Bicontinuous phases microemulsions

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... 

The period of the lamellar structures or the size of the cubic cell can be as large as 1000 A and much larger than the molecular size of the surfactant (25 A). Therefore mesoscopic models like a Landau-Ginzburg model are suitable for their study. In particular, one can address the question whether the bicontinuous microemulsion can undergo a transition to ordered bicontinuous phases. 

A. Ciach, J. S. Hoye, G. Stell. Microscopic model for microemulsion. II. Behavior at low temperatures and critical point. J Chem Phys 90 1222-1228, 1989. A. Ciach. Phase diagram and structure of the bicontinuous phase in a three dimensional lattice model for oil-water-surfactant mixtures. J Chem Phys 95 1399-1408, 1992. 

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. 

Figure 3.28 Illustrative section from the phase prism of a mixture of oil, water, and surfactant. This section is for constant surfactant concentration (T is temperature). The section shows a middle-phase microemulsion phase existing together with oil (upper) and water (lower) phases. The surfactant is partitioned among all of the phases. The cross-hatching shows how the microemulsion can be O/W (to the left), or W/O (to the right), or bicontinuous (centre). From Schwuger et al. [226]. Copyright 1995, American Chemical Society.

In this paper, a molecular thermodynamic approach is developed to predict the structural and compositional characteristics of microemulsions. The theory can be applied not only to oil-in-water and water-in-cil droplet-type microemulsions but also to bicontinuous microemulsions. This treatment constitutes an extension of our earlier approaches to micelles, mixed micelles, and solubilization but also takes into account the self-association of alcohol in the oil phase and the excluded-volume interactions among the droplets. Illustrative results are presented for an anionic surfactant (SDS) pentanol cyclohexane water NaCl system. Microstructur al features including the droplet radius, the thickness of the surfactant layer at the interface, the number of molecules of various species in a droplet, the size and composition dispersions of the droplets, and the distribution of the surfactant, oil, alcohol, and water molecules in the various microdomains are calculated. Further, the model allows the identification of the transition from a two-phase droplet-type microemulsion system to a three-phase microemulsion system involving a bicontinuous microemulsion. The persistence length of the bicontinuous microemulsion is also predicted by the model. Finally, the model permits the calculation of the interfacial tension between a microemulsion and the coexisting phase. 

Microemulsions are thermodynamically stable dispersions of oil and water stabilized by a surfactant and, in many cases, also a cosurfactant.1-4 The microemulsions can be of the droplet type, either with spherical oil droplets dispersed in a continuous medium of water (oil-in-water microemulsions, O/W) or with spherical water droplets dispersed in a continuous medium of oil (water-in-oil microemulsions, W/O). The droplet-type microemulsions can be either a single-phase system or part of a two-phase system wherein the microemulsion phase coexists with an excess dispersed phase (an upper phase of excess oil in the case of O/W and a lower phase of excess water in the case of W/O microemulsions). There are also nondroplet-type microemulsions, referred to as middle-phase microemulsions. In this case, the microemulsion phase is part of a three-phase system with the microemulsion phase in the middle coexisting with an upper phase of excess oil and a lower phase of excess water. One possible structure of this middle-phase microemulsion, characterized by randomly distributed oil and water microdomains and bicontinuity in both oil and water domains, is known as thebiccntinuous microemulsion. Numerous experimental studies have shown1 2 4 that one can achieve a transition... 

In addition to single phase microemulsions, several phase equilibria known as Winsor systems [4] are also shown at low surfactant concentrations. A Winsor I (WI) system consists of an 0/W microemulsion that is in equilibrium with an oil phase, while a Winsor II (WII) system is a W/0 microemulsion in equilibrium with an aqueous phase. A Will system has a middle phase (bicontinuous) microemulsion that coexists with both oil and aqueous phases. 

The microemulsion method utilizes a water/oil/surfactant system to construct a micro reactor, in which NCs could be s)mthesized. The microemulsions have a wide range of applications from oil recovery fo fhe s)mfhesis of nanoparticles. Microemulsion is a system of water, oil, and surfactant, and it is an optically isotropic and thermod3mamically stable solution. At molecular scale, the microemulsion is heterogeneous with an internal structure either of nanospherical monosized droplefs (micelles or reverse micelles) or a bicontinuous phase, depending on the given temperature as well as the ratio of its constituents (Eriksson et al., 2004). The small droplets could be utilized as microreactors in order to s)mthesize the fine NCs in a controllable way. 

Addition of salting-out type electrolytes to oil-water-surfactant (s) systems has also a strong influence on their phase equilibria and interfacial properties. This addition produces a dehydration of the surfactant and its progressive transfer to the oil phase (2). At low salinity, a water-continuous microemulsion is observed in equilibrium with an organic phase. At high salinity an oil-continuous microemulsion is in equilibrium with an aqueous phase. At intermediate salinity, a middle phase microemulsion with a bicontinuous structure coexists with pure aqueous and organic phases. These equilibria were referred by Vinsor as Types I,II and III (33). 

Figure (3) shows the solubilization parameters as functions of water concentration for SDS/2- entanol ratios of 0.25 and 0.40 at 25 C. The solubilization parameters are defined as Vo/Vs and Vw/Vs, where Vo, Vs and Vw are the volumes of organic phase, surfactant and aqueous phase in the microemulsions. The parameters are related to the drop size and also interfacial torsions f7.23). The bicontinuous phase is located around the composition range corresponding to equal values of solubilization parameters. The solubilization parameters are dependent on the initial surfactant and/or cosurfactant concentration. Similar dependence has been observed in other systems as a function of salinity and pH (7.231. Conductivity measurements performed as a function of water content indicate an S-shaped curve as shown in Figure (4). This is typical of microemulsions showing transition from oil-continuous to bicontinuous to water-continuous microstructure with increasing water content. 

Bicontinuous Microemulsion A possible structure for middle-phase microemulsions is one in which both oil and water phases are continuous throughout the microemulsion phase. An analogy is the structure of porous... 

Middle-Phase Microemulsion A microemulsion, with high oil and water contents, that is stable while in contact with either bulk-oil or bulk-water phases. This stability may be due to a bicontinuous structure in which both oil and water phases are continuous at the same time. In laboratory tube or bottle tests involving samples containing unemulsified oil and water, a middle-phase microemulsion will tend to be situated between the two former phases. See also Bicontinuous Microemulsion. 

Fig. 1. The different microstructures of the microemulsion phase (a) the water-in-oil droplet phase, (b) the bicontinuous phase, (c) the oil-in-water droplet phase.

In this section, we summarize our results and discuss their physical implications on the reaction kinetics in the bicontinuous phases. The RG analysis confirmed our mean-field arguments and thereby predicts that the dynamic fluctuations ofthe microemulsion will be irrelevant in impacting the hydrodynamic behavior (long length and time scale) ofthe system. Thus, the kinetics ofthe reaction A B Q is expected to follow the anomalous mean-field regime (AMF), one wherein concentrations decay as ca,cb (nQyi (Dt) l at long times. This constitutes the central result of this part of the article. 

Middle-phase microemulsion Type III microemulsion Winsor Type III microemulsion P-type microemulsion Bicontinuous microemulsion... 

Figure 1.4 T(7)-sections through the phase prism of the systems H20-n-octane-C6E2, C8E3, Q0E4 and C12E5 at an oil/(water + oil) volume fraction of = 0.5. In order to determine the respective X-point the phase boundaries are measured only for surfactant mass fractions 7 > 7. An increase of both the hydrophobic chain length / and the size of the hydrophilic head group j shifts the X-point to lower values of 7, i.e. the efficiency increases. Simultaneously the stability range of the bicontinuous one phase microemulsion shrinks dramatically due to the increased extension of the lamellar mesophase (La). (From Ref. [26], reprinted with permission of Elsevier.)...

This type of microemulsion is usually obtained when the system contains similar amounts of oil and water. In the phase diagram (see Fig. 1.3 in Chapter 1) this is the middle phase found in the three-phase region (hatched area in the left scheme of Fig. 1.3 in Chapter 1, fish body). On the right-hand side of the X-point the system forms a single phase. In this region of the phase diagram the bicontinuous phase extends over the whole... 

Figure 4.9 Phase diagram of the system water-decane-CioE4 at equal volume fractions of water and decane as a function of the temperature T and the surfactant concentration cf>7. At low (f>7 there is a three-phase coexistence, while at moderate cf>7 the one-phase bicontinuous microemulsion appears. At even higher cf>7 the lamellar phase appears. At high and low temperatures a microemulsion phase coexists with either excess water or oil. The polymer fraction cf>p is raised symmetrically for the water- and oil-soluble polymers, and the one-phase microemulsion window closes continuously. The 2 K temperature shift is due to the use of heavy water. (From Ref. [40], reprinted with permission of the American Chemical Society.)...

Szymula investigated the impact of Vitamin C on the flow properties of microemul-sions [31]. Microemulsions based on sodium dodecylsulphate, pentanol and water were evaluated. They exhibit Newtonian flow behaviour for o/w and w/o systems, while the bicontinuous phase is shear thinning. The addition of ascorbic acid leads to an increase in viscosity. 

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