Isotropic—lamellar phase transitions

Phase transitions in condensed phases are characterized by symmetry changes, i.e. by transformations in orientational and translational ordering in the system. Many soft materials form a disordered (isotropic) phase at high temperatures but adopt ordered structures, with different degrees of translational and orientational order, at low temperatures. The transition from the isotropic phase to ordered phase is said to be a symmetry breaking transition, because the symmetry of the isotropic phase (with full rotational and translational symmetry) is broken at low temperatures. Examples of symmetry breaking transitions include the isotropic-nematic phase transition in hquid crystals (Section 5.5.2) and the isotropic-lamellar phase transition observed for amphiphiles (Section 4.10.2) or block copolymers (Section 2.11). 

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 phase behavior of a-ester sulfonates has been studied in detail with methyl laurate and methyl palmitate [58]. In both cases, at higher temperatures, as the surfactant concentration increases, there is a transition from an isotropic solution to a hexagonal liquid crystalline phase and finally, at high surfactant concentrations, to a lamellar liquid crystal (Fig. 4). The crystal/liquid-crys-tal phase transition occurs at even higher temperatures as the chain length increases. On the other hand, chain length has practically no influence on the... 

An A-B diblock copolymer is a polymer consisting of a sequence of A-type monomers chemically joined to a sequence of B-type monomers. Even a small amount of incompatibility (difference in interactions) between monomers A and monomers B can induce phase transitions. However, A-homopolymer and B-homopolymer are chemically joined in a diblock therefore a system of diblocks cannot undergo a macroscopic phase separation. Instead a number of order-disorder phase transitions take place in the system between the isotropic phase and spatially ordered phases in which A-rich and B-rich domains, of the size of a diblock copolymer, are periodically arranged in lamellar, hexagonal, body-centered cubic (bcc), and the double gyroid structures. The covalent bond joining the blocks rests at the interface between A-rich and B-rich domains. 

If the liquid crystalline phase is included in the diagram, the general features are those in Figure 7 (38). At this temperature (the PIT or HLB temperature) increasing amounts of emulsifier first give rise to an isotropic liquid (S) in a small concentration range (A-B), followed by a phase transition to a lamellar liquid crystal (N) in the concentration range C-D. 

Although the so-called a-phase of the fatty alcohols—a thermotropic type smectic B liquid crystal with hexagonal arrangement of molecules within the double layers—is initially formed from the melt during the manufacturing process, it normally transforms into a crystalline modification as it cools. However, the crystallization of the gel matrix can be avoided if the ot-phase can be kept stable as it cools to room temperature. This can be achieved by combining appropriate surfactants such as myristyl or lauryl alcohol and cholesterol, a mixture of which forms a lamellar liquid crystal at room temperature. Due to depression of the melting point, the phase transition temperature of crystalline to liquid crystalline as well as liquid crystalline to isotropic decreases. Therefore, a liquid crystalline microstructure is obtained at room temperature. 

Experimental results (12) showed a transition to a lamellar liquid crystal for 14 added water molecules. Our calculations (to be reported at a later occasion) showed no discontinuity or any other indication of instability of the soap/acid water complex for the subsequent water molecules added in excess of 14. It appears reasonable to assume that the isotropic liquid/liquid crystal transition does not depend on the energy levels of the polar group interactions. The phase transition probably depends on the hydrophobic/hydrophilic volume ratio and estimations according to Israelachvili/Ninham (15) approach may offer a better potential for an understanding. 

Hoffmann, H., Schwandner, B., UlbrichL W., andZana, R., The transition from isotropic micellar solutions to lamellar phases, in Proceedings of the International School of Physics Enrico Fermi, Varenna on Lake Como, Degiorgio, V., and Corti, M., Eds., Elsevier, Amsterdam, 1985, pp. 261-280. 

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