Quenching-driven advancements in functional properties of high-temperature lead-free Sc, Ga modified 0.67BiFeO3-0.33BaTiO3 relaxor ceramics

Abstract

The processing method is one of the most important deciding factors in the fabrication of BiFeO3–BaTiO3 (BF-BT) based piezoceramics because of the Bi2O3 volatization. It significantly influences the functional properties, including the piezoelectric coefficients, dielectric properties, and microstructure. This study presents a significant advancement in the realm of high-temperature lead-free piezoelectric ceramics in terms of understanding effects of processing method on functional properties. In this light, a novel ceramic solid-solution, 0.67{Bi(Fe0.97Ga0.03)1-xScxO3}-0.33(BaTiO3) with x ≤ 0.07, incorporating Scandium (Sc) and Gallium (Ga) modifications, was meticulously designed and synthesized. Impact of two distinct sintering methods, namely air quenching (AQ) and closed sintering (CS) on the structure and properties of the developed materials are investigated. X-ray diffraction (XRD) and Fourier-transform infrared (FTIR) analysis verified the formation of pure perovskite phases with successful incorporation of Sc and Ga into the 0.67BF-0.33BT lattice. The FTIR analysis revealed a sharp absorptive band in the 590-604 cm−1 range, corresponding to the signature of stretching and bending vibrations of (Ti/Fe)O6 octahedra. Rietveld structure refinement confirmed the coexistence of pseudocubic (Pm-3m) and rhombohedral (R3c) phases in AQ samples, with predominantly pseudocubic phase, while CS samples closely approximated the pseudocubic phase. The microstructure of the samples exhibits small average grain size distribution (<2 μm). Temperature-dependent dielectric measurements show strong frequency dispersion in the dielectric permittivity with broadened transition peaks. The ferroelectric studies reveal low Pr and Ec values. These observations suggest a ferroelectric relaxor-like behavior of the developed materials. Moreover, the permittivity peaks maxima (Tm) temperature corresponding to CS samples for 0.04<x < 0.07 is less than 390 °C at 10 Hz while it is above 400 °C for AQ samples. The results of our study reveal that AQ samples exhibit superior electrical and ferroelectric properties as compared to the CS samples. The AQ samples demonstrate improvements in Tm (>400 °C), d33(∼35 pC/N), Pr (∼4–11 μC/cm2), PS (∼8–21 μC/cm2), Ec (∼13–25 kV/cm) with reduced dielectric loss, and a better dielectric constant over a wide temperature range.