Computer simulation techniques have been used to investigate defect formation and the diffusion of Ca and Mg in diopside. It was found that isolated, non-interacting CaO and MgO Schottky defects had the lowest formation energies (3.66 and 3.97 eV respectively); oxygen Frenkel defects are the most favourable oxygen defects (formation energies 3.93 eV). Magnesium and calcium self-diffusion in the c-direction of diopside is easiest by a vacancy mechanism involving either direct jumps along the c-direction, or double jumps in the b-c plane. In the extrinsic regime, diffusion activation energies for Mg are predicted to be 9.82 eV (direct route) and 1.97 eV (double jump route); for Ca diffusion, activation energies are predicted to be 6.62 eV (direct route) and 5.63 eV (double jump route). If additional vacancies (oxygen or magnesium) are present in the vicinity of the diffusion path, Ca migration energies fall to 1.97–2.59 eV. At elevated temperatures in the intrinsic regime, diffusion activation energies of ⩾ 5.95 eV are predicted for Mg self-diffusion and 9.29–10.28 eV for Ca self-diffusion. The values for Ca diffusion are comparable with published experimental data. It is inferred that a divacancy mechanism may operate in diopside crystals.

Bi2Sr2Co2Ox (BSC-222) bulk materials have been prepared in air by single hot pressing or partial melting followed by hot pressing. Thermal transport properties of as-prepared samples were compared with BSC-222 samples prepared by single partial melting. Samples prepared through hot pressing have a high bulk density and improved preferential grain orientation. Bulk density and preferential grain orientation are significantly better in samples processed by partial melting followed by hot pressing. In samples prepared by partial melting, the presence of sub-micrometer-sized secondary phases Bi0.75Sr0.25Ox, Sr-based oxide, and CoO, is observed. The lattice contribution to the total thermal conductivity decreases significantly in partially melted BSC-222 samples. By using a classical phonon transport model, this result demonstrates that the decrease in lattice thermal conductivity in partially melted BSC-222 samples may be linked not only to porosity but also to the presence of defects, induced by partial melting process, which may play an important role in phonon scattering.

The thermoelectric properties of Bi2Sr2Co2Ox (BSC-222) bulk materials prepared by three different processing methods, i.e., conventional sintering, hot pressing, or partial melting, were investigated and compared. The electrical current, temperature difference for Seebeck coefficient, and thermal diffusion were measured in the same direction. The hot pressing and partial melting are effective processing methods for improving the electrical transport property in BSC-222 bulk materials due to an improvement of density in hot-pressed samples or by grain growth during partial melting process. For partially melted samples, a decrease in the thermal conductivity is also observed. The highest dimensionless thermoelectric figure of merit (ZT) values have been obtained in the sample prepared by partial melting method, for which ZT has been increased by a factor of 2.7 by comparison with bulk materials prepared by conventional sintering. At 700 °C in air, ZT value reaches 0.27 for partially melted Bi2Sr2Co2Ox bulk materials. This study shows that optimized electrical and thermal transport properties can be achieved in BSC-222 bulk materials possessing microstructures with both large average grain size and appropriate bulk density.

Ceramics of Ba3.75Nd9.5Ti18O54 substituted with 2, 5, 10, 20 and 50% Sr have been prepared by the mixed oxide route. Specimens were sintered at temperatures in the range 1350–1500°C. Densities were ∼95% theoretical. The solubility limit for Sr replacing Ba was found to be ∼10%. The relative permittivity (∼80) was almost independent of Sr content, but 2% Sr increased the Qxf value to a maximum of 11000. Static simulation of Sr- bearing Ba3.75Nd9.5Ti18O54 successfully reproduced the structure and lattice parameters to within 1–2%. Different site distributions of Ba-Sr ions have been explored.