RESUMO
Next-generation electronics and energy technologies can now be developed as a result of the design, discovery, and development of novel, environmental friendly lead (Pb)-free ferroelectric materials with improved characteristics and performance. However, there have only been a few reports of such complex materials' design with multi-phase interfacial chemistry, which can facilitate enhanced properties and performance. In this context, herein, novel lead-free piezoelectric materials (1-x)Ba0.95 Ca0.05 Ti0.95 Zr0.05 O3 -(x)Ba0.95 Ca0.05 Ti0.95 Sn0.05 O3 , are reported, which are represented as (1-x)BCZT-(x)BCST, with demonstrated excellent properties and energy harvesting performance. The (1-x)BCZT-(x)BCST materials are synthesized by high-temperature solid-state ceramic reaction method by varying x in the full range (x = 0.00-1.00). In-depth exploration research is performed on the structural, dielectric, ferroelectric, and electro-mechanical properties of (1-x)BCZT-(x)BCST ceramics. The formation of perovskite structure for all ceramics without the presence of any impurity phases is confirmed by X-ray diffraction (XRD) analyses, which also reveals that the Ca2+ , Zr4+ , and Sn4+ are well dispersed within the BaTiO3 lattice. For all (1-x)BCZT-(x)BCST ceramics, thorough investigation of phase formation and phase-stability using XRD, Rietveld refinement, Raman spectroscopy, high-resolution transmission electron microscopy (HRTEM), and temperature-dependent dielectric measurements provide conclusive evidence for the coexistence of orthorhombic + tetragonal (Amm2 + P4mm) phases at room temperature. The steady transition of Amm2 crystal symmetry to P4mm crystal symmetry with increasing x content is also demonstrated by Rietveld refinement data and related analyses. The phase transition temperatures, rhombohedral-orthorhombic (TR-O ), orthorhombic- tetragonal (TO-T ), and tetragonal-cubic (TC ), gradually shift toward lower temperature with increasing x content. For (1-x)BCZT-(x)BCST ceramics, significantly improved dielectric and ferroelectric properties are observed, including relatively high dielectric constant εr ≈ 1900-3300 (near room temperature), εr ≈ 8800-12 900 (near Curie temperature), dielectric loss, tan δ ≈ 0.01-0.02, remanent polarization Pr ≈ 9.4-14 µC cm-2 , coercive electric field Ec ≈ 2.5-3.6 kV cm-1 . Further, high electric field-induced strain S ≈ 0.12-0.175%, piezoelectric charge coefficient d33 ≈ 296-360 pC N-1 , converse piezoelectric coefficient ( d 33 ∗ ) ave ${( {d_{33}^*} )}_{{\rm{ave}}}$ ≈ 240-340 pm V-1 , planar electromechanical coupling coefficient kp ≈ 0.34-0.45, and electrostrictive coefficient (Q33 )avg ≈ 0.026-0.038 m4 C-2 are attained. Output performance with respect to mechanical energy demonstrates that the (0.6)BCZT-(0.4)BCST composition (x = 0.4) displays better efficiency for generating electrical energy and, thus, the synthesized lead-free piezoelectric (1-x)BCZT-(x)BCST samples are suitable for energy harvesting applications. The results and analyses point to the outcome that the (1-x)BCZT-(x)BCST ceramics as a potentially strong contender within the family of Pb-free piezoelectric materials for future electronics and energy harvesting device technologies.
RESUMO
Complex (multivalent/mixed valent) oxides involving two or more cations (e.g. ABO3, AB2O4 and A2B2O7) exhibit the most fascinating range of physical and chemical properties amongst the family of materials systems. There is growing interest in nanoscale forms of such oxides which emanates from the novel changes in their properties with size. To obtain nanomaterials with a high degree of crystallinity it is desirable to first make crystalline oxide powders by high temperature processing and then mill them down to nanometer size. In this paper we show that simple citric acid treatment of BiFeO3 and Bi2O3 powders leads to the desired micron-scale to nanoscale transformation, yielding nearly monodispersed nanoparticles. Importantly, these are highly dispersible and stable in water. By performing similar experiments on Fe3O4 and Fe2O3 we have elucidated the possible mechanism, which hinges on valence-controlled dissolution and ripening phenomena.
