研究報告

第26巻(2006)

研究報告26 - 1  論文 - Original

ジルコニウム合金上のメタン分解動力学
Kinetics of Methane Decomposition over Zr-Ni Alloys

渡辺国昭1), 洲 亘2), 松山政夫1)

1) 富山大学水素同位体科学研究センター、〒930-8555 富山市五福3190
2) Present Afflication: Tritium Process Laboratory, JAERI, Japan

K. Watanabe1), W Shu2), M. Matsuyama1)

1) Hydrogen Isotope Research Center, Toyama University, Gofuku 3190, Toyama 930-8555, Japan
2) Present Affliation: Tritium Process Laboratory, JAERI, Japan


Abstract

 The decomposition of methane over Zr, Zr4Ni and Zr2 and Zr2Ni was investigated to develop highly active materials for capturing tritiated methane inevitably formed in tritium handling systems. The entire decomposition or absorption curves, however, could not been described by any simple kinetic equations appearing in the literature. The present paper describes verification of plausible kinetic equations reproducing the observed absorption curves, assuming a reaction mechanism consisting of a progressive removal of hydrogen atoms according to CH4(g) →CH3(a)→ CH2(a)→ CH(a)→ C(a) and its modification including carbon segregation schemes by solving a set of kinetic equations by means of finite difference method, by taking into account of ab-initio calculations of potential energy surfaces by Gaussian 03.
It was found that a step-by-step H-deletion model could not generate the experimentally observed absorption curves, but they could be reproduced quite well in the whole reaction range by a modified reaction scheme assuming coagulation of a carbon residue like CH2(a) or CH(a) to carbonaceous deposits, described as CH4(g)- k1 →CH3(a)-k2 → CH(a)-k3 →C-deposits. It was concluded that the final third step (with a rate constant of k3) governs the overall absorption reactivity (methane consumption beyond 90%) of the materials.

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研究報告26 - 2  論文 - Original

Cr-Cu合金によるメタンの分解挙動
Thermal decomposition of CH4 by Cr-Cu alloy

原 正憲,渡辺国昭,松山政夫

富山大学水素同位体科学研究センター, 〒930-8555 富山市五福3190

Masanori Hara, Kuniaki Watanabe, Masao Matsuyama

Hydrogen Isotope Research Center, Toyama University, Gofuku 3190, Toyama 930-8555, Japan


Abstract

 To examine the applicability of Cr-Cu alloys for thermal decomposition of hydrocarbons, thermal decomposition of methane by Cr-Cu alloy were carried out. Cr-Cu alloys were prepared by the argon arc melting. The argon arc discharge was maintained until the copper only melted. The prepared alloy was constructed the mixture of chromium grains and the fused copper, because chromium is not miscible with copper and no intermetallic compounds are formed. The alloy ingots prepared were chipped to small needles to use for thermal decomposition of methane. The thermal decomposition of methane by Cr-Cu alloy needles was took place by means of the temperature-programmed method which the ramp rate was 2.28 K/min. By pure chromium, methane was decomposed to hydrogen gas and chromium carbides at 1060 K. On the other hand, the Cr-Cu alloy needles initiated the decomposition of methane at 900 K. The initiation temperature of the methane decomposition was reduced about 160 K on comparison pure chromium with the alloy. The alloying effect on the reduction of the initiation temperature of thermal decomposition was, however, appeared on the virgin alloy needles.

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研究報告26 - 3  論文 - Original

真空加熱脱マグネシウム処理によるMg-Ni-Y合金の組織改変
Modification of the Structure of Mg-Ni-Y Alloy by Vacuum-Heating

犀川 浩1、 原 正憲2、渡辺 国昭2、水島 輝夫1、諸住 正太郎3

1 千葉工業大学 工学部機械サイエンス学科 〒275-0016 千葉県習志野市津田沼2-17-1
2 富山大学 水素同位体科学研究センター 〒930-8555 富山市五福3190
3 東北大学 名誉教授 〒980-8577 宮城県仙台市青葉区片平二丁目1-1

Hiroshi SAIKAWA1), Masanori HARA2), Kuniaki WATANABE2),Teruo MIZUSHIMA2),Shotaro MOROZUMI3)

1) 1 Department of Mechanical Science, Chiba Institute of Technology Tsudanuma 2-17-1, Narashino, Chiba 275-0016, JAPAN
2)Hydrogen Isotope Research Center, University of Toyama, Gofuku 3160, Toyama 930-8555, Japan
3) Tohoku University Emeritus Professor Katahira 2-1-1, Aoba, Sendai, Miyagi 980-8577, JAPAN


Abstract

 A 10mm cubic specimen cut from a chill-cast Mg-30%Ni-5%Y alloy block was vacuum-heated for 4 h at 873 K and was then examined under optical and electron microscopes to determine structural changes and to identify constituents along from the inside to the outside at the vertical section of the deformed specimen. The specimen was then pulverized for measuring X-ray diffraction patterns, following to hydrogen absorption tests at room temperature and 473 K. As a result, it was deduced that an angular ternary compound existed in hardly visible size and number in the as-cast alloy, but newly produced largely by the vacuum heating and identified as MgNi3Y by EPMA might behave as a catalyst to enhance the hydrogen absorption rate at room temperature.A similar experiment was also performed on Mg-30%Ni-10%Ho alloy as a reference.

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研究報告26 - 4  論文 - Original

TiC中の水素の拡散挙動
Diffusion of Hydrogen in TiC

波多野 雄治, 野崎 天生, 本間 啓史, 松山 政夫

富山大学水素同位体科学研究センター, 930-8555 富山市五福3190

Y. Hatano, T. Nozaki, H. Homma, M. Matsuyama

Hydrogen Isotope Research Center, Toyama University, Gofuku3190, Toyama 930-8555


Abstract

 The diffusion coefficient of hydrogen in commercially supplied TiC powder was measured at 773, 873 and 973 K by hydrogen absorption experiments. The pre-exponential factor and activation energy were evaluated to be 10-11 m2• s-1 and 87±13 kJ•mol-1, respectively.

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研究報告26 - 5  論文 - Original

バレルスパッタリング法によるPMMAポリマー粉末表面へのAu修飾における修飾効率の検討
Study of the total sputtering yield for Au modification of PMMA polymer particles by barrel-sputtering technique

田口 明1),広見千賀子1),谷澤昌昭1), 北見知士1), 赤丸悟士1),阿部孝之1)

1) 富山大学水素同位体科学研究センター, 930-8555 富山市五福3190
2) 日本ピラー工業株式会社, 669-1333 兵庫県三田市下内神字打場541-1

Akira Taguchi1), Chikako Hiromi1), Masaaki Tanizawa1), Tomohito Kitami2), Satoshi Akamaru2), Takayuki Abe2)

1) Nippon PillarPacking Co., Ltd. 541-1 Utsuba, Shimo Uchigami, Sanda, Hyogo 669-1333
2) Hydrogen Isotope Research Center, Toyama University, Gofuku3190, Toyama 930-8555


Abstract

 Total sputtering yield, defined as the ratio of the amount of metal deposited on a powdery substrate and the total amount of metal sputter-deposited, was investigated from Au modification of glass plates and PMMA polymer particles by using barrel-sputtering technique. The dependence of the angle distribution of Au deposition on RF input power was studied in the beginning. The amount of Au deposition was found to linearly depend on the distance from the center of the barrel, and the total amount of Au deposition was also found to linearly depend on the bias voltage for sputtering performed. On the basis of the amount of Au deposited on the PMMA polymer particle and the total amount of Au sputter-deposited, it was concluded that the total sputtering yield for Au modification of PMMA polymer particles was ca. 11 %.

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研究報告26 - 6  論文 - Original

酸化物ターゲットを取り付けたバレルスパッタリング装置によるアルミフレーク表面へのSiO2修飾
Surface modification of aluminum flakes with SiO2 by using the barrel-sputtering system equipped with oxide target

赤丸悟士, 東出真吾, 田口明, 阿部孝之

富山大学水素同位体科学研究センター, 930-8555 富山市五福3190

Satoshi Akamaru, Shingo Higashide, Akira Taguchi, Takayuki Abe

Hydrogen Isotope Research Center, University of Toyama Gofuku 3190, Toyama 930-8555, Japan


Abstract

 We demonstrated a surface modification of aluminum flakes with SiO2 by using the barrel-sputtering system equipped with a SiO2 target. In order to find suitable sputtering conditions using the system, a SiO2 film was prepared on an Al sheet under various desired oxygen fractions, sputtering gas pressures, and substrate temperatures. XRD analysis and weight of prepared SiO2 film was determined that the suitable sputtering condition for the SiO2 film were 0% oxygen fraction, 3 Pa a total pressure, and 300 K substrate temperature. Surface coating of Al flakes by SiO2 was carried out under these conditions. It was found from SEM and EDS measurements that the surface of Al flakes was coated with a thin uniform SiO2 film.

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研究報告26 - 7  論文 - Original

ステンレス鋼におけるトリチウム放出機構の考察
Consideration for the mechanism of tritium desorption in stainless-steel

赤丸悟士, 東出真吾, 田口明, 阿部孝之

富山大学水素同位体科学研究センター, 930-8555 富山市五福3190

K. Akaishi, Y. Torikai, D. Murata, Ralf-Dieter Penzhorn, K. Watanabe, M. Matsuyama

Hydrogen Isotope Research Center, University of Toyama Gofuku 3190, Toyama 930-8555, Japan


Abstract

Stainless-steel specimens of 15 mm square and 0.5 mm thickness in which tritium was dissolved with a uniform concentration were prepared. After the specimens had been chemically etched the thickness approximately 70 μm, the amount of tritium trapped within the top surface layer was measured as a function of time by β-ray -induced X-ray spectroscopy technique. When the specimen was immersed in an argon gas flow in atmosphere at ambient temperature, more than 99% of tritium desorbed from the specimen was tritiated water, and the amount of released tritium was measured as a function of time by the liquid-scintillation counting technique. In this paper, a model for hydrogen transport is proposed to evaluate quantitatively the above experimental results, and results of numerical simulation for tritium release are shown. It is demonstrated that the numerical simulation accurately predicts the amount of tritium released from the stainless-steel specimen in the experiment.

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研究報告26 - 8  ノート - Note

BIXS法によるトリチウム分圧の測定(II) -混合気体の影響-
Measurement of Tritium Partial Pressure by BIXS(II)-Effects of Mixture Gases-

松山政夫1, 洲 亘2, 鈴木卓美2

1富山大学 水素同位体科学研究センター, 〒930-8555 富山市五福3190
2日本原子力研究開発機構・核融合エネルギー工学研究開発ユニット トリチウム工学研究グループ  〒319-1195 茨城県那珂郡東海村村松4-49

M. Matsuyama1, W.M. Shu2, T.Suzuki2

Hydrogen Isotope Research Center, Toyama University, Gofuku 3190, Toyama 930-8555, Japan
Tritium Tecnology Group, Division of Fusion Energy Tecnology Japan Atomic Energy Agency, Ibaraki319-1195, Japan


Abstract

 The bremsstrahlung X-ray counting method is one of the promising methods for in-situ measurements of high-level tritium, and the applicability of this method to a tritium handling system has been examined. In this study, pressure dependence of X-ray intensity in a high pressure region above 1 kPa was mainly examined using mixtures of H2-,D2-, He- and Ar-1%T2. In a low pressure region below 1 kPa, the X-ray intensity was proportional to the partial pressure of tritium in all of the mixtures, while above that pressure it deviated downward from the proportional tendency. The deviation behavior in the mixtures of H2-, D2-, He-1% T2 was similar, but that in the mixture of Ar-1%T2 was different from that in the other three mixtures: namely, the downward deviation in the three mixtures is mainly caused by the self-absorption of β-rays in the hydrogen isotope and helium gases, whereas in the mixture of Ar-1%T2 the emission of characteristic X-rays from argon atoms plays a major role in the deviation.

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