Microemulsions formation

The application of microemulsions in foods is limited by the types of surfactants used to facilitate microemulsion formation. Many surfactants are not permitted in foods or only at low levels. The solubilization of long-chain triglycerides (LCTs) such as edible oils is more difficult to achieve than the solubilization of short- or medium-chain triglycerides, a reason why few publications on microemulsions are available, especially because food-grade additives are not allowed to contain short-chain alcohols (C3-C5). 

Different methods are used in microemulsion formation a low-energy emulsification method by dilution of an oil surfactant mixture with water and dilution of a water-surfactant mixture with oil and mixing all the components together in the final composition. These methods involve the spontaneous formation of microemulsions and the order of ingredient addition may determine the formation of the microemulsion. Such applications have been performed with lutein and lutein esters. ... 

High pressure homogenization may also be used to form microemulsions but the process of emulsification is generally inefficient (due to the dissipation of heat) and extremely limited as the water-oil-surfactant mixture may be highly viscous prior to microemulsion formation. ... 

Adhikari, S., Kapoor, S., Chattopadhyay, S., and Mukheijee, T. 2000. Pulse radiolytic oxidation of P-carotene with halogenated alkylperoxyl radicals in a quaternary microemulsion Formation of retinal. Biophys. Chem. 88 111-117. 

Water is highly dispersable it has a high tendency to support micelle and/or microemulsion formation. These tendencies may be enhanced by additives such as surfactants... 

Before describing how microemulsion nature and structure are determined by the structure and chain length of surfactant and cosurfactant, it is necessary first to briefly review the theories of microemulsion formation and stability. These theories will highlight the important factors required for microemulsion formation. This constitutes the first part of this review. The second part describes the factors that determine whether a w/o or o/w microemulsion is formed. This is then... 

Solubilisation can best be illustrated by considering the phase diagrams of non-ionic surfactants containing poly(oxyethylene oxide) head groups. Such surfactants do not generally need a cosurfactant for microemulsion formation. At low temperatures, the ethoxylated surfactant is soluble in water... 

With ionic surfactants for which V/1 <0.7, microemulsion formation needs the presence of a cosurfactant. The latter has the effect of increasing V without affecting 1 (if the chain length of the cosurfactant does not exceed that of the surfactant). These cosurfactant molecules act as "padding" separating the head groups. 

Salager JL (1977) Physico-chemical properties of surfactant-oil-water mixture phase behavior, microemulsion formation and interfacial tension. PhD Dissertation, University of Texas at Austin... 

Lopez-Quintela MA (2003) Synthesis of nanomaterials in microemulsions formation mechanisms and growth control. Curr Opin Colloid Interface Sci 8 137-144 Lopez-Quintela MA, Tojo C, Blanco MC, Rio LG, Leis JR (2004) Microemulsion dynamics and reactions in microemulsions. Curr Opin Colloid Interface Sci 9 264-278 Maitra A (1984) Determination of Size Parameters of Water Aerosol Ot Oil Reverse Micelles from Their Nuclear Magnetic-Resonance Data. J Phys Chem 88 5122-5125... 

There are a number o-f processes which have not been discussed (because o-f space) in which mixture o-f sur-f actants are important. Among these are foaming, emulsion formation, liquid crystal formation, microemulsion formation, adsorption as 1iquid—1iquid interfaces, and phase partitioning of surfactants between immiscible liquid phases. These areas will also see increased interest in the use of surfactant mixtures. 

It was observed that the titration of a coarse emulsion by a coemulsifier (a macromonomer) leads in some cases to the formation of a transparent microemulsion. Transition from opaque emulsion to transparent solution is spontaneous and well defined. Zero or very low interfacial tension obtained during the redistribution of coemeulsifier plays a major role in the spontaneous formation of microemulsions. Microemulsion formation involves first a large increase in the interface (e.g., a droplet of radius 120 nm will disperse ca. 1800 microdroplets of radius 10 nm - a 12-fold increase in the interfacial area), and second the formation of a mixed emulsifier /coemulsifier film at the oil/water interface, which is responsible for a very low interfacial tension. 

Baran, J. R. Pope, G. A. Wade, W. H. Weerasooriya, V. Yapa, A. "Microemulsion Formation with Chlorinated Hydrocarbons of Differing Polarity." Environ. Set Technol. 1994, 25, 1361-1366. 

The importance of a surfactant - rich phase, particularly a lamellar one, to detergency performance was noted for liquid soils such as C16 and mineral oil (3.6). Videomicroscopy experiments indicated that middle phase microemulsion formation for C12E04 and Cjg was enhanced at 30 °C, while at 18 °C, oil - in - water, and at 40 °C, water - in - oil microemulsions were found to form at the oil - bath interface (3.6). A strong temperature dependence of liquid soil removal by lamellar liquid crystals, attributed to viscosity effects, has been noted for surfactant - soil systems where a middle - phase microemulsion was not formed (10). 

Leung, R. Hou, M.J. Shah, D.O. Microemulsions Formation, Structure, Properties, and Novel Applications in Surfactants in Chemi-cal/Process Engineering Wasan, D.T. Ginn, M.E. Shah, D.O. (Eds.), Marcel Dekker New York, 1988, pp. 315-367. 

Several theories have been proposed to account for the thermodynamic stability of microemulsions. The most recent theories showed that the driving force for microemulsion formation is the ultralow interfacial tension (in the region of 10 4-10 2 mN m 1). This means that the energy required for formation of the interface (the large number of small droplets) A Ay is compensated by the entropy of dispersion —TAS, which means that the free energy of formation of microemulsions AG is zero or negative. 

For a pure supercritical fluid, the relationships between pressure, temperature and density are easily estimated (except very near the critical point) with reasonable precision from equations of state and conform quite closely to that given in Figure 1. The phase behavior of binary fluid systems is highly varied and much more complex than in single-component systems and has been well-described for selected binary systems (see, for example, reference 13 and references therein). A detailed discussion of the different types of binary fluid mixtures and the phase behavior of these systems can be found elsewhere (X2). Cubic ecjuations of state have been used successfully to describe the properties and phase behavior of multicomponent systems, particularly fot hydrocarbon mixtures (14.) The use of conventional ecjuations of state to describe properties of surfactant-supercritical fluid mixtures is not appropriate since they do not account for the formation of aggregates (the micellar pseudophase) or their solubilization in a supercritical fluid phase. A complete thermodynamic description of micelle and microemulsion formation in liquids remains a challenging problem, and no attempts have been made to extend these models to supercritical fluid phases. 

Because of their widely recognized solubility in SCCO2, fluoropolymers have become extensively used as modifiers in this medium (Figure 4.4). They have formed the basis of surfactants for dispersion polymerizations and water microemulsion formation, as extractants for metals and as modifiers to dissolve insoluble organic reagents, e.g. radical initiators and tin reagents. 

This potential force occurs in microstructured fluids like microemulsions, in cubic phases, in vesicle suspensions and in lamellar phases, anywhere where an elastic or fluid boundary exists. Real spontaneous fluctuations in curvature exist, and in liposomes they can be visualised in video-enhtuiced microscopy [59]. Such membrane fluctuations have been invoked as a mechanism to account for the existence of oil- or water-swollen lamellar phases. Depending on the natural mean curvature of the monolayers boimding an oil region - set by a mixture of surfactant and alcohol at zero -these swollen periodic phases can have oil regions up to 5000A thick With large fluctuations the monolayers are supposed to be stabilised by steric hindrance. Such fluctuations and consequent steric hindrance play some role in these systems and in a complete theory of microemulsion formation. 

The formation of a surfactant film around droplets facilitates the emulsification process and also tends to minimize the coalescence of droplets. Macroemulsion stability in terms of short and long range interactions has been discussed. For surfactant stabilized macroemulsions, the energy barrier obtained experimentally is very high, which prevents the occurrence of flocculation in primary minimum. Several mechanisms of microemulsion formation have been described. Based on thermodynamic approach to these systems, it has been shown that interfacial tension between oil and water of the order of 10- dynes/cm is needed for spontaneous formation of microemulsions. The distinction between the cosolubilized and microemulsion systems has been emphasized. 

During the last four decades, several investigators have proposed various mechanisms of microemulsion formation. The following is a brief description of these mechanisms. 

It has also been shown from thermodynamic consideration (Equation 3), that if the interfacial tension is very low, the thermodynamically stable emulsions can be formed. Previous investigators (20,45,47,48) have calculated that for a situation likely to occur in microemulsion formation, the interfacial tensions would need to be in the order of 10 to 10 5 dynes/cm for thermodynamic stabilization and for spontaneous formation of microemulsions. 

Adamson (51) proposed a model for W/0 microemulsion formation in terms of a balance between Laplace pressure associated with the interfacial tension at the oil/water interface and the Donnan Osmotic pressure due to the total higher ionic concentration in the interior of aqueous droplets in oil phase. The microemulsion phase can exist in equilibrium with an essentially non-colloidal aqueous second phase provided there is an added electrolyte distributed between droplet s aqueous interior and the external aqueous medium. Both aqueous media contain some alcohol and the total ionic concentration inside the aqueous droplet exceeds that in the external aqueous phase. This model was further modified (52) for W/0 microemulsions to allow for the diffuse double layer in the interior of aqueous droplets. Levine and Robinson (52) proposed a relation governing the equilibrium of the droplet for 1-1 electrolyte, which was based on a balance between the surface tension of the film at the boundary in its charged state and the Maxwell electrostatic stress associated with the electric field in the internal diffuse double layer. 

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