Direct and Accelerated Characterization of Formulation Stability

This review deals with the use of rheology for assessment and prediction of the long-term physical stability of emulsions. It starts with an introduction, highlighting the importance of having accelerated test to predict emulsion stability. This is followed by a section on the stability/instability of emulsion systems, giving a brief summary of the driving force of each instability process and its prevention. The classical techniques that can be applied for assessment of creaming or sedimentation, flocculation, Ostwald ripening, coalescence and phase inversion are briefly described. This is followed by several sections on the application of rheological techniques to assess and predict each of these instabilities. This involves the use of steady state shear stress-shear rate measurements, constant stress (creep) measurements and dynamic (oscillatory) techniques. The last section gives an example of model emulsions to illustrate the correlation between the various break-down processes with the rheological characteristics of the system.

The stability and rheology of tricaprylin oil-in-water emulsions containing a mixture of surface-active hydrophilic silica nanoparticles and pure nonionic surfactant molecules are reported and compared with those of emulsions stabilized by each emulsifier alone. The importance of the preparation protocol is highlighted. Addition of particles to a surfactant-stabilized emulsion results in the appearance of a small population of large drops due to coalescence, possibly by bridging of adsorbed particles. Addition of surfactant to a particle-stabilized emulsion surprisingly led to increased coalescence too, although the resistance to creaming increased mainly due to an increase in viscosity. Simultaneous emulsification of particles and surfactant led to synergistic stabilization at intermediate concentrations of surfactant; emulsions completely stable to both creaming and coalescence exist at low overall emulsifier concentration. Using the adsorption isotherm of surfactant on particles and the viscosity and optical density of aqueous particle dispersions, we show that the most stable emulsions are formed from dispersions of flocculated, partially hydrophobic particles. From equilibrium contact angle and oil-water interfacial tension measurements, the calculated free energy of adsorption E of a silica particle to the oil-water interface passes through a maximum with respect to surfactant concentration, in line with the emulsion stability optimum. This results from a competition between the influence of particle hydrophobicity and interfacial tension on the magnitude of E.