Leonard M.C. Sagis

Emulsions, i.e., the dispersion of liquid droplets in a nonmiscible liquid phase, are overwhelmingly present in food products. In such systems, both liquid phases (generally, oil and water) are separated by a narrow region, the oil-water interface. Despite the fact that this interface is very thin (in the nanometer range), it represents a large surface area and controls to a great extent the physicochemical stability of emulsions. This review provides an overview of the aspects that govern the composition, structure, and mechanical properties of interfaces in food emulsions, taking into account the complexity of such systems (presence of numerous surface-active molecules, influence of processing steps, and dynamic evolution due to chemical changes). We also review methods that have conventionally, or recently, been used to study liquid-liquid interfaces at various scales. Finally, we focus on the link between interfacial properties and the physical, chemical, and digestive stability of emulsions at different levels and point out trends to control stability via interfacial engineering.

The dynamic properties of interfaces often play a crucial role in the macroscopic dynamics of multiphase soft condensed matter systems. These properties affect the dynamics of emulsions, of dispersions of vesicles, of biological fluids, of coatings, of free surface flows, of immiscible polymer blends, and of many other complex systems. The study of interfacial dynamic properties, surface rheology, is therefore a relevant discipline for many branches of physics, chemistry, engineering, and life sciences. 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. In this paper recent experiments are reviewed in the field of surface rheology, with particular emphasis on the models used to analyze surface rheological data. Most of the models currently used are straightforward generalizations of models developed for the analysis of rheological data of bulk phases. In general the limits on the validity of these generalizations are not discussed. Not much use is being made of recent advances in nonequilibrium thermodynamic formalisms for multiphase systems, to construct admissible models for the stress-deformation behavior of interfaces. These formalisms are ideally suited to construct thermodynamically admissible constitutive equations for rheological behavior that include the often relevant couplings to other fluxes in the interface (heat and mass), and couplings to the transfer of mass from the bulk phase to the interface. In this review recent advances in the application of classical irreversible thermodynamics, extended irreversible thermodynamics, rational thermodynamics, extended rational thermodynamics, and the general equation for the nonequilibrium reversible-irreversible coupling formalism to multiphase systems are also discussed, and shown how these formalisms can be used to generate a wide range of thermodynamically admissible constitutive models for the surface stress tensor. Some of the generalizations currently in use are shown to have only limited validity. The aim of this review is to stimulate new developments in the fields of experimental surface rheology and constitutive modeling of multiphase systems using nonequilibrium thermodynamic formalisms and to promote a closer integration of these disciplines.