Stability of block copolymer surfactant-based emulsions in the presence of a salt

Abstract

This project deals with the mixed micellar and interfacial properties of mixtures of three surfactants [sodium dodecyl sulphate (SDS), cetyltrimethylammonium bromide (CTAB), and tetraethylene glycol monododecyl ether (C12E4)] with ABA symmetrical triblock copolymer (Pluronic F127), which has many industrial applications. Evidence of F127 micellisation and interaction with surfactants in the aqueous phase is inferred through interfacial tension measurements. The solution containing diluted monomeric F127 showed complex formation with surfactants before the latter self-aggregate as pure micelles. The simultaneous presence of ionic surfactants and micellar F127 in solutions displayed a decrease of interfacial activity and led to the conclusion of F127 micelles disruption. C12E4 was found to interact differently with micellar F127 in forming mixed micelles, and no loss of interfacial activity was recorded. This “association-dissociation” behaviour of F127 and surfactants was leveraged to understand the stability of mineral oil in water emulsions formulated with them in the presence of sodium phosphate (Na3PO4). The mechanisms of emulsions breakdown were found to rely on aggregation behaviour and complex structure of F127 and surfactants mixtures in solution. Laser diffraction showed that unlike SDS and CTAB, mixed-emulsifier systems containing C12E4 are stable to both flocculation, Ostwald ripening and coalescence. Due to electrostatic repulsion between its head group and F127 hydrophilic block, and also because of the combined effect of Ostwald ripening and coalescence, CTAB emulsifier containing systems displayed quicker instability than SDS. SDS containing systems showed a progressive shifting of droplets size distributions to bimodality as SDS concentration was increased and heat exposure pursued, revealing the activity of two distinct population of droplets in the emulsions. More insight on the mechanisms underlying the stability of the three mixed emulsifier systems was gained in performing optical microscopy and rheology measurements; the results were found to be consistent with particle size distribution.