On the nature of phase transitions in the tetragonal tungsten bronze GdK2Nb5O15 ceramics

Abstract

Phase transitions in gadolinium potassium niobate GdK2Nb5O15 (GKN) ceramics have been investigated by x-ray diffraction, dielectric susceptibility, differential scanning calorimetry, and Raman scattering. The results of our complementary studies show that GKN exhibits two phase transitions at Tc1 = 238 °C and Tc2 = 375 °C attributed to the ferroelectric-antiferroelectric-paraelectric (FE-AFE-PE) phase transitions. According to the x-ray diffraction analysis, the FE and PE phases were refined in the polar P4bm and centrosymmetric P4/mbm space groups. For the intermediate phase, the structure is refined in the space group P4nc with doubling of the c unit cell parameter, which is compatible with an AFE phase. This result was confirmed by Raman spectroscopy since new low-frequency lines are activated in the AFE phase due to the Brillouin zone-folding effect, typical for the modulated phases. The presence of the AFE phase between the FE and PE phases and the complex nature of tetragonal tungsten bronze crystal structure can explain the large thermal hysteresis observed at the FE-AFE transition between heating and cooling cycle and the strong depression of the Curie-Weiss temperature T0. The semi-phenomenological Ising-like model based on the obtained experimental data is proposed to account for the observed FE-AFE-PE transition sequence.