Stress-strain relations in finite viscoelastoplasticity of rigid-rod networks: applications to the Mullins effect.

This study is concerned with Mullins effect: a noticeable difference between the mechanical response of rubbery polymers observed in cyclic tests under loading and retraction. This phenomenon was evidenced about 50 years ago, however, the mechanism for hysteresis in elastomers at the micro-level remains obscure hitherto. The authors propose an approach which associates viscoelasticity of a rubbery polymer with relaxation of stresses in individual segments. To simplify the analysis, the authors neglect breakage and reformation of long chains (which is equivalent to the return to the classical theory of rubber elasticity), and focus on changes in conformations of neighboring segments. Constitutive equations are derived for the viscoelastoplastic response of rubbery polymers. An amorphous polymer is treated as a permanent network of rigid-rod chains connected to junctions. The junctions are assumed to deform affinely with the bulk material. The mechanical energy of a chain equals the sum of mechanical energies of individual bonds. Two stable conformations are considered for any bond: flexed (trans) and extended (cis). The energy of a bond with flexed conformation is determined as a function of local strain, while the mechanical energy of a bond with extended conformation is disregarded. The difference between stress-strain curves under active loading and retraction is explained by the kinetics of trans-cis transformation. Stress-strain relations and kinetic equations for the evolution of bonds with various conformations are developed using the laws of thermodynamics. These equations are simplified for small strains (when the constitutive equations are reduced to conventional relations in linear viscoelasticity), and for quasi-linear chains (the mechanical energy of a bond is a quadratic function of strain) at finite strains (when the constitutive relations are transformed into the governing equations for a viscoplastic material). The simplest version of the model is determined by only four adjustable parameters which are found by fitting experimental data in uniaxial tensile tests. It is demonstrated that the model correctly predicts observations under active loading, as well as at retraction. The following conclusions are drawn: The concept of rigid-rod networks is capable of reflecting some characteristic features of the mechanical response of elastomers. The difference between the stress-strain curves under loading and unloading (stress-softening of rubbery polymers) can be explained by transition of bonds from flexed to extended conformations. The constitutive equations ensure acceptable agreement between results of numerical simulation and observations during the first cycle of periodic loading. Adjustable parameters of the model are affected by the filler concentration, \(\phi\), in a physically plausible way, and reveal dramatic changes in their dependences on \(\phi\) at the percolation threshold which is associated with the formation of a spatial network of filler clusters.

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