J.I. Escalante

Structure of reverse microemulsion-templated metal hexacyanoferrate nanoparticles

The droplet phase of a reverse microemulsion formed by the surfactant cetyltrimethylammonium ferrocyanide was used as a matrix to synthesize nanoparticles of nickel hexacyanoferrate by adding just a solution of NiCl2 to the microemulsion media. Dynamic light scattering and small-angle neutron scattering measurements show that the reverse microemulsion droplets employed have a globular structure, with sizes that depend on water content. Transmission electron microscopy and electron diffraction are used to obtain information about the structure of the synthesized nanoparticles. The results show that the size and shape of the coordination compound nanoparticles correspond with the size and shape of the droplets, suggesting that the presented system constitutes an alternative method of the synthesis of metal hexacyanoferrate nanoparticles.

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.

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.

Obtaining NiHCF Nanoparticles Using a Reverse Micellar System

The synthesis of metallic nanoparticles using a reverse microemulsion medium brings controlled size and shape. In this study, reverse micelar system was employed for the synthesis of nickel hexacyanoferrate nanoparticles, NiHCF, by direct encapsulation in the water pools of reverse micelles formed in a pseudoternary system that consist of a mixture of 95 %wt. cetyltrimetyl ammonium bromide (CTAB) and 5 %wt. of a novel modified surfactant cetyltrimetyl ammonium ferrocyanate (CTA[Fe(CN6)]4-, CTAFe)/n-butanol/Hexane/Water. These NiHCF nanoparticles were produced with particle size ranging with 20 – 60 nm.

Time-Dependent Rheological Behavior of Liquid Crystalline Dispersions

The rheological response of Aerosol OT (AOT)/water liquid crystalline dispersions is reported here using shear flows. The dispersions exhibit an apparent yield stress and strong non-Newtonian behavior. Steady state and pre-shear dynamical experiments reveal shear-induced structural changes. Under increasing-and-decreasing shear stress experiments, the dispersions exhibit anti-thixotropic hysteresis loops. Once a critical stress is surpassed, an additional thixotropic loop is observed at high shear stress levels. This inverse loop at high shear stresses depends on the previous shear history and on both the rate of change and the maximum attained value of shear stress. The number density of the globular structures in the sheared sample is larger than in one non-sheared sample, but their sizes are smaller than those of the non-sheared sample.