Obtenção, propriedades e fenomenologia de materiais ferroelétricos com estrutura tungstênio bronze

Abstract

The processing of lead metaniobate (PN) ferroelectric ceramics was optimized, therefore, in this work, the main details to obtain PN ceramics with density higher than 96 % of the ideal density are presented and discussed. Taking into account the potential of the lead metaniobate for different applications, mainly for high temperatures, the phase transition characteristics of this material, in both undoped and doped compositions, were detaily investigated. It was verified that the addition of Ti4+ enhances the densification and increase the Curie temperature. Nevertheless, the ferro-paraelectric phase transition is affected by an electric conductive process, which appears in temperatures below and above the Curie temperature. The double ionized oxygen vacancies are proposed to be the charge carriers responsible for this conductive process. The undoped and Ti4+-doped PN ceramics show low values of the mechanical quality factor and high piezoelectric anisotropy, which are desired characteristics for the fabrication of broad band electro-mechanical transducers, mainly to operate in the thickness mode. The addition of Ba2+ to the PN (PBN) considerably decreases the Curie temperature, but it induces a phase transition, leading to the formation of a morphotropic phase boundary (MPB) around the composition with 37 % of Ba2+, in which some properties are enhanced. In this way, the characteristics of the ferro-paraelectric phase transition, for compositions around the MPB, were investigated for Ba2+-doped PN ceramics, textured by hot forging. It was found that the MPB extends towards a wide composition range, in which both tetragonal 4mm and orthorhombic m2m tungsten bronze (TB) phases coexist. In addition, with the increasing temperature, two phase transitions were observed for this composition range. First, the material portion with orthorhombic (m2m) symmetry transforms into the tetragonal (4mm) phase and, second, the 4mm phase (that represents the material in its totality) transforms into the paraelectric phase with the tetragonal 4/mmm TB symmetry. These results helped to complete the reported PBN phase diagram. Moreover, it was found that the La3+ addition to the PBN, for the composition with 56 % of Pb2+, induces the formation of the orthorhombic (m2m) phase. All the (doped and undoped) PN ceramics showed two dielectric dispersion processes at low temperatures, i.e. from 30 to 300 K, which seems to be an inherent feature of all materials with TB structure and ((A1)x(A2)5-xNb10O30) structural formula. The two processes were associated to a phase transition and the formation of incommensurate structures, respectively. The influence of such incommensurate structures on the relaxor behavior and diffusivity of the ferro-paraelectric phase transition was also analyzed.