Colloid systems

S. Ross and I. D. Morrison, Colloidal Systems and Interfaces, Wiley, New York, 1988. W. B. Russel, D. A. Saville, and W. R. Schowalter, Colloidal Dispersions, Cambridge... 

S. Ross and I. Morrison, Colloidal Systems and Interfaces, Wiley, New York, 1988. 

Table C2.6.2 Some practical examples of colloidal systems.

Although the remainder of this contribution will discuss suspensions only, much of the theory and experimental approaches are applicable to emulsions as well (see [2] for a review). Some other colloidal systems are treated elsewhere in this volume. Polymer solutions are an important class—see section C2.1. For surfactant micelles, see section C2.3. The special properties of certain particles at the lower end of the colloidal size range are discussed in section C2.17. 

In many colloidal systems, both in practice and in model studies, soluble polymers are used to control the particle interactions and the suspension stability. Here we distinguish tliree scenarios interactions between particles bearing a grafted polymer layer, forces due to the presence of non-adsorbing polymers in solution, and finally the interactions due to adsorbing polymer chains. Although these cases are discussed separately here, in practice more than one mechanism may be in operation for a given sample. 

In practice, colloidal systems do not always reach tlie predicted equilibrium state, which is observed here for tlie case of narrow attractions. On increasing tlie polymer concentration, a fluid-crystal phase separation may be induced, but at higher concentration crystallization is arrested and amorjihous gels have been found to fonn instead [101, 102]. Close to the phase boundary, transient gels were observed, in which phase separation proceeded after a lag time. 

Colloidal State. The principal outcome of many of the composition studies has been the delineation of the asphalt system as a colloidal system at ambient or normal service conditions. This particular concept was proposed in 1924 and described the system as an oil medium in which the asphaltene fraction was dispersed. The transition from a coUoid to a Newtonian Hquid is dependent on temperature, hardness, shear rate, chemical nature, etc. At normal service temperatures asphalt is viscoelastic, and viscous at higher temperatures. The disperse phase is a micelle composed of the molecular species that make up the asphaltenes and the higher molecular weight aromatic components of the petrolenes or the maltenes (ie, the nonasphaltene components). Complete peptization of the micelle seems probable if the system contains sufficient aromatic constituents, in relation to the concentration of asphaltenes, to allow the asphaltenes to remain in the dispersed phase. 

Nomenclature. Colloidal systems necessarily consist of at least two phases, the coUoid and the continuous medium or environment in which it resides, and their properties gready depend on the composition and stmcture of each phase. Therefore, it is useful to classify coUoids according to their states of subdivision and agglomeration, and with respect to the dispersing medium. The possible classifications of colloidal systems are given in Table 2. The variety of systems represented in this table underscores the idea that the problems associated with coUoids are usuaUy interdisciplinary in nature and that a broad scientific base is required to understand them completely. 

A lot of natural as well as technological objects of analytical control are colloidal systems, i.e. human blood, biological liquids, sol and suspension forming in different technological processes (ore-dressing, electrochemical deposition, catalysis and other), food, paint-and-lacquer materials, sewage water and other. 

If the colloidal systems are considered as objects of X-ray fluorescence analysis, some special features are to be mentioned. 

Russel, W.B., 1987. The dynamics of colloidal systems. Madison University of Wisconsin Press. 

Smoluchowski, M.V., 1916. Three lectures on diffusion. Brownian movement and coagulation of colloidal systems. Physik Zeitung, 17, 557. 

Smoluchowski, M.V., 1917. Mathematical theory of the kinetics of coagulation of colloidal systems. Zeitschrift fur Physikalische Chemie, 92, 129-168. 

Several colloidal systems, that are of practical importance, contain spherically symmetric particles the size of which changes continuously. Polydisperse fluid mixtures can be described by a continuous probability density of one or more particle attributes, such as particle size. Thus, they may be viewed as containing an infinite number of components. It has been several decades since the introduction of polydispersity as a model for molecular mixtures [73], but only recently has it received widespread attention [74-82]. Initially, work was concentrated on nearly monodisperse mixtures and the polydispersity was accounted for by the construction of perturbation expansions with a pure, monodispersive, component as the reference fluid [77,80]. Subsequently, Kofke and Glandt [79] have obtained the equation of state using a theory based on the distinction of particular species in a polydispersive mixture, not by their intermolecular potentials but by a specific form of the distribution of their chemical potentials. Quite recently, Lado [81,82] has generalized the usual OZ equation to the case of a polydispersive mixture. Recently, the latter theory has been also extended to the case of polydisperse quenched-annealed mixtures [83,84]. As this approach has not been reviewed previously, we shall consider it in some detail. 

As in previous theoretical studies of the bulk dispersions of hard spheres we observe in Fig. 1(a) that the PMF exhibits oscillations that develop with increasing solvent density. The phase of the oscillations shifts to smaller intercolloidal separations with augmenting solvent density. Depletion-type attraction is observed close to the contact of two colloids. The structural barrier in the PMF for solvent-separated colloids, at the solvent densities in question, is not at cr /2 but at a larger distance between colloids. These general trends are well known in the theory of colloidal systems and do not require additional comments. 

The hard sphere (HS) interaction is an excellent approximation for sterically stabilized colloids. However, there are other interactions present in colloidal systems that may replace or extend the pure HS interaction. As an example let us consider soft spheres given by an inverse power law (0 = The energy scale Vq and the length scale cr can be com-... 

The world of colloidal particles is large and fasdnating. Basic simulation techniques rapidly lead to challenging questions and new things to be discovered. Computer simulations are close enough to experiments to allow intellectual inspiration as well as a quantitative comparison of the results. We have reviewed the basic simulation techniques and their principal implementation but could only briefly mention advanced techniques and results. A survey of the recent literature shows the variety of physical effects present in colloidal systems and accessible to computer simulations. 

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