ABSTRACT
The presence of a sufficient concentration of solid particles in a solution gives rise to a large increase in its viscosity and, more importantly, to significant deviations with respect to its original Newtonian behavior. Different rheological techniques are available to characterize such deviations, but the simplest one, obtention of steady-state rheograms, is already extremely useful with that purpose. In this work, this technique is applied to suspensions of zirconia particles, both synthesized with spherical geometry and commercial. The sigma(shear stress)-gamma;(shear rate) curves show that the suspensions are nonideal plastic, thus exhibiting a finite yield stress, sigma(0), and a shear-thinning flow. It is through sigma(0) that a connection can be established between steady-state rheological behavior and interaction energy between particles, since sigma(0) can be estimated as the maximum attractive force between particles multiplied by the number of bonds per unit area between a given particle and its neighbors. Having an experimental determination of sigma(0), the verification of its relation with the attractive forces requires estimation of the potential energy of interaction between any pair of particles. Two approaches will be considered: one is the classical DLVO model, in which the potential energy, V, is the sum of the van der Waals (V(LW)) and electrostatic (V(EL)) contributions. The second approach is the so-called extended DLVO theory, in which the acid-base interaction V(AB) (related to the hydrophilic repulsion or hydrophobic attraction between the particles) is considered in addition to V(LW) and V(EL). The three contributions can be calculated as a function of the interparticle distance if the particle-solution interface is characterized from both the electric and the thermodynamic points of view. The former is carried out by means of electrophoretic mobility measurements and the latter by contact angle determinations for three probe liquids on zirconia powder layers. Comparison between measured and calculated sigma(0) values was carried out for suspensions of spherical, monodisperse ZrO(2) particles, with volume fraction of solids, straight phi, ranging between 4.6 and 21.7%, in 10(-3) M NaCl solutions. In the case of commercial particles, the effects of both NaCl concentration (10(-5) to 10(-1) M) and volume fraction (3.5 to 21%) were investigated. It is found that the classical DLVO theory cannot be used to predict the yield stress when [NaCl]=10(-5) M, since the high zeta potentials and thick double layers never yield partial differential V/ partial differential R>0 (the interaction is repulsive for all distances) in such a case. A similar problem was encountered in 10(-1) M solutions, but now because V is always attractive, and no maximum force can be found. On the contrary, the extended DLVO model always yield physically reasonable sigma(0) values (coincident with those deduced from the classical approach when calculation is possible in the latter case). The comparison with experimental data shows that theory clearly underestimates sigma(0) by one order of magnitude or even more. The possible role of particle aggregation in this underestimation is discussed in terms of the scaling behavior of sigma(0) as a function of straight phi. Copyright 2000 Academic Press.
ABSTRACT
In this article, we describe the rheology of Na montmorillonite suspensions as a function of pH, at constant ionic strength. The observed behavior is discussed quantitatively in terms of the potential energy of interaction between particles, keeping in mind the anisotropic nature of clay particles. The extended DLVO model that includes electrostatic, van der Waals, and polar acid-base contributions to the total energy is used. It is found that face-to-face interactions are virtually independent of pH, whereas edge-to-edge interactions are most attractive at the isoelectric point of edges (pH approximately 7). The most significant variations occur in face-to-edge potential energy, with strong attractions at pH<7. Steady-state viscometry showed that the yield stress decreases up to an order of magnitude between pH 3 and pH 7, with a much slower rate of decrease in the 7-11 pH interval. Concerning oscillatory measurements, it is found that both the elastic (G') and viscous (G") moduli are practically independent of frequency. It is also demonstrated that G'>G", the difference being larger at acid pH values. These results, in addition to potential energy calculations, suggest the existence of an elastic, coagulated structure up to pH 7, whereas as the pH is increased such structure is more relaxed because of electrostatic repulsions. Similar conclusions are reached when creep-recovery data are analyzed. Copyright 2000 Academic Press.
ABSTRACT
The effect of colloidal forces involved in the deposition of spherical zinc sulfide colloidal particles on a packed bed of glass has been studied. Experiments were performed by pumping a suspension of monodisperse colloidal ZnS particles through a cylindrical plug of ground glass, and by continuous determination of the outgoing suspension concentration. The flux density of adhered particles, jexp (number of particles deposited per unit time and unit surface area of glass collector), decreased with both pH and ionic strength of the aqueous electrolyte solution. Qualitative explanation of the experiments has been given in terms of the total energy of interaction between the dispersed particles and the substrate, and between the particles themselves, computed from the extended DLVO theory, including acid-base interactions. The contributions to the total free energy of interaction were determined from the zeta potential and surface free energy of ZnS and glass, measured under different experimental conditions. It was found that at pH 4 (below the isoelectric point of ZnS) the efficiency of the deposition of ZnS on glass was maximum. At higher pH values the amount of ZnS deposited on glass clearly decreased. Increasing NaCl concentration at fixed pH (>/=6) decreased the efficiency of the deposition. Adhesion experiments were also performed at pH 4 in the presence of increasing concentrations of CaCl2 or La(NO3)3 in the dispersion medium. In these cases, the rate of adhesion was qualitatively well correlated with the computed ZnS-glass interactions. Copyright 1999 Academic Press.
