The influence of synthesis parameters and dopants on structure and properties of barium bismuth-titanate ceramics

In this doctoral dissertation the influence of synthesis conditions, i.e. mechanical activation on the structure formation and properties of barium bismuth titanate ceramics was studied. The influence of La3+, as an isovalent dopant and Nb5+, as a donor dopant on the dielectric and electrical properties on this type of ceramics was also systematically studied. An equimolar BaO, TiO2 and Bi2O3 powder mixture was mechanically activated in a planetary mill for 0 - 6 h. The dynamics of new phases formation was monitored by X-ray diffraction. It was found that 6 h of milling leads to the formation of layered Aurivillius structure. Oxide mixtures mechanically activated for 6 h was heat treated at 850°C for 1 h when BaBi4Ti4O15 was formed. Powders of pure and doped barium bismuth titanate were obtained by conventional solid state reaction method. Determination of appropriate structures in powders obtained by this procedure was followed by X-ray diffraction. The mechanism of the formation of barium bismuth titanate was established. The temperature at which it forms a pure phase was specified to be 950°C after 1 h of sintering. The average particle size of powders obtained by conventional method and mechanical activated powder was determing using laser diffraction measurement. Based on these results and the results of scanning electron microscopy a significant influence of mechanical activation on the reduction of pawder particle size was noticed, leading to an increase of reactivity. Using uniaxial press and isothermal sintering at temperatures of 1120-1150°C (depending on the composition) ceramic samples of pure and doped barium bismuth titanate were obtained. Electrical measurements of the obtained materials were performed in the temperature range from 27 to 727°C and the frequency range of 1.21 kHz to 1 MHz, in air atmosphere. The results of dielectric measurements indicate a significant change in the dielectric constant value with the addition of dopants. Phase transition temperature shift and broadening of peaks were noticed as well as the increase of the degree of phase transition relaxation due to the incorporation of ions in the crystal structure of compounds. Exploring the influence of mechanical activation, it was confirmed that the mechanical activation effects the reduction of grain size and thus the change of dielectric constant value at the Curie temperature. Using a modified Curie-Weiss law was observed that mechanical activation increases the degre