Microemulsions are clear, thermodynamically stable, isotropic liquid mixtures of oil, water and surfactant, frequently in combination with a cosurfactant. The aqueous phase may contain salt(s) and/or other ingredients, and the "oil" may actually be a complex mixture of different hydrocarbons. In contrast to ordinary emulsions, microemulsions form upon simple mixing of the components and do not require the high shear conditions generally used in the formation of ordinary emulsions. The three basic types of microemulsions are direct (oil dispersed in water, o/w), reversed (water dispersed in oil, w/o) and bicontinuous. In ternary systems such as microemulsions, where two immiscible phases (water and ‘oil’) are present with a surfactant, the surfactant molecules may form a monolayer at the interface between the oil and water, with the hydrophobic tails of the surfactant molecules dissolved in the oil phase and the hydrophilic head groups in the aqueous phase.
Uses
Microemulsions have many commercially important uses:
Water-in-oil microemulsions for some dry cleaning processes Floor polishers and cleaners Personal care products Pesticide formulations Cutting oils Drugs Much of the work done on these systems have been motivated by their possible use to mobilize petroleum trapped in porous sandstone for enhanced oil recovery. A fundamental reason for the uses of these systems is that a microemulsion phase sometimes has an ultralow interfacial tension with a separate oil or aqueous phase, which may release or mobilize them from solid phases even in conditions of slow flow or low pressure gradients. Microemulsions also have industrial applications, one of them being the synthesis of polymers. Microemulsion polymerization is a complex heterogeneous process where transport of monomers, free radicals and other species (such as chain transfer agent, co-surfactant and inhibitors) between the aqueous and organic phases, takes place. Compared with other heterogeneous polymerization processes (suspension or emulsion) microemulsion polymerization is a more complicated system. Polymerization rate is controlled by monomer partitioning between the phases, particle nucleation, and adsorption and desorption of radicals. Particle stability is affected by the amount and type of surfactant and pH of dispersing medium. It is also used in the process of creating nanoparticles. The kinetics of microemulsion polymerization has much in common with emulsion polymerization kinetics, the most characteristic feature of which is the compartmentalization, where the radicals growing inside the particles are separated from each other, thus suppressing termination to a high extent and, as a consequence, providing high rates of polymerization.
Theory Various theories concerning microemulsion formation, stability and phase behavior have been proposed over the years. For example, one explanation for their thermodynamic stability is that the oil/water dispersion is stabilized by the surfactant present and their formation involves the elastic properties of the surfactant film at the oil/water interface, which involves as parameters, the curvature and the rigidity of the film. These parameters may have an assumed or measured pressure and/or temperature dependence (and/or the salinity of the aqueous phase), which may be used to infer the region of stability of the microemulsion, or to delineate the region where three coexisting phases occur, for example. Calculations of the interfacial tension of the microemulsion with a coexisting oil or aqueous phase are also often of special focus and may sometimes be used to guide their formulation.
History and terminology The term microemulsion was first used by T. P. Hoar and J. H. Shulman, professors of chemistry at Cambridge University, in 1943. Alternative names for these systems are often used, such as transparent emulsion, swollen micelle, micellar solution, and solubilized oil. More confusingly still, the term microemulsion can refer to the single isotropic phase that is a mixture of oil, water and surfactant, or to one that is in equilibrium with coexisting predominantly oil and/or aqueous phases, or even to other non-isotropic phases. As in the binary systems (water/surfactant or oil/surfactant), self-assembled structures of different types can be formed, ranging, for example, from (inverted) spherical and cylindrical micelles to lamellar phases and bicontinuous microemulsions, which may coexist with predominantly oil or aqueous phases.
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