JP2013107822A - Method for generating gaseous hydrogen and material for generating gaseous hydrogen - Google Patents

Method for generating gaseous hydrogen and material for generating gaseous hydrogen Download PDF

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JP2013107822A
JP2013107822A JP2013015529A JP2013015529A JP2013107822A JP 2013107822 A JP2013107822 A JP 2013107822A JP 2013015529 A JP2013015529 A JP 2013015529A JP 2013015529 A JP2013015529 A JP 2013015529A JP 2013107822 A JP2013107822 A JP 2013107822A
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water
hydrogen gas
aluminum alloy
gaseous hydrogen
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Hiroshi Nagata
浩 永田
Yoshinori Aragaki
良憲 新垣
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Ulvac Inc
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    • 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
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Abstract

PROBLEM TO BE SOLVED: To provide a method for generating gaseous hydrogen and a material for generating gaseous hydrogen, by means of which a large amount of gaseous hydrogen can be generated.SOLUTION: In the method for generating gaseous hydrogen, a flaky aluminum alloy A containing at least one of Sn and Bi in the range of 0.5 to 20 wt.% while the remainder being aluminum and inevitable impurities, is used as the material for generating gaseous hydrogen, and is made to react with water or saline. The aluminum alloy is prepared by a strip casting method including a step to cool the melt of the raw material alloy by bringing it into contact with a rotating water-cooled roller 7, wherein the peripheral velocity of the water-cooled roller is set to be in the range of 1 to 20 m/sec.

Description

本発明は、水素ガス発生方法及びこの水素ガス発生方法に用いられる水素ガス生成材に関する。   The present invention relates to a hydrogen gas generation method and a hydrogen gas generation material used in the hydrogen gas generation method.

近年、ＰＣや携帯電話などの機器の普及に伴い、その電源として水素ガスを用いた燃料電池が注目されている。水素ガスを発生させる方法として、アルミニウム粉末と、これよりイオン化傾向の小さい金属粉末とを混合した粉末を用い、この粉末に水を供給し、水とアルミニウムとを反応させることが例えば特許文献１で知られている。   In recent years, with the spread of devices such as PCs and mobile phones, fuel cells using hydrogen gas as a power source have attracted attention. As a method for generating hydrogen gas, for example, Patent Document 1 discloses that a powder obtained by mixing an aluminum powder and a metal powder having a smaller ionization tendency is used, water is supplied to the powder, and water is reacted with aluminum. Are known.

また、常温で安定的に水素を生成させることができる水素ガス生成材として、アルミニウム粉末と酸化カルシウム粉末とを含み、当該アルミニウム粉末の配合比を８５重量％以下としたものが特許文献２で知られている。この場合、アルミニウム粉末としては、粒度分布が５０〜１５０μｍの範囲のものが使用される。   Patent Document 2 discloses that a hydrogen gas generating material capable of stably generating hydrogen at room temperature includes aluminum powder and calcium oxide powder, and the mixing ratio of the aluminum powder is 85 wt% or less. It has been. In this case, aluminum powder having a particle size distribution in the range of 50 to 150 μm is used.

然し、上記特許文献１及び特許文献２記載のように、水素ガス生成材が粉末状であると、常温空気中でのその取扱いが面倒であるという問題がある。また、燃料電池の発電効率は、燃料たる水素に対する効率であることから、その効率を高めるには、水素ガス生成材から発生する水素ガスの量を多くできるようにすることが望まれる。   However, as described in Patent Document 1 and Patent Document 2, when the hydrogen gas generating material is in the form of powder, there is a problem that handling in room temperature air is troublesome. Further, since the power generation efficiency of the fuel cell is the efficiency with respect to hydrogen as a fuel, it is desired to increase the amount of hydrogen gas generated from the hydrogen gas generating material in order to increase the efficiency.

特開２００２−１０４８０１号公報JP 2002-104801 A 特開２００４−２３１４６６号公報JP 2004-231466 A

本発明は、上記点に鑑み、多量の水素ガスを発生させることができる水素ガス発生方法及び水素ガス生成材を提供することをその課題とする。   In view of the above points, an object of the present invention is to provide a hydrogen gas generating method and a hydrogen gas generating material capable of generating a large amount of hydrogen gas.

上記課題を解決するために、本発明の水素ガス発生方法は、水素ガス生成材を、Ｓｎ及びＢｉの少なくとも一方を０．５〜２０重量％の範囲で含有し、残部がアルミニウム及び不回避的な不純物とである薄片状のアルミニウム合金とし、このアルミニウム合金を水または食塩水と反応させてなるものにおいて、前記アルミニウム合金は、原料合金の溶湯を回転する水冷ロールに接触させて冷却する工程を含むストリップキャスティング法により作製され、前記水冷ロールの周速度を１ｍ／ｓｅｃ〜２０ｍ／ｓｅｃの範囲に設定したことを特徴とする。   In order to solve the above-described problems, the hydrogen gas generation method of the present invention includes a hydrogen gas generating material containing at least one of Sn and Bi in a range of 0.5 to 20% by weight, with the balance being aluminum and inevitable. The aluminum alloy is formed by reacting the aluminum alloy with water or a saline solution, and the aluminum alloy is cooled by bringing the molten raw material alloy into contact with a rotating water-cooled roll. The peripheral speed of the water-cooled roll is set in the range of 1 m / sec to 20 m / sec.

また、本発明の水素ガス生成材は、Ｓｎ及びＢｉの少なくとも一方を０．５〜２０重量％の範囲で含有し、残部がアルミニウム及び不回避的な不純物とである薄片状のアルミニウム合金からなるものにおいて、前記アルミニウム合金は、１ｍ／ｓｅｃ〜２０ｍ／ｓｅｃの範囲に設定された周速度で回転する水冷ロールに原料合金の溶湯を接触させて冷却する工程を含むストリップキャスティング法により作製されたものであることを特徴とする。   Moreover, the hydrogen gas generating material of the present invention comprises at least one of Sn and Bi in the range of 0.5 to 20% by weight, and is made of a flaky aluminum alloy with the balance being aluminum and inevitable impurities The aluminum alloy is produced by a strip casting method including a step of bringing a molten material alloy into contact with a water-cooled roll rotating at a peripheral speed set in a range of 1 m / sec to 20 m / sec and cooling it. It is characterized by being.

本発明によれば、所定の重量比でＳｎ及びＢｉの少なくとも一方を含有し、周速度を１ｍ／ｓｅｃ〜２０ｍ／ｓｅｃの範囲に設定した水冷ロールに原料合金の溶湯を接触させて冷却する工程を含むストリップキャスティング法により作製された薄片状のアルミニウム合金は活性であるため、このアルミニウム合金を水または食塩水と反応させるだけで、４０ｍｌ／ｍｉｎ以上の多量の水素ガスを発生させることが可能になる。なお、Ｓｎ及びＢｉの少なくとも一方が０．５〜２０重量％の範囲に含まれないと、アルミニウム合金に対する水素ガスの発生率が十分高くならない。また、水冷ロールの周速度が１ｍ／ｓｅｃより遅いか、または２０ｍ／ｓｅｃを超える場合には、アルミニウム合金に対する水素ガスの発生率が十分高くならない。   According to the present invention, the step of cooling the raw material alloy by bringing it into contact with a water-cooled roll containing at least one of Sn and Bi at a predetermined weight ratio and having a peripheral speed set in the range of 1 m / sec to 20 m / sec. Since the flaky aluminum alloy produced by the strip casting method containing is active, it is possible to generate a large amount of hydrogen gas of 40 ml / min or more simply by reacting the aluminum alloy with water or saline. Become. If at least one of Sn and Bi is not included in the range of 0.5 to 20% by weight, the generation rate of hydrogen gas with respect to the aluminum alloy is not sufficiently high. Further, when the peripheral speed of the water-cooled roll is slower than 1 m / sec or exceeds 20 m / sec, the generation rate of hydrogen gas with respect to the aluminum alloy is not sufficiently high.

本発明の方法で用いられるＳＣ装置の模式点断面図。The schematic point sectional drawing of the SC apparatus used with the method of this invention. 実施例１において、Ｂｉを添加してアルミニウム合金を作製し、市水との反応における水素発生量を示す表。The table | surface which shows the amount of hydrogen generation in reaction with city water by adding Bi in Example 1 and producing an aluminum alloy. 実施例１において、Ｓｎを添加してアルミニウム合金を作製し、市水との反応における水素発生量を示す表。The table | surface which shows the amount of hydrogen generation in reaction with a city water in Example 1, producing Sn alloy by adding Sn. 実施例１において、Ｂｉを添加してアルミニウム合金を作製し、食塩水との反応における水素発生量を示す表。The table | surface which shows the hydrogen generation amount in reaction with salt solution in Example 1, producing Bi alloy by adding Bi.

図１は、本発明の水素ガス生成材を製作することに用いられるストリップキャスティング（以下、「ＳＣ」という）装置である。ＳＣ装置は、公知の構造を有するものであり、真空雰囲気の形成が可能な溶解室１を有する。この場合、ＡｒやＮ２などの不活性ガスを導入するガス導入手段２を接続し、所定圧力まで真空排気した後、不活性ガス雰囲気で溶解を行うようにしてもよい。溶解室１の内部には高周波溶解炉を用いたるつぼ３が設けられている。 FIG. 1 is a strip casting (hereinafter referred to as “SC”) apparatus used for producing the hydrogen gas generating material of the present invention. The SC apparatus has a known structure and has a melting chamber 1 capable of forming a vacuum atmosphere. In this case, gas introducing means 2 for introducing an inert gas such as Ar or N 2 may be connected, and after evacuation to a predetermined pressure, dissolution may be performed in an inert gas atmosphere. A crucible 3 using a high-frequency melting furnace is provided inside the melting chamber 1.

また、溶解室１には、処理室４が連結されている。処理室４には、るつぼ３で溶解した溶湯が、溶解室２及び処理室４間に亘って設けた樋５及びタンディッシュ６を介して導かれる回転自在な２個の水冷ロール７と、水冷ロール７の下側に近接配置された公知の構造の粉砕機８とが設けられている。また、処理室４の下側には、回収ボックス９が配置され、粉砕機８で粉砕されて落下する薄片を回収できるようになっている。そして、所定時間だけ冷却した後、当該回収ボックス９が処理室４から取り出すことができる。   A processing chamber 4 is connected to the melting chamber 1. In the processing chamber 4, the molten metal melted in the crucible 3 is guided by two rotatable water-cooling rolls 7 that are guided through a trough 5 and a tundish 6 provided between the melting chamber 2 and the processing chamber 4, A pulverizer 8 having a known structure is provided below the roll 7 in a close proximity. A recovery box 9 is disposed below the processing chamber 4 so that the flakes crushed by the pulverizer 8 and falling can be collected. Then, after cooling for a predetermined time, the collection box 9 can be taken out from the processing chamber 4.

次に、図１に示すＳＣ装置を用いて本実施の形態の薄片状のアルミニウム合金の作製について説明する。るつぼ３に原料合金を充填する。原料合金は、Ｓｎ及びＢｉの少なくとも一方を０．５〜２０重量％の範囲で含有し、残部がアルミニウム及び不回避的な不純物とからなるものであり、所定の組成比でるつぼ３に充填される。Ｓｎ及びＢｉの少なくとも一方が０．５〜２０重量％の範囲に含まれないと、アルミニウム合金に対する水素ガスの発生率が十分高くならない。   Next, the production of the flaky aluminum alloy of the present embodiment will be described using the SC apparatus shown in FIG. The crucible 3 is filled with a raw material alloy. The raw material alloy contains at least one of Sn and Bi in the range of 0.5 to 20% by weight, and the balance is made of aluminum and unavoidable impurities, and is filled in the crucible 3 at a predetermined composition ratio. The If at least one of Sn and Bi is not included in the range of 0.5 to 20% by weight, the generation rate of hydrogen gas with respect to the aluminum alloy is not sufficiently high.

次いで、るつぼ３に充填した原料合金を真空雰囲気または不活性ガス雰囲気にて高周波溶解し、樋５及びタンディッシュ６を介して、所定の周速度で回転する公知の構造の二つの水冷ロール７の間に溶湯を流し込み、水冷ロール７による冷却で凝固させて、厚さ３０μｍ〜３ｍｍ程度の板材片Ａ１を得る。水冷ロール７による冷却の際に、水冷ロール７の周速度を制御することによって、０．５ｍ／ｓｅｃ〜２０ｍ／ｓｅｃの範囲の速度で冷却する。この冷却する速度が０．５ｍ／ｓｅｃより遅い速度であるか、または２０ｍ／ｓｅｃを超えた速度である場合には、アルミニウム合金に対する水素ガスの発生率が十分高くならない。   Next, the raw material alloy filled in the crucible 3 is melted at a high frequency in a vacuum atmosphere or an inert gas atmosphere, and the two water-cooled rolls 7 having a known structure rotating at a predetermined peripheral speed through the basket 5 and the tundish 6. The molten metal is poured in between and solidified by cooling with the water-cooled roll 7 to obtain a plate material piece A1 having a thickness of about 30 μm to 3 mm. During the cooling by the water-cooled roll 7, the peripheral speed of the water-cooled roll 7 is controlled to cool at a speed in the range of 0.5 m / sec to 20 m / sec. If the cooling speed is slower than 0.5 m / sec or exceeds 20 m / sec, the generation rate of hydrogen gas for the aluminum alloy is not sufficiently high.

最後に、当該板状片Ａ１を粉砕機８に導き、細かく破砕して厚さ３０μｍ〜３ｍｍ程度の薄片状とする。この場合、得ようするアルミニウム合金の厚さや形状によっては、粉砕機８による粉砕を省略することができる。その後、薄片状のアルミニウム合金Ａを回収ボックス９にて回収する。そして、所定時間冷却した処理室４から取り出す。   Finally, the plate-like piece A1 is guided to the pulverizer 8 and finely crushed into a thin piece having a thickness of about 30 μm to 3 mm. In this case, pulverization by the pulverizer 8 can be omitted depending on the thickness and shape of the aluminum alloy to be obtained. Thereafter, the flaky aluminum alloy A is collected in the collection box 9. And it takes out from the processing chamber 4 cooled for the predetermined time.

このように本実施の形態においては、水素ガス生成材たるアルミニウム合金Ａが、所定の重量比でＳｎ及びＢｉの少なくとも一方を含有する薄片状のものであるため、常温空気中で安定となり、その取扱いが容易となる。その際、ＳＣ法を用いることで、アルミニウム合金中でのＳｎ及びＢｉの少なくとも一方の分散性が向上し、ＳｎやＢｉが原子状で分散して存在するようになる。その結果、常温空気中での安定性が一層向上する。   As described above, in the present embodiment, the aluminum alloy A, which is a hydrogen gas generating material, is in the form of a flake containing at least one of Sn and Bi at a predetermined weight ratio. Handling becomes easy. At that time, by using the SC method, the dispersibility of at least one of Sn and Bi in the aluminum alloy is improved, and Sn and Bi are dispersed in an atomic state. As a result, the stability in normal temperature air is further improved.

そして、このように作製した薄片状のアルミニウム合金Ａは活性であるため、水または０．５〜５％の範囲の濃度の食塩水と反応させるだけで、４０ｍｌ／ｍｉｎ以上で連続して水素ガスを発生させることが可能になる。その結果、燃料電池に適用する場合に特に有用となる。   And since the flaky aluminum alloy A produced in this way is active, it can be continuously reacted at a rate of 40 ml / min or more by simply reacting with water or saline having a concentration in the range of 0.5 to 5%. Can be generated. As a result, it is particularly useful when applied to a fuel cell.

なお、本実施の形態においては、ＳＣ法を用いる場合について説明したが、これに限定されるものではなく、アルミニウム合金を得るのに、公知の遠心鋳造法により作製することもできる。   In the present embodiment, the case where the SC method is used has been described. However, the present invention is not limited to this. The aluminum alloy can also be produced by a known centrifugal casting method.

（実施例１）
実施例１では、図１に示すＳＣ装置を用いて、所定の組成（純度が９９．９％のアルミニウムにＳｎまたはＢｉのいずれか一方を所定の重量比で添加したもの）をそれぞれ有する薄片状のアルミニウム合金たる試験片を作製することとした。水冷ロール７としては、直径６００ｍｍ、ロール幅２００ｍｍのものを用い、水冷ロール７の周速度が所定値とそれぞれなるように水冷ロールの回転数を調節した（冷却速度を変化させた）。また、水冷ロール７への溶湯の供給量は、水冷ロール７の周速度で連続した０．０５ｍｍ〜１ｍｍのストリップが生成できるように、適宜調節することとした。 Example 1
In Example 1, using the SC apparatus shown in FIG. 1, flaky shapes each having a predetermined composition (aluminum having a purity of 99.9% and one of Sn or Bi added at a predetermined weight ratio) are used. A test piece which is an aluminum alloy was prepared. A water-cooled roll 7 having a diameter of 600 mm and a roll width of 200 mm was used, and the rotation speed of the water-cooled roll was adjusted so that the peripheral speed of the water-cooled roll 7 became a predetermined value (the cooling speed was changed). In addition, the amount of the molten metal supplied to the water-cooled roll 7 is appropriately adjusted so that a continuous strip of 0.05 mm to 1 mm can be generated at the peripheral speed of the water-cooled roll 7.

次いで、ＳｎまたはＢｉの重量割合及び冷却速度を変化させて作製した各試料１ｇを容器に入れ、１２ｇの水または食塩水を注ぎ、１時間の間に発生した水素を水上置換法で捕集し、水素発生量（ｍｌ／ｍｉｎ）を求めた。   Next, 1 g of each sample prepared by changing the weight ratio of Sn or Bi and the cooling rate is put in a container, 12 g of water or saline is poured, and hydrogen generated during 1 hour is collected by the water replacement method. The hydrogen generation amount (ml / min) was determined.

（比較例１）
比較例１では、ＢＭ（ブックモールド)キャスティング法により鋳造した所定の組成をそれぞれ有するアルミニウム合金たるインゴットを０．２〜０．８ｍｍの薄板状に圧延し、水素発生量を調査した。尚、実施例１及び比較例１において水との反応には市水（神奈川県茅ヶ崎市）を用い、その水に１％の食塩を添加した食塩水として使用した。 (Comparative Example 1)
In Comparative Example 1, ingots, which are aluminum alloys each having a predetermined composition cast by a BM (book mold) casting method, were rolled into a thin plate of 0.2 to 0.8 mm, and the amount of hydrogen generated was investigated. In Example 1 and Comparative Example 1, city water (Chigasaki City, Kanagawa Prefecture) was used for the reaction with water, and it was used as a salt solution in which 1% sodium chloride was added to the water.

図２乃至図４に、上記実施例１及び比較例１により作製したアルミニウム合金の水素発生量を示す。これによれば、比較例１では、市水との反応においてＳｎまたはＢｉの重量比（添加量）を適宜調節すれば、約３０ｍｌ／ｍｉｎ程度の水素発生量が得られていることが判る（図２及び図３参照）。また、Ｂｉを添加したアルミニウム合金と食塩水との反応においては若干水素発生量が増えていることが判る（図４参照）。   2 to 4 show the hydrogen generation amounts of the aluminum alloys produced according to Example 1 and Comparative Example 1 described above. According to this, in Comparative Example 1, it can be seen that if the weight ratio (addition amount) of Sn or Bi is appropriately adjusted in the reaction with city water, a hydrogen generation amount of about 30 ml / min is obtained ( 2 and 3). It can also be seen that the amount of hydrogen generated is slightly increased in the reaction between the aluminum alloy to which Bi is added and saline (see FIG. 4).

それに対し、実施例１では、ＳｎまたはＢｉの重量比（添加量）を０．５〜２０重量％の範囲にすると共に、水冷ロール７の周速度を１〜２０ｍ／ｓｅｃの範囲に設定すれば、市水との反応においては、４０ｍｌ／ｍｉｎ以上、条件によっては７０ｍｌ／ｍｉｎの水素発生量が得られ、また、食塩水との反応においてはさらに水素発生量が増えていることが判る（図２乃至図４参照）。   On the other hand, in Example 1, while setting the weight ratio (addition amount) of Sn or Bi within the range of 0.5 to 20% by weight, the peripheral speed of the water-cooled roll 7 is set within the range of 1 to 20 m / sec. In the reaction with city water, a hydrogen generation amount of 40 ml / min or more and 70 ml / min depending on the conditions was obtained, and it was found that the hydrogen generation amount was further increased in the reaction with saline (Fig. 2 to 4).

１…溶解室、３…るつぼ、４…処理室、７…水冷ロール、８…粉砕機、９…回収ボックス、Ａ…薄片状のアルミニウム合金。































DESCRIPTION OF SYMBOLS 1 ... Melting | dissolving chamber, 3 ... Crucible, 4 ... Processing chamber, 7 ... Water-cooled roll, 8 ... Crusher, 9 ... Collection box, A ... Flaky aluminum alloy.































Claims (2)

水素ガス生成材を、Ｓｎ及びＢｉの少なくとも一方を０．５〜２０重量％の範囲で含有し、残部がアルミニウム及び不回避的な不純物とである薄片状のアルミニウム合金とし、このアルミニウム合金を水または食塩水と反応させてなる水素ガス発生方法において、
前記アルミニウム合金は、原料合金の溶湯を回転する水冷ロールに接触させて冷却する工程を含むストリップキャスティング法により作製され、前記水冷ロールの周速度を１ｍ／ｓｅｃ〜２０ｍ／ｓｅｃの範囲に設定したことを特徴とする水素ガス発生方法。 The hydrogen gas generating material is a flaky aluminum alloy containing at least one of Sn and Bi in the range of 0.5 to 20% by weight and the balance being aluminum and unavoidable impurities. Alternatively, in a method for generating hydrogen gas by reacting with a saline solution,
The aluminum alloy was manufactured by a strip casting method including a step of bringing a molten raw material alloy into contact with a rotating water-cooled roll and cooling it, and the peripheral speed of the water-cooled roll was set in the range of 1 m / sec to 20 m / sec. A method for generating hydrogen gas. Ｓｎ及びＢｉの少なくとも一方を０．５〜２０重量％の範囲で含有し、残部がアルミニウム及び不回避的な不純物とである薄片状のアルミニウム合金からなる水素ガス生成材において、
前記アルミニウム合金は、１ｍ／ｓｅｃ〜２０ｍ／ｓｅｃの範囲に設定された周速度で回転する水冷ロールに原料合金の溶湯を接触させて冷却する工程を含むストリップキャスティング法により作製されたものであることを特徴とする水素ガス生成材。
In a hydrogen gas generating material comprising a flaky aluminum alloy containing at least one of Sn and Bi in the range of 0.5 to 20% by weight and the balance being aluminum and unavoidable impurities,
The aluminum alloy is produced by a strip casting method including a step of bringing a molten material alloy into contact with a water-cooled roll rotating at a peripheral speed set in a range of 1 m / sec to 20 m / sec and cooling it. A hydrogen gas generating material characterized by
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104226941A (en) * 2014-09-12 2014-12-24 沈阳中北真空技术有限公司 Vacuum melting and rapid hardening equipment with collecting tank and manufacturing methods of permanent magnetic alloy and permanent magnet

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62263946A (en) * 1986-05-12 1987-11-16 Mitsubishi Alum Co Ltd Aluminum alloy for hydrogen formation
JPS632801A (en) * 1986-06-21 1988-01-07 Ofic Co Gaseous hydrogen generating material
JPH1043886A (en) * 1996-07-31 1998-02-17 Ngk Spark Plug Co Ltd Manufacture of brazing filler metal
JP2003012301A (en) * 2001-06-28 2003-01-15 Ulvac Japan Ltd Composition for hydrogen gas generation, production method for hydrogen gas, production apparatus for hydrogen gas and generator
JP2006273609A (en) * 2005-03-28 2006-10-12 Hitachi Maxell Ltd Hydrogen generator and fuel cell using the same
JP2007157864A (en) * 2005-12-02 2007-06-21 Mitsubishi Electric Corp Alloy for rare-earth iron-boron based magnet, manufacturing method therefor and manufacturing device thereof
JP2007290888A (en) * 2006-04-24 2007-11-08 Hitachi Maxell Ltd Method for producing hydrogen

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62263946A (en) * 1986-05-12 1987-11-16 Mitsubishi Alum Co Ltd Aluminum alloy for hydrogen formation
JPS632801A (en) * 1986-06-21 1988-01-07 Ofic Co Gaseous hydrogen generating material
JPH1043886A (en) * 1996-07-31 1998-02-17 Ngk Spark Plug Co Ltd Manufacture of brazing filler metal
JP2003012301A (en) * 2001-06-28 2003-01-15 Ulvac Japan Ltd Composition for hydrogen gas generation, production method for hydrogen gas, production apparatus for hydrogen gas and generator
JP2006273609A (en) * 2005-03-28 2006-10-12 Hitachi Maxell Ltd Hydrogen generator and fuel cell using the same
JP2007157864A (en) * 2005-12-02 2007-06-21 Mitsubishi Electric Corp Alloy for rare-earth iron-boron based magnet, manufacturing method therefor and manufacturing device thereof
JP2007290888A (en) * 2006-04-24 2007-11-08 Hitachi Maxell Ltd Method for producing hydrogen

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104226941A (en) * 2014-09-12 2014-12-24 沈阳中北真空技术有限公司 Vacuum melting and rapid hardening equipment with collecting tank and manufacturing methods of permanent magnetic alloy and permanent magnet
CN104226941B (en) * 2014-09-12 2016-10-05 沈阳中北真空技术有限公司 With batch can vacuum melting rapid hardening equipment and permanent-magnet alloy and the manufacture method of permanent magnet

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