The thermal evolution of the crystal structure and phase transitions of KNbO ₃ were investigated by high-temperature powder X-ray diffraction and Rietveld refinement of the diffraction data. Two phase transitions from orthorhombic ( Amm 2) to tetragonal ( P 4 mm ) and from tetragonal to cubic ( P m 3 ¯ m ) were confirmed, both on heating and cooling. Both phase transitions are first order based on the observed hysteresis. The mixed displacive and order–disorder nature of the tetragonal to cubic transition is argued based on symmetry and apparent divergence of the atomic positions from pseudo-cubic values. The transition between the orthorhombic and tetragonal phase shows no temperature-dependence for atomic positions and only thermal expansion of the unit cell parameters and is thus discussed in relation to a lattice dynamical instability.

Sodium niobate (NaNbO₃) attracts attention for its great potential in a variety of applications, for instance, due to its unique optical properties. Still, optimization of its synthetic procedures is hard due to the lack of understanding of the formation mechanism under hydrothermal conditions. Through in situ X-ray diffraction, hydrothermal synthesis of NaNbO₃ was observed in real time, enabling the investigation of the reaction kinetics and mechanisms with respect to temperature and NaOH concentration and the resulting effect on the product crystallite size and structure. Several intermediate phases were observed, and the relationship between them, depending on temperature, time, and NaOH concentration, was established. The reaction mechanism involved a gradual change of the local structure of the solid Nb₂O₅ precursor upon suspending it in NaOH solutions. Heating gave a full transformation of the precursor to HNa₇Nb₆O₁₉·15H₂O, which destabilized before new polyoxoniobates appeared, whose structure depended on the NaOH concentration. Following these polyoxoniobates, Na₂Nb₂O₆·H₂O formed, which dehydrated at temperatures ≥285 °C, before converting to the final phase, NaNbO₃. The total reaction rate increased with decreasing NaOH concentration and increasing temperature. Two distinctly different growth regimes for NaNbO₃ were observed, depending on the observed phase evolution, for temperatures below and above ≈285 °C. Below this temperature, the growth of NaNbO₃ was independent of the reaction temperature and the NaOH concentration, while for temperatures ≥285 °C, the temperature-dependent crystallite size showed the characteristics of a typical dissolution–precipitation mechanism.