Study of the tetragonal-to-cubic phase transition in PbTio3 nanopowders

The CPP (combined polymerization and pyrolysis) preparation route, in its enhanced liquid-precursor-based version, was combined with consecutive soft milling. For studies of temperature- and size-dependent structural changes Occurring in ferroelectric lead titanate, this combined route yields a nanopowder series covering the relevant particle-size region at target quality. This material basis enables consistent SEM, TEM, XRD, Raman, EPR and dielectric measurements, which furnish a comprehensive picture of the cooperation between temperature rise and size reduction to eliminate tetragonality and concomitant ferroelectricity. Our previous original EPR studies on nanosized barium titanate are now extended to the lead titanate case. Furthermore, as compared to the pertinent literature standard, the materials basis is extended to powder samples of smaller mean particle sizes, comprising the critical size at which a PbTiO3 particle undergoes a transition into cubic paraelectric phase. Thus, the size-driven phase transition can be observed in a direct way (at 7nm, which compares to 40 nm for BaTiO3), and the EPR data suggest a much less spacious gradient shell at the particle surfaces (thickness approximate to 2 nm) than in previous analogous investigations on BaTiO3 (15 nm).