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The Dynamics of a Collapsing Polyelectrolyte Gel

Celora, Giulia L; Hennessy, Matthew G; Muench, Andreas; Wagner, Barbara; Waters, Sarah; (2023) The Dynamics of a Collapsing Polyelectrolyte Gel. SIAM Journal on Applied Mathematics , 83 (3) pp. 1146-1171. 10.1137/21M1419726. Green open access

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Abstract

We analyse the dynamics of different routes to collapse of a constrained polyelectrolyte gel in contact with an ionic bath. The evolution of the gel is described by a model that incorporates non-linear elasticity, Stefan-Maxwell diffusion and interfacial gradient free energy to account for phase separation of the gel. A bifurcation analysis of the homogeneous equilibrium states reveals three solution branches at low ion concentrations in the bath, giving way to only one above a critical ion concentration. We present numerical solutions that capture both the spatial heterogeneity and the multiple timescales involved in the process of collapse. These solutions are complemented by two analytical studies. Firstly, a phase-plane analysis that reveals the existence of a depletion front for the transition from the highly swollen to the new collapsed equilibrium state. This depletion front is initiated after the fast ionic diffusion has set the initial condition for this time regime. Secondly, we perform a linear stability analysis about the homogeneous states that show that for a range of ion concentrations in the bath, spinodal decomposition of the swollen state gives rise to localized solvent-rich(poor) and, due to the electroneutrality condition, ion-poor(rich) phases that coarsen on the route to collapse. This dynamics of a collapsing polyelectrolyte gel has not been described before.

Type: Article
Title: The Dynamics of a Collapsing Polyelectrolyte Gel
Open access status: An open access version is available from UCL Discovery
DOI: 10.1137/21M1419726
Publisher version: http://doi.org/10.1137/21M1419726
Language: English
Additional information: This version is the version of record. For information on re-use, please refer to the publisher’s terms and conditions.
Keywords: Collapse, HYDROGELS, KINETICS, Mathematics, Mathematics, Applied, MECHANICS, MODEL, phase -space analysis, Physical Sciences, polyelectrolyte gel, POLYMERS, Science & Technology, spinodal decomposition, stability, SWOLLEN, VOLUME PHASE-TRANSITION
UCL classification: UCL
UCL > Provost and Vice Provost Offices > UCL BEAMS
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Mathematics
URI: https://discovery.ucl.ac.uk/id/eprint/10173883
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