Lead-free Na_0.5Bi_0.5TiO₃ -BaTiO₃ ceramics have been prepared in the whole range of concentrations and studied at room-temperature by means of X-ray, Raman scattering and infrared techniques. X-ray measurements revealed rhombohedral, rhombohedral-tetragonal boundaries and tetragonal modifacations depending on the contents of BaTiO₃. The distinct changes of the Raman and infrared spectra with increasing of BaTiO₃ content, which were correlated with X-ray results, were observed. The broad phonon spectra indicated the disorder in the A site of Na_0.5Bi_0.5TiO₃ -BaTiO₃ system.

Dielectric permittivity studies of Na_0.5Bi_0.5TiO₃ single crystals in a broad range of frequency up to 10 MHz and temperature 300—823 K are reported. In this temperature range dielectric dispersion below 1 MHz has been found. The obtained data were fitted to the Cole-Cole relation. The mean relaxation time τ is strongly temperature dependent (0.04 − 2.6 × 10⁻⁵ s). A remarkable hysteresis effect in the values of τ on cooling and heating took place. The Δε(T) dependence (the maximal value of Δε ∼ 400) is similar to the global ε′(T) response at low frequency. An isothermal structural transformation in Na_0.5Bi_0.5TiO₃ was observed by X-ray measurements. The order of the time in which the transformation takes place (∼300 minutes) corresponds to the time in which the strongest time evolution of electric permittivity and time changes of dielectric dispersion were detected.