Colloids electrostatic stabilization

Colloidal suspensions stabilized by electrostatic repulsion are very sensitive to any phenomenon able to disrupt the double layer like ionic strength or thermal motion. 

Solvents such as organic liquids can act as stabilizers [204] for metal colloids, and in case of gold it was even reported that the donor properties of the medium determine the sign and the strength of the induced charge [205]. Also, in case of colloidal metal suspensions even in less polar solvents electrostatic stabilization effects have been assumed to arise from the donor properties of the respective liquid. Most common solvent stabilizations have been achieved with THF or propylenecarbonate. For example, smallsized clusters of zerovalent early transition metals Ti, Zr, V, Nb, and Mn have been stabilized by THF after [BEt3H ] reduction of the pre-formed THF adducts (Equation (6)) [54,55,59,206]. Table 1 summarizes the results. 

Many investigators of steric stabilization have measured colloidal stability without taking the effort to find out whether the stability actually resulted from electrostatic stabilization. In many published articles it has been concluded that steric stabilization had been attained and further study showed this was not the case. One such example is a recent paper on "steric" stabilization by an additive of the same type used in this work. (12) The published photograph shows the silica particles in oil stabilized at interparticle separations several times the distances provided by the adsorbed films no electrical measurements had been made, but it they had, this particular dispersant would have provided about -200 mV of zeta-potential and given excellent electrostatic repulsion. The reader should be wary of any claims of steric stabilization unless the electrostatic contribution has been measured. 

Scheme 9.1 Schematic representation of electrostatic stabilization a coulombic repulsion between metal colloid particles.

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. 

Theoretical studies of the role of polymer additives lag behind their analogs in electrostatic stability since polymer molecules have considerably more configurational freedom and since the interaction of the polymer molecules with the solvent is an inseparable part of phenomena in polymer-colloid mixtures. We begin with some of the general issues and a thermodynamic analysis of the role of polymer on stability in Section 13.5. 

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 role of polymers on colloid stability is considerably more complicated than electrostatic stability due to low molecular weight electrolytes considered in Chapter 11. First, if the added polymer moieties are polyelectrolytes, then we clearly have a combination of electrostatic effects as well as effects that arise solely from the polymeric nature of the additive this combined effect is referred to as electrosteric stabilization. Even in the case of nonionic... 

Reaction of the sandwich-type POM [(Fc(0H2)2)j(A-a-PW9034)2 9 with a colloidal suspension of silica/alumina nanopartides ((Si/A102)Cl) resulted in the production of a novel supported POM catalyst [146-148]. In this case, about 58 POM molecules per cationic silica/alumina nanoparticle were electrostatically stabilized on the surface. The aerobic oxidation of 2-chloroethyl ethyl sulfide (mustard simulant) to the corresponding harmless sulfoxide proceeded efficiently in the presence of the heterogeneous catalyst and the catalytic activity of the heterogeneous catalyst was much higher than that of the parent POM. In addition, this catalytic activity was much enhanced when binary cupric triflate and nitrate [Cu(OTf)2/Cu(N03)2 = 1.5] were also present [148],... 

Many food colloids are stabilized from proteins from milk or eggs [817]. Milk and cream, for example, are stabilized by milk proteins, such as casein micelles, which form a membrane around the oil (fat) droplets [817]. Mayonnaise, hollandaise, and bearnaise, for example, are O/W emulsions mainly stabilized by egg-yolk protein, which is a mixture of lipids (including lecithin), proteins, and lipoproteins [811,817]. The protein-covered oil (fat) droplets are stabilized by a combination of electrostatic and steric stabilization [817]. Alcohols may also be added, such as glycerol, propylene glycol, sorbitol, or sucrose sometimes these are modified by esterification or by... 

Part of the process to make cheese involves the flocculation of an electrostatically stabilized colloidal O/W emulsion of oil droplets coated with milk casein. The flocculation is caused by the addition of a salt, leading to the formation of networks which eventually gel. The other part of the process involves reaction with an enzyme (such as rennet), an acid (such as lactic acid), and possibly heat, pressure and microorganisms, to help with the ripening [811]. The final aggregates (curd) trap much of the fat and some of the water and lactose. The remaining liquid is the whey, much of which readily separates out from the curd. Adding heat to the curd (-38 °C) helps to further separate out the whey and convert the curd from a suspension to an elastic solid. There are about 20 different basic kinds of cheese, with nearly 1000 types and regional names. Potter provides some classification [811]. 

The electrostatic stabilization theory was developed for dilute colloidal systems and involves attractive van dcr Waals interactions and repulsive double layer interactions between two particles. They may lead to a potential barrier, an overall repulsion and/or to a minimum similar to that generated by steric stabilization. Johnson and Morrison [1] suggest that the stability in non-aqueous dispersions when the stabilizers are surfactant molecules, which arc relatively small, is due to scmi-stcric stabilization, hence to a smaller ran dcr Waals attraction between two particles caused by the adsorbed shell of surfactant molecules. The fact that such systems are quite stable suggests, however, that some repulsion is also prescni. In fact, it was demonstrated on the basis of electrophoretic measurements that a surface charge originates on solid particles suspended in aprotic liquids even in the absence of traces of... 

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... 

Using an interparticle potential, the characterization of the equilibrium state is possible by thermodynamic analysis. Van Megen and Snook [10,11] have adopted the statistical approach to predict the disorder—order phase transitions in concentrated dispersions that are stabilized electrostatically. Using the perturbation theory for the disordered phase and the cell model for the ordered phase, they have estimated the particle concentrations in the two coexisting phases when an electrostatically stabilized dispersion undergoes phase separation. Recently, Cast et al. [12] have used a similar approach to construct phase diagrams for colloidal dispersions that have free polymer molecules in solution. Using the interaction potential of Asakura... 

Addition of different kinds of charged polymers (polyelectrolytes) offers one effective way to control the stability of a colloidal solution. When charged polymers adsorb on neutral colloids, the colloids repel each other for electrostatic reasons. This behavior is called electrostatic stabilization and is responsible for the long shelf-life of certain latex paints. Polymers can also stabilize a dispersion for steric reasons when they are grafted or adsorbed to the particles. If two polymer covered particles approach it will lead to a restriction on the configurational freedom for the polymers giving rise to a repulsive force. 

Studies of the doublet formation rate in polymer stabilized systems are far less numerous than those on electrostatically stabilized systems. Chang [68] has studied the doublet formation rate for 0.57 fim in diameter Si02 particles as a function of the amount of hydroxyl propyl cellulose (HPC) adsorbed onto their surface. Figure 10.32 is a plot of the colloid stability ratio as a function of the amount of HPC added to... 

This section on concentrated suspensions discusses the rheological behavior of sj tems which are colloidally stable and colloidally unstable suspensions. For stable sj tems, the rheology of sterically stabilized and electrostatically stabilized systems wiU be considered. For sterically stabilized suspensions, a hard sphere (or hard particle) model has been successfid. Concentrated suspensions in some cases behave rheologically like concentrated polymer solutions. For this reason, a discussion of the viscosity of concentrated polymer solutions is discussed next before a discussion of concentrated ceramic suspensions. 

The sol-gel reactions have mainly been investigated in alcoholic solution, which is a reaction medium easily allows electrostatic stabilization by propriate choice of the pH. This type of stabilization can only be used in a few cases as a means for incorporating the colloidal particle agglomerate-free into tailored matrices, since these matrices, as a rule, destroy the electrostatic "coating" around the particles. As a consequence, agglomeration takes place, and the high transparency required for optical application is lost For this reason, another type, the so-called short organic molecule stabilization by tailored surface modification for colloidal particles, has been developed, the principles of which in comparison to the electrostatic stabilization is schematically shown in Fig. 14. 

Surfactants are employed in emulsion polymerizations to facilitate emulsification and impart electrostatic and steric stabilization to the polymer particles. Sicric stabilization was described earlier in connection with nonaqueous dispersion polymerization the same mechanism applies in aqueous emulsion systems. Electrostatic stabilizers are usually anionic surfactants, i.e., salts of organic acids, which provide colloidal stability by electrostatic repulsion of charges on the particle surfaces and their associated double layers. (Cationic surfactants are not commonly used in emulsion polymerizations.)... 

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