Hypothesis -Hydrogen-bonding capacities of polar nonaqueous media significantly affect selfassembly 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 rheology measurements. Further nanostructural 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 ~ 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 ~ 0.5 μm. 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 ~ 45 o C.Conclusions -These unprecedented observations highlight the markedly different selfassembly 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.
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