Nonequilibrium thermodynamic modeling of the structure and rheology of concentrated wormlike micellar solutions

In the last decade considerable interest has emerged in understanding and modeling the flow behavior of concentrated wormlike micellar solutions. A significant advance was made through the two-species modeling approach originally proposed by Vasquez, Cook, and McKinley. In the present work we revisit their model from a nonequilibrium thermodynamic perspective. By employing an extension to the nonequilibrium treatment of chemical reaction kinetics for media with an internal structure, we develop a thermodynamic model that closely resembles the one based on more ad hoc assumptions. Thus, we not only validate that model, but now also have a mechanism to systematically produce further refinements. One particular refinement, namely, the inclusion of an additional intermediate length species, is explored.

► We revisit the VCM model from a nonequilibrium thermodynamic perspective.
► The theory of reaction kinetics is extended to viscoelastic multicomponent systems.
► The new model has fewer parameters and predicts a nonmonotonic stress–strain curve.