BiFeO3 with perovskite structure is a well-known material that has both ferroelectric and antiferromagnetic properties called multiferroics. However, leaky electrical properties and difficulty of controlling stoichiometry due to Bi volatility and difficulty of obtaining high relative density due to high dependency on the ceramic process are issues for BiFeO3 applications. In this work we investigated the sintering behavior of samples with different stoichiometries and sintering conditions. To understand the optimum sintering conditions, nonstoichiometric Bi1±xFeO3±δ ceramics and Ti-doped Bi1.03Fe1-4x/3TixO3 ceramics were synthesized by a conventional solid-state route. Dense single phase BiFeO3 ceramics were successfully fabricated using a two-step sintering and quenching process. The effects of Bi volatility on microstructure were determined by Bi-excess and Ti doping. Bi-excess increased grain size, and Ti doping increased sintering temperature and decreased grain size. It should be noted that Ti-doping suppressed Bi volatility and stabilized the BiFeO3 phase.
The effects of an excess of Bi on the piezoelectric and dielectric properties of 0.60Bi1+xFeO3-0.40BaTiO3 (x = 0, 0.01, 0.03, 0.05, 0.07) were investigated. The ceramics were processed through a conventional solid state reaction method and then quenched after sintering at different temperatures in the range of 980~1070 oC. A single perovskite structure without any secondary phase was confirmed for all compositions and temperatures. It was found that excess Bi reduced the sintering temperatures, acted as a sintering aid and enhanced the properties in combination with quenching. Curie temperature (TC) was found to slightly increase due to the presence of excess Bi; electrical properties were also improved by quenching. At x = 0.03 and 1030 oC, remnant polarization (2Pr) was as high as 45.4 μC/cm2 and strain at 40 kV/cm was up to 0.176 %.
The effects of Nb doping on the crystal structure, microstructure, and dielectric ferroelectric and piezoelectric properties of (Bi0.5Na0.5)0.935Ba0.065Ti(1-x)NbxO3-0.01SrZrO3 (BNBTNb-SZ, with x = 0, 0.01 and 0.02) ceramics have been investigated. X-ray diffraction patterns revealed that all ceramics have a pure perovskite structure with tetragonal symmetry. The grain size of the ceramics slightly decreased and a change in grain morphology from square to spherical shape was observed in the Nb-doped samples. The maximum dielectric constant temperature (Tm) increases with increasing amount of Nb; however, ferroelectric-relaxor transition temperature (TF-R) and maximum dielectric constant (εm) values decrease gradually. Nb addition disrupted the polarization hysteresis loops of the BNBT-SZ ceramics by leading a reduction in the remnant polarization coercive field and piezoelectric constant.