Cosurfactant effect

The polymerization of a water-soluble monomer such as AM, acrylic acid (AA), sodium acrylate (NaA), or 2-hydroxyethylmethacrylate (HEMA), can be carried out easily in inverse microemulsion or/and bicontinuous microemulsion. These water-soluble monomers also act as cosurfactants, increasing the flexibility and the fluidity of the interfaces, which enhances the solubilization of the monomer. A cosurfactant effect during the polymerization of vinyl acetate in anionic microemulsions has also been reported [12]. 

Pattarino, F., Marengo, E., Trotta, M. and Gasco, M.R. (2000) Combined use of lecithin and decyl polyglucoside in microemulsions domain of existence and cosurfactant effect. /. Disp. Sci. Technol, 21, 345-363. 

Most notably, the solubilization capacity of polysoaps is not correlated with their surface activity [78, 343], Thus any combination of these two properties can be realized in polysoaps, even unusual ones such as low surface activity with high solubilization capacity. The phenomenon is not understood, but might be related to different conformations taken at the gas-water interface and in solution (cf. Sect. 6.1), or to cosurfactant effects of the solubilizates. 

The monomer consumption from the intetfacial layer (cosurfactant effect) modifies the film curvature energy. The formation of spherical polymo- particles dispersed in the oily phase corresponds to the minimum free energy of the system. 

The monomer cosurfactant effect alone is not enough to explain the very high values of HLBopt- Electrolytic effects of certain monomers must also be taken into account. For example, adding sodium acrylate or MADQUAT to water/surfactant/oil systems drastically reduces solubility of non-ionic surfactants in water. This is called salting out. Reducing solubility in this way shifts HLBopt to higher values. 

Cationic surfactants may be used [94] and the effect of salinity and valence of electrolyte on charged systems has been investigated [95-98]. The phospholipid lecithin can also produce microemulsions when combined with an alcohol cosolvent [99]. Microemulsions formed with a double-tailed surfactant such as Aerosol OT (AOT) do not require a cosurfactant for stability (see, for instance. Refs. 100, 101). Morphological hysteresis has been observed in the inversion process and the formation of stable mixtures of microemulsion indicated [102]. 

In the 1990s, the thmst of surfactant flooding work has been to develop surfactants which provide low interfacial tensions in saline media, particularly seawater require less cosurfactant are effective at low concentrations and exhibit lower adsorption on rock. Nonionic surfactants such as alcohol ethoxylates, alkylphenol ethoxylates (215) and propoxylates (216), and alcohol propoxylates (216) have been evaluated for this appHcation. More recently, anionic surfactants have been used (216—230). 

These surfactants, in conjunction with soap, produce bars that may possess superior lathering and rinsing in hard water, greater lather stabiUty, and improved skin effects. Beauty and skin care bars are becoming very complex formulations. A review of the Hterature clearly demonstrates the complexity of these very mild formulations, where it is not uncommon to find a mixture of synthetic surfactants, each of which is specifically added to modify various properties of the product. Eor example, one approach commonly reported is to blend a low level of soap (for product firmness), a mild primary surfactant (such as sodium cocoyl isethionate), a high lathering or lather-boosting cosurfactant, eg, cocamidopropyl betaine or AGS, and potentially an emollient like stearic acid (27). Such benefits come at a cost to the consumer because these materials are considerably more expensive than simple soaps. 

Amoco developed polybutene olefin sulfonate for EOR (174). Exxon utilized a synthetic alcohol alkoxysulfate surfactant in a 104,000 ppm high brine Loudon, Illinois micellar polymer small field pilot test which was technically quite successful (175). This surfactant was selected because oil reservoirs have brine salinities varying from 0 to 200,000 ppm at temperatures between 10 and 100°C. Petroleum sulfonate apphcabdity is limited to about 70,000 ppm salinity reservoirs, even with the use of more soluble cosurfactants, unless an effective low salinity preflush is feasible. 

As will be explained later, the presence of a cosurfactant can have a significant effect on the Ca(LAS)2 precipitation boundary [37]. 

Another example of chemical-potential-driven percolation is in the recent report on the use of simple poly(oxyethylene)alkyl ethers, C, ), as cosurfactants in reverse water, alkane, and AOT microemulsions [27]. While studying temperature-driven percolation, Nazario et al. also examined the effects of added C, ) as cosurfactants, and found that these cosurfactants decreased the temperature threshold for percolation. Based on these collective observations one can conclude that linear alcohols as cosurfactants tend to stiffen the surfactant interface, and that amides and poly(oxyethylene) alkyl ethers as cosurfactants tend to make this interface more flexible and enhance clustering, leading to more facile percolation. 

These microdroplets can act as a reaction medium, as do micelles or vesicles. They affect indicator equilibria and can change overall rates of chemical reactions, and the cosurfactant may react nucleophilically with substrate in a microemulsion droplet. Mixtures of surfactants and cosurfactants, e.g. medium chain length alcohols or amines, are similar to o/w microemulsions in that they have ionic head groups and cosurfactant at their surface in contact with water. They are probably best described as swollen micelles, but it is convenient to consider their effects upon reaction rates as being similar to those of microemulsions (Athanassakis et al., 1982). 

This transition may j-.e. reducing the specific surface energy, f. The reduction of f to sufficiently small values was accounted for by Ruckenstein (15) in terms of the so called dilution effect". Accumulation of surfactant and cosurfactant at the interface not only causes significant reduction in the interfacial tension, but also results in reduction of the chemical potential of surfactant and cosurfactant in bulk solution. The latter reduction may exceed the positive free energy caused by the total interfacial tension and hence the overall Ag of the system may become negative. Further analysis by Ruckenstein and Krishnan (16) have showed that micelle formation encountered with water soluble surfactants reduces the dilution effect as a result of the association of the the surfactants molecules. However, if a cosurfactant is added, it can reduce the interfacial tension by further adsorption and introduces a dilution effect. The treatment of Ruckenstein and Krishnan (16) also highlighted the role of interfacial tension in the formation of microemulsions. When the contribution of surfactant and cosurfactant adsorption is taken into account, the entropy of the drops becomes negligible and the interfacial tension does not need to attain ultralow values before stable microemulsions form. 

With ionic surfactants for which V/1 <0.7, microemulsion formation needs the presence of a cosurfactant. The latter has the effect of increasing V without affecting 1 (if the chain length of the cosurfactant does not exceed that of the surfactant). These cosurfactant molecules act as "padding" separating the head groups. 

A microemulsion is defined as a thermodynamically stable and clear isotropic mixture of water-oil-surfactant-cosurfactant (in most systems, it is a mixture of short-chain alcohols). The cosurfactant is the fourth component, which effects the formation of very small aggregates or drops that make the microemulsion almost clear. 

Nazario LMM, Hatton TA, Crespo JPSG (1996) Nonionic cosurfactants in AOT reversed micelles Effect on percolation, size, and solubilization site. Langmuir... 

Maidment LJ, Chen V, Warr GG (1997) Effect of added cosurfactant on ternary microemulsion structure and dynamics. Colloids Simf A 130 311-319... 

Williams [105] investigated the effect on stability of water-in-styrene/divinyl-benzene HIPEs, stabilised with nonionic surfactants, on addition of a range of cosurfactants. Generally, stability was reduced, with higher degrees of coalescence being observed with cosurfactant addition. The stability appeared to be inversely related to the HLB number of the cosurfactant. 

The effectiveness of the method is most probably based on the fact that alkyl hypochlorite is formed at the oil/water interface where the cosurfactant alcohol resides. The oxidation that follows takes place either inside or on the surface of oil droplet. The rate of the reaction can result from a large hydrocarbon/water contact area permitting interaction between oil-soluble sulfide with interfacial cosurfactant that served as an intermediary. An extension ofthis procedure to mustard deactivation has also been proposed [20b]. Such systems could be also applied to the degradation of several environmentally contaminating materials The formation of microemulsions, micelles and vesicles is promoted by unfavourable interactions at the end sections of simple bilayer membranes. There is no simple theory of solute-solvent interactions. However, the formation of... 

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