Influence of surface processes on the dilational visco-elasticity of surfactant solutions.

The mechanical properties of liquid-fluid systems, like the dynamic interfacial tension and interfacial rheology are closely related to the kinetic processes involved and to the behaviour of the adsorbed molecules. Therefore, provided suitable models and experimental methods are set, investigating these properties allows qualitative and quantitative information on these processes to be drawn. This paper presents recent developments in dilational rheology of liquid-fluid adsorption layers, including experimental methods, models and experimental data concerned with surfactants undergoing transformations in the adsorption layer. Models account both for relaxation due to surfactant diffusion and to processes internal to the adsorption layer. In particular surfactant reorientation, aggregation phase transitions and interfacial chemical reactions have been considered as possible reorganisation processes. The presented approach, allows the dilational viscoelasticity to be derived as a function of the perturbation frequency and of the equilibrium and kinetic parameters of the system. The results can also be easily specified for insoluble monolayer. The principal experimental techniques are reviewed and the recent progresses in the implementation of an Oscillation Bubble/Drop method for Capillary Pressure Tensiometer are discussed in detail. Two experimental studies of surfactants characterised by re-orientation and aggregation phase transition are presented. Beside providing a wider comprehension of these mechanisms, the interpretation of the dilational visco-elasticity data, according to the developed models, allows the effective estimation of the equilibrium and kinetic parameters.