It is shown that the phase angle of the third harmonic of polarization response (δ3) is very sensitive to the aging state of hard, Fe-doped lead zirconate titanate [Pb(Zr,Ti)O3 or PZT] ceramics and may thus provide rich information on processes responsible for aging in hard ferroelectrics. When hard PZT ceramics experience hardening (aged state)-softening (deaged state) transition, δ3 changes by about 90° at subswitching fields and by about 180° at switching conditions. Evolution of δ3 with time, temperature and electric field amplitude during deaging suggests that at least two mechanisms of charge migration, one short-range and one long-range, may participate in the deaging process.
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Morozov et al. (2008) studied this question.