Wormlike Micelles of Polyoxyethylene Alkyl Ether Mixtures C10E5 + C14E5 and C14E5 + C14E7: Hydrophobic and Hydrophilic Chain Length Dependence of the Micellar Characteristics

Abstract

The wormlike micelles formed with the binary mixtures of surfactant polyoxyethylene alkyl ethers (CiEj), C10E5 + C14E5 (Mix1) and C14E5 + C14E7 (Mix2), were characterized by static (SLS) and dynamic light scattering (DLS) experiments. The SLS results have been analyzed with the aid of the light scattering theory for micelle solutions, thereby yielding the molar mass Mw(c) as a function of c along with the cross-sectional diameter d of the micelle. The observed Kc/DeltaR0 as a function of c, the mean-square radius of gyration (S2) and the hydrodynamic radius RH as functions of Mw have been well described by the theories for the wormlike spherocylinder model. It has been found that the micellar length increases with increasing concentration c or with raising temperature T irrespective of the composition of the surfactant mixtures. The length of the Mix1 and Mix2 micelles at fixed c and T steeply increases with increasing weight fraction wt of C14E5 in both of the surfactant mixtures, implying that the micelles greatly grow in length when the surfactant component with longer alkyl group or with shorter oxyethylene group increases in the mixture. The results are in line with the findings for the micelles of the single surfactant systems where the CiEj micelles grow in length to a greater extent for larger i and smaller j. Although the values of d and the spacing s between the adjacent surfactant molecules on the micellar surface do not significantly vary with composition of the surfactant mixture, the stiffness parameter lambda-1 remarkably decreases with wt in both Mix1 and Mix2 micelles, indicating that the stiffness of the micelle is controlled by the relative strength of the repulsive force due to the hydrophilic interactions between oxyethylene groups to the attractive one due to the hydrophobic interactions between alkyl groups among the surfactant molecules.