Coming to Order: Adsorption and Structure of Nonionic Polymer at the Oil/Water Interface as Influenced by Cationic...

Polymer-surfactant mixtures are versatile chemical systems because of their ability to form a variety of complexes both in bulk solution and at surfaces. The adsorption and structure of polymer-surfactant complexes at the oil/water interface define their use surface chemistry applications. Previous studies have investigated the interactions between charged polyelectrolytes and surfactants; however, a similar level of insight into the interfacial behavior of nonionic polymers in mixed systems is lacking. The study herein uses vibrational sum frequency (VSF) spectroscopy to elucidate the molecular details of nonionic polyacrylamide (PAM) adsorption to the oil/water interface in the presence of surfactant. The polymer's adsorption and conformational structure at the interface is investigated as it interacts with cationic and anionic surfactants. Where the polymer will not adsorb to the interface on its own in solution, the presence of either cationic or anionic surfactant causes favorable adsorption of the polymer to the oil/water interface. VSF spectra indicate that the cationic surfactant interacts with PAM at the interface through charge-dipole interactions to induce conformational ordering of the polymer backbone. However, conformational ordering of polymer is not induced at the interface when anionic surfactant is present.