• Journal of Hydrogen and New Energy
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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.

• Nuclear Engineering and Technology
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• v.35 no.5
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• pp.378-386
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• 2003

Recently failures of nuclear fuel rods in Korean nuclear power plants were reported and their failure causes have been investigated by using PIE techniques. Destructive and physico-chemical examinations reveal that the clad hydriding phenomena had caused the rod failures primarily and secondarily in each case. In this study, the basic mechanisms of the primary and the secondary hydriding failures are reviewed, PIE data such as cladding inner and outer surface oxide thickness and the restructuring of the fuel pellets are analyzed, and they are compared with the predicted behaviors by a fuel performance code. In addition, post-defected fuel behaviors are reviewed and qualitatively analyzed. The results strongly support that the hydriding processes, primary and secondary, played critical roles in the respective fuel rods failures and the secondary hydriding failure can take place even in the fuel rod with low linear heat generation rate.

• 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.

• Journal of Hydrogen and New Energy
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• v.9 no.4
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• pp.143-150
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• 1998

The hydriding and dehydriding properties of a Mg-10wt.%Ni mixture, mechanically-alloyed in order to improve the hydriding and dehydriding kinetics of pure Mg, were investigated. The $Mg_2Ni$ phase develops along with hydriding-dehydriding cycling. The principal effects of mechanical alloying in a planetary mill and hydriding-dehydriding cycling are considered to be the augmentation in the density of defects and the enlargement in the specific surface area. The mechanically-alloyed Mg-10wt.%Ni mixture is activated easily. It has much higher hydriding rate and hydrogen-storage capacity and relatively high dehydriding rate as compared with the pure Mg, the Mg-10wt.%Ni alloy, the Mg-25wt.%Ni alloy and the $Mg_2Ni$ alloy.

• Journal of Hydrogen and New Energy
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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 $H_d$.

• Journal of the Korean Ceramic Society
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• v.47 no.2
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• pp.106-112
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• 2010

This paper presents some experimental results on incubation time for massive hydriding of Zr alloys with oxide thickness. Oxide effects experiments on massive hydriding reaction of commercial Zr alloy claddings and pre-oxidized Zr alloys with hydrogen gas were carried out in the temperature range from 300 to $400^{\circ}C$ with thermo-gravimetric apparatus. Experimental results for oxide effects on massive hydriding kinetics show that incubation time is not proportional to oxide thickness and that the massive hydriding kinetics of pre-filmed Zr alloys follows linear kinetic law and the hydriding rate are similar to that of oxide-free Zr alloys once massive hydriding is initiated. There was a difference in micro-structures between oxide during incubation time and oxide after incubation time. Physical defects such as micro-cracks and pores were observed in only oxide after incubation time. Therefore, the massive hydriding of Zr alloys seems to be ascribed to short circuit path, mechacical or physical defects, such as micro-cracks and pores in the oxide rather than hydrogen diffusion through the oxide resulting from the increase of oxygen vacancies in the hypostoichiometric oxide.

• Korean Journal of Materials Research
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• v.10 no.1
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• pp.15-20
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• 2000

The hydrogen-storage properties of a mechanically-alloyed Mg-18wt.%Ni mixture were investigated. Among the mixtures mechanically alloyed for 1h, 3h, and 6h, the mixture mechanically alloyed for 6h(MA 6h sample) shows the best properties of activation, hydriding, and dehydriding. The $Mg_2Ni$ phase forms in the mechanically-alloyed Mg-18wt.%Ni mixture along with hydriding-dehydriding cycling. The MA 6h sample is relatively easily activated and has higher hydriding rate than the pure Mg, the Mg-10wt.%Ni alloy, and a little lower hydriding rate than the $Mg_2Ni$alloy. The MA 6h sample lower dehydriding rate than the $Mg_2$Ni alloy but higher dehydriding rate than the pure Mg and the Mg-25wt.%Ni alloy. The MA 6h sample has larger hydrogen-storage capacity than the pure Mg and the other alloys.

• Korean Journal of Materials Research
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• v.24 no.3
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• pp.129-134
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• 2014

Pure $MgH_2$ was milled under a hydrogen atmosphere (reactive mechanical grinding, RMG). The hydrogen storage properties of the prepared samples were studied at a relatively low temperature of 423 K and were compared with those of pure Mg. The hydriding rate of the Mg was extremely low (0.0008 wt% H/min at n = 4), and the $MgH_2$ after RMG had higher hydriding rates than that of Mg at 423 K under 12 bar $H_2$. The initial hydriding rate of $MgH_2$ after RMG at 423 K under 12 bar $H_2$ was the highest (0.08 wt% H/min) at n = 2. At n = 2, the $MgH_2$ after RMG absorbed 0.39 wt% H for 5 min, and 1.21 wt% H for 60 min at 423K under 12 bar $H_2$. At 573 K under 12 bar $H_2$, the $MgH_2$ after RMG absorbed 4.86 wt% H for 5 min, and 5.52 wt% H for 60 min at n = 2. At 573 K and 423 K under 1.0 bar $H_2$, the $MgH_2$ after RMG and the Mg did not release hydrogen. The decrease in particle size and creation of defects by reactive mechanical grinding are believed to have led to the increase in the hydriding rate of the $MgH_2$ after RMG at a relatively low temperature of 423 K.

• Journal of Hydrogen and New Energy
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• v.5 no.1
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• pp.9-17
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• 1994

Activation behavior, hydriding rate and disintegration were studied for a compact in pellet form and hydrogen storage alloy particles treated with newly developed inorganic solution. Cylindrical disc of 12.95mm diameter and of 7.1mm thickness was prepared by compressing(8ton) a mixture of $MmNi_{4.5}Al_{0.47}$ and PTFE. Chemical treatment of particles with 1mol of solution was performed at room temperature for several hours until the pH of solution did not change. Chemical treatment made much accelerated activation without any incubation period which generally exists in the untreated alloys and the hydriding reaction rate after full activation also was improved.

• Journal of Hydrogen and New Energy
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• v.9 no.4
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• pp.151-160
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• 1998

The variation of the hydrogen-storage properties of Mg contained in the mechanically-allyed mixture with the weight percentage of nickel in the sample is investigated. The weight percentage of nickel transformed into the Mg2Ni phase, on the basis of the nickel weight, is highest in the Mg-10 wt.%Ni sample. For the first hydriding cycle, the effect of mechanical alloying on the hydriding rate of Mg is highest in the Mg-25 wt.%Ni sample. After activation, the effects of mechanical alloying and hydriding-dehydriding cycling on the hydriding rate of Mg are highest in the Mg-10 wt.%Ni sample. After sufficient hydriding-dehydriding cycling, the effects on the hydrogen-storage capacity of Mg are highest in the Mg-10 wt.%Ni sample. The effects on the hydriding and dehydriding rates of Mg are highest in the Mg-25wt.%Ni sample. Mg-25wt.%Ni, followed by Mg-10 wt.%Ni, is the optimum composition which has the best effects on the hydrogen-storage properties of Mg contained in the sample. The mechanical alloying and the hydriding-dehydriding cycling produce many defects, which can act as active nucleation sites, and increase the specific surface area, shortening the diffusion distance of hydrogen.