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In piezoelectric ceramics the changes in the phase stabilities versus stressand temperature in the vicinity of the phase boundary play a central role. Thepresent study was dedicated to the classical piezoelectric,lead-zirconate-titanate (PZT) ceramic with compositionPb(Zr$_{0.54}$Ti$_{0.46}$)O$_3$ at the Zr-rich side of the morphotropic phaseboundary at which both intrinsic and extrinsic contributions topiezoelectricity are significant. The pressure-induced changes in thistwo-phase (rhombohedral $R3c$+monoclinic $Cm$ at room temperature and$R3c+P4mm$ above 1 GPa pressures) system were studied by high-pressure neutronpowder diffraction technique. The experiments show that applying pressurefavors the $R3c$ phase, whereas the $Cm$ phase transforms continuously to the$P4mm$, which is favored at elevated temperatures due to the competing entropyterm. The $Cm\rightarrow R3c$ phase transformation is discontinuous. Thetransformation contributes to the extrinsic piezoelectricity. An importantcontribution to the intrinsic piezoelectricity was revealed: a largedisplacement of the $B$ cations (Zr and Ti) with respect to the oxygen anionsis induced by pressure. Above 600 K a phase transition to a cubic phase tookplace. Balance between the competing terms dictates the curvature of the phaseboundary. After high-pressure experiments the amount of rhombohedral phase waslarger than initially, suggesting that on the Zr-rich side of the phaseboundary the monoclinic phase is metastable.

High-pressure neutron study of the morphotropic PZT: phase transitions in a two-phase system