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Keywords:

  • morphotropic phase boundary;
  • perovskites;
  • piezoelectricity;
  • Glazer tilt system

The structure of the A-site substituted perovskite KxNa1 − xNbO3, x = 0.24–0.36, where a phase boundary was previously reported, has been determined by high-resolution X-ray powder and neutron powder diffraction studies. The structure of the x = 0.3 compound was refined in the monoclinic space group Pm at 293 K and in P4mm at 523 K. The Glazer tilt system of the room-temperature monoclinic phase is a0b+c0, which has implications for the nature of the next symmetry change with composition towards pure potassium niobate. A phase-coexistence region at the transition between monoclinic and tetragonal phases was also identified, consistent with a first-order phase boundary. There is also evidence for an intermediate oxygen-octahedra tilted tetragonal phase.