The Role of Structure in Polymer Rheology: Review

The review is devoted to the analysis of the current state of understanding relationships among the deformation-induced structure transformations, observed rheological properties, and the occurrence of non-linear effects for polymer liquids (melts, solutions, and composites). Three levels of non-linearity are the base for consideration. The first one concerns changes in the relaxation spectra of viscoelastic liquids, which are responsible for weak non-linear phenomena. The second one refers to the strong non-linearity corresponding to such changes in the structure of a medium that leads to the emergence of a new relaxation state of a matter. Finally, the third one describes the deformation-induced changes in the phase state and/or the occurring of bifurcations and instability in flow and reflects the thermodynamic non-linear behavior. From a structure point of view, a common cause of the non-linear effects is the orientation of macromolecules and changes in intermolecular interaction, while a dominant factor in describing fluid dynamics of polymer liquids is their elasticity. The modern understanding of thixotropic effects, yielding viscoplastic materials, deformation-induced phase transition, and the experimental observations, demonstrating direct correlations between the structure and rheology of polymer liquids, are the main objects for discussion. All these topics are reviewed and discussed mainly on the basis of the latest five-year publications.

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This review focuses on the analysis of nonlinear effects in polymer liquids, discussing weak, strong, and thermodynamic nonlinearity, and how they are influenced by structure changes, viscoelasticity, and fluid dynamics.