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    90° magnetic coupling in a NiFe/FeMn/biased NiFe multilayer spin valve component investigated by polarized neutron reflectometry

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    We have observed 90° magnetic coupling in a NiFe/FeMn/biased NiFe multilayer system using polarized neutron reflectometry. Magnetometry results show magnetic switching for both the biased and free NiFe layers, the latter of which reverses at low applied fields. As these measurements are only capable of providing information about the total magnetization within a sample, polarized neutron reflectometry was used to investigate the reversal behavior of the NiFe layers individually. Both the non-spin-flip and spin-flip neutron reflectometry signals were tracked around the free NiFe layer hysteresis loop and were used to detail the evolution of the magnetization during reversal. At low magnetic fields near the free NiFe coercive field, a large spin-flip signal was observed, indicating magnetization aligned perpendicular to both the applied field and pinned layer. © 2020 AIP Publishing LLC

    BioPEGylation of Polyhydroxybutyrate promotes nerve cell health and migration

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    This study reports on the superior suitability of Polyhydroxybutyrate-polyethylene glycol hybrid polymers biosynthesised by Cupriavidus necator over PHB as biomaterials for tissue engineering. Incorporation of PEG106 (DEG) during PHB biosynthesis reduced crystallinity, molecular weight, and hydrophobicity while improving mechanical properties. In vitro olfactory ensheathing cell (OEC) proliferation was enhanced by cultivation on PHB-b-DEG films. Cultivation on PHB and PHB-b-DEG films showed no cytotoxic responses and cell viability and membrane integrity was sustained. PHB-b-DEG films promoted OECs entering into the DNA replication (S) phase and mitotic (G2-M) phase during the cell growth cycle and apoptosis was low. This study also confirmed an association between the level of neurite-outgrowth inhibitory protein (Nogo) and receptor pair Ig-like receptor B (PirB) expression and cell proliferation, both being down-regulated in cells grown on hybrid films when compared with PHB and asynchronous growth. Thus, DEG-terminated PHB-based biomaterials have great potential as biological scaffolds supporting nerve repair. © 2013 American Chemical Society

    Swelling due to the partition of soluble fission products between the grey phase and uranium dioxide

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    The change in volume associated with the partition of soluble cations from uranium dioxide into the (Ba,Sr)ZrO3 grey phase has been investigated using atomic scale simulations. Here past work on the thermodynamic drive for the segregation of trivalent and tetravalent cations from uranium dioxide is built upon in the context of fuel swelling. Only small tetravalent cations segregate into the grey phase and this is predicted to result in an overall reduction in fuel volume. Individual trivalent cations that segregate, can cause either a contraction or an expansion of the overall fuel volume. Cr2O3 doped UO2 promotes co-partition forming mixed cation clusters in the grey phase and causing an overall reduction in fuel volume for all trivalent cations. This may have implications for fuel performance and may alter other fuel swelling mechanisms.© 2013 Elsevier Ltd

    Kinetics of the Thermally-Induced Structural Rearrangement of γ-MnO2

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    This work presents a temperature-dependent and time-resolved X-ray and neutron diffraction study of the thermally induced structural rearrangement of γ-MnO2. Here, we study electrochemically prepared γ-MnO2, the manganese dioxide phase used in the majority of battery applications, which we find to be ∼64% ramsdellite [a = 4.4351(6) Å, 9.486(2) Å, c = 2.8128(7) Å, and V = 118.33(3) Å3] and ∼36% pyrolusite [a = 4.718(3) Å, c = 2.795(2) Å, and V = 62.22(8) Å3]. Taking a deeper look at the kinetics of the structural rearrangement, we find two steps: a fast transition occurring within 4–8 min with a temperature-dependent ramsdellite to pyrolusite transformation (rate constant 0.11–0.74 min–1) and a slow transition over 4 h that densifies (with changes in unit cell and volume) the ramsdellite and pyrolusite phases to give structures that appear to be temperature-independent. This effectively shows that γ/β-MnO2 prepared in the range of 200–400 °C consists of temperature-independent structures of ramsdellite, unit cell a = 4.391(1) Å, b = 9.16(5) Å, c = 2.847(1) Å, and V = 114.5(6) Å3, and pyrolusite, unit cell a = 4.410(2) Å, c = 2.869(2) Å, and V = 55.79(4) Å3, with a temperature-dependent pyrolusite fraction between 0.45 and 0.77 and increasing with temperature. Therefore, we have linked the temperature and time of heat treatment to the structural evolution of γ-MnO2, which will aid the optimization of γ/β-MnO2 as used in Li-primary batteries. © 2014, American Chemical Society

    ENSO–cave drip water hydrochemical relationship: a 7-year dataset from south-eastern Australia

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    Speleothems (cave deposits), used for palaeoenvironmental reconstructions, are deposited from cave drip water. Differentiating climate and karst processes within a drip-water signal is fundamental for the correct identification of palaeoenvironmental proxies and ultimately their interpretation within speleothem records. We investigate the potential use of trace element and stable oxygen-isotope (δ18O) variations in cave drip water as palaeorainfall proxies in an Australian alpine karst site. This paper presents the first extensive hydrochemical and δ18O dataset from Harrie Wood Cave, in the Snowy Mountains, south-eastern (SE) Australia. Using a 7-year long rainfall δ18O and drip-water Ca, Cl, Mg / Ca, Sr / Ca and δ18O datasets from three drip sites, we determined that the processes of mixing, dilution, flow path change, carbonate mineral dissolution and prior calcite precipitation (PCP) accounted for the observed variations in the drip-water geochemical composition. We identify that the three monitored drip sites are fed by fracture flow from a well-mixed epikarst storage reservoir, supplied by variable concentrations of dissolved ions from soil and bedrock dissolution. We constrained the influence of multiple processes and controls on drip-water composition in a region dominated by El Niño–Southern Oscillation (ENSO). During the El Niño and dry periods, enhanced PCP, a flow path change and dissolution due to increased soil CO2 production occurred in response to warmer than average temperatures in contrast to the La Niña phase, where dilution dominated and reduced PCP were observed. We present a conceptual model, illustrating the key processes impacting the drip-water chemistry. We identified a robust relationship between ENSO and drip-water trace element concentrations and propose that variations in speleothem Mg / Ca and Sr / Ca ratios may be interpreted to reflect palaeorainfall conditions. These findings inform palaeorainfall reconstruction from speleothems regionally and provide a basis for palaeoclimate studies globally, in regions where there is intermittent recharge variability. © Author(s) 2016

    A Monte Carlo software for the 1-dimensional simulation of IBIC experiments

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    The ion beam induced charge (IBIC) microscopy is a valuable tool for the analysis of the electronic properties of semiconductors. In this work, a recently developed Monte Carlo approach for the simulation of IBIC experiments is presented along with a self-standing software equipped with graphical user interface. The method is based on the probabilistic interpretation of the excess charge carrier continuity equations and it offers to the end-user the full control not only of the physical properties ruling the induced charge formation mechanism (i.e., mobility, lifetime, electrostatics, device’s geometry), but also of the relevant experimental conditions (ionization profiles, beam dispersion, electronic noise) affecting the measurement of the IBIC pulses. Moreover, the software implements a novel model for the quantitative evaluation of the radiation damage effects on the charge collection efficiency degradation of ion-beam-irradiated devices. The reliability of the model implementation is then validated against a benchmark IBIC experiment. © 2014, Elsevier B.V

    Vertical distribution of charcoal in a sandy soil: evidence from DRIFT spectra and field emission scanning electron microscopy

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    This study uses diffuse reflectance infrared Fourier Transform (DRIFT) spectrometry and field emission scanning electron microscopy to investigate the vertical distribution of charcoal in a sandy soil from SE Australia. The soil was sampled to bedrock (120 cm) at varying depths and bulk samples were fractionated into three particle-sizes: macro- (2000–200 µm), micro- (200–60 µm) and mineral-associated organic matter (MAOM, < 60 µm). Charcoal was isolated from 0–30 and 30–60-cm depths. Soil charcoal was detected by using a DRIFT band centred at 1590 cm−1 and scanning electron microscopy combined with energy dispersive spectroscopy. Charcoal content as a proportion of soil organic carbon (SOC) was estimated with linear regressions of cumulative DRIFT bands. At 0–30 cm, charcoal content as a portion of SOC did not differ significantly between particle-size fractions, constituting 5–26% of SOC. At a depth of 30–60 cm, charcoal constituted 19–39% of SOC in the fractions. At 60–100 cm, charcoal was only detectable in the mid-sized fraction, where it constituted about 17% of SOC. These results support our previous hypothesis of charcoal enrichment in the micro-fraction inducing a greater SOC stability in this fraction as inferred from radiocarbon ages (Hobley et al., 2013). Our findings indicate that DRIFT spectra can be used to detect the presence and amount of charcoal in soil, which may prove to be a simple and low-cost alternative to more laborious and costly detection methods.© 2014, British Society of Soil Science

    Structural study of monoclinic Li2FeSiO4 by X-ray diffraction and Mössbauer spectroscopy

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    A composite powder Li2FeSiO4/C is synthesized through a solid state reaction at 750 °C. The Rietveld crystal structure refinement is done in the monoclinic P21/n space group. It is found that the crystal structure is prone to “antisite” defect where small part of iron ion occupies exclusively Li(2) crystallographic position, of two different lithium tetrahedral positions (Li(1) and Li(2)). This finding is also confirmed by Mössbauer spectroscopy study: the sextet evidenced in the Mössbauer spectrum is assigned to the iron ions positioned at the Li(2) sites. A bond-valence energy landscape calculation is used to predict the conduction pathways of lithium ions. The calculations suggest that Li conductivity is two-dimensional in the (101) plane. Upon galvanostatic cyclings the structure starts to rearrange to inverse βII polymorph. © 2014, Elsevier B.V

    Competing Exchange Interactions on the Verge of a Metal-Insulator Transition in the Two-Dimensional Spiral Magnet Sr 3 Fe 2 O 7

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    We report a neutron scattering study of the magnetic order and dynamics of the bilayer perovskite Sr 3 Fe 2 O 7 , which exhibits a temperature-driven metal-insulator transition at 340 K. We show that the Fe 4+ moments adopt incommensurate spiral order below T N =115  K and provide a comprehensive description of the corresponding spin-wave excitations. The observed magnetic order and excitation spectra can be well understood in terms of an effective spin Hamiltonian with interactions ranging up to third-nearest-neighbor pairs. The results indicate that the helical magnetism in Sr 3 Fe 2 O 7 results from competition between ferromagnetic double-exchange and antiferromagnetic superexchange interactions whose strengths become comparable near the metal-insulator transition. They thus confirm a decades-old theoretical prediction and provide a firm experimental basis for models of magnetic correlations in strongly correlated metals. © 2014, American Physical Society

    Hydrothermal Synthesis, Structure Investigation, and Oxide Ion Conductivity of Mixed Si/Ge-Based Apatite-Type Phases

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    Apatite-type oxides ([AI4][AII6][(BO4)6]O2), particularly those of the rare-earth silicate and germanate systems, are among the more promising materials being considered as alternative solid oxide fuel cell electrolytes. Nonstoichiometric lanthanum silicate and germanate apatites display pure ionic conductivities exceeding those of yttria-stabilized zirconia at moderate temperatures (500–700 °C). In this study, mixed Si/Ge-based apatites were prepared by hydrothermal synthesis under mild conditions rather than the conventional solid-state method at high temperatures. Single-phase and highly crystalline nanosized apatite powders were obtained with the morphology changing across the series from spheres for the Si-based end member to hexagonal rods for the Ge-based end member. Powder X-ray and neutron analysis found all of these apatites to be hexagonal (P63/m). Quantitative X-ray microanalysis established the partial (<15 at%) substitution of La3+ by Na+ (introduced from the NaOH hydrothermal reagent), which showed a slight preference to enter the AI 4f framework position over the AII 6h tunnel site. Moreover, retention of hydroxide (OH–) was confirmed by IR spectroscopy and thermogravimetric analysis, and these apatites are best described as oxyhydroxyapatites. To prepare dense pellets for conductivity measurements, both conventional heat treatment and spark plasma sintering methods were compared, with the peculiar features of hydrothermally synthesized apatites and the influence of sodium on the ionic conductivity considered.© 2014, American Chemical Society

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