Light-scattering investigations on dilute nonionic oil-in-water microemulsions

Abstract

Dilute 3-component nonionic oil-in-water microemulsions formulated with either a polyoxyethylene surfactant (C_18∶1E₁₀ or C₁₂E₁₀) or the alkylamine-N-oxide surfactant, DDAO (C₁₂AO), and containing either a triglyceride or an ethyl ester oil have been examined using dynamic and static light-scattering techniques. Analysis of the results showed distinct differences in the tested oils mode of incorporation into the microemulsion droplets, with both the molecular volume of the oil and the hydrophobic chain length of the surfactant being important. For example, microemulsions formulated by C_18∶1E₁₀ and containing one of the larger molecular volume oils (that is, either a triglyceride, Miglyol 812, or soybean oil) or the ethyl ester of fatty acid oil, ethyl oleate, exhibited first a decrease and then an increase in hydrodynamic size and surfactant aggregation number, suggesting that the asymmetric C_18∶1E₁₀ micelles became spherical upon the addition of a small amount of oil and grew thereafter because of further oil being incorporated into the core of the spherical microemulsion droplet. A similar conclusion of sphericity could not be drawn for microemulsions stabilized by C_18∶1E₁₀ and containing one of the oils smaller in molecular volume (namely tributyrin, ethyl butyrate, or ethyl caprylate) where neither the aggregation number nor the hydrodynamic radius changed much upon the addition of oil. This result suggested that these oils were preferentially located in the interfacial surfactant monolayer, behaving in much the same way as a cosurfactant. A different trend of results, however, was seen for microemulsions prepared using C₁₂E₁₀ and C₁₂AO, most likely because these surfactants produced approximately spherical micelles. In this case, the microemulsions containing the oils larger in molecular volume tended to exhibit an increase in surfactant aggregation number and hydrodynamic size, suggesting the growth of spherical micelles, while the smaller oils (in particular ethyl butyrate) caused a significant decrease in surfactant aggregation number incompatible with their being incorporated into the centre of the droplet, suggesting that the oils were being located in the interfacial surfactant monolayer. These results suggest that the various oils are incorporated into the microemulsions in very different ways.