Colloidal dispersions attractive forces

While the confirmation of the predicted long-range dispersion attraction between surfaces in air has been a major experimental triumph, the forces between particles in solution are of more general interest in colloid and surface chemistry. The presence of a condensed medium between the surfaces... 

Various diverse systems qualify as gels if one assumes that in these systems the common features are the solid-like behavior and the presence of a continuous structure of macroscopic nature (6,7). For the purpose of the discussion in this paper, we describe a gel as a colloidal system comprised of a dispersed component and a dispersion medium both of which the junction points are formed by covalent bonds, secondary valence bonds, or long range attractive forces that cause association between segments of polymer chains or formation of crystalline regions which have essentially infinite life time (8). 

When two similarly charged colloid particles, under the influence of the EDL, come close to each other, they will begin to interact. The potentials will detect one another, and this will lead to various consequences. The charged molecules or particles will be under both van der Waals and electrostatic interaction forces. The van der Waals forces, which operate at a short distance between particles, will give rise to strong attraction forces. The potential of the mean force between colloid particle in an electrolyte solution plays a central role in the phase behavior and the kinetics of agglomeration in colloidal dispersions. This kind of investigation is important in these various industries ... 

Coagulation of colloidal dispersions (Fig. 1.26h) as a function of salt concentration, pH, or temperature of the suspending liquid medium can also be used to obtain information on the interplay of repulsive and attractive forces between particles in pure liquids as well as in surfactant and polymer solutions. 

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. 

Several repulsive and attractive forces operate between colloidal species and determine their stability [12,13,15,26,152,194], In the simplest example of colloid stability, dispersed species would be stabilized entirely by the repulsive forces created when two charged surfaces approach each other and their electric double layers overlap. The overlap causes a coulombic repulsive force acting against each surface, which will act in opposition to any attempt to decrease the separation distance (see Figure 5.2). One can express the coulombic repulsive force between plates as a potential energy of repulsion. There is another important repulsive force causing a strong repulsion at very small separation distances where the atomic electron clouds overlap, called Born repulsion. 

Lyophobic colloids (sols) may be prepared by grinding crystalline materials or running an electric arc between metallic electrodes, both in the dispersing medium. More commonly, they are prepared by precipitating the solid from a strongly supersaturated solution, which produces a large number of precipitation nuclei. Because there is little attractive interaction between the particles and the medium, attractive forces between the particles would soon lead to their aggregation flocculation). This tendency, however, is counterbalanced by repulsive electrical forces between the particles. 

The possibility of occurrence of instability of colloidal dispersions in the presence of free polymer was first predicted by Asakura and Oosawa (5), who have shown that the exclusion of the free polymer molecules from the interparticle space generates an attractive force between particles, DeHek and Vrij (1) have developed a model in which the particles and the polymer molecules are treated as hard spheres and rederived in a simple and illuminating way the interaction potential proposed by Asakura and Oosawa. Using this potential, they calculated the second virial coefficient for the particles as a function of the free polymer concentration and have shown that... 

Colloidal dispersions, in general, are rendered stable either by electrostatic stabilization or by steric stabilization. In the former case, the repulsive electrical double layer forces between two particles counteract the attractive van der Waals forces and generate a potential barrier between the primary and secondary minima. If the potential barrier is sufficiently higher than the... 

Addition of soluble macromolecules (polymers) in the colloidal dispersion can stabilize the colloidal particles due to the adsorption of the polymers to the particle surfaces. The soluble polymers are often called protective agents or colloids. If the protective agents are ionic and have the same charge as the particles, the electrical double-layer repulsive forces will be increased and thus the stability of the colloidal particles will be enhanced. In addition, the adsorbed polymers may help weaken the van der Waals attraction forces among particles. However, the double-layer repulsion and the van der Waals attraction cannot account for the entire stabilization of the particle dispersions. 

Based on Equations 9.1 and 9.2, colloidal stability (maximum dispersion) depends on maximum R, which describes the maximum repulsive energy between two planar colloidal surfaces. It also appears from these equations that Rf is controlled by or CECV. However, in addition to the repulsive force, there is an attraction force (Af) between soil colloidal particles. The force of attraction (van der Waals force) between two particles separated by a distance of 2d (d = particle diameter) is described by... 

The U.S. Soil Salinity Laboratory Staff (1954) reported that SAR values of 10-15 (mmol L )1/2 usually correspond to ESP values in the range of 10-15 at which values clays will undergo dispersion. This relationship may vary among colloids with different mineralogy (Oster et al., 1980) and/or mixtures of colloids with different mineralogy (Arora and Coleman, 1979). Consequently, the force by which given types of colloidal particles attract or repulse each other in a Na-Ca or Na-Mg solution is a function of the total concentration of the salt, the type of divalent cation (Ca or Mg), and SAR. Therefore, pH, salt concentration, type of divalent cation, and SAR are expected to play important roles on soil colloid flocculation. 

Monte Carlo techniques were first applied to colloidal dispersions by van Megen and Snook (1975). Included in their analysis was Brownian motion as well as van der Waals and double-layer forces, although hydrodynamic interactions were not incorporated in this first study. Order-disorder transitions, arising from the existence of these forces, were calculated. Approximate methods, such as first-order perturbation theory for the disordered state and the so-called cell model for the ordered state, were used to calculate the latter transition, exhibiting relatively good agreement with the exact Monte Carlo computations. Other quantities of interest, such as the radial distribution function and the excess pressure, were also calculated. This type of approach appears attractive for future studies of suspension properties. 

The van der Waals force is ubiquitous in colloidal dispersions and between like materials, always attractive and therefore the most common cause of dispersion destabilization. In its most common form, intermolecular van der Waals attraction originates from the correlation, which arises between the instantaneous dipole moment of any atom and the dipole moment induced in neighbouring atoms. On this macroscopic scale, the interaction becomes a many-body problem where allowed modes of the electromagnetic field are limited to specific frequencies by geometry and the dielectric properties of the system. 

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