softening and hardening transitions in ferroelectric pb(zr,ti)o3 ceramics

Hysteretic and nonlinear dielectric behaviour in ferroelectric ceramics has been of interest since 1950s, when these materials found application in various electronic devices. Presently, these phenomena concern with important areas of science, technology and engineering. In particular, nonlinearity and hysteresis are the key factors in performance, precision and accuracy of modern devices. Many theoretical and experimental studies have been aimed at understanding the origins of hysteresis and nonlinearity in ferroelectrics. Nowadays, there are several models that describe major contributions to nonlinearity and hysteresis on phenomenological, microscopical or statistical levels. These models have a limited area of applicability due to the complexity of physical processes occurring in real materials. Empirically, hysteresis and nonlinearity in ferroelectrics can be controlled by softening and hardening of the material. This is the case of most widely used ferroelectric, lead zirconate titanate (PZT). The soft compositions possess large electro-mechanical coefficients but also large hysteresis and nonlinearity while the opposite is true for the hard compositions. After fifty years since introduction of these materials, the mechanisms of softening and hardening remain poorly understood. The present study is aimed at a better understanding of the processes leading to hardening and softening of Pb(Zr,Ti)O3 ceramics in order to verify the key principles required for a more universal physical model of hysteresis and nonlinearity. Based on the present state of knowledge, such model should consider domain wall contribution to nonlinear and hysteretic polarization response and at the same time account for hardening and softening of the ferroelectric. For this purpose the well known lead zirconate titanate (PZT) ceramics doped with various concentrations of niobium (soft materials) or iron (hard materials) are chosen as a prototype of the ferroelectric system. The starting hypothesis of the thesis’ approach is that the softening and hardening are a result of electrostatic arrangement of charged defects in the ceramic bulk: the hard materials are characterized by the ordered and the soft by disordered defects. The thesis then develops in detail the idea that hardening-softening transitions in a ferroelectric system may occur under the influence of (i) dopants, depending on their type and concentration, (ii) a cyclically applied electric field, (iii) a thermal treatment, and (iv) time. The transition from microscopic order to microscopic disorder is confirmed experimentally using carefully