Dielectric Titanate Ceramics : Contributions From Uncommon Substituents And Microstructural Modifications

Abstract

This thesis deals with the investigations on the dielectric properties of polycrystalline ceramics having uncommon substitutions in barium titanate and other related phases of BaTiO3-CaTiO3, MgTiO3-CaTiO3 and MgTiO3-BaTiO3 systems. After presenting a brief introduction on the ceramic materials studied in terms of their crystal structures, electrical properties, nonstoichiometry and microstructural characteristics. The thesis describes the synthesis of the ceramics and the methodology of different techniques utilized in characterizing the samples. Barium calcium titanate was synthesized through novel wet chemical techniques and the dielectric properties of calcium substituted barium titanate do not reveal multi-site occupancy whereas they are predominantly influenced by the A/B cationic ratio. The role of transition metals of the 3d series from vanadium (Z=23) to zinc (Z=30) in modifying the crystallographic phase content, microstructure and the dielectric properties of BaTiO3 ceramics containing 10 at% impurities were studied. All the transition metals brought about the phase conversion to hexagonal BaTiO3, although no systematics could be arrived at relating the hexagonal content to the 3d electronic configuration of the impurities. The relaxor dielectrics arising from the titanate solid solution with uncommon substitution and its interconversion to normal ferroelectrics is studied. The effects of cationic substitutions of iron and niobium for titanium in BaTiO3 pervoskite lattice in crystal symmetry and dielectric properties were investigated. The above dielectric characteristics are comparable in a converse way to those of the well known Pb(Mg1/3Nb2/3)O3-PbTiO3 system wherein the relaxor behaviour occurs within the lower lead titanate compositional limits. The modification in -T characteristics of positive temperature coefficient in resistance (PTCR) by the addition of segregative additives such as B2O3, Al2O3 etc in BaTiO3 and its conversion to grain boundary layer capacitance is studied. The presence of Al-related hole centers at the grain boundary regions resulted in charge redistribution across the modified phase transition temperatures due to symmetry-related vibronic interactions, which result in broad PTCR characteristics extending to higher temperatures. The processing of high permittivity ceramics by the manipulation of microstructural features in semiconducting BaTiO3 is studied wherein the grain boundary layer effect superimposed with the contributions from the barrier layers formed during electroding related to microstructure is proposed to be responsible for the unusual high permittivity in semiconducting BaTiO3. The influence of Mg2+ as a substituent in modifying the crystallographic phase contents, microstructure and the dielectric properties of (Ba1-xMgx)TiO3 ceramics, (x ranging from zero to 1.0 ) is studied. The results point to the dual occupancy of Mg2+ both in A and B sublattice and the role of oxygen vacancy as well as (Ti3+ –VO) defects in stabilization of hexagonal phase to lower temperatures. The microwave dielectrics of the BaMg6Ti6O19 phase formed in the compositional range of x=0.4 to 0.7 was investigated for suitable application in microwave dielectrics. Extensive miscibility between the ilmenite-type MgTiO3 and perovskite-type CaTiO3 over a wide compositional range is brought about by the simultaneous equivalent substitution of Al3+ and La3+. The resulting Mg1-(x+y)CaxLay)(Ti1-yAly)O3 ceramics exhibit improved microwave dielectric properties by way of high permittivity, low TCK and high quality factor. The elemental distribution reveals the complexity in the Mg/Ca distribution and its correlation with the solid state miscibility as well as dielectric properties. Microwave dielectric property of Mg4Al2Ti9O25 which is detected as secondary phase is studied in detail.