Microemulsion aqueous

Dairy and livestock sprays were usually oil-based at 0.10% pyrethrins and 1.00% PBO, and are typically applied as a fog or fine mist, using about 2 o i of spray per IOOO ft (203 ml/iOO m ) of space. Microemulsion aqueous sprays are now preferred. 

Various structures derived from water-soluble neutral or ionic benzophenones, benzils, thioxanthones (10.54) have been studied for the photopolymerization of water-soluble monomers, monomers in direct and reverse micelles or microemulsions, aqueous dispersions of monomers, water-based coatings [185-188], and so on. 

The system CTAB/l-hexanol/water was utilized by Fang and Yang [258] for preparation of Zr02-Y203 nanoparticles. In one (reverse) microemulsion, aqueous ammonium hydroxide was introduced as precipitant while the other contained Zr-oxychloride and Y-nitrate (ZrA = 94/6) the two were mixed under stirring. The precipitate obtained by centrifugation was ultrasonically washed in pure ethanol, dried at 85 C under vacuum and calcined at 600 C/2h. The particle size distribution was wide, from about 10 nm to 70 nm. 

The phase behavior studies reported in Figure 4 were performed in a brine of similar salinity as in Figure 3, but containing additives to ensure long-term chemical stability of the polymer among these additives was 0.4% isopropanol. These additives have a marginal effect on phase behavior and the same increase in microemulsion/ aqueous phase interfacial tension has been observed. However, we did not find the drastic increases in viscosity reported in Figure 3. 

Most of the earlier femtosecond RIKES studies were conducted to clarify the intermolecular vibrational and orientational dynamics in pure molecular hquids and binary mixtures (Kinoshita et al., 1996 Castner Maroncelli, 1998 Smith Meech, 2002 Zhong Fourkas, 2008 Shirota et al, 2009). Nowadays, femtosecond RIKES is also used to study the intermolecular vibrational dynamics, reorientation, and microscopic intermolecular interactions of complex condensed phases (Hunt et al., 2007 Farrer Fourkas, 2003) such as polymer liquids and solutions, microemulsions, aqueous protein films and solutions, and solvents in nanoporous glasses. As mentioned above, femtosecond RIKES has also been used to investigate ILs (Castner et al., 2007). 

Figure C2.3.8. Self-diffusion coefficients at 45°C for AOT ( ), water ( ) and decane ( ) in ternary AOT, brine (0.6% aqueous NaCl) and decane microemulsion system as a function of composition, a. This compositional parameter, a, is tire weight fraction of decane relative to decane and brine. Reproduced by pennission from figure 3 of [46].

Other solubilization and partitioning phenomena are important, both within the context of microemulsions and in the absence of added immiscible solvent. In regular micellar solutions, micelles promote the solubility of many compounds otherwise insoluble in water. The amount of chemical component solubilized in a micellar solution will, typically, be much smaller than can be accommodated in microemulsion fonnation, such as when only a few molecules per micelle are solubilized. Such limited solubilization is nevertheless quite useful. The incoriDoration of minor quantities of pyrene and related optical probes into micelles are a key to the use of fluorescence depolarization in quantifying micellar aggregation numbers and micellar microviscosities [48]. Micellar solubilization makes it possible to measure acid-base or electrochemical properties of compounds otherwise insoluble in aqueous solution. Micellar solubilization facilitates micellar catalysis (see section C2.3.10) and emulsion polymerization (see section C2.3.12). On the other hand, there are untoward effects of micellar solubilization in practical applications of surfactants. Wlren one has a multiphase... 

In Figure 1, the pairs (or triad) of phases that form ia the various multiphase regions of the diagram are illustrated by the corresponding test-tube samples. Except ia rare cases, the densities of oleic phases are less than the densities of conjugate microemulsions and the densities of microemulsions are less than the densities of conjugate aqueous phases. Thus, for samples whose compositions He within the oleic phase-microemulsion biaodal, the upper phase (ie, layer) is an oleic phase and the lower layer is a microemulsion. For compositions within the aqueous phase-microemulsion biaodal, the upper layer is a microemulsion and the lower layer is an aqueous phase. When a sample forms two layers, but the amphiphile concentration is too low for formation of a middle phase, neither layer is a microemulsion. Instead the upper layer is an oleic phase ("oil") and the lower layer is an aqueous phase ("water"). 

In three-phase systems the top phase, T, is an oleic phase, the middle phase, Af, is a microemulsion, and the bottom phase, B, is an aqueous phase. Microemulsions that occur ia equiUbrium with oae or two other phases are sometimes called "limiting microemulsions," because they occur at the limits of the siagle-phase regioa. 

The locations of the tietriangle and biaodal curves ia the phase diagram depead oa the molecular stmctures of the amphiphile and oil, on the concentration of cosurfactant and/or electrolyte if either of these components is added, and on the temperature (and, especially for compressible oils such as propane or carbon dioxide, on the pressure (29,30)). Unfortunately for the laboratory worker, only by measuriag (or correcdy estimatiag) the compositions of T, Af, and B can one be certain whether a certain pair of Hquid layers are a microemulsion and conjugate aqueous phase, a microemulsion and oleic phase, or simply a pair of aqueous and oleic phases. 

However, often the identities (aqueous, oleic, or microemulsion) of the layers can be deduced rehably by systematic changes of composition or temperature. Thus, without knowing the actual compositions for some amphiphile and oil of poiats T, Af, and B ia Figure 1, an experimentaUst might prepare a series of samples of constant amphiphile concentration and different oil—water ratios, then find that these samples formed the series (a) 1 phase, (b) 2 phases, (c) 3 phases, (d) 2 phases, (e) 1 phase as the oil—water ratio iacreased. As illustrated by Figure 1, it is likely that this sequence of samples constituted (a) a "water-continuous" microemulsion (of normal micelles with solubilized oil), (b) an upper-phase microemulsion ia equiUbrium with an excess aqueous phase, ( ) a middle-phase microemulsion with conjugate top and bottom phases, (d) a lower-phase microemulsion ia equiUbrium with excess oleic phase, and (e) an oA-continuous microemulsion (perhaps containing iaverted micelles with water cores). 

Nevertheless, possibiUties for confusion abound. From the definitions of microemulsions and macroemulsions and from Figure 1, it immediately follows that in many macroemulsions one of the two or three phases is a microemulsion. Until recentiy (49), it was thought that all nonmultiple emulsions were either oil-in-water (O/W) or water-in-oil (W/O). However, the phase diagram of Figure 1 makes clear that there are six nonmultiple, two-phase morphologies, of which four contain a microemulsion phase. These six two-phase morphologies are oleic-in-aqueous (OL/AQ, or O/W) and aqueous-in-oleic (AQ/OL, or W/O), but also, oleic-in-microemulsion (OL/MI), microemulsion-in-oleic (MI/OL), aqueous-in-microemulsion (AQ/MI), and microemulsion-in-aqueous (MI/AQ) (49). 

Fig. 8. Emulsion morphology diagram, illustrating where the microemulsion in various macroemulsion morphologies is a continuous phase or dispersed phase. Morphology boundaries (—), aqueous, continuous (--------------), oleic, continuous (--), microemulsion, continuous.

Manufacturing processes have been improved by use of on-line computer control and statistical process control leading to more uniform final products. Production methods now include inverse (water-in-oil) suspension polymerization, inverse emulsion polymerization, and continuous aqueous solution polymerization on moving belts. Conventional azo, peroxy, redox, and gamma-ray initiators are used in batch and continuous processes. Recent patents describe processes for preparing transparent and stable microlatexes by inverse microemulsion polymerization. New methods have also been described for reducing residual acrylamide monomer in finished products. 

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). 

Microemulsions or reverse micelles are composed of enzyme-containing, surfactant-stabiHzed aqueous microdroplets in a continuous organic phase. Such systems may be considered as a kind of immobilization in enzymatic synthesis reactions. 

The main supramolecular self-assembled species involved in analytical chemistry are micelles (direct and reversed), microemulsions (oil/water and water/oil), liposomes, and vesicles, Langmuir-Blodgett films composed of diphilic surfactant molecules or ions. They can form in aqueous, nonaqueous liquid media and on the surface. The other species involved in supramolecular analytical chemistry are molecules-receptors such as calixarenes, cyclodextrins, cyclophanes, cyclopeptides, crown ethers etc. Furthermore, new supramolecular host-guest systems arise due to analytical reaction or process. 

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. 

Solubilizing activity are also used in enhanced oil recovery. Tar and extremely viscous hydrocarbons are recovered by the injection of an aqueous solution of an anionic orthophosphate ester surfactant into a petroleum formation, retaining the surfactant in the formation for about 24 h, and displacing the solubilized hydrocarbons toward a recovery well. The surfactant forms an oil microemulsion with the hydrocarbons in the formation. An anionic monoorthophosphate ester surfactant which is a free acid of an organic phosphate ester was dissolved in water. The input of surfactant solution was 2-25% of the pore volume of the formation [250]. To produce a concentrate for the manufacture... 

Non-aqueous microemulsions have been prepared by replacing water with formamide, a highly structured polar solvent [71]. Formamide enhances the solubility of organic compounds and is also used as a reactant. 

The influence of pH, ionic strength, and protein concentration on the extraction of a-lactalbumin and 3-lactoglobulin from an aqueous solution with water/AOT/isooctane microemulsions and their separation has been reported [168],... 

As a result of the micellar environment, enzymes and proteins acquire novel conformational and/or dynamic properties, which has led to an interesting research perspective from both the biophysical and the biotechnological points of view [173-175], From the comparison of some properties of catalase and horseradish peroxidase solubilized in wa-ter/AOT/n-heptane microemulsions with those in an aqueous solution of AOT it was ascertained that the secondary structure of catalase significantly changes in the presence of an aqueous micellar solution of AOT, whereas in AOT/n-heptane reverse micelles it does not change. On the other hand, AOT has no effect on horseradish peroxidase in aqueous solution, whereas slight changes in the secondary structure of horseradish peroxidase in AOT/n-heptane reverse micelles occur [176],... 

Even entrapment of entire cells within reversed micelles without loss of their functionality has been achieved. For example, mitochondria and bacteria (Actinobacter cal-coaceticus, Escherichia coli, Corynebacterium equi) have been successfully solubilized in a microemulsion consisting of isopropyl pahnitate, polyoxyethylene sorbitan trioleate [162], Enhanced hydrogen photoproduction by the bacterium Rhodopseudomonas sphaeroides or by the coupled system Halobacterium halobium and chloroplasts organelles entrapped inside the aqueous core of reversed micelles with respect to the same cells suspended in normal aqueous medium has been reported [183,184],... 

Solubilization of a graft copolymer comprising a hydrophobic poly(dodecyl-methacrylate) backbone and hydrophilic poly(ethylene glycol) monomethyl ether side chains in water/AOT/cyclohexane w/o microemulsions was rationalized in terms of the backbone dissolved in the continuous apolar phase and the side chains entrapped within the aqueous micellar cores [189],... 

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