Langmuir, Vol.17, No.26, 8055-8061, 2001
Concentration fluctuations in CTAB/NaSal solutions
This report details a dynamic light scattering investigation of CTAB/NaSal solution concentration fluctuations over a wide range of CTAB concentration and NaSal:CTAB mole ratio. Two distinct relaxation times are observed for CTAB concentrations greater than or equal to 0.02 M. The hydrodynamic correlation length, Il, associated with the fast, relaxation mode is observed to depend on both the CTAB concentration and NaSal:CTAB mole ratio. In particular, the CTAB concentration scaling of xi (H) is shown to vary in a nonmonotonic manner with the NaSal:CTAB mole ratio. The scaling exponent is found to range from -0.25 to -0.67, where its minimum value is found for NaSal:CTAB mole ratios near 1.5-2.0. The amplitude of the slow relaxation mode is strongly correlated with the hydrodynamic correlation length for NaSal:CTAB mole ratios less than or equal to 2 thereby suggesting polymer/polyelectrolyte solution behavior at these conditions. The overall picture that emerges is that of a system where the competition among micellar charge, electrostatic screening, and micelle breaking controls the system dynamics. The behavior of the hydrodynamic correlation length and slow-mode amplitude can be understood quite well within a framework of micelle ionization and electrostatic screening effects. However, the NaSal:CTAB mole ratio and CTAB concentration dependence of the slow relaxation time cannot be entirely explained within the context of electrostatic interactions. To account for the observed behavior it is proposed that the micelle breaking time is influenced by bound salicylate ions whose degree of binding depends on both the NaSal:CTAB mole ratio and CTAB concentration.