Search Results (4)

In order to study the relationship between the rheology of a surfactant’s concentrated dispersions and the oil and water liquid crystals from which O/W nanoemulsions (NEs) can be produced by water dilution, the phase diagram of a model SOW (surfactant–oil–water) system was constructed. The dispersion’s compositions to be characterized by rheology were chosen in the diagram’s regions that contain liquid crystal phases. For this, the dilution lines S/O = 25/75, 55/45, and 70/30 with a water content of 20 and 40 wt% (corresponding to surfactant concentrations between 15 and 55 wt%) were chosen. By adding these dispersions to a water pool, NEs were obtained, and it was shown that droplet size distribution depends on the amount of the liquid crystal phase in the initial dispersion and its rheology. The study of the oscillatory amplitude of the dispersion showed a linear viscoelastic plateau (G’ > G”) and a softening deformation region (G” > G’), indicating a viscoelastic behavior of the dispersions. The study was carried out at a constant temperature of 30 °C, and the results show that rheological characterization by itself is not enough to predict that monomodal droplet distributions are obtained. However, the presence and quantity of lamellar liquid crystal phase are important to obtain monodisperse and kinetically stable NEs. Full article

The use of equivalent alkane carbon numbers (EACN) to characterize oils is important in surfactant-oil-water (SOW) systems. However, the measurement of EACN values is non-trivial and thus it becomes desirable to predict EACN values from structure. In this work, we present a simple linear model that can be used to estimate the EACN value of oils with known Abraham solute parameters. We used linear regression with leave-one-out cross validation on a dataset of N = 80 oils with known Abraham solute parameters to derive a general model that can reliably estimate EACN values based upon the Abraham solute parameters: E (the measured liquid or gas molar refraction at 20 °C minus that of a hypothetical alkane of identical volume), S (dipolarity/polarizability), A (hydrogen bond acidity), B (hydrogen bond basicity), and V (McGowan characteristic volume) with good accuracy within the chemical space studied (N = 80, R² = 0.92, RMSE = 1.16, MAE = 0.90, p < 2.2 × 10⁻¹⁶). These parameters are consistent with those in other models found in the literature and are available for a wide range of compounds. Full article

Formulation is an ancient concept, although the word has been used only recently. The first formulations made our civilization advance by inventing bronze, steel, and gunpowder; then, it was used in medieval alchemy. When chemistry became a science and with the golden age of organic synthesis, the second formulation period began. This made it possible to create new chemical species and new combinations “à la carte.” However, the research and developments were still carried out by trial and error. Finally, the third period of formulation history began after World War II, when the properties of a system were associated with its ingredients and the way they were assembled or combined. Therefore, the formulation and the systems’ phenomenology were related to the generation of some synergy to obtain a commercial product. Winsor’s formulation studies in the 1950s were enlightening for academy and industries that were studying empirically surfactant-oil-water (SOW) systems. One of its key characteristics was how the interfacial interaction of the adsorbed surfactant with oil and water phases could be equal by varying the physicochemical formulation of the system. Then, Hansen’s solubility parameter in the 1960s helped to reach a further understanding of the affinity of some substances to make them suitable to oil and water phases. In the 1970s, researchers such as Shinoda and Kunieda, and different groups working in Enhanced Oil Recovery (EOR), among them Schechter and Wade’s group at the University of Texas, made formulation become a science by using semiempirical correlations to attain specific characteristics in a system (e.g., low oil-water interfacial tension, formulation of a stable O/W or W/O emulsion, or high-performance solubilization in a bicontinuous microemulsion system at the so-called optimum formulation). Nowadays, over 40 years of studies with the hydrophilic-lipophilic deviation equation (HLD) have made it feasible for formulators to improve products in many different applications using surfactants to attain a target system using HLD in its original or its normalized form, i.e., HLD_N. Thus, it can be said that there is still current progress being made towards an interdisciplinary applied science with numerical guidelines. In the present work, the state-of-the-art of formulation in multiphase systems containing two immiscible phases like oil and water, and therefore systems with heterogeneous or micro-heterogeneous interfaces, is discussed. Surfactants, from simple to complex or polymeric, are generally present in such systems to solve a wide variety of problems in many areas. Some significant cases are presented here as examples dealing with petroleum, foods, pharmaceutics, cosmetics, detergency, and other products occurring as dispersions, emulsions, or foams that we find in our everyday lives. Full article

The effects of surfactant molecules involved in macro-, mini-, nano-, and microemulsions used in cosmetics and pharmaceuticals are related to their amphiphilic interactions with oil and water phases. Basic ideas on their behavior when they are put together in a system have resulted in the energy balance concept labeled the hydrophilic-lipophilic deviation (HLD) from optimum formulation. This semiempirical equation integrates in a simple linear relationship the effects of six to eight variables including surfactant head and tail, sometimes a cosurfactant, oil-phase nature, aqueous-phase salinity, temperature, and pressure. This is undoubtedly much more efficient than the hydrophilic-lipophilic balance (HLB) which has been used since 1950. The new HLD is quite important because it allows researchers to model and somehow predict the phase behavior, the interfacial tension between oil and water phases, their solubilization in single-phase microemulsion, as well as the corresponding properties for various kinds of macroemulsions. However, the HLD correlation, which has been developed and used in petroleum applications, is sometimes difficult to apply accurately in real cases involving ionic–nonionic surfactant mixtures and natural polar oils, as it is the case in cosmetics and pharmaceuticals. This review shows the confusion resulting from the multiple definitions of HLD and of the surfactant parameter, and proposes a “normalized” Hydrophilic-Lipophilic Deviation (HLD_N) equation with a surfactant contribution parameter (SCP), to handle more exactly the effects of formulation variables on the phase behavior and the micro/macroemulsion properties. Full article