The interfacial tensions between water- and oil-rich phases in the presence of microemulsions have been measured for ternary systems of water, n-alkanes, and nonionic alkylpolyglycolether surfactants (CiEj). It is found that the minimum of the interfacial tension curve, which is observed for each system in conjunction with the well-known phenomenon of phase inversion, depends sensitively, but systematically, on the chemical nature of the oil and the surfactant. Specifically, the minimum value of the interfacial tension σ̄ab decreases by 1 order of magnitude on decreasing either the carbon number of the alkane k by 6, or the number of oxyethylene groups j by 3, or by increasing the number of carbon atoms in the surfactant tail i by 2. The numerical values of the interfacial tensions as a function of temperature are presented along with an empirical description previously suggested [R. Strey, Colloid and Polymer Sci. 272, 1005 (1994)]. From the analysis, in terms of bending energy one obtains estimates for the bending and saddle-splay constants. The similar shape of the interfacial tension curves permits a superposition of the data for all 19 systems in support of a scaling relation recently derived [S. Leitao, A. M. Somoza, M. M. Telo da Gama, T. Sottmann, and R. Strey, J. Chem. Phys. 105, 2875 (1996)]. Furthermore, we note a striking coincidence of the numerical values of critical amplitude ratio R=σ0ξ02=0.37 kT in near-critical systems and the product σ̄abξ̄2=0.44(±0.10) kT where ξ̄ is the maximum length scale in the bicontinuous microemulsions.

The small-angle neutron scattering (SANS) of bicontinuous microemulsions of 19 different water-n-alkane-CiEj (n-alkylpolyglycolether) systems has been measured. All scattering curves exhibit a broad scattering peak which permits determining the characteristic length scale ξ for bicontinuous structures at symmetric water and oil volume fractions, i.e., φ=0.5. Various random models predict ξ=aδφ(1−φ)/φc. We find that ξ is indeed inversely proportional to the surfactant volume fraction φc. Approximating the effective surfactant chain length δ by δ=νc/ac, where ac and νc are the area and the volume of the surfactant molecule, the numerical value for a is determined to be a=7.16, which is close to, but significantly different from those used in theoretical models. The head group area ac at the water–oil interface is obtained from the large q part of the scattering curves. It is found to be independent of i and k, the carbon numbers of the alkyl chain of the surfactant and of the alkane, respectively. However, it depends strongly, and nearly linearly, on the head group size j of the surfactant. Within experimental error it is described by ac=29.3+6.20j (Å2).

In this paper we highlight the advantageous features of both short-and long-chain surfactant systems in determining the most important properties of three-phase bodies and genuine microemulsions. To this end Ðrst the phase behavior of the simple system (n-butyl monoglycol ether) is discussed. From H 2 OÈn-dodecaneÈC 4 E 1 temperatureÈconcentration sections through the phase prism at various water-to-oil ratios, a number of isothermal Gibbs triangles are constructed, which can quantitatively be compared with theories. Furthermore, the critical tie-lines of the three-phase body have been precisely determined. From these measurements it is evident that there is a non-negligible monomeric solubility of the surfactant in the excess phases. For long-chain surfactant systems, the more efficient the surfactant, the larger is the size of the microstructure of the microemulsion. We report a striking correlation between the efficiency of a surfactant and its monomeric solubility in the excess phases for 23 systems of the type These Ðndings suggest that the H 2 OÈn-alkaneÈC i E j . monomeric solubility of the surfactant in oil and water might be the key to describing the main features of these microemulsion systems.

The effect of amphiphilic diblock copolymers of several molecular weights on the structure and phase behavior of ternary amphiphilic systems (water, oil, and nonionic surfactant) is investigated. Small amounts of amphiphilic block copolymer polyethyleneoxide–polyethylpropylene lead to a dramatic decrease of the amount of total surfactant needed to solubilize given equal volumes of water and oil in a bicontinuous microemulsion. Neutron scattering experiments employing a high-precision two-dimensional contrast variation technique demonstrate that the polymer is distributed uniformly on the surfactant membrane. Based on these observations, we propose a mechanism for the enhancement of swelling behavior, which is due to the variation of the membrane curvature elasticity by polymer mushrooms anchored to the interface.

We predict theoretically the thermodynamics and relaxation kinetics of solutions of cylindrical branched micelles. Using a recently developed theory in combination with the experimental data, we explain the unusual, inverted temperature dependence of the phase separation observed in wormlike micelles and dilute microemulsions. We extend the model to treat the temperature dependence of the relaxation kinetics and explain the observations.