It has been established that sodium dodecyl sulfate (SDS) binds to the micelles and monomers of the block copolymer F127. SDS binds to the monomeric unassociated F127 in the form of polymer/bound SDS micellar complexes. SDS binds to F127 micelles first forming mixed micelles, which dissociate into smaller mixed aggregates and then to single F127 unassociated monomers. A third interaction of SDS, which involves promotion of F127 micelles at concentrations up to 3 °C below the critical micellar temperature of pure F127, was identified and is investigated in the present work. The formation of such SDS-induced mixed micelles was monitored using differential scanning calorimetry, light scattering, isothermal titration calorimetry, and a SDS selective electrode for electromotive force measurements. These investigations have shown how the different binding and aggregation processes between SDS and F127 involving induced micellization, growth of mixed micelles, breakdown of mixed micelles, and binding of SDS to monomeric F127 can be identified and characterized.

We applied isothermal titration calorimetry (ITC) and surface tension (ST) and electromotive force (emf) measurements using a coated wire sodium dodecyl sulfate membrane-selective electrode to measure the mixed micellar composition of various mixtures of the triblock copolymer EO97PO69EO97, a nonionic surfactant code-named Pluronic F127, with sodium dodecyl sulfate (SDS). In the region where mixed micelles are formed, the interaction between the two surfactants showed synergistic behavior and interaction parameters β, which characterize the nonideal interaction in the mixed micelles, could be calculated over a range of mole ratios. For several compositions, the critical micelle concentrations of the mixed micelles were determined using ITC and ST measurements. In addition, small-angle neutron scattering (SANS) experiments were carried out in order to investigate the structure and provide additional information about the composition of the mixed micelles, taking advantage of contrast variation between SDS-h12 and SDS-d12. Mixed F127/SDS aggregates could be confirmed, and from an examination of the results of all methods the mixed F127/SDS system can be explained in considerable detail.