Comparison of drag reduction, rheology, microstructure and stress-induced precipitation of dilute cationic surfactant solutions with odd and even alkyl chains

Cationic surfactant systems of different alkyl chain lengths with counterion, CnTAC(5 mmol/l)/3-Cl-Benzoate(12.5 mmol/l) (n=15, 16, 17, 18), were investigated for drag reduction, rheological behaviors, microstructure, and stress-induced precipitation. These are the first measurements of these characteristics for odd chain length (C15 and C17) quaternary ammonium surfactants. The lower and upper effective drag reduction temperature limits, viscoelasticity, and stress-induced precipitation temperature increased with alkyl chain length. Krafft temperature, critical turbidity temperature, and lower drag reduction effectiveness temperature limit showed a zigzag odd-even effect, while the stress-induced precipitation temperature did not. Light microscopy and cryo-TEM showed that cooling the C15 solution below 20 °C produced crystals, while above that temperature threadlike micelles were present. The same was true for the solutions of C18 that had threadlike micellar network microstructures when clear and crystals formed upon cooling. Micellar solutions can remain in a homogenous metastable state at a temperature below the Krafft temperature and above the critical turbidity temperature for days without external disturbance. Imposition of flow stress causes the systems to overcome the energy barrier and precipitate.