1,720,971 research outputs found
Characterization of a nanocrystalline Mg–Ni alloy processed by high-pressure torsion during hydrogenation and dehydrogenation
Ball-milled Mg-Ni powder has been cold-compacted and subsequently processed by severe shear deformation under high-pressure torsion. The effect of high pressure torsion on morphology and microstructure of the disk-shape samples has been characterized by scanning electron microscopy and X-ray diffraction, respectively. In order to achieve partially hydrogenated and dehydrogenated states of deformed samples, the hydrogen uptake or release was interrupted at 25%, 50% and 75% hydrogen contents in a Sieverts' type apparatus. In this paper we present the characterization of the microstructure during a full absorption-desorption cycle of the nanocrystalline Mg–Ni alloy
Dehydrogenation-hydrogenation characteristics of nanocrystalline Mg2Ni powders compacted by high-pressure torsion
High-pressure torsion technique was applied on nanocrystalline Mg2Ni powders to produce bulk disks by simultaneous uniaxial compression and severe shear deformation. The hydrogen absorption and desorption behavior of the disks has been characterized by high-pressure calorimetry. During desorption, the decomposition of the Mg2NiH4 phase takes place, which is followed by the dehydrogenation of Mg2NiH0.3 solid solution. In order to monitor the sorption properties in details, partially dehydrogenated states of the fully absorbed disk have been performed by interrupting the desorption process at 75%, 50% and 25% hydrogen contents in a Sieverts’ type apparatus. Microstructural evolution during dehydrogenation has been investigated by X-ray diffraction. The variation of average crystallite size, lattice parameters and unit cell of the competing phases has been determined by the Rietveld refinement method of X-ray diffractograms. The unit cell volume of the Mg2NiH0.3 hydride solid solution decreases with decreasing hydrogen content. Coupled differential scanning calorimetry and thermogravimetry measurements were also taken on the partially desorbed states in order to determine the activation energy of hydrogen release
Hydrogen Desorption below 150 °c in MgH2-TiH2 Composite Nanoparticles: Equilibrium and Kinetic Properties
Reversible hydrogen sorption coupled with the MgH2 <-> Mg phase transformation was achieved in the remarkably low 340-425 K temperature range using MgH2-TiH2 composite nanoparticles obtained by reactive gas-phase condensation of Mg Ti vapors under He/H-2 atmosphere. The equilibrium pressures determined by in situ measurements at low temperature were slightly above those predicted using enthalpy Delta H and entropy Delta S of bulk magnesium. A single van't Hoff fit over a range extended up to 550 K yields the thermodynamic parameters Delta H = 68.1 0.9 kJ/molH(2) and Delta S = 119 2 J/(Kmo1H2) for hydride decomposition. A desorption rate of 0.18 wt % H-2/min was measured at T = 423 K and p(H-2) approximate to 1 mbar, i.e., close to equilibrium, without using a Pd catalysts. The nanoparticles displayed a small absorption desorption pressure hysteresis even at low temperatures. We critically discuss the influence exerted by nanostructural features such as interface free energy, elastic clamping, and phase mixing at the single nanopartide level on equilibrium and kinetic properties of hydrogen sorption
Interface Enthalpy-Entropy Competition in Nanoscale Metal Hydrides
We analyzed the effect of the interfacial free energy on the thermodynamics of hydrogen sorption in nano-scaled materials. When the enthalpy and entropy terms are the same for all interfaces, as in an isotropic bi-phasic system, one obtains a compensation temperature, which does not depend on the system size nor on the relative phase abundance. The situation is different and more complex in a system with three or more phases, where the interfaces have different enthalpy and entropy. We also consider the possible effect of elastic strains on the stability of the hydride phase and on hysteresis. We compare a simple model with experimental data obtained on two different systems: (1) bi-phasic nanocomposites where ultrafine TiH2 crystallite are dispersed within a Mg nanoparticle and (2) Mg nanodots encapsulated by different phases
Local Structure of v Dopants in TiO2 Nanoparticles: X-ray Absorption Spectroscopy, Including Ab-Initio and Full Potential Simulations
Doping with transition metals is an effective method to enhance visible-light absorption in TiO2 nanoparticles and to improve the efficiency of many photocatalytic processes under solar radiation. A determination of the incorporation site of the dopant and an understanding of the local bonding arrangement and electronic structure is a necessary step for knowledge-based materials design. In this paper, we report an in-depth X-ray absorption spectroscopy study of V dopants in TiO2 nanoparticles deposited by gas-phase condensation with a local structure similar to anatase, rutile, or intermediate. The combination of K- and L-edge spectra in the pre-edge, edge, and extended energy regions with full potential ab initio spectral simulations shows that V ions occupy substitutional cationic sites in the TiO2 structure, irrespective of whether it is similar to rutile, anatase, or mixed
Mg–Ti nanoparticles with superior kinetics for hydrogen storage
Mg nanoparticles (NPs) with addition of Ti catalysts were synthesised by inert gas condensation and in situ hydrogenation at 150 °C. The NPs size and composition were systematically investigated by scanning electron microscopy, energy dispersive X-ray spectroscopy and powder X-ray diffraction (PXD), while time resolved in situ synchrotron radiation-PXD was used to monitor the mechanism for hydrogen uptake and release at 280 °C. The Mg–Ti NPs reveal activation energies of 68 kJ mol−1 for absorption and 78 kJ mol−1 for desorption by isothermal kinetics analysis, similar to the lowest values reported in the literature for MgH2 using Nb2O5 as a catalyst. Hence, hydrogen desorption (pdes = 8 mbar) and absorption (pabs = 260 mbar) is achieved at 200 °C in ∼2000 s, while keeping 5.3 wt% storage capacity. Thermodynamic data extracted from van ’t Hoff plots reveal unchanged values compared to bulk MgH2. Therefore, the improved hydrogen storage performances are assigned to the enhanced kinetics only
Going Beyond Counting First Authors in Author Co-citation Analysis
The present study examines one of the fundamental aspects of author co-citation analysis (ACA) - the way co-citation
counts are defined. Co-citation counting provides the data on which all subsequent statistical analyses and mappings
are based, and we compare ACA results based on two different types of co-citation counting - the traditional type that
only counts the first one among a cited work's authors on the one hand and a non-traditional type that takes into
account the first 5 authors of a cited work on the other hand. Results indicate that the picture produced through this non-traditional author co-citation counting contains more coherent author groups and is therefore considerably clearer. However, this picture represents fewer specialties in the research field being studied than that produced through the traditional first-author co-citation counting when the same number of top-ranked authors is selected and analyzed. Reasons for these effects are discussed
Variations on the Author
“Variations on the Author” discusses two of Eduardo Coutinho’s recent films (Um Dia na Vida, from 2010, and Últimas Conversas, posthumously released in 2015) and their contribution to the general question of documentary authorship. The director’s filmography is characterized by a consistent yet self-effacing form of authorial self-inscription: Coutinho often features as an interviewer that rather than express opinions propels discourses; an interviewer that is good at listening. This mode of self-inscription characterizes him as an author who is not expressive but who is nonetheless markedly present on the screen. In Um Dia na Vida, however, Coutinho is completely absent form the image, while Últimas Conversas, on the contrary, includes a confessional prologue that moves the director from the margins to the center of his films. This article examines the ways in which these works stand out in the filmography of a director who offers new insights into the notion of cinematic authorship
Appropriate Similarity Measures for Author Cocitation Analysis
We provide a number of new insights into the methodological discussion about author cocitation analysis. We first argue that the use of the Pearson correlation for measuring the similarity between authors’ cocitation profiles is not very satisfactory. We then discuss what kind of similarity measures may be used as an alternative to the Pearson correlation. We consider three similarity measures in particular. One is the well-known cosine. The other two similarity measures have not been used before in the bibliometric literature. Finally, we show by means of an example that our findings have a high practical relevance.information science;Pearson correlation;cosine;similarity measure;author cocitation analysis
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