Knudsen cell mass spectrometric investigation of the PbO-ZrO(2)-TiO(2) system

Knudsen effusion mass spectrometry (KEMS) was used for direct determination of lead oxide activity as a function of temperature in various regions of the PbO-ZrO(2)-TiO(2) system. From the results, the enthalpy, Gibbs free energy and entropy of formation of PbTiO(3) (PT), PbZrO(3) (PZ) and Pb(Zr,Ti)O(3) (PZT) were evaluated. In addition, the single phase widths of Pb(Zr(0.5)Ti(0.5))O(3) and PbTiO(3) perovskite structures were determined at 1100 K. The reaction rate of PZT synthesis in vacuo was followed by direct measurement of the change of PbO activity with time. Lead oxide activity in stoichiometric Pb(Zr(0.5)Ti(0.5))O(3), PbTiO(3) and Pb(0.968)(Zr(0.5)Ti(0.5))O(2.968) (3% lead deficient) at 850 degrees C was found to be 0.40, 0.45 and 0.1, respectively. PZT, PT and PZ powder samples prepared by a solid state procedure were also measured, all revealing lead deficiency. Copyright 1999 John Wiley & Sons, Ltd.