Amphiphiles microemulsions

M. Kahlweit and R. Strey. Phase-behavior of ternary-systems of the type H20-oil-nonionic amphiphile (microemulsions). Angewandte Chemie. International edition in English, 24(8) 654—668,1985. 

Key words Amphiphile -microemulsion - lamella - partial structure function - mean curvature... 

J. C. Lang, Physics of Amphiphiles Micelles, Vesicles and Microemulsions, Soc. Italiana di Fisica, XC Corso, Bologna, 1985. 

Lattice models have been studied in mean field approximation, by transfer matrix methods and Monte Carlo simulations. Much interest has focused on the occurrence of a microemulsion. Its location in the phase diagram between the oil-rich and the water-rich phases, its structure and its wetting properties have been explored [76]. Lattice models reproduce the reduction of the surface tension upon adsorption of the amphiphiles and the progression of phase equilibria upon increasmg the amphiphile concentration. Spatially periodic (lamellar) phases are also describable by lattice models. Flowever, the structure of the lattice can interfere with the properties of the periodic structures. 

Fig. 1. Phase diagram of an amphiphile—oil—water system that forms a middle-phase microemulsion, definition of microemulsion, and illustration of the...

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"). 

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). 

A (macro)emulsion is formed when two immiscible Hquids, usually water and a hydrophobic organic solvent, an oil, are mechanically agitated (5) so that one Hquid forms droplets in the other one. A microemulsion, on the other hand, forms spontaneously because of the self-association of added amphiphilic molecules. During the emulsification agitation both Hquids form droplets, and with no stabilization, two emulsion layers are formed, one with oil droplets in water (o /w) and one of water in oil (w/o). However, if not stabilized the droplets separate into two phases when the agitation ceases. If an emulsifier (a stabilizing compound) is added to the two immiscible Hquids, one of them becomes continuous and the other one remains in droplet form. 

Lattice models for bulk mixtures have mostly been designed to describe features which are characteristic of systems with low amphiphile content. In particular, models for ternary oil/water/amphiphile systems are challenged to reproduce the reduction of the interfacial tension between water and oil in the presence of amphiphiles, and the existence of a structured disordered phase (a microemulsion) which coexists with an oil-rich and a water-rich phase. We recall that a structured phase is one in which correlation functions show oscillating behavior. Ordered lamellar phases have also been studied, but they are much more influenced by lattice artefacts here than in the case of the chain models. 

V. Degiorgio, M. Corti, eds. Physics of Amphiphiles Micelles, Vesicles and Microemulsions. Amsterdam North-Holland, 1985 W. M. Gelbart, A. Ben-Shaul, D. Roux, eds. Micelles, membranes, microemulsions and monolayers. Berlin Springer, 1994. 

S. Carra, M. Morbidelli, and G. Storti, in Proceedings of the International School of Physics Enrico Fermi, Course XC Physics of Amphiphiles Micelles, Vesicles and Microemulsions (V. Degiorgio and M. Corti, ed.), North-Holland, Amsterdam, 1985, pp. 483-512. 

A microemulsion (p.E) is a thermodynamically stable, transparent (in the visible) droplet type dispersion of water (W) and oil (O a saturated or unsaturated hydrocarbon) stabilized by a surfactant (S) and a cosurfactant (CoS a short amphiphile compound such as an alcohol or an amine) [67]. Sometimes the oil is a water-insoluble organic compound which is also a reactant and the water may contain mineral acids or salts. Because of the small dispersion size, a large amount of surfactant is required to stabilize microemulsions. The droplets are very small (about 100-1000 A [68]), about 100 times smaller than those of a typical emulsion. The existence of giant microemulsions (dispersion size about 6000 A) has been demonstrated [58]. 

By small-angle neutron scattering experiments on water/AOT/hydrocarbon microemulsions containing various additives, the change of the radius of the miceUar core with the addition of small quantities of additives has been investigated. The results are consistent with a model in which amphiphilic molecules such as benzyl alcohol and octanol are preferentially adsorbed into the water/surfactant interfacial region, decreasing the micellar radius, whereas toluene remains predominantly in the bulk hydrocarbon phase. The effect of n-alcohols on the stability of microemulsions has also been reported [119],... 

Moreover, stable liquid systems made up of nanoparticles coated with a surfactant monolayer and dispersed in an apolar medium could be employed to catalyze reactions involving both apolar substrates (solubilized in the bulk solvent) and polar and amphiphilic substrates (preferentially encapsulated within the reversed micelles or located at the surfactant palisade layer) or could be used as antiwear additives for lubricants. For example, monodisperse nickel boride catalysts were prepared in water/CTAB/hexanol microemulsions and used directly as the catalysts of styrene hydrogenation [215]. 

In an earlier study calorimetry achieved this objective for the compositional boundaries between two and three phases (2). Such boundaries are encountered both in "middle-phase microemulsion systems" of low tension flooding, and as the "gas, oil, and water" of multi-contact miscible EOR systems (LZ). The three-phase problem presents by far the most severe experimental and interpretational difficulties. Hence, the earlier results have encouraged us to continue the development of calorimetry for the measurement of phase compositions and excess enthalpies of conjugate phases in amphiphilic EOR systems. 

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... 

Part II starts with the possibilities of ACE for characterizing the relevant physicochemical properties of drugs such as lipophilicity/hydrophilicity as well as thermodynamic parameters such as enthalpy of solubilization. This part also characterizes interactions between pharmaceutical excipients such as amphiphilic substances (below CMC) and cyclodextrins, which are of interest for influencing the bioavailability of drugs from pharmaceutical formulations. The same holds for interactions of drugs with pharmaceutical vehicle systems such as micelles, microemulsions, and liposomes. 

One advantage of using a cleavable acetal surfactant instead of a conventional amphiphile has been elegantly demonstrated in a work by Bieniecki and WUk [51]. A cationic 1,3-dioxolane derivative was used as surfactant in a microemulsion formulation that was employed as a reaction medium for an organic synthesis. When the reaction was complete, the surfactant was decomposed by addition of acid and the reaction product easily recovered from the resulting two phase system. Through this procedure the problems of foaming and emulsion formation, frequently encountered with conventional surfactants, could be avoided. 

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-... 

Friberg SE, Yang CC, Sjoblom J (1992) Amphiphilic Associahon Structiues and the Microemulsion Gel Method for Ceramics - Influence on Original Phase Regions by Hydrolysis and Condensahon of Silicon Tetraethoxide. Langmuir 8 372-376... 

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