Non-entropic theory of rubber elasticity: flexible chains with weak excluded-volume interactions

Strain energy density is calculated for a network of flexible chains with weak excluded-volume interactions (whose energy is small compared with thermal energy). Constitutive equations are developed for an incompressible network of chains with segment interactions at finite deformations. These relations are applied to the study of uniaxial and equi-biaxial tension (compression), where the stress–strain diagrams are analyzed numerically. It is demonstrated that intra-chain interactions (i) cause an increase in the Young’s modulus of the network and (ii) induce the growth of stresses (compared to an appropriate network of Gaussian chains), which becomes substantial at relatively large elongation ratios. The effect of excluded-volume interactions on the elastic response strongly depends on the deformation mode, in particular, it is more pronounced at equi-biaxial tension than at uniaxial elongation. Key-words: Flexible chain, Excluded-volume interaction, Polymer network, Finite deformation, Path integral