Emulsions—General Properties

An emulsion may be defined as a mixture of particles of one liquid with some second liquid. The two common types of emulsions are oil-in-water (O/W) and water-in-oil (W/0), where the term oil is used to denote the water-insoluble fiuid. These two types are illustrated in Fig. XIV-1, where it is clear that the majority or outer phase is continuous, whereas the minority or inner phase is not. These two emulsion types are distinguished by their ability to disperse oil or water-soluble dyes, their dilution with oil or water, and their conductivity (O/W emulsions have much higher conductivity than do W/0 ones see Ref. 1 for reviews). 

Apart from chemical composition, an important variable in the description of emulsions is the volume fraction, j), or the ratio of the volume of the inner to outer phase. For spherical droplets, of radius a, the volume fraction is given by the number density, n, times the spherical volume, 0 = Ava nl2 . It is easy to show that the maximum packing fraction of spheres is 0 = 0.74 (see Problem XIV-2). Many physical properties of emulsions can be characterized by their volume fraction. The viscosity of a dilute suspension of rigid spheres is an example where the Einstein limiting law is [2] 

Since emulsion droplets are not rigid spheres, the coefficient of 0 is around 3-6 for many emulsion systems [3-5], More concentrated emulsions are non-Newtonian depends on shear rate and are thixotropic (ri decreasing with 

The conductivity of a dilute emulsion can be treated by classic theory (see Maxwell [6]) assuming spherical droplets 

Increasingly, dielectric measurements are being used to characterize the water content of emulsions. One model for the dielectric constant of a suspension,  

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Sherman, P. (1968) General properties of emulsions and their constituents, in Emubim Science (ed. P. Sherman). Academic Press, London, 131-216. 

Compounds containing such metals as copper, barium, lead, molybdenum, and nickel generally are not used in processing solutions. However, trace quantities of certain metal dopants occasionally are used to impart desired soHd-state and photographic properties to emulsion grains. Because of its... 

Monobutylamines are easily soluble in water and hydrocarbons and can generally be steam distilled. These properties lead to uses in soaps for water and oil emulsions, and as corrosion inhibitors in steam boiler appHcations (see Corrosion and corrosion inhibitors Emulsions). Morpholine is also extensively used as a corrosion inhibitor in steam boiler systems. In addition, it is widely used as an intermediate in the production of delayed-action mbber accelerators. 

Styrene is a colorless Hquid with an aromatic odor. Important physical properties of styrene are shown in Table 1 (1). Styrene is infinitely soluble in acetone, carbon tetrachloride, benzene, ether, / -heptane, and ethanol. Nearly all of the commercial styrene is consumed in polymerization and copolymerization processes. Common methods in plastics technology such as mass, suspension, solution, and emulsion polymerization can be used to manufacture polystyrene and styrene copolymers with different physical characteristics, but processes relating to the first two methods account for most of the styrene polymers currendy (ca 1996) being manufactured (2—8). Polymerization generally takes place by free-radical reactions initiated thermally or catalyticaHy. Polymerization occurs slowly even at ambient temperatures. It can be retarded by inhibitors. 

Adhesives. Poly(vinyl alcohol) is used as a component in a wide variety of general-purpose adhesives to bond ceUulosic materials, such as paper and paperboard, wood textiles, some metal foils, and porous ceramic surfaces, to each other. It is also an effective binder for pigments and other finely divided powders. Both fully and partially hydrolyzed grades are used. Sensitivity to water increases with decreasing degree of hydrolysis and the addition of plasticizer. Poly(vinyl alcohol) in many appHcations is employed as an additive to other polymer systems to improve the cohesive strength, film flexibiUty, moisture resistance, and other properties. It is incorporated into a wide variety of adhesives through its use as a protective coUoid in emulsion p olymerization. 

In pharmaceutical uses, the general inertness of lanolin and its derivatives, together with their ease of emulsification (185), have been important criteria. These properties are also important in cosmetics, but with emphasis also on the abiHty to absorb large quantities of water or, after suitable modification, to stabilize o/w emulsions. 

Random copolymers of vinyl chloride and other monomers are important commercially. Most of these materials are produced by suspension or emulsion polymerization using free-radical initiators. Important producers for vinyl chloride—vinyUdene chloride copolymers include Borden, Inc. and Dow. These copolymers are used in specialized coatings appHcations because of their enhanced solubiUty and as extender resins in plastisols where rapid fusion is required (72). Another important class of materials are the vinyl chloride—vinyl acetate copolymers. Principal producers include Borden Chemicals Plastics, B. F. Goodrich Chemical, and Union Carbide. The copolymerization of vinyl chloride with vinyl acetate yields a material with improved processabihty compared with vinyl chloride homopolymer. However, the physical and chemical properties of the copolymers are different from those of the homopolymer PVC. Generally, as the vinyl acetate content increases, the resin solubiUty in ketone and ester solvents and its susceptibiUty to chemical attack increase, the resin viscosity and heat distortion temperature decrease, and the tensile strength and flexibiUty increase slightly. 

In the early days of the commercial development of PVC, emulsion polymers were preferred for general purpose applications. This was because these materials exist in the form of the fine primary particles of diameter of the order of 0.1-1.0 p,m, which in the case of some commercial grades aggregate into hollow secondary particles or cenospheres with diameters of 30-100 p,m. These emulsion polymer particles have a high surface/volume ratio and fluxing and gelation with plasticisers is rapid. The use of such polymers was, however, restricted because of the presence of large quantities of soaps and other additives necessary to emulsion polymerisation which adversely affect clarity and electrical insulation properties. 

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