Langmuir, Vol.12, No.11, 2654-2662, 1996
Rheology of the Cetyltrimethylammonium Tosilate-Water System .2. Linear Viscoelastic Regime
In this work, the linear viscoelastic properties of the cetyltrimethylammonium tosilate (CTAT)-water system are examined in detail. This system forms elongated micelles at low and intermediate concentrations, and it yields a hexagonal phase above 27 wt % CTAT at 25 degrees C. Rheological behavior at low frequencies in a small-amplitude oscillatory shear experiments or at long times in stress relaxation measurements is governed by a single dominant relaxation time, although deviations from the limiting slope of the elastic modulus in the terminal region are observed at high CTAT concentrations. For higher frequencies, however, there is an additional mechanism whose dependence on frequency is analyzed with several rheological models. Analysis of data in terms of the theory of Cates demonstrates that the system consists of flexible micelles in the slow-breaking limit and it exhibits a constant entanglement density along the whole micellar region, even though the average micellar length decreases monotonically with concentration. Under these conditions, reptation speed up by the kinetics process of breaking and re-forming is the controlling relaxation mechanism.
Keywords:NONEQUILIBRIUM ALIGNMENT PHENOMENA;DETERGENT MOLECULES;MICELLE FORMATION;LIQUID-CRYSTALS;AQUEOUS-MEDIA;IRREVERSIBLE THERMODYNAMICS;SURFACTANT SYSTEMS;WORMLIKE MICELLES;LIVING POLYMERS;RELAXATION