Electron diffraction of tilted perovskites

Simulations of electron diffraction patterns for each of the known perovskite tilt systems have been performed. The conditions for the appearance of superlattice reflections arising from rotations of the octahedra are modified to take into account the effects of different tilt systems for kinematical diffraction. The use of selected-area electron diffraction as a tool for perovskite structure determination is reviewed and examples are included

HRTEM study of a new non-stoichiometric BaTiO(3-δ) structure

BaTiO3-based multilayer ceramic capacitors (MLCCs) with Ni internal electrodes are co-fired in reducing atmospheres to avoid oxidation of the electrode. Although dielectric materials are doped by acceptor, donor and amphoteric dopants to minimize the oxygen vacancy content, there is still a large concentration of oxygen vacancies that are accommodated in the BaTiO3 active layers. In general, ABO3 perovskites demonstrates a strong ability to accommodate the oxygen vacancies and maintain a regular pseudo-cubic structure. Oxygen deficient barium titanate can be transformed to a hexagonal polymorph (h-BT) at high temperatures1,2. In this paper, we report the new modulated and long range ordered structures of non-stoichiometric BaTiO3-δ that are observed in the electrically degraded Ni-BaTiO3 MLCCs at low temperature

Designing pseudocubic perovskites with enhanced nanoscale polarization

A crystal-chemical framework has been proposed for the design of pseudocubic perovskites with nanoscale ferroelectric order, and its applicability has been demonstrated using a series of represen- tative solid solutions that combined ferroelectric (K 0.5 Bi 0.5 TiO 3 , BaTiO 3 , and PbTiO 3 ) and antifer- roelectric (Nd-substituted BiFeO 3 ) end members. The pseudocubic structures obtained in these systems exhibited distortions that were coherent on a scale ranging from sub-nanometer to tens of nanometers, but, in all cases, the macroscopic distortion remained unresolvable even if using high- resolution X-ray powder diffraction. Different coherence lengths for the local atomic displacements account for the distinctly different dielectric, ferroelectric, and electromechanical properties exhib- ited by the samples. The guidelines identified provide a rationale for chemically tuning the coher- ence length to obtain the desired functional response

Guar gum: A novel binder for ceramic extrusion

Ceramic honeycomb extrusion is a technique capable of attaining high strength, porous ceramics. However, challenges prevent the realisation of its potential. These include the design of an intricate honeycomb die and the formulation of an extrudable paste. The present study addresses the latter by using guar gum (GG) as a binder. GG was rationally selected because hydrogels thereof exhibit strong shear-thinning and high stiffness properties, which are required for extrusion. Rheological analyses demonstrated ceramic pastes with similar qualities were achieved, with hydroxyapatite (HA) used as the model ceramic. The shear stiffness modulus of HA pastes was determined as 8.4 MPa with a yield stress of 1.1 kPa. Moreover, this was achieved with GG as the sole additive, which further facilitates the overall fabrication process. The binder extraction notably occurred at relatively low temperatures when other high molecular weight polymers demand temperatures above 1000 °C; therefore the latter precludes the use of ceramics with low sintering onset. The process culminated in a porous HA scaffold with similar porosity to that of a commercial HA graft, but with higher compressive strength. Lastly, the study notes that the biological and water-soluble properties of GG can broaden its application into other ceramic fabrication processes

Nanoscale polar heterogeneities and branching Bi-displacement directions in K0.5Bi0.5TiO3

K0.5Bi0.5TiO3 (KBT)—one of the few perovskite-like ferroelectric compounds with room-temperature tetragonal symmetry—differs from other members of its family (BaTiO3 and PbTiO3) by the presence of a disordered mixture of K and Bi on cuboctahedral sites. This disorder is expected to affect local atomic displacements and their response to an applied electric field. We have derived nanoscale atomistic models of KBT by refining atomic coordinates to simultaneously fit neutron/X-ray total scattering and extended X-ray absorption fine-structure data. Both Bi and Ti ions were found to be offset relative to their respective oxygen cages in the high-temperature cubic phase; in contrast, the coordination environment of K remained relatively undistorted. In the cubic structure, Bi displacements prefer the ⟨100⟩ directions and the probability density distribution of Bi features six well-separated sites; a similar preference exists for the much smaller Ti displacements, although the split sites for Ti could not be resolved. The cation displacements are correlated, yielding polar nanoregions, whereas on average, the structure appears as cubic. The cubic ↔ tetragonal phase transition involves both order/disorder and displacive mechanisms. A qualitative change in the form of the Bi probability density distribution occurs in the tetragonal phase on cooling to room temperature because Bi displacements “branch off” to ⟨111⟩ directions. This change, which preserves the average symmetry, is accompanied by the development of nanoscale polar heterogeneities that exhibit significant deviations of their polarization vectors from the average polar axis

Nanoscale Mapping of Bromide Segregation on the Cross Sections of 2 Complex Hybrid Perovskite Photovoltaic Films Using Secondary 3 Electron Hyperspectral Imaging in a Scanning Electron Microscope

Mixed halide (I/Br) complex organic/inorganic hybrid perovskite materials have attracted much attention recently because of their excellent photovoltaic properties. Although it has been proposed that their stability is linked to the chemical inhomogeneity of I/Br, no direct proof has been offered to date. Here, we report a new method, secondary electron hyperspectral imaging (SEHI), which allows direct imaging of the local variation in Br concentration in mixed halide (I/Br) organic/inorganic hybrid perovskites on a nanometric scale. We confirm the presence of a nonuniform Br distribution with variation in concentration within the grain interiors and boundaries and demonstrate how SEHI in conjunction with low-voltage scanning electron microscopy can enhance the understanding of the fundamental physics and materials science of organic/inorganic hybrid photovoltaics, illustrating its potential for research and development in “real-world” applications

Drivers of U.S. toxicological footprints trajectory 1998–2013

By exploiting data from the Toxic Release Inventory of the United States, we have established that the toxicological footprint (TF) increased by 3.3% (88.4 Mt) between 1998 and 1999 and decreased by 39% (1088.5 Mt) between 1999 and 2013. From 1999 to 2006, the decreasing TF was driven by improvements in emissions intensity (i.e. gains in production efficiency) through toxic chemical management options: cleaner production; end of pipe treatment; transfer for further waste management; and production scale. In particular, the mining sector reduced its TF through outsourcing processes. Between 2006 and 2009, decreasing TF was due to decrease in consumption volume triggered by economic recession. Since 2009, the economic recovery increased TF, overwhelming the influence of improved emissions intensity through population growth, consumption and production structures. Accordingly, attaining a less-toxic economy and environment will be influenced by a combination of gains in production efficiency through improvement in emissions mitigation technologies and changes in consumption patterns. Overall, the current analysis highlights the structural dynamics of toxic chemical release and would inform future formulation of effective mitigation standards and management protocols towards the detoxification of the environmen

Local structure, pseudosymmetry, and phase transitions in Na1/2Bi1/2TiO3-K1/2Bi1/2TiO3 ceramics

The structural behavior of ceramic solid solutions (1 - x)Na1/2Bi1/2TiO3-xK(1/2)Bi(1/2)TiO(3) (NBT-KBT) was studied using high-resolution powder diffraction and transmission electron microscopy. A temperature-independent morphotropic phase boundary (MPB) separating NBT-like pseudorhombohedral (R) and KBT-like pseudotetragonal (T) phases was observed at x approximate to 0.2. For x 0.2 exhibit a tetragonal-like distortion; however, complex splitting of reflections in XRD patterns suggests that the actual symmetry is lower than tetragonal. For 0.2 0.5 the structure becomes untilted. In-phase tilting evolves above the ferroelectric transition and occurs around a nonpolar (a or b) axis of the average T structure. The onset of polar order has no significant effect on the coherence length of in-phase tilting, which suggests only weak coupling between the two phenomena. The average symmetry of the T phase is determined by the effective symmetry (Imm2) of assemblages of coherent in-phase tilted nanodomains. Near the MPB, the coexistence of extended R-and T-like regions is observed, but lattice distortions within each phase are small, yielding narrow peaks with a pseudocubic appearance in XRD. The temperature of the FE phase transition exhibits a minimum at the MPB. The structured diffuse scattering observed in electron diffraction patterns for all the compositions suggests that polar order in NBT-KBT solid solutions is modulated away from the average displacements refined using powder diffraction data.open13