The curious case of SDS self-assembly in glycerol: Formation of a lamellar gel

Hypothesis: Hydrogen-bonding capacities of polar nonaqueous media significantly affect self-assembly behaviours of surfactants in these media. Introduction: Glycerol, a nonaqueous hydrogen-bonding solvent, is widely used in industrial formulations due to its desirable physical properties. Surfactants are ubiquitous in such applications; however, surfactant self-assembly in glycerol is not well understood. Methods: The microscopic structure of the gel phase was studied using a series of imaging techniques: polarised light microscopy (PLM), confocal laser scanning microscopy (CLSM), and environmental scanning electron microscopy (ESEM). The rheological properties of the gel were studied using viscometry and oscillation theology measurements. Further nano-structural characterisation was carried out using small-angle neutron scattering (SANS). Results: We have observed the unexpected formation of a microfibrillar gel in SDS and glycerol mixtures at a critical gelation concentration (CGC) as low as similar to 2 wt%; such SDS gelation has not been observed in aqueous systems. The microscopic structure of the gel consisted of microfibres some mm in length and with an average diameter of D similar to 0.5 mu m. The fibres in the gel phase exhibited shear-induced alignment in the viscometry measurements, and oscillation tests showed that the gel was viscoelastic, with an elastic-dominated behaviour. Fitting to SANS profiles showed lamellar nano-structures in the gel microfibres at room temperature, transforming into cylindrical-micellar solutions above a critical gelation temperature, T-CG similar to 45 degrees C. Conclusions: These unprecedented observations highlight the markedly different self-assembly behaviours in aqueous and nonaqueous H-bonding solvents, which is not currently well understood. Deciphering such self-assembly behaviour is key to furthering our understanding of self-assembly on a fundamental level. (C) 2020 Elsevier Inc. All rights reserved.