Water in oil microemulsions

The term microemulsion is applied in a wide sense to different types of liquid liquid systems. In this chapter, it refers to a liquid-liquid dispersion of droplets in the size range of about 10-200 nm that is both thermodynamically stable and optically isotropic. Thus, despite being two phase systems, microemulsions look like single phases to the naked eye. There are two types of microemulsions oil in water (O/W) and water in oil (W/O). The simplest system consists of oil, water, and an amphiphilic component that aggregates in either phase, or in both, entrapping the other phase to form... 

Keywords Microemulsion polymerization Microemulsion reaction Water-in-Oil (W/O) microemulsion Oil-in-Water (0/W) microemulsion Bicontinuous microemulsion Functional membranes and inorganic/polymer nanocomposites... 

Intraveous administration of microemulsions, oil in water, that are pharmaceutically acceptable have also been reported. An example of this micromeulsion is composed of MCT, soybean PC and poly(ethylene glycol)(660)-12-hydroxystearate (12-HSA- E015) as amphiphUes, and poly(ethylene glycol) 400 (PEG 400) and ethanol as cosolvents (61). The mean droplet diameter of the oil-in-water emulsion reported was between 60 and 200 nm. It was concluded that it is possible to administer it without producing any... 

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). 

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. 

On a microscopic scale, a microemulsion is a heterogeneous system and, depending on the relative amounts of the constituents, three main types of structures can be distinguished [69] oil in water (OAV, direct micellar structure), water in oil (W/O, reverse micellar structure) and a bicontinuous structure (B) (Figure 6.1). By adding oil in water, OAV dispersion evolves smoothly to a W/O dispersion via bicontinuous phases. 

The rates of multiphase reactions are often controlled by mass tran.sfer across the interface. An enlargement of the interfacial surface area can then speed up reactions and also affect selectivity. Formation of micelles (these are aggregates of surfactants, typically 400-800 nm in size, which can solubilize large quantities of hydrophobic substance) can lead to an enormous increase of the interfacial area, even at low concentrations. A qualitatively similar effect can be reached if microemulsions or hydrotropes are created. Microemulsions are colloidal dispersions that consist of monodisperse droplets of water-in-oil or oil-in-water, which are thermodynamically stable. Typically, droplets are 10 to 100 pm in diameter. Hydrotropes are substances like toluene/xylene/cumene sulphonic acids or their Na/K salts, glycol.s, urea, etc. These. substances are highly soluble in water and enormously increase the solubility of sparingly. soluble solutes. 

Various additives have been proposed to assist in freeing a stuck drill pipe, the most common of which is diesel oil that is added directly to the drilling mud as a spotting fluid. However, this is not always successful. An additive comprising an oil-in-water microemulsion has been proposed. Sodium dodecyl... 

The last, and less extensively studied field variable driving percolation effects is chemical potential. Salinity was examined in the seminal NMR self-diffusion paper of Clarkson et al. [12] as a component in brine, toluene, and SDS (sodium dodecylsulfate) microemulsions. Decreasing levels of salinity were found to be sufficient to drive the microemulsion microstructure from water-in-oil to irregular bicontinuous to oil-in-water. This paper was... 

Surfactant molecules can be considered as building blocks for certain forms of geometry in colloidal chemistry. Various forms of association molecules can be obtained as the concentration of surfactant in water is increased and/or physicochemical conditions are changed (e.g. CMC, Craft-point, etc.). Figure 2 schematically shows the most likely structural configurations and assemblages of surfactants association in an aqueous system (26). Upon addition of oil and a short-chain alcohol, for example, one can convert the oil-in-water micelles into water-in-oil microemulsions. It is therefore possible to induce a transition from one structure to another by changing the physicochemical conditions such as temperature, pH and addition of mono or di-valent cations to the surfactant solution. It should be also noted that the sur-... 

It is convenient to differentiate between oil-in-water (o/w) microemulsions and water-in-oil (w/o) microemulsions in which water and oil are the respective major components. It is reasonable to regard (o/w) microemulsions as akin to swollen normal micelles and w/o microemulsions as reverse micelles (Section 1). 

Similar investigations have been carried out on water in oil microemulsions. A microemulsion is a clear, transparent, and stable system consisting of essentially monodisperse oil in water (OAV) or water in oU (W/O) droplets with diameters generally in the range of 10-200 nm. Microemulsions are transparent because of their small particle size, they are spherical aggregates of oil or water dispersed in the other liquid, and they are stabilized by an interfacial film of one or more surfactants. 

The influence of surfactant structure on the nature of the microemulsion formed can also be predicted from the thermodynamic theory by Overbeek (17,18). According to this theory, the most stable microemulsion would be that in which the phase with the smaller volume fraction forms the droplets, since the osmotic term increases with increasing i. For w/o microemulsion prepared using an ionic surfactant, the hard sphere volume is only slightly larger than the water volume, since the hydrocarbon tails of the surfactant may interpenetrate to a certain extent, when two droplets come close together. For an oil in water microemulsion, on the other hand, the double layer may extend to a considerable extent, depending on the electrolyte concentration... 

The rate constants for the reaction of a pyridinium Ion with cyanide have been measured in both a cationic and nonlonic oil in water microemulsion as a function of water content. There is no effect of added salt on the reaction rate in the cationic system, but a substantial effect of ionic strength on the rate as observed in the nonionic system. Estimates of the ionic strength in the "Stern layer" of the cationic microemulsion have been employed to correct the rate constants in the nonlonic system and calculate effective surface potentials. The ion-exchange (IE) model, which assumes that reaction occurs in the Stern layer and that the nucleophile concentration is determined by an ion-exchange equilibrium with the surfactant counterion, has been applied to the data. The results, although not definitive because of the ionic strength dependence, indicate that the IE model may not provide the best description of this reaction system. 

A pseudophase ion exchange model has been applied to reactions in micellar systems with varying success (1-7). According to this model, the distribution of nucleophile is considered to depend on the ion-exchange equilibrium between the nucleophile and the surfactant counterion at the micelle surface. This leads to a dependence on the ion-exchange constant (K g) as well as on the degree of dissociation (a) of the surfactant counterion. The ion exchange (IE) model has recently been extended to oil in water microemulsions (8). 

In contrast to the above results, all three "picket fence" porphyrins are solubilized in an oil-in-water microemulsion to yield a clear solution having a Soret band at 419-421 nm resembling that of H2PF,TPro solubilized in micelles. In this case the microemulsion (composed of SDS, n-pentanol and dodecane) consists of oil "droplets" dissolved in bulk water the radius of the droplet has been estimated to be 37 A ( ), well over twice that estimated for an SDS micelle (16 A). Since the droplet in the microemulsion contains a much larger "interior", it is reasonable that it may be a better medium for solubilizing the porphyrin. 

The effect of adding a surfactant, (NaDDS), was also investigated. One such case only is shown in Fig. 6 where BE is replaced by a 5 1 mixture of BE-NaDDS. The main effect of NaDDS is to increase the miscibility range of the oil in water. Various ratios of BE-NaDDS were used and, as a first approximation, the change in the phase diagram is directly proportional to the concentration of NaDDS. The addition of a surfactant probably stabilizes the microstructures which were already present in the ternary system BE-DEC-H O and decreases the quantity of BE needed to solubilize DEC. Therefore the presence of a surfactant is useful but not essential to the stability of microemulsions. 

Terpene-based microemulsion cleaning composition has been reported in some industrial applications. Oil-in-water microemulsion cleaning compositions comprising four principal components were described based on four components. These were... 

Berthod, A., De Carvalho, M. (1992). Oil in water microemulsion as mobile phase in liquid chromatography. Anal. Chem. 64 2267-2272. 

For a given surfactant, the ability to form a single-phase w/o microemulsion is a function of the type of oil, nature of the electrolyte, solution composition, and temperature (54-58). When microemulsions are used as reaction media, the added reactants and the reaction products can also influence the phase stability. Figure 2.2.4 illustrates the effects of temperature and ammonia concentration on the phase behavior of the NP-5/cyclohexane/water system (27). In the absence of ammonia, the central region bounded by the two curves represents the single-phase microemulsion region. Above the upper curve (the solubilization limit), a water-in-oil microemulsion coexists with an aqueous phase, while below the lower curve (the solubility limit), an oil-in-water water microemulsion coexists with an oil phase. It can be seen that introducing ammonia into the system results in a shift of the solubilization... 

Clear, stable dispersions of particles whose sizes are larger than those of micelles. Conceptually, they can be derived from miscelles by increasing the surfactant concentration above the CMC (or above the region where reversed miscelles predominate) and/or by adding a third component (alcohol, for example) which leads to the formation of larger aggregates oil-in-water (o/w) or water-in-oil (w/o) microemulsions. 

Chapter 8 discusses self-assembly of surfactants to form micelles, models of micelliza-tion, use of micelles in catalysis and solubilization, and oil-in-water and water-in-oil microemulsions. 

An overview of other forms of micellar systems follows in the next three sections. Formation of reverse micelles, in nonaqueous media, is discussed briefly in Section 8.8. Sections 8.9 and 8.10 present an introduction to microemulsions (oil, or water, droplets stabilized in water or oil, respectively) and their applications. 

---