Downscaling grain size toward the nanometre range – A key-factor for tuning the crystalline structure, phase transitions, dielectric and ferroelectric behaviour in Ba0·8Sr0·2TiO3 ceramics

The present study aims to describe the role of the grain size on the properties of submicron- and nano-structured Ba_0·8Sr_0·2TiO₃ (BST) ceramics. Dense (1 − 2% porosity) ceramics with average grain sizes in the range of (77 − 234) nm were consolidated under different spark plasma sintering conditions starting from nanopowders with a mean particle size of 70 nm, synthesized via the acetate variant of the sol-gel method. The structural analysis based on XRD data revealed a mixture of cubic and tetragonal modifications at room temperature for the precursor powders and for all the investigated ceramics. The structural heterogeneity of the individual ceramic grains with coexistence of cubic and tetragonal polymorphs was confirmed by HR-TEM investigations. Accordingly, a “brick-wall" model with cubic grain boundary regions and tetragonal grain cores is proposed. By increasing the grain size, from 77 to 234 nm, a decrease of the phase transitions diffuseness accompanied by an increase of the permittivity maxima (from 650 to 4500) and dielectric losses (from 5 to 7.5%, at 100 Hz), was detected by broadband dielectric spectroscopy. No variation of the Curie temperature in the investigated Ba_0·8Sr_0·2TiO₃ ceramics was detected, unlike typically reported for BaTiO₃ ceramics with similar grain sizes. The Curie-Weiss temperature and the Curie constant decrease when grain size is diminished, indicating an overall reduction of the ferroelectric active volume, as a scaling effect. The ferroelectric switching was demonstrated for all the selected fine-grained BST ceramics, either at nanoscale or macroscopically, with an increased ferroelectric character for the coarser submicron-structured ceramics, with respect to the nanocrystalline one. The observed properties of the fine-grained Ba_0·8Sr_0·2TiO₃ ceramics are explained in the frame of multiphase coexistence and ferroelectricity “dilution” due to the increasing role of non-ferroelectric grain boundaries when reducing grain size and complete the knowledge on the scale-dependent properties of dense fine-grained BaTiO₃-based ceramics.