Enhanced Bipolar Strain and Electrocaloric Response in Gadolinium/Tantalum Co-Substituted Sodium Bismuth Titanate Lead-Free Ceramics

Abstract

High performance piezoelectric materials with an ABO3 perovskite structure have received growing attention in recent research due to their technological applications in sophisticated research, medical and defence devices like piezoelectric sensors, transducers, ultrasonic motors, nano-positioners, actuators and imaging devices, etc. The technical utility of these materials stems from the various possibilities they offer for cation substitution in the A (or) B sites, which provide valuable opportunities for the optimization and tailoring of desired properties. To date, lead based perovskites, such as lead zirconate titanate (PZT), PZN-PT, and PMN-PT materials, have been extensively investigated in the literature. Although lead based materials exhibit highest piezoelectric coefficients, their wide-scale application has often been hampered by considering the toxicity of lead and its effect on environment and health. This triggered the search for alternative materials that could replace the lead-based ceramics and results in less-hazardous production methods, use and recycling. This has led to a continuous search of potentially attractive alternative lead-free ceramic materials to their counterpart lead based materials for specific applications. Among various kinds of lead-free piezoelectric materials, Na0.5Bi0.5TiO3 (NBT)-based materials are considered to be promising candidates for replacing the lead-based materials. They have been extensively investigated by the condensed materials physics community because of their complicate phase transitions and superior piezo-response. Compared to various chemical substitutions, tantalum (Ta) substitution provides superior electro-strain for the NBT- based ferroelectrics, while the effect of tantalum oxide additive was rarely reported. Gd3+ and Ta5+ co-substituted (Na0.5Bi0.497Gd0.003)Ti1-xTaxO3 (NBGT-Tax) lead-free piezoelectric ceramics are synthesized by using hydrothermal technique. The influence of Ta5+ substitution on the sintering, microstructure, phase transition, and various electrical properties of NBGT ceramics was investigated. Tantalum substitution has no remarkable effect on the microstructure and densification within the studied doping composition. The X-ray diffraction studies revealed that both NBGT-Tax (x=0.000) and NBGT-Tax (x=0.003) ceramics exhibited single phases monoclinic crystal structure with Cc phase. However, with substitution of tantalum the antiferroelectric phase zone gets broader. Simultaneously, the temperature for a ferroelectric to antiferroelectric phase transition is reduced along with an increase in temperature for a transition from antiferroelectric phases to paraelectric phases. This results indicate that tantalum occupies B site of the perovskite structure behaving as a donor, producing A-site cation vacancies. The undoped NBGT ceramics shows good ferroelectric and piezoelectric properties (remnant polarization Pr = 34.2 μC/cm2). The value of remnant polarization was found to increase with Ta substitution along with an increase in coercive field as shown in the figure attached. This is because of the ferroelectric properties being influenced by composition and its homogeneity, defects, external field and orientation of domains, which eventually contributed to the materials response. Meanwhile, the addition of Ta leads to an increase in the electro-strain, together with a higher normalized strain. Moreover, the materials with temperature dependent polarization can be used for solid state cooling applications. The NBGT-Tax compositions shows decrement in the remnant polarization with the increasing temperature which causes increment in the change in entropy. Consequently, the material exhibits the conventional electrocaloric effect (ECE). This simultaneous presence of large field-induced bipolar strain and ECE response along with isothermal change in entropy opens window for great potential applications in the field of electronic devices. Figure 1