BaTiOs

AI2O3, BeO, AIN BaTiO, SrTiO, Ti02 Pb(Zr2 Ti )03, Si02 (quartz)... 

Powder Preparation. The goal in powder preparation is to achieve a ceramic powder which yields a product satisfying specified performance standards. Examples of the most important powder preparation methods for electronic ceramics include mixing/calcination, coprecipitation from solvents, hydrothermal processing, and metal organic decomposition. The trend in powder synthesis is toward powders having particle sizes less than 1 p.m and Httie or no hard agglomerates for enhanced reactivity and uniformity. Examples of the four basic methods are presented in Table 2 for the preparation of BaTiO powder. Reviews of these synthesis techniques can be found in the Hterature (2,5). 

Table 2. Methods Used to Prepare BaTiO Electronic Ceramic Powders...

Si02, BaTiO capacitors sol—gel, sputtering, chemical vapor deposition (CVD)... 

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 ... 

Fig. 3. Crystal structure and lattice distortion of the BaTiO unit ceU showiag the direction of spontaneous polarization, and resultant dielectric constant S vs temperature. The subscripts a and c relate to orientations parallel and perpendicular to the tetragonal axis, respectively. The Curie poiat, T, is also shown.

Perovskite-type compounds, especially BaTiO, have the abiUty to form extensive soHd solutions. By this means a wide variety of materials having continuously changing electrical properties can be produced ia the polycrystaUine ceramic state. By substituting ions for ions, T can be... 

Fig. 4. Effect of isovalent substitutions on crystal stmcture transition temperatures of ceramic BaTiO where ( ) represents Pb (—), Ca and ( ) substitution for Ba and (—) and ( ) substitution for. Transition temperatures for pure BaTiO are 135, 15, and...

Calcination. Calcination involves a low (<1000° C) temperature soHd-state chemical reaction of the raw materials to form the desired final composition and stmcture such as perovskite for BaTiO and PZT. It can be carried out by placing the mixed powders in cmcibles in a batch or continuous kiln. A rotary kiln also can be used for this purpose to process continuously. A sufficiendy uniform temperature has to be provided for the mixed oxides, because the thermal conductivity of powdered materials is always low. 

Fig. 8. Dielectric constant (1 kHz) vs temperature for BaTiO ceramics of A, l-)Tm grain size, and B, 50-)Tm grain size.

Relaxor Ferroelectrics. The general characteristics distinguishing relaxor ferroelectrics, eg, the PbMg 2N b2 302 family, from normal ferroelectrics such as BaTiO, are summari2ed in Table 2 (97). The dielectric response in the paraelectric-ferroelectric transition region is significantly more diffuse for the former. Maximum relative dielectric permittivities, referred to as are greater than 20,000. The temperature dependence of the dielectric... 

Fig. 11. Fundamental characteristics of relaxor materials compared to BaTiO. Temperature dependence for the relaxor ferroelectric 0.93...

The most significant commercial product is barium titanate, BaTiO, used to produce the ceramic capacitors found in almost all electronic products. As electronic circuitry has been rniniaturized, demand has increased for capacitors that can store a high amount of charge in a relatively small volume. This demand led to the development of highly efficient multilayer ceramic capacitors. In these devices, several layers of ceramic, from 25—50 ]lni in thickness, are separated by even thinner layers of electrode metal. Each layer must be dense, free of pin-holes and flaws, and ideally consist of several uniform grains of fired ceramic. Manufacturers are trying to reduce the layer thickness to 10—12 ]lni. Conventionally prepared ceramic powders cannot meet the rigorous demands of these appHcations, therefore an emphasis has been placed on production of advanced powders by hydrothermal synthesis and other methods. 

Materials. For holographic information storage, materials are required which alter their index of refraction locally by spotwise illumination with light. Suitable are photorefractive inorganic crystals, eg, LiNbO, BaTiO, LiTaO, and Bq2 i02Q. Also suitable are photorefractive ferroelectric polymers like poly(vinyhdene fluoride-i o-trifluorethylene) (PVDF/TFE). Preferably transparent polymers are used which contain approximately 10% of monomeric material (so-called photopolymers, photothermoplasts). These polymers additionally contain different initiators, photoinitiators, and photosensitizers. 

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). 

Barium titanate is usually produced by the soHd-state reaction of barium carbonate and titanium dioxide. Dielectric and pie2oelectric properties of BaTiO can be affected by stoichiometry, micro stmcture, and additive ions that can enter into soHd solution. In the perovskite lattice, substitutions of Pb ", Sr ", Ca ", and Cd " can be made for part of the barium ions, maintaining the ferroelectric characteristics. Similarly, the TP" ion can partially be replaced with Sn +, Zr +, Ce +, and Th +. The possibihties for forming solution alloys in all these stmctures offer a range of compositions, which present a... 

Typical positive temperature coefficient (PTC) device behavior for a doped polycrystaHine BaTiO thermistor is presented in Figure 4. At temperatures below - 100° C and above - 200° C the material shows the expected negative resistivity vs temperature associated with semiconductors as expressed by ... 

Fig. 4. Effect of dopant additions on the resistivity versus temperature behavior of BaTiO PTCR ceramics. A, undoped B, doped with 0.134 mol % Cr ...

Standard ceramic processing conditions are controlled so that the resulting ceramic microstmcture is composed of semiconducting 2inc oxide grains (pZnO < IHcm) and electrically insulating grain boundaries > 10 0cm)). The microstmcture is thus similar to that of the BaTiO thermistor and... 

Solution deposition processing has been used to prepare thin films (qv) of PbTiOg, PZT, PLT, PLZT, BaTiO, LiNbOg, PMN, PMN-PT,... 

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