelson, ARJen_AU
dc.contributor.authorLe Brun, APen_AU
dc.contributor.authorWebber, GBen_AU
dc.contributor.authorPrescott, SWen_AU
dc.contributor.authorCraig, VSJen_AU
dc.contributor.authorWanless, EJen_AU
dc.contributor.authorWillott, JDen_AU
dc.date.accessioned2025-04-08T04:53:35Zen_AU
dc.date.available2025-04-08T04:53:35Zen_AU
dc.date.issued2023-09-30en_AU
dc.date.statistics2024-11-27en_AU
dc.description.abstractHypersaline environments are ubiquitous in nature and are found in myriad technological processes. Recent empirical studies have revealed a significant discrepancy between predicted and observed screening lengths at high salt concentrations, a phenomenon referred to as underscreening. Herein we investigate underscreening using a cationic polyelectrolyte brush as an exemplar. Poly(2-(methacryloyloxy)ethyl)trimethylammonium (PMETAC) brushes were synthesised and their internal structural changes and swelling response was monitored with neutron reflectometry and spectroscopic ellipsometry. Both techniques revealed a monotonic brush collapse as the concentration of symmetric monovalent electrolyte increased. However, a non-monotonic change in brush thickness was observed in all multivalent electrolytes at higher concentrations, known as re-entrant swelling; indicative of underscreening. For all electrolytes, numerical self-consistent field theory predictions align with experimental studies in the low-to-moderate salt concentration regions. Analysis suggests that the classical theory of electrolytes is insufficient to describe the screening lengths observed at high salt concentrations and that the re-entrant polyelectrolyte brush swelling seen herein is consistent with the so-called regular underscreening phenomenon. © the Owner Societies 2023 This article is Open Access - CC-BY-NCen_AU
dc.description.sponsorshipThis research was supported by the Australian Research Council (DP190100788) and ANSTO (PP9789 and PPR13123). HR would like to thank the Australian Government for providing financial assistance (Research Training Program Scholarship). AINSE Ltd is thanked for a Post Graduate Research Awards to HR, and an Early Career Researcher Grant to JDW. The SPATZ neutron beam instrument operations are supported through the National Collaborative Research Infrastructure Strategy (NCRIS), an Australian Government initiative. Jack Matthey is thanked for help with sample changes during the neutron beamtime. Frans Leermakers is thanked for allowing us to use SFbox to run the nSCFT calculations.en_AU
dc.format.mediumElectronicen_AU
dc.identifier.citationRobertson, H., Elliott, G. R., Nelson, A. R. J., Le Brun, A. P., Webber, G. B., Prescott, S. W., Craig, V. S. J., Wanless, E. J., & Willott, J. D. (2023). Underscreening in concentrated electrolytes: re-entrant swelling in polyelectrolyte brushes. Physical Chemistry Chemical Physics, 25(36), 24770-24782. doi:10.1039/D3CP02206Den_AU
dc.identifier.issn1463-9076en_AU
dc.identifier.issn1463-9084en_AU
dc.identifier.issue36en_AU
dc.identifier.journaltitlePhysical Chemistry Chemical Physicsen_AU
dc.identifier.pagination24770-24782en_AU
dc.identifier.urihttps://doi.org/10.1039/d3cp02206den_AU
dc.identifier.urihttps://apo.ansto.gov.au/handle/10238/16134en_AU
dc.identifier.volume25en_AU
dc.languageEnglishen_AU
dc.language.isoenen_AU
dc.publisherRoyal Society of Chemistryen_AU
dc.subjectElectrolytesen_AU
dc.subjectSwellingen_AU
dc.subjectSaltsen_AU
dc.subjectSynthesisen_AU
dc.subjectNeutron reflectorsen_AU
dc.subjectSpectroscopic factorsen_AU
dc.subjectScreeningen_AU
dc.subjectConcentration ratioen_AU
dc.subjectColloidsen_AU
dc.subjectDebye Lengthen_AU
dc.titleUnderscreening in concentrated electrolytes: re-entrant swelling in polyelectrolyte brushesen_AU
dc.typeJournal Articleen_AU
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