title: Effect of monomeric and polymeric co-solutes on cetyltrimethylammonium bromide wormlike micelles: rheology, Cryo-TEM and small-angle neutron scattering.
abstract: The effect of hydrophobic and hydrophilic co-solutes on the rheological properties of wormlike micelles of cetyltrimethylammonium bromide (CTAB) and sodium salicylate (NaSal) or sodium bromide (NaBr) was investigated. Monomeric (ethanol, 2-propanol, benzene and benzylic alcohol) and polymeric species (poly(ethylene oxide), poly(vinyl alcohol) and poly(propylene oxide), respectively PEO, PVA and PPO) of varying molecular weight were studied in order to assess the effect of co-solute 'length' on the interactions with the wormlike micelles. Rheological properties were characterised by the plateau modulus G(0) and the relaxation time τ(R) obtained from fits to the Maxwell model, and by the zero-shear viscosity η(0). The rheological properties were unaltered by the addition of all hydrophilic solutes (up to 20 mM). With hydrophobic co-solutes instead, both η(0) and τ(R) decreased considerably, while G(0) was unaffected. The effects were particularly remarkable with PPO for concentrations as low as 5 mM (ca. 0.3 g L(-1)), and τ(R) was seen to follow an exponential decrease with polymer M(w). The effect of the aromatic solutes (benzene and benzyl alcohol) on the rheology was highly dependent on the counterions used to induce micellar growth (Sal(-) or Br(-)), revealing a different type of interaction. Surprisingly, small-angle neutron scattering and Cryo-TEM measurements showed that the drastic changes observed in the rheology were not correlated to any visible structural change. Therefore the strong decrease in viscosity and relaxation time are to be attributed to other mechanisms than micellar break-up or rod-to-sphere transition.
authors.affiliation: Department of Physical-Chemistry, Institute of Chemistry, University of Campinas, Campinas, P.O. Box 6154, 13084-862, SP, Brazil.
authors.forename: Kelly R
authors.initials: KR
authors.lastname: Francisco
authors.forename: Marcelo A
authors.initials: MA
authors.lastname: da Silva
authors.forename: Edvaldo
authors.initials: E
authors.lastname: Sabadini
authors.forename: Göran
authors.initials: G
authors.lastname: Karlsson
authors.forename: Cécile A
authors.initials: CA
authors.lastname: Dreiss
mesh_terms: D001965:Bromides / Q000737:chemistry*; D000077286:Cetrimonium; D002593:Cetrimonium Compounds / Q000737:chemistry*; D020285:Cryoelectron Microscopy / Q000379:methods; D033363:Neutron Diffraction / Q000379:methods; D012212:Rheology / Q000379:methods; D053838:Scattering, Small Angle; D017670:Sodium Compounds / Q000737:chemistry*; D012980:Sodium Salicylate / Q000737:chemistry*
chemical_list: D001965:Bromides; D002593:Cetrimonium Compounds; D017670:Sodium Compounds; C027938:sodium bromide; D012980:Sodium Salicylate; D000077286:Cetrimonium