Barium-titanate

Barium titanate (BaTiOs) is historically one of the most important ferroelectric ceramic materials its main use in modern applications is as a base composition for capacitors, due to its high dielectric constant [98]. 

The quality of the barium titanate starting powders used in ceramic fabrication is a key factor in determining the microstructure and properties of the final ceramic. 

BaTiOs nanopowders were synthesized from the alkoxide solution precursor by the sol-gel process [99]. The barium titanate sol synthesis route employed 

3- propanediol, together with barium acetate and titanium isopropoxide, modified with acetylacetonate. Barium acetate was dissolved in acetic acid and heated under reflux conditions for 90 min. In another flask, titanium diisopropoxide bis (acetylacetonate), abbreviated TIAA (75wt% in isopropanol), was mixed with 

3- propanediol in a 1 1 molar ratio of titanium to diol, and then maintained under reflux conditions for 60 min. Afterward, distillation was carried out at a reflux temperature of 80°C. Finally, the barium acetate solution was added to the TIAA solution to give a 1 1 molar ratio of Ba to Ti. This mixture was maintained under reflux for 60 min. 

A detailed sol-emulsion-gel process was developed by Chatterjee etal. [195] for the synthesis of barium titanate, BaTi03. Three varieties of sols were prepared as the aqueous phase while titanium isopropoxide (Ti(0 Pr)4) remained the source 

Calcination of the gel products at 1(X)0°C showed that only the sol composition containing the acetate as the source of Ba produced phase-pure BaTi03. Further acetate sols were therefore prepared with 2-25 vol% Span 80 in the support solvent (oil phase + surfactant), and the gel product calcined at 1000°C. The particles were not only large (tens to hundreds of nm width) but of a variety of shapes dependent on surfactant contents in the sols. The variations in shape with increasing surfactant content are described below  

Ill-formed sphere — Sphere - Distorted sphere Rod+Distorted sphere — Cube-like/lamellar+rod Cube-like/lamellar — Irregular. 

Though no conscious attempt was made by the authors to prepare microemulsions, the shape development of BaTiOj particles with increasing surfactant content resembled similar results reported on changes in shape of dispersed phases in microemulsions (Chapter 5). 

The process, thus, has been marked by the following steps  

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K. Osseo-Asare, F. J. Arriagada, and J. H. Adair, "Solubility Relationships in the Coprecipitation Synthesis of Barium Titanate Heterogeneous Equihbria in the Ba—Ti—C2O4—H2O System," in G. L. Messing, E. R. Fuller, Jr., and Hans Hausin, eds.. Ceramic Powder Science Vol. 2,1987, pp. 47-53. 

D. Miller, J. H. Adair, W. Huebner, and R. E. Newnham, "A Comparative Assessment of Chemical Synthesis Techniques for Barium Titanate," Paper, 88th Annual Meeting of the American Ceramic Society, Pittsburgh, Pa., April 27—30, 1987. 

Oxygen Octahedra. An important group of ferroelectrics is that known as the perovskites. The perfect perovskite stmcture is a simple cubic one as shown in Figure 2, having the general formula ABO, where A is a monovalent or divalent metal such as Na, K, Rb, Ca, Sr, Ba, or Pb, and B is a tetra- or pentavalent cation such as Ti, Sn, Zr, Nb, Ta, or W. The first perovskite ferroelectric to be discovered was barium titanate [12047-27-7] and it is the most thoroughly investigated ferroelectric material (10). 

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. 

Table 2. Commercial Hydrothermal Barium Titanate Powders ...

Other. Insoluble alkaline-earth metal and heavy metal stannates are prepared by the metathetic reaction of a soluble salt of the metal with a soluble alkah—metal stannate. They are used as additives to ceramic dielectric bodies (32). The use of bismuth stannate [12777-45-6] Bi2(Sn02)3 5H20, with barium titanate produces a ceramic capacitor body of uniform dielectric constant over a substantial temperature range (33). Ceramic and dielectric properties of individual stannates are given in Reference 34. Other typical commercially available stannates are barium stannate [12009-18-6] BaSnO calcium stannate [12013 6-6] CaSnO magnesium stannate [12032-29-0], MgSnO and strontium stannate [12143-34-9], SrSnO. ... 

Alkaline-Earth Titanates. Some physical properties of representative alkaline-earth titanates ate Hsted in Table 15. The most important apphcations of these titanates are in the manufacture of electronic components (109). The most important member of the class is barium titanate, BaTi03, which owes its significance to its exceptionally high dielectric constant and its piezoelectric and ferroelectric properties. Further, because barium titanate easily forms solid solutions with strontium titanate, lead titanate, zirconium oxide, and tin oxide, the electrical properties can be modified within wide limits. Barium titanate may be made by, eg, cocalcination of barium carbonate and titanium dioxide at ca 1200°C. With the exception of Ba2Ti04, barium orthotitanate, titanates do not contain discrete TiO ions but ate mixed oxides. Ba2Ti04 has the P-K SO stmcture in which distorted tetrahedral TiO ions occur. 

Barium titanate [12047-27-7] has five crystaUine modifications. Of these, the tetragonal form is the most important. The stmcture is based on corner-linked oxygen octahedra, within which are located the Ti" " ions. These can be moved from their central positions either spontaneously or in an apphed electric field. Each TiO octahedron may then be regarded as an electric dipole. If dipoles within a local region, ie, a domain, are oriented parallel to one another and the orientation of all the dipoles within a domain can be changed by the appHcation of an electric field, the material is said to be ferroelectric. At ca 130°C, the Curie temperature, the barium titanate stmcture changes to cubic. The dipoles now behave independentiy, and the material is paraelectric (see Ferroelectrics). 

Composite Oxyalkoxides. Composite oxyalkoxides can be prepared by reaction of tetraalkyl titanates and alkaline-earth metal hydroxides. These oxyalkoxides and their derivatives can be hydroly2ed and thermally decomposed to give alkaline-earth metal titanates such as barium titanate (150). 

Barium titanate thin films can be deposited on various substances by treating with an aqueous solution containing barium salts and an alkanolamine-modifted titanate such as TYZOR TE (151). In a similar fashion, reaction of a tetraalkyl titanate with an alkah metal hydroxide, such as potassium hydroxide, gives oxyalkoxide derivatives (KTi O(OR) ), which can be further processed to give alkali metal titanate powders, films, and fibers (152—155). The fibers can be used as adsorbents for radioactive metals such as cesium, strontium, and uranium (156). 

A pliotornicrograpli of barium carbonate fomied by precipitation using pure soda asli (eq. 9), is shown in Figure 3. Tire av erage particle size is 1.2 ]lm. Tire exclusive use of soda ash results in a barium carbonate having included sodium that cannot be reduced below a certain level by repeated washings. Tire sodium can be detrimental if the BaCO is to be used for barium titanate production. 

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 has widespread use ia the electronics iadustry. Its high dielectric constant and the ease with which its electrical properties can be modified by combination with other materials make it exceptionally suitable for a variety of items, ie, miniature capacitors (see Ceramics as electrical materials). 

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... 

Historically, materials based on doped barium titanate were used to achieve dielectric constants as high as 2,000 to 10,000. The high dielectric constants result from ionic polarization and the stress enhancement of k associated with the fine-grain size of the material. The specific dielectric properties are obtained through compositional modifications, ie, the inclusion of various additives at different doping levels. For example, additions of strontium titanate to barium titanate shift the Curie point, the temperature at which the ferroelectric to paraelectric phase transition occurs and the maximum dielectric constant is typically observed, to lower temperature as shown in Figure 1 (2). 

Fig. 1. Effect of compositional variations on the dielectric properties of strontium titanate-barium titanate solid solutions. A, BaQ SrQ QTiO B,...

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