Other Chiral Smectic Phases

FIGURE 2.15 The structure of the antiferroelectric liquid crystal phase (center) and electric-field-induced switching states. 

FIGURE 2.16 Polarized microscopic image of a planar texture in the antiferroelectric phase. 

FIGURE 2.17 Polarized microscopic image of the homeotropic texture of the three-layer intermediate (also known as the ferrielectric phase). The three-layer phase is optically indistinguishable from the four-layer phase, but the two phases can be clearly differentiated using the resonant x-ray scattering technique.  

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Nematic gels are very interesting systems, thus deserving further study. Actually, these systems are being studied experimentally for applications. Examples are polymer dispersed liquid crystal displays are sometimes dispersed not in a polymer, but in a polymer network. Displays by means of the polymer stabilized cholesteric texture change, are also achieved in crosslinked systems. In addition, the chiral smectic phase has been obtained in such systems as well. Other types of liquid crystal gels have been applied or are expected to be applied in such devices. 

On the other hand, it has been shown on LMWLCs that the well-known SmC, where the molecules are tilted with respect to the layer normal, is no longer the only possibility to obtain a fluid biaxial phase [63], As a consequence, a strict determination of the chiral smectic phase structure requires not only a careful analysis of the X-ray diagrams obtained on powder as well as on aligned samples, but also a study of the electrooptic response, which allows discrimination between the ferroelectric, the antiferro-electric, and the ferrielectric behavior. 

Other more exotic types of calamitic liquid crystal molecules include those having chiral components. This molecular modification leads to the formation of chiral nematic phases in which the director adopts a natural helical twist which may range from sub-micron to macroscopic length scales. Chirality coupled with smectic ordering may also lead to the formation of ferroelectric phases [20]. 

The earliest approach to explain tubule formation was developed by de Gen-nes.168 He pointed out that, in a bilayer membrane of chiral molecules in the Lp/ phase, symmetry allows the material to have a net electric dipole moment in the bilayer plane, like a chiral smectic-C liquid crystal.169 In other words, the material is ferroelectric, with a spontaneous electrostatic polarization P per unit area in the bilayer plane, perpendicular to the axis of molecular tilt. (Note that this argument depends on the chirality of the molecules, but it does not depend on the chiral elastic properties of the membrane. For that reason, we discuss it in this section, rather than with the chiral elastic models in the following sections.)... 

Chirality (or a lack of mirror symmetry) plays an important role in the LC field. Molecular chirality, due to one or more chiral carbon site(s), can lead to a reduction in the phase symmetry, and yield a large variety of novel mesophases that possess unique structures and optical properties. One important consequence of chirality is polar order when molecules contain lateral electric dipoles. Electric polarization is obtained in tilted smectic phases. The reduced symmetry in the phase yields an in-layer polarization and the tilt sense of each layer can change synclinically (chiral SmC ) or anticlinically (SmC)) to form a helical superstructure perpendicular to the layer planes. Hence helical distributions of the molecules in the superstructure can result in a ferro- (SmC ), antiferro- (SmC)), and ferri-electric phases. Other chiral subphases (e.g., Q) can also exist. In the SmC) phase, the directions of the tilt alternate from one layer to the next, and the in-plane spontaneous polarization reverses by 180° between two neighbouring layers. The structures of the C a and C phases are less certain. The ferrielectric C shows two interdigitated helices as in the SmC) phase, but here the molecules are rotated by an angle different from 180° w.r.t. the helix axis between two neighbouring layers. 

The enhanced chirality by doping SmC with BSMs can be explained qualitatively in the same way as in the N phase. However, the situation is more complicated in SmC because of spontaneous polarization and flexoelectric effect, and (3) must be replaced by an equation including such effects. Actually, the contribution of flexoelectric effect has been discussed by Gorecka et al. [4]. The other important effect is caused by the fact that the BSMs are in the tilted smectic phase. As mentioned above, the tilt of BSMs induces chirality as observed in the B2 phase. 

The same authors increased the complexity of their systems by introducing in a polyester chain both ionic and chiral chain segments. The series containing both the isosorbide chiral units and the ionic moieties yielded chiral smectic C (SmC ) and chiral smectic B (SmB ) liquid-crystalline phases, exhibiting broken focal-conic texture and schlieren texture. Not surprisingly, the analogous polymer without the chiral units exhibited only the nonchiral SmC mesophase. On the other hand, in this case, the effect of ionic units on the phase behavior was negligible [91]. 

Other attempts at synthesizing chiral smectic polymers have reached the conclusion that no general conclusion can be made so far as for what molecular structure will yield the desired phase. Again, all the structural elements including the main chain, the spacer, and the mesogenic unit are playing a part. Nevertheless, a longer spacer and more flexible main chain seem to favor the chiral Sc phase (Le Barny and Dubois, 1989). 

The texture of polymeric chiral liquid crystalline phases. The chiral liquid crystalline phases include the chiral smectics and the chiral nematic or cholesteric phase. Poly(7-benzyl-L-glutamate) and derivatives of cellulose are popular examples of polymers that form a chiral mesophase. Side-chain type copolymers of two chiral monomers with flexible spacers of different, lengths and copolymers of one chiral and the other non-chiral mesogenic monomers may also form a cholesteric phase (Finkelmann et al., 1978 1980). In addition, a polymeric nematic phase may be transformed to a cholesteric phase by dissolving in a chiral compound (Fayolle et al., 1979). The first polymer that formed a chiral smectic C phase was reported by Shibaev et al. (1984). It has the sequence of phase transition of g 20-30 Sc 73-75 Sa 83-85 I with the Sc phase at the lower temperature side of Sa- More examples of Sc polymers are given by Le Barny and Dubois (1989). 

Other metallomesogens containing the optically active butadienetricarbonyliron(O) moiety, incorporated into promesogenic chiral nematic ligands derived from cholesteryl, have been reported. " Both the diastereoisomers exhibited a chiral nematic phase and a monotropic smectic phase, the chiral nematic phase being monotropic for the (-l-)-isomer (Cr 193 (S 93 N 131) I), and enantiotropic for the (—(-isomer (Cr 117 (S 99) N 133 I). 

Experimentally, piezoelectricity in cholesteric and chiral smectic C phases was reported for liquid-crystalline networks [140-147]. Multidomain lightly cross-linked systems were synthesized, then the orientation is obtained by mechanical strain [140] or by poling [147]. In other samples this orientation is performed prior to the crosslinking process [144, 146]. Macro-scopically oriented samples were subjected to either a static or a periodically varying strain. Open circuit voltages across the samples were measured that are linear functions of the applied strain [140-142, 144, 145],... 

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