Probing spin waves in CoO nanoparticles for magnonics applications.

The magnetic properties of spinel nanoparticles can be controlled by synthesizing particles of a specific shape and size. The synthesized nanorods, nanodots and cubic nanoparticles have different crystal planes selectively exposed on the surface. The surface effects on the static magnetic properties are well documented, while their influence on spin waves dispersion is still being debated.

Unravelling Magnetic Nanochain Formation in Dispersion for In Vivo Applications.

Self-assembly of iron oxide nanoparticles (IONPs) into 1D chains is appealing, because of their biocompatibility and higher mobility compared to 2D/3D assemblies while traversing the circulatory passages and blood vessels for in vivo biomedical applications. In this work, parameters such as size, concentration, composition, and magnetic field, responsible for chain formation of IONPs in a dispersion as opposed to spatially confining substrates, are examined. In particular, the monodisperse 27 nm IONPs synthesized by an extended LaMer mechanism are shown to form chains at 4 mT, which are lengthened with applied field reaching 270 nm at 2.

Mechanism of magnetization reduction in iron oxide nanoparticles.

Iron oxide nanoparticles are presently considered as main work horses for various applications including targeted drug delivery and magnetic hyperthermia. Several questions remain unsolved regarding the effect of size onto their overall magnetic behavior. One aspect is the reduction of magnetization compared to bulk samples.

Structural water and disordered structure promote aqueous sodium-ion energy storage in sodium-birnessite.

Birnessite is a low-cost and environmentally friendly layered material for aqueous electrochemical energy storage; however, its storage capacity is poor due to its narrow potential window in aqueous electrolyte and low redox activity. Herein we report a sodium rich disordered birnessite (NaMnO) for aqueous sodium-ion electrochemical storage with a much-enhanced capacity and cycling life (83 mAh g after 5000 cycles in full-cell). Neutron total scattering and in situ X-ray diffraction measurements show that both structural water and the Na-rich disordered structure contribute to the improved electrochemical performance of current cathode material.

Incommensurate Magnetism Near Quantum Criticality in CeNiAsO.

We report the discovery of incommensurate magnetism near quantum criticality in CeNiAsO through neutron scattering and zero field muon spin rotation. For T View Article and Find Full Text PDF

Impact of Average, Local, and Electronic Structure on Visible Light Photocatalysis in Novel BiREWO (RE = Eu and Tb) Nanomaterials.

Crystal structures of hydrothermally synthesized BiEuWO and BiTbWO nanomaterials are deduced for the first time by combined Rietveld refinement of neutron and synchrotron data using the ordered and disordered models available in literature. The ordered model is validated for the average structure of these nanomaterials, and it is further supported by the local structure analysis using neutron pair distribution function. Nanomaterials are characterized by field-emission scanning electron microscopy, transmission electron microscopy, Brunauer-Emmett-Teller surface area, diffused reflectance spectroscopy, and Raman Spectroscopy.

Universal geometric frustration in pyrochlores.

Materials with the pyrochlore/fluorite structure have diverse technological applications, from magnetism to nuclear waste disposal. Here we report the observation of structural instability present in the pyrochlores AZrOO' (A = Pr, La) and YbTiOO', that exists despite ideal stoichiometry, ideal cation-ordering, the absence of lone pair effects, and a lack of magnetic order. Though these materials appear to have good long-range order, local structure probes find displacements, of the order of 0.

Liquid-like thermal conduction in intercalated layered crystalline solids.

As a generic property, all substances transfer heat through microscopic collisions of constituent particles . A solid conducts heat through both transverse and longitudinal acoustic phonons, but a liquid employs only longitudinal vibrations. As a result, a solid is usually thermally more conductive than a liquid.

Nanostructured NaTiO for Hybrid Sodium-Ion Capacitors with Excellent Rate Capability.

Herein, we report a new Na-insertion electrode material, NaTiO, as a potential candidate for Na-ion hybrid capacitors. We study the structural properties of nanostructured NaTiO, synthesized by a hydrothermal technique, upon electrochemical cycling vs Na. Average and local structures of NaTiO are elucidated from neutron Rietveld refinement and pair distribution function (PDF), respectively, to investigate the initial discharge and charge events.

Inversion in MgNiAlO Spinel: New Insight into Local Structure.

A wide variety of compositions adopt the isometric spinel structure (ABO), in which the atomic-scale ordering is conventionally described according to only three structural degrees of freedom. One, the inversion parameter, is traditionally defined as the degree of cation exchange between the A- and B-sites. This exchange, a measure of intrinsic disorder, is fundamental to understanding the variation in the physical properties of different spinel compositions.

Pressure induced polymerization of acetylide anions in CaC and 10 fold enhancement of electrical conductivity.

Transformation between different types of carbon-carbon bonding in carbides often results in a dramatic change of physical and chemical properties. Under external pressure, unsaturated carbon atoms form new covalent bonds regardless of the electrostatic repulsion. It was predicted that calcium acetylide (also known as calcium carbide, CaC) polymerizes to form calcium polyacetylide, calcium polyacenide and calcium graphenide under high pressure.

Structural water engaged disordered vanadium oxide nanosheets for high capacity aqueous potassium-ion storage.

Aqueous electrochemical energy storage devices using potassium-ions as charge carriers are attractive due to their superior safety, lower cost and excellent transport properties compared to other alkali ions. However, the accommodation of potassium-ions with satisfactory capacity and cyclability is difficult because the large ionic radius of potassium-ions causes structural distortion and instabilities even in layered electrodes. Here we report that water induces structural rearrangements of the vanadium-oxygen octahedra and enhances stability of the highly disordered potassium-intercalated vanadium oxide nanosheets.

BiTaOCl Nano-Photocatalyst: Influence of Local, Average, and Band Structure.

The average structure, local structure, and band structure of nanoparticles of photocatalyst BiTaOCl, an Aurivillius-Sillen layered material, has been studied by powder neutron Rietveld refinement, neutron pair distribution function technique, Raman scattering, and density functional theory calculations. A significant local structural deviation of nano-BiTaOCl was established in contrast to the local structure of bulk-BiTaOCl. Local structure was further supported by Raman scattering measurements.

Empirically testing vaterite structural models using neutron diffraction and thermal analysis.

Otoliths, calcium carbonate (CaCO) ear bones, are among the most commonly used age and growth structures of fishes. Most fish otoliths are comprised of the most dense CaCO polymorph, aragonite. Sturgeon otoliths, in contrast, have been characterized as the rare and structurally enigmatic polymorph, vaterite-a metastable polymorph of CaCO.

Bivalence MnO with hydroxylated interphase for high-voltage aqueous sodium-ion storage.

Aqueous electrochemical energy storage devices have attracted significant attention owing to their high safety, low cost and environmental friendliness. However, their applications have been limited by a narrow potential window (∼1.23 V), beyond which the hydrogen and oxygen evolution reactions occur.

Polymerization of Acetonitrile via a Hydrogen Transfer Reaction from CH3 to CN under Extreme Conditions.

Acetonitrile (CH3 CN) is the simplest and one of the most stable nitriles. Reactions usually occur on the C≡N triple bond, while the C-H bond is very inert and can only be activated by a very strong base or a metal catalyst. It is demonstrated that C-H bonds can be activated by the cyano group under high pressure, but at room temperature.

Sturgeon and paddlefish (Acipenseridae) sagittal otoliths are composed of the calcium carbonate polymorphs vaterite and calcite.

This study sought to resolve whether sturgeon (Acipenseridae) sagittae (otoliths) contain a non-vaterite fraction and to quantify how large a non-vaterite fraction is using neutron diffraction analysis. This study found that all otoliths examined had a calcite fraction that ranged from 18 ± 6 to 36 ± 3% by mass. This calcite fraction is most probably due to biological variation during otolith formation rather than an artefact of polymorph transformation during preparation.

Mercury Sulfide Dimorphism in Thioarsenate Glasses.

Crystalline mercury sulfide exists in two drastically different polymorphic forms in different domains of the P,T-diagram: red chain-like insulator α-HgS, stable below 344 °C, and black tetrahedral narrow-band semiconductor β-HgS, stable at higher temperatures. Using pulsed neutron and high-energy X-ray diffraction, we show that these two mercury bonding patterns are present simultaneously in mercury thioarsenate glasses HgS-As2S3. The population and interconnectivity of chain-like and tetrahedral dimorphous forms determine both the structural features and fundamental glass properties (thermal, electronic, etc.

Probing disorder in isometric pyrochlore and related complex oxides.

There has been an increased focus on understanding the energetics of structures with unconventional ordering (for example, correlated disorder that is heterogeneous across different length scales). In particular, compounds with the isometric pyrochlore structure, A2B2O7, can adopt a disordered, isometric fluorite-type structure, (A, B)4O7, under extreme conditions. Despite the importance of the disordering process there exists only a limited understanding of the role of local ordering on the energy landscape.

Realistic molecular model of kerogen's nanostructure.

Despite kerogen's importance as the organic backbone for hydrocarbon production from source rocks such as gas shale, the interplay between kerogen's chemistry, morphology and mechanics remains unexplored. As the environmental impact of shale gas rises, identifying functional relations between its geochemical, transport, elastic and fracture properties from realistic molecular models of kerogens becomes all the more important. Here, by using a hybrid experimental-simulation method, we propose a panel of realistic molecular models of mature and immature kerogens that provide a detailed picture of kerogen's nanostructure without considering the presence of clays and other minerals in shales.

Enhanced spin-phonon-electronic coupling in a 5d oxide.

Enhanced coupling of material properties offers new fundamental insights and routes to multifunctional devices. In this context 5d oxides provide new paradigms of cooperative interactions that drive novel emergent behaviour. This is exemplified in osmates that host metal-insulator transitions where magnetic order appears intimately entwined.

Synthesis, Structure, and Pressure-Induced Polymerization of Li3Fe(CN)6 Accompanied with Enhanced Conductivity.

Pressure-induced polymerization of charged triple-bond monomers like acetylide and cyanide could lead to formation of a conductive metal-carbon network composite, thus providing a new route to synthesize inorganic/organic conductors with tunable composition and properties. The industry application of this promising synthetic method is mainly limited by the reaction pressure needed, which is often too high to be reached for gram amounts of sample. Here we successfully synthesized highly conductive Li3Fe(CN)6 at maximum pressure around 5 GPa and used in situ diagnostic tools to follow the structural and functional transformations of the sample, including in situ X-ray and neutron diffraction and Raman and impedance spectroscopy, along with the neutron pair distribution function measurement on the recovered sample.

Average and Local Crystal Structures of (Ga(1-x)Znx)(N(1-x)Ox) Solid Solution Nanoparticles.

We report a comprehensive study of the crystal structure of (Ga(1-x)Znx)(N(1-x)Ox) solid solution nanoparticles by means of neutron and synchrotron X-ray scattering. In our study, we used four different types of (Ga(1-x)Znx)(N(1-x)Ox) nanoparticles, with diameters of 10-27 nm and x = 0.075-0.