Influence of Tail Group Length, Amide Functionality and Added Salt Ion Identity on the Behaviour of Betaine Surfactants.

Hypothesis The behaviour of surfactants in solution and at interfaces is governed by a combination of steric and electrostatic effects experienced by surfactant molecules as they interact with solvent, other species in solution, and each other. It would therefore be anticipated that highly interacting groups would significantly influence surfactant behaviour. The widely used amide functionality has polar H-bond donor/acceptor properties, and therefore its inclusion into a surfactant structure should have a profound effect on surface activity and self-assembly of that surfactant when compared to the equivalent molecule without an amide linker. Further, chaotropic or kosmotropic salt ions that affect water structuring and hydrogen bonding may provide opportunities for further tuning surfactant interactions in such cases. Experiments A library of betaine surfactant with tail lengths n=14-22 both with and without an amidopropyl linker were synthesised to study the effect of the amide functionality on surfactant properties. Characterisation of the molecules interfacial properties were performed using pendant drop tensiometry and their solution state formulation properties were probed using small-angle neutron scattering (SANS) and rheological measurements. Findings Presence of an amidopropyl linker had little effect on aggregation propensity (as evidenced by critical micelle concentration) and aggregate morphology of betaine surfactants, but did increase the Krafft temperature of these surfactants. SANS analysis indicated that aggregate morphology of alkyl betaine surfactants could be influenced by the addition of sodium salts with chaotropic counterions (I- and SCN-), but they were insensitive to more kosmotropic anions (SO42-, F- and Cl-), providing unique and novel solution control methods for this (supposedly salt-insensitive) class of surfactants.