Papers by Author: Tomaz Toshimi Ishikawa

Abstract: Magnesium is light, abundant and it can store up to 7.6 wt. % of hydrogen forming MgH₂ and accordingly it is a promising material for hydrogen storage. Processing of Mg-based mixtures by high-energy ball milling (HEBM) can produce materials with high level H-sorption properties. In the present report, we display and compare the effects of different nanocrystalline additives (MgF₂, Fe, NbH_0,89, FeF₃, VF₃) on the formation of MgH₂ by reactive milling. The H-desorption behavior of the as-prepared nanocomposites is also evaluated. A combined catalytic effect is observed due to the synergic action of MgF₂ and Fe (or NbH_0,89) on the hydrogenation rate during processing. The transition metal fluorides promote as well the MgH₂ synthesis. By using more energy-intensive milling conditions and adequate additives in given proportions (e.g. 5 mol. % FeF₃), is shown to be very effective for a full and fast synthesis (4 h) of MgH₂ by reactive milling.

Abstract: Magnesium complex hydrides as Mg2FeH6 are interesting phases for hydrogen storage in the solid state, mainly due to its high gravimetric and volumetric densities of H2. However, the synthesis of this hydride is not trivial because the intermetallic phase Mg2Fe does not exist and Mg and Fe are virtually immiscible under equilibrium conditions. In this study, we have systematically studied the influence of the most important processing parameters in reactive milling under hydrogen (RM) for Mg2FeH6 synthesis: milling time, ball-to-powder weight ratio (BPR), hydrogen pressure and type of mill. Low cost 2Mg-Fe mixtures were used as raw materials. An important control of the Mg2FeH6 direct synthesis by RM was attained. In optimized combinations of the processing parameters, very high proportions of the complex hydride could be obtained.

Abstract: In the present work, we have processed 2Mg-Fe mixtures by reactive milling (RM) under hydrogen atmosphere to synthesize Mg2FeH6 phase in the powder form which were then systematically processed by High Pressure Torsion (HPT) to produce bulk samples. The bulk samples were characterized in terms of microstructural and structural analyses and of hydrogen desorption properties. The hydrogen sorption properties after HPT processing was evaluated in comparison with the Mg2FeH6 powder obtained by RM and with commercial MgH2. HPT processing of Mg2FeH6 can produce bulks with a high density of defects that drastically lower the activation barrier for hydrogen desorption. Therefore, the bulk nanocrystalline Mg2FeH6 samples show endothermic hydrogen decomposition peak at a temperature around 320°C. In addition, when compared with the Mg2FeH6 and MgH2 powders, the Mg2FeH6 HPT disks showed the same results presented by the Mg2FeH6 powders and certainly decreases the onset transition temperature by as much as 160°C when compared with the MgH2 powders.

Abstract: Severe plastic deformation (SPD) techniques are being considered as low cost processing routes for Mg alloys, aiming hydrogen storage applications. The main objective is to develop air-resistant materials, with lower specific surface area in comparison with ball-milled powders, but with still attractive H-sorption kinetics associated to the microstructural refinement. In this study, the effects of different SPD processing routes (high-pressure torsion, extensive cold rolling and cold forging) in the hydrogen activation behavior of Mg was evaluated. The results show that both microstructural and textural aspects should be controlled during SPD processing to obtain Mg alloys with good H-sorption properties and enhanced activation kinetics.

Abstract: A good method to store hydrogen is in it atomic form in crystalline structure of metals at low pressure. Thanks to magnesium’s high hydrogen storage capacity, its low weight and its high natural abundance, it is an attractive material to develop hydrogen solid state storage. The production of Mg-based nanocomposites can enhance the kinetics of H-sorption of magnesium and the temperature of release of hydrogen. Transition metals as iron, which have important catalytic activity in hydrogen reactions with Mg, and the surface protective compound MgF2, are interesting additions for magnesium mixtures for hydrogen storage. In this work, Mg-based nanocomposites containing Fe and MgF2 were produced by reactive milling under hydrogen using the addition of FeF3, or directly MgF2 and Fe. The efficiency of centrifugal and planetary mill in MgH2 synthesis was compared. The phase evolution during different milling times (from 1 to 96 h) using the planetary was investigated. The different H-desorption behavior of selected milled mixtures was studied and associated with the different present phases in each case.

Abstract: Interstitial solutes in body-centered cubic metals, such as oxygen in tantalum, produce ideally Snoek effects when they are in solutions enough diluted. However, for higher concentration of these solutes, more complex relaxation process can occur, as interaction between interstitial solutes and dislocations. Anelastic relaxation measurements were carried out in polycrystalline tantalum samples, using torsion pendulum inverted, operating between 300 K and 680 K and oscillation frequencies in the hertz bandwidth, for three different experimental sample conditions: as received sample, annealed and annealed followed by a treatment in an oxygen atmosphere. These measurements have revealed the following behavior: the intensity of the internal friction peak associated to matrix-interstitial interaction Ta-O decreased between the first run and the next runs, and this phenomenon did not occur for the others conditions. The variation of relaxation strength of Ta-O peak, with number of runs is due to a decrease of an amount of oxygen in solid solution, which can be associated with the precipitation of new phases in Ta sample and with the trapping of oxygen atoms by dislocations.

Abstract: Anelastic relaxation measurements have been used in order to obtain information about several aspects of the behavior of solutes in metals, for example, matrix-solute interaction, interstitial diffusion, etc. The diffusion coefficient for interstitial solutes in body centered-cubic metals is accurately determined by anelastic relaxation measurements. The kind of preferential occupation of the interstitial solutes in body centered-cubic metals, such as oxygen and nitrogen in tantalum, is still controversial. Internal friction and frequency measurements as a function of temperature in tantalum sample were performed using a torsion pendulum operating in a frequency oscillation in the hertz bandwidth. These results presented the following phenomenon: the intensity of the internal friction peak decreased between the first run and the other runs. These results were decomposed, by the successive subtraction method, in elementary Debye peaks, for determination of characteristic anelastic relaxation parameters (relaxation strength, peak temperature, activation energy and relaxation time). Interstitial diffusion coefficients for oxygen in tantalum were determined, for different intensities of internal friction peaks, and when compared with literature, these results introduced a better adjustment for the tetrahedral preferential occupation sites of oxygen in tantalum.