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Lead-free (Ba0.85Ca0.15) (Ti0.90Zr0.10)O3 (15/10 BCZT) piezoelectric ceramics were prepared by a standard solid solution and sintered at different temperature of 1300 °C and 1500 °C at a time. The 15/10BCZT piezoceramics were prepared at 1300 °C sintering temperature by doping different amount of MnO2.The ceramics show a phase transition from a freoelectric tetragonal phase to a rhombohedral and tetragonal ferroelctric phase and to a single rhombohedral phase with increasing MnO2 content. The addition of MnO2 significantly improves the sinterbility of the 15/10BCZT piezoceramics, and reducing the sintering temperature from 1500 °C to 1300 °C by 200 °C but showing comparable piezoelectric properties. With 0.4 mol% of the dopant, ∼96.5% of the theoretical density of the ceramics was achieved with excellent piezoelectric coefficient d33 ~ 534pC/N, which is nearly equal to the value obtained from the ceramics sintered at 1500 °C which has a piezoelectric coefficient d33 ~ 570pC/N, high density (~ 5.59 g/cm3), maximum remnant polarization (Pr = 24 μC/cm2), relatively large grain size (10.4 μm) and the least coercieve field (Ec = 0.42 kV/mm). However, a high concentration of MnO2 deterioated the properties of the ceramics because of increasing of oxygen vacancies and associated defects. The results indicate that the BCTZ-y mol% MnO2 ceramics are one of the promising lead-free piezoelectric candidates for high temperature applications.

There is a general perception that a large piezoelectric response in ferroelectric solid solutions requires a morphotropic/polymorphic phase boundary (MPB/PPB), i.e., a composition driven interferroelectric instability. This correlation has received theoretical support from models which emphasize field driven polarization rotation and/or interferroelectric transformations. Here, we show that the ferroelectric system ( 1 − x ) PbTi O 3 − ( x ) Bi ( Zr 1 / 2 Ni 1 / 2 ) O 3 (PT-BNZ), which shows d 33 ( ∼ 400 p C / N ) comparable to the conventional MPB/PPB systems, does not belong to this category. In the unpoled state the compositions of PT-BNZ showing large d 33 exhibit a coexistence of tetragonal and cubiclike (CL) phases on the global length scale. A careful examination of the domain strucures and global structures (both in the unpoled and poled states) revealed that the CL phase has no symptom of average rhombohedral distortion even on the local scale. The CL phase is rather a manifestation of tetragonal regions of short coherence length. Poling increases the coherence length irreversibly which manifests as poling induced CL → P 4 m m transformation on the global scale. PT-BNZ is therefore qualitatively different from the conventional MPB piezoelectrics. In the absence of the composition and temperature driven interferroelectric instability in this system, polarization rotation and interferroelectric transformation are no longer plausible mechanisms to explain the large electromechanical response. The large piezoelectricity is rather associated with the increased structural-polar heterogeneity due to domain miniaturization without the system undergoing a symmetry change. Our study proves that attainment of large piezoelectricity does not necessarily require interferroelectric instability (and hence morphotropic/polymorphic phase boundary) as a criterion.

Although, as part of a general phenomenon, the piezoelectric response of $\mathrm{Ba}(\mathrm{T}{\mathrm{i}}_{1\ensuremath{-}y}{M}_{y}){\mathrm{O}}_{3}$ ($M=\mathrm{Zr}$, Sn, Hf) increases in the vicinity of the orthorhombic ($Amm2$)-tetragonal ($P4mm$) and orthorhombic ($Amm2$)-rhombohedral ($R3m$) polymorphic phase boundaries, experiments in the last few years have shown that the same phase boundaries show significantly enhanced weak-field piezoproperties in the Ca-modified variants of these ferroelectric alloys, i.e., $(\mathrm{Ba},\mathrm{Ca})(\mathrm{Ti},M){\mathrm{O}}_{3}$. So far there is a lack of clarity with regard to the unique feature(s) which Ca modification brings about that enables this significant enhancement. Here, we examine this issue from a structural standpoint with $M=\mathrm{Sn}$ as a case study. We carried out a comprehensive comparative structural, ferroelectric, and piezoelectric analysis of the $Amm2$ phase in the immediate vicinity of the $P4mm\text{\ensuremath{-}}Amm2$ phase boundaries of (i) Ca-modified $\mathrm{Ba}(\mathrm{Ti},\mathrm{Sn}){\mathrm{O}}_{3}$, as per the nominal formula $(1\ensuremath{-}x)\mathrm{BaT}{\mathrm{i}}_{0.88}\mathrm{S}{\mathrm{n}}_{0.12}{\mathrm{O}}_{3}\text{\ensuremath{-}}(x)\mathrm{B}{\mathrm{a}}_{0.7}\mathrm{C}{\mathrm{a}}_{0.3}\mathrm{Ti}{\mathrm{O}}_{3}$ and (ii) without Ca modification, i.e., $\mathrm{Ba}(\mathrm{T}{\mathrm{i}}_{1\ensuremath{-}y}\mathrm{S}{\mathrm{n}}_{y}){\mathrm{O}}_{3}$. We found that the spontaneous lattice strain of the $Amm2$ phase is noticeably smaller in the Ca-modified counterpart. Interestingly, this happens along with an improved spontaneous polarization by enhancing the covalent character of the Ti-O bond. Our study suggests that the unique role of Ca modification lies in its ability to induce these seemingly contrasting features (reduction in spontaneous lattice strain but increase in polarization).

The exceptionally large piezoelectric response of the morphotropic- phase-boundary (MPB) composition of the lead-free piezoelectric system (1 - x) Ba(Ti0.8Zr0.2)O-3 - x(Ba0.7Ca0.3) TiO3 has attracted great attention in recent years. Here in this paper we report a detailed investigation of the structural phase transformation behavior of the MPB composition (x = 0.50) driven by electric field, stress, and temperature. We show that the system exhibits metastable phases in a wide temperature range, and that the large piezoresponse at room temperature has a significant contribution from the increased fraction of the metastable phases induced by the poling field. Using a ``powder poling'' technique we also demonstrate the equivalence of stress and electric field with regard to the nature of the structural transformation. The fundamental significance of this interesting observation is discussed.

There is great interest in lead-free (Ba0.85Ca0.15)(Ti0.90Zr0.10)O-3 (15/10BCTZ) because of its exceptionally large piezoelectric response Liu and Ren, Phys. Rev. Lett. 103, 257602 (2009)]. In this paper, we have analyzed the nature of: (i) crystallographic phase coexistence at room temperature, (ii) temperature-and field-induced phase transformation to throw light on the atomistic mechanisms associated with the large piezoelectric response of this system. A detailed temperature-dependent dielectric and lattice thermal expansion study proved that the system exhibits a weak dielectric relaxation, characteristic of a relaxor ferroelectric material on the verge of exhibiting a normal ferroelectric-paraelectric transformation. Careful structural analysis revealed that a ferroelectric state at room temperature is composed of three phase coexistences, tetragonal (P4mm)+ orthorhombic (Amm2) + rhombohedral (R3m). We also demonstrate that the giant piezoresponse is associated with a significant fraction of the tetragonal phase transforming to rhombohedral. It is argued that the polar nanoregions associated with relaxor ferroelectricity amplify the piezoresponse by providing an additional degree of intrinsic structural inhomogeneity to the system.