Thermodynamics of microphase separation in a swollen, strain-stiffening polymer network

Fuente: arXiv
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Main Authors: Fernández-Rico, Carla, Style, Robert W., Heyden, Stefanie, Wang, Shichen, Olmsted, Peter D., Dufresne, Eric R.
Format: Preprint
Published: 2025
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_version_ 1866918053380358144
author Fernández-Rico, Carla
Style, Robert W.
Heyden, Stefanie
Wang, Shichen
Olmsted, Peter D.
Dufresne, Eric R.
author_facet Fernández-Rico, Carla
Style, Robert W.
Heyden, Stefanie
Wang, Shichen
Olmsted, Peter D.
Dufresne, Eric R.
contents Elastic MicroPhase Separation (EMPS) provides a simple route to create soft materials with homogeneous microstructures by leveraging the supersaturation of crosslinked polymer networks with liquids. At low supersaturation, network elasticity stabilizes a uniform mixture, but beyond a critical threshold, metastable microphase-separated domains emerge. While previous theories have focused on describing qualitative features about the size and morphology of these domains, they do not make quantitative predictions about EMPS phase diagrams. In this work, we extend Flory-Huggins theory to quantitatively capture EMPS phase diagrams by incorporating strain-stiffening effects. This model requires no fitting parameters and relies solely on independently measured solubility parameters and large-deformation mechanical responses. Our results reveal that strain-stiffening enables metastable microphase separation within the swelling equilibrium state and why the microstructures can range from discrete droplets to bicontinuous networks. This works highlights the critical role of nonlinear elasticity in controlling phase-separated morphologies in polymer gels.
format Preprint
id arxiv_https___arxiv_org_abs_2506_08958
institution arXiv
publishDate 2025
record_format arxiv
spellingShingle Thermodynamics of microphase separation in a swollen, strain-stiffening polymer network
Fernández-Rico, Carla
Style, Robert W.
Heyden, Stefanie
Wang, Shichen
Olmsted, Peter D.
Dufresne, Eric R.
Soft Condensed Matter
Materials Science
Elastic MicroPhase Separation (EMPS) provides a simple route to create soft materials with homogeneous microstructures by leveraging the supersaturation of crosslinked polymer networks with liquids. At low supersaturation, network elasticity stabilizes a uniform mixture, but beyond a critical threshold, metastable microphase-separated domains emerge. While previous theories have focused on describing qualitative features about the size and morphology of these domains, they do not make quantitative predictions about EMPS phase diagrams. In this work, we extend Flory-Huggins theory to quantitatively capture EMPS phase diagrams by incorporating strain-stiffening effects. This model requires no fitting parameters and relies solely on independently measured solubility parameters and large-deformation mechanical responses. Our results reveal that strain-stiffening enables metastable microphase separation within the swelling equilibrium state and why the microstructures can range from discrete droplets to bicontinuous networks. This works highlights the critical role of nonlinear elasticity in controlling phase-separated morphologies in polymer gels.
title Thermodynamics of microphase separation in a swollen, strain-stiffening polymer network
topic Soft Condensed Matter
Materials Science
url https://arxiv.org/abs/2506.08958