Dual Transient Networks of Polymer and Micellar Chains: Structure and Viscoelastic Synergy.

Dual transient networks were prepared by mixing highly charged long wormlike micelles of surfactants with polysaccharide chains of hydroxypropyl guar above the entanglement concentration for each of the components. The wormlike micelles were composed of two oppositely charged surfactants potassium oleate and n-octyltrimethylammonium bromide with a large excess of anionic surfactant. The system is macroscopically homogeneous over a wide range of polymer and surfactant concentrations, which is attributed to a stabilizing effect of surfactants counterions that try to occupy as much volume as possible in order to gain in translational entropy. At the same time, by small-angle neutron scattering (SANS) combined with ultrasmall-angle neutron scattering (USANS), a microphase separation with the formation of polymer-rich and surfactant-rich domains was detected. Rheological studies in the linear viscoelastic regime revealed a synergistic 180-fold enhancement of viscosity and 65-fold increase of the longest relaxation time in comparison with the individual components. This effect was attributed to the local increase in concentration of both components trying to avoid contact with each other, which makes the micelles longer and increases the number of intermicellar and interpolymer entanglements. The enhanced rheological properties of this novel system based on industrially important polymer hold great potential for applications in personal care products, oil recovery and many other fields.

Disruption of Cationic/Anionic Viscoelastic Surfactant Micellar Networks by Hydrocarbon as a Basis of Enhanced Fracturing Fluids Clean-Up.

Studies of the effects produced by the solubilization of hydrophobic substances by micellar aggregates in water medium are quite important for applications of viscoelastic surfactant solutions for enhanced oil recovery (EOR), especially in hydraulic fracturing technology. The present paper aims at the investigation of the structural transformations produced by the absorption of an aliphatic hydrocarbon (n-decane) by mixed wormlike micelles of cationic (n-octyltrimethylammonium bromide, C8TAB) and anionic (potassium oleate) surfactants enriched by C8TAB. As a result of contact with a small amount (0.5 wt%) of oil, a highly viscoelastic fluid is transformed to a water-like liquid. By small-angle neutron scattering (SANS) combined with cryo-TEM, it was shown that this is due to the transition of long wormlike micelles with elliptical cross-sections to ellipsoidal microemulsion droplets. The non-spherical shape was attributed to partial segregation of longer- and shorter-tail surfactant molecules inside the surfactant monolayer, providing an optimum curvature for both of them. As a result, the long-chain surfactant could preferably be located in the flatter part of the aggregates and the short-chain surfactant-at the ellipsoid edges with higher curvature. It is proven that the transition proceeds via a co-existence of microemulsion droplets and wormlike micelles, and upon the increase of hydrocarbon content, the size and volume fraction of ellipsoidal microemulsion droplets increase. The internal structure of the droplets was revealed by contrast variation SANS, and it was shown that, despite the excess of the cationic surfactant, the radius of surfactant shell is controlled by the anionic surfactant with longer tail. These findings open a way for optimizing the performance of viscoelastic surfactant fluids by regulating both the mechanical properties of the fluids and their clean-up from the fracture induced by contact with hydrocarbons.