Textures smectics

Gray G W and Goodby J G W 1984 Smectic Liquid Crystais Textures and Structures (Glasgow Hill)... 

Fig. 9. Smectic fan-shaped texture observed between crossed polarizers. Courtesy of G. H. Brown, Liquid Crystal Institute, Kent State University.

Thermotropic liquid-crystalline properties of different metal alkanesulfonates are studied by microscopy and X-ray diffraction [59]. Sodium soaps show smectic polymorphism of smectic A and smectic B phases. Ammonium soaps only show smectic A phases but polymorphism in the crystalline state. Calcium soaps show columnar mesophases. In Figs. 32 and 33 some textures and x-ray diffraction patterns are depicted. 

FIG. 32 Textures of Sodium Pentadecane 1-Sulfonate, (a), Crystalline phase at 80°C (b), smectic B phase at 113°C (c), smectic A phase at 250°C. Sample window 1.4 mm2, crossed Nicols. 

Gray GW, Goodby JWG (1984) Smectic Liquid Crystals, Textures and Structures. Blackie, Glasgow... 

Preliminary room temperature x-ray data of 0.65 Me4C00-PECH indicates that the sample presents a highly ordered smectic mesophase which was not yet completely assigned. The textures seen by polarized optical microscopy are also typical of smectic phases. Due to the very high molecular weights involved, textures specific to mesophase in thermodynamic equilibrium could not be developed within a reasonable amount of time by annealing. 

Figure 7.1 Illustration of different aggregation states obtained (from left to right) by increasing temperature crystal (K), smectic C (SmC), nematic (N) and isotropic (I). Row a shows macroscopic appearance of samples in row b, short-range microscopic ordering is represented (each bar represents a molecule) thermotropic phase diagram of row c illustrates relevant transition temperatures (Tm melting temperature Tsmc-N transition temperature between SmC and N Tc clearing temperature) row d shows different texture of different states as seen through polarizing microscope (with crossed polars, isotropic phase appears black).

FIG. 2. Schematic representation of different calamitic and discotic thermotropic liquid crystals (a) nematic, (b) cholesteric, (c-e) smectic, (f) columnar hexagonal, (g) columnar hexagonal tilted a-e adapted from Demus, D., and Richter, L., Textures of Liquid Crystals, Verlag Chemie, Weinheim, Germany, 1978 f,g adapted from Eidenschenk, R., Flussige Kristalle, Chem. Unserer Zeit, 18, 168-176 (1978). 

The smectic mesophases of the thermotropic liquid crystals show a variety of textures but resemble mainly the fan-shape texture of the lyotropic hexagonal meso-phase. For further reading more comprehensive literature is recommended [11]. 

The mesophases of LC diols la-lg were also observed directly in polarized optical micrographs taken immediately after melting the sample. Textures were identified only by comparison with published micrographs (2 ), and are therefore tentative. A nematic texture is observed for If (Fig. 2), while more highly ordered smectic textures are observed for Ib-le and Ig (Fig. 3). 

Note 4 At one time, a number of mesophases were identified as smectic on the basis of their optical textures, but they are in fact soft crystals characterised by very low yield stresses. Hence, these three-dimensionally ordered phases should no longer be called smectic mesophases. They are akin to plastic crystals with some elementary long-range order and are referred to by the letters E, J, G, H, and K. 

Note 4 A thin sample of a smectic C phase with the layers parallel to the sample surfaces gives schlieren textures with centers that have four brushes. However, a smectic C phase formed by odd-membered liquid-crystal dimers (see Definition 2.11.2.9, Note 5) has schlieren textures with two or four brushes. 

Fig. 25. Arrangement of a smectic A polygonal texture (a) general view of the focal-conic domains filling space efficiently (b) cross-section of the domains showing arrangement of...

Fig. 26. Elements of a smectic A complex polygonal texture. Upper surface one polygon with four ellipses. Lower surface two polygons. The whole space may be divided into three pyramids (ABCDK, AEHKJ, BFGKJ) and three tetrahedra (ABJK, ADHK, BCGK).

It was first reported in the early 1970s that these melt processible polymers could best be described as thermotropic systems which usually display an nematic texture in the melt phase [5]. Subsequently, a number of additional phases have been reported ranging from discotic structures to highly ordered smectic E G systems with three dimensional order. In the last several years an IUPAC sponsored study on nomenclature on thermotropic LPCs has been underway. A more complete set of definitions will be available shortly as a result of Recommendation No. 199 IUPAC [6]. 

With respect to the higher temperature transition at 445 °C, there are two conflicting views of this transition, namely that the phase above 445 °C is a smectic C and the other that it is nematic. Based on high temperature X-ray diffraction studies, Yoon et al. have concluded that it is a smectic C (see Fig. 4) [28], Thus, in Fig. 4, the disappearance of the 211 peak indicates that the nematic E structure is converting to a nematic C. In our work, using polarizing optical microscopy, we have observed a nematic texture for high molar mass specimens heated rapidly to 480 °C, sheared, and then quenched. In the case of a... 

Figure 7.1. Categories of smectic liquid crystals. From Smectic Liquid Crystals, Textures and Structures, Gray, G.W. and Goodby, J.W.G. 1984 (Leonard Hill, Glasgow). (Reproduced by kind permission of the authors and publishers.) Side elevation and plan representation of molecular ordering in each of the smectic modifications. Triangles or arrows are used to represent tilt direction.

Price and Wendorff31 > and Jabarin and Stein 32) analyzed the solidification of cholesteryl myristate. Under equilibrium conditions it changes at 357.2 K from the isotropic to the cholesteric mesophase and at 352.9 K to the smectic mesophase (see Sect. 5.1.1). At 346.8 K the smectic liquid crystal crystallized to the fully ordered crystal. Dilatometry resulted in Avrami exponents of 2, 2, and 4 for the respective transitions. The cholesteric liquid crystal has a second transition right after the relatively quick formation of a turbid homeotropic state from the isotropic melt. It aggregates without volume change to a spherulitic texture. This process was studied by microscopy32) between 343 and 355.2 K and revealed another nucleation controlled process with an Avrami exponent of 3. 

Fig. 32 a. Micrograph of a freshly prepared smectic polymer (magnification 40) b SA-texture of copolymer No. 4 of Table 8 (magnification 40)... 

As in the case of low-molecular liquid crystals the majority of information about the structure of LC polymers is obtained from their optical textures and X-ray diffraction data. Because of high viscosity of polymer melts, which results in retardation of all structural and relaxation processes it is quite difficult to obtain characteristic textures for LC polymers. As is noted by the majority of investigators smectic LC polymers form strongly birefringent films as well from solutions, as from melts11 27-... 

Smectic phases described up to date in the literature, are restricted mainly to A, B and C phases (SA, SB and Sc — respectively) for low-molecular liquid crystals at the same time, there are already reported around ten smectic phases. Identification of polymeric smectics according to their optical textures is, with rare exceptions, impossible, as their textures are quite alike. 

On the other hand, polymer B.3.2 (Table 9), which according to the X-ray analysis, does not exhibit a layer structure, displays fan texture, typical for low-molecular and polymeric smectics. It might be suggested, that this polymer also possesses some elements of layer ordering, which are different from those known for low-molecular sibotactic nematics. 

This study has concentrated on the defects observed in lyotropic lamellar phases, and it has put into evidence the specific character of the textures compared to classical thermotropic smectic phases. In leci-... 

G. W. Gray and J. W. G. Goodby, Smectic Liquid Crystals—Textures and Structures, Leonard Hill, Glasgow and London, 1984. 

The methyl-substituted ester model compound, shown below, also shows both smectic and nematic phases, as well as a smectic C-to-nematic transitional phase (18) from 169 to 170°C. Figure 3 shows two of the textures observed in this model. 

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