New two-parameter constitutive models for rubber-like materials: Revisiting the relationship between single chain stretch and continuum deformation

The connection between macroscopic deformation and microscopic chain stretch is a key element in constitutive models for rubber-like materials that are based on the statistical mechanics of polymer chains. A new micro-macro chain stretch relation is proposed, using the Irving-Kirkwood-Noll procedure to construct a Cauchy stress tensor from forces along polymer chains. This construction assumes that the deformed polymer network remains approximately isotropic for low to moderate macroscopic stretches, a starting point recently adopted in the literature to propose a non-affine micro-macro chain stretch relation (Amores et al., 2021). Requiring the constructed Cauchy stress to be consistent with the stress tensor derived from the strain energy density results in a new chain stretch relation involving the exponential function. A hybrid chain stretch relation combining the new chain stretch with the well-known affine relation is then proposed to account for the whole range of stretches in experimental datasets. Comparison of the model predictions to experimental data in the literature shows that the two new micro-macro chain stretch relations in this work result in two- parameter constitutive models that outperform those based on existing chain stretches with no increase in the number of fitting parameters used.