Monolayers of Some Poly(oxyethylene)-Based Surfactants at the Air-Water Interface: The Effect of Structural...

The Langmuir surface balance technique has been used to study the interfacial behavior of six structurally different poly(oxyethylene) (POE)-based polymer surfactants at the air-water interface. On a pure water subphase the surfactants have collapse surface pressures dependent on the POE chain length. The surfactant monolayers collapse at well-determined surface pressures, and the lower POE chain-length surfactants collapse at higher pressures than those with high POE content. This difference vanishes as increasing amounts of salt are added to the subphase. The PiA-isotherms are smooth, which is normal for polymeric surfactants. A closer analysis of the isotherms reveals characteristic behavior that can be attributed to structural differences. Similarities in thermodynamic behavior suggest that the molecular orientation is the same despite the structural differences. A new expression for the compressibility factor is developed to explain the relationship between this parameter and surface pressure for polymeric monolayers. Copyright 1999 Academic Press.