There has been considerable progress in the development of large strain lead-free perovskite ferroelectrics over the past decade. Under certain conditions, the electromechanical properties of some compositions now match or even surpass commercially available lead-containing materials over a wide temperature range, making them potentially attractive for non-resonant displacement applications. However, the phenomena responsible for the large unipolar strains and piezoelectric responses can be markedly different to classical ferroelectrics such as Pb(Zr,Ti)O ₃ and BaTiO ₃ . Despite the promising electromechanical properties, there is little understanding of the mechanical properties and fracture behavior, which is crucial for their implementation into applications where they will be exposed to large electrical, mechanical, and thermal fields. This work discusses and reviews the current understanding of the mechanical behavior of large-strain perovskite lead-free ferroelectrics for use in actuators and provides recommendations for further work in this important field.

The relative permittivity of polycrystalline BaTiO₃ was measured from –150 °C to 250 °C at compressive bias stresses up to −500 MPa. Mechanical loading shifted the rhombohedral-orthorhombic, orthorhombic-tetragonal, and tetragonal-cubic phase transition temperatures and produced a pronounced broadening of the dielectric softening in the vicinity of all three transitions. The inter-ferroelectric rhombohedral-orthorhombic and orthorhombic-tetragonal phase transitions were found to be less stress sensitive than the ferroelectric-paraelectric transition occurring between tetragonal and cubic phases at the Curie point. The application of compressive stress resulted in a strong suppression of the relative permittivity, such that at the highest applied stress of −500 MPa, the permittivity in the single phase regions away from the phase transitions was found to display only a weak dependence on temperature between −100 °C and 125 °C. The experimental observations closely followed the predictions of a 2-4-6 Landau polynomial wherein the dielectric stiffness and higher-order dielectric stiffness coefficients are linear functions of uniaxial stress.

Aerosol deposition (AD) is a room‐temperature film deposition method for the fabrication of scalable ferroelectric ceramic films on different substrates, which is particularly appealing for thick film energy storage applications. However, the electrical and mechanical properties of AD ferroelectric films are not yet satisfactorily understood. Here, we report the dielectric, energy storage, and mechanical properties of aerosol‐deposited BaTiO₃ (AD‐BT) thick films with nanosized grains by combining macroscopic electric measurements with indentation tests. We find that thermal annealing is an effective way to improve dielectric permittivity and polarization of the AD‐BT film, as well as to increase the hardness and Young's modulus of the film. However, crack formation in the annealed AD‐BT film is promoted in comparison to the as‐processed sample, suggesting that the interplay between the nanosized grains and release of the internal stress during annealing may have major consequences for the mechanical properties and hence should be taken into consideration in application.