JPS624321B2 - - Google Patents
Info
- Publication number
- JPS624321B2 JPS624321B2 JP57144609A JP14460982A JPS624321B2 JP S624321 B2 JPS624321 B2 JP S624321B2 JP 57144609 A JP57144609 A JP 57144609A JP 14460982 A JP14460982 A JP 14460982A JP S624321 B2 JPS624321 B2 JP S624321B2
- Authority
- JP
- Japan
- Prior art keywords
- powder
- hydrogen
- metal
- alloy
- metal hydride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000843 powder Substances 0.000 claims description 59
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 50
- 239000001257 hydrogen Substances 0.000 claims description 50
- 229910052739 hydrogen Inorganic materials 0.000 claims description 50
- 239000002184 metal Substances 0.000 claims description 37
- 229910052751 metal Inorganic materials 0.000 claims description 37
- 239000000956 alloy Substances 0.000 claims description 27
- 229910045601 alloy Inorganic materials 0.000 claims description 26
- 229910052987 metal hydride Inorganic materials 0.000 claims description 19
- 150000004681 metal hydrides Chemical class 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 150000002739 metals Chemical class 0.000 claims description 9
- 239000011232 storage material Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 238000004381 surface treatment Methods 0.000 claims description 7
- 229910000743 fusible alloy Inorganic materials 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 5
- 239000011800 void material Substances 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910010340 TiFe Inorganic materials 0.000 description 12
- 238000000354 decomposition reaction Methods 0.000 description 12
- 238000005984 hydrogenation reaction Methods 0.000 description 12
- 239000010949 copper Substances 0.000 description 11
- 238000003860 storage Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 150000004678 hydrides Chemical class 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910000978 Pb alloy Inorganic materials 0.000 description 2
- 229910020816 Sn Pb Inorganic materials 0.000 description 2
- 229910020922 Sn-Pb Inorganic materials 0.000 description 2
- 229910008783 Sn—Pb Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- 238000004453 electron probe microanalysis Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000010191 image analysis Methods 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
Description
本発明は水素貯蔵材料の製造方法に関し、より
詳細には容易に水素を貯蔵する金属もしくは合金
粉末（以下金属粉末と略記する）及び金属水素化
物に熱伝導度及び機械的強度を付加することを目
的とするものである。
最近水素を容易に吸蔵する材料例えばNi、
Ｖ、TiFe、Mg2Ni、LaNi5のような金属粉末を利
用した水素貯蔵、輸送、廃熱回収、コンプレツサ
ー、高純度水素精製、動力変換、あるいは燃料電
池などへの実用研究が盛んに試みられている。
ところで、金属粉末に水素を吸蔵させる際に
は、多量の熱を発生し、この熱を速やかに除去し
ないと局部的な発熱によつて水素の均一な吸蔵が
行なわれないばかりか、吸蔵により生成した金属
水素化物の解離による水素の放出が起り、円滑な
吸蔵反応は著しく阻害される。そして、この水素
吸蔵時の発熱を除去するために、従来は金網や多
孔質の金属からなる管等の容器内に水素吸蔵用の
金属粉末を収容し、この金網や多孔質金属からな
る容器を介して吸蔵用金属と水素ガスとを接触さ
せ、容器周囲に冷却媒体を流して発生熱を除去す
る手段、あるいは水素吸蔵用の金属粉末の中に金
属小片、ステンレスウールなどを充填し、熱伝導
率の改善を試みる手段がとられていた。しかしな
がら、金属水素化物は超微細粉（５μ以下）で熱
の不良導体であり、又、水素の比熱が小さく熱伝
導率も小さいために発生熱の伝導速度が遅く、発
生熱の効果的な除去が困難であつた。更に悪いこ
とには、金属粉末あるいは金属水素化物は比重が
極めて小さいので水素の流れにより粉末移動を生
じ、又、金属粉末は水素ガスを吸蔵する際に膨脹
して緻密になるので容器壁部に局部的に非常に大
きな応力がかかる危険があり、又これにより水素
ガスがますます浸透しにくく、かつ発生熱がより
蓄積されて不均一な反応が起り易くなる欠点があ
つた。
このような欠点から従来の金属水素化物粉末の
充填密度は安全上約50％以下にとらなければなら
なかつた。
本発明は、以上の従来の欠点を改善せんとする
もので、その要旨とするところは、まず第１項発
明は、金属粉末あるいは既に水素を吸蔵した金属
水素化物の粉末の表面をAl、Ni、Cuおよびこれ
らの金属を主元素とする合金もしくは融点が100
〜400℃の低溶融合金をもつて表面処理後成形す
ることを特徴とする水素貯蔵材料の製造方法であ
る。
本発明において金属粉末などのAl等による表
面処理は、無電解メツキ法、電気メツキ法、浸漬
法、エピタキシヤルグロース法、蒸着法、スパツ
タリング法、C.V.D.法、溶湯浸漬法、電子ビー
ム溶解法などの方法が利用可能である。
表面処理に用いられるAl、Ni、Cu及これらの
金属を主元素とする合金もしくは低溶融合金は水
素の透過率および熱伝導度が大きいので本発明に
は有効である。
そして、かかる方法により表面処理した金属粉
末あるいは金属水素化物は成形されるが、成形は
プレス成形あるいは押出粉砕機により、粒状、ペ
レツト、角柱、円柱などの形状を有する圧粉体と
することによつて行なう。
この圧粉成形体は、金属粉末等があらかじめ
Al、Ni、Cuなどにより表面処理されているの
で、従来のものよりも熱伝導度が大幅に改善さ
れ、粉末の飛散移動を防止するための機械的強度
が付加され、水素化および分解反応を繰返し実施
した場合でも、水素流による粉末の飛散および移
動が少なく、粉末移動による団塊化が防止でき、
水素化反応に伴なう粉末体積の膨脹により発生す
る応力は、表面処理された被覆材料内に膨脹する
空間が存在することで緩和され、局部あるいは容
器底部などで発生する応力は著しく低減される。
第２項発明は前記第１項発明に更に、Al、
Ni、Cu、Zn、Sn、Pbより選ばれた金属もしくは
その合金材をバインダとして添加して成形する方
法である。
これらのバインダ金属は熱伝導度が高く、結合
力も大きく、さらに水素化物をつくらないので成
形安定性が良い。
こうすることによつて、更に熱伝導度は改善さ
れ、水素化反応時の発生熱を速かに外部に排除
し、又、分解反応時に必要な熱の吸収は外部から
バインダ金属を通じ速やかに行なつて所定の温度
に保持することができ、又、粉末の飛散移動防止
効果もさらに増大する。
以上の第１項、第２項発明による圧粉成形体は
１〜50％の空間率を有していことが望ましい。こ
の空間率は、金属水素化物の充填量及びその方
法、反応時間、導水素圧力、実用機器の種類及び
運転状況などの種類により決定するが、空間率が
50％を越えると、圧粉成形体の機械的強度が小さ
く、水素吸蔵量が著しく小さくなつて好ましくな
い。
以上の第１、第２項発明に係る圧粉成形体は水
素貯蔵などの小規模の定置式機器に適している。
第４項発明は前記第１項の発明で得られた圧粉
成形体を、又第５項の発明は前記第２項の発明で
得られた圧粉成形体を、それぞれ非酸化性雰囲気
下で焼結熱処理する方法である。
これらの発明は、水素の運搬、蓄熱用、コンプ
レツサ、動力交換用、燃料電池用などの用途に金
属水素化物が大規模に使用される場合、水素化あ
るいは分解反応時の発熱あるいは吸熱の総量が著
しく大きくなり、外部へあるいは外部からの熱伝
導により、金属水素化物温度を速やかに所定の温
度に保つ必要がある場合、更に使用水素量、水素
圧力及び流量が大となり、より成形体の機械的強
度が必要な場合に有用である。
この場合、焼結熱処理温度は、例えば100〜
1300℃の範囲で行なうが、これは添加金属あるい
は合金の種類によつて異なり、その融点付近の温
度を用いる。
かかる熱処理により、成形体の結合はより強固
になり、熱伝導度並びに機械的強度がさらに改善
され、前述の大規模な用途への使用が可能とな
る。
なお、この場合の焼結体の空間率は１〜40％が
好適である。空間率が40％を越えると水素吸蔵量
が著しく小さくなつて好ましくない。
以下実施例に基づき本発明を説明する。
実施例 １
TiFe合金にSn―Pb合金（融点100℃）のアト
マイズ粉末（粒度200メツシユ以下）を20重量％
添加し、ボールミルで攪拌混合した。この混合粉
末を、アルゴン雰囲気の石英管中で110℃で約30
分間保持し、TiFe合金粉末の表面にSn―Pb合金
を被覆した。
熱処理後のTiFe合金は、EPMA観察によつて
SnおよびPbの存在が確認され、、また湿式分析の
結果18.0重量％のSn―Pb合金が存在しているこ
とが確認された。
機械的強度試験のためそれぞれ下記のものにつ
いて抗折力試験を行なつた。なお成形体は5ton／
cm2の圧力で10mm×６mm×35mmの角柱にプレス成形
したものである。
ａ TiFe合金粉末単独の成形体。
ｂ 前記Sn―Pb合金被覆材料の成形体。
ｃ 前記ｂの成形体をさらに110℃で約30分間焼
結熱処理したもの。
試験の結果、それぞれの試験片の抗折力は、ａ
は約38Kg／cm2、ｂは約65Kg／cm2、ｃは約78Kg／cm2
であり、ａに比較してｂおよびｃは機械的強度が
増大することが判つた。
また、水素圧力30Kg／cm2での水素吸蔵速度は、
約100ｇのTiFeがTiFeH1.5を生成するまでの時間
で比較したところ、ａは15分、ｂは16分、ｃは17
分であつた。
また水素放出試験は、TiFeH1.5の試料が充填
された耐圧容器を50℃に保持された浴中に浸漬さ
せ、出口先端部を水中に浸し、ここから大気中に
放出する方法で観察し、その水素放出が終了する
までの時間を計測し、比較した。その結果ａは32
分、ｂは22分、ｃは18分であつた。
かかる試験から本発明の材料は、水素を吸蔵さ
せる水素化反応の場合よりも、むしろ外からの熱
の供給を必要とする吸熱での分解反応に対する反
応時間の短縮に極めて効果のあることが判つた。
さらに、水素圧力30Kg／cm2での水素化および真
空排気による分解反応を10回繰返して実施した
後、アルゴン雰囲気中に試料を取出して観察した
ところ、ａは完全に成形体が崩壊し粉末となつた
のに対し、ｂおよびｃは角柱のままの形状であつ
た。この結果より、本発明の材料は水素化物ある
いは金属粉末の飛散移動に対しても極めて効果の
あることが判つた。
実施例 ２
２〜３mm以上に粗粉砕したTiFe合金を耐圧容
器に充填し、真空排気しながら約450℃まで昇温
し、約10分間脱ガス処理を行なつた後に約10Kg／
cm2の水素ガスを容器に導入し、炉外に容器を取出
して冷却した。その後、真空排気してからアルゴ
ンガスを容器内に導入した。
このTiFe合金は、当初の形状を維持している
が、乳鉢で粉砕したところ極めてもろく、粉砕が
容易な粒子に変化していることが判つた。
一方、同じTiFe合金を、硫酸銅（20ｇ／）、
硫酸（0.75ｇ／）の液中に、25℃で10〜15分浸
漬し、無電解メツキで、表面にCu被覆を施し
た。このTiFe合金を浴に浸漬し、浴中でアルミ
ナ製丸棒により粉砕し、Cu被覆の微粉末とし
た。ついで、アセトン洗浄を３回実施した後乾燥
した。
TiFe粉末表面には、EPMA観察による元素分
析を行なつたところ、多量のCuが存在すること
を確認した。
つぎに熱伝導度および機械的強度の比較のため
に下記試料を用意した。なお、成形体は5ton／cm2
で10mm×６mm×35mmの角柱にプレス成形したもの
である。
ｄ 上記Cuを被覆したTiFe合金成形体。
ｅ 試料ｄの材料に７重量％のCu粉末（200メツ
シユ以下）をバインダとして添加混合して成形
したもの。
ｆ 試料ｄを1050℃で１時間真空中で焼結熱処理
したもの。
ｇ 試料ｅを試料ｆと同様に焼結熱処理したも
の。
熱伝導度の比較は、表面温度が100℃に保持さ
れた平板状ヒーターに角柱状試料を載せ、断熱材
で試料を覆い、ヒーターからの輻射熱を防ぐよう
にし、角柱試料の長尺方向の対面温度が70℃に達
するまでの時間を計測して比較した。
また空間率は水中法による見掛け密度の測定、
画像解析装置（Q.T.M）から求めた。
以上の試験結果を表にして示す。
The present invention relates to a method for producing a hydrogen storage material, and more specifically to a method for adding thermal conductivity and mechanical strength to a metal or alloy powder (hereinafter abbreviated as metal powder) and metal hydride that easily stores hydrogen. This is the purpose. Recently, materials that easily absorb hydrogen, such as Ni,
Practical research using metal powders such as V, TiFe, Mg 2 Ni, and LaNi 5 is actively being attempted for hydrogen storage, transportation, waste heat recovery, compressors, high-purity hydrogen purification, power conversion, and fuel cells. ing. By the way, when hydrogen is stored in metal powder, a large amount of heat is generated, and if this heat is not removed promptly, not only will hydrogen not be stored uniformly due to localized heat generation, but hydrogen will be generated due to storage. Hydrogen is released due to the dissociation of the metal hydride, and the smooth storage reaction is significantly inhibited. In order to eliminate the heat generated during hydrogen absorption, metal powder for hydrogen storage is conventionally housed in a container such as a wire mesh or porous metal tube; A method for removing the generated heat by bringing the storage metal into contact with hydrogen gas through a container and flowing a cooling medium around the container, or by filling small pieces of metal, stainless steel, etc. into the metal powder for hydrogen storage Steps were taken to try to improve the rate. However, metal hydrides are ultrafine powders (less than 5μ) and are poor conductors of heat, and hydrogen has a small specific heat and low thermal conductivity, so the conduction speed of generated heat is slow, making it difficult to effectively remove generated heat. was difficult. To make matters worse, the metal powder or metal hydride has an extremely low specific gravity, so the flow of hydrogen causes the powder to move, and when the metal powder absorbs hydrogen gas, it expands and becomes dense, causing it to stick to the container wall. There is a risk that a very large stress will be applied locally, and this has the disadvantage that it becomes increasingly difficult for hydrogen gas to penetrate, and that the generated heat is more likely to accumulate, making it more likely that non-uniform reactions will occur. Due to these drawbacks, the packing density of conventional metal hydride powders had to be kept at about 50% or less for safety reasons. The present invention aims to improve the above-mentioned conventional drawbacks, and the gist of the invention is as follows: First, the first aspect of the present invention is to cover the surface of metal powder or metal hydride powder that has already absorbed hydrogen with Al, Ni, etc. , Cu and alloys containing these metals as main elements or with a melting point of 100
This is a method for producing a hydrogen storage material, which is characterized in that it is molded after surface treatment using a low melting alloy at ~400°C. In the present invention, the surface treatment with Al etc. of metal powder etc. can be carried out by electroless plating method, electroplating method, dipping method, epitaxial growth method, vapor deposition method, sputtering method, CVD method, molten metal immersion method, electron beam melting method, etc. methods are available. Al, Ni, Cu, and alloys or low melting alloys containing these metals as main elements used for surface treatment are effective in the present invention because they have high hydrogen permeability and thermal conductivity. Then, the metal powder or metal hydride that has been surface-treated by this method is molded, and the molding is performed by press molding or an extrusion pulverizer to form a green compact in the shape of granules, pellets, prisms, cylinders, etc. Let's go. This powder compact is pre-filled with metal powder, etc.
Surface treated with Al, Ni, Cu, etc., greatly improves thermal conductivity compared to conventional products, adds mechanical strength to prevent powder scattering, and prevents hydrogenation and decomposition reactions. Even when repeated tests are performed, there is little scattering and movement of powder due to the hydrogen flow, and agglomeration due to powder movement can be prevented.
The stress generated by the expansion of the powder volume accompanying the hydrogenation reaction is alleviated by the presence of expansion space within the surface-treated coating material, and the stress generated locally or at the bottom of the container is significantly reduced. . Item 2 invention further includes Al,
This is a molding method in which a metal selected from Ni, Cu, Zn, Sn, and Pb or an alloy thereof is added as a binder. These binder metals have high thermal conductivity and strong bonding strength, and also have good molding stability because they do not form hydrides. By doing this, the thermal conductivity is further improved, the heat generated during the hydrogenation reaction is quickly removed to the outside, and the heat required during the decomposition reaction is quickly absorbed from the outside through the binder metal. As a result, the temperature can be maintained at a predetermined level, and the effect of preventing scattering and movement of the powder is further increased. It is desirable that the powder compact according to the inventions described in Items 1 and 2 above has a void ratio of 1 to 50%. This void ratio is determined by the amount of metal hydride packed, its method, reaction time, hydrogen introduction pressure, type of practical equipment, operating conditions, etc.
If it exceeds 50%, the mechanical strength of the powder compact will be low and the hydrogen storage capacity will be extremely small, which is not preferable. The powder compacts according to the first and second inventions described above are suitable for small-scale stationary equipment such as hydrogen storage. The invention in item 4 is a powder molded product obtained by the invention in item 1, and the invention in claim 5 is a powder molded product obtained in the invention in item 2, under a non-oxidizing atmosphere. This method uses sintering heat treatment. These inventions require that when metal hydrides are used on a large scale for hydrogen transportation, heat storage, compressors, power exchange, fuel cells, etc., the total amount of heat generated or absorbed during hydrogenation or decomposition reactions is If the size of the metal hydride becomes significantly large and it is necessary to quickly maintain the metal hydride temperature at a predetermined temperature by heat conduction to or from the outside, the amount of hydrogen used, hydrogen pressure, and flow rate will further increase, which will further reduce the mechanical strength of the compact. Useful when strength is required. In this case, the sintering heat treatment temperature is, for example, 100~
The temperature range is 1300°C, but this varies depending on the type of added metal or alloy, and a temperature near the melting point of the metal is used. Such heat treatment makes the bond of the molded body stronger and further improves the thermal conductivity as well as the mechanical strength, making it possible to use it in the large-scale applications mentioned above. In this case, the porosity of the sintered body is preferably 1 to 40%. If the porosity exceeds 40%, the amount of hydrogen storage becomes significantly small, which is not preferable. The present invention will be explained below based on Examples. Example 1 20% by weight of atomized powder (particle size 200 mesh or less) of Sn-Pb alloy (melting point 100℃) in TiFe alloy
and stirred and mixed using a ball mill. This mixed powder was heated at 110℃ for about 30 minutes in a quartz tube in an argon atmosphere.
After holding for a minute, the surface of the TiFe alloy powder was coated with Sn--Pb alloy. The TiFe alloy after heat treatment was determined by EPMA observation.
The presence of Sn and Pb was confirmed, and wet analysis confirmed the presence of 18.0% by weight Sn-Pb alloy. For mechanical strength testing, a transverse rupture strength test was conducted on each of the following items. The molded product is 5 tons/
It was press-formed into a 10 mm x 6 mm x 35 mm square column using a pressure of cm 2 . a Molded body of TiFe alloy powder alone. b A molded article of the Sn--Pb alloy coating material. c The molded body of b was further sintered and heat-treated at 110°C for about 30 minutes. As a result of the test, the transverse rupture strength of each test piece was a
is approximately 38Kg/cm 2 , b is approximately 65Kg/cm 2 , c is approximately 78Kg/cm 2
It was found that mechanical strength of samples b and c was increased compared to sample a. In addition, the hydrogen absorption rate at a hydrogen pressure of 30Kg/ cm2 is
When comparing the time it takes for approximately 100g of TiFe to generate TiFeH 1.5 , it is 15 minutes for a, 16 minutes for b, and 17 minutes for c.
It was hot in minutes. In addition, the hydrogen release test was conducted by immersing a pressure vessel filled with a TiFeH 1.5 sample in a bath maintained at 50° C , immersing the outlet tip in water, and releasing the sample into the atmosphere. The time taken for hydrogen release to finish was measured and compared. As a result, a is 32
minutes, b was 22 minutes, and c was 18 minutes. These tests have shown that the material of the present invention is extremely effective in shortening the reaction time for endothermic decomposition reactions that require external heat supply, rather than for hydrogenation reactions that absorb hydrogen. Ivy. Furthermore, after repeating the decomposition reaction by hydrogenation at a hydrogen pressure of 30 kg/cm 2 and vacuum evacuation 10 times, the sample was taken out in an argon atmosphere and observed. In contrast, b and c remained prismatic in shape. From these results, it was found that the material of the present invention is extremely effective against scattering and movement of hydrides or metal powders. Example 2 A pressure-resistant container was filled with a TiFe alloy coarsely ground to a size of 2 to 3 mm or more, heated to about 450°C while being evacuated, and degassed for about 10 minutes.
cm 2 of hydrogen gas was introduced into the container, and the container was taken out of the furnace and cooled. Thereafter, the container was evacuated and argon gas was introduced into the container. This TiFe alloy maintained its original shape, but when crushed in a mortar, it was found that it had changed into particles that were extremely brittle and easy to crush. On the other hand, the same TiFe alloy was mixed with copper sulfate (20g/),
It was immersed in a solution of sulfuric acid (0.75 g/) at 25°C for 10 to 15 minutes, and the surface was coated with Cu by electroless plating. This TiFe alloy was immersed in a bath and ground in the bath using an alumina round rod to form a Cu-coated fine powder. Then, it was washed with acetone three times and then dried. Elemental analysis using EPMA observation confirmed that a large amount of Cu was present on the TiFe powder surface. Next, the following samples were prepared for comparison of thermal conductivity and mechanical strength. In addition, the molded body is 5ton/cm 2
It is press-formed into a 10mm x 6mm x 35mm square column. d TiFe alloy molded body coated with the above Cu. e A product formed by adding and mixing 7% by weight of Cu powder (200 mesh or less) as a binder to the material of sample d. f Sample d was sintered and heat treated in vacuum at 1050°C for 1 hour. g Sample e was sintered and heat treated in the same manner as sample f. Thermal conductivity comparisons were made by placing a prismatic sample on a flat heater whose surface temperature was maintained at 100°C, covering the sample with a heat insulating material to prevent radiant heat from the heater, and placing the prismatic sample in the longitudinal direction of the sample. The time taken for the temperature to reach 70°C was measured and compared. In addition, the void ratio can be determined by measuring the apparent density using the underwater method.
Obtained from image analysis device (QTM). The above test results are shown in a table.
【表】
上記表に示した結果から明らかなように、本発
明材料は機械的強度を表わす抗折力および熱伝導
度において大幅に改善されていることが判つた。
また、試料ｄおよびｇについて、実施例１に記
載した方法で水素化および分解反応を10回実施し
た。その結果水素吸蔵速度はどちらも15分前後で
あるが、水素放出速度は試料ｄは26分、試料ｇは
25分であつた。
さらに形状は、水素化および分解反応の繰返し
によつても粉末化せず、角柱を維持していること
が判つた。
実施例 ３
水素化物TiH2粉末をプレス圧力1ton／cm2で15
mm×15mm×10mmの角柱成形体とした。
SUS製箱の底部にアルミナ製海綿状平板を置
き、その上に上記成形体を10箇並置した。さらに
その上にアルミナ製海綿状平板を載せ、この平板
上に純度99.9％のAl厚板を載せた。
このように準備した箱を真空電気炉中に装入
し、真空排気しつつ670℃まで約１時間で昇温し
た。昇温期間中TiH2粉末は、約300℃付近から分
解反応を開始し、吸蔵水素ガスを放出し、約650
℃では完全に水素ガスの放出は停止し、金属Ti
に変化した。熱処理加工は670℃で30分保持した
後炉冷した。
角柱試料は全面にAlを被覆した状態で取出さ
れた。Alの含浸状態を観察するため切断したと
ころ、内部までAlが浸透していることが判明し
た。
この角柱試料を粉砕後、振動ミルで粉砕混合
し、5ton／cm2で10mm×10mm×15mmの角柱にプレス
成形した。この成形体のAl量は約45重量％であ
つた。又空間率は画像解析装置（Q.T.M）で観
察したところ約28％であつた。
別に単にTi粉末に対して300メツシユ以下のAl
粉末を約45重量％添加混合したものを5ton／cm2で
プレス成形し、真空含浸法による成形体とその内
部構造について比較した。
その結果、空間率についてはほぼ同等な値であ
るが、走査電子顕微鏡による観察から、真空含浸
の成形体はTiとAl金属との接触面が均一であ
り、かつ空孔が一様に分散しているのに対して、
単なる混合成形体は局部的にTiおよびAl金属の
富む領域が多数分布し、さらに空孔の大きさ、そ
の分布についても一様でないことが判つた。
抗折力試験の結果、真空含浸法により処理した
成形体は88Kg／cm2、単なる混合成形体は64Kg／cm2
であり、機械的強度の面からも本発明材料は有利
であることが判つた。
実施例 ４
Mg2Ni粉末を真空蒸着装置内で平底の薄型ガラ
スポートに約２mm厚さで充填した後、真空排気後
高周波加熱によるNi蒸着を施した。蒸着時間は
約５分間であり、この期間中外部マニピレーター
によりガラスボートを左右に移動させることで粉
末の表面に均一にNiの蒸着膜を作製させるよう
にし、さらにこの蒸着を２回繰返して実施した。
蒸着Ni膜厚は干渉型厚膜計により同時に装着し
ておいたガラス板から求めると約0.7μｍであつ
た。
TiH2水素化物粉末に対しても上記と同様の処
理をした。
上記表面処理されたMg2Ni粉末およびTiH2粉
末を5ton／cm2でプレス成形したものと、さらには
これらにバインダとして200メツシユ以下のCu粉
末を30重量％添加混合して成形したものと、それ
ぞれ10mm×10mm×15mmの角柱成形体とした。
また比較材としてMg2NiおよびTiH2粉末をそ
れぞれ5ton／cm2で同様にプレス成形した。
Mg2Ni成形体の水素化および分解反応は280℃
の温度で導入水素圧力20Kg／cm2で水素化、真空排
気による水素放出で分解反応を実施し、この操作
を10回繰返した。
TiH2成形体は650〜700℃の温度範囲で、
Mg2Niの場合と同様な条件で水素化および分解反
応を10回行なつた。
その結果、Mg2NiやTiH2粉末のみを圧粉成形
体としたものは、水素化および分解反応の繰返し
により完全に粉末に戻り、Ni蒸着膜を施したも
のやさらにバインダーとしてCu粉末を添加した
ものは角柱形状を維持しており、蒸着膜あるいは
バインダーが成形体の崩壊を防止する上で極めて
効果的であることが判つた。
以上説明したとおり、本発明により得られる水
素吸蔵材料の圧粉成形体あるいは焼結体は、従来
の粉末のままの充填材料と比較すると、機械的強
度が付加され、さらに熱伝導度を改善した成形体
であるので、充填密度の向上、粉末の飛散移動が
ないことで充填方法および熱伝達機器などの簡単
化、取扱いなど作業性の向上を図ることが可能で
あり、水素吸蔵材料を利用した実用機器の開発に
対して大きな効果を示すものである。[Table] As is clear from the results shown in the table above, it was found that the material of the present invention was significantly improved in transverse rupture strength, which indicates mechanical strength, and thermal conductivity. Further, for samples d and g, hydrogenation and decomposition reactions were performed 10 times by the method described in Example 1. As a result, the hydrogen absorption rate is around 15 minutes in both cases, but the hydrogen release rate is 26 minutes for sample d and 26 minutes for sample g.
It was hot in 25 minutes. Furthermore, it was found that the shape did not turn into powder even after repeated hydrogenation and decomposition reactions, but maintained a prismatic shape. Example 3 Hydride TiH 2 powder was pressed at a pressure of 1 ton/cm 2 at 15
A prismatic molded body measuring mm x 15 mm x 10 mm was made. A spongy flat plate made of alumina was placed at the bottom of a SUS box, and 10 of the above-mentioned molded bodies were placed side by side on it. Furthermore, a spongy flat plate made of alumina was placed on top of this, and a thick Al plate with a purity of 99.9% was placed on top of this flat plate. The box prepared in this way was placed in a vacuum electric furnace, and the temperature was raised to 670° C. in about 1 hour while evacuating the furnace. During the temperature rising period, the TiH 2 powder starts decomposition reaction at around 300°C, releases occluded hydrogen gas, and heats up to around 650°C.
At ℃, the release of hydrogen gas completely stops, and the metal Ti
It changed to Heat treatment was performed by holding at 670°C for 30 minutes and then cooling in the furnace. The prismatic sample was taken out with the entire surface covered with Al. When it was cut to observe the state of Al impregnation, it was found that Al had penetrated to the inside. This prismatic sample was pulverized, mixed using a vibrating mill, and press-molded at 5 tons/cm 2 into a 10 mm x 10 mm x 15 mm prismatic sample. The amount of Al in this molded body was about 45% by weight. Furthermore, the void ratio was approximately 28% when observed using an image analysis device (QTM). In addition, Al with less than 300 mesh for Ti powder
A mixture of about 45% by weight of powder was press-molded at 5 tons/cm 2 and its internal structure was compared with a molded product made by vacuum impregnation. As a result, the porosity values are almost the same, but observation using a scanning electron microscope shows that the contact surface between the Ti and Al metals in the vacuum-impregnated molded product is uniform, and the pores are uniformly distributed. In contrast,
It was found that in a simple mixed molded body, many regions rich in Ti and Al metals were locally distributed, and the size and distribution of pores were also not uniform. As a result of the transverse rupture strength test, the molded product treated by the vacuum impregnation method had a strength of 88Kg/cm 2 , and the simple mixed molded product had a strength of 64Kg/cm 2
Therefore, it was found that the material of the present invention is advantageous also in terms of mechanical strength. Example 4 Mg 2 Ni powder was filled in a flat-bottomed thin glass port to a thickness of about 2 mm in a vacuum evaporation apparatus, and after evacuation, Ni evaporation was performed by high-frequency heating. The deposition time was approximately 5 minutes, and during this period the glass boat was moved from side to side by an external manipulator to create a uniform Ni deposition film on the powder surface, and this deposition was repeated twice. did.
The thickness of the deposited Ni film was determined to be approximately 0.7 μm using an interferometric thickness meter from a glass plate attached at the same time. TiH 2 hydride powder was also treated in the same manner as above. The above-mentioned surface-treated Mg 2 Ni powder and TiH 2 powder are press-molded at 5 tons/cm 2 , and further, 30% by weight of Cu powder of 200 mesh or less is added and mixed as a binder to these and then molded. Each was made into a prismatic molded body of 10 mm x 10 mm x 15 mm. Furthermore, as comparative materials, Mg 2 Ni and TiH 2 powders were each press-molded at 5 tons/cm 2 in the same manner. Hydrogenation and decomposition reaction of Mg 2 Ni molded body at 280℃
Hydrogenation was carried out at a temperature of 20 Kg/cm 2 and a hydrogen pressure of 20 kg/cm 2 was applied, followed by decomposition reaction by releasing hydrogen by vacuum evacuation, and this operation was repeated 10 times. TiH 2 compacts in the temperature range of 650-700℃,
Hydrogenation and decomposition reactions were carried out 10 times under the same conditions as for Mg 2 Ni. As a result, compacted compacts made from only Mg 2 Ni or TiH 2 powder completely return to powder through repeated hydrogenation and decomposition reactions, and those with a Ni vapor-deposited film or those with Cu powder added as a binder. The molded product maintained its prismatic shape, and it was found that the deposited film or binder was extremely effective in preventing the molded product from collapsing. As explained above, the compacted or sintered body of the hydrogen storage material obtained by the present invention has added mechanical strength and improved thermal conductivity compared to conventional filling materials in the form of powder. Since it is a molded product, it is possible to improve the packing density, simplify the filling method and heat transfer equipment, and improve workability such as handling by eliminating the scattering and movement of powder. This will have a great effect on the development of practical equipment.
Claims (1)
る金属もしくは合金粉末あるいは既に水素を吸蔵
した金属水素化物の粉末の表面をAl、Ni、Cu及
びこれらの金属を主元素とする合金もしくは融点
が100〜400℃の低溶融合金をもつて表面処理後、
成形することを特徴とする水素貯蔵材料の製造方
法。 ２ 水素を吸蔵し、容易に金属水素化物を生成す
る金属もしくは合金粉末あるいは既に水素を吸蔵
した金属水素化物の粉末の表面をAl、Ni、Cu及
びこれらの金属を主元素とする合金もしくは融点
が100〜400℃の低溶融合金をもつて表面処理後、
Al、Ni、Cu、Zn、Sn、Pbより選ばれた金属もし
くはその合金材をバインダとして成形することを
特徴とする水素貯蔵材料の製造方法。 ３ 成形体の空間率を１〜50％とする特許請求の
範囲第１項又は第２項記載の水素貯蔵材料の製造
方法。 ４ 水素を吸蔵し、容易に金属水素化物を生成す
る金属もしくは合金粉末あるいは既に水素を吸蔵
した金属水素化物の粉末の表面をAl、Ni、Cu及
びこれらの金属を主元素とする合金もしくは融点
が100〜400℃の低溶融合金をもつて表面処理後成
形し、ついでこの成形体を非酸化性雰囲気下で
100〜1300℃の温度範囲で焼結熱処理することを
特徴とする水素貯蔵材料の製造方法。 ５ 水素を吸蔵し、容易に金属水素化物を生成す
る金属もしくは合金粉末あるいは既に水素を吸蔵
した金属水素化物の粉末の表面をAl、Ni、Cu及
びこれらの金属を主元素とする合金もしくは融点
が100〜400℃の低溶融合金をもつて表面処理後、
Al、Ni、Cu、Zn、Sn、Pbより選ばれた金属もし
くはその合金材をバインダとして成形し、ついで
この成形体を非酸化性雰囲気下で100〜1300℃の
温度範囲で焼結熱処理することを特徴とする水素
貯蔵材料の製造方法。 ６ 焼結成形体の空間率を１〜40％とする特許請
求の範囲第４項又は第５項記載の水素貯蔵材料の
製造方法。[Claims] 1. The surface of a metal or alloy powder that absorbs hydrogen and easily forms a metal hydride, or a powder of a metal hydride that has already absorbed hydrogen, is coated with Al, Ni, Cu, or these metals as the main elements. After surface treatment with an alloy or a low melting alloy with a melting point of 100 to 400℃,
A method for producing a hydrogen storage material, the method comprising molding the material. 2. The surface of a metal or alloy powder that absorbs hydrogen and easily forms a metal hydride, or a powder of a metal hydride that has already absorbed hydrogen, is coated with Al, Ni, Cu, or alloys containing these metals as main elements or whose melting point is After surface treatment with low melting alloy at 100~400℃,
A method for producing a hydrogen storage material, characterized by forming a metal selected from Al, Ni, Cu, Zn, Sn, and Pb or an alloy thereof as a binder. 3. The method for producing a hydrogen storage material according to claim 1 or 2, wherein the molded body has a porosity of 1 to 50%. 4. The surface of a metal or alloy powder that absorbs hydrogen and easily forms a metal hydride, or a powder of a metal hydride that has already absorbed hydrogen, is coated with Al, Ni, Cu, or alloys containing these metals as main elements or whose melting point is After surface treatment with a low-melting alloy at 100 to 400°C, the molded body is molded in a non-oxidizing atmosphere.
A method for producing a hydrogen storage material, characterized by carrying out a sintering heat treatment in a temperature range of 100 to 1300°C. 5. The surface of a metal or alloy powder that absorbs hydrogen and easily forms a metal hydride, or a powder of a metal hydride that has already absorbed hydrogen, is coated with Al, Ni, Cu, alloys containing these metals as main elements, or alloys with melting points. After surface treatment with low melting alloy at 100~400℃,
Forming a metal selected from Al, Ni, Cu, Zn, Sn, and Pb or its alloy material as a binder, and then subjecting this formed body to sintering heat treatment at a temperature range of 100 to 1300°C in a non-oxidizing atmosphere. A method for producing a hydrogen storage material characterized by: 6. The method for producing a hydrogen storage material according to claim 4 or 5, wherein the sintered compact has a void ratio of 1 to 40%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57144609A JPS5935001A (en) | 1982-08-23 | 1982-08-23 | Preparation of hydrogen storing material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57144609A JPS5935001A (en) | 1982-08-23 | 1982-08-23 | Preparation of hydrogen storing material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5935001A JPS5935001A (en) | 1984-02-25 |
| JPS624321B2 true JPS624321B2 (en) | 1987-01-29 |
Family
ID=15366001
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57144609A Granted JPS5935001A (en) | 1982-08-23 | 1982-08-23 | Preparation of hydrogen storing material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5935001A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6419880U (en) * | 1987-07-27 | 1989-01-31 |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59162102A (en) * | 1983-03-03 | 1984-09-13 | Chuo Denki Kogyo Kk | Conjugated molded article of alloy for hydrogen occlusion and its preparation |
| JPS6119063A (en) * | 1984-07-05 | 1986-01-27 | Sanyo Electric Co Ltd | Hydrogen occlusion electrode |
| JPS61132501A (en) * | 1984-11-30 | 1986-06-20 | Agency Of Ind Science & Technol | Formed hydrogen storage alloy |
| JPS61144499A (en) * | 1984-12-19 | 1986-07-02 | Sanyo Electric Co Ltd | Metal hydride container |
| JP2001289397A (en) * | 2000-04-10 | 2001-10-19 | Japan Metals & Chem Co Ltd | Hydrogen storage alloy storing container |
| CN109898002B (en) * | 2019-04-30 | 2020-10-27 | 三桥惠(佛山)新材料有限公司 | Magnesium-based hydrogen storage alloy and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50111546A (en) * | 1973-10-18 | 1975-09-02 | ||
| JPS5220423A (en) * | 1975-08-09 | 1977-02-16 | Matsushita Electric Ind Co Ltd | Hydrogen preserving equipment |
| JPS5366852A (en) * | 1976-11-26 | 1978-06-14 | Chiyoo Komori | Hydrogen absorbloting sponge titanium foil and said manufacturing process |
| JPS53103543A (en) * | 1977-02-23 | 1978-09-08 | Matsushita Electric Ind Co Ltd | Hydrogen occlusion electrode |
| JPS5590401A (en) * | 1978-12-22 | 1980-07-09 | Daimler Benz Ag | Hydrogenated metal stimulator and making method thereof |
| JPS55158101A (en) * | 1979-05-25 | 1980-12-09 | Tokai Daigaku | Hydrogen occluding body |
| JPS55167101A (en) * | 1979-06-15 | 1980-12-26 | Matsushita Electric Ind Co Ltd | Hydrogen storing material and its manufacture |
| JPS5719041A (en) * | 1980-07-11 | 1982-02-01 | Japan Organo Co Ltd | Regeneration of thermoregenerative type ion exchange resin |
| JPS581032A (en) * | 1981-06-27 | 1983-01-06 | Nippon Steel Corp | Production of hydrogen absorbing metallic material |
-
1982
- 1982-08-23 JP JP57144609A patent/JPS5935001A/en active Granted
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50111546A (en) * | 1973-10-18 | 1975-09-02 | ||
| JPS5220423A (en) * | 1975-08-09 | 1977-02-16 | Matsushita Electric Ind Co Ltd | Hydrogen preserving equipment |
| JPS5366852A (en) * | 1976-11-26 | 1978-06-14 | Chiyoo Komori | Hydrogen absorbloting sponge titanium foil and said manufacturing process |
| JPS53103543A (en) * | 1977-02-23 | 1978-09-08 | Matsushita Electric Ind Co Ltd | Hydrogen occlusion electrode |
| JPS5590401A (en) * | 1978-12-22 | 1980-07-09 | Daimler Benz Ag | Hydrogenated metal stimulator and making method thereof |
| JPS55158101A (en) * | 1979-05-25 | 1980-12-09 | Tokai Daigaku | Hydrogen occluding body |
| JPS55167101A (en) * | 1979-06-15 | 1980-12-26 | Matsushita Electric Ind Co Ltd | Hydrogen storing material and its manufacture |
| JPS5719041A (en) * | 1980-07-11 | 1982-02-01 | Japan Organo Co Ltd | Regeneration of thermoregenerative type ion exchange resin |
| JPS581032A (en) * | 1981-06-27 | 1983-01-06 | Nippon Steel Corp | Production of hydrogen absorbing metallic material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6419880U (en) * | 1987-07-27 | 1989-01-31 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5935001A (en) | 1984-02-25 |
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