PROPERTIES OF SURFACTANT MONOLAYERS IN RELATION TO MICROEMULSION PHASE-BEHAVIOR

The relationship between the properties of surfactant monolayers at oil-water interfaces and the phase behaviour in bulk of mixtures of oil + water + surfactant is discussed. Such monolayer properties include the spontaneous curvature, c(o), the interfacial, tension, gamma, the elasticity K (or rigidity) associated with the mean curvature, and the elasticity KBAR associated with the Gaussian curvature. The model system chosen for investigation is the anionic surfactant AOT + aqueous NaCl + n-alkane at 20-degrees-C. In such systems, inversion of microemulsion type from oil-in-water (o/w) to water-in-oil (w/o) is possible with increasing electrolyte concentration. The tension, gamma, passes through an ultralow minimum value at conditions corresponding to the formation of three phases. Using small angle neutron scattering, we have determined the structure of surfactant-rich third phases (c(o) approximately 0) formed with the different alkanes. Lamellar phases consisting of surfactant monolayers separated alternately by oil and water appear with short alkanes, whereas L3 and bicontinuous phases form in systems containing longer alkanes. The bending elasticity K has been measured for planar monolayers at the oil-water interface by ellipsometry. K is independent of salt concentration but depends markedly on alkane chain length N, falling from approximately 1 k(B)T for N < 11 to approximately 0.1 k(B)T for N = 14. This is discussed in terms of the differing extents of oil penetration into the surfactant chains. Higher rigidities favouring lamellar phases and lower rigidities favouring bicontinuous microemulsions are in line with the theoretical predictions of de Gennes and Taupin. Estimates of the constant KBAR have been obtained in droplet microemulsions (w/o) from a knowledge of their size, K and gamma. The sign of the constant is in agreement with the geometry of the phases formed in three phase systems. Finally, the ideas and concepts developed in the oil-water systems described above are used to explain the wetting behaviour by alkanes of AOT monolayers at the air-water surface.