Ferroelectric phase transitions

The PTC materials already mentioned depend directly on the ferroelectric phase transition in solid solutions based on BaTi03, suitably doped to render them semiconducting. This is a typical example of the interrelations between different electrical phenomena in ceramics. 

The phase transition of NaNOz at 164 °C from the paraelectric to the ferroelectric form involves a change of space group from /2/m 2/m 2/m to Imml. Will the ferroelectric phase be twinned ... 

As can be seen from Fig. 11c, the anisotropic frozen polar cluster component increases in intensity if the crystal is cooled at low enough temperatures in an electric field larger than the critical field and applied along the (111) direction. A transition to the ferroelectric phase is induced for E > Eq. The difference between the FC and ZFC Pb NMR spectra is striking and... 

The concept of quantum ferroelectricity was first proposed by Schneider and coworkers [1,2] and Opperman and Thomas [3]. Shortly thereafter, quantum paraelectricity was confirmed by researchers in Switzerland [4], The real part of the dielectric susceptibihty of KTO and STO, which are known as incipient ferroelectric compounds, increases when temperature decreases and becomes saturated at low temperature. Both of these materials are known to have ferroelectric soft modes. However, the ferroelectric phase transition is impeded due to the lattice s zero point vibration. These materials are therefore called quantum paraelectrics, or quantum ferroelectrics if quantum paraelectrics are turned into ferroelectrics by an external field or elemental substitution. It is well known that commercially available single crystal contains many defects, which can include a dipolar center in the crystal. These dipolar entities can play a certain role in STO. The polar nanoregion (PNR originally called the polar microregion) may originate from the coupling of the dipolar entities with the lattice [5-7]. When STO is uniaxially pressed, it turns into ferroelectrics [7]. 

According to the concept of the displacive-type ferroelectric phase transition [10], an increase in the dielectric constant corresponds directly to the softening of the IR-active transverse phonon. When the crystal can be regarded as an assembly of the vibrators of normal coordinates, the soft phonon... 

As shown in Fig. 13a, An for the (llO)c face is composed of two contributions from the antiferrodistortive phase transition and the ferroelectric transition (see data for 7 x 2 x 0.3 mm ). On the other hand, only the ferroelectric transition is seen for the (OOl)c face. The inequality Px 7 Py means the breaking of symmetry in the (OOl)c plane. Therefore, the symmetry of the ferroelectric phase is below orthorhombic. 

It has been widely recognized that the Ught scattering technique yields essential information on a dynamic mechanism of ferroelectric phase transition because it clearly resolves the dynamics of the ferroelectric soft mode that drives the phase transition. Quantum paraelectricity is caused by the non-freezing of the soft mode. Therefore, the isotope-exchange effect on the soft mode is the key to elucidating the scenario of isotopically induced ferroelectricity. 

Static dielectric measurements [8] show that all crystals in the family exhibit a very large quantum effect of isotope replacement H D on the critical temperature. This effect can be exemphfied by the fact that Tc = 122 K in KDP and Tc = 229 K in KD2PO4 or DKDP. KDP exhibits a weak first-order phase transition, whereas the first-order character of phase transition in DKDP is more pronounced. The effect of isotope replacement is also observed for the saturated (near T = 0 K) spontaneous polarization, Pg, which has the value Ps = 5.0 xC cm in KDP and Ps = 6.2 xC cm in DKDP. As can be expected for a ferroelectric phase transition, a decrease in the temperature toward Tc in the PE phase causes a critical increase in longitudinal dielectric constant (along the c-axis) in KDP and DKDP. This increase follows the Curie-Weiss law. Sc = C/(T - Ti), and an isotope effect is observed not only for the Curie-Weiss temperature, Ti Tc, but also for the Curie constant C (C = 3000 K in KDP and C = 4000 K in DKDP). Isotope effects on the quantities Tc, P, and C were successfully explained within the proton-tunneling model as a consequence of different tunneling frequencies of H and D atoms. However, this model can hardly reproduce the Curie-Weiss law for Sc-... 

Ferroelectric-paraelectric transitions can be understood on the basis of the Landau-Devonshire theory using polarization as an order parameter (Rao Rao, 1978). Xhe ordered ferroelectric phase has a lower symmetry, belonging to one of the subgroups of the high-symmetry disordered paraelectric phase. Xhe exact structure to which the paraelectric phase transforms is, however, determined by energy considerations. 

Fig. 9. Phase diagram showing the temperature versus the copolymer composition. The dashed areas correspond to the transition region. The frontiers among the different regions depend on sample preparation as well as on sample thermal and processing history. The fraction of ferroelectric phase, Ff, increases with increasing PVF2 content...

Determination of the critical temperature after equation (1), T0 = En/Syl, is considered in the cooperative JT and PJT effects [2,3,8,9]. In particular, the origin of structural ferroelectric phase transitions as due to the PJT effect (the vibronic theory of ferroelectricity) was suggested first in the sixties [10] (see also Ref. [9]). JT structural phase transitions are reviewed in Ref. [8]. 

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