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 Title: Effect of minor phase additions on the microstructure and dielectric properties of barium titanate ceramics Author(s): Armstrong, Timothy Robert Doctoral Committee Chair(s): Buchanan, Relva C. Department / Program: Materials Science and Engineering Discipline: Materials Science and Engineering Degree Granting Institution: University of Illinois at Urbana-Champaign Degree: Ph.D. Genre: Dissertation Subject(s): Materials Science and Engineering Abstract: Grain growth in BaTiO$\sb3$ can be significantly inhibited by insoluble or slightly soluble second phase additions such as ZrO$\sb2$, or by fluxes in the CaO$\cdot$Al$\sb2$O$\sb3\cdot$B$\sb2$O$\sb3$ system. SEM and TEM observations revealed enhanced microstructural uniformity in these specimens. For the ZrO$\sb2$ modified BaTiO$\sb3$ system, Zr diffused into the BaTiO$\sb3$ lattice when sintered above 1320$\sp\circ$C, resulting in a chemical modification of the tetragonal structure and the development of core-shell grains. TEM analysis of ZrO$\sb2$ modified BaTiO$\sb3$ sintered at temperatures less than 1320$\sp\circ$C, revealed the presence of ZrO$\sb2$ at the grain boundaries as discrete particles ($\approx$0.03 $\mu$m). Modification of BaTiO$\sb3$ with organically derived ZrO$\sb2$ resulted in the formation of substantial chemical inhomogeneities in the microstructure. These inhomogeneities were observed by TEM as large ZrO$\sb2$ particles ($>$75nm) and as a Ti and Zr rich phase, Ba$\sb2$(ZrTi)$\sb5$O$\sb{12}$. In the CaO$\cdot$Al$\sb2$O$\sb3\cdot$B$\sb2$O$\sb3$ modified BaTiO$\sb3$, fluxed samples had an amorphous grain boundary phase, which became microcrystalline upon addition of ZrO$\sb2$. For these samples core-shell grains were observed in specimens sintered at 1175$\sp\circ$C for 2h. More noticeable in the samples were regions near the grain boundaries where significant diffusion of the flux constituents into the BaTiO$\sb3$ occurred, resulting in the formation of a fine domain structure. These fine-grained samples were accompanied by an increase in the internal stress level with decreasing grain size and increasing concentration of core-shell grains. The core-shell grains are comprised of a core of unmodified BaTiO$\sb3$ and a shell of Zr modified BaTiO$\sb3$, Ba(Zr$\sb{\rm x}$Ti$\sb{\rm 1-x}$)O$\sb3$. This condition leads to high internal stress levels, arising from the thermal expansion mismatch between the core and the shell. The stress was found to be compressive in nature and dependent on temperature, time and grain size. The combination of internal stress and core-shell grains resulted in a decrease in the axial ratio $(c/a)$ with decreasing grain size and an essentially flat permittivity response with temperature, a condition consistent with a distribution of Curie points within the ceramic. These modified dielectrics also show a decrease in the aging rate with increasing temperature, resulting from the internal stress condition. Issue Date: 1989 Type: Text Language: English URI: http://hdl.handle.net/2142/19069 Rights Information: Copyright 1989 Armstrong, Timothy Robert Date Available in IDEALS: 2011-05-07 Identifier in Online Catalog: AAI9010797 OCLC Identifier: (UMI)AAI9010797
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