Self-emulsification

The emulsion blocking mechanism involves formation of emulsion in the pores either by self-emulsification of water-based filtrate with the crude oil, or oil filtrate from an oil-based fluid emulsifying formation water. The emulsions are viscous and can block the pores. The remedial design is to prevent emulsification either by eliminating oil from completion fluid or by the use of demulsifiers. 

Self-emulsification The polymer molecules are modified chemically by the introduction of basic (e.g., amino) or acidic (e.g., carboxyl) groups in such concentration and location that the polymer undergoes self-emulsification without surfactant after dispersion in an acidic or basic solution. 

For self-emulsification the molar mass of the EUP must be within a certain range. If the molar mass is too high, the solubility of the EUP is too low. If the molar mass is too low, the solubilizing efficiency is insufficient. With an EUP from maleic anhydride (MA) and hexanediol-1,6 (HD) and acid terminal groups, the optimal molar mass for the solubilization of a hydrophobic comonomer, such as styrene (S), was found to be between about 1700 and 2200 [116]. 

M.G. Wakerly, C.W. Pouton, B.J. Meakin, and E.S. Morton Self emulsification of vegetable oil non-ionic mixtures a proposed mechanism of action. In Phenomena in Mixed Surf actant Systems. American Chemical Society, Washington, DC (1986). 

Figure 1. Effect of Binary Mixture Surfactant Concentration and Self-Emulsification Temperature on Emulsion Droplet Size for the Miglyol 812-Tagat TO System as Determined by Laser Diffraction. Bars Represent Standard Errors.

During the studies of phase behaviour two types of liquid crystalline phases were identified. LC material was viscous and exhibited intense "white" birefingence. material was apparently homogeneous but of low viscosity and exhibited "multi-coloured" birefringence. The liquid crystalline phases observed in the equilibrium studies of surfactant concentrations up to 25 are unlikely to take part in the self-emulsification process due to the presence of two-phase regions between L2 and liquid crystalline phases however, LC material may account for the improved stability of emulsions formed by 25 surfactant systems (Table II). Figure 4c indicates that by increasing the surfactant concentration to 30 the... 

The concept of interfacial mesophases promoting spontaneous emulsification (21.22) can be applied to the Tagat TO - Miglyol 812 system, where stable liquid crystalline dispersion phases are adequate to promote the process of self-emulsification. The stability of the resulting emulsion systems can also be accounted for by liquid crystalline interface stabilisation (23.24). Phase separation of material as observed above 55f surfactant, in conjuction with the increased viscosities of such systems, will inhibit the dynamics of the self-emulsification process and hence the quality of self-emulsified systems declines when the surfactant concentration is increased above 55. ... 

Figure 5. Schematic Representation of the Proposed Self-Emulsification Mechanism. A. Water Penetration. B. Formation of Liquid Crystal. C. Disruption and Emulsification.

This phenomenon of self-emulsification was first observed by Johannes Gad in 1878 when he gently layered a solution of lauric acid on top of an aqueous alkaline solution, thereby making a soap in situ but also forming an emulsion without the aid of external agitation. A laboratory curiosity for the next 50 or so years, the principle became recognized as being valuable for the formulation of herbicides and insecticides such as DDT. The concentrate could be reconstituted with ditch water and sprayed without the need to carry water to the site. 

Wakerly, M.G., Pouton, C.W., Meakin, . J., and Morton, F.S. (1986). Self-emulsification of vegetable oil-nonionic surfactant mixtures A proposed mechanism of action. A.C.S. Symposium, 311, 242-255. 

Emulsions are two-phase systems formed from oil and water by the dispersion of one liquid (the internal phase) into the other (the external phase) and stabilized by at least one surfactant. Microemulsion, contrary to submicron emulsion (SME) or nanoemulsion, is a term used for a thermodynamically stable system characterized by a droplet size in the low nanorange (generally less than 30 nm). Microemulsions are also two-phase systems prepared from water, oil, and surfactant, but a cosurfactant is usually needed. These systems are prepared by a spontaneous process of self-emulsification with no input of external energy. Microemulsions are better described by the bicontinuous model consisting of a system in which water and oil are separated by an interfacial layer with significantly increased interface area. Consequently, more surfactant is needed for the preparation of microemulsion (around 10% compared with 0.1% for emulsions). Therefore, the nonionic-surfactants are preferred over the more toxic ionic surfactants. Cosurfactants in microemulsions are required to achieve very low interfacial tensions that allow self-emulsification and thermodynamic stability. Moreover, cosurfactants are essential for lowering the rigidity and the viscosity of the interfacial film and are responsible for the optical transparency of microemulsions [136]. 

D. Q. Craig, S. A. Barker, D. Banning, and S. W. Booth, Investigation into the mechanisms of self-emulsification using particle size analysis and low frequency dielectric spectroscopy, Int. J. Pharmaceut. 114 103-110 (1995). 

C. W. Pouton, Formulation of self-emulsifing drug delivery systems, Adv. Drug. Deliv. Rev. 25 47-58 (1997). 

Other acrylic latices have a specific application in the coatings industry. One product based on butyl acrylate and acrylo nitrile also contains 2.75t of isobornyl methacrylate with 2.84 of NM U. Self - emulsification takes place with 2-sulfoothyl methao rylate and suiprisingly, sodium vinyl sulfonate. C[Pg.332]

Lubricants/Knitting oils Modem mineral oil formulation usually contain their own self-emulsification system. 

In some cases under the conditions similar to those corresponding to the formation of lyophilic colloidal systems, a spontaneous formation of emulsions, the so-called self-emulsification, may take place. This is possible e.g. when two substances, each of which is soluble in one of the contacting phases, react at the interface to form a highly surface active compound. The adsorption of the formed substance under such highly non-equilibrium conditions may lead to a sharp decrease in the surface tension and spontaneous dispersion (see, Chapter III, 3), as was shown by A.A. Zhukhovitsky [42,43], After the surface active substance has formed, its adsorption decreases as the system reaches equilibrium conditions. The surface tension may then again rise above the critical value, acr. Similar process of emulsification, which is an effective method for preparation of stable emulsions, may take place if a surfactant soluble in both dispersion medium and dispersed liquid is present. If solution of such a surfactant in the dispersion medium is intensively mixed with pure dispersion medium, the transfer of surfactant across the low surface tension interface occurs (Fig. VIII-10). This causes turbulization of interface... 

Microemulsions are transparent systems of two immiscible fluids, stabilized by an interfacial film of surfactant or a mixture of surfactants, frequently in combination with a cosurfactant. These systems could be classified as water-in-oil, bicontinuous, or oil-in-water type depending on their microstructure, which is influenced by their physicochemical properties and the extent of their ingredients. - SMEDDSs form transparent microemulsions with a droplet size of less than 50 nm. Oil is the most important excipient in SMEDDSs because it can facilitate self-emulsification and increase the fraction of lipophilic drug transported through the intestinal lymphatic system, thereby increasing absorption from the gastrointestinal tract. Long-chain and medium-chain... 

Later studies included those of Pouton (6) who examined the relationship between panicle size and composition of Miglyol-812/Tween-8S mixes, dernmi-sirating marked composition dependence of the emulsification process. The correlation between liquid crystal formation and self-emulsification has been funher supported by Iranloye (11). who examined a range of pure hydrocarbon oils. The authcH- reported a correlatton between the extent of liquid crystal formation, the oil-water interfacial tension, and the ease of emulsification. Pouton (12) has also... 

T. A. Iranfoye. Some factors affecting the self-emulsification of hydrocarbon oils. Prog Coll Polym Sci 70 119-126. 1985. 

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