Advantages and limitations of different methods to determine the optimum formulation in surfactant–oil–water systems: A review

Abstract The optimum formulation in a surfactant–oil–water (SOW) system is defined as the physicochemical situation at which the surfactant adsorbed at the interface exhibits exactly equal interactions for both oil and water. Identifying the optimum formulation of SOW systems is crucial in various industrial applications, ranging from pharmaceuticals to cosmetics and to petroleum issues like dehydration and enhanced oil recovery. Multiple techniques are available to identify the optimum formulation, often with its own advantages and limitations. In this comprehensive review, we provide an in‐depth analysis of the systematic use of formulation scans to identify the optimum formulation in SOW systems. We critically assess different methods, including conventional ones, such as phase behavior observation, determination of the minimum interfacial tension from equilibrated systems, and the localization of the minimum emulsion stability using formulation scans. We also mention a new promising technique that can be applied in practice, such as oscillating spinning drop interfacial rheology (OSDIR) as well as others that allow an understanding of some structural features of the domains present in the surfactant‐rich phase in SOW systems. Among these methods, dynamic light scattering (DLS), small angle scattering (SAXS and SANS), nuclear magnetic resonance (NMR), X‐ray microcomputed tomography (Micro‐CT), and differential scanning calorimeter (DSC), can be found in the literature. Finally, we discuss potentially unusual behaviors that can appear in complex systems, thus providing guidance on the selection of the most suitable method tailored to the specific application.