Dilational rheological properties of extended anionic surfactants at decane-water interface

Abstract

The dynamic interfacial dilational properties of extended surfactants octadecyl-(polypropylene oxide)m-(polyethylene oxide)n-carboxylic sodium (C18POmEOnC) with different numbers of polypropylene oxide (PO) and polyethylene oxide (EO) groups at the decane–water interface were investigated by means of oscillating drop method. The influences of interface ageing time, dilational frequency, bulk concentration and interfacial pressure on the dilational properties were investigated. The experimental results demonstrate that, at low concentrations, the adsorption film is predominantly influenced by diffusion exchange, while intermolecular interactions at the interface play a more significant role at high concentrations. Beyond the critical micelle concentration (CMC), the primary relaxation process in the adsorption film is driven by the formation of micellar structures. Additionally, the weak hydrophobic PO groups exhibit compressibility and extensibility, facilitating the formation of spring-like helical structures at the decane–water interface. As a result, the dilational modulus increases and the phase angle decreases in low concentration with the increase of PO number. With increasing concentration, the weak hydrophilic EO chains gradually transition from a partially flat state to an upright orientation toward the aqueous phase, forming sublayer structures through polar interactions. At this stage, the increase in EO group chain length has a more pronounced impact on the elastic modulus compared to PO groups. These experimental findings suggest the existence of a mechanistic model for the extended surfactant adsorption films.