Effect of A-site and B-site ion replaced with small ions on the intermediate phase in PbZrO3 ceramic

• The relative permittivity curves for the composition, 0.02 ≤ x ≤ 0.06, showed two anomalous peaks.
• The intermediate phase in PZ–NN system is antiferroelectric-like structure.
• The ferroelectric phase diagram of PZ–NN was established in this work.

The solid solution of (1 − x)PbZrO3–xNaNbO3 ceramics, where x = 0.0–0.08, was synthesized by solid state reaction. The basic characterizations were performed using X-ray diffraction (XRD), dielectric spectroscopy, hysteresis measurement and differential scanning calorimetry (DSC) techniques. The results indicated that the crystal structure of the solid solution, (1 − x)PZ–xNN, where x = 0.00–0.08, is of orthorhombic symmetry. It was found that the effect of NN being replaced with small ions at the A-site and B-site can induce an AFE-like phase in PZ. The FE intermediate phase of PZ cannot be induced, although Zr4+ ions were substituted by small Nb5+ ions. This is due to the decreasing average rate of radii in the A-site (0.1 Å mol−1) being higher than that in the B-site (0.08 Å mol−1).