No abstract

The morphotropic phase boundary in the phase diagram of the technologically important Pb(Zr x Ti 1Àx )O 3 (PZT) ceramics has been traditionally believed to separate ferroelectric tetragonal and rhombohedral phase regions. This old picture has come under close scrutiny during the last eight years following the discovery of new monoclinic phases in the Cm and Cc space groups. This article presents a brief overview of these discoveries in which the use of multiple diffraction probes (X-ray, electron, neutron diffraction) in conjunction with physical property measurements has played a crucial role. A new phase diagram of PZT showing the stability fields of these structures below room temperature is also presented.

Phase transitions in semiwet derived (Pb1−xBax)ZrO3 ceramics for the composition range 0⩽x⩽0.30 have been investigated by dielectric measurements at various frequencies during heating and cooling cycles. The paraelectric (PE) to ferroelectric (FE) to antiferroelectric (AFE) sequence of phase transitions is observed for 0⩽x<0.20. On increasing the Ba2+ content from x=0 to x=0.05, the thermal hysteresis associated with the AFE–FE phase transition increases from 11 to 100 °C. This is attributed to the increase in the piezoelectric coupling between the strain and polarization. For x=0.20, the FE phase does not transform into the AFE phase on cooling. Pronounced deviations from the regular FE behavior are observed on increasing the Ba2+ content to x=0.25. For x=0.30, the temperatures corresponding to the peak values of the real and imaginary parts of the dielectric constant become frequency dependent indicating relaxor FE behavior. It is shown that the polar clusters present in the PE phase undergo Vogel–Fulcher type relaxational freezing in the relaxor FE phase. The results of temperature dependent polarization measurements confirm the findings of the dielectric studies. It is proposed that Ba2+ substitution modifies the AFE and FE interactions of the PbZrO3 matrix in such a manner that their strengths become comparable for x=0.30 leading to the glassy or relaxor behavior.

The structure of (1-x)[Pb(Mg1/3Nb2/3)O3]-xPbTiO3 is tetragonal and rhombohedral for x⩾0.35 and x⩽0.30, respectively. The intrinsic width of the morphotropic phase boundary region (0.30