Synthesis and characterization of a pyrochlore solid solution in the Na2O‐Bi2O3‐TiO2 system

The compositional limits of a previously reported (J. Am. Ceram. Soc., 61, 5‐8. (1978)) but relatively unstudied sodium‐bismuth titanate pyrochlore solid solution are revised and their electrical properties presented. The pyrochlore solid solution we report forms via a different mechanism to that originally reported and occurs in a different location within the Na2O‐Bi2O3‐TiO2 ternary system. In both cases, relatively large amounts of vacancies are required on the A‐sites and on the oxygen sites, similar to that reported for undoped ‘Bi2Ti2O7’ pyrochlore. In contrast to ‘Bi2Ti2O7’, this ternary pyrochlore solid solution can be prepared and ceramics sintered using conventional solid‐state methods; however, the processing requires several challenges to be overcome to obtain dense ceramics. This cubic pyrochlore series has low electrical conductivity (and does not exhibit any evidence of oxide‐ion conduction) and exhibits relaxor ferroelectric behavior with a broad permittivity maximum of ~100 near room temperature. Variable temperature neutron diffraction data do not provide any conclusive evidence for a phase transition in the pyrochlore solid solution between ~4 and 873 K

Use of the time constant related parameter fmax to calculate the activation energy of bulk conduction in ferroelectrics

The activation energy associated with bulk electrical conduction in functional materials is an important quantity which is often determined by impedance spectroscopy using an Arrhenius-type equation. This is achieved by linear fitting of bulk conductivity obtained from complex (Z*) impedance plots versus T-1 which gives an activation energy Ea(σ) or by linear fitting of the characteristic frequency fmax obtained from the large Debye peak in M’’-logf spectroscopic plots against T-1 which gives an activation energy Ea(fmax). We report an analysis of Ea(σ) and Ea(fmax) values for some typical non-ferroelectric and ferroelectric materials and employ numerical simulations to investigate combinations of different conductivity-temperature and permittivity-temperature profiles on the logfmax – T-1 relationship and Ea(fmax). Results show the logfmax – T-1 relationship and Ea(fmax) are strongly dependent on the permittivity-temperature profile and the temperature range measured relative to Tm (temperature of the permittivity maximum). Ferroelectric materials with a sharp permittivity peak can result in non-linear logfmax – T-1 plots in the vicinity of Tm. In cases where data are obtained either well above or below Tm, linear logfmax – T-1 plots can be obtained but overestimate or underestimate the activation energy for conduction, respectively. It is therefore not recommended to use Ea(fmax) to obtain the activation energy for bulk conduction in ferroelectric materials, instead Ea(σ) should be used

Dramatic impact of the TiO2 polymorph on the electrical properties of ‘stoichiometric’ Na0.5Bi0.5TiO3 ceramics prepared by solid-state reaction

Bulk conductivity (σb) values of nominally stoichiometric Na0.5Bi0.5TiO3 (NBT) prepared by solid-state reaction collated from literature show random variation between 10−6 to 10−3 S cm−1 (at 600 °C). This makes it challenging to obtain reliable and reproducible performances of NBT-based devices, especially as the underlying reason(s) for this variance are not fully understood. Here we report the dramatic impact of the TiO2 reagent, in particular, the polymorphic form of TiO2 on the electrical conductivity and conduction mechanism of NBT. Based on our solid-state processing route, NBT ceramics prepared by rutile TiO2 are ionically conductive, and those prepared by anatase TiO2 are insulating. The dramatic difference in electrical properties of NBT prepared using rutile and anatase TiO2 is related to the NBT formation process: the intermediate phase Bi12TiO20 is more stable during formation of NBT in the case of anatase TiO2, which reduces the volatility of Bi2O3 during solid-state reaction. These results give plausible explanations for the large variation of σb reported in the literature and highlight the importance of selecting an appropriate TiO2 reagent when targeting controllable σb in NBT-based ceramics. For ion-conducting applications (such as in intermediate-temperature solid oxide fuel cells, IT-SOFCs), rutile TiO2 should be used, and for dielectric applications (such as in multilayer ceramic capacitors, MLCC) anatase TiO2 should be used