F. Bautista

Understanding thixotropic and antithixotropic behavior of viscoelastic micellar solutions and liquid crystalline dispersions. I. The model

Abstract A simple model consisting of the Upper Convected Maxwell constitutive equation and a kinetic equation for destruction and construction of structure, first proposed by Fredrickson in 1970, is used here to reproduce the complex rheological behavior of viscoelastic systems that also exhibit thixotropy and rheopexy under shear flow. The model requires five parameters that have physical significance and that can be estimated from rheological measurements. Several steady and unsteady flow situations were analyzed with the model. The model predicts creep behavior, stress relaxation and the presence of thixotropic loops when the sample is subjected to transient stress cycles. Such behavior has been observed with surfactant-based solutions and dispersions. The role of the characteristic time for structure built up, λ, in the extent and shape of the thixotropic loops is demonstrated.

On the shear banding flow of elongated micellar solutions

Abstract Under steady shear flow, elongated micellar solutions show shear stress saturation above a critical shear rate due to the formation of shear bands that result in non-homogeneous flow. Long transients and oscillations accompany this stress plateau. When measurements are done with a controlled stress rheometer, frequently a metastable branch is observed. At higher shear rates, a second upturn is observed above a second critical shear rate, which indicates that homogeneous flow is recovered. Here, a model consisting of the codeformational Maxwell constitutive equation coupled to a kinetic equation to account for the breaking and reformation of the micelles is presented to reproduce the features described above in steady shear flow. The model also predicts a second metastable branch and long transients at higher shear rates and the existence of an inflexion point in stress-shear rate plots above which no shear banding behavior is detected.

Dynamics of worm-like micelles: the Cox-Merz rule

Abstract The viscoelastic behaviour of worm-like micelles in small-amplitude oscillatory, steady simple shear and uniaxial extensional flows are analyzed with a model that couples the Oldroyd-B constitutive equation with a kinetic equation that accounts for the structural changes induced by the flow. In some cases, the constitutive equation predicts a viscoelastic behaviour that is consistent with the Cox–Merz rule. Departures from this rule are also predicted. Experimental data obtained for two worm-like micellar systems indicate that in these solutions, the Cox–Merz rule is not usually followed, in agreement with the predictions of our model. In uniaxial extensional flow, the model predicts a strain hardening in the extensional viscosity at low extensional rates and a strain-thinning at high extensional rates.

Rheology of the Pluronic P103/water system in a semidilute regime: Evidence of nonequilibrium critical behavior

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.

Effect of ionic strength on rheological behavior of polymer-like cetyltrimethylammonium tosylate micellar solutions

The influence of ionic strength on the rheological properties of polymer-like aqueous micellar solutions of cetyltrimethylammonium tosylate (CTAT) containing different salts (KCl, KBr, (COONa)2, K2SO4 or K3PO4) is investigated. The rheological behavior of the solutions is analyzed above the concentration where a micellar entanglement network is formed, varying surfactant and salt concentration, salt counterion valency and temperature. A master curve of the linear viscoelastic properties is obtained by multiple superposition of time, temperature, salt type, and surfactant and salt concentration. Application of the existent kinetic theory provides information suggesting that the micellar solutions are in the fast breaking regime (i.e., the relaxation is kinetically controlled) regardless of salt type and concentration. Moreover, these solutions exhibit shear-banding flow with a reduced stress plateau (σ/G0, being σ and G0 the shear stress and the plateau modulus, respectively) that increases with salt content and counterion valency. The zero-shear viscosity (η0) and the main relaxation time (τC) diminish with increasing salt content according to a step-like function, in which the number of steps increases with the salt counterion valence. In contrast, G0 only increases slightly with increasing salt content for the five salts employed. These results are discussed in terms of ionic strength and screening of the electrostatic-interactions caused by the addition of salt. In addition, it was found that the influence of anions on the viscoelastic properties of the polymer-like micelles follows the Hofmeister series commonly encountered in macromolecular and biological systems. This finding opens a challenge for scientists in the experimental and theoretical fields.

Critical phenomenon analysis of shear-banding flow in polymer-like micellar solutions. 1. Theoretical approach.

The shear-banding flow in polymer-like micellar solutions is examined here with the generalized Bautista-Manero-Puig model. The coupling between flow and diffusion naturally arises in this model, which is derived from the extended irreversible thermodynamic formalism. The limit of an abrupt interface is treated here. The model predicts a dynamic master steady-flow diagram, in which all data collapse at low shear rates. Moreover, the model predicts that a nonequilibrium critical line is reached upon decreasing the shear-banding intensity parameter of the model, which corresponds to increasing temperature, increasing surfactant concentration, or varying salt-to-surfactant concentration ratio. By employing nonequilibrium critical theory and the concept of dissipated energy (or extended Gibbs free energy), a set of symmetrical reduced stress versus reduced shear-rate curves are obtained similar to gas-liquid transitions around the critical point. In addition, the nonequilibrium critical exponents are derived, which follow the extended Widoms rule and the extended Rushbroke relationship, but they are nonclassical.

Effects of electrolyte concentration and counterion valence on the microstructural flow regimes in dilute cetyltrimethylammonium tosylate micellar solutions

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.

Rheological behavior of surfactant-based precursors of silica mesoporous materials.

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.

On the modelling of the shear thickening behavior in micellar solutions

AbstractThe steady and transient nonlinear rheological behaviors of dilute rod-like micellar solutions are predicted here with a particular case of the generalized Bautista–Manero–Puig (BMP) model that consists of the upper-convected Maxwell constitutive equation and a dissipative power-dependent kinetic equation, which takes into account the formation and disruption of shear-induced structures (SISs). This model has been derived using the extended irreversible thermodynamic (EIT) formalism. In steady shear, the model predicts a Newtonian region at low shear rates and a characteristic shear rate (γ̇c