Effect of Different Ca²⁺ and Zr⁴⁺ Contents on Microstructure and Electrical Properties of (Ba,Ca)(Zr,Ti)O₃ Lead-Free Piezoelectric Ceramics

In the preparation of (Ba,Ca)(Zr,Ti)O3 lead-free piezoelectric ceramics, different Ca2+ and Zr4+ contents will greatly affect the phase structure, microstructure, and electrical properties of the ceramics. XRD shows that all samples have pure perovskite phase structure, and the (Ba0.85Ca0.15)(ZryTi1−y)O3 ceramics morphotropic phase boundary region from tetragonal phase to rhombohedral phase near 0.08 ≤ y ≤ 0.1. From the dielectric temperature curve, the phase transition temperature (TO-T) was found near room temperature at 0.12 ≤ x ≤ 0.18 for the (Ba1−xCax)(Zr0.1Ti0.9)O3 ceramics. Both Ca2+ and Zr4+ increase have a significant decrease on the Curie temperature Tc. All samples were revealed as relaxers with diffusivities in the range 1.29 ≤ γ ≤ 1.82. Different from the undoped ceramics, ceramics doped with Ca and Zr ions exhibit saturated P–E hysteresis loops, and their ferroelectric properties are significantly optimized. In particular, the (Ba0.85Ca0.15)(Zr0.1Ti0.9)O3 ceramic demonstrated optimal properties, namely d33 = 330 pC/N, kp = 0.41, εr = 4069, Pr = 4.8 μC/cm2, and Ec = 3.1 kV/cm, indicating that it is a viable lead-free piezoelectric contender. Variations in Ca and Zr content have a significant effect on the crystal grain sizes and densities of ceramics, which is strongly associated with their piezoelectricity.