Separate Kinetics of the Polar and Antiferrodistortive Order Parameters in the Antiferroelectric Transition of PbZr1-xTixO3 and the Influence of Defects

The transition from the rhombohedral-ferroelectric to the lower temperature orthorhombic-antiferroelectric phase in Zr-rich PZT involves two order parameters (OPs): 1) the polar OP for the displacements of the cations with respect to the O octahedra; 2) an antiferrodistortive OP responsible for tilting of the octahedra. It is shown that at Ti compositions near the morphotropic boundary with the FE phase (0.046 ≤ x ≤ 0.054), the two OPs may be almost independent of each other at cooling rates of 0.5 K/min or faster, depending on the sample history. This fact gives rise to a great variety of shapes of the curves of the elastic compliance s(T), but all of them can be fitted very well as superpositions of variously broadened steps for each of the modes involved in the transitions, including the tilt transition occurring in the untransformed FE fraction. The evolution of the s(T) curves includes enhancements up to a factor of four during aging for weeks in the region of the AFE/FE coexistence. Restiffening and reduction of the thermal hysteresis of the AFE/FE transition are recovered by heating up to 800-900 K. It is proposed that ageing is due to the clustering of relatively mobile defects, most likely O vacancies, at the domain walls in the coexisting AFE/FE phases. Such defect structures are probably at the origin of intense thermally activated relaxation processes observed above TC in the dielectric and anelastic spectra, and can be annealed out above 800 K, allowing the AFE transition to recover a fast kinetics.