The role of interfacial rheological properties on Ostwald ripening in emulsions

The coarsening of emulsion droplets by Ostwald ripening is studied by means of numerical simulations in which time-dependent (elastic) interfacial behaviour is taken into account. Theoretical calculations on the dissolution of a single emulsion droplet in an infinite medium at saturated conditions show that the dissolution process can be stopped only when the interfacial tension goes to zero. When interfacial stress relaxation is included, which prevents a continuous zero interfacial tension, no stabilisation of the dissolution process is observed and the droplet dissolves completely. In the case of an ensemble of droplets, numerical calculations on the coarsening of emulsion droplets with finite interfacial elasticity show that a stable situation occurs at finite interfacial tensions of the droplets. This applies for a closed system with the same assumptions as those made in the Lifshitz-Slyozov-Wagner (LSW) theory. The coarsening behaviour strongly depends on the saturation of the dispersed phase in the continuous phase. If the system is in contact with atmosphere, saturation will finally go to unity and stabilisation will only occur for zero interfacial tension of the droplets. For an ensemble of droplets in a closed system, the calculations show that stress-relaxation of the interface causes the Ostwald-ripening process to continue, so no stable situation is reached. Stabilisation can only be accomplished by adding insoluble species to the dispersed phase, by using particles as stabilisers or by micro-encapsulation of the emulsion droplets by thick insoluble interfacial layers, which have a thickness that is in the order of the radius of the droplet.