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.

/pdf/ferroelectric-ceramics-history-and-technology-40j9enkrwl.pdf

Ferroelectric ceramics : History and technology

A revised regular solution-type thermodynamic model for twelve-component silicate liquids in the system SiO2-TiO2-Al2O3-Fe2O3-Cr2O3-FeO-MgO-CaO-Na2O-K2O-P2O5-H2O is calibrated. The model is referenced to previously published standard state thermodynamic properties and is derived from a set of internally consistent thermodynamic models for solid solutions of the igneous rock forming minerals, including: (Mg,Fe2+,Ca)-olivines, (Na,Mg,Fe2+,Ca)M2 (Mg,Fe2+, Ti, Fe3+, Al)M1 (Fe3+, Al,Si)2TETO6-pyroxenes, (Na,Ca,K)-feldspars, (Mg,Fe2+) (Fe3+, Al, Cr)2O4-(Mg,Fe2+)2 TiO4 spinels and (Fe2+, Mg, Mn2+)TiO3-Fe2O3 rhombohedral oxides. The calibration utilizes over 2,500 experimentally determined compositions of silicate liquids coexisting at known temperatures, pressures and oxygen fugacities with apatite ±feldspar ±leucite ±olivine ±pyroxene ±quartz ±rhombohedral oxides ±spinel ±whitlockite ±water. The model is applicable to natural magmatic compositions (both hydrous and anhydrous), ranging from potash ankaratrites to rhyolites, over the temperature (T) range 900°–1700°C and pressures (P) up to 4 GPa. The model is implemented as a software package (MELTS) which may be used to simulate igneous processes such as (1) equilibrium or fractional crystallization, (2) isothermal, isenthalpic or isochoric assimilation, and (3) degassing of volatiles. Phase equilibria are predicted using the MELTS package by specifying bulk composition of the system and either (1) T and P, (2) enthalpy (H) and P, (3) entropy (S) and P, or (4) T and volume (V). Phase relations in systems open to oxygen are determined by directly specifying the fo2 or the T-P-fo2 (or equivalently H-P-fo2, S-P-fo2, T-V-fo2) evolution path. Calculations are performed by constrained minimization of the appropriate thermodynamic potential. Compositions and proportions of solids and liquids in the equilibrium assemblage are computed.

Chemical mass transfer in magmatic processes IV. A revised and internally consistent thermodynamic model for the interpolation and extrapolation of liquid-solid equilibria in magmatic systems at elevated temperatures and pressures

https://zirconia.typepad.com/files/zirconia-as-a-ceramic-biomaterial---piconi---biomaterials-1999.pdf

Zirconia as a ceramic biomaterial

Use of CeO2-based oxides in the three-way catalysis

The theory of phase separation from a single phase fluid by a spinodal mechanism is given. The predicted structure may be described in terms of a superpositioning of sinusoidal composition modulations of a fixed wavelength, but random in amplitude, orientation, and phase. Sections through a calculated structure are shown. These show that the structure has many of the geometrical features found in phase separable glasses, in particular the high degree of connectivity among particles of each phase.

Phase Separation by Spinodal Decomposition in Isotropic Systems

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Phase diagrams for ceramists

The effect of small oxide additions on the polymorphism of Bi2O3 was studied by means of high-temperature x-ray diffractometry. Solidus and occasional liquidus temperatures were approximated, so that tentative partial phase diagrams for 33 oxide additions were constructed. Only the monoclinic and the cubic forms of Bi2O3 were found to be stable. Other phases, frequently reported by previous investigators, such as tetragonal and body-centered cubic (b.c.c.), were shown to form metastably from cooled liquid or cubic. An impure b.c.c. phase of distinct but variable composition appeared in systems of ZnO, PbO, B2O3, Al2O3, Ga2O3, Fe2O3, SiO2, GeO2, TiO2, and P2O5. The impure b.c.c. phase in the systems with SiO2, GeO2, and TiO2 melted congruently about 100 °C above the m.p. of Bi2O3. The impure b.c.c. phase was formed metastably in systems with Rb2O, NiO, MnO, CdO, V2O5, and Nb2O5; the conditions of formation were dependent on composition, preparation, and heating schedules. The impure b.c.c. phases, both stable and metastable, had smaller unit cell dimensions than that of pure Bi2O3.

/pdf/polymorphism-of-bismuth-sesquioxide-ii-effect-of-oxide-hdfz1gjjtp.pdf

Polymorphism of Bismuth Sesquioxide. II. Effect of Oxide Additions on the Polymorphism of Bi2O3.

Phase diagrams for ceramists 1975 Supplement

The phase diagram for the system Bi2O3-B2O3 has been determined experimentally. The melting point of Bi2O3 has been redetermined as 825° C with an estimated overall uncertainty of about ±3°C, and the molal heat of fusion of Bi2O3, calculated from the slope of the liquidus curve, is 2050 cal per mole. The system contains a body-centered cubic phase of approximate composition 12Bi2O3·B2O3, which melts incongruently at 632°C. Four congruently melting compounds exist in the system: 2Bi2O3· B2O3·5B2O3, Bi2O3·3B2O3, and Bi2O3·4B2O3, with melting points, respectively, of 675°, 722°, 708°, and 715°C. The Bi2O3·4B2O3 compound exhibits a sluggish transformation at 696°C. Compositions containing up to 97.5 wt% (85 mole %) Bi2O3 can be partly or totally quenched to glass. Indices of the quenched glasses are greater than 1.74. A region of liquid immiscibility extends at 709°C from almost pure B2O3 to 19.0 mole % Bi2O3. The extent of immiscibility theoretically calculated agrees with the experimentally determined value when 1.20 A is used for the ionic radius of Bi3+.

Ernest M. Levin

Papers

Phase diagrams for ceramists

Polymorphism of Bismuth Sesquioxide. II. Effect of Oxide Additions on the Polymorphism of Bi2O3.

Phase diagrams for ceramists 1975 Supplement

The System Bi2O,—B2O3

Polymorphism of ABO3 type rare earth borates