Tilted smectic layers, ferroelectrics

Since P must remain normal to z and n, the polarization vector forms a helix, where P is everywhere normal to the helix axis. While locally a macroscopic dipole is present, globally this polarization averages to zero due to the presence of the SmC helix. Such a structure is sometimes termed a helical antiferroelectric. But, even with a helix of infinite pitch (i.e., no helix), which can happen in the SmC phase, bulk samples of SmC material still are not ferroelectric. A ferroelectric material must possess at least two degenerate states, or orientations of the polarization, which exist in distinct free-energy wells, and which can be interconverted by application of an electric field. In the case of a bulk SmC material with infinite pitch, all orientations of the director on the tilt cone are degenerate. In this case the polarization would simply line up parallel to an applied field oriented along any axis in the smectic layer plane, with no wells or barriers (and no hysteresis) associated with the reorientation of the polarization. While interesting, such behavior is not that of a true ferroelectric. 

The molecular origin of ferroelectricity in FLCs is attributed to a pronounced anisotropy of the angular orientations of the lateral dipole moments, induced by the tilt of the molecular long axes with respect to the normal of the smectic layers. This is supported by the results of broadband dielectric spectroscopy performed on a low molecu-... 

Smectic elastomers, due to their layered structure, exhibit distinct anisotropic mechanical properties and mechanical deformation processes that are parallel or perpendicular to the normal orientation of the smectic layer. Such elastomers are important due to their optical and ferroelectric properties. Networks with a macroscopic uniformly ordered direction and a conical distribution of the smectic layer normal with respect to the normal smetic direction are mechanically deformed by uniaxial and shear deformations. Under uniaxial deformations two processes were observed [53] parallel to the direction of the mechanical field directly couples to the smectic tilt angle and perpendicular to the director while a reorientation process takes place. This process is reversible for shear deformation perpendicular and irreversible by applying the shear force parallel to the smetic direction. This is illustrated in Fig. 2.14. 

As we know, chiral tilted mesophases, manifest ferroelectric (C, F, 1 and other less symmetric phases), antiferroelectric (SmCA, SmC ) and ferrielectric (SmC/7/ ) properties. These properties owe to a tilt of elongated chiral molecules, and polar ordering of the molecular short axes (and transverse dipole moments) perpendicular to the tilt plane. The head-to-tail symmetry n = n is conserved. The Ps vector lies in the plane of a smectic layer perpendicularly to the tilt plane. Such materials belong to improper ferro-, ferri and antiferroeiectrics. 

Fig. 13.29 Bent-shape molecules form polar smectic layers in the polar plane xz with polarization (a). Upon cooling, the molecules can spontaneously acquire a tilt forward or back within the tilt plane yz. The stack of the layers may be either synclinic SmCs or anticlinic SmCA (b). Additionally, depending on the direction of polarization P both the synclinic and anticlinic structure may have uniform (ferroelectric Pp) or alternating (antiferroelectric P ) distribution of polarization within the stack. In the field absence there are four stractures marked by symbols below. Note that the leftmost structure is chiral SmC and rightmost structure is also chiral because, for any pair of neighbours, the directions of the tilt and polarization change together leaving the same handedness of the vector triple. In the electric field, the phase transitions fixjm chiral SmCAPA <> chiral SmCsPp and from racemic SmCsPA to racemic SmCAPp structures are possible (shown by ark arrows)...

Ferroelectric materials are a subclass of pyro- and piezoelectric materials (Fig. 1) (see Piezoelectric Polymers). They are very rarely foimd in crystalline organic or polymeric materials because ferroelectric hysteresis requires enough molecular mobility to reorient molecular dipoles in space. So semicrystalline poly(vinylidene fluoride) (PVDF) is nearly the only known compoimd (1). On the contrary, ferroelectric behavior is very often observed in chiral liquid crystalline materials, both low molar mass and poljuneric. For an overview of ferroelectric liquid crystals, see Reference 2. Tilted smectic liquid crystals that are made from chiral molecules lack the symmetry plane perpendicular to the smectic layer structure (Fig. 2). Therefore, they develop a spontaneous electric polarization, which is oriented perpendicular to the layer normal and perpendicular to the tilt direction. Because of the liquid-like structure inside the smectic layers, the direction of the tilt and thns the polar axis can be easily switched in external electric fields (see Figs. 2 and 3). 

The process of the director reorientation in polymer ferroelectrics, as in their low-molecular counterparts, involves changes in the tilt 0) and azimuthal (f) angles. These two modes are characterized by quite different rates. The 6 process corresponds to the soft-mode distortion, and the corresponding time To diverges at the C A phase transition point. The process means the motion of the director over the conical surface around the normal to the smectic layer (the Goldstone mode). In the helical structure the latter involves the twisting-untwisting mode, tq and differ considerably from each other, because backbones participate in those modes to a different extent. This can be seen in the dielectric spectra [172], and in the pyroelectric and electrooptical response. 

B5 + switching from antiferroelectric ferroelectric G 001 002 1 m m tilt of the molecules, chiral smectic layers antiferroelectric structure fan-shaped or schlieren texture ... 

The optical pattern may be observed for several months after switching off the dc field. The theoretical model is based on the consideration of a stabilizing role of the structural defects (dislocations) interacting with free charges in a FLC layer. The tilted layer structure responsible for such defects has been observed by direct X-ray investigation. The field-off domain structure has also been observed after the application of the electric field to the smectic A phase of a ferroelectric substance with very high spontaneous polarization [196]. The phenomenon is assumed to arise due to a break in the smectic layers (very similar to that just mentioned) induced by a strong electroclinic effect. 

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