Emulsion coalescence, surfactant

If water is emulsified into fuel as a water-in-oil emulsion, coalescence cannot affect the removal of water from the fuel. The outer oil or surfactant layer surrounding water will not permit water to hydrogen bond to the hydrophilic demulsifier sites. 

If the disjoining pressures, flj and Il2, are zero, the ratio in Equation 5.292 will be very small. Hence, emulsion 1 (surfactant soluble in the continuous phase) will coalesce much more slowly and it will survive. This underlines the crucial importance of the surfactant location (which is connected with its solubility), thus providing a theoretical foundation for Bancroft s rule. The emulsion behavior in this case will be controlled almost entirely by the hydrodynamic factors (kinetic stability). 

Stable emulsion formation] [surfactants present] /contamination by particulates example, products of [corrosion products, see Section 1.3], amphoteric precipitates of aluminum or iron/pH far from the 2pc/contamination by polymers/tem-perature change/decrease in electrolyte concentration/the dispersed phase does not preferentially wet the materials of construction/coalescence -promoter mal-fimctioning/improper cleaning during shutdown/[rag buildup]. ... 

How does the nature of a surfactant molecule aflFect the emulsion stability Which molecular parameters directly affect the emulsion stability and which are less important Why do some surfactants tend to stabilize OAV emulsions and others W/0 What surfactant concentration is sufficient to prevent coalescence Why does the addition of some surfactants to a stable emulsion cause rapid coalescence and demulsification These questions have been addressed since the beginning of this century. Already in these very early studies, correct experimental trends were established. However, only relatively recently, with the advances in the physics of surfactant monolayers, has a mechanistic picture of emulsion coalescence started to emerge. 

An important aspect of the stabilization of emulsions by adsorbed films is that of the role played by the film in resisting the coalescence of two droplets of inner phase. Such coalescence involves a local mechanical compression at the point of encounter that would be resisted (much as in the approach of two boundary lubricated surfaces discussed in Section XII-7B) and then, if coalescence is to occur, the discharge from the surface region of some of the surfactant material. 

It was pointed out in Section XIII-4A that if the contact angle between a solid particle and two liquid phases is finite, a stable position for the particle is at the liquid-liquid interface. Coalescence is inhibited because it takes work to displace the particle from the interface. In addition, one can account for the type of emulsion that is formed, 0/W or W/O, simply in terms of the contact angle value. As illustrated in Fig. XIV-7, the bulk of the particle will lie in that liquid that most nearly wets it, and by what seems to be a correct application of the early oriented wedge" principle (see Ref. 48), this liquid should then constitute the outer phase. Furthermore, the action of surfactants should be predictable in terms of their effect on the contact angle. This was, indeed, found to be the case in a study by Schulman and Leja [49] on the stabilization of emulsions by barium sulfate. 

Emulsion Adhesives. The most widely used emulsion-based adhesive is that based upon poly(vinyl acetate)—poly(vinyl alcohol) copolymers formed by free-radical polymerization in an emulsion system. Poly(vinyl alcohol) is typically formed by hydrolysis of the poly(vinyl acetate). The properties of the emulsion are derived from the polymer employed in the polymerization as weU as from the system used to emulsify the polymer in water. The emulsion is stabilized by a combination of a surfactant plus a coUoid protection system. The protective coUoids are similar to those used paint (qv) to stabilize latex. For poly(vinyl acetate), the protective coUoids are isolated from natural gums and ceUulosic resins (carboxymethylceUulose or hydroxyethjdceUulose). The hydroHzed polymer may also be used. The physical properties of the poly(vinyl acetate) polymer can be modified by changing the co-monomer used in the polymerization. Any material which is free-radically active and participates in an emulsion polymerization can be employed. Plasticizers (qv), tackifiers, viscosity modifiers, solvents (added to coalesce the emulsion particles), fillers, humectants, and other materials are often added to the adhesive to meet specifications for the intended appHcation. Because the presence of foam in the bond line could decrease performance of the adhesion joint, agents that control the amount of air entrapped in an adhesive bond must be added. Biocides are also necessary many of the materials that are used to stabilize poly(vinyl acetate) emulsions are natural products. Poly(vinyl acetate) adhesives known as "white glue" or "carpenter s glue" are available under a number of different trade names. AppHcations are found mosdy in the area of adhesion to paper and wood (see Vinyl polymers). 

Many different combinations of surfactant and protective coUoid are used in emulsion polymerizations of vinyl acetate as stabilizers. The properties of the emulsion and the polymeric film depend to a large extent on the identity and quantity of the stabilizers. The choice of stabilizer affects the mean and distribution of particle size which affects the rheology and film formation. The stabilizer system also impacts the stabiUty of the emulsion to mechanical shear, temperature change, and compounding. Characteristics of the coalesced resin affected by the stabilizer include tack, smoothness, opacity, water resistance, and film strength (41,42). 

A stable cloud of water ia fuel usually means that a surfactant is present to form a stable water-ia-oil emulsion. Smaller droplets resist natural coalescence processes. A surfactant that is potent as an emulsifying agent is apt to disarm the coalescing filters, aHowiag excess water to be deUvered with fuel. 

Studies of flow-induced coalescence are possible with the methods described here. Effects of flow conditions and emulsion properties, such as shear rate, initial droplet size, viscosity and type of surfactant can be investigated in detail. Recently developed, fast (3-10 s) [82, 83] PFG NMR methods of measuring droplet size distributions have provided nearly real-time droplet distribution curves during evolving flows such as emulsification [83], Studies of other destabilization mechanisms in emulsions such as creaming and flocculation can also be performed. 

A. Nandi, A. Mehra, D. V. Khakhar 1999, (Suppression of coalescence in surfactant stabilized emulsions by shear flow), Phys. Rev. Lett. 83, 2461. 

Finely divided solid particles that are wetted to some degree by both oil and water can also act as emulsifying agents. This results from the fact that they can form a particulate film around dispersed droplets, preventing coalescence. Powders that are wetted preferentially by water form O/W emulsions, whereas those more easily wetted by oil form W/O emulsions. The compounds most frequently used in pharmacy are colloidal clays, such as bentonite (aluminum silicate) and veegum (magnesium aluminum silicate). These compounds tend to be adsorbed at the interface and also increase the viscosity of the aqueous phase. They are frequently used in conjunction with a surfactant for external purposes, such as lotions or creams. 

A reduction in the electrical charge is known to increase the flocculation and coalescence rates. Sufficient high zeta potential (> — 30 mV) ensures a stable emulsion by causing repulsion of adjacent droplets. The selection of suitable surfactants can help to optimize droplet surface charges and thus enhance emulsion stability. Lipid particles with either positive or negative surface charges are more stable and are cleared from the bloodstream more rapidly than those with neutral charge [192, 193]. 

As noted earlier (see section 12.3.1), the Amex process, which uses long-chain amines, is preferred over the Dapex process, which uses HDEHP, for solvent extraction of uranium from H2SO4 leach solutions. Because the surfactant properties of amine sulfates are conducive to formation of objectionable emulsions, the Amex process is very sensitive to the presence of solids in the H2SO4 leachate. For acceptable phase coalescence in the Amex process, feeds should contain no more than 20 ppm solids. The Dapex process can tolerate feeds containing as much as 100 ppm solids. 

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