Activation energy, spatial confinement, and mean first passage and escape times of a tracer in a wormlike micellar fluid: an effective potential approach

Abstract

Abstract Wormlike micelles are long semiflexible cylindrical polymer structures formed by amphiphiles. In solution, these linear micelles percolate in multiconected entangled networks, where cross-links can break and recombine dynamically. Technological applications of wormlike micellar fluids include tunable encapsulation/delivery of molecules or colloids in biomedicine, oil industry, and/or cleaning processes. In this work, we propose that the experimental activation energy, the spatial confinement, and the mean first passage and escape times of a spherical tracer immersed in wormlike micellar network, in which caging effects are observed, can be estimated from economic Brownian dynamics simulations of a single particle interacting with an effective one-dimensional cosine-like potential of amplitude U 0 and periodicity L. The proposed one-fitting parameter method has been used to characterize the long-time dynamics of wormlike micellar solutions formed by the self-assembly of a mixture of zwitterionic and anionic surfactants at several temperatures and different concentrations of surfactant and brine. The amplitude U 0 has displayed a good agreement regarding the corresponding experimental activation energy at different temperatures. The periodicity L has shown to be an upper bound of the mesh size ξ and of the same order of magnitude regarding the entanglement length l e, obtained from rheology and microrheology experiments. The escape time of the tracer in the effective potential τ escape and the time t*, at which a change of curvature in the mean square displacement occurs, are upper and lower limits, respectively, of the experimental relaxation time. Our method is simple and fast, and we foresee that it should be applicable to model the long-time behaviour of tracers in other polymer systems, in which caging effects are present.