Stress-induced phase transition in lead-free relaxor ferroelectric composites

Piezoelectric materials are considered an enabling technology generating an annual turnover of about 20 billion $. At present, lead-based materials dominate the market with the known risk to health and environment. One of the three key competitors for their replacement is the class of sodium bismuth titanate (NBT)-based relaxor ferroelectrics, the use of which is limited by thermal depolarization. An increased thermal stability has recently been experimentally demonstrated for composites of Na_1/2Bi_1/2TiO₃-6BaTiO₃ with ZnO inclusions (NBT-6BT:xZnO). However, the exact mechanism for this enhancement still remains to be clarified. In this study, piezoresponse force microscopy and ²³Na NMR spectroscopy were used to demonstrate that the incorporation of ZnO leads to a stabilization of the induced ferroelectric state at room temperature. Temperature-dependent measurements of the relative dielectric permittivity ε′(T), the piezoelectric coefficient d₃₃ and the strain response revealed an increase of the working temperature by 37 °C. A simple mechanics model suggests that thermal deviatoric stresses stabilize the ferroelectric phase and increase, as well as broaden, the temperature range of depolarization. Our results reveal a generally applicable mechanism of enhancing phase stability in relaxor ferroelectric materials, which is also valid for phase diagrams of other ceramic matrix composites.