Neutron powder-diffraction study of phase transitions in strontium-doped bismuth ferrite: 1. Variation with chemical composition.

We report results from a study of the crystal and magnetic structures of strontium-doped BiFeO3using neutron powder diffraction and the Rietveld method. Measurements were obtained over a wide range of temperatures from 300-800 K for compositions between 10%-16% replacement of bismuth by strontium. The results show a clear variation of the two main structural deformations-symmetry-breaking rotations of the FeO6octahedra and polar ionic displacements that give ferroelectricity-with chemical composition, but relatively little variation with temperature. On the other hand, the antiferromagnetic order shows a variation with temperature and a second-order phase transition consistent with the classical Heisenberg model. There is, however, very little variation in the behaviour of the antiferromagnetism with chemical composition, and hence with the degree of the structural symmetry-breaking distortions. We therefore conclude that there is no significant coupling between antiferromagnetism and ferroelectricity in Sr-doped BiFeO3and, by extension, in pure BiFeO3.

Nanostructured Cu2O Synthesized via Bipolar Electrochemistry.

Cuprous oxide (Cu2O) was synthesized for the first time via an open bipolar electrochemistry (BPE) approach and characterized in parallel with the commercially available material. As compared to the reference, Cu2O formed through a BPE reaction demonstrated a decrease in particle size; an increase in photocurrent; more efficient light scavenging; and structure-correlated changes in the flat band potential and charge carrier concentration. More importantly, as-synthesized oxides were all phase-pure, defect-free, and had an average crystallite size of 20 nm. Ultimately, this study demonstrates the impact of reaction conditions (e.g., applied potential, reaction time) on structure, morphology, surface chemistry, and photo-electrochemical activity of semiconducting oxides, and at the same time, the ability to maintain a green synthetic protocol and potentially create a scalable product. In the proposed BPE synthesis, we introduced a common food supplement (potassium gluconate) as a reducing and complexing agent, and as an electrolyte, allowing us to replace the more harmful reactants that are conventionally used in Cu2O production. In addition, in the BPE process very corrosive reactants, such as hydroxides and metal precursors (required for synthesis of oxides), are generated in situ in stoichiometric quantity, providing an alternative methodology to generate various nanostructured materials in high yields under mild conditions.

Investigation of the role of morphology on the magnetic properties of Ca2Mn3O8 materials.

Ca2Mn3O8 exhibits a complex layered structure comprised of Mn3O84- layers separated by Ca2+ ions. In contrast with the more traditional triangular delafossite layered materials the Mn3O84- layers additionally exhibit an ordered vacancy, which forms a 'bow-tie' like arrangement of the Mn4+ ions. We report a comprehensive study of the magnetic properties of a series of Ca2Mn3O8 materials with different morphologies. EXAFS and XANES analysis confirm no differences in either manganese environment or oxidation state between materials. Apparent differences in magnetic order from SQUID magnetometry can be rationalised by uncompensated surface spins arising as a result of changes to the surface to volume ratio between morphologies. Furthermore, these data suggest these materials are potentially frustrated in nature, due to the triangular connectivity of Mn4+ spins, with a simple 'spin-up/spin-down' (↑↓) antiferromagnetic model unable to explain the data collected.

PZT-like structural phase transitions in the BiFeO3-KNbO3 solid solution.

Despite the high prominence of the perovskites BiFeO(3) and KNbO(3) the solid solution between the two has received little attention. We report a detailed neutron and synchrotron X-ray powder diffraction, and Raman spectroscopy study which demonstrates an R3c→P4mm→Amm2 series of structural phase transitions similar to that exhibited by the PbZrO(3)-PbTiO(3) solid solution.

Effect of local A-site strain on dipole stability in A6GaNb9O30 (A = Ba, Sr, Ca) tetragonal tungsten bronze relaxor dielectrics.

A series of isovalently A-site substituted relaxor dielectric tetragonal tungsten bronzes of general formula Ba(6-x-y)Sr(x)Ca(y)GaNb(9)O(30) were investigated. The long-range (average) crystal structure as determined by conventional diffraction techniques varies monotonically according to Vegard's law. The dielectric properties, however, do not display a similar, simple "average size" dependence and instead show a dependence on the statistical size variance, i.e. size mismatch, of the A-cation. The difficulties in Vogel-Fulcher analysis of relative permittivity and the complementary approach of using dielectric loss data fitted to Jonscher's empirical universal dielectric relaxation model is discussed.

Composition-driven structural phase transitions in rare-earth-doped BiFeO3 ceramics: a review.

Bismuth ferrite suffers from high leakage currents and the presence of a complex incommensurate spin cycloidal magnetic ordering, which has limited its commercial viability and has led researchers to investigate the functionality of doped BiFeO3 ceramics. In particular, the substitution of rare earths onto the Bi(3+) site of the perovskite lattice have been shown to lead to improved functional properties, including lower leakage currents and the suppression of the magnetic spin cycloid. There is particular interest in materials with compositions close to structural morphotropic phase boundaries, because these may lead to materials with enhanced electronic and magnetic properties analogous to the highly relevant PbZrO3- PbTiO3 solid solution. However, many contradictory crystal structures and physical behaviors are reported within the literature. To understand the structure-property relationships in these materials, it is vital that we first unravel the complex structural phase diagrams. We report here a comprehensive review of structural phase transitions in rare-earth-doped bismuth ferrite ceramics across the entire lanthanide series. We attempt to rationalize the literature in terms of the perovskite tool kit and propose an updated phase diagram based on an interpretation of the literature.

Towards novel multiferroic and magnetoelectric materials: dipole stability in tetragonal tungsten bronzes.

We discuss the strategy for development of novel functional materials with the tetragonal tungsten bronze structure. From the starting composition Ba6GaNb9O30, the effect of A- and B-site substitutions on the dielectric properties is used to develop an understanding of the origin and stability of the dipolar response in these compounds. Both tetragonal strain induced by large B-site cations and local strain variations created by isovalent A-site substitutions enhance dipole stability but result in a dilute, weakly correlated dipolar response and canonical relaxor behaviour. Decreasing cation size at the perovskite A2-site increases the dipolar displacements in the surrounding octahedra, but insufficiently to result in dipole ordering. Mechanisms introducing small A-site lanthanide cations and incorporation of A-site vacancies to induce ferroelectricity and magnetism are presented.

Ferroelectric-paraelectric transition in BiFeO3: crystal structure of the orthorhombic beta phase.

A detailed investigation using variable temperature powder neutron diffraction demonstrates that BiFeO3 undergoes a phase transition from the ferroelectric alpha phase (rhombohedral, R3c) to a paraelectric beta phase (orthorhombic, Pbnm) between 820 degrees C and 830 degrees C. Coexistence of both phases over a finite temperature interval, together with abrupt changes in key structural parameters, confirms that the transition is first order. The beta phase corresponds to a GdFeO3-type perovskite structure.

The synthesis and characterisation of ferromagnetic CaMn2O4 nanowires.

The synthesis of marokite CaMn(2)O(4) nanowires using a hydrothermal method is reported. Transmission electron microscopy and electron diffraction measurements show that the nanowires are polycrystalline in nature with diameters between 10 and 20 nm and lengths ranging from approximately 100 to 500 nm. Most interestingly, in contrast with the bulk material, magnetization measurements show that these nanowires exhibit ferromagnetic ordering with a Curie temperature (T(C)) of approximately 40 K.

Synthesis and characterization of highly ordered cobalt-magnetite nanocable arrays.

Magnetically tunable, high-density arrays of coaxial nanocables within anodic aluminum oxide (AAO) membranes have been synthesized. The nanocables consist of magnetite nanowires surrounded by cobalt nanotube sheaths and cobalt nanowires surrounded by magnetite nanotube sheaths. These materials are a combination of separate hard (Co) and soft (Fe3O4) magnetic materials in a single nanocable structure. The combination of two or more magnetic materials in such a radial structure is seen as a very powerful tool for the future fabrication of magnetoresistive, spin-valve and ultrafast spin-injection devices with nonplanar geometries. The nanocable arrays were prepared using a supercritical-fluid inclusion process, whereby the nanotube was first deposited onto the pore walls of the nanoporous membranes and subsequently filled with core material to form coaxial nanocables. In essence, this paper describes a technique for placing novel magnetic technologies into well-defined building blocks that may ultimately lead to new multifunctional devices, such as spin valves and high-density magnetic storage devices.

A new series of sodium cobalt oxyhydrates.

We report a new series of sodium cobalt oxyhydrates that contains the same two dimensional building blocks as superconducting NaxCoO2.yH2O. The absence of superconductivity emphasises the importance of the CoO2 stacking arrangement on the resultant electronic properties.