Dilational Rheology of Extended Surfactants at the Air/Water and Oil/Water Interfaces: Effect of Propylene Oxide Group Numbers

In this paper, the interfacial properties of extended surfactants with different oxypropylene (PO) groups were comprehensively investigated by using interfacial dilational rheology. The differences in molecular orientation, spatial configuration, and relaxation process were compared at the gas-water interface and oil-water interface. The influences of the PO groups on the interface viscoelasticity were analyzed, providing important theoretical support for the wide application of extended surfactants. Experimental results show that the lower number of PO groups in extended surfactants does not cause differences in their presence states on the interface; however, once it increases, the longer PO segment will spiral up in the direction perpendicular to the interface, forming a spatial configuration like a thin cylinder. Compared with air, the PO group has better solubility in the oil phase. The chain segment can still maintain a helical extension from the beginning to the end as a result. However, the upper layer of the thin cylinder will collapse to a certain extent at the surface. Moreover, the orientation of the hydrophobic side has a dynamic process of "tilting to upright" with the increase of adsorption amount or in response to interfacial dilation and compression. The increase of PO number or the insertion of oil molecules has little effect on dilational modulus, and the interfacial film strength is generally relatively low. That is to say, the better emulsifying and solubilizing ability of PO-containing extended surfactants may be more attributed to the matching steric effect at interface or better packing action in bulk phase than to higher film strength.