Study of the interactions between poly(ethylene oxide) and anionic surfactants in elongational flow

The rheology of polymer solutions is important in a wide variety of applications. In particular, solutions of high-molecular-weight, flexible polymers exhibit an increase in their apparent extensional viscosity with strain rate under extensional flow conditions. This extension thickening is due to formation of transient entanglements of polymer molecules. Certain commercial fluids contain both polymers and surfactants that might interact at the molecular level. These interactions affect the conformation of the polymer chain and, therefore, the rheological behavior of the solution. For instance, addition of anionic surfactants to solutions of nonionic polymers is known to induce increases in the shear viscosity of aqueous solution. This work investigates the behavior of aqueous solutions of a high-molecular-weight poly(ethylene oxide) (PEO), a nonionic, flexible polymer, and the anionic surfactants sodium dodecyl sulfate (SDS), sodium dodecyl benzene sulfonate (SDBS) and a commercial α-olefin sulfonate (AOS) in extensional flows. The extensional rheology of polymer/surfactant solutions is studied in an opposed-jets device, which generates a flow field close to uniaxial extension. For PEO/SDS mixtures, the results show that formation of micellar aggregates of SDS along the PEO chains results in an increase in the strength of extension thickening of PEO solutions by promoting intermolecular interactions between polymer chains. The minimum PEO concentration required to form intermolecular entanglements is substantially reduced in the presence of micellar aggregates. In solutions containing NaCl, intramolecular interactions are observed at low PEO concentrations. These reduce the strength of extension thickening. Addition of a co-solvent is investigated. The presence of alcohols in the aqueous solutions affects their rheology by changing the solvent nature for both PEO and SDS. In particular, n-octanol promotes aggregation of SDS along the PEO chains, enhancing intermolecular network formation in extensional flow. Results with mixtures of PEO with sulfonated surfactants (SDBS and AOS) show that both intermolecular and intramolecular interactions are promoted by these surfactants, depending on PEO concentration and molecular weight. The effect of ageing on these polymer/surfactant systems was studied. In extensional flows, extension thickening is suppressed in solutions of PEO with SDBS or AOS over a few-day period, whereas PEO and PEO/SDS solutions show no change.