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

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 confirm that strain-stiffening enables metastable microphase separation within the swelling equilibrium state and reveal 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.