We investigated phase behavior and rheological properties of aqueous micellar phase formed in water/cocoyl glutamate neutralized with triethanol amine (CGT-n)/hexadecyl trimethylammonium salt (CTAB or CTAC) systems, where n is a degree of neutralization. Micellar phase appears in wide composition range with respect to the surfactant mixing fraction in ternary phase diagrams at 25˚C. At high mixing fraction of cationic surfactant in the water/CGT-n/CTAB systems, one can observe a highly viscous micellar phase in which worm-like micelles are expected to form. Contrary to conventional systems in which worm-like micelles are formed, the zero-shear viscosity of the micellar solution in the water/CGTn/CTAB system with n=1.2 increases with the addition of cationic cosurfactant and once decreases after a maximum, then increases again and decreases after the second maximum. At n=1.5 and 2, highly viscous solution is observed in the relatively wide range of surfactant mixing fraction instead of two maxima of the viscosity curve observed at n=1.2. In the case of CTAC instead of CTAB we can observe narrow composition range for the maximum viscosity. Frequency sweep measurements were performed on the highly viscous samples in the water/CGT-1.5/CTAB system. Typical viscoelastic behavior of worm-like micellar solutions is observed; i.e. the curves of storage (G') and loss (G") moduli make a crossover and the data points of G' and G" can be fitted to the Maxwell model. Relaxation time against the mixing fraction of two surfactants behaves similarly to the zero-shear viscosity change, whereas the plateau modulus continuously increases in the plateau region for the zero-shear viscosity curve.
jjocs agents can be broadly classified into organogelators and hydrogelators, depending on the type of target solvent used. Organogelators for cosmetics include waxes that form card-house structures 2) , and solid oils such as higher fatty acids and higher alcohols; and 12-hydroxystearic acid, which forms supramolecular structures through hydrogen bonding between the hydroxy groups 3) , as a low-molecularweight organogelator 4) . On the other hand, many of the hydrogelators used in skin care creams and aqueous gels in cosmetics are natural polysaccharides, such as agar or xanthan gum, which are covalent polymers 5) ; cellulose de-Abstract: Surfactant-mediated gelation (SMG) is a technique used to form hydrogels by solubilizing waterinsoluble low-molecular-weight organogelators in surfactant micelles. In this study, we investigated the viscoelastic behavior of SMG hydrogels and the effect of micellar shape on their gel network structure using a glutamic acid-based organogelator. Stress-strain curves obtained from static viscoelasticity measurements showed that a wormlike micelle-mediated gel (W-SMG) exhibited a higher stress than a spherical micellemediated gel (S-SMG). From the viscosity-shear rate curve (flow curve), we inferred that the SMG gel exhibited a shear thickening behavior, particularly W-SMG. Microscopic observations revealed that W-SMG formed a denser and more uniform gel network than S-SMG when subjected to strong shearing. W-SMG showed remarkable adhesiveness and a significantly higher tensile normal stress than S-SMG. The storage modulus and loss modulus of W-SMG and the wormlike micellar solution obtained from frequency sweep measurements of the dynamic viscoelasticity were analyzed by Maxwell fitting. The wormlike micellar solution produced a good fit with the single Maxwell model, whereas W-SMG produced the best fit with the generalized Maxwell model comprising two Maxwell elements. From the relaxation time characteristics obtained from the Maxwell model, W-SMG was found to be a viscoelastic material coexisting with a structure having a short relaxation time derived from the gel network and a long relaxation time derived from the wormlike micelle. Under the oscillation strain measured by a rheometer, W-SMG showed a greater normal stress than the wormlike micellar solution, indicating a significant Weissenberg effect.
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