• Title/Summary/Keyword: 수소화물형성속도

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Development of Mg-10wt.%Ni Hydrogen-Storage Alloy by Mechanical Alloying (기계적인 합금에 의한 Mg-10wt.%Ni 수소저장합금의 개발)

  • Song, MyoungYoup
    • Transactions of the Korean hydrogen and new energy society
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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.

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Influence of Mechanical Alloying and Hydriding-Dehydriding Cycling on the Hydrogen-Storage Properties of Mg (기계적 합금처리와 수소화물 형성·분해 싸이클링이 Mg의 수소 저장성질에 미치는 영향)

  • Song, MyoungYoup
    • Transactions of the Korean hydrogen and new energy society
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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.

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A Study on the Hydriding and Dehydriding Kinetics of a Mechanically-Alloyed Mg-25wt.%Ni Mixture (기계적 합금처리된 Mg-25wt.%Ni 혼합물의 수소화물 형성 및 분해에 대한 반응속도론적 연구)

  • Song, Myoung Youp
    • 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 $H_d$.

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Development of Mg-18wt.%Ni-Hydrogen-Storage Alloy by Mechanical Alloying (기계적인 합금화에 의한 Mg-18wt.%Ni 수소저장합금의 개발)

  • Song, Myoung-Youp;Ahn, Dong-Su;Kwon, Ik-Hyun;Ahn, Hyo-Jun
    • 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.

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상용 핵연료 피복관의 대량수소화 반응속도 연구

  • 김선기;김용수
    • Proceedings of the Korean Nuclear Society Conference
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    • 1998.05b
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    • pp.243-249
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    • 1998
  • 상용 핵연료 피복관 재료로 사용되고 있는 Zircaloy-2와 Zircaloy-4 및 ZIRLO$^{TM}$에 대한 수소와의 반응거동 및 속도론적(kinetic) 자료를 얻기 위하여 electro-microbalance가 장착된 TGA (thermogravimetric analysis) 장치를 이용하여 30$0^{\circ}C$~50$0^{\circ}C$의 온도범위에서 1기압 수소와의 반응에 따른 무게증가를 in-situ로 측정하였다. Zircaloy와 수소와의 반응거동은 chamber내 온도상승시 생성되는 산화막에 의해 초기에는 느린 반응이 진행되는 영역이 존재하고 온도가 낮은 35$0^{\circ}C$ 이하에서는 이것이 잠복기 형태로 나타난 후 직선속도법칙(linear rate law)을 따르며 반응이 가속화되는 것으로 나타났고 40$0^{\circ}C$ 이하의 저온에서는 직선속도법칙에서 반응이 지연되는 방향으로 약간의 편차(deviation)가 관찰되었다. 그 결과 Zircaloy-2와 ZIRLO$^{TM}$가 Zircaloy-4보다 수소와의 반응속도가 빠르고 활성화에너지가 낮은 것으로 나타났으며 직선속도법칙을 근거로 하여 각각 1.1x$10^{7}$ exp(-20,800/RT)와 1.5x$10^{6}$exp(-18,000/RT) 및 6.9x$10^{7}$ exp(-23,800/RT) (mg/dm$^2$/min) 의 속도상수를 도출하였다. 또한, 열구배가 존재하지 않는 out-of-pile 조건하에서도 'sunburst' 형태의 국부적 수소침투가 발생할 수 있음이 ~l,000 ppm이상의 수소침투 시편에서 확인되었다. ~3,000ppm이상 침투하게 되면 표면에 수소화물이 농축되어 있는 hydride layer가 형성됨을 관찰하였으며 ~5,000ppm 이상의 경우에는 수소화물의 방향성이 random하였으며 특히, ZIRLO$^{TM}$ 시편의 경우에서는 원주방향으로 길게 이어진 수소화물과 기계적 성질에 치명적인 반경방향의 수소화물이 평행하게 배열된 것을 관찰하였다.

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Hydrogen Storage Properties of Mg-10wt.%MnO Prepared by Reactive Mechanical Grinding (반응성 기계적 분쇄에 의해 제조한 Mg-10wt.% MnO의 수소 저장 성질)

  • Song, Myoung-Youp;Kwon, Ik-Hyun;Kwon, Sung-Nam;Park, Chan-Gi;Bae, Jong-Soo
    • Transactions of the Korean hydrogen and new energy society
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    • v.16 no.1
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    • pp.25-30
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    • 2005
  • 수소 분위기에서 10wt.%MnO와 기계적인 분쇄(반응성 기계적 분쇄)에 의해 Mg의 수소 저장 성질을 향상시켰다. 회전 속도는 250 rpm, 밀링시간은 2 h, 그리고 시료 대 볼 중량비는 1/45이었다. 준비한 Mg-10wt.%MnO 시료는 활성화를 위한 수소화물 형성 분해 싸이클링이 필요없었으며, 첫 번째 싸이클 593k 12 bar $H_2$에서, 10분 동안에 3.12wt.%, 60분 동안에 3.95wt.%의 수소를 흡수하였다. 또한 Mg-10wt.%MnO는 593k 0.8 bar $H_2$에서 60분 동안에 2.12wt.%의 수소를 방출하였다. MnO와 Mg의 방응성 분쇄는, 핵생성을 용이케하고 (Mg 입자의 표면에 결함 형성과 첨가물에 의해), Mg 입자의 표면에 crack을 만들어 Mg의 입자 크기를 줄여 그 결과 수소 원자의 확산 거리를 작게 함으로써 수소 흡수 방출 속도를 증가시킨다. 수소화물 형성 분해 싸이클링은 Mg 입자의 표면에 crack을 만들고 Mg의 입자 크기를 줄여 수소 흡수 방출 속도를 증가시킨다.

Development of Hydrogen-Storage Alloy by Mechanical Alloying of Mg and Ni (Mg과 Ni의 기계적인 합금화에 의한 수소 저장 합금의 개발)

  • Song, Myoung-Youp
    • Transactions of the Korean hydrogen and new energy society
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    • v.7 no.2
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    • pp.181-191
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    • 1996
  • Samples with the compositions of Mg-10wt.%Ni and Mg-25wt.%Ni were prepared by mechanical alloying in a planetary mill. $Mg_2Ni$ phase was formed in the mixture with hydriding dehydriding cycling. The activation of Mg-10wt.%Ni and Mg-25wt.%Ni was completed after n=7 and n=6 around, respectively, at 583K, $0{\sim}8barH_2$. Mg-10wt.% Ni and Mg-25wt. %Ni are considered as excellent hydrogen-storage materials with very high hydriding rates, high dehydriding rates and relatively large hydrogen-storage capacity. The effets of mechanical alloying and hydriding dehydriding cycling are considered the augmentation in the density of active nucleation sites and the diminution in the particle size.

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Detection of Hydride Blisters in Zirconium Pressure Tubes using Ultrasonic Mode Conversion and Velocity Ratio Method (초음파 모드 변환 및 속도비 방법에 의한 지르코늄 압력관의 수소화물 블리스터 탐지)

  • Cheong, Yong-Moo;Lee, Dong-Hoon;Kim, Young-Suk
    • Journal of the Korean Society for Nondestructive Testing
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    • v.23 no.4
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    • pp.334-341
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    • 2003
  • When the pressure tubes(f are in contact with the calandria tube(CT) in the pressurized heavy water reactor(PHWR), the temperature difference between inner and outer wall of W results in a thermal diffusion of hydrogen (deuterium) and hydride blisters are formed on the outer surface of PT. Because the hydride blisters and zirconium matrix are acoustically continuous, it is not easy to distinguish the blisters from the matrix with conventional ultrasonic method. An ultrasonic velocity ratio method was developed to detect small hydride blisters on the zirconium pressure tube. Hydride blisters were grown in the PT specimen using a steady state thermal diffusion device. The flight times of longitudinal echo and reflected shear echo from the outer surface were measured accurately. The velocity ratio of the longitudinal wave to the shear wave was calculated and displayed using contour plot. Compared to the conventional flight time method of longitudinal wave, the velocity ratio method shows superior sensitivity to detect smaller blisters as well as better images for the blister shapes. Detectable limit of the outer shape of the hydride blisters was conservatively estimated as $500{\mu}m$, with the same specifications of ultrasonic transducer used in the actual PHWR pressure tube inspection.

The Corrosion Behavior of Hydrogen-Charged Zircaloy-4 Alloys (수소 장입된 Zircaloy-4 합금에서의 부식거동)

  • Kim, Seon-Jae;Kim, Gyeong-Ho;Baek, Jong-Hyeok;Choe, Byeong-Gwon;Jeong, Yo-Hwan
    • Korean Journal of Materials Research
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    • v.8 no.3
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    • pp.268-273
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    • 1998
  • Standard Zircaloy-4 sheets, charged with 230-250ppm hydrogen by the gas-charging method and homogenized at $400^{\circ}C$ for 72hrs in a vacuum, were corroded in pure water and aqueous LiOH solutions using static autoclaves at $350^{\circ}C$. Their corrosion behaviors were characterized by measuring their weight gains with the corrosion time and observing their microstructures using an optical microscope and a scanning electron microscope. The elemental depth profiles for hydrogen and lithium were measured using a secondary ion mass spectrometry(S1MS) to confirm their distributions at the oxidelmetal interface. The normal Zircaloy-4 specimens corroded abruptly and heavily at the concentration of Li ions more than 30ppm in the aqueous solution. This is due to accelerations by the rapid oxidation of many Zr- hydrides formed by the large amount of absorbed hydrogen, resulting from the increased substitution of $Li^{+}$ ions with $Zr^{4+}$-sites in the oxide as the Li ion concentration increased. The specimens that had been charged with amounts of hydrogen greater than its solubility corroded early with a more rapid acceleration than normal specimens, regardless of the corrosion solutions. At longer corrosion times. however, normal specimens showed a rather accelerated corrosion rate compared to the hydrogen-charged specimens. These slower corrosion rates of the hydrogen-charged specimens at the longer corrosion times would be due to the pre-existent Zr-hydride in the matrix, which causes the hydrogen pick- up into the specimen to be depressed, when the oxide with an appropriate thickness formed.

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Hydrogen-storage Properties of CoO-Added Mg by Reactive Grinding (반응성분쇄에 의해 CoO를 첨가한 Mg의 수소저장특성)

  • Song, Myoungyoup;Lee, Dongsub
    • Transactions of the Korean hydrogen and new energy society
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    • v.14 no.4
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    • pp.321-326
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    • 2003
  • We tried to improve the $H_2$-sorption properties of Mg by mechanical grinding under $H_2$ (reactive grinding) with CoO. The sample Mg+10wt.%CoO as prepared absorbs 1.25wt.% hydrogen and the activated sample absorbs 2.39wt.% hydrogen for 60min at 598K, $11.2barH_2$. The reactive grinding of Mg with CoO increases the $H_2$-sorption rates by facilitating nueleation(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. Hydriding-dehydriding cycling increases the $H_2$-sorption rates by making cracks on the surface of Mg particles and reducing the particle size of Mg.