Langmuir, Vol.25, No.8, 4435-4442, 2009
Tunable Parameters for the Structural Control of Reverse Micelles in Glycerol Monoisostearate/Oil Systems: A SAXS Study
Formation of reverse micelles in surfactant/oil binary systems without water addition and the tunable parameters for the structure control of such micelles are presented. The small-angle X-ray scattering (SAXS) technique has been used for the structural characterization of micelles. It has been found that the nonionic surfactant glycerol monoisostearate (abbreviated as iso-C(18)G(1)) forms reverse micelles in different organic solvents such as cyclohexane, n-decane, and n-hexadecane without the addition of water. The structure (shape and size) of the reverse micelles has been found to depend on the solvent nature (alkyl chain length of oil), composition, temperature, and added water. Phase behavior study has shown that iso-C(18)G(1) forms isotropic single-phase solutions in the aforementioned oils at 25 degrees C. At lower temperatures (< 20 degrees C) 11 phases (dispersion of solid or liquid crystal phase) has been observed. SAXS data were evaluated by the generalized indirect Fourier transformation (GIFT) method, which has drawn a clear picture on the structural variations of the reverse micellar aggregates. Small globular types of micelles are found in the iso-C(18)G(1)/cyclohexane system. On the other hand, elongated ellipsoidal prolatelike or rodlike micelles are found in iso-C(18)G(1)/decane or iso-C(18)G(1)/hexadecane systems. The underlying mechanism of this structural evolution may be explained in terms of the transfer free energy of hydrophilic glycerol moiety from hydrophilic to hydrophobic environment of oils with different chain lengths. Besides, the penetration of oils to the lipophilic chain of the surfactant in reverse micellar systems differs depending on the chain length of oils. Lowering temperature and increasing surfactant concentration similarly lead to micellar growth while the cross-section structure remains essentially unchanged. Addition of trace water induced micellar growth, which is accompanied by the rapid swelling of the micellar core. The results obtained by this study demonstrate that the solvent nature, temperature, composition, and water addition can be the tunable parameters for the size, shape, and internal structure control of the iso-C(18)G(1)-based reverse micelles.