Ferroelectric ceramics were born in the early 1940s with the discovery of the phenomenon of ferroelectricity as the source of the unusually high dielectric constant in ceramic barium titanate capacitors. Since that time, they have been the heart and soul of several multibillion dollar industries, ranging from high-dielectric-constant capacitors to later developments in piezoelectric transducers, positive temperature coefficient devices, and electrooptic light valves. Materials based on two compositional systems, barium titanate and lead zirconate titanate, have dominated the field throughout their history. The more recent developments in the field of ferroelectric ceramics, such as medical ultrasonic composites, high-displacement piezoelectric actuators (Moonies, RAINBOWS), photostrictors, and thin and thick films for piezoelectric and integrated-circuit applications have served to keep the industry young amidst its growing maturity. Various ceramic formulations, their form (bulk, films), fabrication, function (properties), and future are described in relation to their ferroelectric nature and specific areas of application.

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Ferroelectric ceramics : History and technology

The dielectric relaxation of a solid solution of 10‐mol % lead titanate in lead magnesium niobate is found to be similar to the magnetic relaxation in spin‐glass systems.1–3 Based on this analogy, it is proposed that the relaxor ferroelectric is a polar‐glassy system which has thermally activated polarization fluctuations above a static freezing temperature. An activation energy and freezing temperature of 0.0407 eV and 291.5 K, respectively, were found by analyzing the frequency dependence of the temperature of the dielectric maximum using the Vogel–Fulcher relationship.4,5 It has also been shown that a macroscopic polarization is sustained on heating up to this freezing temperature. A coupling between nanometer scale clusters is believed to control the kinetics of the fluctuations and the development of a frustration as the system freezes into states of local equilibrium. The possibility of an orientational freezing associated with the ferroelastic nature of the nanosized polar regions in the rhombohedr...

Freezing of the polarization fluctuations in lead magnesium niobate relaxors

A comprehensive review is presented of the extractive metallurgy of rare earths. The topics covered are: world rare earth resources and production; ore processing and separation of individual rare earths; reduction, refining, and ultrapurification of rare earth elements; methods for rare earth materials analysis; and a selection of the numerous rare earth applications. World rare earth reserves are abundant and would last for well beyond the next century. However, all of the 16 naturally occurring rare earth elements are not equally distributed in the ore minerals. This, compounded with the problems specific to the isolation and recovery of each of the rare earths, sets the stage for an unequal rare earth availability. The close chemical similarity of rare earths looses its importance when divergent physical properties determine the processes for rare earth element reduction and refining. The rare earth metals, alloys, and compounds have been as pure as could be determined. Finally, the commercial...

Extractive Metallurgy of Rare Earths

Transparent ferroelectric ceramic materials suitable for a variety of electrooptic applications were found in the quaternary (Pb,La)(Zr,Ti)O3 system. These PLZT materials are prepared from mixed oxides and hot-pressed typically at 1100°C for 16 h at 2000 psi. Modifying the lead zirconate-titanate system with lanthana linearly reduces the Curie point with increasing lanthana. Transmission measurements in the visible and infrared show that these materials exhibit a nearly constant response from the absorption edge of 0.37 μ to ∼6 μm. The highest transmission values, essentially 100% (neglecting reflection losses of ∼18%) for thin polished plates, were noted for compositions containing 8 at.% La or more. Specific compositions within the system display electrooptic memory or conventional linear or quadratic electrooptic effects; on the basis of the magnitude of the electrooptic effects, they compare quite favorably with single crystals.

Hot‐Pressed (Pb,La)(Zr,Ti)O3 Ferroelectric Ceramics for Electrooptic Applications

The processing, electromechanical properties, and microstructure of lead zirconate titanate (PZT) ceramics over the grain-size range of 0.1-10 μm were studied. Using measurements over a large temperature range (15-600 K), the relative role of extrinsic contribution (i.e., domain-wall motion) was deduced to be influenced strongly by the grain size, particularly for donor-doped PZT. Analytical transmission electron microscopy studies were conducted to investigate the trend in domain configurations with the reduction of grain size. The correlations between domain density, domain variants, domain configurations (before and after poling), spontaneous deformation, and the elastodielectric properties were qualitatively discussed, leading to new insights into the intrinsic and extrinsic effects and relevant size effects in ferroelectric polycrystalline materials.

Intrinsic and Extrinsic Size Effects in Fine-Grained Morphotropic-Phase-Boundary Lead Zirconate Titanate Ceramics

Physical, electrical, and optical properties of selected compositions within the lead lanthanum zirconate-titanate (PLZT) system are presented, including chemically and thermally etched microstructures, examples of residual porosity defects, temperature dependence of remanent polarization and coercive field, lateral switching strains, and thermal expansion and optical transmission data. Optical-quality ceramics were produced by stringent raw material selection and improved ceramic processing and hot-pressing. Optimum results were obtained from starting oxides with higher purity (99.9%) and smaller particle size (<2 μm) than those used in previous investigations. These oxides were processed by methods developed to minimize segregation and promote chemical homogeneity and hot-pressed at temperatures (1050° to 1250°C) higher than those used previously to remove residual porosity.

Improved Hot-Pressed Electrooptic Ceramics in the (Pb,La)(Zr,Ti)O3 System

Grain growth and densification were studied in a hot-pressed ferroelectric composition of 65/35 (Zr/Ti molar ratio) lead zirconate-lead titanate containing 2 at.% bismuth. The grain growth and densification rate processes were measurable from 1050° to 1300°C and from 700° to 1100°C, respectively. Grain growth as a function of time followed a ⅓ power law (D (grain size) =kt⅓). An activation energy of 95 kcal/mole was calculated. Densification was a two-stage process as a function of time: a rapid initial stage and a slower final stage. The initial stage of densification behaved viscously with an activation energy of 36.7 kcal/mole. Grain boundary sliding and the Nabarro-Herring mechanism of stress-directed movement of vacancies are suggested as the densification mechanisms. Results indicated that densification is sensitive to stoichiometry and to additives.

G. H. Haertling

Papers

Hot‐Pressed (Pb,La)(Zr,Ti)O3 Ferroelectric Ceramics for Electrooptic Applications

Improved Hot-Pressed Electrooptic Ceramics in the (Pb,La)(Zr,Ti)O3 System

Grain Growth and Densification of Hot‐Pressed Lead Zirconate‐Lead Titanate Ceramics Containing Bismuth