Colloidal forces steric

A variety of interaction behaviours can be observed between liquid/liquid interfaces based on the types of colloidal forces present. In general, they can be separated into static and dynamic forces. Static forces include electrostatic, steric, van der Waals and hydrophobic forces, relevant to stable shelf life and coalescence of emulsions or dispersions. Dynamic forces arise ftom flow in the system, for instance during shear of an emulsion or dispersion. EHrect force measurements tend to center on static force measurements, and while there is a large body of work on the study of film drainage between both liquid or solid interfaces, there are very few direct force measurements in the dynamic range between liquid interfaces. Below are general descriptions of some of the types of force observed and brief discussions of their origins. 

Abstract. The stability of suspensions/emulsions is under consideration. Traditionally consideration of colloidal systems is based on inclusion only Van-der-Waals (or dispersion) and electrostatic components, which is refereed to as DLVO (Derjaguin-Landau-Verwey-Overbeek) theory. It is shown that not only DLVO components but also other types of the inter-particle forces may play an important role in the stability and colloidal systems. Those contributions are due to hydrodynamic interactions, hydration and hydrophobic forces, steric and depletion forced, oscillatory structural forces. The hydrodynamic and colloidal interactions between drops and bubbles emulsions and foams are even more complex (as compared to that of suspensions of solid particles) due to the fluidity and deformability of those colloidal objects. The latter two features and thin film formation between the colliding particles have a great impact on the hydrodynamic interactions, the magnitude of the disjoining pressure and on the dynamic and thermodynamic stability of such colloidal systems. 

Figure 10 Force-distance curves for colloidal forces van der Waals attraction forces balanced against increasing steric or electrostatic repulsion forces.

We have not studied all types of colloidal systems in detail but limited ourselves to suspensions, siufac-tants, emulsions and foams. In terms of properties, the stability and associated concepts (double layer, van der Waals forces, steric effects) as well as the DLVO theory have been presented in detail, while kinetic and especially the optical properties have been discussed more briefly. 

Two kinds of barriers are important for two-phase emulsions the electric double layer and steric repulsion from adsorbed polymers. An ionic surfactant adsorbed at the interface of an oil droplet in water orients the polar group toward the water. The counterions of the surfactant form a diffuse cloud reaching out into the continuous phase, the electric double layer. When the counterions start overlapping at the approach of two droplets, a repulsion force is experienced. The repulsion from the electric double layer is famous because it played a decisive role in the theory for colloidal stabiUty that is called DLVO, after its originators Derjaguin, Landau, Vervey, and Overbeek (14,15). The theory provided substantial progress in the understanding of colloidal stabihty, and its treatment dominated the colloid science Hterature for several decades. 

The process of adsorption of polyelectrolytes on solid surfaces has been intensively studied because of its importance in technology, including steric stabilization of colloid particles [3,4]. This process has attracted increasing attention because of the recently developed, sophisticated use of polyelectrolyte adsorption alternate layer-by-layer adsorption [7] and stabilization of surfactant monolayers at the air-water interface [26], Surface forces measurement has been performed to study the adsorption process of a negatively charged polymer, poly(styrene sulfonate) (PSS), on a cationic monolayer of fluorocarbon ammonium amphiphilic 1 (Fig. 7) [27],... 

The pair potential of colloidal particles, i.e. the potential energy of interaction between a pair of colloidal particles as a function of separation distance, is calculated from the linear superposition of the individual energy curves. When this was done using the attractive potential calculated from London dispersion forces, Fa, and electrostatic repulsion, Ve, the theory was called the DLVO Theory (from Derjaguin, Landau, Verwey and Overbeek). Here we will use the term to include other potentials, such as those arising from depletion interactions, Kd, and steric repulsion, Vs, and so we may write the total potential energy of interaction as... 

In Section 3.4a we examine a model for the second virial coefficient that is based on the concept of the excluded volume of the solute particles. A solute-solute interaction arising from the spatial extension of particles is the premise of this model. Therefore the potential exists for learning something about this extension (i.e., particle dimension) for systems for which the model is applicable. In Section 3.4b we consider a model that considers the second virial coefficient in terms of solute-solvent interaction. This approach offers a quantitative measure of such interactions through B. In both instances we only outline the pertinent statistical thermodynamics a somewhat fuller development of these ideas is given in Flory (1953). Finally, we should note that some of the ideas of this section are going to reappear in Chapter 13 in our discussions of polymer-induced forces in colloidal dispersions and of coagulation or steric stabilization (Sections 13.6 and 13.7). 

From a technical standpoint, it is also important to note that colloids display a wide range of rheological behavior. Charged dispersions (even at very low volume fractions) and sterically stabilized colloids show elastic behavior like solids. When the interparticle interactions are not important, they behave like ordinary liquids (i.e., they flow easily when subjected to even small shear forces) this is known as viscous behavior. Very often, the behavior falls somewhere between these two extremes the dispersion is then said to be viscoelastic. Therefore, it becomes important to understand how the interaction forces and fluid mechanics of the dispersions affect the flow behavior of dispersions. 

Colloid stabilization with amphiphilic polymers [2,114,115] requires the formation of a thick polymer layer around each particle in order to create a repulsive steric force that overcomes the van der Waals attraction. This is usually done by adsorbing on the colloidal particle a polymer solution in a good solvent, which builds up on the surface a fluffy layer with a thickness of the order of the radius of gyration of isolated polymer chains, in general of the order of a few hundred angstroms. 

Steric stabilization appears to be the dominant stabilizing force in most food colloids [78,824], Casein-coated emulsion droplets provide an example. The presence of protein in an adsorption layer can also contribute viscoelasticity and provide a barrier to coalescence. 

Colloidal suspensions are often stabilized by the adsorption of polymers that are expected to exert additional configurational-steric repulsive forces. The additional, potentially significant van der Waals interactions between polymer coatings... 

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