Piezoelectrics piezoelectric perovskites

Certain ternary solid solutions containing BTO as one of their major phase components show excellent piezoelectric properties in the vicinity of MPB. They have been considered as a potential replacement for existing lead-based piezoelectric perovskite, PbZrOs-PbTiOs, PMT-PT, and so on. In fact, the extremely high piezoelectric response of PZT and PMN-PT has been partially attributed to the presence of a MPB between rhombohedral and tetragonal phases at that concentration [12]. Therefore, the presence of a MPB is considered as a necessary component of a lead-free replacement material due of the enhancement in properties observed for compositions at or near MPB. The basic approach to achieve high piezoelectricity is to choose the composition of the material at the proximity of a MPB of the phase diagram. The strong piezoelectric and dielectric responses at the vicinity of MPB have been ascribed to the low polarization anisotropy (rotation of FE polarization between two equivalent states) and elastic softness at MPB. 

Titanium IV) oxide, T1O2. See titanium dioxide. Dissolves in concentrated alkali hydroxides to give titanates. Mixed metal oxides, many of commercial importance, are formed by TiOj. CaTiOj is perovskite. BaTiOa, per-ovskite related structure, is piezoelectric and is used in transducers in ultrasonic apparatus and gramophone pickups and also as a polishing compound. Other mixed oxides have the il-menite structure (e.g. FeTiOj) and the spinel structure (e.g. MgjTiO ). 

Lead zirconate [12060-01 -4] PbZrO, mol wt 346.41, has two colorless crystal stmctures a cubic perovskite form above 230°C (Curie point) and a pseudotetragonal or orthorhombic form below 230°C. It is insoluble in water and aqueous alkaUes, but soluble in strong mineral acids. Lead zirconate is usually prepared by heating together the oxides of lead and zirconium in the proper proportion. It readily forms soHd solutions with other compounds with the ABO stmcture, such as barium zirconate or lead titanate. Mixed lead titanate-zirconates have particularly high piezoelectric properties. They are used in high power acoustic-radiating transducers, hydrophones, and specialty instmments (146). 

Barium carbonate also reacts with titania to form barium titanate [12047-27-7] BaTiO, a ferroelectric material with a very high dielectric constant (see Ferroelectrics). Barium titanate is best manufactured as a single-phase composition by a soHd-state sintering technique. The asymmetrical perovskite stmcture of the titanate develops a potential difference when compressed in specific crystallographic directions, and vice versa. This material is most widely used for its strong piezoelectric characteristics in transducers for ultrasonic technical appHcations such as the emulsification of Hquids, mixing of powders and paints, and homogenization of milk, or in sonar devices (see Piezoelectrics Ultrasonics). 

Certain perovskites with Pb on the A site are particularly important and show pronounced piezoelectric characteristics (PbTiO, PZT, PLZT). Different responses are found in BaTiO and PZT to the addition of donor dopants such as La ". In PZT, lead monoxide [1317-36-8] PbO, lost by volatilization during sintering, can be replaced in the crystal by La202, where the excess positive charge of the La " is balanced by lead vacancies, leading to... 

Chlorates and bromates feature the expected pyramidal ions X03 with angles close to the tetrahedral (106-107°). With iodates the interatomic angles at iodine are rather less (97-105°) and there are three short I-O distances (177-190 pm) and three somewhat longer distances (251-300 pm) leading to distorted perovskite structures (p. 963) with pseudo-sixfold coordination of iodine and piezoelectric properties (p. 58). In Sr(I03)2.H20 the coordination number of iodine rises to 7 and this increases still further to 8 (square antiprism) in Ce(I03)4 and Zr(I03)4. 

Most niobates and tantalates, however, are insoluble and may be regarded as mixed oxides in which the Nb or Ta is octahedrally coordinated and with no discrete anion present. Thus KMO3, known inaccurately (since they have no discrete MO3 anions) as metaniobates and metatantalates, have the perovskite (p. 963) stmcture. Several of these perovskites have been characterized and some have ferroelectric and piezoelectric properties (p. 57). Because of these properties, LiNb03 and LiTa03 have been found to be attractive alternatives to quartz as frequency filters in communications devices. 

A wide array of ferroelectric, piezoelectric and pyroelectric materials have titanium, zirconium and zinc metal cations as part of their elemental composition Many electrical materials based on titanium oxide (titanates) and zirconium oxide (zirconates) are known to have structures based on perovskite-type oxide lattices Barium titanate, BaTiOs and a diverse compositional range of PZT materials (lead zirconate titanates, Pb Zr Tij-yOs) and PLZT materials (lead lanthanum zirconate titanates, PbxLai-xZryTii-yOs) are among these perovskite-type electrical materials. 

An alternative structure that has also been widely investigated both for high temperature piezoelectric, as well as for ferroelectric memory applications is the bismuth layer structure family as shown in Figure 1.14 for SrBi2Ta209 (sbt), e.g. [8], The structure consists of perovskite layers of different thicknesses, separated by Bi20 + layers. It has been shown that when the perovskite block is an even number of octahedra thick, the symmetry imposes a restriction on the polarization direction, confining it to the a-b plane. In contrast, when the perovskite block is an odd number of octahedra thick, it is possible to develop a component of the polarization along the c axis (nearly perpendicular to the layers). This could be used in... 

Figure 2.1 Schematic illustrations of intrinsic and extrinsic contributions to the piezoelectric constant of perovskite ferroelectrics. (a) and (b) correspond to the intrinsic unit cell shape (a) without and (b) with applied electric field, (c) and (d) correspond to the extrinsic response associated with the change in position of a non-180° domain wall (shown as a black line) (c) before and (d) after an electric field is applied. Note that both intrinsic and extrinsic responses lead to a change in shape of the material due to application of an electric field (and hence to a piezoelectric response). In both cases, the actual distortions are significantly exaggerated to make visualization easier.

The first piezoceramic to be developed commercially was BaTi03, the model ferroelectric discussed earlier (see Section 2.7.3). By the 1950s the solid solution system Pb(Ti,Zr)03 (PZT), which also has the perovskite structure, was found to be ferroelectric and PZT compositions are now the most widely exploited of all piezoelectric ceramics. The following outline description of their properties and fabrication introduces important ideas for the following discussion of the tailoring of piezoceramics, including PZT, for specific applications. It is assumed that the reader has studied Sections 2.3 and 2.7.3. 

As discussed in Section 5.7.2, in the case of niobium-containing perovskites it is necessary to avoid the formation of pyrochlore-type phases if reproducible and optimum dielectric and piezoelectric properties are to be achieved. G. Roberts et al. [13] developed a modification of the B-site precursor ( columbite process) route to produce high quality PNN-PZT ceramics. 

Ferroelectric ceramics and single crystals have found wide applications in many electronic, acoustoptic and piezoelectric devices [1,2], Perovskites represent one of the most important classes of inorganic powders that are of great interest in functional ceramics used for electronic components among them BaTiOj is a typical and most frequently used representative. 

Technically useful properties of such perovskite ceramics are their high permittivities (relative dielectric constants), the semiconductor properties of certain chemical compositions and their piezoelectric properties. 

An important group of piezoelectric ceramics are solid solutions of PbZrOj and PbTiOs represented as Pb(Zr, Ti)03 (and commonly referred to as PZT). At high temperature these compounds have the cubic perovskite structure (Fig. 1). In the ferroelectric phase, which is stable at room temperature, the lattice is distorted, and the asymmetry of the positive and negative ions results in a net dipole moment. Spontaneous polarization is the dipole moment per unit volume. 

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