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Polymer/surfactant mixtures have a wide range of industrial and technological applications, one of them being the use in microencapsulation and emulsion stabilization processes. These mixtures are able to form adsorption layers at the surface of oil droplets and so affect the emulsion stability, which depends on the polyelectrolyte/surfactant nature, concentrations ratio, method of the emulsification, etc. Polyelectrolytes alone show low surface activity in contrast to surfactants, which adsorb at the water/oil interface, making the droplets charged, but they are insufficient to stabilize emulsions. When an oppositely-charged polymer is added to the surfactant solution, a steric barrier is formed, which prevents coalescence and enhances the stability. The present review is devoted to the recent studies of the use of polymer/surfactant mixtures for the encapsulation of active ingredients and stabilization of single and double emulsions. Active ingredients are added to the oil phase prior to emulsification so that any subsequent dissolution of the core, like in other encapsulation protocols, can be omitted. By measuring the interfacial tension and dilational rheology it is possible to find optimum conditions for the emulsion formation and hence for encapsulation. Therefore, such systems have become a prominent approach for the encapsulation of active ingredients.

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