Hydrothermal powders of BaTiO 3 and (Ba,Ca)(Ti,Zr)O 3 contain large amounts of protons in the oxygen sublattice. The proton defects are compensated by vacancies on metal sites. When the powder is annealed, water is released and the point defects disappear in the temperature range of 100°-600°C. Metal and oxygen vacancies combine to small nanometer-sized intragranular pores. At temperatures of >800°C, the intragranular pores migrate to the grain boundaries and disappear. In multilayer ceramic capacitors that have been prepared from hydrothermal powders, the intragranular pores are preferentially collected at the inner electrodes, which results in "bloating," cracks, and delamination.
The microstructures of BME-X7R ceramics have been investigated by imaging and analytical TEM. By varying the sintering conditions (pressing, sintering temperature and atmosphere), the microstructure changes drastically, and dislocation loops can be observed. These defects most probably are caused by an ordering of oxygen vacancies in the lattice, and the density appears to be correlated to the oxygen partial pressure applied during the reoxidation step. For pressed and unpressed ceramic foils, a model for different sintering behaviors according to liquid-phase assistance is given that is based on a kinetically determined microstructure rather than thermodynamic equilibrium.
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