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German Urbina-Villalba

Publications and source records attributed to German Urbina-Villalba.

6 recordsLinked to original sources

Theoretical estimation of stability ratios for hexadecane-in-water (H/W) emulsions stabilized with nonylphenol ethoxylated surfactants.

The effect of steric interactions on the stability of oil-in-water emulsions is studied here by means of emulsion stability simulations (ESS). For this purpose, a new steric potential based on a modification of the one formerly proposed by Vincent et. al. is employed. The parameters of the calculation correspond to hexadecane in water emulsions stabilized with nonylphenol ethoxylated surfactants of different chain lengths (NPEm). Stability ratios (W) were calculated using the half life time of the number of drops per unit volume of these systems. A functional relationship between W and the repulsive potential barrier, (DeltaV), similar to the one previously found by Prieve and Ruckenstein for electrostatically stabilized suspensions was obtained. However, according to our simulations there exists a threshold for the stability of emulsions with respect to coalescence which is approximately located around 12.7 k(B)T.

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Steric interaction between spherical colloidal particles.

The reliability of the Derjaguin approximation for the calculation of the mixing term between sterically stabilized colloidal particles is studied. For this purpose, the steric potential obtained from the experiment of Doroszkowski and Lambourne [J. Polym. Sci., Part C: Polym. Symp. 34, 253 (1971)] is regarded as an exact result. Several analytical expressions corresponding to the mixing term of the steric potential are tested. Vincent et al. [Colloids Surf. 18, 261 (1986)] obtained four of them using the Derjaguin approximation along with different profiles for the volume fraction of segments in grafted polymer layers. As will be shown, the exact calculation of the volume of interaction between two spheres with adsorbed polymer layers already leads to a considerable improvement of the theoretical prediction for the simplest case of constant spatial distribution of polymer monomers. This equation is also better than the four additional expressions that result from using Bagchi's formalism [J. Colloid Interface Sci. 47, 86 (1974)] with similar segment profiles. The deviations of Bagchi's formalism can be substantially minimized using Flory-Krigbaum theory instead of the Flory-Huggins formalism for the calculation of the free energy of mixing. The equations derived here for the steric potentials were derived for particles of distinct radii.

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Role of the secondary minimum on the flocculation rate of nondeformable droplets.

The kinetic stability of suspensions is usually associated with a decrease in the flux of flocculating particles due to the action of a repulsive potential. However, previous calculations on bitumen drops suggest the possible occurrence of relatively fast aggregation rates in systems with large electrostatic barriers for primary minimum flocculation. This indicates a strong effect of the secondary minimum in the process of aggregation. Here, emulsion stability simulations (ESS) are used to study the aggregation behavior of 11 systems showing different depths of the secondary minimum and three particle sizes. Micron size drops (as those of Bitumen emulsions) usually exhibit deep secondary minima, which rarely occur between nanometer size particles. At high surfactant concentrations, these drops do not coalesce but can still show fast aggregation rates caused by irreversible secondary-minimum flocculation. On the other hand, the extent of coalescence in nanometer-size systems markedly depends on the height of the repulsive barrier. Furthermore, the secondary minimum of these smaller particles is usually shallow, causing reversible aggregation or no aggregation at all. In this article, the consequences of the referred behaviors on the magnitude of the stability ratio are discussed.

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Calculation of flocculation and coalescence rates for concentrated dispersions using emulsion stability simulations.

A simple procedure for the quantification of flocculation (k(f)) and coalescence (k(c)) rates from emulsion stability simulations (ESS) of concentrated systems is presented. It is based on a simple analytical equation, which results from the sum of well-known formulas for the separate processes of flocculation and coalescence. The expression contains k(f) and k(c) as fitting parameters and is found to reproduce the behavior predicted by ESS spanning a wide range of volume fractions (1 < phi < 30%) and surfactant concentrations (1.2 x10(-5) < C < 1.2 x 10(-4) M). This procedure allows interpretation of ESS data in terms of the referred kinetic rates. Furthermore, it could also provide an additional mean for the direct comparison of the simulation data with experimental results.

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Effect of dynamic surfactant adsorption on emulsion stability.

The effect of dynamic surfactant adsorption on the stability of concentrated oil in water emulsions is studied. For this purpose, a modification of the standard Brownian dynamics algorithm (Ermak, D.; McCammon, J. A. J. Chem. Phys. 1978, 69, 1352) previously used to study the behavior of bitumen emulsions assuming instantaneous adsorption (Urbina-Villalba, G.; García-Sucre, M. Langmuir 2000, 16, 7975) was employed. In the present case, dynamic adsorption (DA) was accounted for through a time-dependent electrostatic repulsion between the drops, a function of the surfactant surface excess. The surface excess was allowed to evolve with time according to well-established analytical expressions which depend parametrically on the surfactant diffusion constant (Ds) and the total surfactant concentration (C). The investigation required appropriate incorporation of hydrodynamic interactions in concentrated systems. This was achieved through a novel methodology, which expresses the diffusion constant of each particle as a function of its local concentration and the shortest distance of separation between nearest neighbors. In model systems, the variation of the number of drops as a function of time was followed for different magnitudes of the apparent diffusion constant D(app) of the surfactant. For each of these values, the effect of C and the volume fraction of internal phase (phi) was considered. DA was found to influence emulsion stability appreciably at moderately high phi. In this case, the average collision time between drops is comparable to the time required for the occurrence of a substantial surfactant adsorption, but the interdrop separation is sufficiently large to prevent a considerable slowdown of particle movement due to hydrodynamic interactions.

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Average hydrodynamic correction for the Brownian dynamics calculation of flocculation rates in concentrated dispersions.

In order to account for the hydrodynamic interaction (HI) between suspended particles in an average way, Honig et al. [J. Colloid Interface Sci. 36, 97 (1971)] and more recently Heyes [Mol. Phys. 87, 287 (1996)] proposed different analytical forms for the diffusion constant. While the formalism of Honig et al. strictly applies to a binary collision, the one from Heyes accounts for the dependence of the diffusion constant on the local concentration of particles. However, the analytical expression of the latter approach is more complex and depends on the particular characteristics of each system. Here we report a combined methodology, which incorporates the formula of Honig et al. at very short distances and a simple local volume-fraction correction at longer separations. As will be shown, the flocculation behavior calculated from Brownian dynamics simulations employing the present technique, is found to be similar to that of Batchelor's tensor [J. Fluid. Mech. 74, 1 (1976); 119, 379 (1982)]. However, it corrects the anomalous coalescence found in concentrated systems as a result of the overestimation of many-body HI.

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