A systematic study of equilibrium structure, thermodynamics, and rheology of aqueous CTAB/NaNO3 wormlike micelles

We present a systematic study of the self-assembly of wormlike micelles (WLMs) comprised of cetyltrimethylammonium bromide (CTAB) and sodium nitrate (NaNO3) in aqueous solution as a function of CTAB concentration, NaNO3 concentration, and temperature throughout the dilute and semi-dilute regions of the phase diagram where linear micelles are observed. Combining measurements using isothermal titration calorimetry, rheometry, flow-birefringence, cryo-transmission electron microscopy (cryo-TEM), and small angle neutron scattering (SANS) enables complete characterization of the structure, thermodynamics, and rheology of CTAB/NaNO3 micelles. The addition of NaNO3 is found to increase the micellization enthalpy as well as the micellar scission energy, resulting in the elongation and growth of WLMs. We find quantitative agreement between the scission energy determined from rheology and the enthalpy of micellization determined from ITC, as well as for contour lengths extracted from rheology and SANS. At fixed molar ratio of NaNO3 and CTAB, the solution rheology exhibits scaling consistent with dilute, semi-dilute overlapping, and semi-dilute entangled regimes typically found in polymer solutions, as confirmed by cryo-TEM and SANS. The transition between these scaling regimes coincides with the structural transitions identified by SANS. The results validate the relationship between structural parameters and rheological behavior underlying theories for ionic WLMs.

Dilution viscometry of wormlike micelles from the entangled to dilute regimes. Combined with SANS and calorimetry,these measurements yield structure–property relationships for self-assembled micellar solutions.Figure optionsDownload high-quality image (57 K)Download as PowerPoint slide