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Abstract: The addition of transition metals to alkali intercalated fullerides proved to enhance their already good hydrogen absorption properties. Herein we present a study based on two different synthetic strategies, allowing the addition of nickel as aggregates with different size to the lithium fulleride Li6C60: the former is based on the metathesis of nickel chloride, while the latter on the thermal decomposition of nickel carbonyl clusters. The hydrogen-storage properties of the obtained materials have been investigated with manometric and calorimetric measurements, which indicated a clear enhancement of the final absorption value and kinetics with respect to pristine Li6C60, as a consequence of nickel surface catalytic activity towards hydrogen molecules dissociation. We found up to 10 % increase of the total H2 weight % absorbed (5.5 wt% H2) in presence of Ni aggregates. Furthermore, the control of the transition metal particles size distribution allowed reducing the hydrogen desorption enthalpy of the systems.

Open Access

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Abstract: X-ray imaging of soft materials is often difficult because of the low contrast of the components. This particularly applies to frozen hydrated biological cells where the feature of interest can have a similar density to the surroundings. As a consequence, a high dose is often required to achieve the desired resolution. However, the maximum dose that a specimen can tolerate is limited by radiation damage. Results from 3D coherent diffraction imaging (CDI) of frozen hydrated specimens have given resolutions of ∼80 nm compared with the expected resolution of 10 nm predicted from theoretical considerations for identifying a protein embedded in water. Possible explanations for this include the inapplicability of the dose-fractionation theorem, the difficulty of phase determination, an overall object-size dependence on the required fluence and dose, a low contrast within the biological cell, insufficient exposure, and a variety of practical difficulties such as scattering from surrounding material. A recent article [Villaneuva-Perez et al. (2018), Optica, 5, 450–457] concluded that imaging by Compton scattering gave a large dose advantage compared with CDI because of the object-size dependence for CDI. An object-size dependence would severely limit the applicability of CDI and perhaps related coherence-based methods for structural studies. This article specifically includes the overall object size in the analysis of the fluence and dose requirements for coherent imaging in order to investigate whether there is a dependence on object size. The applicability of the dose-fractionation theorem is also discussed. The analysis is extended to absorption-based imaging and imaging by incoherent scattering (Compton) and fluorescence. This article includes analysis of the dose required for imaging specific low-contrast cellular organelles as well as for protein against water. This article concludes that for both absorption-based and coherent diffraction imaging, the dose-fractionation theorem applies and the required dose is independent of the overall size of the object. For incoherent-imaging methods such as Compton scattering, the required dose depends on the X-ray path length through the specimen. For all three types of imaging, the dependence of fluence and dose on a resolution d goes as 1/d4 when imaging uniform-density voxels. The independence of CDI on object size means that there is no advantage for Compton scattering over coherent-based imaging methods. The most optimistic estimate of achievable resolution is 3 nm for imaging protein molecules in water/ice using lensless imaging methods in the water window. However, the attainable resolution depends on a variety of assumptions including the model for radiation damage as a function of resolution, the efficiency of any phase-retrieval process, the actual contrast of the feature of interest within the cell and the definition of resolution itself. There is insufficient observational information available regarding the most appropriate model for radiation damage in frozen hydrated biological material. It is advocated that, in order to compare theory with experiment, standard methods of reporting results covering parameters such as the feature examined (e.g. which cellular organelle), resolution, contrast, depth of the material (for 2D), estimate of noise and dose should be adopted.

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Abstract: The effect of gravity on thermo-solutal convection and its impact on solidification dynamics of an Al-15 wt%Cu alloy were studied using high speed synchrotron tomography. A method for mapping the composition of the solidifying samples was developed, enabling three-dimensional quantification of the time evolved solute concentration and dendrite morphology. Differences in solute segregation, dendrite morphology and fragmentation between upwards and downwards solidification were identified, which were attributed to buoyancy-modulated thermal-solutal convection.

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Abstract: The adsorbate interactions of furans as probe molecules in H-ZSM-5 and H-USY with and without metal ion modification have been revealed by synchrotron X-ray powder diffraction (SXRD). The Rietveld refinements give both qualitatively and quantitatively the spatial arrangements and adsorption geometries of furan and 2,5-dimethylfuran (DMF) on the Brønsted acid sites (BAS) and metal Lewis acid sites (LAS). The bonding information between the adsorbate-framework can also be correlated with thermogravimetric findings. The use of probe molecule-SXRD can be used as a new characterisation tool which can spatially interrogate the acidity of crystalline porous catalysts, leading to molecular engineering of new catalytic systems.

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Abstract: Simultaneous synchrotron small- and wide-angle X-ray scattering (SAXS/WAXS) was used to follow the crystalline morphology evolution of poly-L- lactic acid (PLLA) during uniaxial deformation at various draw temperatures (Td). The mechanical behaviour of PLLA, was found to be strongly dependent on Td. 2D SAXS/WAXS data taken during the draw showed that at low Tds cavitation and voiding occurred and the initial crystallites underwent ‘overdrawing’ where they slip and are partially destroyed. SEM confirmed that surface voiding and cavitation had occurred at Td = 60 and 65 °C but was absent at higher Tds. During the draw, no long-range macromolecular lamellar structure was seen in the SAXS, but small crystallites of the disordered α′ crystal form of PLLA were observed in the WAXS at all Tds. The PLLA samples were then step annealed in a second processing stage (post-draw) to develop the oriented crystalline lamellar structure and increase the amount of the stable α crystalline form. SAXS/WAXS data showed that a highly oriented lamellar stack macrostructure developed on annealing, with increased crystallite size and crystallinity at all Tds. Furthermore, step annealing drove the crystalline transition in all samples from the disordered α′ crystal form to the stable α crystal form. Therefore, varying pre- and post-processing parameters can significantly influence the mechanical properties, orientation, crystalline morphology and crystal phase transition of the final PLLA material.