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The aggregation properties of 2-, 3-, and 4-fluorobenzoic acids (2FBA, 3FBA, and 4FBA, respectively) and their salts with hexadecyltrimethylammonium cations (HTA2FB, HTA3FB, and HTA4FB) in water were studied with a battery of techniques. Their activity at the air/solution interface has been also studied. The position of the fluorine atom in the acid affected the solubility, adsorption, and aggregation in the pure acids solutions. The 4FBA is less water soluble, more hydrophobic, and has the lower critical aggregation concentration of the three isomers. The behavior of the HTA2FB compound in aqueous solution is different from that of HTA3FB and HTA4FB. The critical micelle concentration, critical concentration for sphere-to-rod-like micelle transition, and Krafft point of HTA3FB and HTA4FB are lower than those of the other surfactant but their surface activities are higher. The differences between the HTA2FB and the other two surfactants have been explained on the basis of the regular solution theory of mixed micelles and in light of the analysis of the hydration shell of the acids through molecular dynamic simulations. The results of the present work suggest that the different behaviors are due to a combination of different dehydration tendencies and the steric possibility of inclusion of the counterions in the micelle palisade layer. The formation of rod-like micelles by HTA2FB, while the tetradecyltrimethylammonium 2-fluorobenzoate only forms spherical aggregates, is explained on the basis of the packing parameter. The mentioned factors are complementary to others presented in literature. These conditions may be used in the rational design of micelles by means of molecular dynamics simulations, reducing the trial-and-error approach used to date., (Copyright © 2011 Elsevier Inc. All rights reserved.)

The shear thickening behavior and the transition to shear thinning are examined in dilute cetyltrimethylammonium tosylate (CTAT) micellar solutions as a function of surfactant concentration and ionic strength using electrolytes with different counterion valence. Newtonian behavior at low shear rates, followed by shear thickening and shear thinning at higher shear rates, are observed at low and intermediate surfactant and electrolyte concentrations. Shear thickening diminishes with increasing surfactant concentration and ionic strength. At higher surfactant or electrolyte concentration, only a Newtonian region followed by shear thinning is detected. A generalized flow diagram indicates two controlling regimes: one in which electrostatic screening dominates and induces micellar growth, and another, at higher electrolyte and surfactant concentrations, where chemical equilibrium among electrolyte and surfactant counterions controls the rheological behavior by modifying micellar breaking and reforming. Analysis of the shear thickening behavior reveals that not only a critical shear rate is required for shear thickening, but also a critical deformation, which appears to be unique for all systems examined, within experimental error. Moreover, a superposition of the critical shear rate for shear thickening with surfactant and electrolyte concentration is reported., (Copyright © 2011 Elsevier Inc. All rights reserved.)

The phase and rheological behavior of hexadecyl(trimethyl)azanium; 2-hydroxybenzoate (CTAS), and water as a function of surfactant concentration and temperature are investigated here. The critical micellization concentration (cmc(1)) and the concentration at which the structure of aggregates changes (cmc(2)) as well as the Krafft temperature (T(K)) are reported. A large micellar solution region exhibiting high viscosity, as well as hexagonal- and lamellar-phase regions were identified. In the dilute region, below the overlapping entanglement concentration (C*), the micellar solutions exhibit shear thickening. Above C*, wormlike micelles form and the solutions show strong viscoelasticity with Maxwell behavior in the linear regime and shear banding flow in the non-linear regime. The linear viscoelastic regime was analyzed with the Granek-Cates model, showing that the relaxation is controlled by the kinetics of reformation-and-scission of the micelles. The steady response in the non-linear regime is compared with the predictions of the Bautista-Manero-Puig (BMP) and the Giesekus models., (Copyright 2010 Elsevier Inc. All rights reserved.)

The linear and nonlinear rheological behaviors of semidilute aqueous solutions of the amphiphile triblock polymer Pluronics P103 in water are reported here. For C(surf) < or = 20 wt%, micelles are spherical at temperatures lower than ca. 27 degrees C and grow with increasing temperature to form long polymer-like micelles. These polymer-like micelles exhibit strong viscoelasticity and a shear-banding region that shrinks as the cloud point is approached. Master time-temperature-concentration curves were obtained for the dynamic moduli using traditional shifting factors. In the nonlinear regime, P103 polymer-like micellar solutions follow the master dynamic phase diagram proposed by Berret and colleagues, in which the flow curves overlap in the low-shear-rate homogeneous flow region. Within the nonhomogeneous flow region (confirmed by flow birefringence and small-angle light-scattering measurements), oscillations and overshoots are detected at the inception of shear flow, and two main relaxation mechanisms are apparent after cessation of steady shear flow. Evidence for nonequilibrium critical behavior is presented, in which the order parameter is the difference of critical shear rates that limit the span of the plateau stress. Most of the steady-state and transient features of the nonlinear rheology of the P103 polymer-like micelles are reproduced with the Bautista-Manero-Puig (BMP) model, including the predictions of nonequilibrium critical behavior under flow.

The detailed temperature-composition phase diagram of the P103/water system in the dilute and semidilute regions is reported here using density and ultrasound velocity measurements, differential scanning calorimetry (DSC), rheometry and dynamic (DLS) and static light scattering (SLS). These techniques allow a precise determination of the critical micellar temperature (CMT), the sphere-to-rod micellar transition temperature (GMT) and the cloud point temperature (CPT) as a function of concentration. DLS and SLS measurements were employed to gain information on unimers and aggregate sizes and on the transition from spherical-to-rod micelles.

The linear and non-linear viscoelastic behaviors of polymer-like micellar solutions of cetyltrimethylammonium tosilate (CTAT) with added NaOH and tetraethyl orthosilicate (TEOS) to produce precursors of mesoporous materials are studied. The effect of TEOS/CTAT (T/C) ratio at fixed CTAT concentration, CTAT concentration at fixed T/C and aging time are reported. The systems show increasingly larger deviations from near-Maxwell behavior upon increasing T/C ratio, CTAT concentration and aging. Moreover, in steady and unsteady shear-flow, shear banding develops between two critical shear rates, which tend to fade as the T/C ratio and aging increase. The Granek-Cates model is employed to analyze linear viscoelastic behavior. The Bautista-Manero-Puig (BMP) model is used here to reproduce the steady and transient nonlinear rheology of these systems. We explain these results in terms of the changes in inter-macromolecular interactions that arise out of the presence of colloidal additives in the viscoelastic gel. The ordered mesoporous materials were identified by X-ray diffractometry (XRD) and high-resolution transmission electron microscopy.

The phase and rheological behaviors of the polymerizable surfactant, cetyltrimethylammonium benzoate (CTAVB), and water as a function of surfactant concentration and temperature are investigated here. The critical micelle concentration (cmc) and the (cmc(2)), as well as the Krafft temperature (T(K)), are reported. A large highly viscous micellar solution region and hexagonal- and lamellar-phase regions were identified. The micellar solutions exhibit shear thickening in the dilute regime, below the overlapping or entanglement concentration. At higher concentrations, wormlike micelles form and the solutions show strong viscoelasticity and Maxwell behavior in the linear regime and shear banding flow in the nonlinear regime. The linear viscoelastic regime is analyzed with the Granek-Cates model, showing that the relaxation is controlled by the kinetics of reformation and scission of the micelles. The steady and unsteady responses in the nonlinear regime are compared with the predictions of the Bautista-Manero-Puig (BMP) model. Model predictions follow the experimental data closely.