Tuning Nanoparticle-Micelle Interactions and Resultant Phase Behavior.

The evolution of the interaction between an anionic nanoparticle and a nonionic surfactant and their resultant phase behavior in aqueous solution in the presence of electrolyte and ionic surfactants have been studied. The mixed system of anionic silica nanoparticles (Ludox LS30) with nonionic surfactant decaethylene glycol monododecylether (C12E10) forms a highly stable clear phase over a wide concentration range of surfactant. Small-angle neutron scattering (SANS) and dynamic light scattering data show that the surfactant micelles adsorb on the surface of the nanoparticle, resulting in micellar-decorated nanoparticle structures. With the addition of a small amount of electrolyte into this system, the stability gets disturbed substantially and turns to a two-phase (turbid) system. The evolution of interaction in this system has been examined, and it was found that micelle-induced long-range depletion attraction (modeled by a double Yukawa potential) between nanoparticles leads to their aggregation. Interestingly, the addition of anionic surfactant sodium dodecyl sulfate (SDS) in this two-phase system transforms it to a transparent one-phase state, suppressing the depletion-mediated aggregation of nanoparticles. This is attributed to the formation of anionic C12E10-SDS mixed micelles, and it is their repulsive micelle-micelle interaction that disrupts the depletion phenomenon. On the other hand, the addition of cationic surfactant dodecyl trimethylammonium bromide (DTAB) to the turbid LS30-C12E10 electrolyte system shows no change in the turbidity arising from an aggregated nanoparticle system. The driving interaction, in this case, is different from that of the surfactant-mediated depletion attraction; it is due to the attraction between the nanoparticles mediated by the presence of oppositely charged DTAB micelles between them, resulting in a charge-driven bridging aggregation of nanoparticles. Each of these multicomponent systems has been investigated using contrast variation SANS measurements for different contrast conditions where the role of individual components (nanoparticle or surfactant) in the mixed system has been selectively studied. These results thus show that nanoparticle-surfactant micelle interactions can be tuned by the presence of electrolyte and/or choice of surfactant combination.