Non-linear rheology and flow-induced transition of a lamellar-to-vesicle phase in ternary systems of alkyldimethyl oxide/alcohol/water

The time-dependent transformation of an ionically charged lamellar phase (L-alpha-phase) into a vesicle phase under the influence of shear is investigated using rheological and conductivity measurements. The L-alpha-phase consists of the zwitterionic surfactant tetradecyldimethylaminoxide (C(14)DMAO), hexanol, oxalic acid and water. The experiments were carried out on the L-alpha-phase in a well defined state. It was prepared by a special route from the neighbouring L-3-phase that consists of 100 mM C(14)DMAO, 250 mM hexanol and 5 mM oxalic-diethylester (OEE). The OEE hydrolyses in the L-3-phase to oxalic acid and ethanol. The result is a virgin L-alpha-phase which consists of stacked bilayers and which has not been exposed to shear. When this low-viscous phase is subjected to shear it is transformed into a highly viscous vesicle phase. The transformation of the L-alpha-phase into vesicles under constant shear was monitored by recording the viscosity and conductivity with time. It is observed that at least three different time constants can be distinguished in the transformation process. The conductivity passes through a minimum (tau(1)) in the direction of shear. The viscosity first passes through a minimum (tau(2)) and then over a maximum (tau(3)) It is concluded that tau(1) belongs to the complete alignment of the bilayer parallel to the wall, tau(2) to the beginning of the break-up of the bilayers to the vesicles and tau(3) to the complete transformation of the L-alpha- to the vesicle phase. When the shear rate was varied, it was noted that the product of the time constants and shear is constant.