Statistical field theory for nonlinear elasticity of polymer networks with excluded volume interactions
Polymer networks formed by cross linking flexible polymer chains are ubiquitous in many natural and synthetic soft-matter systems. Current micromechanics models generally do not account for excluded volume interactions except, for instance, through imposing a phenomenological incompressibility constraint at the continuum scale. This work aims to examine the role of excluded volume interactions on the mechanical response. The approach is based on the framework of the self-consistent statistical field theory of polymers, which provides an efficient mesoscale approach that enables the accounting of excluded volume effects without the expense of large-scale molecular modeling. A mesoscale representative volume element is populated with multiple interacting chains, and the macroscale nonlinear elastic deformation is imposed by mapping the end-to-end vectors of the chains by this deformation. In the absence of excluded volume interactions, it recovers the closed-form results of the classical theory of rubber elasticity. With excluded volume interactions, the model is solved numerically in three dimensions using a finite element method to obtain the energy, stresses, and linearized moduli under imposed macroscale deformation. Highlights of the numerical study include: (i) the linearized Poisson's ratio is very close to the incompressible limit without a phenomenological imposition of incompressibility; (ii) despite the harmonic Gaussian chain as a starting point, there is an emergent strain-softening and strain-stiffening response that is characteristic of real polymer networks, driven by the interplay between the entropy and the excluded volume interactions; and (iii) the emergence of a deformation-sensitive localization instability at large excluded volumes.