Amphiphilic molecules, colloidal aggregates

A micelle is a colloidal aggregate of amphiphilic molecules (50-100 molecules per micelle) which forms at a specific concentration termed the critical micelle concentration. As illustrated in Fig. 1, in polar media such as water, the hydrophobic part of the amphiphilic molecule tends to locate away from the polar phase while the polar groups of the molecule tend to locate in the water phase, forming the micelle aggregate. Micellar systems are able to solubilize both hydrophobic and hydrophilic compounds. 

A dispersion Is a system made of discrete objects separated by a homogeneous medium In colloidal dispersions the objects are very small In at least one dimension. Colloidal sizes range from 1 to 100 nm however these limits are somewhat arbitrary, and It Is more useful to define colloids as dispersions where surface forces are large compared to bulk forces. Here we are concerned with systems where the dispersion medium Is a liquid examples are droplets In emulsions or mlcroemulslons (oll/water or water/oll), aggregates of amphiphilic molecules (surfactant micelles), foams, and all the dispersions of solid particles which are used as Intermediates In the manufacture of ceramics. At this stage we are not too concerned with the nature of the constituents, but rather with the structures which they form this Is a geometrical problem, where the system Is characterized by Its surface area A, by the shapes of Its Interfaces (curvatures - b ), and by the distances between opposing surfaces (d — concentration parameter). 

The use of surfactants or amphiphilic molecules in electrochemistry dates back over four decades [1,2]. Extensive research on electrochemistry in surfactant systems has been reported primarily in the last 20 years. Surfactant systems are ubiquitous. The aggregation of surfactant molecules may produce a variety of systems including micelles, monolayers and bilayers, vesicles, lipid films, emulsions, foams, and microemulsions. Developments in the area of electrochemistry in such association colloids and dispersions have been documented by Mackay and Texter [3]. Mackay [4] reviewed the developments in association colloids, particularly micelles and microemulsions. Rusling [5,6] also reviewed electrochemistry in micelles, microemulsions, and related organized media. This chapter focuses on microemulsions and does not deal with micelles, monolayers, emulsions, and other surfactant systems per se. 

The thermodynamic equilibria of amphiphilic molecules in solution involve four fundamental processes (1) dissolution of amphiphiles into solution (2) aggregation of dissolved amphiphiles (3) adsorption of dissolved amphiphiles at an interface and (4) spreading of amphiphiles from their bulk phase directly to the interface (Fig. 1.1). All but the last of these processes are presented and discussed throughout this book from the thermodynamic standpoint (especially from that of Gibbs s phase rule), and the type of thermodynamic treatment that should be adopted for each is clarified. These discussions are conducted from a theoretical point of view centered on dilute aqueous solutions the solutions dealt with are mostly those of the ionic surfactants with which the author s studies have been concerned. The theoretical treatment of ionic surfactants can easily be adapted to nonionic surfactants. The author has also concentrated on recent applications of micelles, such as solubilization into micelles, mixed micelle formation, micellar catalysis, the protochemical mechanisms of the micellar systems, and the interaction between amphiphiles and polymers. Fortunately, almost all of these subjects have been his primary research interests, and therefore this book covers, in many respects, the fundamental treatment of colloidal systems. 

The steric stabilization, which is imparted by polymer molecules grafted onto the colloidal particles, is extensively employed.3 Amphiphilic block copolymers are widely used as steric stabilizers. The solvent-incompatible moieties of the block copolymer provide anchors for the polymer molecules that are adsorbed onto the surface of the colloidal particles, and the solvent-compatible (buoy) moieties extend into the solvent phase. When two particles with block copolymers on their surface approach each other, a steric repulsion is generated bet ween the two particles as soon as the tips of the buoy moieties begin to contact, and this repulsion increases the stability of the colloidal system.4-6 Polymers can also induce aggregation due to either depletion 7-11 or bridging interactions.12 15... 

A surfactant molecule is an amphiphile, which means it has a hydrophilic (water-soluble) moiety and a hydrophobic (water-insoluble) moiety separable by a mathematical surface. The hydrophobic tails of the most common surfactants are hydrocarbons. Fluorocarbon and perfluorocarbon tails are, however, not unusual. Because of the hydrophobic tail, a surfactant resists forming a molecular solution in water. The molecules will tend to migrate to any water-vapor interface available or, at sufficiently high concentration, the surfactant molecules will spontaneously aggregate into association colloids, i.e., into micelles or liquid crystals. Because of the hydrophilic head, a surfactant (with a hydrocarbon tail) will behave similarly when placed in oil or when put in solution with oil and water mixtures. Some common surfactants are sodium or potassium salts of long-chained fatty acids (soaps), sodium ethyl sulfates and sulfonates (detergents), alkyl polyethoxy alcohols, alkyl ammonium halides, and lecithins or phospholipids. 

Surfactant molecules commonly self-assemble in water (or in oil). Even single-surfactant systems can display a quite remarkably rich variety of structures when parameters such as water content or temperature are varied. In dilute solution they form an isotropic solution phase consisting of micellar aggregates. At more concentrated surfactant-solvent systems, several isotropic and anisotropic liquid crystalline phases will be formed [2]. The phase behavior becomes even more intricate if an oil (such as an alkane or fluorinated hydrocarbon) is added to a water-surfactant binary system and the more so if other components (such as another surfactant or an alcohol) are also included [3], In such systems, emulsions, microemulsions, and lyotropic mesophases with different geometries may be formed. Indeed, the ability to form such association colloids is the feature that singles out surfactants within the broader group of amphiphiles [4]. No wonder surfactants phase behavior and microstructures have been the subject of intense and profound investigation over the course of recent decades. 

Using deuterium labelling methods, it is possible to obtain orientational order parameters for C-D bonds via nnclear qnadrnpolar splittings. This provides information on the orientational ordering of thermotropic liqnid crystals and of labelled hydrocarbon chains in amphiphilic aggregates snch as micelles and lamellae. As another example, the orientation (and motions) of molecules adsorbed on colloidal particles has been stndied. 

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