Formation of nano-emulsions has been studied in the system water/Brij 30/decane at 25 °C by three low-energy emulsification methods: (A) stepwise addition of oil to a water-surfactant mixture, (B) stepwise addition of water to a solution of the surfactant in oil, and (C) mixing all the components in the final composition. Nano-emulsions with average droplet size of 50 nm and high kinetic stability have been obtained only at oil weight fractions, R, lower than 0.3 by emulsification method B. Independent of the oil weight fraction, R, emulsions obtained by method B have lower polydispersity than those obtained by methods A and C. Phase behavior studies have revealed that compositions giving rise to nano-emulsions consist of Wm, (O/W microemulsion), LR (lamellar liquid crystalline), and O (oil) phases, at equilibrium. It has been shown that equilibrium properties cannot fully explain nano-emulsion formation. Low values of equilibrium interfacial tensions and phase equilibrium involving a lamellar liquid crystalline phase are probably required but not sufficient to obtain nano-emulsions in this system. The key factor for nanoemulsion formation has been attributed to the kinetics of the emulsification process. The change in the natural curvature of the surfactant during the emulsification process may play a major role in achieving emulsions with small droplet size.

Enhanced recovery of crude oil by surfactant flooding requires the attainment of an ultralow interfacial tension. Since Winsor's work in the 1950s it has been known that a minimum interfacial tension and a concomitant three‐phase behavior of a surfactant–oil–water system occurs when the interactions of the surfactant and the oil and water phases are exactly equal. It has been known since the 1970s that these conditions are attained when a linear correlation is satisfied between the formulation variables, which are characteristic parameters of the substances as well as the temperature. This first part of our review on how to attain ultralow interfacial tension for enhanced oil recovery shows how formulation scan techniques using these correlations are used to determine an optimum formulation and to characterize unknown surfactants and oils. The physicochemical significance of the original empirical correlation is reported as the surfactant affinity difference or hydrophilic–lipophilic deviation model. We report the range of accurate validity of, and how to test, this simple model with four variables.

The minimum interfacial tension occurrence along a formulation scan at the so-called optimum formulation is discussed to be related to the interfacial curvature. The attained minimum tension is inversely proportional to the domain size of the bicontinuous microemulsion and to the interfacial layer rigidity, but no accurate prediction is available. The data from a very simple ternary system made of pure products accurately follows the correlation for optimum formulation, and exhibit a linear relationship between the performance index as the logarithm of the minimum tension at optimum, and the formulation variables. This relation is probably too simple when the number of variables is increased as in practical cases. The review of published data for more realistic systems proposed for enhanced oil recovery over the past 30 years indicates a general guidelines following Winsor’s basic studies concerning the surfactant–oil–water interfacial interactions. It is well known that the major performance benefits are achieved by blending amphiphilic species at the interface as intermolecular or intramolecular mixtures, sometimes in extremely complex formulations. The complexity is such that a good knowledge of the possible trends and an experienced practical know-how to avoid trial and error are important for the practitioner in enhanced oil recovery.

We have studied emulsions made with two- and three-phase oil-water-surfactant systems in which one of the phases is a microemulsion, the other phases being water or/and oil excess phases. Such systems have been extensively studied in the 1970-1980s for applications in enhanced oil recovery. It was found at that time that the emulsions became very unstable in the three-phase systems, but so far few explanations have been proposed. In the most complete one, Kabalnov and colleagues related the emulsion stability to the probability of hole nucleation in the liquid film separating two nearby emulsion drops and associated this probability to the curvature elastic energy of the surfactant layer covering drop surfaces. We propose a different explanation, linked to another type of interfacial elastic energy, associated with compression of the surfactant layers. As found long ago, the three-phase systems are found near optimum formulation (hydrophile lipophile difference, HLD = 0), where the interfacial tension exhibits a deep minimum. The determination of interfacial elastic properties in low interfacial tension systems is not straightforward. In our present work, we used a spinning drop tensiometer with an oscillating rotation velocity. We show that the interfacial compression elastic modulus and viscosity also exhibit a minimum at optimum formulation. We propose that this minimum is related to the acceleration of the surfactant exchanges between the interface, oil and water, near the optimum formulation. Furthermore, we find that the surfactant partitions close to equally between oil and water at the optimum, as in earlier studies. The interfacial tension gradients that slow the thinning of liquid films between drops are reduced by surfactant exchanges between drops and the interface, which are fast whatever the type of drop, oil or water; film thinning is therefore very rapid, and emulsions are almost as unstable as in the absence of surfactant.