Lamellar phases phase behaviour

Fig. 21 Schematic summary of thermodynamic phase behaviour for neat, composition-ally symmetric PI-fc-PS-fc-PDMS (ISD) and PS-fc-PI-fc-PDMS (SID) terpolymers. Heating PI-fc-PS-fc-PDMS or decreasing molecular weight causes transition from three-domain lamellae to hexagonally packed two-domain cylindrical morphologies, followed by disordering. PS-fc-PI-fc-PDMS disorders directly from three-domain lamellar state. From [88], Copyright 2002 American Chemical Society...

MAS has been applied to a highly viscous cubic phase of a lyotropic LC formed by 1-monooleolyl-rac-glycerol and water in order to obtain liquid-like and 13C spectra.330 Deuterium, sodium, and fluorine NMR spectroscopy have been applied to study the phase behaviour of several dilute lamellar systems formed by low concentrations of an ra-hexadecylpyridinium salt, a sodium salt (e.g., NaBr, NaCl, or sodium trifluoroacetate), 1-hexanol, and D20.331 The 2H, 19F, and 23Na splittings were used to monitor the phase equilibria. The last two studies are motivated by the search of new lyotropic LC for the alignment of biomolecules. 

In conclusion, the synthesis of mesostructured aluminophosphate / surfactant materials in alcoholic systems yields a mixture of an inverse hexagonal and a lamellar phase, the latter of which is more stable, as its formation is relatively favoured by higher temperatures and/or longer reaction times. The synthesis is highly cooperative the surfactant / alcohol systems without the inorganic species do not show any lyotropic behaviour. 

The potential for novel phase behaviour in rod-coil block copolymers is illustrated by the recent work of Thomas and co-workers on poly(hexyl iso-cyanate)(PHIC)-PS rod-coil diblock copolymers (Chen etal. 1996). PHIC, which adopts a helical conformation in the solid state, has a long persistence length (50-60 A) (Bur and Fetters 1976) and can form lyotropic liquid crystal phases in solution (Aharoni 1980). The polymer studied by Thomas and co-workers has a short PS block attached to a long PHIC block. A number of morphologies were reported—wavy lamellar, zigzag and arrowhead structures—where the rod block is tilted with respect to the layers, and there are different alternations of tilt between domains (Chen et al. 1996) (Fig. 2.37). These structures are analogous to tilted smectic thermotropic liquid crystalline phases (Chen et al. 1996). 

For a quenched lamellar phase it has been observed that G = G"scales as a>m for tv < tvQ. where tvc is defined operationally as being approximately equal to 0.1t and r is a single-chain relaxation time defined as the frequency where G and G" cross (Bates et al. 1990 Rosedale and Bates 1990). This behaviour has been accounted for theoretically by Kawasaki and Onuki (1990). For a PEP-PEE diblock that was presheared to create two distinct orientations (see Fig. 2.7(c)), Koppi et al. (1992) observed a substantial difference in G for quenched samples and parallel and perpendicular lamellae. In particular, G[ and the viscosity rjj for a perpendicular lamellar phase sheared in the plane of the lamellae were observed to exhibit near-terminal behaviour (G tv2, tj a/), which is consistent with the behaviour of an oriented lamellar phase which flows in two dimensions. These results highlight the fact that the linear viscoelastic behaviour of the lamellar phase is sensitive to the state of sample orientation. 

This chapter is concerned with experiments and theory for semidilute and concentrated block copolymer solutions.The focus is on the thermodynamics, i.e. the phase behaviour of both micellar solutions and non-micellar (e.g. swollen lamellar) phases. The chapter is organized very simply Section 4.2 contains a general account of gelation in block copolymer solutions. Section 4.3 is concerned with the solution phase behaviour of poly(oxyethylene)-containing diblocks and tri-blocks. The phase behaviour of styrenic block copolymers in selective solvents is discussed in Section 4.4. Section 4.5 is then concerned with theories for ordered block copolymer solutions, including both non-micellar phases in semidilute solutions and micellar gels. There has been little work on the dynamics of semidilute and concentrated block copolymer solutions, and this is reflected by the limited discussion of this subject in this chapter. 

The phase behaviour of blends of PS-PI or PS-PB diblocks with PS homopolymer was summarized by Winey et al. (19926). Regions of stability of lamellar, bicontinuous cubic, hexagonal-packed cylindrical and cubic-packed spherical structures were mapped out as a function of homopolymer molecular weight, copolymer composition and homopolymer concentration. All blends were... 

The phase behaviour of a blend of a PS-PI diblock and a PS homopolymer with a = 1.2 was investigated as a function of blend composition by Koizumi et al. (1992). The neat, symmetric, diblock formed a lamellar phase, as shown by the TEM image in Fig. 6.14. Upon increasing the concentration of homopolymer the domain spacing increases, and the distribution of domain spacings becomes broader as apparent from the TEM images in Fig. 6.14. At the same time, the thickness of the PI lamellae remains approximately constant and uniform. The... 

In case of non-ionic surfactants in water, the behaviour of the water structure outlines three main concentration regions, which closely coincide with the three phases intersected by the experimental isotherms. In the micellar solution phase, no significant changes in the water structure are indicated, while, in the lamellar phase, rapid destruction of the tetrahedral hydrogen bond network occurs due to the confinement of the water between the hydrophilic surfaces of the lamellae. The dehydration of the surfactant head groups was found to start near the border between the lamellar and the reverse micellar solution phases. At higher concentrations, water demonstrates its trend to form clusters of tetrahedrally bonded molecules even at the very low content in the system. The results with surfactant solutions have been obtained by Raman spectroscopy (Marinov el al., 2001). 

Figure 4.12. (Top ) The binary phase diagram of didodecyl phosphatidylethanolamine -water mixtures. (Adapted from [15].) Single-phase regions are white, two-pha% regions shaded. The thermotropic behaviour at about 20% w/w water is illustrated by die line ABC. (Bottom ) The trajectory of the line ABC in the local/global domain (see previous figure), showing the variation of molecular shape as a function of temperature for this l d. The phase diagram can be reconciled with the local/global behaviour if the "lamellar" (L) phase is in fact a mesh structure, i.e. porous lamellae.

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