Phase Transitions in Nanocrystalline Barium Titanate Ceramics Prepared by Spark Plasma Sintering

The bulk dense nanocrystalline BaTiO3 (BT) ceramics ranging from 20 to 100 nm have been successfully prepared by the spark plasma sintering (SPS) method. Raman spectra and X‐ray diffraction were used in combination with electron microscopy to study the evolution of lattice structure and phase transformation behavior with grain growth from nanoscale to micrometer scale for BT ceramics. The results reveal that the SPS technique provides exceptional opportunity to compact ceramics to full density with nanograin size. It is also demonstrated that all structural modifications in nanocrystalline BT and low‐symmetry structures still exist in 20 nm nanograin BT ceramics. The ferroelectric properties of crystalline structures were investigated by scanning force microscopy in piezoresponse mode. Piezoelectric hysteresis loop was recorded, demonstrating that 20 nm BT ceramics has a remanent polarization and is switchable by an electric field. Thus, if a critical grain size exists for ferroelectricity, it is less than 20 nm for polycrystalline BT ceramics.