Smectic liquid-crystalline state

Properties have been determined for a series of block copolymers based on poly[3,3-bis(ethoxymethyl)oxetane] and poly [3,3-bis(methoxymethyl)oxetane]-(ro-tetrahydrofuran. The block copolymers had properties suggestive of a thermoplastic elastomer (308). POX was a good main chain for a well-developed smectic liquid crystalline state when cyano- or fluorine-substituted biphenyls were used as mesogenic groups attached through a four-methylene spacer (309,310). Other side-chain liquid crystalline polyoxetanes were observed with a spacer-separated azo moiety (311) and with laterally attached mesogenic groups (312). 

Liquid crystals can be in the smectic, nematic, or isotropic states. In the smectic liquid crystalline state there is a long-range order in the direction of the long axis of the molecules. These molecules may be in single- or bilayer conformation, have molecular axis normal or tilted to the plane of the layer, and frozen or melted chains. In the nematic liquid crystalline state the molecules are aligned side by side but not in specific layers. The isotropic liquid crystalline state is more or less a liquid state, but where clusters with short-range order persist (Small, 1986, pp. 49-51). 

Figure 25.10 Schematic iiiustration of the ceiis for the anisotropic ion conductive measurements. The samples forming homeotropicaiiy aligned monodomains in the smectic liquid crystalline states are filled between electrodes.

The nematic phase of all the compounds CBn is characterized by a coherence length of about 1.4 times the elongated structure of the molecule. Based on this behaviour local associations in form of dimers with cyano-phenyl interactions were postulated. For the smectic A phase a partial bilayer arrangement of the molecules (SAd) is most likely. But there are also example for the smectic A phase with a monolayer (Sai) or a bilayer (Sa2) arrangement of the molecules as well as a commensurate structure A large number of X-ray measurements were carried out in the liquid crystalline state to clear up the structural richness and variability (see Chap. 2, this Vol. [52]). 

An orthogonal layered structure in the solid state of rod-like molecules is the exception rather than the rule. Therefore, there is no conclusive evidence that a tilted layer structure in the solid state melts to a tilted smectic phase. In other words, if we consider the solid state as precursor for the type of the liquid crystalline state, no real precursor for an orthogonal fluid smectic phase would exist. As demonstrated in Fig. 19, the compound B-A for example exhibiting a smectic A phase has a tilted layer structure in the solid state. 

In membrane systems, temperature at which the crystalline state is converted to the liquid-crystalline state (smectic phases). 

A detailed insight into the freezing-in process is given by optical investigations. As described in 2.3.1.4 for nematics, 2.3.2.3 for cholesterics and 2.3.3.3 for smectics, the optical uniaxial character of the polymers in the liquid crystalline state has been proved by birefringence measurements and the state of order was calculated from these measurements. This method also provides information about the glassy state. For conventional l.c s it has been demonstrated, that the temperature dependence of... 

Nakata M, Link DR, Takanishi Y, Takahasi Y, Thisayukta J, Niwano H, Coleman DA, Watanabe J, Iida A, Clark NA, Takezoe H (2005) Electric-field-induced transition between the polarization-modulated and ferroelectric smectic-CgPf liquid crystalline states studied using microbeam X-ray diffraction. Phys Rev E 71 011705... 

The fact that the structure of a solid monomer influences its polymerization substantially now seems obvious. It is not as clear whether structural phenomena can effect polymerization if the monomer is a liquid. It has long been known that ordered regions or clusters exist in liquids, and several years ago it was assumed that in some cases these regions in liquid monomers can influence the polymerization. One of the most vivid examples—namely, polymerization in the liquid-crystalline state—was accomplished by Krentzel and co-workers (I, 2, 3). The object of their study was p-methacrylylhydroxybenzoic acid, which forms conventional crystals in the pure state and does not polymerize in the solid state. However, when mixed with alkoxybenzoic acid, it forms liquid crystals of both smectic and nematic forms. Polymerization of p-meth-acryllylhydroxybenzoic acid in various forms of liquid crystals was compared with polymerization of the same substance dissolved in dioxane and dimethylformamide (DMF). 

The rotational crystalline phase has conceptually the same meaning as that of the smectic liquid crystal [8]. Molecules of substances forming liquid crystals have, as a rule, an anisometrically elongated shape and low symmetry. The main structural feature of the liquid-crystalline state is a parallel array of molecules with very light contacts between them. 

PHBA goes through an orthorhombic-to-hexagonal phase transformation (a rotational crystalline phase or a smectic liquid-crystalline phase). Other structures [720-/22] were recently described as belonging to the rotational crystalline state. 

In order to understand the basic principles of operation of the many different kinds of LCDs being developed and/or manufactured at the present time, it is necessary to briefly describe the liquid crystalline state and then define the physical properties of direct relevance to LCDs. First, the nematic, smectic and columnar liquid crystalline states will be described briefly. However, the rest of the monograph dealing with liquid crystals will concentrate on nematic liquid crystals and their physical properties, since the vast majority of LCDs manufactured operate using mixtures of thermotropic, non-amphiphilic rodlike organic compounds in the nematic state. 

A change in rate and/or mode of propagation can be brought about by orientation of monomer molecules in the liquid crystalline state. For vinylo-leate in the smectic phase, a higher polymerization rate than in the isotropic phase was observed by Amerik and Krentsel [28]. A significant reduction in the polymerization rate of a relatively complex monomer [N-(p-acryloyl-oxybenzylidene)-p-methoxyaniline] in the nematic state was described by Perplies et al. [29], On the other hand, Paleos and Labes observed no change in the polymerization kinetics of a monomer, also of Schiff base character... 

Figure 25.9 Polarizing optical micrographs of the equimolar mixture of 14 and 16 in the smectic A liquid crystalline state (a) homeotropically aligned monodomain is formed on a glass substrate when the sample is cooled slowly from the isotropic state at the rate of 3° C min Inset is a conoscopic image (b) unaligned polydomains are formed on a glass substrate when the sample is cooled from the isotropic state at the rate of 20°C min ...

If the concentration of surfactant becomes high enough, surfactant structures often develop long-range order, and hence they become liquid crystalline. They are lyotropic liquid crystals, because the transition to the liquid-crystalline state is induced by concentration changes. Surfactant solutions can form nematic and smectic-A liquid-crystalline phases analogous to those discussed in Chapter 10. In addition, hexagonal and cubic phases are common in surfactant solutions. 

Because the molecular forces producing liquid crystalline states are very weak, the structures are easily affected by changes in mechanical stress, electromagnetic fields, temperature, and chemical environment. Three main categories have been recognized smectic, nematic, and cholesteric ... 

The mesogenic structure of a benzoic acid dimer has been introduced as a noncovalent cross-linker for polysiloxanes [79]. Polymer 57 exhibits a smectic C phase due to the dynamics of H-bonding. In contrast, mesomorphic order is locked in the solid state of poly[(4-acryloyl)benzoic acid] by polymerization in its mesophase [128]. No liquid-crystalline state is observed for this material because of the lack of flexibility of the structures. Main-chain-type polymeric liquid-crystal associates are formed from carboxyl-bifunctionalized aromatic compounds [129]. 

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