The aim of this paper is to present a short overview of the main mechanisms operative in the formation and stabilization of emulsions by solid particles and, on this basis, to make comparisons between solid particles, surfactants and globular proteins as emulsifiers. When available, simple quantitative relations are presented, with the respective numerical estimates and discussion of the applicability of these relations to particle-stabilized systems. Non-obvious similarities between the different types of emulsifiers are outlined in several cases in which the description of the system can be performed at a phenomenological level. Examples are presented for the process of emulsification, where we show that several simple theoretical expressions, derived originally in the studies of surfactants and protein emulsifiers, can be successfully applied to particle-stabilized emulsions. In contrast, for the phenomena in which the detailed mechanisms of particle adsorption and film stabilization are important, the differences between the various emulsifiers prevail, thus making it impossible to use the same theoretical description. The most important specific characteristics of the solid particles which strongly affect their behavior are the high barrier to particle adsorption, high desorption energy and strong capillary forces between particles trapped in liquid films, which all originate in the relatively large particle size (as compared to the size of surfactant and protein molecules). The capillary mechanism of stabilization of liquid films by solid particles is reviewed in some detail, to emphasize its specific features and to demonstrate the applicability of several simple expressions for approximate estimates. Interestingly, we found that the hypothesis for some exceptionally high coalescence stability of the particle-stabilized emulsions is not supported by the experimental data available in literature. On the other hand, the particles are able to completely arrest the process of Ostwald ripening in foams and emulsions, and this effect can be easily explained with the high desorption energy of the particles and the resulting capillary effects.
A new class of surfactant mixtures is described, which is particularly suitable for studies related to foam dynamics, such as studies of foam rheology, liquid drainage from foams and foam films, and bubble coarsening and rearrangement. These mixtures contain an anionic surfactant, a zwitterionic surfactant, and fatty acids (e.g., myristic or lauric) of low concentration. Solutions of these surfactant mixtures exhibit Newtonian behavior, and their viscosity could be varied by using glycerol. Most importantly, the dynamic surface properties of these solutions, such as their surface dilatational modulus, strongly depend on the presence and on the chain-length of fatty acid(s). Illustrative results are shown to demonstrate the dependence of solution properties on the composition of the surfactant mixture, and the resulting effects on foam rheological properties, foam film drainage, and bubble Ostwald ripening. The observed high surface modulus in the presence of fatty acids is explained with the formation of a surface condensed phase of fatty acid molecules in the surfactant adsorption layer.
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