Piezoelectric structures, crystal systems

Piezoelectricity links the fields of electricity and acoustics. Piezoelectric materials are key components in acoustic transducers such as microphones, loudspeakers, transmitters, burglar alarms and submarine detectors. The Curie brothers [7] in 1880 first observed the phenomenon in quartz crystals. Langevin [8] in 1916 first reported the application of piezoelectrics to acoustics. He used piezoelectric quartz crystals in an ultrasonic sending and detection system - a forerunner to present day sonar systems. Subsequently, other materials with piezoelectric properties were discovered. These included the crystal Rochelle salt [9], the ceramics lead barium titanate/zirconate (pzt) and barium titanate [10] and the polymer poly(vinylidene fluoride) [11]. Other polymers such as nylon 11 [12], poly(vinyl chloride) [13] and poly (vinyl fluoride) [14] exhibit piezoelectric behavior, but to a much smaller extent. Strain constants characterize the piezoelectric response. These relate a vector quantity, the electrical field, to a tensor quantity, the mechanical stress (or strain). In this convention, the film orientation direction is denoted by 1, the width by 2 and the thickness by 3. Thus, the piezoelectric strain constant dl3 refers to a polymer film held in the orientation direction with the electrical field applied parallel to the thickness or 3 direction. The requirements for observing piezoelectricity in materials are a non-symmetric unit cell and a net dipole movement in the structure. There are 32-point groups, but only 30 of these have non-symmetric unit cells and are therefore capable of exhibiting piezoelectricity. Further, only 10 out of these twenty point groups exhibit both piezoelectricity and pyroelectricity. The piezoelectric strain constant, d, is related to the piezoelectric stress coefficient, g, by... 

In the ceramics field many of the new advanced ceramic oxides have a specially prepared mixture of cations which determines the crystal structure, through the relative sizes of the cations and oxygen ions, and the physical properties through the choice of cations and tlreh oxidation states. These include, for example, solid electrolytes and electrodes for sensors and fuel cells, fenites and garnets for magnetic systems, zirconates and titanates for piezoelectric materials, as well as ceramic superconductors and a number of other substances... 

Sintered ceramics made of lead-zirconium titanate (PZT Pb(Tii jZr,)03 x S 0.5) are usually used for phoioacoustic experiments [105, 106]. The unit cell of the lead-zirconium titanate has a perovskite structure. Below the Curie temperature (328 °C for the PZT-4 (Vemitron) used by us [24]), the cells are tetragonally deformed, i.e., positive and negative charges are shifted and electric dipole moments are produced. In analogy to ferromagnetism, domains with randomly distributed polarization direction are formed. By the application of an electric field, these can be orientated in a preferred direction, and the sintered polycrystalline ceramic is then remanently polarized. The properties of these anisotropic piezoelectric materials are described by various parameters which depend on the polarization and deformation direction. In the common terminology, the < ordinate system shown in Fig. 3 is obtained for the cylindrical piezoelectric crystals [24]. 

Liquid crystalline elastomers are produced by the introduction of cross linking into liquid crystal polymer systems. This cross linking results in materials with a number of unusual properties, for example, stress-induced phase transitions and spontaneous ekmgatioo of samples in the liquid crystelline phase. When they contain chiral units. Sr elastomers are formed. For such materials piezoelectricity was predicted by Brand 103]. The helical structure of those systems can be untwisted by applicatioo of a mechanical stress, generating an electrical signal. This possibility provi the basis for the developnient of materials with piezoelectric properties. Such materials are of comaderablc interest, since the basis for their piezoelec c properties is rather different from that in the best-known piezoelectric polymer, poly(vinylidenefluoride) (PVDF). There exists rather more scope for the modification of their properties for example, the nature of the chiral unit may be varied to alter the helkal superstructure, or differences in cross link density can change the mechanical properties of the sample. 

As an example of the effect of solid solution substitutions on crystal structure and properties, consider the PbZrOj-PbTiOj system (PZT materials). Several compositions within this system are important for piezoelectric transducers, and, with fairly large concentrations of La ions (PLZT materials), are of potential for imaging and storage devices. As mentioned earlier, PbZr03... 

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