Structure of Polystyrenesulfonate/Surfactant Mixtures at Air–Water Interfaces and Their Role as Building Blocks for Macroscopic Foam

[Image: see text] Air/water interfaces were modified by oppositely charged poly(sodium 4-styrenesulfonate) (NaPSS) and hexadecyltrimethylammonium bromide (CTAB) polyelectrolyte/surfactant mixtures and were studied on a molecular level with vibrational sum-frequency generation (SFG), tensiometry, surface dilatational rheology and ellipsometry. In order to deduce structure property relations, our results on the interfacial molecular structure and lateral interactions of PSS(–)/CTA(+) complexes were compared to the stability and structure of macroscopic foam as well as to bulk properties. For that, the CTAB concentration was fixed to 0.1 mM, while the NaPSS concentration was varied. At NaPSS monomer concentrations <0.1 mM, PSS(–)/CTA(+) complexes start to replace free CTA(+) surfactants at the interface and thus reduce the interfacial electric field in the process. This causes the O−H bands from interfacial H(2)O molecules in our SFG spectra to decrease substantially, which reach a local minimum in intensity close to equimolar concentrations. Once electrostatic repulsion is fully screened at the interface, hydrophobic PSS(–)/CTA(+) complexes dominate and tend to aggregate at the interface and in the bulk solution. As a consequence, adsorbate layers with the highest film thickness, surface pressure, and dilatational elasticity are formed. These surface layers provide much higher stabilities and foamabilities of polyhedral macroscopic foams. Mixtures around this concentration show precipitation after a few days, while their surfaces to air are in a local equilibrium state. Concentrations >0.1 mM result in a significant decrease in surface pressure and a complete loss in foamability. However, SFG and surface dilatational rheology provide strong evidence for the existence of PSS(–)/CTA(+) complexes at the interface. At polyelectrolyte concentrations >10 mM, air–water interfaces are dominated by an excess of free PSS(–) polyelectrolytes and small amounts of PSS(–)/CTA(+) complexes which, however, provide higher foam stabilities compared to CTAB free foams. The foam structure undergoes a transition from wet to polyhedral foams during the collapse.