Ferroelectric liquid crystalline polymers spontaneous polarization

Shibaev et al. (1984) first synthesized a ferroelectric side chain polymeric liquid crystal. In the following years a lot of liquid crystalline polymers of such kind were synthesized. In early research studies techniques used to understand polymers and whether they showed the liquid crystal phase were limited so that the conclusion was ambiguous. It was only in 1988 when Uchida et al. (1988) measured the spontaneous polarization and the tilt angle that people became convinced that this side chain polymer in the literature (Shibaev et al., 1984) is indeed a ferroelectric liquid crystal. 

It has been found experimentally that the spontaneous polarization Ps of side chain liquid crystalline polymers is more or less the same as that of small molecular mass liquid crystals, i.e., so far as the chemical formula of the side group of a side chain liquid crystalline polymer is the same as that of a small molecular mass liquid crystal. This phenomenon illustrates that either the side groups in the side chain liquid crystalline polymer or the small molecular mass ferroelectric liquid crystal in their Sc phase are aligned in same way. The dependence of Ps on temperature for the three small molecular mass ferroelectric liquid crystals LI, L2 and L3 and their polymer counterparts PI, P2 and P3 are depicted in Figure 6.40. 

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 symmetry requirements necessary for ferroelectricity in low-molecular mass compounds, which were discussed in Section 1.1.3, are valid for polymer mesophases too. If a tilted chiral smectic phase is stable after a polymerization process it must be ferroelectric. Following this idea, the first polymer liquid crystalline ferroelectric has been synthesized by Shibayev et al. [160]. Its spontaneous polarization did not differ very much from the precursor monomer [161]. After polyvinylidene fiuoride (PVF2)... 

---