Grain-size effect on structure and phase transformations for barium titanate

Abstract

We report the results of an investigation into the grain-size dependence of lattice structure for barium titanate (${\mathrm{BaTiO}}_{3}$) ceramics prepared by a sol-gel method. Raman and infrared spectroscopy, x-ray diffraction, and differential scanning calorimetry were used in combination with electron microscopy to study the evolution of lattice structure and phase transformation behavior with heat treatment and grain growth from the nano scale to the micron scale for ${\mathrm{BaTiO}}_{3}$ polycrystals. Raman spectroscopy and optical second-harmonic-generation measurements indicated the onset of local room-temperature acentric crystal symmetry with heat treatment and crystallite growth, well before the observation of any tetragonal structure by x-ray diffraction. Analysis of the room-temperature Raman spectra for ultrafine grain (grain size 0.1 \ensuremath{\mu}m) polycrystals suggested that a locally orthorhombic structure preceded the globally tetragonal form with grain growth. In support of this observation, differential scanning calorimetry suggested the orthorhombic-tetragonal phase transformation shifts up through room temperature with decreasing grain size. Hot-stage transmission electron microscopy studies revealed that fine grain (grain size \ensuremath{\approxeq}0.1 \ensuremath{\mu}m) ceramics, which showed a thermal anomaly associated with the cubic-tetragonal phase transformation, were untwinned at room temperature, as well as on cycling through the normal Curie temperature, suggesting a single-domain state for individual grains. The findings are discussed in light of a number of possible causes, including the presence of processing-related hydroxyl defects and the effect of elastic constraints on phase transformation behavior for ${\mathrm{BaTiO}}_{3}$ grains in a polycrystalline microstructure. \textcopyright{} 1996 The American Physical Society.