Dynamics of encapsulation and controlled release systems based on water-in-water emulsions: Liposomes and polymersomes

The deformation relaxation behavior of two types of vesicles, liposomes and polymersomes, was investigated using a general nonequilibrium thermodynamics theory based on the interfacial transport phenomena (ITP) formalism. Liposomes and polymersomes are limiting cases of this theory with respect to rheological behavior of the interfaces. They represent respectively viscous, and viscoelastic surface behavior. We have determined the longest relaxation time for a small perturbation of the interfaces for both these limiting cases. Parameter maps were calculated which can be used to determine when surface tension, bending rigidity, spontaneous curvature, interfacial permeability, or surface rheology dominate the response of the vesicles. In these systems up to nine different scaling regimes were identified for the relaxation time of a deformation with droplet size, with scaling exponent n ranging from 0 to 4.     

Modelling surface rheology of complex interfaces with extended irreversible thermodynamics

The rheological properties of the interfaces in complex multiphase systems often play a crucial role in the dynamic behavior of these systems. For example, these properties affect the dynamics of emulsions, of dispersions of vesicles, of biological fluids, or of free surface flows. In the past three to four decades a vast amount of literature has been produced dealing with the rheological properties of interfaces stabilized by low molecular weight surfactants, proteins, (bio)polymers, lipids, colloidal particles, and various mixtures of these surface active components. The data of these surface rheological experiments are often analyzed with ad hoc generalizations of rheological models used for the analysis of rheological properties of bulk phases. The validity of these generalizations is in general not discussed. Here we show how the extended irreversible thermodynamics (EIT) formalism can be used to generate a wide range of thermodynamically admissible constitutive models for the surface stress tensor, which not only encompass currently used constitutive models, but also suggest several new ones, particularly useful for modelling the nonlinear response of interfaces.