Emulsifiers and Emulsions

Emulsion and emulsifiers. An. .emulsion is a mixture of two liquids that do not mix very well—they are immiscible—but are held in stable suspension by the addition of a substance called an emulsifier. Emulsifiers are composed of molecules that attract the two liquids, one each at either end of the molecule, reducing the surface tension between the two liquids. 

St. Angelo, A.J. A Brief Introduction to Food Emulsions and Emulsifiers in Food Emulsifiers Chemistry, Technology, Functional Proper-... 

The selection of emulsifiers to prepare food emulsions is mainly based on their HLB number. This index is based on the relative percentage of hydrophilic to lipophilic groups within the emulsifier molecule. Lower HLB numbers indicate a more lipophilic emulsifier, while higher numbers indicate a more hydrophilic emulsifier. Emulsifiers showing HLB numbers between 3 and 6 are best for water-in-oil (W/O) emulsions, and emulsifiers with numbers between 8 and 18 are best for O/W emulsions. 

McClements, J.D. Lipid based emulsions and emulsifiers (eds. C.C. Akoh and B.D. Min), Food Lipid Chemistry, Nutrition and Biotechrwlogy. Marcel Dekker, New York. 1997. 

St. Angelo, A.J., A Brief Introduction to Food Emulsions and Emulsifiers, in Food Emulsifiers Chemistry, Technology, Functional Properties and Applications, Charalambous, G. and Doxastakis, G., Eds., Elsevier, Amsterdam, 1989, pp. 1-8. 

FIGURE 15.1. When water and oil are mixed in the presence of an emulsifier, an emulsion is formed. The type of emulsifier influences the type of emulsion Emulsifier A (hydrophilic) forms o/w emulsions and Emulsifier B (lipophilic ) forms w/o emulsions. Heating an o/w emulsion can convert it to a w/o emulsion (phase inversion). 

One may rationalize emulsion type in terms of interfacial tensions. Bancroft [20] and later Clowes [21] proposed that the interfacial film of emulsion-stabilizing surfactant be regarded as duplex in nature, so that an inner and an outer interfacial tension could be discussed. On this basis, the type of emulsion formed (W/O vs. O/W) should be such that the inner surface is the one of higher surface tension. Thus sodium and other alkali metal soaps tend to stabilize O/W emulsions, and the explanation would be that, being more water- than oil-soluble, the film-water interfacial tension should be lower than the film-oil one. Conversely, with the relatively more oil-soluble metal soaps, the reverse should be true, and they should stabilize W/O emulsions, as in fact they do. An alternative statement, known as Bancroft s rule, is that the external phase will be that in which the emulsifying agent is the more soluble [20]. A related approach is discussed in Section XIV-5. 

The successful employment of any insecticide depends on its proper formulation into a preparation that can be appHed for insect control with safety to the apphcator, animals, and plants. Insecticides are commonly formulated as dusts, water dispersions, emulsions, and solutions. The preparation and use of such formulations involves accessory agents such as dust carriers, solvents, emulsifiers, wetting and dispersing agents, stickers, and deodorants or masking agents (1). 

Propagation. The rate of emulsion polymerization has been found to depend on initiator, monomer, and emulsifier concentrations. In a system of vinyl acetate, sodium lauryl sulfate, and potassium persulfate, the following relationship for the rate of polymerization has been suggested (85) ... 

Pasteurized Process Cheese. Sodium citrate is used in pasteurized process and sHced cheese as an emulsifying salt to stabilize the water and oil emulsion and improve process cheese body and texture (64). 

Free-radical copolymerizations have been performed ia bulb (comonomers without solvent), solution (comonomers with solvent), suspension (comonomer droplets suspended ia water), and emulsion (comonomer emulsified ia water). On the other hand, most ionic and coordination copolymerizations have been carried out either ia bulb or solution, because water acts as a poison for many ionic and coordination catalysts. Similarly, few condensation copolymerizations iavolve emulsion or suspension processes. The foUowiag reactions exemplify the various copolymerization mechanisms. 

Before determining the degree of stabiUty of an emulsion and the reason for this stabiUty, the mechanisms of its destabilization should be considered. When an emulsion starts to separate, an oil layer appears on top, and an aqueous layer appears on the bottom. This separation is the final state of the destabilization of the emulsion the initial two processes are called flocculation and coalescence (Fig. 5). In flocculation, two droplets become attached to each other but are stiU separated by a thin film of the Hquid. When more droplets are added, an aggregate is formed, ia which the iadividual droplets cluster but retain the thin Hquid films between them, as ia Figure 5a. The emulsifier molecules remain at the surface of the iadividual droplets duiing this process, as iadicated ia Figure 6. 

The polymer may be prepared readily in bulk, emulsion and suspension, the latter technique apparently being preferred on an industrial scale. The monomer must be free from oxygen and metallic impurities. Peroxide such as benzoyl peroxide are used in suspension polymerisations which may be carried out at room temperature or at slightly elevated temperatures. Persulphate initiators and the conventional emulsifying soaps may be used in emulsion polymerisation. The polymerisation rate for vinylidene chloride-vinyl chloride copolymers is markedly less than for either monomer polymerised alone. 

An emulsion is a suspension of one liquid in a second, immiscible, liquid. Emulsifiers are agents that facilitate the formation of emulsions and play a role in stabilizing the emulsion so formed. There are two main types of emulsions oil in water and water in oil. Predominantly hydrophilic emulsifiers (for example, PI88) will stabilize the former predominantly hydrophobic emulsifiers (for example, P181) will stabilize the latter. 

Polyvinyl chloride can also be produced in emulsion. Water is used as the emulsion medium. The particle size of the polymer is controlled using the proper conditions and emulsifier. Polymers produced by free radical initiators are highly branched with low crystallinity. 

Machine operators working with emulsions can become susceptible to skin infections because of the combination of the de-fatting effect of soluble-oil emulsifiers and the abrasive action of metallic scarf, but bacteria in cutting fluids are seldom the source of such infections. High standards of personal hygiene and the use of barrier creams should prevent such problems. A more difficult situation arises when a soluble-oil emulsion becomes infected with bacteria capable of utilizing the emulsifier and mineral-oil components in the system. Even in clean conditions, untreated soluble-oil emulsions and solutions cannot remain completely sterile for any length of time. 

Recently, Mark and co-workers also reported on organophilic silica formed by the combination of the sol-gel procedure and water-in-oil micro-emulsion method, in which methacryloyloxypropyltrimethoxysilane was used as one component of silica matrix [8]. The size of the silica particle was controlled by the content of water and emulsifier used. The surface of the particles was effectively covered with methacryloyl. organic groups. This organophilic silica is expected to be used as a novel component of composite materials. 

Ether carboxylates can be used in oil-in-water (O/W) emulsions as emulsifiers, stabilizers, and to maintain the pH at 4.5-7.5 [101,102]. Also silicones can be emulsified [103]. Stearylamidether carboxylic acid is used as a mild and effective O/W emulsifer [68,69]. 

Salts of a-sulfo fatty acid esters can work as emulsifying agents for the preparation of asphalt emulsions and asphalt-latex emulsions. The ester sulfonates improve the storage stability of the emulsions [101,102]. In the manufacture of lightweight gypsum products air bubbles have to be mixed into the slurries. The use of salts of sulfonated C10 l8 fatty acid alkyl esters as foaming agents produces uniformly distributed fine bubbles [103]. Salts of C10 16 fatty acid alkyl ester sulfonates can also be added to cement mixtures to prevent slump loss of the mixtures [104]. 

Emulsifiers are used in many technical applications. Emulsions of the oil-in-water and the water-in-oil type are produced on a large scale in the cosmetic industry. Other fields of employment are polymerization of monomers in emulsions and emulsification of oily and aqueous solutions in lubricants and cutting oils. In enhanced oil recovery dispersing of crude oil to emulsions or even microemulsions is the decisive step. 

Hand lotions, of the emulsion type, are also, in most cases, oil in water emulsions. A true emulsifying agent is usually used to form the emulsion and for cleansing properties. Vegetable gums, like tragacanth or Irish moss extract, are added, not only to stabilize the emulsion but to increase the emollient properties, because of the added viscosity effect. 

An important problem in emulsified organic-aqueous systems is that of scale-up, which is concerned with the realization of stable emulsions and the separation of phases after the reaction. The use of biphasic membrane systems that contain the enzyme and keep the two phases separated is likely to solve this problem. In the case of 5-naproxen an ee of 92% has been demonstrated without any decay in activity over a period of two weeks of continuous operation. A number of examples of biocatalytic membrane reactors have been provided by Giorno and Drioli (2000) and include the conversion of fumaric acid to L-aspartic acid, L-aspartic acid to L-alanine, and cortexolone to hydrocortisone and prednisolone. 

A wellbore fluid has been developed that has a nonaqueous continuous liquid phase that exhibits an electrical conductivity increased by a factor of 10 to 10 compared with conventional invert emulsion. 0.2% to 10% by volume of carbon black particles and emulsifying surfactants are used as additives. Information from electrical logging tools, including measurement while drilling and logging while drilling, can be obtained [1563]. 

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