• Transactions of the Korean hydrogen and new energy society
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• v.1 no.1
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• pp.1-8
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• 1989

The hydriding kinetic mechanism and the change of the hydriding reaction rate of $MmNi_{4.5}Al_{0.5}$ during the thermally induced hydrogen absorption-desorption cycling are investigated. Comparison of the reaction rate data which are obtained by the pressure sweep method with the theoretical rate equations suggests that the hydriding rate controlling step has changed from the dissociative chemisorption of hydrogen molecules at the surface to the hydrogen diffusion through the hydride phase with the increase of the hydriding fraction. These hydriding kinetic mechanism is not changed during the cycling. However, the intrinsic hydriding reaction rate of $MmNi_{4.5}Al_{0.5}$ after 5500 cycles increases significantly comparing with the activated one. It is suggested that the change of the hydriding kinetic behavior due to intrinsic degradation of $MmNi_{4.5}Al_{0.5}$ can be interpreted as follows ; the formation of nickel cluster at the surface of the sample and the host metal atom exchange in bulk by thermal cycling.

• 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.

• Transactions of the Korean hydrogen and new energy society
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• v.17 no.2
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• pp.174-180
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• 2006

The eutectic Mg-23.5%Ni alloy was casted by melting and solidification. The powders of Mg-23.5%Ni and (Mg-23.5%Ni)-10% iron oxide were prepared by mechanical grinding of casted Mg-Ni alloy and casted Mg-Ni alloy+oxide, respectively. As milling time increases, hydriding and dehydriding rates of Mg-Ni and Mg-Ni-oxide alloy powders increase. The additions of iron oxide to Mg-Ni alloy and Mg-Ni-oxide increase hydriding rates and slightly decrease dehydriding rates.

• 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.6
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• pp.463-468
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• 2012

A 71.5 wt%Mg-23.5 wt%Ni-5 wt%$Fe_2O_3$ (Mg-23.5Ni-$5Fe_2O_3$) sample was prepared by a quite simple process, reactive mechanical grinding, and its hydriding and dehydriding properties were then investigated. The reactive mechanical grinding of Mg with Ni and $Fe_2O_3$ is considered to facilitate nucleation and shorten the diffusion distances of the hydrogen atoms. After the hydriding-dehydriding cycling, the Mg-23.5Ni-$5Fe_2O_3$ sample contained $Mg_2Ni$ phase. Expansion and contraction of the hydride-forming materials (Mg and $Mg_2Ni$) with the hydriding and dehydriding reactions are also considered to increase the hydriding and dehydriding rates of the mixture by forming defects and cracks leading to the fragmentation of the particles. The temperature dependence of the hydriding rate of the sample is discussed.

• Korean Journal of Materials Research
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• v.18 no.11
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• pp.597-603
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• 2008

Oxide effects experiments on massive hydriding reactions of Zr alloy with hydrogen gas were carried out at $400^{\circ}C$ under 1 atm in a $H_2$ environment with a thermo-gravimetric apparatus (TGA). Experimental results for oxide effects on massive hydriding kinetics show that incubation time is not proportional to oxide thickness. The results also show that the massive hydriding kinetics of pre-filmed Zr alloys follows linear kinetic law and that the hydriding rates are similar to that of oxide-free Zr alloys once massive hydriding is initiated. Unlikely microstructure of the oxide during incubation time, physical defects such as micro-cracks and pores were observed in the oxide after incubation time. Therefore, it seems that the massive hydriding of Zr alloys can be ascribed to short circuit paths and mechanical or physical defects, such as micro-cracks and pores in the oxide, rather than to hydrogen diffusion through the oxide resulting from the increase of oxygen vacancies in the hypo-stoichiometric oxide.

• Korean Journal of Metals and Materials
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• v.50 no.5
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• pp.383-387
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• 2012

The activation of Mg-10 wt%$Fe_2O_3$ was completed after one hydriding-dehydriding cycle. Activated Mg-10 wt%$Fe_2O_3$ absorbed 5.54 wt% H for 60 min at 593 K under 12 bar $H_2$, and desorbed 1.04 wt% H for 60 min at 593 K under 1.0 bar $H_2$. The effect of the reactive grinding on the hydriding and dehydriding rates of Mg was weak. The reactive grinding of Mg with $Fe_2O_3$ is believed to increase the $H_2$-sorption rates by facilitating nucleation (by creating defects on the surface of the Mg particles and by the additive), by making cracks on the surface of Mg particles and reducing the particle size of Mg and thus by shortening the diffusion distances of hydrogen atoms. The added $Fe_2O_3$ and the $Fe_2O_3$ pulverized during mechanical grinding are considered to help the particles of magnesium become finer. Hydriding-dehydriding cycling is also considered to increase the $H_2$-sorption rates of Mg by creating defects and cracks and by reducing the particle size of Mg.

• Transactions of the Korean hydrogen and new energy society
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• v.10 no.1
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• pp.9-17
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• 1999

The hydriding and dehydriding kinetics were studied for a Mg-25wt.%Ni mixture which has the most excellent hydrogen-storage characteristics among many mechanically-alloyed mixtures. The hydriding and dehydriding rates were measured and the rate-controlling steps were determined by comparing the hydriding and dehydriding rates with the theoretical rate equations. The rate-controlling step in the hydriding reaction is the Knudsen flow and the ordinary gaseous diffusion of hydrogen molecules through interparticle channels, cracks, etc. in the various ranges of weight percentage of absorbed hydrogen $H_a$ below $H_a$=4.0. In the $H_a$ range 4.0 < $H_a{\leq}4.25$, the diffusion of hydrogen atoms through the growing hydride layer is considered the rate-controlling step. The rate-controlling step in the dehydriding reaction is the Knudsen flow and the ordinary gaseous diffusion of hydrogen molecules for all the ranges of weight percentage of desorbed hydrogen $H_d$.

• Korean Journal of Metals and Materials
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• v.50 no.1
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• pp.64-70
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• 2012

Samples of pure Mg, 76.5 wt%Mg-23.5 wt%Ni, and 71.5 wt%Mg-23.5 wt%Ni-5 wt%$Fe_2O_3$ were prepared by reactive mechanical grinding and their hydriding and dehydriding properties were then investigated. The reactive mechanical grinding of Mg with Ni is considered to facilitate nucleation and to shorten diffusion distances of hydrogen atoms. After hydriding-dehydriding cycling, the 76.5 wt%Mg-23.5 wt%Ni and 71.5 wt%Mg-23.5 wt%Ni-5 wt%$Fe_2O_3$ samples contained $Mg_2Ni$ phase. In addition to the effects of the creation of defects and the decrease in particle size, the addition of Ni increases the hydriding and dehydriding rates by the formation of $Mg_2Ni$. Expansion and contraction of the hydride-forming materials (Mg and $Mg_2Ni$) with the hydriding and dehydriding reactions are also considered to increase the hydriding and dehydriding rates of the mixture by forming defects and cracks leading to the fragmentation of particles. The reactive mechanical grinding of Mg-Ni alloy with $Fe_2O_3$ is considered to decrease the particle size.

• Transactions of the Korean hydrogen and new energy society
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• v.22 no.6
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• pp.787-793
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• 2011

A 76.5wt%Mg - 23.5wt%Ni (Mg-23.5Ni) sample was prepared by reactive mechanical grinding (RMG) and its hydriding and dehydriding properties were then investigated. Activation of the Mg-23.5Ni sample was completed only after two hydriding (under 12 bar $H_2$) - dehydriding (under 1.0 bar $H_2$) cycles at 593K. The reactive mechanical grinding of Mg with Ni is considered to facilitate nucleation and shorten diffusion distances of hydrogen atoms. After hydriding - dehydriding cycling, the Mg-23.5Ni sample contained Mg2Ni phase.