Emulsions spontaneous

Emulsion Stability. An emulsion is defined as a macroscopic dispersion of two liquids, one of which forms the continuous phase of the system and the other forms the discrete phase. An emulsion of two liquids without a stabilizer will quickly break into two liquid layers. Emulsions destabilize by three distinct processes breaking, creaming, and flocculation (Figure 14). When emulsions break, the initial small droplets of the emulsion spontaneously join to form larger droplets. This process is termed coalescence , and it ultimately leads to two separate liquid layers. 

The importance of the properties of the interfacial region for spontaneous emulsification was first demonstrated by Gad (4), who observed that when a solution of lauric acid in oil was carefully placed on an aqueous alkaline solution, an emulsion spontaneously formed at the interface. The reason for this spontaneous emulsification is the formation of a mixed film of lauric acid and sodium laurate (produced by partial neutralization of the acid by alkali) which produces an ultra-low interfacial tension. 

Prepolymer ionomers with isocyanate end-groups and of sufficiently low molecular weight can be mixed with water in the presence of hydrophobic organic solvents, such as methylene chloride or toluene, or, in the case of sufficiently low viscosities, even without solvent. The prepolymers form emulsions, which in turn form polymer dispersion after chain extension by reaction of the isocyanate. Such a process requires powerful high-shear mixing equipment in the presence or absence of solvents. Solutions of ionomers in hydrophilic solvents form emulsions spontaneously in the presence of water. The formation of the emulsion must be... 

Resins are incorporated in Neoprene latex as solvent-cut emulsions, solventless pebble-milled dispersions, or sometimes as solvent-free emulsions prepared using invert emulsification techniques. In the latter case a resin with a melting point of 80°C (176 F) or lower is melted. Water and surfactants are added to the molten resin and the temperature of the mixture is decreased. Upon reaching a certain temperature, known as the phase inversion temperature, the water in molten resin emulsion spontaneously inverts to form a resin in water emulsion suitable for use in latex adhesives. A resin dispersion which can be prepared in this manner is shown in Table 16. This particular resin dispersion can be used to produce adhesives with moderate hot strength and good open time using the following recipe ... 

They form emulsions spontaneously when mixed with water. 

It is quite clear, first of all, that since emulsions present a large interfacial area, any reduction in interfacial tension must reduce the driving force toward coalescence and should promote stability. We have here, then, a simple thermodynamic basis for the role of emulsifying agents. Harkins [17] mentions, as an example, the case of the system paraffin oil-water. With pure liquids, the inter-facial tension was 41 dyn/cm, and this was reduced to 31 dyn/cm on making the aqueous phase 0.00 IM in oleic acid, under which conditions a reasonably stable emulsion could be formed. On neutralization by 0.001 M sodium hydroxide, the interfacial tension fell to 7.2 dyn/cm, and if also made O.OOIM in sodium chloride, it became less than 0.01 dyn/cm. With olive oil in place of the paraffin oil, the final interfacial tension was 0.002 dyn/cm. These last systems emulsified spontaneously—that is, on combining the oil and water phases, no agitation was needed for emulsification to occur. 

Then filter off the solid azoxybenzene at the pump, wash it thoroughly with water, and drain well. Recrystallise from a minimum of m ethylated spirit, allowing the hot solution to cool spontaneously (with occasional stirring) until crystallisation starts, and then cool in ice-water. If crystallisation is delayed, seed the solution with a trace of the crude product if on the other hand the azoxybenzene separates at first as an emulsion, add methylated spirit, drop by drop, with stirring until the solution is clear, and then allow the cooling to proceed as before. The... 

Finally, add an excess of concentrated hydrochloric acid slowly with stirring to the alkaline filtrate remaining from the original reaction product. As the solution becomes acid, the sulphonyl-aniline separates as a thick sticky syrup which, when stirred, rapidly crystallises. Cool the mixture in ice-water if necessary, and then filter off the solid product at the pump, wash well with water, and drain. Recrystallise from a mixture of 2 volumes of ethanol and i volume of water to prevent the sulphonyl-aniline from separating as an emulsion, allow the hot solution to cool spontaneously (with occasional stirring) until crystallisation starts, and... 

Photographic Ag halide emulsions are stabilized against the formation of spontaneous fog by incorporation of this product Additive for developing photographic materials... 

Microemulsion Polymerization. Polyacrylamide microemulsions are low viscosity, non settling, clear, thermodynamically stable water-in-od emulsions with particle sizes less than about 100 nm (98—100). They were developed to try to overcome the inherent settling problems of the larger particle size, conventional inverse emulsion polyacrylamides. To achieve the smaller microemulsion particle size, increased surfactant levels are required, making this system more expensive than inverse emulsions. Acrylamide microemulsions form spontaneously when the correct combinations and types of oils, surfactants, and aqueous monomer solutions are combined. Consequendy, no homogenization is required. Polymerization of acrylamide microemulsions is conducted similarly to conventional acrylamide inverse emulsions. To date, polyacrylamide microemulsions have not been commercialized, although work has continued in an effort to exploit the unique features of this technology (100). 

In addition to chemical and spectral sensitizers, several other classes of chemical compounds are added to emulsions before coating. Additives are used to facihtate coating operations, eg, surfactants (qv) and viscosity enhancers to reduce spontaneous development ia unexposed regions, eg, tetraazaiadenes and mercaptotetrazoles and to reduce abrasion and permit high temperature processing, eg, aldehydes (qv). 

A (macro)emulsion is formed when two immiscible Hquids, usually water and a hydrophobic organic solvent, an oil, are mechanically agitated (5) so that one Hquid forms droplets in the other one. A microemulsion, on the other hand, forms spontaneously because of the self-association of added amphiphilic molecules. During the emulsification agitation both Hquids form droplets, and with no stabilization, two emulsion layers are formed, one with oil droplets in water (o /w) and one of water in oil (w/o). However, if not stabilized the droplets separate into two phases when the agitation ceases. If an emulsifier (a stabilizing compound) is added to the two immiscible Hquids, one of them becomes continuous and the other one remains in droplet form. 

In the simplest emulsions just described, the final separation is into two Hquid phases upon destabilization. The majority of emulsions are of this kind, but in some cases the emulsion is divided into more than two phases. One obvious reason for such a behavior is the presence of a material that does not dissolve in the oil or the water. One such case is the presence of soHd particles, which is common in emulsions for food, pharmaceuticals, and cosmetics. Another less trivial reason is that the surfactant associates with the water and/or the oil to form a colloidal stmcture that spontaneously separates from the two hquid phases. This colloidal stmcture may be an isotropic Hquid or may be a semisoHd phase, a Hquid crystal, with long-range order. 

In solid form, Mg is difficult to ignite because heat is conducted rapidly away from the source of ignition it must be heated above its mp before it will bum. However, in finely divided form it may be ignited by a spark dr the flame of a, match. Mg fires do not flare up violently unless there is moisture present. Therefore it must be kept away from w, moisture, etc. It m y. be ignited by a spark, match flame, or even spontaneously when the Mg is finely divided and damp, particularly with w-oil emulsion. Also, Mg reacts with moisture, acids, etc to evolve H2 which is a highly dangerous fire arid explosion hazard (Ref 23)... 

Bouchemal, K., Briangon, S., Perrier, E. and Fessi, H. (2004) Nano-emulsion formulation using spontaneous emulsification solvent, oil and surfactant optimisation. International Journal of Pharmaceutics, 280, 241-251. 

An emulsion, formed during extraction of a strongly alkaline liquor with trichloroethylene, decomposed with evolution of the spontaneously flammable gas, dichloro-acetylene [1]. This reaction could also occur if alkaline metal-stripping preparations were used in conjunction with trichloroethylene degreasing preparations, some of which also contain amines as inhibitors, which could also cause the same reaction [2], Apparently accidental contact of the solvent with potassium hydroxide solution led to generation of flames in the charging port of a stirred reactor [3], See Tetrachloroethylene Sodium hydroxide... 

Obviously the lowest free energy is given by the most stable state for a system at constant pressure and, therefore, in due course an emulsion shall break spontaneously to the two-layered system. However, the breaking of an emulsion could be relatively a rather slow phenomenon. There are a number of factors which may be responsible for the slow-coalescence of an emulsion, namely ... 

The most frequent emulsiflcation using phase inversion is known as the PIT (Phase Inversion Temperature) method [81-83] and occurs through a temperature quench. This method is based on the phase behavior of nonionic surfactants and the correlation existing between the so-called surfactant spontaneous curvature and the type of emulsion obtained. 

Figure 1.4. For a nonionic surfactant, influence of the temperature on (a) the surfactant morphology and hence the spontaneous curvature, (b) the type of self-assembly, (c) the phase diagram, the number of coexisting phases is indicated (d) the coexisting phases at equilibrium, and (e) the corresponding emulsions.

M.J. Rang and C.A. Miller Emulsions and Microemulsions—Spontaneous Emulsification of Oil Drops Containing Surfactants and Medium-Chain Alcohols. Prog. Colloid Polym. Sci. 109, 101 (1998). 

N. Shahidzadeh, D. Boim, and J. Meunier A New Mechanism of Spontaneous Emulsification Relation to Surfactant Properties. Europhys. Lett 40, 459 (1997). R.W. Greiner and D.F. Evans Spontaneous Formation of a Water-Continuous Emulsion from a W/O Microemulsion. Langmuir 6, 1793 (1990). 

H. Kunieda, Y. Fukui, H. Uchiyama, and C. Solans Spontaneous Formation of Highly Concentrated Water-in-Oil Emulsions (Gel-Emulsions). Langmuir 12,2136 (1996). 

K. Ozawa, C. Solans, and H. Kunieda Spontaneous Formation of Highly Concentrated Oil-in-Water Emulsions. J. Colloid Interface Sci. 188, 275 (1997). 

Figure 5.3. Scheme explaining the influence of the spontaneous curvature on the activation energy for coalescence in a W/O emulsion. 

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