On the representation of chemical ageing of rubber in continuum mechanics

In order to represent the chemical ageing behaviour of rubber under finite deformations a three-dimensional theory is proposed. The fundamentals of this approach are different decompositions of the deformation gradient in combination with an additive split of the Helmholtz free energy into three parts. Its first part belongs to the volumetric material behaviour. The second part is a temperature-dependent hyperelasticity model which depends on an additional internal variable to consider the long-term degradation of the primary rubber network. The third contribution is a functional of the deformation history and a further internal variable; it describes the creation of a new network which remains free of stress when the deformation is constant in time. The constitutive relations for the stress tensor and the internal variables are deduced using the Clausius–Duhem inequality. In order to sketch the main properties of the model, expressions in closed form are derived with respect to continuous and intermittent relaxation tests as well as for the compression set test. Under the assumption of near incompressible material behaviour, the theory can also represent ageing-induced changes in volume and their effect on the stress relaxation. The simulations are in accordance with experimental data from literature.

► Chemical ageing of rubber under finite strains is modelled by a new three-dimensional approach.
► The model is based on decompositions of the deformation gradient and the specific free energy.
► Ageing is modelled by state variables which consider chain-scission and crosslinking reactions.
► Continuous and intermittent relaxation, permanent set and ageing-induced shrinkage is modelled.