The solid solution of Pb1-x Sm2x/3 (Zr0.6 Ti0.4) O3 ceramics with x = 0.1, 0.2, 0.3, and 0.4 was prepared via the high-energy ball milling technique. Further, the effect of excessive Sm2O3 substitution at Pb-site on structural, dielectric, and dc-conductivity properties was studied. The X-ray diffraction (XRD) analysis confirmed that all samples were crystallized with perovskite and pyrochlore diphase form. Excess Sm3+ substitution in the PZT system increases the pyrochlore volume fraction from 5 to 20% and induces a structural phase transition from rhombohedral to a tetragonal structure. The microstructural study by TEM and SEM indicated that the particles were spherical with an average size of 43–55 nm. The frequency and temperature-dependent dielectric constant for all compositions was carried out and it is obtained that the dielectric constant decreases with Sm3+ content. The phase transition temperature first decreases up to x = 0.2 and then increases for the higher concentration of samarium. The dc-conductivity studies revealed that all samples showed an unusual mixed TCR effect (both positive and negative temperature coefficient of resistance). Such properties of the studied samples indicate that the material is suitable for potential applications in thermistors, and temperature sensors of the automotive, and petroleum industries.
