Isotropic microemulsion

While the order parameters derived from the self-diffusion data provide quantitative estimates of the distribution of water among the competing chemical equilibria for the various pseudophase microstructures, the onset of electrical percolation, the onset of water self-diffusion increase, and the onset of surfactant self-diffusion increase provide experimental markers of the continuous transitions discussed here. The formation of irregular bicontinuous microstructures of low mean curvature occurs after the onset of conductivity increase and coincides with the onset of increase in surfactant self-diffusion. This onset of surfactant diffusion increase is not observed in the acrylamide-driven percolation. This combination of conductivity and self-diffusion yields the possibility of mapping pseudophase transitions within isotropic microemulsions domains. 

FIGURE 4.25 Three-component phase diagram for the solubilization. Cre, Cremophor RH 40 Gly, glyceride Pol, poloxamer 124 L, isotropic microemulsion G, gel E, crude OAV emulsion E2, W/O emulsion. [Graph reconstructed from data by Kim et al. Pharm. Res., 18, 454 (2002).]... 

The goal of the present work is to obtain a consistent structural model for a microemulsion system. In particular, we are interested in carrying this model down to the molecular level so that the intermolecular effects which are responsible for the stability of these systems can be elucidated. We have studied the system consisting of water, SLS and MMA with and without n-hexanol or n-pentanol. We have determined the phase boundaries of the isotropic microemulsion and Lj phases and determined how these are affected by surfactant concentration and alcohol chain length. Measurements were also made of the vapor pressure of MMA over these systems to determine the concentration of MMA in the water surrounding the microemulsion droplets. From these data, the energetics of transfer of the MMA from aqueous to micellar solution were determined. Finally, a 1,C NMR chemical shielding study was performed to find how the MMA and the alcohol were distributed within the microemulsion. 

Fig. 37.11 Pseudoternary phase diagram of the system water - - dodecane -I- polyoxyethylene-(7)-lauryl ether -1-decanol, where the dodecane fraction is maintained at a constant 40% (v/v), for which reason the scales run from zero to 60% instead of 100% of a full diagram. The areas labelled 1, 2 and 3 delineate the domain of the oil-continuous isotropic microemulsion at 20, 25 and 35°C, respectively. Redrawn from Ziegenmeyer and Fuhrer.2 ...

When comparable amounts of oil and water are mixed with surfactant a bicontinuous, isotropic phase is formed [6]. This bicontinuous phase, called a microemulsion, can coexist with oil- and water-rich phases [7,1]. The range of order in microemulsions is comparable to the typical length of the structure (domain size). When the strength of the surfactant (a length of the hydrocarbon chain, or a size of the polar head) and/or its concentration are large enough, the microemulsion undergoes a transition to ordered phases. One of them is the lamellar phase with a periodic stack of internal surfaces parallel to each other. In binary water-surfactant mixtures, or in... 

In 1959, J. H. Schulman introduced the term microemulsion for transparent-solutions of a model four-component system [126]. Basically, microemulsions consist of water, an oily component, surfactant, and co-surfactant. A three phase diagram illustrating the area of existence of microemulsions is presented in Fig. 6 [24]. The phase equilibria, structures, applications, and chemical reactions of microemulsion have been reviewed by Sjoblom et al. [127]. In contrast to macroemulsions, microemulsions are optically transparent, isotropic, and thermodynamically stable [128, 129]. Microemulsions have been subject of various... 

In that case the self diffusion coefficient - concentration curve shows a behaviour distinctly different from the cosurfactant microemulsions. has a quite low value throughout the extension of the isotropic solution phase up to the highest water content. This implies that a model with closed droplets surrounded by surfactant emions in a hydrocarbon medium gives an adequate description of these solutions, found to be significantly higher them D, the conclusion that a non-negligible eimount of water must exist between the emulsion droplets. 

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... 

Winsor [15] classified the phase equilibria of microemulsions into four types, now called Winsor I-IV microemulsions, illustrated in Fig. 15.5. Types I and II are two-phase systems where a surfactant rich phase, the microemulsion, is in equilibrium with an excess organic or aqueous phase, respectively. Type III is a three-phase system in which a W/O or an O/W microemulsion is in equilibrium with an excess of both the aqueous and the organic phase. Finally, type IV is a single isotropic phase. In many cases, the properties of the system components require the presence of a surfactant and a cosurfactant in the organic phase in order to achieve the formation of reverse micelles one example is the mixture of sodium dodecylsulfate and pentanol. 

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. 

Microemulsions are thermodynamically stable mixtures. The interfacial tension is almost zero. The size of drops is very small, and this makes the microemulsions look clear. It has been suggested that microemulsion may consists of bicontinuous structures, which sounds more plausible in these four-component microemulsion systems. It has also been suggested that microemulsion may be compared to swollen micelles (i.e., if one solubilizes oil in micelles). In such isotropic mixtures, short-range order exists between droplets. As found from extensive experiments, not all mixtures of water-oil-surfactant-cosurfactant produce a microemulsion. This has led to studies that have attempted to predict the molecular relationship. 

Microemulsions are thermodynamically stable, homogeneous, optically isotropic solutions comprised of a mixture of water, hydrocarbons and amphiphilic compoxmds. The microemulsions are usually four- or three-component systems consisting of surfactant and cosurfactant (termed as emulsifier), oil and water. The cosurfactants are either lower alkanols (like butanol, propanol and hexanol) or amines (Hke butylamine, hexylamine). Microemulsions are often called swollen micelles (Fig. 3) and swollen re-... 

Many reports are available where the cationic surfactant CTAB has been used to prepare gold nanoparticles [127-129]. Giustini et al. [130] have characterized the quaternary w/o micro emulsion of CTAB/n-pentanol/ n-hexane/water. Some salient features of CTAB/co-surfactant/alkane/water system are (1) formation of nearly spherical droplets in the L2 region (a liquid isotropic phase formed by disconnected aqueous domains dispersed in a continuous organic bulk) stabilized by a surfactant/co-surfactant interfacial film. (2) With an increase in water content, L2 is followed up to the water solubilization failure, without any transition to bicontinuous structure, and (3) at low Wo, the droplet radius is smaller than R° (spontaneous radius of curvature of the interfacial film) but when the droplet radius tends to become larger than R° (i.e., increasing Wo), the microemulsion phase separates into a Winsor II system. 

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