Temperature response of sucrose palmitate solutions: Role of ratio between monoesters and diesters.

HYPOTHESIS: Aqueous solutions of long-chain water-soluble sucrose ester surfactants exhibit non-trivial response to temperature variations, revealing a peak in viscosity around 40-50 °C. While previous investigations have explored the structures within sucrose stearate systems at various constant temperatures, a comprehensive understanding of the entire temperature dependence and the underlying molecular factors, contributing to this phenomenon is currently missing. EXPERIMENTS: Temperature dependent properties and supramolecular structures formed in aqueous solutions of commercial sucrose palmitate were examined using SAXS/WAXS, DSC, optical microscopy, rheological measurements, NMR, and cryo-TEM. FINDINGS: The underlying mechanism governing this unusual behavior is revealed and is shown to relate to the mono- to di-esters ratio in the solutions. Solutions primarily containing sucrose monoesters (monoesters molecules ≳ 98% of all surfactant molecules) exhibit behavior typical of nonionic surfactants, with minimal changes with temperature. In contrast, the coexistence of mono- and di-esters results in the formation of discrete monodisperse diester particles and a network of partially fused diester particles at low temperature. As the temperature approaches the diesters' melting point, wormlike mixed micelles form, causing a viscosity peak. The height of this peak increases significantly with the diester concentration. Further temperature increase leads to fluidization of surfactant tails and formation of branched micelles, while excess diester molecules phase separate into distinct droplets.

Efficient control of the rheological and surface properties of surfactant solutions containing C8-C18 fatty acids as cosurfactants.

Systematic experimental study is performed about the effects of chain length (varied between C8 and C18) and concentration of fatty acids (FAc), used as cosurfactants to the mixture of the anionic surfactant SLES and the zwitterionic surfactant CAPB. The following properties are studied: bulk viscosity of the concentrated solutions (10 wt % surfactants), dynamic and equilibrium surface tensions, surface modulus, and foam rheological properties for the diluted foaming solutions (0.5 wt % surfactants). The obtained results show that C8-C10 FAc induce formation of wormlike micelles in the concentrated surfactant solutions, which leads to transformation of these solutions into viscoelastic fluids with very high apparent viscosity. The same FAc shorten the characteristic adsorption time of the diluted solutions by more than 10 times. In contrast, C14-C18 FAc have small effect on the viscosity of the concentrated solutions but increase the surface modulus above 350 mN/m, which leads to higher friction inside sheared foams and to much smaller bubbles in the formed foams. The intermediate chain C12 FAc combines some of the properties seen with C10 FAc and other properties seen with C14 FAc. These results clearly demonstrate how appropriate cosurfactants can be used for efficient control of the rheological properties of concentrated surfactant solutions and of some important foam attributes, such as bubble size and foam rheology.