Hexagonal soap phase

Hexagonal phosphorus pentoxide, 29 49 Hexagonal prism lattice, 8 114t Hexagonal soap phase, 22 726, 727 mixed soap crystals in, 22 729 Hexagonal structure... 

T extures of lyotropic mesophases have been the object of numerous observations by optical (1,2,3) and electronic (4, 5, 6,7) microscopy. Except for the pioneering work of Lehmann (1) and Friedel (2) who intended to identify the various kinds of defects which constitute the textures, the purpose of these observations was to recognize the different existing phases—lamellar, hexagonal (or in the soaps language neat phase, median phase, etc.)—in correlation with x-ray data. 

Figure 1 shows the results obtained by Francois and Skoulios (27) on the conductivity of various liquid crystalline phases in the binary systems water-sodium lauryl sulfate and water-potassium laurate at 50 °C. As might be expected, the water-continuous normal hexagonal phase has the highest conductivity among the liquid crystals while the lamellar phase with its bimolecular leaflets of surfactant has the lowest conductivity. Francois (28) has presented data on the conductivity of the hexagonal phases of other soaps. She has also discussed the mechanism of ion transport in the hexagonal phase and its similarity to ion transport in aqueous solutions of rodlike polyelectrolytes. 

Figure 1. Schematic representation of two lyotropic mesophases. The lamellar phase (left) is a periodical stacking along one dimension of soap and water lamellae. In the hexagonal phase (right), the soap cylinders are organized in a two-dimensional array.

A mesomorphic (liquid-crystal) phase of soap micelles, oriented in a hexagonal array of cylinders. Middle soap contains a similar or lower proportion of soap (e.g., 50%) as opposed to water. Middle soap is in contrast to neat soap, which contains more soap than water and is also a mesomorphic phase, but has a lamellar structure rather than a hexagonal array of cylinders. Also termed clotted soap . See Neat Soap. 

A few words of clarification about the nomenclature are relevant here. Columnar phases have been known for many years they were evident, for example, in the work of Spegt and Skoulios (28) on metal soaps, although these are not classical disk-shaped molecules. In 1977, however, a hexasubstituted benzene derivative was reported (29), this derivative was the first example of a properly disk-like mesogen, and the term discotic was coined to describe the mesophases it formed. Thus, for example, the discotic hexagonal phase was labeled Dh- The introduction of this nomenclature has actually caused confusion as disk-like molecules are not alone in their capacity to form columnar phases (indeed, some... 

A central issue in the field of surfactant self-assembly is the structure of the liquid crystalline mesophases denoted bicontinuous cubic, and "intermediate" phases (i.e. rhombohedral, monoclinic and tetragonal phases). Cubic phases were detected by Luzzati et al. and Fontell in the 1960 s, although they were believed to be rare in comparison with the classical lamellar, hexagonal and micellar mesophases. It is now clear that these phases are ubiquitous in surfactant and Upid systems. Further, a number of cubic phases can occur within the same system, as the temperature or concentration is varied. Luzzati s group also discovered a number of crystalline mesophases in soaps and lipids, of tetragonal and rhombohedral symmetries (the so-called "T" and "R" phases). More recently, Tiddy et al. have detected systematic replacement of cubic mesophases by "intermediate" T and R phases as the surfactant architecture is varied [22-24]. The most detailed mesophase study to date has revealed the presence of monoclinic. 

Figure b. Time-dependence of interfacial tensions of oil drops spinning in 0.5% soap solutions (25°). Triangles - no salt. Hexagons and circles - 0.3 M salt. Squares - 0.4 M salt. Interfacial tensions rise as middle phase films are spun off. 

Monoglycerides form an inverse hexagonal phase with glycerol, as in water [112], Mixtures of triethanolamine and oleic acid form a nonaqueous lamellar liquid crystal with a surfactant bilayer of soap and acid with intercalated ionized and unionized alkanolamine as solvent [113,114], Lamellar liquid crystals form analogously with dodecylbenzenesulfonic acid and triethanolamine [115]. 

Fig. 22a. Schematic representation of the stacking of the transition metal soap polar heads in a the crystalline phase and in b the columnar hexagonal phase...

The first liquid crystals of disc-shaped molecules, now generally referred to as discotic liquid crystals, were prepared and identified in 1977. Since then a large number of discotic compounds have been synthesized and a variety of mesophases discovered. Structurally, most of them fall into two distinct categories, the columnar and the nematic. The columnar phase in its simplest form consists of discs stacked one on top of the other aperiodically to form liquid-like columns, the different columns constituting a two-dimensional lattice (fig. 1.1.8 (a)). The structure is somewhat similar to that of the hexagonal phase of soap-water and other lyotropic... 

Conformationally disordered crystals (condis crystals) were discovered in the 1980 s. They show positional and orientational order, but are partially or fully conformationally mobile. The condis crystals complete the comparison of mesophases in Figs. 2.103 and 2.107. Linear, flexible molecules can show chain mobility that leaves the position and orientation of the molecule unchanged, but introduces large-amplitude conformational motion about the chain axis. Again, the symmetry of the molecule is in this case increased. Condis crystals have often a hexagonal, columnar crystal structure. Typical examples of condis crystals are the high-temperature phase of polyethylene, polytetrafluoroethylene, frawj-1,4-polybutadiene, and the low-temperature phases of soaps, lipids and other liquid-crystal forming, flexible molecules. 

There are two types of lipid-water phase diagrams. The first type, discussed above, is obtained from polar lipids, which are insoluble in water (i.e. the solubility is quite small, monolaurin for example has a solubility of about 10 m). Fig. 8.12 illustrates the principles of phase equilibria in this type of lipid-water system. The second type of binary system is obtained when the lipid is soluble as micelles in water. Examples of such lipids are fatty acid salts and lysolecithin. An aqueous soap system is illustrated in Fig. 8.13. When the lipid concentration in the micellar solution is increased, the spherical micelles are transformed into rod-shaped micelles. At still higher lipid concentrations the lipid cylinders are hexagonally arranged and the liquid-crystalline phase Hi is formed. The lamellar liquid-crystalline phase is usually formed in the region between Hi and the anhydrous lipid. Excellent reviews of the association behaviour of amphiphiles of this type have been published (Wennerstrom and Lindman, 1979 Lindman and Wennerstrom, 1980). 

The phase described by Lutton (1966) as a middle phase, which is the term used in soap-water systems for the hexagonal phase Hi, is in fact the inverse structure, i.e. phase Hu. Furthermore the phase... 

Different materials such as salts, free fatty acids, polyols, fatty alcohols, fatty esters, and per-fiunery components can influence the formation of liquid crystalline phases. Free fatty acids and fatty alcohols promote the formation of lamellar liquid crystalline phase [26], One can expect solid, isotropic solution, and hexagonal liquid crystalline phases coexisting in normal soaps, but in superfatted soaps, part of the hexagonal liquid crystalline phase is converted to lamellar, which is responsible for product softness during processing. 

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