On the statistical physics and thermodynamics of polymer networks: a Eulerian theory for entropic elasticity

TL;DR

This paper introduces a Eulerian thermodynamic framework for polymer networks that captures molecular kinematics and predicts entropic elasticity, outperforming traditional models and revealing a novel biaxial instability phase transition.

Contribution

It develops a new Eulerian variational approach based on thermodynamic equilibrium, linking molecular chain behavior to continuum deformation with improved predictive accuracy.

Findings

The hyperelastic model with two parameters outperforms existing models.

The model aligns with Biot-chain and Hencky strain energies in respective limits.

A new biaxial instability phase transition is identified in chain orientation.

Abstract

This study presents a Eulerian theory to elucidate the molecular kinematics in polymer networks and their connection to continuum deformation, grounded in fundamental statistical physics and thermodynamics. Three key innovations are incorporated: 1. The network behavior is described through a global thermodynamic equilibrium condition that maximizes the number of accessible microstates for all segments, instead of directly dealing with the well-established single-chain models commonly adopted in traditional approaches. A variational problem is then posed in the Eulerian framework to identify this equilibrium state under geometric fluctuation constraints. Its solution recaptures the classical single-chain model and reveals the dependence of chain kinematics upon continuum deformation. 2. The chain stretch and orientation probability are found to be explicitly specified through the Eulerian logarithmic strain and spatial direction. The resulting hyperelastic model, with only two physical parameters, outperforms the extant models with same number of parameters. It further provides a physical justification for prior models exhibiting superior predictive capabilities: the model becomes equivalent to the Biot-chain model at moderate deformations, while converging to the classical Hencky strain energy in the small strain limit. 3.A novel biaxial instability emerges as a phase transition in chain orientation. At sufficiently large deformation, chains increasingly align with the primary stretched direction, depleting their density in other directions. Consequently, the stresses in non-primary stretched directions would decrease as the loss in chain density outweighs the gain in chain force. For equal biaxial tension, instability is therefore triggered because perfect equality of the two principal stretches without any perturbation is practically unachievable.