• 한국수소및신에너지학회논문집
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• 제1권1호
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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.

• 대한금속재료학회지
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• 제50권5호
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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.

• 한국수소및신에너지학회논문집
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• 제17권2호
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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.

• 대한금속재료학회지
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• 제49권12호
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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.

• 대한금속재료학회지
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• 제50권6호
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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.

• 한국재료학회지
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• 제18권11호
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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.

• 대한금속재료학회지
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• 제50권5호
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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.

• 한국수소및신에너지학회논문집
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• 제10권1호
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• pp.9-17
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• 1999

기계적인 합금처리된 여러 Mg-Ni 혼합물 중에서 가장 우수한 수소저장 성질을 가지고 있는 Mg-25wt.%Ni 혼합물의 수소화물 형성 및 분해 반응에 대한 반응속도론적 연구를 하였다. 수소화물 형성 및 분해 속도를 측정하여 이론적인 반응 속도식과 비교함으로써 율속 단계를 결정하였다. Mg-25wt.%Ni의 수소화물 형성의 율속단계는 $H_a$ = 4.0 미만의 여러 $H_a$ 범위에서는 입자간 통로 (interparticle channel), 입자의 갈라진 틈(crack) 등을 통한 수소 분자의 이동 단계인 Knudsen 유동과 보통의 기체 확산이고, 4.0 < $H_a{\leq}4.25$ 범위에서는 성장하는 수소화물 층을 통한 수소 원자의 확산으로 생각된다. Mg-25wt.%Ni의 수소화물 분해의 율속 단계는 전 $H_d$ 범위에 걸쳐 수소 분자의 이동 단계인 Knusden 유동과 보통의 기체 확산이다.

• 대한금속재료학회지
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• 제50권1호
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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.

• 한국수소및신에너지학회논문집
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• 제22권6호
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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.