Effect of droplet charge density on stabilization of oil-in-dispersion emulsions co-stabilized by binary mixed surfactants and nanoparticles

Abstract

Ionic surfactant and similarly charged nanoparticles can co-stabilize oil-in-dispersion (OID) emulsions at extremely low concentrations (0.001 cmc/0.001 wt%), in which particles do not adsorb at the oil/water interface but distribute in the aqueous phase forming a dispersion. In this paper, the effect of droplet charge density on stabilization of the n-decane-in-water OID emulsion was examined by using a cetyl trimethyl ammonium bromide (CTAB)/C₁₂B (dodecyl dimethyl carboxyl betaine) binary mixture at a low fixed total concentration (0.01 mM) with varying molar fractions of CTAB. A model based on the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory is proposed to calculate interaction energies between droplets and between droplets and particles. It is found that the droplet charge density can be well compensated by particle concentration along the stabilization boundary, and the OID emulsion still follows the DLVO stabilization. Particles tend to surround droplets at large distances but may form a monolayer between approaching droplets at shorter distances, which significantly reduces the van der Waals attraction between droplets. In addition, the induced auxiliary droplet–particle repulsion is proportional to the number of particles per unit area of droplet surfaces, which together with the droplet–droplet repulsion ensures a large total repulsion preventing droplets from flocculation and coalescence. This work explains quantitatively the stabilization of OID emulsions, which have potential applications in emulsion products such as foods, cosmetics, pesticides, and various industrial emulsion systems. Moreover, the development of the OID emulsions represents an important advancement in green chemistry as it substantially reduces the required amounts of emulsifiers and their environmental impact after use.