Nonlinear time-dependent behavior of rheodictic polymers: A theoretical and experimental investigation

The present study examined the nonlinear time-dependent behavior of rheodictic polymers, a class of noncrosslinked materials that exhibit flow. Such behavior was addressed with extended Schapery's nonlinear viscoelastic model by introducing new physical quantities, i.e., the flow term ${\Phi }_{\text{flow}}$ and corresponding nonlinear shift parameter $g_{2,\text{flow}}$. While ${\Phi }_{\text{flow}}$ portrays irrecoverable deformation, $g_{2,\text{flow}}$ depicts a nonlinear contribution to flow acceleration. This theory was accompanied by analytical and experimental methodologies for identifying all the parameters in the linear and nonlinear viscoelastic domains. Predictions of long-term time-dependent behavior (in shear) at various stress states show excellent agreement with the experimental data, i.e., within $5\%$ error, obtained for polycarbonate at $130°C$. Surprisingly, the newly introduced $g_{2,\text{flow}}$ indicates that flow retardation occurs with increasing stress, implying that a highly deformed entangled system hinders molecular reptation/disentanglement. Nevertheless, the proposed extension of Schapery's nonlinear viscoelastic model not only allows accurate predictions of the nonlinear time-dependent behavior of rheodictic polymers but also enables a detailed outlook on the underlying molecular mechanisms under severe environmental and loading conditions.