Ceramic, single-phase

Ferroelectric Ceramic—Polymer Composites. The motivation for the development of composite ferroelectric materials arose from the need for a combination of desirable properties that often caimot be obtained in single-phase materials. For example, in an electromechanical transducer, the piezoelectric sensitivity might be maximized and the density minimized to obtain a good acoustic matching with water, and the transducer made mechanically flexible to conform to a curved surface (see COMPOSITE MATERIALS, CERAMiC-MATRix). 

Most pairs of homopolymers are mutually immiscible, so that phase diagrams are little used in polymer science... another major difference between polymers on the one hand, and metals and ceramics on the other. Two-phase fields can be at lower or higher temperatures than single-phase fields... another unique feature. 

The quality of a ceramic sample is a function of the degree to which it consists of the desired product. An essential tool for the characterization of a polycrystalline sample is powder X-ray diffraction. The powder pattern is a fingerprint of the sample. For a sample to be declared single phase, all low angle peaks (below 60 20 for CuKq radiation) which are above the noise must be accounted for. Powder X-ray diffraction is often unable to see impurity phases present below the 5% level. Visual inspection (using a microscope)... 

It should be clear from the above sections that the idealized formula Bi2Sr2Can iCun02n+4 with n = 1, 2, and 3 does not accurately describe the actual stoichiometry of single-phase ceramic samples. Substantial cation intersite substitution and/or vacancies probably occur in these materials. The role of these defects in the stabilization of the superconducting phases and their contribution to the superconducting properties is still being investigated. 

However, at this point we should note that the electron-doped superconductors are not strictly single phase. Electron diffraction studies on both single crystals and ceramic superconducting samples have shown that they almost invariably, contain two phases one phase has the undistorted T -Nd2Cu04 structure,... 

The hosts for ACT and REE immobilization are phases with a fluorite-derived structure (cubic zirconia-based solid solutions, pyrochlore, zirco-nolite, murataite), and zircon. The REEs and minor ACTs may be incorporated in perovskite, monazite, apatite-britholite, and titanite. Perovskite and titanite are also hosts for Sr, whereas hollandite is a host phase for Cs and corrosion products. None of these ceramics is truly a single-phase material, and other phases such as silicates (pyroxene, nepheliiie, plagioclase), oxides (spinel, hibonite/loveringite, crichtonite), or phosphates may be present and incorporate some radionuclides and process contaminants. A brief description of the most important phases suitable for immobilization of ACTs and REEs is given below. 

The ideal condition for carrying out a solid state reaction in order to obtain a homogeneous product in the shortest time at the lowest possible temperature is to ensure homogeneous mixing of the reactants on an atomic scale. This, however, cannot be achieved in the ceramic method or its modifications. The only way to achieve this is to prepare a single phase (a chemical compound) in which the reactants are present in... 

H.E. Exner. Principles of single phase sintering. Reviews on Powder Metallurgy and Physical Ceramics, 1 1-237, 1979. 

In the past, most solids were prepared on a large scale by standard ceramic techniques, in which accurate control of the composition, as well as uniform homogeneity of the product, were not readily achieved. Unfortunately, this has sometimes led to uncertainty in the interpretation of the physical measurements. In recent years more novel methods have been developed to facilitate the reaction between solids. This is particularly true for the preparation of polycrystalline samples, on which the most measurements have been made. It is of utmost importance to prepare pure single-phase compounds, and this may be very difficult to attain. Even for a well-established reaction, careful control of the exact conditions is essential to ensure reproducible results. For any particular experiment, it is essential to devise a set of analytical criteria to which each specimen must be subjected. It will be seen from the solid-state syntheses included in this volume that one or more of the following common tests of purity are used to characterize a product. 

On heating to higher temperatures, no crystalline phases are observed until anatase crystallizes at 1000 °C. At 1400 °C, anatase, rutile and crystobalite are the only products. No single-phase material is obtained. The lack of correspondence between the TGA ceramic yield and the theoretical ceramic yield calculated for TiSi04 presages this problem. The exact reasons for the formation of a mixed-oxide phase are unknown at the moment, but they clearly contrast with the behavior of the Zr and Hf analogs. 

Figure 13.6 Piezoelectric coefficient d and tan<5p of a single phase Bi4Ti30i2 ferroelectric ceramic with highly anisotropic grains, at room temperature. On the right are shown charge-pressure hysteresis loops at selected frequencies, with a clockwise hysteresis at 0.07 Hz and counter-clockwise hysteresis at 70 Hz. See [17] for details.

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