Jennifer S. Forrester

Temperature-induced local and average structural changes in BaTiO3−xBi(Zn1/2Ti1/2)O3 solid solutions: The origin of high temperature dielectric permittivity

The existence of local tetragonal distortions is evidenced in the BaTiO3–xBi(Zn1/2Ti1/2)O3 (BT–xBZT) relaxor dielectric material system at elevated temperatures. The local and average structures of BT-xBZT with different compositions are characterized using in situ high temperature total scattering techniques. Using the box-car fitting method, it is inferred that there are tetragonal polar clusters embedded in a non-polar pseudocubic matrix for BT-xBZT relaxors. The diameter of these polar clusters is estimated as 2–3u2009nm at room temperature. Sequential temperature series fitting shows the persistence of the tetragonal distortion on the local scale, while the average structure transforms to a pseudocubic paraelectric phase at high temperatures. The fundamental origin of the temperature stable permittivity of BT-xBZT and the relationship with the unique local scale structures are discussed. This systematic structural study of the BT-xBZT system provides both insight into the nature of lead-free perovskite r...

Time-of-flight neutron total scattering with applied electric fields: Ex situ and in situ studies of ferroelectric materials

Characterizing the structural response of functional materials (e.g., piezoelectrics and ferroelectrics) to electric fields is key for the creation of structure-property relationships. Here, we present a new sample environment and data reduction routines which allow the measurement of time-of-flight neutron total scattering during the in situ or ex situ application of high voltage (<10 kV) to a sample. Instead of utilizing the entire detector space of the diffractometer, only selected regions of detector pixels with scattering at the desired angle to the sample electric field are interrogated, which allows the generation of orientation-dependent reciprocal space patterns and real-space pair distribution functions (PDFs). We demonstrate the method using the relaxor ferroelectric Na1/2Bi1/2TiO3 and observe lattice expansion parallel and contraction perpendicular to the electric field for both in situ and ex situ experiments, revealing the irreversible nature of the local scale structural changes to this composition. Additionally, changes in the distributions of nearest neighbor metal-oxygen bond lengths are observed, which have been difficult to observe in previously measured analogous orientation-dependent X-ray PDFs. Considerations related to sample positioning and background subtraction are discussed, and future research directions are suggested.

Effect of mechanical depoling on piezoelectric properties of Na0.5Bi0.5TiO3–xBaTiO3 in the morphotropic phase boundary region

The effect of mechanical stress on the direct piezoelectric properties of pre-poled (1xa0−xa0x)(Na0.5Bi0.5)TiO3–xBaTiO3 (NBT–xBT) in the range 4%xa0≤xa0xxa0≤xa013% was studied in situ using a mechanical load frame. Prior to mechanical loading, compositions near the morphotropic phase boundary (MPB, xxa0=xa06–7% BT) exhibited enhanced ferroelectric and piezoelectric properties compared to compositions further from the MPB. Specifically, the lowest ferroelectric coercive field and highest piezoelectric coefficient within this composition range occur at xxa0=xa07% BT. During mechanical compression, the MPB compositions exhibited the lowest depoling stress. The results demonstrate that, while favorable piezoelectric and ferroelectric properties can be obtained at compositions near the MPB, these compositions are also the most susceptible to the effects of mechanical depoling. Ferroelastic domain wall motion is suggested as the primary factor that may be responsible for these behaviors.

Unexpectedly high piezoelectricity of Sm-doped lead zirconate titanate in the Curie point region

Large piezoelectric coefficients in polycrystalline lead zirconate titanate (PZT) are traditionally achieved through compositional design using a combination of chemical substitution with a donor dopant and adjustment of the zirconium to titanium compositional ratio to meet the morphotropic phase boundary (MPB). In this work, a different route to large piezoelectricity is demonstrated. Results reveal unexpectedly high piezoelectric coefficients at elevated temperatures and compositions far from the MPB. At temperatures near the Curie point, doping with 2 at% Sm results in exceptionally large piezoelectric coefficients of up to 915u2009pm/V. This value is approximately twice those of other donor dopants (e.g., 477u2009pm/V for Nb and 435u2009pm/V for La). Structural changes during the phase transitions of Sm-doped PZT show a pseudo-cubic phase forming ≈50u2009°C below the Curie temperature. Possible origins of these effects are discussed and the high piezoelectricity is posited to be due to extrinsic effects. The enhancement of the mechanism at elevated temperatures is attributed to the coexistence of tetragonal and pseudo-cubic phases, which enables strain accommodation during electromechanical deformation and interphase boundary motion. This work provides insight into possible routes for designing high performance piezoelectrics which are alternatives to traditional methods relying on MPB compositions.

Promising solid electrolyte material for an IT-SOFC: crystal structure of the cerium gadolinium holmium oxide Ce0.8Gd0.1Ho0.1O1.9 between 295 and 1023 K

The crystal structure of Ce0.8Gd0.1Ho0.1O1.9 (cerium gadolinium holmium oxide) has been determined from powder X-ray diffraction data. This is a promising material for application as a solid electrolyte for intermediate-temperature solid oxide fuel cells (IT-SOFCs). Nanoparticles were prepared using a novel sodium alginate sol-gel method, where the sodium ion was exchanged with ions of interest and, after washing, the gel was calcined at 723u2005K in air. The crystallographic features of Gd and Ho co-doped cerium oxide were investigated around the desired operating temperatures of IT-SOFCs, i.e. 573 ≤ T ≤ 1023u2005K. We find that the crystal structure is a stable fluorite structure with the space group Fm-3m in the entire temperature range. In addition, the trend in lattice parameters shows that there is a monotonic increase with increasing temperature.