Iranian Journal of Materials Science and Engineering

    The structural and dielectric properties of iron and bismuth co-substituted BaTiO₃ ceramic with the formula: B_0.95Bi_0.05Ti_1-xFe_xO₃ for x=0.00 to 1.00, synthesis with solid state route, were characterized.     The X-ray diffraction results show a tetragonal phase for x=0.00. While for x=0.40 to 0.80 we observed a coexistence of tree phase tetragonal, hexagonal and pseudo-cubic. And at x=1.00 only the pseudo-cubic phase is present and the other phase disappeared. The Raman results indicate the existence of tetragonal band for x≤0.40, and an appearance of characteristic bands of Fe³⁺ ions for more than 0.40 of Fe content. The SEM micrographs show an increase in grain size with the increase of Fe content and it reaches a maximum at x=0.40.  And the Mossbauer spectroscopy indicates that our samples is paramagnetic at room temperature and that the Fe is   oxidized under Fe³⁺ with no existence of Fe²⁺ and Fe⁴⁺ ions. The temperature dependence of dielectric permittivity was investigated in the frequency range from 20 Hz to 2MHz. The results show three dielectric relaxation phase transitions from a rhombohedral ferroelectric to orthorhombic ferroelectric (T_R-O) then to a tetragonal ferroelectric phase (at T_O-T), and finally to cubic paraelectric at the Curie temperature (T_C).  In addition, the temperature of phase transition shifted to the lower temperature with the increase of Fe content for all the phase transitions. And the maximum of dielectric permittivity increases for T_R-O while for T_T-O and T_m phases transitions, it reaches a maximum at x=0.60 and x=0.80 respectively and then decreases.

      In this study we have synthesis the Zr substituted BaTi_0.80Fe_0.20O₃ ceramics at different content of Zr from x=0.00 to 0.10 by using the solid-state route. The room temperature X-ray diffraction results confirmed the coexistence of the two tetragonal and hexagonal phases for x ≤ 0.050 of Zr content. While above 0.050 the hexagonal phase disappears in benefit of tetragonal phase. The Raman results confirmed the formation of these phases obtained with XRD. The scanning electron micrographs consist of both spherical and straight grain forms for x=0.000 to 0.075, and only spherical grain form for x=0.100 attributed to the tetragonal phase. Also, the grain size increases accompanied with a decrease in density of ceramics with increasing Zr content up to 0.050 then decreases accompanied with an increase in density. Detailed studies of dielectric permittivity measurement have provided a presence of two anomalies T_e and T_R-O at different temperatures, with a relaxation phenomenon and diffuse behavior which is very important for ceramic at x=0.075 of Zr content. The dielectric permittivity values of the two anomalies of Zr substituted BaTi_0.80Fe_0.20O₃ ceramics increase with increase of Zr content and the dielectric loss is minimal at x=0.100 of Zr content. The conductivity increases with the increasing of Zr substitution from 0.025 to 0.075 levels while for x = 0.100 the dielectric conductivity decreases.  And the Cole-Cole analysis indicates a negative thermal resistivity coefficient (NTCR) behavior of these materials and an ideal Debye-type behavior.