Elastic and anelastic relaxations accompanying relaxor ferroelectric behaviour of Ba6GaNb9O30 tetragonal tungsten bronze from resonant ultrasound spectroscopy

Tetragonal tungsten bronze (TTB) structures offer some promise as lead-free ferroelectrics and have an advantage of great flexibility in terms of accessible composition ranges due to the number of crystallographic sites available for chemical substitution. The ferroic properties of interest are coupled with strain, which will be important in the context of stability, switching dynamics and thin film properties. Coupling of strain with the ferroelectric order parameter gives rise to changes in elastic properties, and these have been investigated for a ceramic sample of Ba6GaNb9O30 (BGNO) by resonant ultrasound spectroscopy. Room temperature values of the shear and bulk moduli for BGNO are rather higher than for TTBs with related composition which are orthorhombic at room temperature, consistent with suppression of the ferroelectric transition. Instead, a broad, rounded minimum in the shear modulus measured at ~1 MHz is accompanied by a broad rounded maximum in acoustic loss near 115 K and signifies relaxor freezing behaviour. Elastic softening with falling temperature from room temperature, ahead of the freezing interval, is attributed to the development of dynamical polar nanoregions (PNRs), whilst the nonlinear stiffening below ~115 K is consistent with a spectrum of relaxation times for freezing of the PNR microstructure

Giant thermally-enhanced electrostriction and polar surface phase in La2Mo2O9 oxygen ion conductors

Ferroelectrics possess spontaneous electric polarization at macroscopic scales which nonetheless imposes strict limitations on the material classes. Recent discoveries of untraditional symmetry-breaking phenomena in reduced material dimensions have indicated feasibilities to extend polar properties to broader types of materials, potentially opening up the freedom for designing materials with hybrid functionalities. Here, we report the unusual electromechanical properties of La2Mo2O9 (LAMOX) oxygen ion conductors, systematically investigated at both bulk and surface length levels. We first observed giant electrostriction effects in La2Mo2O9 bulk ceramics that are thermally enhanced in concert with their low-energy oxygen-vacancy hopping dynamics. Moreover, while no clear bulk polarization was detected, the surface phases of LAMOX were found to be manifestly polar, likely originating from the coupling between the intrinsic structural flexibilities with strain gradients (i.e., flexoelectricity) and/or chemical heterogeneities present in the materials. These findings identify La2Mo2O9 as a promising electromechanical material system and suggest that the flexible structural and chemical configurations in ionically active materials could enable fundamentally different venues to accommodate electric polarization.Q.L. and H.W. were supported by the US Department of Energy, Office of Science, Materials Science and Engineering Division. T.L. and Y.L. acknowledge the support of the Australian Research Council (ARC) in the form of Discovery Projects (DP160104780). N.L. was supported by the Eugene P. Wigner Fellowship program at ORNL (No. DE-AC05-00OR22725). The PFM experiments were performed at the Center for Nanophase Materials Sciences, which is a DOE Office of Science User Facility at Oak Ridge National Laboratory (ORNL). The use of Advanced Photon Source was supported by the US DOE, Basic Energy Science under Contract No. DE-AC02-06CH11357

Giant thermally-enhanced electrostriction and polar surface phase in La2Mo2O9 oxygen ion conductors

Ferroelectrics possess spontaneous electric polarization at macroscopic scales which nonetheless imposes strict limitations on the material classes. Recent discoveries of untraditional symmetry-breaking phenomena in reduced material dimensions have indicated feasibilities to extend polar properties to broader types of materials, potentially opening up the freedom for designing materials with hybrid functionalities. Here, we report the unusual electromechanical properties of La2Mo2O9 (LAMOX) oxygen ion conductors, systematically investigated at both bulk and surface length levels. We first observed giant electrostriction effects in La2Mo2O9 bulk ceramics that are thermally enhanced in concert with their low-energy oxygen-vacancy hopping dynamics. Moreover, while no clear bulk polarization was detected, the surface phases of LAMOX were found to be manifestly polar, likely originating from the coupling between the intrinsic structural flexibilities with strain gradients (i.e., flexoelectricity) and/or chemical heterogeneities present in the materials. These findings identify La2Mo2O9 as a promising electromechanical material system and suggest that the flexible structural and chemical configurations in ionically active materials could enable fundamentally different venues to accommodate electric polarization

Elastic and anelastic relaxations associated with phase transitions in EuTiO3

Elastic and anelastic properties of single crystal samples of EuTiO3 have been measured between 10 and 300 K by resonant ultrasound spectroscopy at frequencies in the vicinity of 1 MHz. Softening of the shear elastic constants C44 and 12(C11−C12) by ∼20–30% occurs with falling temperature in a narrow interval through the transition point, Tc=284 K, for the cubic-tetragonal transition. This is accounted for by classical coupling of macroscopic spontaneous strains with the tilt order parameter in the same manner as occurs in SrTiO3. A peak in the acoustic loss occurs a few degrees below Tc and is interpreted in terms of initially mobile ferroelastic twin walls, which rapidly become pinned with further lowering of temperature. This contrasts with the properties of twin walls in SrTiO3, which remain mobile down to at least 15 K. No further anomalies were observed that might be indicative of strain coupling to any additional phase transitions above 10 K. A slight anomaly in the shear elastic constants, independent of frequency and without any associated acoustic loss, was found at ∼140 K. It marks a change from elastic stiffening to softening with falling temperature and perhaps provides evidence for coupling between strain and local fluctuations of dipoles related to the incipient ferroelectric transition. An increase in acoustic loss below ∼80 K is attributed to the development of dynamical magnetic clustering ahead of the known antiferromagnetic ordering transition at ∼5.5 K. Detection of these elastic anomalies serves to emphasize that coupling of strain with tilting, ferroelectric, and magnetic order parameters is likely to be a permeating influence in determining the structure, stability, properties, and behavior of EuTiO3

Ca-doping of BiFeO 3 : the role of strain in determining coupling between ferroelectric displacements, magnetic moments, octahedral tilting, and oxygen-vacancy ordering

Elastic and anelastic properties of a member of the BiFeO 3-CaFeO2.5 perovskite solid solution (BCFO), which is known to have multiple instabilities, have been investigated by resonant ultrasound spectroscopy. This phase, with 64% Bi and 36% Ca on the A

The Effect of Ta Doping on the Phase Transitions and the Piezoelectric and Ferroelectric Properties of K0.35Na0.65NbO3

The ferroelectric, piezoelectric and phase transition behavior of high-density K0.35Na0.65 NbO3 samples prepared by solid state synthesis, and changes in these properties with Ta doping are reported, including improvement of piezoelectric coefficient d33s. Piezoresponse force microscopy is used to investigate the ferroelectric domain structure. Temperature-dependent resonant ultrasound spectroscopy is used to investigate phase transitions as well as internal friction. Tuning of the monoclinic to tetragonal phase transition to room temperature is predicted at ∼35% Ta doping

Ca-Doping of BiFeO3: The Role of Strain in Determining Coupling between Ferroelectric Displacements, Magnetic Moments, Octahedral Tilting, and Oxygen-Vacancy Ordering

Elastic and anelastic properties of a member of the BiFeO3?CaFeO2.5 perovskite solid solution (BCFO), which is known to have multiple instabilities, have been investigated by resonant ultrasound spectroscopy. This phase, with 64% Bi and 36% Ca on the A site, is antiferromagnetic (TN ?650 K) and has an ordered arrangement of oxygen vacancies with tetragonal lattice geometry. The inverse mechanical quality factor, Q?1, has a maximum near 100 K, correlating closely with a peak in dielectric loss, reported previously, consistent with a loss mechanism that involves the movement of oxygen vacancies accompanied by local lattice distortion. At higher temperature, there is a further acoustic loss peak that is correlated with complex impedance anomalies. There is no clear relationship to the magnetic transition, and the observations are interpreted as relating to ionic conductivity. A small stiffening, scaling with the square of the magnetic order parameter below TN, indicates that the main coupling with strain is biquadratic, confirming that conventional coupling of magnetic order with symmetry-breaking shear strains is weak in BCFO. Data from the literature for BCFO indicates that local strain fields are likely to be responsible for suppressing the spin cycloid present in BiFeO3

K0.46Na0.54NbO3 ferroelectric ceramics: chemical synthesis, electro-mechanical characteristics, local crystal chemistry and elastic anomalies

K0.46Na0.54NbO3 ceramics have been fabricated via a chemical synthesis route. It was found that 500 [degree]C heat treatment is sufficient to crystallize the niobate powder and the ceramic sintered at 1080 [degree]C in air shows good ferroelectric and piezoelectric properties (Pr [similar] 15 [small mu ]C cm-2, d33 [similar] 120 pC N-1). Electron diffraction patterns not only determine the space group symmetry of Pcm21 for the first time, but also reveal structural disorder in K0.46Na0.54NbO3, and 1-D correlated strings of Nb-O atomic displacements are suggested to account for the polar behaviour. Elastic constants such as the bulk and shear moduli as well as their evolution with temperature were also measured using the resonant ultrasound spectroscopy method