• Korean Journal of Metals and Materials
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• v.56 no.12
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• pp.878-884
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• 2018

In the present work, we selected a polymer, polyvinylidene fluoride (PVDF), as an additive to improve the hydrogenation and dehydrogenation properties of Mg. 95 wt% Mg + 5 wt% PVDF (designated Mg-5PVDF) samples were prepared via milling in hydrogen atmosphere (reactive milling), and the hydrogenation and dehydrogenation characteristics of the prepared samples were compared with those of Mg milled in hydrogen atmosphere. The dehydrogenation of magnesium hydride formed in the as-prepared Mg-5PVDF during reactive milling began at 681 K. In the fourth cycle (n=4), the initial hydrogenation rate was 0.75 wt% H/min and the quantity of hydrogen absorbed for 60 min, $H_a$ (60 min), was 3.57 wt% H at 573 K and in 12 bar $H_2$. It is believed that after reactive milling the PVDF became amorphous. The milling of Mg with the PVDF in hydrogen atmosphere is believed to have produced defects and cracks. The fabrication of defects is thought to ease nucleation. The fabrication of cracks is thought to expose fresh surfaces, resulting in an increase in the reactivity of the particles with hydrogen and a decrease in the diffusion distances of hydrogen atoms. As far as we know, this investigation is the first in which a polymer PVDF was added to Mg by reactive milling to improve the hydrogenation and dehydrogenation characteristics of Mg.

• Korean Journal of Metals and Materials
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• v.48 no.4
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• pp.347-352
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• 2010

This study reports a novel method off abricating highly sensitive hydrogen gas sensors based on PdO thin films. The PdO thin films with a thickness of 40 nm were deposited on Si substrates under Ar and $O_2$ ambient conditions using a reactive de magnetron sputtering system. Considerable changes in the resistance of the palladium oxide thin films were observed when they were initially exposed to hydrogen gas, as a result of the reduction process. The sensitivity of the PdO thin films was found to be as high as 90%. After the thin films were exposed to hydrogen gas, the nano-sized cracks were discovered to have formed on the surface of the PdO thin films. These types of nano-cracks that formed on the deoxidized PdO thin films are known to play a key role incausing a four-fold reduction of the response time of the absorption process. The results of this study demonstrate that deoxidized PdO thin films can be applied for use in the creation of high-sensitivity hydrogen sensors.

• Korean Journal of Metals and Materials
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• v.49 no.12
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• pp.989-994
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• 2011

Samples with compositions of 80 wt% Mg-14 wt% Ni-6 wt% $Fe_2O_3$ (named $Mg-Ni-Fe_2O_3$), and 78 wt% Mg-14 wt% Ni-6 wt% $Fe_2O_3-2$ wt% CNT (named $Mg-Ni-Fe_2O_3-CNT$ ) were prepared by reactive mechanical grinding. Hydriding and dehydriding properties and effects of CNT addition on the hydriding and dehydriding rates of $Mg-Ni-Fe_2O_3$ were then investigated. Activation of the $Mg-14Ni-6Fe_2O_3$ sample was completed after three hydriding (under 12 bar $H_2$)-dehydriding (under 1.0 bar $H_2$) cycles at 573 K. The addition of CNT to the $Mg-14Ni-6Fe_2O_3$ sample made the activation process unnecessary, with a small decrease in the hydrogen-storage capacity.

• Korean Journal of Metals and Materials
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• v.50 no.5
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• pp.375-381
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• 2012

Magnesium prepared by mechanical grinding under $H_2$ (reactive mechanical grinding) with transition elements or oxides showed relatively high hydriding and dehydriding rates when the content of additives was about 20 wt%. Ni was chosen as a transition element to be added. $Fe_2O_3$ was selected as an oxide to be added. Ti was also selected since it was considered to increase the hydriding and dehydriding rates by forming Ti hydride. A sample $Mg-14Ni-3Fe_2O_3-3Ti$ was prepared by reactive mechanical grinding, and its hydrogen storage properties were examined. This sample absorbs 4.02 wt% H for 5 min, and 4.15 wt% H for 10 min, and 4.42 wt% H for 60 min at n = 2. It desorbs 2.46 wt% H for 10 min, 3.98 wt% H for 30 min, and 4.20 wt% H for 60 min at n = 2. The effects of the Ni, $3Fe_2O_3$, and Ti addition, and hydriding-dehydriding cycling were discussed.

• Korean Journal of Metals and Materials
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• v.50 no.12
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• pp.949-953
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• 2012

$MgH_2$ was employed as a starting material instead of Mg in this work. A sample with a composition of 94 wt% $MgH_2-6$ wt% Ni (called $MgH_2-6Ni$) was prepared by reactive mechanical grinding. The hydriding and dehydriding properties were then examined. An $MgH_2-Ni$ hydrogen storage alloy that does not require an activation process was developed. The alloy was prepared in a planetary ball mill by grinding for 4 h at a ball disc revolution speed of 250 rpm under a hydrogen pressure of about 12 bar. The sample absorbed 3.74 wt% H for 5 min, 4.07 wt% H for 10 min, and 4.41 wt% H for 60 min at 573 K under 12 bar $H_2$, and desorbed 0.93 wt% H for 10 min, 1.99 wt% H for 30 min, and 3.16 wt% H for 60 min at 573 K under 1.0 bar $H_2$. $MgH_2-6Ni$ after reactive mechanical grinding contained ${\beta}-MgH_2$ (a room temperature form of $MgH_2$), Ni, ${\gamma}-MgH_2$ (a high pressure form of $MgH_2$), and a very small amount of MgO. Reactive mechanical grinding of Mg with Ni is considered to facilitate nucleation, and to reduce the particle size of Mg. $Mg_2Ni$ formed during reactive mechanical grinding also increases the hydriding and dehydriding rates of the sample.

• Transactions of the Korean Society of Automotive Engineers
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• v.17 no.3
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• pp.142-148
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• 2009

The direct injection(DI) diesel engine has become a prime candidate for future transportation needs because of its high thermal efficiency. However, nitrogen oxides(NOx) increase in the local high temperature regions and particulate matter (PM) increases in the diffusion flame region within diesel combustion. Therefore, the demand for developing a suitable after treatment device has been increased. NOx absorbing catalysts are based on the concept of NOx storage and release making it possible to reduce NOx emission in net oxidizing gas conditions. This De-NOx system, called the LNT(Lean NOx Trap) catalyst, absorbs NOx in lean exhaust gas conditions and release it in rich conditions. This technology can give high NOx conversion efficiency, but the right amount of reducing agent should be supplied into the catalytic converter at the right time. In this research, a performance characteristics of LNT with a hydrogen enriched gas as a reductant was examined and strategies of controlling the injection and rich exhaust gas condition were studied. The NOx reduction efficiency is closely connected to the injection timing and duration of reductant. LNT can reduce NOx efficiently with only 1 % fuel penalty.

• Journal of Powder Materials
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• v.13 no.5 s.58
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• pp.327-335
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• 2006

In the development of new hydrogen absorbing materials for a next generation of metal hydride electrodes for rechargeable batteries, metastable Mg-Ni-based compounds find currently special attention. Amor phous-nanocrystalline $Mg_{63}Ni_{30}Y_7$ and $Mg_{50}Ni_{30}Y_{20}$ alloys were produced by mechanical alloying and melt-spinning and characterized by means of XRD, TEM and DSC. On basis of mechanically alloyed Mg-Ni-Y powders, complex hydride electrodes were fabricated and their electrochemical behaviour in 6M KOH (pH=14,8) was investigated. The electrodes made from $Mg_{63}Ni_{30}Y_7$ powders, which were prepared under use of a SPEX shaker mill, with a major fraction of nanocrystalline phase reveal a higher electrochemical activity far hydrogen reduction and a higher maximum discharge capacity (247 mAh/g) than the electrodes from alloy powder with predominantly amorphous microstructure (216 mAh/g) obtained when using a Retsch planetary ball mill at low temperatures. Those discharge capacities are higher that those fur nanocrystalline $Mg_2Ni$ electrodes. However, the cyclic stability of those alloy powder electrodes was low. Therefore, fundamental stability studies were performed on $Mg_{63}Ni_{30}Y_7$ and $Mg_{50}Ni_{30}Y_{20}$ ribbon samples in the as-quenched state and after cathodic hydrogen charging by means of anodic and cathodic polarisation measurements. Gradual oxidation and dissolution of nickel governs the anodic behaviour before a passive state is attained. A stabilizing effect of higher fractions of yttrium in the alloy on the passivation was detected. During the cathodic hydrogen charging process the alloys exhibit a change in the surface state chemistry, i.e. an enrichment of nickel-species, causing preferential oxidation and dissolution during subsequent anodization. The effect of chemical pre-treatments in 1% HF and in $10\;mg/l\;YCl_3/1%\;H_2O_2$ solution on the surface degradation processes was investigated. A HF treatment can improve their anodic passivation behavior by inhibiting a preferential nickel oxidation-dissolution at low polarisation, whereas a $YCl_3/H_2O_2$ treatment has the opposite effect. Both pre-treatment methods lead to an enhancement of cathodically induced surface degradation processes.

• Transactions of the Korean hydrogen and new energy society
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• v.30 no.1
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• pp.8-13
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• 2019

In order to apply the Sievert's type automatic apparatus to thermal analysis of hydrogen absorbing materials, the Sievert's type automatic apparatus was modified in my laboratory. In this study, an experiment was conducted to see if hydrogen absorption and desorption reactions are possible under near constant pressure (${\pm}0.05atm$) using this device. The hydrogenation and dehydrogenation of the Mg-H system was investigated. And the program was also modified for the kinetics. It was found that it is possible to measure the hydrogen absorption rate under near constant pressure of Mg by using the modified Sievert's type automatic apparatus at 573 K and 598 K. And using this system, the hydrogen desorption rate of Mg hydride under near constant pressure at 623 K was also measurable. However, since the hydrogen desorption rate of Mg hydride is fast at 648 K, the hydrogen desorption reaction did not proceed within a constant pressure range of $0.15{\pm}0.05atm$.

• Transactions of the Korean hydrogen and new energy society
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• v.15 no.4
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• pp.257-265
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• 2004

Numerical analysis, as EAM(Embedded Atom Method), in the atomic level is necessary to analyze the relation between the hydrogen and hydrogen absorption metals. EAM established on density functional theory was developed as a new means for calculating various properties and phenomena of realistic metal systems. In this study, we had constructed the EAM program from constitutive formulae and parameters of the hydrogen, nickel and palladium for the purpose of predicting the expansion behavior on hydrogen absorbing. In result, not only the ground state properties of metals but also lattice constants and the volume expansion ratio of metal hydrides show good agreement with Daw's data and experiment data.

• Transactions of the Korean hydrogen and new energy society
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• v.31 no.6
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• pp.553-557
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• 2020

It is possible that hydrogen could replace coal and petroleum as the predominant energy source in the near future, but several challenges including cost, efficiency, and stability. Mg and Mg alloys are attractive hydrogen storage materials because of their lightweight and high absorption capacity. Their range of applications could be further extended if their hydrogenation properties could be improved. The main emphasis of this study was to investigate their hydrogenation properties for Synthesis of 10wt.% CaF2 in Mg2NiHx systems. The effect of BCR (66:1) and MA time (96 hours) on the hydrogenation properties of the composite was investigated. also, Mg2NiHx-10wt% CaF2 composites prepared by Mechanical Alloying are used in this work to illustrate the effect of catalysts on activation energy and kinetics of Magnesium hydride.