Chain breaking in the statistical mechanical constitutive theory of polymer networks

TL;DR

This paper develops a statistical mechanical framework to model the mechanics and chain breaking/reforming kinetics in polymer networks, capturing the behavior of elastomers with reversible bonds and their failure mechanisms.

Contribution

It introduces a novel statistical mechanical derivation that links single-chain models to macroscopic network behavior, including chain breakage and healing dynamics.

Findings

The framework accurately predicts network response under large deformation.

It models reversible and irreversible chain breaking in elastomers.

Application to hydrogels with metal-coordination crosslinks demonstrates versatility.

Abstract

Elastomers are used in a wide range of applications because of their large strain to failure, low density, and tailorable stiffness and toughness. The mechanical behavior of elastomers derives mainly from the entropic elasticity of the underlying network of polymer chains. Elastomers under large deformation experience bonds breaking within the polymer network. This breaking of chains damages the network, can lead to material failure, and can be utilized as an energy dissipation mechanism. In the case of reversible bonds, broken chains may reform and heal the damage in the network. If the reversible bonds are dynamic, chains constantly break and reform and create a transient network. A fundamental constitutive theory is developed to model the mechanics of these polymer networks. A statistical mechanical derivation is conducted to yield a framework that takes in an arbitrary single-chain model (a Hamiltonian) and outputs: the single-chain mechanical response, the breaking and reforming kinetics, the equilibrium distribution of chains in the network, and the partial differential equations governing the deformation-coupled network evolution. This statistical mechanical framework is then brought into the continuum scale by using macroscopic thermodynamic constitutive theory to obtain a constitutive relation for the Cauchy stress. The potential-supplemented freely jointed chain ($u$FJC) model is introduced, and a parametric study of its mechanical response and breaking kinetics is provided. This single-chain model is then implemented within the constitutive framework, which we specialize and apply in two exemplary cases: the mechanical response and irreversible breakdown of a multinetwork elastomer, and the mechanical response of a dual crosslink gel. After providing a parametric study of the general constitutive model, we apply it to a hydrogel with reversible metal-coordination crosslinks.