Andrew J. Studer

Direct measurement of the domain switching contribution to the dynamic piezoelectric response in ferroelectric ceramics

The dynamic piezoelectric response of ferroelectric ceramics is comprised of both intrinsic (piezoelectric lattice strain) and extrinsic (non-180° domain wall motion) components. Here the authors report direct measurements of non-180° domain wall motion in ceramic lead zirconate titanate during application of subcoercive cyclic driving electric fields using an in situ stroboscopic neutron diffraction technique. During unipolar cycling at 1Hz and half of the coercive field, non-180° domain switching gives rise to approximately 34% of the measured d33 coefficient of 400pm∕V.

Electric-field-induced strain mechanisms in lead-free 94%(Bi1/2Na1/2)TiO3–6%BaTiO3

High resolution neutron diffraction has been used to investigate the structural origin of the large electric-field-induced remanent strain in 94(Bi1/2Na1/2)TiO3–6BaTiO3 ceramics. The virgin material was found to be a mixture of near-cubic phases with slight tetragonal and rhombohedral distortions of a0a0c+ and a−a−a− octahedral tilt type, respectively. Application of an electric field of 4.57 kV/mm transformed the sample to a predominantly rhombohedral a−a−a− modification with a significantly higher degree of structural distortion and a pronounced preferred orientation of the c-axis along the field direction. These electric field-induced structural effects contribute significantly to the macroscopic strain and polarization of this system.

A kinetic study of the exsolution of pentlandite (Ni, Fe)9S8 from the monosulfide solid solution (Fe, Ni)S

Abstract The kinetics of the exsolution of pentlandite from the monosulfide solid solution (mss) have been investigated using a series of anneal/quench and in situ cooling neutron diffraction experiments. Five mss compositions were examined by anneal/quench techniques covering the composition range Fe0.9Ni0.1S to Fe0.65Ni0.35S and using annealing temperatures between 423 and 773 K for periods from I h to 5 months. In situ cooling experiments were performed on four mss compositions in the range Fe0.9Ni0.1S to Fe0.7Ni0.3S. The samples of these solid solutions were heated to 973 K, and then cooled to 373 K in steps of 50 K over a 24 h period. The extent of exsolution was monitored by Rietveld phase analysis using powder neutron diffraction data. The anneal/quench experiments established that initial exsolution of pentlandite from mss above 573 K is very rapid and is effectively complete within 1 h of annealing. However, the mss/pyrrhotite compositions remained Ni rich (17 at% Ni) after 5 months annealing, indicating that compositional readjustment at low-temperatures occurs over long periods. Below 573 K, exsolution is less rapid with rate constants in the range 6 × 1O-6 to 1 × 10-5/s and the activation energy for exsolution of pentlandite from mss Fe0.5Ni0.2S between 473 and 423 K is 5 kJ/mol. The in situ cooling experiments showed that the temperature at which exsolution commences upon cooling decreases from 873 K for Fe0.7Ni0.3S to 823 K for Fe0.9Ni0.1S and that exsolution effectively ceased on the time scale of the experiments at temperatures between 598 and 548 K. The kinetic data were analyzed using the Avrami model where y = 1 - exp(-kntn) and the initial rates of exsolution were found to increase with Ni content from 2 × 1O-6Zs for Fe0.9Ni0.3S to 4 × 10-5/s for Fe0.7Ni0.3S. Both high Ni content and high M: S ratio served to facilitate nucleation rate, indicating that nucleation occurs at S vacancies within mss crystals rather than at grain boundaries. Values of the Avrami geometric constant n vary during exsolution upon cooling indicating three possible changes in the growth mechanism during the reaction. The roles of impurities and S fugacity on reaction rates are discussed. The rate constants for exsolution of pentlandite from mss/pyrrhotite in nature are estimated to be 4 or 5 orders of magnitude slower than those reported here, still very rapid on a geological time scale. High metal mobility persists in this system at low temperatures, even at room temperature, and the textures and compositions observed in nature are a consequence of very low-temperature (<100 0C) equilibration of assemblages over geological time scales.

Magnetocaloric effect in layered NdMn2Ge0.4Si1.6

A giant magnetocaloric effect has been observed in NdMn2Ge0.4Si1.6 associated with the first-order magnetic phase transition from antiferromagnetism to ferromagnetism around TC=36K. The magnetic entropy change –ΔSM and adiabatic temperature change ΔTad have been determined from magnetization and specific heat measurements (B=0–5 T) with –ΔSM calculated by the Maxwell relation and Clausius–Clapeyron method. The values –ΔSMmax=12.3 J kg−1 K−1 and refrigerant capacity ∼95 J/kg for ΔB=0–2 T as derived from the Maxwell relation, together with the small hysteresis (thermal <0.5 K; magnetic field <0.1 T), indicate the potential of NdMn2Ge0.4Si1.6 for refrigeration applications.

Origin of large recoverable strain in 0.94(Bi0.5Na0.5)TiO3-0.06BaTiO3 near the ferroelectric-relaxor transition

Piezoceramics of composition 0.94(Bi0.5Na0.5)TiO3-0.06BaTiO3 demonstrate large recoverable strain at elevated temperature (T > 75 °C), which is absent at room temperature. In situ neutron diffraction was used to measure changes in the crystallographic and domain structures during electric field application at temperatures ranging from 25 °C to 100 °C. Quantitative evaluation of the ferroelastic domain volume fraction in the field-induced phases enabled calculation of the strain contribution from non-180° domain switching. The large recoverable strain is shown to be associated with the reversible nature of the phase transformation. These findings have implications to additional BNT-xBT-based composition and other relaxor ferroelectrics.

Time-resolved diffraction measurements of electric-field-induced strain in tetragonal lead zirconate titanate

The dynamic electric-field-induced strain in piezoelectric ceramics enables their use in a broad range of sensor, actuator, and electronic devices. In piezoelectric ceramics which are also ferroelectric, this macroscopic strain is comprised of both intrinsic (piezoelectric) and extrinsic (non-180° domain switching) strain components. Extrinsic contributions are accompanied by hysteresis, nonlinearity, and fatigue. Though technologically significant, direct measurement of these mechanisms and their relative contributions to the macroscopic response has not yet been achieved at driving frequencies of interest. Here we report measurements of these mechanisms in ceramic lead zirconate titanate during application of subcoercive cyclic driving electric fields using an in-situ stroboscopic neutron diffraction technique. Calculations are made from the diffraction measurements to determine the relative contributions of these different strain mechanisms. During applied electric field square waves of +0.5Ec unipolar and ±0.5Ec bipolar, at 1 Hz, non-180° domain switching is found to contribute 34% and 40% of the macroscopically measured strain, respectively.The dynamic electric-field-induced strain in piezoelectric ceramics enables their use in a broad range of sensor, actuator, and electronic devices. In piezoelectric ceramics which are also ferroelectric, this macroscopic strain is comprised of both intrinsic (piezoelectric) and extrinsic (non-180° domain switching) strain components. Extrinsic contributions are accompanied by hysteresis, nonlinearity, and fatigue. Though technologically significant, direct measurement of these mechanisms and their relative contributions to the macroscopic response has not yet been achieved at driving frequencies of interest. Here we report measurements of these mechanisms in ceramic lead zirconate titanate during application of subcoercive cyclic driving electric fields using an in-situ stroboscopic neutron diffraction technique. Calculations are made from the diffraction measurements to determine the relative contributions of these different strain mechanisms. During applied electric field square waves of +0.5Ec unipolar...

Extreme compressibility in LnFe(CN) 6 coordination framework materials via molecular gears and torsion springs

The mechanical flexibility of coordination frameworks can lead to a range of highly anomalous structural behaviours. Here, we demonstrate the extreme compressibility of the LnFe(CN)6 frameworks (Ln = Ho, Lu or Y), which reversibly compress by 20% in volume under the relatively low pressure of 1 GPa, one of the largest known pressure responses for any crystalline material. We delineate in detail the mechanism for this high compressibility, where the LnN6 units act like torsion springs synchronized by rigid Fe(CN)6 units performing the role of gears. The materials also show significant negative linear compressibility via a cam-like effect. The torsional mechanism is fundamentally distinct from the deformation mechanisms prevalent in other flexible solids and relies on competition between locally unstable metal coordination geometries and the constraints of the framework connectivity, a discovery that has implications for the strategic design of new materials with exceptional mechanical properties.

Neutron diffraction study of the polarization reversal mechanism in [111]c-oriented Pb(Zn1∕3Nb2∕3)O3−xPbTiO3

The polarization reversal mechanism in [111]c-oriented Pb(Zn1∕3Nb2∕3)O3−xPbTiO3 has been investigated by in-situ neutron diffraction. Stepwise static-field measurements of the (222)c rocking curves confirm a two-stage polarization reversal mechanism via a sequence of non-180° domain reorientations. The time-resolved response has also been measured upon application of a bipolar square wave with a 30 s period to observe directly the relaxation times of diffracted neutron intensity during the reversal process. Upon application of a large antipolar field, the diffraction intensity increases quickly, before relaxing over a longer time period with an exponential decay constant, τ, of approximately 5.7 s. These large time constants correlate with a frequency dependence of the macroscopic strain-field response.

Room-Temperature Polar Ferromagnet ScFeO3 Transformed from a High-Pressure Orthorhombic Perovskite Phase

Multiferroic materials have been the subject of intense study, but it remains a great challenge to synthesize those presenting both magnetic and ferroelectric polarizations at room temperature. In this work, we have successfully obtained LiNbO3-type ScFeO3, a metastable phase converted from the orthorhombic perovskite formed under 15 GPa at elevated temperatures. A combined structure analysis by synchrotron X-ray and neutron powder diffraction and high-angle annular dark-field scanning transmission electron microscopy imaging reveals that this compound adopts the polar R3c symmetry with a fully ordered arrangement of trivalent Sc and Fe ions, forming highly distorted ScO6 and FeO6 octahedra. The calculated spontaneous polarization along the hexagonal c-axis is as large as 100 μC/cm(2). The magnetic studies show that LiNbO3-type ScFeO3 is a weak ferromagnet with TN = 545 K due to a canted G-type antiferromagnetic ordering of Fe(3+) spins, representing the first example of LiNbO3-type oxides with magnetic ordering far above room temperature. A comparison of the present compound and rare-earth orthorhombic perovskites RFeO3 (R = La-Lu and Y), all of which possess the corner-shared FeO6 octahedral network, allows us to find a correlation between TN and the Fe-O-Fe bond angle, indicating that the A-site cation-size-dependent octahedral tilting dominates the magnetic transition through the Fe-O-Fe superexchange interaction. This work provides a general and versatile strategy to create materials in which ferroelectricity and ferromagnetism coexist at high temperatures.

Domain fragmentation during cyclic fatigue in 94%(Bi1/2Na1/2)TiO3-6%BaTiO3

The fatigue of the lead-free piezoceramic 94%(Bi1/2Na1/2)TiO3-6%BaTiO3 was investigated under bipolar electric fields. Degradation of the polarization, strain, and permittivity was measured during the fatigue process, and correlated with structural data measured at incremental points in the fatigue process using neutron diffraction. The results suggest a two-stage fatigue mechanism whereby, following a field-induced phase transformation to a poled ferroelectric state, the domain structure becomes progressively fragmented by a repetitive process of domain wall pinning and subdivision.