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

Abstract

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 Φflow and corresponding nonlinear shift parameter g2,flow. While Φflow portrays irrecoverable deformation, g2,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 g2,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.