Cubic surfactants

The structure of MCM-48 is based on a bicontinuous cubic surfactant phase with symmetry laid shown in Figure 8.2. MCM-48 structure may be represented by an enantiometic pair of three-dimensional channel systems (Q230), which are wrapped by the silica wall corresponding to the continuous gyroid minimal surface, periodic G-surface, i.e., Equation (8.2) holds. 

For surfactant aggregates of the interfacial complex type under discussion, Eq. (205) will be fulfilled for the same sequence of elementary shapes as the one we have already discussed for microemulsions, that is, spheres and cylinders with radii in correspondence with the spontaneous curvature, infinite periodical CMC structures for which tOsO H—Hq are equal to zero but where K is less than zero, yielding cubic surfactant phases and lamellar structures. However, it is probably worth stressing once more that noninteracting surfactant-laden interfaces are in focus here. With this in mind, we can discuss just interactionless aggregate geometries but not the whole issue about the possible formation of three-dimensional structures of these aggregates. 

In the latter the surfactant monolayer (in oil and water mixture) or bilayer (in water only) forms a periodic surface. A periodic surface is one that repeats itself under a unit translation in one, two, or three coordinate directions similarly to the periodic arrangement of atoms in regular crystals. It is still not clear, however, whether the transition between the bicontinuous microemulsion and the ordered bicontinuous cubic phases occurs in nature. When the volume fractions of oil and water are equal, one finds the cubic phases in a narrow window of surfactant concentration around 0.5 weight fraction. However, it is not known whether these phases are bicontinuous. No experimental evidence has been published that there exist bicontinuous cubic phases with the ordered surfactant monolayer, rather than bilayer, forming the periodic surface. 

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. 

The model has been successfully used to describe wetting behavior of the microemulsion at the oil-water interface [12,18-20], to investigate a few ordered phases such as lamellar, double diamond, simple cubic, hexagonal, or crystals of spherical micelles [21,22], and to study the mixtures containing surfactant in confined geometry [23]. 

The lowest value of Qeff corresponds to different structures for different along the bifurcation line. The sequence of phases is always the same for various strengths of surfactant (with 7 > 27/4) and for increasing p it is L—>G—>D—>P—>C. For 7 = 50 (strong surfactant, like C10E5) the portion of the phase diagram corresponding to the stable cubic phases is shown in Fig. 14(b). For surfactants weaker than in the case shown in Fig. 14 the cubic phases occur for a lower surfactant volume fraction for example, for 7=16 cubic phases appear for p 0.45. 

P. Sakya, J. M. Seddon, R. H. Templer, R. J. Mirkin, G. J. T. Tiddy. Micellar cubic phases and their structural relationships the nonionic surfactant system Ci2EOi2/water. Langmuir 75 3706-3714, 1997. 

Figure 2a shows a schematic phase diagram for lyotropic liquid crystals. This figure shows the formation of micelles, cubic phases, bicontinuous cubic phases, and lamellar phases as the concentration of surfactant increases. Also shown in this figure is a schematic diagram of an ordered bicontinuous cubic phase (Fig. 2b). Another interesting example in...

As has been discussed in the preceding sections, it is expected that the surfactant monolayer exhibits "N"-shape nonlinearity in its dynamic tt-T characteristics. Thus, we would like to discuss the kinetics, assuming that G(Z0 is a cubic function. 

MCM-50 consists of stacks of silica and surfactant layers. Obviously, no pores are formed upon removal of the surfactant layers. The silica layers contact each other resulting in a nonporous silica. It is noteworthy to mention that materials of M41S type were probably already synthesized by Sylvania Electric Products in 1971 [32], However, at that time the high ordering of the materials was not realized [33], M41S-type materials are synthesized under basic reaction conditions. Scientists from the University of Santa Barbara developed an alternative synthesis procedure under acidic conditions. They also used alkyltrimethyl ammonium as the surfactant. The porous silica materials obtained (e.g., hexagonal SBA-3 Santa BArbara [SBA]) had thicker pore walls but smaller pore diameters. Furthermore, they developed materials with novel pore topologies, e g., the cubic SBA-1 with spherical pores. 

Figure 4.23 Synthesis space diagram for a ternary system composed of tetraethylorthosilicate (TEOS), cetyltrimethylammonium bromide (CTAB), and sodium hydroxide (H, hexagonal phase [MCM-41] C, cubic phase [MCM-48] L, lamellar phase [MCM-50] H20/Si02 = 100, reaction temperature 100°C, reaction time 10 days). (Reprinted from Science, Vol. 267, A. Firouzi, D. Kumar, L.M. Bull, T. Besier, R Sieger, Q. Huo, S.A. Walker, J.A. Zasadzinski, C. Glinka, J. Nicol, D.l. Margolese, G.D. Stucky, B.F. Chmelka, Cooperative Organization of Inorganic-Surfactant and Biomimetic Assemblies, pp. 1138-1143. Copyright 1995. With permission of AAAS.)...

Most thermoplastics and thermosets can be foamed, many of them into either flexible or rigid foams. The choice is controlled by the blowing agent, additives, surfactants, and mechanical handling. Some polymers can be expanded as much as 40 times their original density and still retain a substantial part of their strength. Most commercial foams are expanded to derisities of two to five pounds per cubic foot. (Water is 62 pounds per cubic foot.)... 

FIG. 11. Transmission electron micrographs of freeze fractured oily droplets dispersed (a) in a hexagonal and (b) in a cubic liquid crystalline phase, bar 100 nm. From Mueller-Goymann, C., Liquid crystals in emulsions, creams and gels, containing ethoxylated sterols as surfactant, Pharm. Res. 1 154-158 (1984). 

A simple and general method for the preparation of surfactant-free, thiol-functionalized iridium nanoparticles was reported by Ulman and coworkers in 1999 [11], The synthesis consisted of a reduction of the dihydrogen hexachloroiri-date (IV) H2lrCl6 H20 precursor by lithium triethylborohydride ( super-hydride ) in the presence of octadecanethiol (C18H37SH) in tetrahydrofuran (THF) (Scheme 15.1). The obtained iridium nanoparticles were crystaUine with fee (face-centered cubic) packing, and showed a wider size distribution with diameters ranging from 2.25 to 4.25 nm. 

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