Perovskite niobate

Simple ABO compounds in addition to BaTiO are cadmium titanate [12014-14-17, CdTiO lead titanate [12060-00-3] PbTiO potassium niobate [12030-85-2] KNbO sodium niobate [12034-09-2], NaNbO silver niobate [12309-96-5], AgNbO potassium iodate [7758-05-6], KIO bismuth ferrate [12010-42-3], BiFeO sodium tantalate, NaTaO and lead zirconate [12060-01 -4], PbZrO. The perovskite stmcture is also tolerant of a very wide range of multiple cation substitution on both A and B sites. Thus many more complex compounds have been found (16,17), eg, (K 2 i/2) 3 ... 

There is often a wide range of crystalline soHd solubiUty between end-member compositions. Additionally the ferroelectric and antiferroelectric Curie temperatures and consequent properties appear to mutate continuously with fractional cation substitution. Thus the perovskite system has a variety of extremely usehil properties. Other oxygen octahedra stmcture ferroelectrics such as lithium niobate [12031 -63-9] LiNbO, lithium tantalate [12031 -66-2] LiTaO, the tungsten bron2e stmctures, bismuth oxide layer stmctures, pyrochlore stmctures, and order—disorder-type ferroelectrics are well discussed elsewhere (4,12,22,23). 

Certain glass-ceramic materials also exhibit potentially useful electro-optic effects. These include glasses with microcrystaUites of Cd-sulfoselenides, which show a strong nonlinear response to an electric field (9), as well as glass-ceramics based on ferroelectric perovskite crystals such as niobates, titanates, or zkconates (10—12). Such crystals permit electric control of scattering and other optical properties. 

Perovskites have the chemical formula ABO, where A is an 8- to 12-coordinated cation such as an alkaU or alkaline earth, and B is a small, octahedraHy coordinated high valence metal such as Ti, Zr, Nb, or Ta. Glass-ceramics based on perovskite crystals ate characteri2ed by their unusual dielectric and electrooptic properties. Examples include highly crystalline niobate glass-ceramics which exhibit nonlinear optical properties (12), as well as titanate and niobate glass-ceramics with very high dielectric constants (11,14). 

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. 

Figure 11.6 AMF3 crystal structures, (a) Ideal cubic perovskite structure, (b) Tilting of MXg octahedra in orthorhombically distorted AMF3 perovskites. (c) RbNiF3 CSC0F3 and CsNiF3 crystal structures, (d) Crystal structure of lithium niobate.

Yoshimura, J., Ebina, Y, Kondo, J., Domen, K., Tanaka, A. 1993. Visible-light induced photocatalytic behavior of a layered perovskite type niobate. J Phys Chem B 97 1970-1973. 

Barium titanate is one example of a ferroelectric material. Other oxides with the perovskite structure are also ferroelectric (e.g., lead titanate and lithium niobate). One important set of such compounds, used in many transducer applications, is the mixed oxides PZT (PbZri-Ji/Ds). These, like barium titanate, have small ions in Oe cages which are easily displaced. Other ferroelectric solids include hydrogen-bonded solids, such as KH2PO4 and Rochelle salt (NaKC4H406.4H20), salts with anions which possess dipole moments, such as NaNOz, and copolymers of poly vinylidene fluoride. It has even been proposed that ferroelectric mechanisms are involved in some biological processes such as brain memory and voltagedependent ion channels concerned with impulse conduction in nerve and muscle cells. 

BaTiO and SrTiO are both perovskites and have nearly the same optical band gaps. Yet the flat-band potential of SrTiO is 0.6 volts more negative than for the barium analog, a difference comparable in magnitude to that noted above for the niobates. Furthermore, it can be seen from Figure 1 that the band gap in the rutile TiO is significantly lower than in these perovskite ti-tanates. 

Swartz, S.L. and Shrout, T.R. (1982) Fabrication of perovskite lead magnesium niobate, Mater. Res. Bull. 17, 1245-50. 

We have seen in the preceding Section that oxides with MCE octahedra can form perovskite structures and this trend applies to some tantatates and niobates as well. 

PMN-PT) are notorious for the difficulty to obtain as phase pure perovskite. To fabricate phase pure PMN it is necessary to prepare magnesium niobate (columbite) first, and then to heat a mixture of columbite with other oxide species. PbO is usually added in a small excess over exact stoichiometry that is a complicated and tedious process. 

IR spectroscopy can be used to distinguish several different phases characterized by the stoichiometry ABO3 (Table 3.4), such as cubic, tetragonal, orthorombic and rhombohedral perovskites (such as SrTiOs, BaTiOs, LaFeOs and LaMnOs, respectively [56, 64, 65]), from ilmenites and lithium niobate structures. In Figure 3.10 the spectrum of LaFeOs is reported. It shows some of the 26 IR active modes expected. 

Preparation of Ferroelectric Ceramics 17.3.11.3. Other Ferroeiectctric Ceramics 17.3.11.3.2. Perovskite Niobates and Tantalates. 

Randall CA, Guo R, Bhalla AS, Cross LE (1991) Microstracture-properly relations in tungsten bronze lead barium niobate, Pbi tBa Nb206. J Mater Res 6 1720-1728 Reaney IM (1995) TEM observations of domains in ferroelectric and nonferroelectric perovskites. Ferroelectrics 172 115-125... 

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