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Lead-free Ba0.85Ca0.15Zr0.1Ti0.9O3 (BCZT) piezoceramics with Bi2O3 additive were synthesized using solid-state ceramic processing. Various amounts of Bi2O3 (0.05, 0.1, 0.5, and 1.0 mol%) were added after calcination, milled, compacted, and sintered with no compensation at A- or B-sites. Addition of up to 0.5 mol% Bi2O3 was found to greatly enhance the densification and increase the piezoelectric properties, while higher amounts decreased the grain size and induced relaxor-like electrical behavior, obeying the Vogel-Fulcher model. The highest properties were obtained for the BCZT with 0.1 mol% Bi2O3 sintered at 1350 °C: d33 = 325 pC/m, d33* = 509 pm/V (at 3 kV/mm), kp = 0.42, and Pr = 10.4 μC/cm2. The microstructure, phase composition, and local structure were investigated by scanning electron microscopy, X-ray diffraction, and Raman spectroscopy. The appearance of the A1g vibration mode in the Raman spectra and the shift of diffraction peaks to lower 2θ values indicate the incorporation of Bi3+ into the B-site of the perovskite BCZT structure.

The Bi1/2Na1/2TiO3-based materials exhibit the largest electric-field-induced strains among lead-free piezoceramics and are considered as promising candidates for actuation applications. A typical representative of this group is (1-x)Bi1/2Na1/2TiO3-xSrTiO3, where its excellent electromechanical properties were recently related to the existence of a core–shell microstructure. Although the latter was also reported in other Bi1/2Na1/2TiO3-based ceramics, the formation mechanism remains unknown. In the present work we therefore first investigated the solid-state reaction occurring during calcination using simultaneous thermogravimetric analysis, X-ray diffraction, scanning and transmission electron microscopy. The reaction occurred in two steps, whereby the cores and shells had different formation reaction temperatures, which resulted in a metastable heterogeneous microstructure. Furthermore, a series of sintered samples with different relative densities, grain sizes, and core densities was prepared. Modifications of these microstructural parameters resulted in variation of the maximal strain by 17% and in the electric-field required to trigger the phase transitions by 38%.