Phase evolution of lead titanate from its amorphous precursor synthesized by the OPM wet-chemical route

Lead titanate was synthesized by the OPM wet-chemical route by the dissolution of Ti metal in H₂O₂ followed by the addition of Pb²⁺ at high pH, resulting in a reactive and amorphous precipitate with (Pb:Ti=1:1) mole ratio, which was heat treated between 400°C and 700°C. The amorphous precipitate was characterized by DSC, and all of the powders were characterized by X-ray diffraction, Raman and XAS (EXAFS and XANES) spectroscopy at the Ti K edge. A metastable, stoichiometric and cubic pyrochlore phase (Pb₂Ti₂O₆, Fd3m) was identified by XRD and Raman spectroscopy up to approx. 450°C. Only tetragonal PbTiO₃ was identified at higher temperatures. XAS spectra showed that the local structure around the absorbing Ti atom of the intermediate pyrochlore phase is similar to that observed in the amorphous precursor. This fact indicates that the metastable intermediate pyrochlore (Pb₂Ti₂O₆) is kinetically favored to be formed because of its similarity to the amorphous precipitate, instead of the slightly different and thermodynamically favored tetragonal (PbTiO₃, P4/mmm) perovskite structure that is only formed at higher temperatures, after the crystallization of the metastable intermediate pyrochlore.     

Multi-ion quantitative mass spectrometry by orthogonal projection method with periodic signal of electrostatic ion beam trap

In this article, orthogonal projection method (OPM) is introduced which could perform multi-ion quantitative MS with signal of electrostatic ion beam trap (EIBT), and its application has been demonstrated by numerical modeling. To acquire periodic current signal, a model of EIBT with cylindrical-detector is set up to simulate ions' oscillatory motion. Whereafter, OPM is introduced and applied for quantitative MS with sampling time being as short as 200 μs. Comparing with fast Fourier transform (FFT), the MS acquired by OPM is characterized by a more readable spectrum, a much shortened sampling time and the ability to do quantitative analysis. Within the optimum sampling time range, quantitative MS could be performed with accuracy of over 90%. It is found that the lower limit and the upper limit of the optimum sampling time range are all proportional to M(3/2)/δM and its relation is specified by linear regression. Aided by the results of FFT, OPM is applied to a compound tested signal induced by three kinds of ions. It shows that OPM could be performed respectively to each kind of ions without interference from other component of the signal. The resolving power acquired by OPM is about 75 000 with sampling time as short as 10 ms, and the quantitative result that acquired is quite accurate.