Electrostatic forces colloid stability

Based on the application of the established theory of colloid stability of water treatment particles [8,85-88], the colloidal particles in untreated water are attached to one another by van der waals forces and, therefore, always tend to aggregate unless kept apart by electrostatic repulsion forces arising from the presence of electrical charges on the particles. The aggregation process... 

The DLVO theory, a quantitative theory of colloid fastness based on electrostatic forces, was developed simultaneously by Deryaguin and Landau [75] and Verwey and Overbeek [76], These authors view the adsorptive layer as a charge carrier, caused by adsorption of ions, which establishes the same charge on all particles. The resulting Coulombic repulsion between these equally charged particles thus stabilizes the dispersion. This theory lends itself somewhat less to non-aqueous systems. 

A theoretical analysis of the stability of such colloidal crystals of spherical latex particles has been carried out by Marcel ja et al (28.). They employ the Lindemann criterion that a crystal will be stable if the rms thermal displacement of the particles about their equilibrium positions is a small fraction f of the lattice spacing R. Comparison with Monte Carlo simulations shows that f is about 0.1 for "hard crystals, and 0.08 for "soft crystals stabilized by long-ranged electrostatic forces. This latter criterion translates into a critical ratio... 

As we saw in Chapter 11, surfaces of colloidal particles typically acquire charges for a number of reasons. The electrostatic force that results when the electrical double layers of two particles overlap, if repulsive, serves to counteract the attraction due to van der Waals force. The stability in this case is known as electrostatic stability, and our task is to understand how it depends on the relevant parameters. 

In contrast to the situation in the case of van der Waals and electrostatic forces, very little is known about polymer-induced forces. The development of the surface force apparatus and scanning tunneling and atomic force microscopies have begun to shed light on this very difficult topic. In Section 13.6, we take a brief look at some of the polymer-induced forces of interest in colloid stability and structure. 

Despite the fact that there is much that is unknown about colloid stability, the topics covered in the chapter are sufficient to solve many routine problems of industrial interest, particularly in the case of electrostatic stability. More advanced information on polymer-induced forces is available in specialized monographs (Napper 1983 Israelachvili 1991 Sato and Ruch 1980) and in other texts on colloid science (Hunter 1987). 

The stability of latexes during and after polymerization may be assessed at least qualitatively by the theoretical relationships describing the stability of lyophobic colloids. The Verwey-Overbeek theory (2) combines the electrostatic forces of repulsion between colloidal particles with the London-van der Waals forces of attraction. The electrostatic forces of repulsion arise from the surface charge, e.g., from adsorbed emulsifier ions, surface sulfate endgroups introduced by persulfate initiator, or ionic groups introduced by using functional monomers. These electro-... 

In this discussion of colloid stability we will explore the reasons why colloidal dispersions can have different degrees of kinetic stability and how these are influenced, and can therefore be modified, by solution and surface properties. Encounters between species in a dispersion can occur frequently due to any of Brownian motion, sedimentation, or stirring. The stability of the dispersion depends upon how the species interact when this happens. The main cause of repulsive forces is the electrostatic repulsion between like charged objects. The main cause of attractive forces is the van der Waals forces between objects. 

The DLVO-theory is named after Derjaguin, Landau, Verwey and Overbeek and predicts the stability of colloidal suspensions by calculating the sum of two interparticle forces, namely the Van der Waals force (usually attraction) and the electrostatic force (usually repulsion) [19],... 

The combined effect of attraction and repulsion forces has been treated by many investigators in terms borrowed from theories of colloidal stability (Weiss, 1972). These theories treat the adhesion of colloidal particles by taking into account three types of forces (a) electrostatic repulsion force (Hogg, Healy Fuerstenau, 1966) (b) London-Van der Waals molecular attraction force (Hamaker, 1937) (c) gravity force. The electrostatic repulsion force is due to the negative charges that exist on the cell membrane and on the deposition surface because of the development of electrostatic double layers when they are in contact with a solution. The London attraction force is due to the time distribution of the movement of electrons in each molecule and, therefore, it exists between each pair of molecules and consequently between each pair of particles. For example, this force is responsible, among other phenomena, for the condensation of vapors to liquids. 

Here a mixture of sterically stabilized colloidal particles, solvent, and free polymer molecules in solution is considered. When two particles approach one another during a Brownian collision, the interaction potential between the two depends not only on the distance of separation between them, but also on various parameters, such as the thickness and the segment density distribution of the adsorbed layer, the concentration and the molecular weight of the free polymer. The various types of forces that are expected lo contribute to the interaction potential are (i) forces due to the presence of the adsorbed polymer, (ii) forces due to the presence of the free polymer, and (iii) van der Waals forces. It is assumed here that there are no electrostatic forces. A brief account of the nature of these forces as... 

A quantitative treatment of the effects of electrolytes on colloid stability has been independently developed by Deryagen and Landau and by Verwey and Over-beek (DLVO), who considered the additive of the interaction forces, mainly electrostatic repulsive and van der Waals attractive forces as the particles approach each other. Repulsive forces between particles arise from the overlapping of the diffuse layer in the electrical double layer of two approaching particles. No simple analytical expression can be given for these repulsive interaction forces. Under certain assumptions, the surface potential is small and remains constant the thickness of the double layer is large and the overlap of the electrical double layer is small. The repulsive energy (VR) between two spherical particles of equal size can be calculated by ... 

Aggregation of liposomes both in vitro and in vivo is one of their main stability problems. According to the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory, or theory of colloidal stability, a colloidal system is stable if the electrostatic repulsion forces between two particles are larger than the attraction van der Waals forces. Therefore charged liposomal formulations are highly desirable. Manipulation of... 

According to Deijaguin-Landau-Verwey-Overbeek (DLVO) theory, a cornerstone of modem colloid science, two types of forces exist between colloidal particles suspended in a dielectric medium electrostatic forces, which result from an unscreened surface charge on the particle, and London-van der Waals attractive forces, which are universal in nature. The colloidal stability and rheology of oxide suspensions, in the absence of steric additives, can be largely understood by combining these two forces (assumption of additivity). 

The DLVO theory, which was developed independently by Derjaguin and Landau and by Verwey and Overbeek to analyze quantitatively the influence of electrostatic forces on the stability of lyophobic colloidal particles, has been adapted to describe the influence of similar forces on the flocculation and stability of simple model emulsions stabilized by ionic emulsifiers. The charge on the surface of emulsion droplets arises from ionization of the hydrophilic part of the adsorbed surfactant and gives rise to electrical double layers. Theoretical equations, which were originally developed to deal with monodispersed inorganic solids of diameters less than 1 pm, have to be extensively modified when applied to even the simplest of emulsions, because the adsorbed emulsifier is of finite thickness and droplets, unlike solids, can deform and coalesce. Washington has pointed out that in lipid emulsions, an additional repulsive force not considered by the theory due to the solvent at close distances is also important. 

In conventional latices, the colloidal stability of the particles arises from the predominance of the electrostatic forces of repulsion over the London-van der Waal s forces of attraction. These electrostatic forces of repulsion result from the electric double layer formed by the emulsifier ions adsorbed on the hydrophobic polymer particle surface and the counterions from the aqueous phase. The London-van der Waal s forces of attraction are strongest when the particle-particle distance is very small. Therefore, in most particle-particle collisions, the particles repel one another until the particle-particle distance is decreased to the point where the London-van der Waal s forces of attraction are predominant over the electrostatic forces of repulsion. Thus, many conventional latices remain stable indefinitely without significant stratification or flocculation of the particles. 

Consideration of the electrostatic repulsion and van der Waals forces of attraction by the Russians Deryagin and Landau and the Dutch scientists Verwey and Overbeek produced a satisfactory quantitative approach to the stability of hydrophobic suspensions. Their theory is known as the DLVO theory of colloid stability, the briefest outline of which is given here. 

Figure 14-19 Stabilization of a colloid (Fe203 sol) by electrostatic forces. Each colloidal particle of this red sol is a cluster of many formula units of hydrated Fe203. Each attracts positively charged Fe + ions to its surface. (Fe + ions fit readily into the crystal structure, so they are preferentially adsorbed rather than the Cl ions.) Each particle is then surrounded by a shell of positively charged ions, so the particles repel one another and cannot combine to the extent necessary to cause acmal precipitation. The suspended particles scatter light, making the path of the light beam through the suspension visible.

It is customarily assumed that the overall particle-particle interaction can be quantified by a net surface force, which is the sum of a number of independent forces. The most often considered force components are those due to the electrodynamic or van der Waals interactions, the electrostatic double-layer interaction, and other non-DLVO interactions. The first two interactions form the basis of the celebrated Derjaguin-Landau-Verwey-Overbeek (DLVO) theory on colloid stability and coagulation. The non-DLVO forces are usually determined by subtracting the DLVO forces from the experimental data. Therefore, precise prediction of DLVO forces is also critical to the determination of the non-DLVO forces. The surface force apparatus and atomic force microscopy (AFM) have been used to successfully quantify these interaction forces and have revealed important information about the surface force components. This chapter focuses on improved predictions for DLVO forces between colloid and nano-sized particles. The force data obtained with AFM tips are used to illustrate limits of the renowned Derjaguin approximation when applied to surfaces with nano-sized radii of curvature. 

The forces acting on a colloidal system include gravitational, diffusion, viscous, inertial, attractive Van der Waals, and electrical repulsive forces. Because most of these forces are functions of the particle size, it is important to know both particles size and size distribution. The classical Derjaguin-Landau-Verwey-Overbeek (DLVO) theory describes colloid stability on the basis of pair interaction, considering only attractive van der Waals forces and repulsive electrostatic forces (Molina-Bolfvar and Ortega-Vinuesa, 1999). The total potential energy of interaction, Ujc, between two particles is defined as ... 

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