Abstract

Appearance of the polar nanoregions (PNR) and their manifestation in the dielectric spectra is discussed for lead-free Ba(ZrxTi1−x)O3 (BZT-x) and (Na1/2Bi1/2)TiO3 (NBT) ceramics. Phonon softening is not as pronounced as in the lead-based relaxors, but the relaxation contribution is dominating in all cases, caused by the dynamics of the off-centred ions (Ti4+, Bi3+, Pb2+). In the lead-based relaxors, where there is no relation between the quenched chemical clusters at the B-sites and PNR, which concern the A-site Pb-ion correlations, the relaxation dynamics follows the Vogel–Fulcher behaviour with a clear freezing. However, in BZT and NBT, the PNR are smaller, since they are localised within the small quenched chemical clusters of BaTiO3 and BiTiO3, respectively. Their dynamics is Arrhenius-like, which indicates hopping of the off-centred Ti4+ and Bi3+ ions, respectively, without their complete freezing. BZT can be classified as a dipolar glass and NBT as a nanoscopic ferroelectric with peculiar Bi-ion dynamics.

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