New long tail gemini surfactant in aqueous solution: Self-assembly, rheological properties and responsiveness to hydrocarbon

Abstract

Gemini surfactants are promising to replace conventional monomeric surfactants in various applications. In this paper, a new gemini surfactant with long unsaturated oleyl tails and bis(hydroxyethyl) ammonium head groups linked by butyl spacer was synthesized. Its critical micelle concentration in salt-free water (12 µM) is much lower than for its monomeric analog (220 µM). Without any additives this surfactant can form viscoelastic solutions with the viscosity of up to 1 kPa·s and elastic modulus of 15 Pa at the conditions, when the viscosity of the single-chained monomeric analog is close to that of pure water. These are one of the highest values reported so far for C18-tailed gemini surfactants without additives. The structure of the gemini surfactant solutions was studied by cryo-TEM and SAXS. Cryo-TEM revealed the presence of closed-looped micelles coexisting with linear wormlike micelles as well as the regular spacing between the micelles arising from strong electrostatic repulsion between them. The SAXS curves were well-fitted by a form-factor of core–shell cylinder, which yielded the radius of the core and the thickness of the shell equal to 1.4 nm each. Addition of n-decane induced the drop of viscosity by 6 orders of magnitude accompanied by the transformation of wormlike micelles into microemulsion droplets with 4.4 nm radius. Such gemini surfactants providing high viscoelasticity to aqueous solution that is responsive to added hydrocarbon are promising for the application in oil recovery as thickeners of fracturing fluids that can be cleaned up without any breakers at the backflow of oil.