Colloids electrostatic interactions

We also attempt to distinguish between surface physical chemistry and colloid and polymer physical chemistry. This distinction is not always possible, and clearly many of the features of physical chemistry of surfaces, such as the electrostatic interactions and adsorption of macromolecules, have a significant... 

A detailed study by Grieser and co-workers [169] of the forces between a gold-coated colloidal silica sphere and a gold surface reveals the preferential adsorption of citrate ions over chloride to alter the electrostatic interaction. 

Vakarelski et al. [88] also investigated the adhesive forces between a colloid particle and a flat surface in solution. In their case they investigated a sihca sphere and a mica surface in chloride solutions of monovalent cations CsCl, KCl, NaCl, and LiCl. The pH was kept at 5.6 for all the experiments. To obtain the adhesive force in the presence of an electrostatic interaction, they summed the repulsive force and the pull-off force (coined foe by the authors ) to obtain a value for the adhesive force that is independent of the electrostatic component. 

In 1997, a Chinese research group [78] used the colloidal solution of 70-nm-sized carboxylated latex particles as a subphase and spread mixtures of cationic and other surfactants at the air-solution interface. If the pH was sufficiently low (1.5-3.0), the electrostatic interaction between the polar headgroups of the monolayer and the surface groups of the latex particles was strong enough to attract the latex to the surface. A fairly densely packed array of particles could be obtained if a 2 1 mixture of octadecylamine and stearic acid was spread at the interface. The particle films could be transferred onto solid substrates using the LB technique. The structure was studied using transmission electron microscopy. 

The stability of colloids can also be dramatically altered by inclusion of polymeric materials. If the polymer interacts favourably with the particle surfaces, i.e. it adsorbs, then both an increase and a reduction in stability is possible, via modification of the electrostatic interaction of the polymer is charged or a reduction in the van der Waals attraction. 

Stahlberg J, Appelgren U, Jonsson B (1995) Influence of charge regulation in electrostatic interaction chromatography of proteins. J Colloid Interf Sci 176 397 107... 

A scaled-up version of this central template-concentric sphere surface assembly approach has been demonstrated for the growth of multi-layer core-shell nano- and microparticles, based upon the repeated layer-by-layer deposition of linear polymers and silica nanoparticles onto a colloidal particle template (Figure 6.8) [60]. In this case, the regioselective chemistry occurs via electrostatic interactions, as opposed to the covalent bond formation of most of the examples in this chapter. The central colloidal seed particle dictates the final particle... 

Figure 6.8 Illustration of colloid-templated nanoparticle assemblies. The process involves the layer-by-layer adsorption of charged polymers and oppositely charged nanoparticles onto the surfaces of the colloidal template. The colloidal core particles may then be removed to generate a hollow sphere of nanoparticles, held together by electrostatic interactions with the linear polymer glue ...

In a qualitative way, colloids are stable when they are electrically charged (we will not consider here the stability of hydrophilic colloids - gelatine, starch, proteins, macromolecules, biocolloids - where stability may be enhanced by steric arrangements and the affinity of organic functional groups to water). In a physical model of colloid stability particle repulsion due to electrostatic interaction is counteracted by attraction due to van der Waal interaction. The repulsion energy depends on the surface potential and its decrease in the diffuse part of the double layer the decay of the potential with distance is a function of the ionic strength (Fig. 3.2c and Fig. 

Polyelectrolytes provide excellent stabilisation of colloidal dispersions when attached to particle surfaces as there is both a steric and electrostatic contribution, i.e. the particles are electrosterically stabilised. In addition the origin of the electrostatic interactions is displaced away from the particle surface and the origin of the van der Waals attraction, reinforcing the stability. Kaolinite stabilised by poly(acrylic acid) is a combination that would be typical of a paper-coating clay system. Acrylic acid or methacrylic acid is often copolymerised into the latex particles used in cement sytems giving particles which swell considerably in water. Figure 3.23 illustrates a viscosity curve for a copoly(styrene-... 

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 ... 

Kamo et al. [Biochim. Biophys. Acta, 367, 1 and 11 (1974)] have shown that nonionic sugars modify the zeta potential of slime mold cells. Aggregation of colloids is related to their surface charge and their surface potential. This fact shows evidence of long-range electrostatic interactions controlled by metabolic reactions taking place at the membrane and able to modify the composition of the membrane medium interface. In this process the diffusion is not relevant, as indicated by Mrs. Babloyantz. 

Ganzevles, R.A., van Vliet, T., Cohen Stuart, M.A., de Jongh, H.H.J. (2007). Manipulation of adsorption behaviour at liquid interfaces by changing protein-polysaccharide electrostatic interactions. In Dickinson, E., Leser, M.E. (Eds). Food Colloids Self-Assembly and Material Science, Cambridge, UK Royal Society of Chemistry, pp. 195-208. 

It is important to note that the concept of osmotic pressure is more general than suggested by the above experiment. In particular, one does not have to invoke the presence of a membrane (or even a concentration difference) to define osmotic pressure. The osmotic pressure, being a property of a solution, always exists and serves to counteract the tendency of the chemical potentials to equalize. It is not important how the differences in the chemical potential come about. The differences may arise due to other factors such as an electric field or gravity. For example, we see in Chapter 11 (Section 11.7a) how osmotic pressure plays a major role in giving rise to repulsion between electrical double layers here, the variation of the concentration in the electrical double layers arises from the electrostatic interaction between a charged surface and the ions in the solution. In Chapter 13 (Section 13.6b.3), we provide another example of the role of differences in osmotic pressures of a polymer solution in giving rise to an effective attractive force between colloidal particles suspended in the solution. 

The electrostatic forces also play an important role in the conformation and structure of macromolecules such as polymers, polyelectrolytes, and proteins. The self-assembly of proteins from disks to virus is triggered by electrostatic interactions between neighboring subunits. In the case of polyelectrolytes (polymer molecules with charges) and charged colloids, transport behavior such as rheology is also affected significantly by charge effects, as we have already seen in Chapter 4. 

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