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International audience; Phase diagram of the solid solution system K 0.5 Na 0.5 NbO 3-Bi ½ Na ½ TiO 3 [(1-x)KNN-xBNT] has been established from dielectric permittivity measurement and structure analyses. The unit cell volumes continuously decrease depending on the composition, while the local structure maintains distortions away from the cubic average structure in the range 0.10 ≤ x ≤ 0.90. No clear correspondence for the temperatures of phase transition exists between structural studies and physical properties. The dielec-tric behavior is depicted successively from normal ferroelectric, diffuse phase transition, re-entrant-like relaxor, relaxor + dipolar glass-like relaxor, BNT-like relaxor with the increase of BNT. A comprehensive composition-property phase diagram for this system has been given to understand the various ferro-electric phenomena. The result could be mainly elucidated by the nanoclusters and the disorder driven nucleation of polar nanoregions contributed by a valence mismatch at one of the cation sites.

Recently developed lead-free incipient piezoceramics are promising candidates for off-resonance actuator applications with their exceptionally large electromechanical strains. Their commercialization currently faces two major challenges: high electric field required for activating the large strains and large strain hysteresis. It is demonstrated that design of a relaxor/ferroelectric composite provides a highly effective way to resolve both challenges. Experimental results in conjunction with numerical simulations provide key parameters for the development of viable incipient piezoceramics.

Coupling of order parameters provides a means to tune functionality in advanced materials including multiferroics, superconductors, and ionic conductors. We demonstrate that the response of a frustrated ferroelectric state leads to coupling between order parameters under electric field depending on grain orientation. The strain of grains oriented along a specific crystallographic direction, ⟨h00⟩, is caused by converse piezoelectricity originating from a ferrodistortive tetragonal phase. For ⟨hhh⟩ oriented grains, the strain results from converse piezoelectricity and rotostriction, as indicated by an antiferrodistortive instability that promotes octahedral tilting in a rhombohedral phase. Both strain mechanisms combined lead to a colossal local strain of (2.4 ± 0.1) % and indicate coupling between oxygen octahedral tilting and polarization, here termed “rotopolarization”. These findings were confirmed with electromechanical experiments, in situ neutron diffraction, and in situ transmission electron microscopy in 0.75Bi1/2Na1/2TiO3-0.25SrTiO3. This work demonstrates that polar and non-polar instabilities can cooperate to provide colossal functional responses This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0

The temperature- and field-dependent degradation properties of bulk Pb(Zr,Ti)O3 material (PZT) under a unipolar electric field were investigated. Unipolar cycling leads to the build-up of an internal bias field based on the agglomeration of charges at grain boundaries. A simple model was developed which describes the general dynamics of unipolar fatigue and its dependence on temperature and driving field. Comparing the large and small signal permittivity before and after fatigue led to the conclusion that domain walls became clamped by the agglomerated charges. This clamping effect could be visualized by transmission electron microscopy (TEM). Additionally, the TEM investigations revealed that unipolar fatigue leads to a weakening of the microstructure and to the development of microcracks.

In this letter, conclusive experimental evidence is presented for the coexistence of two phases within individual grains in the system ( Bi 0.5 Na 0.5 TiO 3)0.91-( BaTiO 3)0.06-( K 0.5 Na 0.5 NbO 3)0.03. Electron diffraction data unequivocally reveal the presence of a rhombohedral and a tetragonal phase with space group R3c and P4bm, respectively, both on the nanoscale level. Superlattice reflections, observed in the corresponding selected area electron diffraction, were used to identify the rhombohedral and tetragonal phase present at different regions within one grain. It is thought that the rhombohedral phase acts as a nucleation site for the phase transformation monitored under applied electrical field. The coexistence of these two phases in conjunction with the triggered tetragonal to rhombohedral phase transformation rationalizes the high bipolar and unipolar strain recorded for this lead-free ferroelectric material.

Applications ranging from microphones to AFM transducers exploit the interplay between mechanical stress and electric field arising from structural transitions in certain perovskite oxides. The classic material contains lead, however, and efficient, environmentally friendly alternatives have long been sought. The authors use a challenging technique to visualize the real-time microstructural evolution of a lead-free ferroelectric system, and the multidomain states and transitions they find are expected to inform the search for additional systems, as well as the applications that will rely on them.

Ferroelectric materials play an important role in today’s functional material discussion and are widely used in industrial applications as injection systems, actuators or sensors. A detailed knowledge of the microstructure is prerequisite to optimise these materials for further applications.

In recent years, the stability field of a monoclinic phase at the morphotropic phase boundary in lead zirconate titanate, $\mathrm{Pb}[{\mathrm{Zr}}_{1\ensuremath{-}x}{\mathrm{Ti}}_{x}]{\mathrm{O}}_{3}$, has been under discussion. In the present study, we investigated samples in the compositional range between $0.40\ensuremath{\leqslant}x\ensuremath{\leqslant}0.475$ and $x=0.55$ using high-resolution synchrotron x-ray diffraction in combination with transmission electron microscopy and electron paramagnetic resonance to correlate average structure and microstructural information. It is shown that the microstructure plays a crucial role in the analysis of diffraction data. The appearance of intensity in diffraction patterns formerly linked to a monoclinic phase [B. Noheda et al., Phys. Rev. B 61, 8687 (2000)] can directly be correlated to a miniaturization of the average domain structure of the material visible in the presence of nanodomains. The internal symmetry of the nanodomains is not necessarily monoclinic due to coherence effects in diffraction and is discussed with respect to martensitic theory.

In this work, the lead-free Ba(Zr0.2Ti0.8)O3-0.3(Ba0.7Ca0.3)TiO3 piezoelectric ceramic was investigated in situ under an applied electric field by transmission electron microscopy. Significant changes in domain morphology of the studied material have been observed under an applied electric field. During the poling process, the domain configurations disappeared, forming a single-domain state. This multi- to single-domain state transition occurred with the formation of an intermediate nanodomain state. After removing the electric field, domain configurations reappeared. Selected area electron diffraction during electrical poling gave no indication of any structural changes as for example reflection splitting. Rather, a contribution of the extrinsic effect to the piezoelectric response of the Ba(Zr0.2Ti0.8)O3-0.3(Ba0.7Ca0.3)TiO3 was found to be dominant.

Temperature-dependent dielectric permittivity of 0.94(Bi1/2Na1/2)TiO3-0.06BaTiO3 (BNT-6BT) lead-free piezoceramics was studied to disentangle the existing unclear issues over the crystallographic aspects and phase stability of the system. Application of existing phenomenological relaxor models enabled the relaxor contribution to the entire dielectric permittivity spectra to be deconvoluted. The deconvoluted data in comparison with the temperature-dependent dielectric permittivity of a classical perovskite relaxor, La-modified lead zirconate titanate, clearly suggest that BNT-6BT belongs to the same relaxor category, which was also confirmed by a comparative study on the temperature- dependent polarization hysteresis loops of both materials. Based on these results, we propose that the low-temperature dielectric anomaly does not involve any phase transition such as ferroelectric- to-antiferroelectric. Supported by transmission electron microscopy and X-ray diffraction experiments at ambient temperature, we propose that the commonly observed two dielectric anomalies are attributed to thermal evolution of ferroelectric polar nanoregions of R3c and P4bm symmetry, which coexist nearly throughout the entire temperature range and reversibly transform into each other with temperature.

Institute for Materials Science, Darmstadt University of Technology, Petersenstr.23, 64287 Darmstadt, Germany CELLS, P.O.B 68, 08193 Barcelona, Spain Institute of Ceramics in Mechanical Engineering, University of Karlsruhe, Haid-und-Neu-Str.7, 76131 Karlsruhe, Germany d Dept. of Materials Engineering and Industrial Technologies, University of Trento, Via Mesiano 77, 38050 Trento, Italy. E-mail: schoenau@matgeo.tu-darmstadt.de