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Adding excessive metal oxide doping to a powder batch is a known way to compensate for the loss of volatile cation species during high temperature sintering. An important case in the piezoelectric ceramics is the bismuth oxide in the lead-free ferroelectric ceramic bismuth sodium titanate (BNT). Building from the earlier knowledge about excessive bismuth oxide's influences on the properties of BNT, we further note that varying the sintering temperature can both control the distribution of excessive Bi3+ and impact the relaxor/normal ferroelectric behaviors and corresponding phase transition. In addition to the nature of polarization, the sintering temperature also significantly manipulates the electrical conductivity. A hypothetical mechanism for the resistive grain boundary is proposed, based on inferences from electrical—microstructure—processing relations in 85% Bi0.5Na0.5TiO3-15% BaTiO3 with batched Bi2O3 excess and acceptor Mg2+ in a co-doped strategy.

To fulfill the demands of more bandwidth in 5G and 6G communication technology, new dielectric substrates that can be co‐fired into packages and devices that have low dielectric loss and improved thermal conductivity are desired. The motivation for this study is to design composites with low dielectric loss (tan δ) and high thermal conductivity (κ), while still limiting the electrical conductivity, for microwave applications involving high power and high frequency. This work describes the fabrication of high‐density electroceramic composites with a model dielectric material for cold sintering, namely sodium molybdate (Na₂Mo₂O₇), and fillers with higher thermal conductivity such as hexagonal boron nitride. The physical properties of the composites were characterized as a function of filler vol.%, temperature, and frequency. Understanding the variation in measured properties is achieved through analyzing the respective transport mechanisms.