We present a critical review that encompasses the fundamentals and state-of-the-art knowledge of barium titanate-based piezoelectrics. First, the essential crystallography, thermodynamic relations, and concepts necessary to understand piezoelectricity and ferroelectricity in barium titanate are discussed. Strategies to optimize piezoelectric properties through microstructure control and chemical modification are also introduced. Thereafter, we systematically review the synthesis, microstructure, and phase diagrams of barium titanate-based piezoelectrics and provide a detailed compilation of their functional and mechanical properties. The most salient materials treated include the (Ba,Ca)(Zr,Ti)O3, (Ba,Ca)(Sn,Ti)O3, and (Ba,Ca)(Hf,Ti)O3 solid solution systems. The technological relevance of barium titanate-based piezoelectrics is also discussed and some potential market indicators are outlined. Finally, perspectives on productive lines of future research and promising areas for the applications of these materials are presented.

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The diffusionless pseudobinary phase diagram, monodomain properties, and free energy of (1 − x)Ba(Zr 0.2 Ti 0.8 )O 3 -x(Ba 0.7 Ca 0.3 )TiO 3 are computed for comparison with experimental results. Specifically, the variation of the spontaneous polarization, anisotropy energy, and free energy with respect to temperature, composition, and polarization direction are discussed relative to the results of resonant piezoelectric measurements performed over a wide compositional range as a function of temperature. The phase angle, relative permittivity, piezoelectric and coupling coefficients, and elastic compliances were used to investigate relations between the computed and measured pseudobinary phase diagrams and the measured piezoelectric and elastic properties. It was found that d 33 values along the orthorhombic to tetragonal phase boundary are ∼30% higher than those both along the rhombohedral to orthorhombic phase boundary and in the region where phases converge. It is shown that the reduction in anisotropy energy in these regions of the phase diagram is by itself insufficient to explain the measured properties. The highest small signal piezoelectric activity is found along the orthorhombic to tetragonal phase boundary due to a combination of reduced anisotropy energy, high remanent/spontaneous polarization, and increased elastic softening. The combined computed and experimental results are used to demonstrate that the interdependent behavior of these properties should be considered in the design of engineered piezoelectric ceramics.

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The electrocaloric (EC) effect in a BaTiO3 single crystal oriented along the [001] direction has been studied by direct high-resolution EC measurements in the vicinity of the fieldinduced critical point. It is shown that the observed behavior of the EC temperature change ΔT , as well as the heat capacity anomalies are in good agreement with the predictions of the Landau theory. We also present the electric field-temperature phase diagram for the field-induced paraelectric-to-ferroelectric phase transition line, derived from the calculated latent heat.

Compositional engineering with a focus on structural phase transitions has been considered as the most important approach for enhancement of the functional properties of ferroelectric materials due to the critical fluctuation of physical properties. Of special interest are electric‐field‐induced phase transitions, which can terminate in a liquid–vapor‐type critical point with a strong enhancement of functional properties. Whereas the critical point in liquid–vapor space considers changes in temperature and pressure, the critical point in this study is placed in electric field–temperature diagrams. In single crystals, temperature and electric field of a critical point are sharply defined and therefore not appealing for practical applications. However, in ceramics, it is demonstrated that the orientational dependence of the critical point leads to a broadened temperature and electric field range. The presence of a diffuse critical point in ceramics provides a conceptually novel approach for the enhancement of functional properties, such as piezoelectric and electrocaloric (EC) responses, as validated here on the example of the 0.75Bi1/2Na1/2TiO3‐0.25SrTiO3 lead‐free relaxor ferroelectric ceramics. The realization of a broad criticality range will further facilitate the development of the piezoelectric and EC materials and provide an alternative concept to manipulate the functional properties by application of an electric field.

Articles you may be interested inLarge strain response based on relaxor-antiferroelectric coherence in Bi0.5Na0.5TiO3-SrTiO3-(K0.5Na0.5)NbO3 solid solutions Structural stability and depolarization of manganese-doped (Bi0.5Na0.5)1− x Ba x TiO3 relaxor ferroelectrics J. Appl. Phys. 116, 154101 (2014); 10.1063/1.4898322Electromechanical strain and bipolar fatigue inThe electric-field-temperature phase diagram for the lead-free relaxor material (1 À x)(Bi 1/2 Na 1/2 ) TiO 3 À xBaTiO 3 (x ¼ 0.03, 0.06, and 0.09) doped with 0.5 mol% Mn (BNT-100xBT:Mn) was established. Transition lines between ergodic or nonergodic relaxor states and the field-induced ferroelectric state were determined at constant temperatures with electric-field-dependent measurements of the polarization as well as of the piezoelectric coefficient and permittivity. Near the depolarization temperature T d , the switching between two ferroelectric poling directions occurs in two steps via an intermediate relaxor state. This effect is closely related to the pinching of the ferroelectric hysteresis loop. V C 2014 AIP Publishing LLC. [http://dx.

Motivated by the long-standing unresolved enigma of the relaxor ferroelectric ground state, we performed a high-resolution heat capacity and polarization study of the field-induced phase transition in the relaxor ferroelectric single crystal Pb(Mg(1/3)Nb(2/3))O3 (PMN) oriented along the [110] direction. We show that the discontinuous evolution of polarization as a function of the electric field or temperature is a consequence of a true first order transition from a glassy to ferroelectric state, which is accompanied by an excess heat capacity anomaly and released latent heat. We also find that in a zero field there is no ferroelectric phase transition in bulk PMN at any temperature, indicating that the nonergodic dipolar glass phase persists down to the lowest temperatures.