Rheo-SANS study on relationship between micellar structures and rheological behavior of cationic gemini surfactants in solution.

ABSTRACT

HYPOTHESIS: Gemini surfactant 12-2-12 (dimethylene-1,2-bis(dodecyl dimethylammonium bromide)) solutions are known to show shear thickening and thinning under salt-free conditions. Because the rheological behavior of the wormlike micelles formed by 12-2-12 in solution is related to their structure, we expected that changes to the precursor structure would affect their rheological behaviors. It is also important to understand the effect of the introduction of a spacer group in the 12-2-12 molecules on the rheological behavior and structure of the wormlike micelles under shear flow. EXPERIMENTS Simultaneous small-angle neutron scattering and rheological measurements (Rheo-SANS) of the 12-2-12 solutions were performed. We exhaustively studied the structural changes in the wormlike micelles upon increasing shear rate. FINDINGS: We found that the wormlike micelles were oriented in the direction of the flow due to elongation and that changes to the precursor of the wormlike micelles did not affect the shear thickening. As a precursor structural change of shear thinning, the wormlike micelles elongated while maintaining their orientation. We found that an increase in the molecular curvature of the 12-2-12 due to the introduction of a spacer-group contributed to the unusual rheological behaviors of the wormlike micelles in a solution under shear flow.