JP2004074020A - Hydrogen dissociation and separation membrane - Google Patents
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Abstract
Description
【０００１】
【発明の属する技術分野】
この発明は、水素ガスを含有する混合ガスの中から水素ガスのみを透過し、高純度の水素ガスを分離・精製することができる水素解離・分離用膜に関するものである。
【０００２】
【従来の技術】
一般に、半導体製造工程などに用いられる超高純度の水素ガスの分離精製には水素を選択的に透過させることができる水素解離・分離用膜が用いられており、この水素解離・分離用膜として、ＰｄまたはＰｄ合金からなる水素透過性金属膜が用いられている。しかし、ＰｄまたはＰｄ合金からなる水素透過性金属膜は価格が高いためにＰｄまたはＰｄ合金に代わる各種の合金からなる水素解離・分離用膜が開発されている。例えば、特開２０００−２５６００２号公報では、ＺｒとＮｉを主成分とする非晶質多元系合金からなる水素解離・分離用膜が提案されている。
【０００３】
【発明が解決しようとする課題】
前記ＺｒとＮｉを主成分とする非晶質多元系合金からなる従来の水素解離・分離用膜はいずれも初期の水素解離・分離特性（いわゆる初期活性）が不十分であり、さらに長時間水素の解離・分離を行うと、水素の解離・分離性能が低下し、そのために水素解離・分離用膜を頻繁に交換しなければならないなどの欠点があった。
【０００４】
【課題を解決するための手段】
そこで、本発明者等は、上述のような観点から、初期の水素の解離・分離性能が優れ、かつ長時間水素の解離・分離を行ってもその効率が低下することのないＺｒとＮｉを主成分とする非晶質多元系合金からなる水素解離・分離用膜の開発を行った。
その結果、ＺｒとＮｉを主成分とする多元系合金を不活性ガス中で融点以上に加熱し、液体急冷法を用いてＺｒとＮｉを主成分とする非晶質多元系合金膜を製造し、この合金膜を酸化雰囲気中で加熱する熱処理を施したのち水素雰囲気中に保持すると、ＺｒとＮｉを主成分とする非晶質多元系合金膜の表面に、ＺｒとＮｉを主成分とする非晶質多元系合金に比べてＮｉ含有量の多いニッケル富化下地層およびこのニッケル富化下地層の上に覆い被さるようにして酸化ジルコニウムとＮｉを主体とする混合層からなる最表面層が同時に生成し、このニッケル富化下地層および最表面層が表面に形成されたＺｒとＮｉを主成分とする被覆非晶質多元系合金膜を水素解離・分離用膜として使用すると、水素解離・分離性能が一段と向上し、しかも優れた水素解離・分離性能を長時間保持することができるという研究結果が得られたのである。
【０００５】
この発明は、上記の研究結果に基づいてなされたものであって、
ＺｒとＮｉを主成分とする非晶質多元系合金膜の一方の表面または両表面に、前記ＺｒとＮｉを主成分とする非晶質多元系合金に比べてＮｉ含有量の多いニッケル富化下地層と、このニッケル富化下地層の上に酸化ジルコニウムとＮｉを主体とする混合層からなる最表面層が形成されている被覆非晶質多元系合金膜からなる水素解離・分離用膜、に特徴を有するものである。
【０００６】
この発明の水素解離・分離用膜を構成するＺｒとＮｉを主成分とする非晶質多元系合金は、具体的には、Ｎｉ：１０〜９０原子％を含有し、必要に応じてＣｕ：
５〜５０原子％を含有し、残部がＺｒおよび不可避不純物からなる組成を有する非晶質合金である。ＺｒとＮｉを主成分とする非晶質多元系合金膜の表面に形成されるニッケル富化下地層のＮｉ含有量は、ＺｒとＮｉを主成分とする非晶質多元系合金に含まれるＮｉ含有量よりも１．１〜４．０倍多いＺｒとＮｉを主成分とする合金からなり、さらにニッケル富化下地層の上に形成される酸化ジルコニウムとＮｉを主体とする混合層からなる最表面層は、ＺｒとＮｉを主成分とする非晶質多元系合金に含まれるＺｒ含有量よりも１．１〜４．０倍多いＺｒが優先的に酸化して酸化ジルコニウムとなることにより形成された酸化ジルコニウムと金属Ｎｉと混合した層である。この最表面層は酸化ジルコニウムと金属Ｎｉが混合している混合層であることが必要であり、Ｎｉが含まれないと水素解離・分離性能が大幅に低下する。
【０００７】
この発明の水素解離・分離用膜において、ＺｒとＮｉを主成分とする非晶質多元系合金膜の表面にニッケル富化下地層とその上に形成される酸化ジルコニウムとＮｉを主体とする混合層からなる最表面層とを形成させることにより、最表面層とニッケル富化下地層との界面で触媒的効果が最も発現し、水素分子の原子状水素への解離反応が一層促進される。このように最表面層とニッケル富化下地層との界面で発生した原子状水素は、それ自体が水素透過性金属膜で発生水素量に比べて十分に速い拡散速度を持った非晶質多元系合金膜内部を通じて拡散し、水素解離・分離用膜としての水素透過速度が向上するものと考えられる。
【０００８】
【発明の実施の形態】
つぎに、この発明の水素解離・分離用膜を実施例により具体的に説明する。
実施例１
原料として、純Ｎｉおよび純Ｚｒを用い、これらを高純度アルゴンガス中にてアーク溶解し、Ｎｉ：６４原子％、Ｚｒ：３６原子％からなる組成を持った合金鋳塊１５０ｇを得た。この合金鋳塊をさらに高純度アルゴンガス中にて溶解し、噴射圧：０．０５ＭＰａ、ロール速度：２０ｍ／ｓで回転している水冷銅モールドに吹きつけて、幅：３０ｍｍ、厚さ：３０μｍのＮｉ６４Ｚｒ３６からなる組成の非晶質金属リボンを作製した。この非晶質金属リボンを切断して幅：３０ｍｍ×長さ：６０ｍｍ×厚さ：３０μｍの寸法を有する従来水素解離・分離用膜１を作製した。
【０００９】
従来水素解離・分離用膜１を２０％塩酸水溶液に浸漬して表面処理した後、この表面処理した従来水素解離・分離用膜１を０．１ＭＰａのＡｒ−１０％Ｏ２の雰囲気中で２００℃、１０分間加熱後、０．２ＭＰａのＨ２雰囲気中で４００℃、１時間保持の加熱を行うことにより、前記従来水素解離・分離用膜１の片面の表面にＮｉ：９０原子％、Ｚｒ：１０原子％からなる組成のニッケル富化下地層と、このニッケル富化下地層の上に形成された酸化ジルコニウムとＮｉを主体とする最表面層とを形成した被覆非晶質多元系合金膜からなる本発明水素解離・分離用膜１を作製した。
さらに、従来水素解離・分離用膜１の両面の表面に同じ方法によりニッケル富化下地層および酸化ジルコニウムとＮｉを主体とする最表面層を形成した被覆非晶質多元系合金膜からなる本発明水素解離・分離用膜２を作製した。
【００１０】
従来水素解離・分離用膜１および本発明水素解離・分離用膜１〜２をそれぞれ水素透過セルに固定し、水素透過部分の実効面積が幅：２０ｍｍ×長さ：５０ｍｍ（１０ｃｍ２）となるようにしたのち、水素透過速度の測定温度：３００℃、水素導入面と透過面との水素分圧差：０．２ＭＰａとなるようにし、水素透過速度の測定を５０時間連続して行い、水素透過速度の経時変化について測定し、その結果を表１に示した。
【００１１】
【表１】
表１に示される結果から、ニッケル富化下地層とその上に形成される酸化ジルコニウムとＮｉを主体とする混合層からなる最表面層を片面に形成した本発明水素解離・分離用膜１および両面に形成した本発明水素解離・分離用膜２は、これら被覆層のない従来水素解離・分離用膜１に比べて水素透過速度が大幅に向上しており、さらに初期の水素透過速度に及ぼす活性化特性が優れており、さらに長時間経過しても水素透過速度が低下することが無いところから、長期間優れた水素解離・分離性能を維持できることが分かる。
【００１３】
実施例２
原料として、純Ｎｉ、純Ｚｒおよび純Ｃｕを用い、これらを高純度アルゴンガス中にてアーク溶解し、Ｎｉ：４５原子％、Ｚｒ：４５原子％、Ｃｕ：１０原子％からなる組成を持った合金鋳塊１５０ｇを得た。この合金鋳塊をさらに高純度アルゴンガス中にて溶解し、噴射圧：０．０５ＭＰａ、ロール速度：２０ｍ／ｓで回転している水冷銅モールドに吹きつけて、幅：３０ｍｍ、厚さ：３０μｍのＮｉ４５Ｚｒ４５Ｃｕ１０からなる組成の非晶質金属リボンを作製した。この非晶質金属リボンを切断して幅：３０ｍｍ×長さ：６０ｍｍ×厚さ：３０μｍの寸法を有する従来水素解離・分離用膜２を作製した。
【００１４】
従来水素解離・分離用膜２を２０％塩酸水溶液に浸漬して表面処理した後、この表面処理した従来水素解離・分離用膜１を０．１ＭＰａのＡｒ−１０％Ｏ２の雰囲気中で２００℃、１０分間加熱後、０．２ＭＰａのＨ２雰囲気中で４００℃、１時間保持の加熱を行うことにより、前記従来水素解離・分離用膜１の片面表面にＮｉ：７０原子％、Ｚｒ：２０原子％、Ｃｕ：１０原子％からなる組成のニッケル富化下地層と、このニッケル富化下地層の上に形成された酸化ジルコニウムとＮｉを主体とする最表面層を形成した被覆非晶質多元系合金膜からなる本発明水素解離・分離用膜３を作製した。
さらに、従来水素解離・分離用膜１の両面の表面に同じ方法によりニッケル富化下地層および酸化ジルコニウムとＮｉを主体とする最表面層を形成した被覆非晶質多元系合金膜からなる本発明水素解離・分離用膜４を作製した。
【００１５】
従来水素解離・分離用膜２および本発明水素解離・分離用膜３〜４をそれぞれ水素透過セルに固定し、水素透過部分の実効面積が幅：２０ｍｍ×長さ：５０ｍｍ（１０ｃｍ２）となるようにしたのち、水素透過速度の測定温度：３００℃、水素導入面と透過面との水素分圧差：０．２ＭＰａとなるようにし、水素透過速度の測定を５０時間連続して行い、水素透過速度の経時変化について測定し、その結果を表２に示した。
【００１６】
【表２】
表２に示される結果から、ニッケル富化下地層とその上に形成される酸化ジルコニウムとＮｉを主体とする混合層からなる最表面層を形成した被覆非晶質多元系合金膜からなる本発明水素解離・分離用膜３〜４は、これら被覆層のない従来水素解離・分離用膜２に比べて水素透過速度が大幅に向上しており、さらに初期の水素透過速度に及ぼす活性化特性が優れており、さらに長時間経過しても水素透過速度が低下することが無いところから、長期間優れた水素解離・分離性能を維持できることが分かる。
【００１８】
【発明の効果】
上述のように、この発明の水素解離・分離用膜は、初期の水素解離・分離性能がすぐれかつ長期間水素解離・分離性能を維持することができるので、これを水素精製装置に適用した場合、水素解離・分離用膜の交換回数が軽減されてメンテナンスの負担が軽減されるなど優れた効果を奏するものである。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a hydrogen dissociation / separation membrane capable of separating and purifying high-purity hydrogen gas by permeating only hydrogen gas from a mixed gas containing hydrogen gas.
[0002]
[Prior art]
Generally, a hydrogen dissociation / separation membrane that can selectively permeate hydrogen is used for separation and purification of ultra-high-purity hydrogen gas used in semiconductor manufacturing processes and the like. A hydrogen-permeable metal film made of Pd, Pd, or a Pd alloy is used. However, a hydrogen-permeable metal membrane made of Pd or a Pd alloy is expensive, so that a hydrogen dissociation / separation membrane made of various alloys instead of Pd or a Pd alloy has been developed. For example, Japanese Patent Application Laid-Open No. 2000-256002 proposes a hydrogen dissociation / separation membrane made of an amorphous multi-component alloy containing Zr and Ni as main components.
[0003]
[Problems to be solved by the invention]
The conventional hydrogen dissociation / separation membranes composed of an amorphous multi-component alloy containing Zr and Ni as main components have insufficient initial hydrogen dissociation / separation characteristics (so-called initial activity), and further have a long hydrogen When the dissociation / separation of hydrogen is performed, the dissociation / separation performance of hydrogen deteriorates, and therefore, there is a disadvantage that the hydrogen dissociation / separation membrane must be frequently replaced.
[0004]
[Means for Solving the Problems]
In view of the above, the present inventors consider that Zr and Ni have excellent initial hydrogen dissociation / separation performance and do not decrease their efficiency even when hydrogen is dissociated / separated for a long time. We have developed a hydrogen dissociation / separation membrane composed of an amorphous multi-component alloy as the main component.
As a result, a multi-component alloy mainly composed of Zr and Ni is heated to a temperature equal to or higher than the melting point in an inert gas, and an amorphous multi-component alloy film mainly composed of Zr and Ni is manufactured using a liquid quenching method. When the alloy film is subjected to a heat treatment for heating in an oxidizing atmosphere and then kept in a hydrogen atmosphere, the surface of the amorphous multi-component alloy film containing Zr and Ni as main components has Zr and Ni as main components. A nickel-enriched underlayer containing more Ni than the amorphous multi-element alloy and an outermost surface layer composed of a mixed layer mainly composed of zirconium oxide and Ni are formed so as to cover the nickel-enriched underlayer. When the coated amorphous multi-component alloy film containing Zr and Ni as main components and having the nickel-enriched base layer and the outermost surface layer formed on the surface at the same time is used as a hydrogen dissociation / separation film, Separation performance is further improved and excellent Finding that the hydrogen dissociation and separation performance can be held for a long time is that obtained.
[0005]
The present invention has been made based on the above research results,
One or both surfaces of an amorphous multi-component alloy film mainly composed of Zr and Ni are nickel-rich with a higher Ni content than the amorphous multi-component alloy mainly composed of Zr and Ni. An underlayer, a hydrogen dissociation / separation film composed of a coated amorphous multi-component alloy film in which an outermost surface layer composed of a mixed layer mainly composed of zirconium oxide and Ni is formed on the nickel-enriched underlayer, It is characterized by the following.
[0006]
The amorphous multi-component alloy mainly composed of Zr and Ni constituting the hydrogen dissociation / separation membrane of the present invention specifically contains 10 to 90 atomic% of Ni, and optionally contains Cu:
It is an amorphous alloy containing 5 to 50 atomic%, with the balance being Zr and unavoidable impurities. The Ni content of the nickel-enriched underlayer formed on the surface of the amorphous multi-component alloy film containing Zr and Ni as main components is determined by the Ni content in the amorphous multi-component alloy containing Zr and Ni as main components. It is composed of an alloy containing Zr and Ni as main components, which is 1.1 to 4.0 times larger than the content, and further a mixed layer mainly composed of zirconium oxide and Ni formed on the nickel-enriched underlayer. The surface layer is formed by preferentially oxidizing Zr, which is 1.1 to 4.0 times larger than the Zr content contained in the amorphous multi-component alloy containing Zr and Ni as main components, to form zirconium oxide. This is a layer in which zirconium oxide and metal Ni are mixed. The outermost surface layer needs to be a mixed layer in which zirconium oxide and metal Ni are mixed. If Ni is not included, hydrogen dissociation / separation performance is significantly reduced.
[0007]
In the hydrogen dissociation / separation membrane of the present invention, a nickel-rich underlayer and a mixture mainly composed of zirconium oxide and Ni formed on the surface of an amorphous multi-component alloy film containing Zr and Ni as main components are formed. By forming the outermost surface layer composed of a layer, a catalytic effect is most exhibited at the interface between the outermost surface layer and the nickel-enriched underlayer, and the dissociation reaction of hydrogen molecules into atomic hydrogen is further promoted. Atomic hydrogen generated at the interface between the outermost surface layer and the nickel-enriched underlayer is a hydrogen-permeable metal film that is an amorphous multi-element that has a sufficiently high diffusion rate compared to the amount of generated hydrogen. It is thought that the hydrogen is diffused through the inside of the system alloy membrane, and the hydrogen permeation rate as a hydrogen dissociation / separation membrane is improved.
[0008]
BEST MODE FOR CARRYING OUT THE INVENTION
Next, the hydrogen dissociation / separation membrane of the present invention will be specifically described with reference to examples.
Example 1
As raw materials, pure Ni and pure Zr were arc-melted in a high-purity argon gas to obtain 150 g of an alloy ingot having a composition of 64 atomic% of Ni and 36 atomic% of Zr. The alloy ingot is further melted in a high-purity argon gas, and sprayed on a water-cooled copper mold rotating at an injection pressure of 0.05 MPa and a roll speed of 20 m / s to obtain a width of 30 mm and a thickness of 30 μm. An amorphous metal ribbon having a composition of Ni 64 Zr 36 was produced. The amorphous metal ribbon was cut to prepare a conventional hydrogen dissociation / separation membrane 1 having a size of 30 mm in width × 60 mm in length × 30 μm in thickness.
[0009]
After the conventional hydrogen dissociation / separation membrane 1 is immersed in a 20% hydrochloric acid aqueous solution and subjected to surface treatment, the surface-treated conventional hydrogen dissociation / separation membrane 1 is subjected to a 200 MPa atmosphere of Ar-10% O 2 at 0.1 MPa. After heating for 10 minutes at a temperature of 400 ° C. for 1 hour in a H 2 atmosphere of 0.2 MPa, Ni: 90 atomic% and Zr are formed on one surface of the conventional hydrogen dissociation / separation membrane 1. : A coated amorphous multi-element alloy film formed of a nickel-enriched underlayer having a composition of 10 atomic% and an outermost surface layer mainly composed of zirconium oxide and Ni formed on the nickel-enriched underlayer. The hydrogen dissociation / separation membrane 1 of the present invention was prepared.
Further, the present invention comprises a coated amorphous multi-component alloy film in which a nickel-enriched underlayer and an outermost surface layer mainly composed of zirconium oxide and Ni are formed on both surfaces of the conventional hydrogen dissociation / separation membrane 1 by the same method. A hydrogen dissociation / separation membrane 2 was prepared.
[0010]
The conventional hydrogen dissociation / separation membrane 1 and the hydrogen dissociation / separation membranes 1 and 2 of the present invention are fixed to a hydrogen permeable cell, and the effective area of the hydrogen permeable portion is 20 mm in width × 50 mm in length (10 cm 2 ). After that, the measurement temperature of the hydrogen permeation rate was set to 300 ° C., the hydrogen partial pressure difference between the hydrogen introduction surface and the permeation surface was set to 0.2 MPa, and the hydrogen permeation speed was measured continuously for 50 hours. The change in speed over time was measured, and the results are shown in Table 1.
[0011]
[Table 1]
From the results shown in Table 1, the hydrogen dissociation / separation membrane 1 of the present invention in which the nickel-enriched base layer and the outermost surface layer composed of a mixed layer mainly composed of zirconium oxide and Ni formed thereon were formed on one surface, The hydrogen dissociation / separation membrane 2 of the present invention formed on both surfaces has a significantly higher hydrogen permeation rate than the conventional hydrogen dissociation / separation membrane 1 without these coating layers, and further has an effect on the initial hydrogen permeation rate. Since the activation characteristics are excellent and the hydrogen permeation rate does not decrease even after a long time, it is understood that excellent hydrogen dissociation / separation performance can be maintained for a long time.
[0013]
Example 2
As raw materials, pure Ni, pure Zr and pure Cu were arc-melted in a high-purity argon gas to have a composition of 45 atomic% of Ni, 45 atomic% of Zr, and 10 atomic% of Cu. 150 g of an alloy ingot was obtained. The alloy ingot is further melted in a high-purity argon gas, and sprayed on a water-cooled copper mold rotating at an injection pressure of 0.05 MPa and a roll speed of 20 m / s to obtain a width of 30 mm and a thickness of 30 μm. An amorphous metal ribbon having a composition of Ni 45 Zr 45 Cu 10 was produced. The amorphous metal ribbon was cut to prepare a conventional hydrogen dissociation / separation membrane 2 having a size of 30 mm in width × 60 mm in length × 30 μm in thickness.
[0014]
After the conventional hydrogen dissociation / separation membrane 2 is immersed in a 20% hydrochloric acid aqueous solution and subjected to surface treatment, the surface-treated conventional hydrogen dissociation / separation membrane 1 is subjected to a 200 MPa Ar-10% O 2 atmosphere at 0.1 MPa. After heating at 10 ° C. for 10 minutes, heating at 400 ° C. for 1 hour in a H 2 atmosphere of 0.2 MPa causes Ni: 70 atomic% and Zr: on one surface of the conventional hydrogen dissociation / separation membrane 1. A coated amorphous layer comprising a nickel-enriched underlayer having a composition of 20 at% and Cu: 10 at%, and an outermost layer mainly composed of zirconium oxide and Ni formed on the nickel-enriched under layer. The hydrogen dissociation / separation membrane 3 of the present invention comprising a multi-component alloy membrane was produced.
Further, the present invention comprises a coated amorphous multi-component alloy film in which a nickel-enriched underlayer and an outermost surface layer mainly composed of zirconium oxide and Ni are formed on both surfaces of the conventional hydrogen dissociation / separation membrane 1 by the same method. A hydrogen dissociation / separation membrane 4 was prepared.
[0015]
The conventional hydrogen dissociation / separation membrane 2 and the hydrogen dissociation / separation membranes 3 to 4 of the present invention are fixed to a hydrogen permeable cell, and the effective area of the hydrogen permeable portion is 20 mm wide × 50 mm long (10 cm 2 ). After that, the measurement temperature of the hydrogen permeation rate was set to 300 ° C., the hydrogen partial pressure difference between the hydrogen introduction surface and the permeation surface was set to 0.2 MPa, and the hydrogen permeation speed was measured continuously for 50 hours. The change in speed over time was measured, and the results are shown in Table 2.
[0016]
[Table 2]
From the results shown in Table 2, the present invention comprises a coated amorphous multi-element alloy film formed with a nickel-enriched underlayer and an outermost surface layer composed of a mixed layer mainly composed of zirconium oxide and Ni formed thereon. The hydrogen dissociation / separation membranes 3 and 4 have a greatly improved hydrogen permeation rate as compared with the conventional hydrogen dissociation / separation membrane 2 without these coating layers, and furthermore have an activation property that affects the initial hydrogen permeation rate. It is excellent and the hydrogen permeation rate does not decrease even after a long time, indicating that excellent hydrogen dissociation / separation performance can be maintained for a long time.
[0018]
【The invention's effect】
As described above, the hydrogen dissociation / separation membrane of the present invention has excellent initial hydrogen dissociation / separation performance and can maintain the hydrogen dissociation / separation performance for a long period of time. In addition, the number of replacements of the hydrogen dissociation / separation membrane is reduced, so that the maintenance burden is reduced.
Claims (1)
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| JP2002238245A JP4029123B2 (en) | 2002-08-19 | 2002-08-19 | Hydrogen dissociation / separation membrane |
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| JP2002238245A JP4029123B2 (en) | 2002-08-19 | 2002-08-19 | Hydrogen dissociation / separation membrane |
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| JP4029123B2 JP4029123B2 (en) | 2008-01-09 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006055831A (en) * | 2004-07-21 | 2006-03-02 | Iwatani Internatl Corp | Hydrogen separation membrane and its manufacturing method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS634829A (en) * | 1986-06-24 | 1988-01-09 | Matsushita Electric Ind Co Ltd | Production of hydrogen-permeable medium |
| JPH08291391A (en) * | 1995-02-22 | 1996-11-05 | Toyota Central Res & Dev Lab Inc | Surface treatment of hydrogen occlusion alloy material, activation treatment of hydrogen occlusion alloy electrode, activating solution, and hydrogen occlusion alloy electrode having excellent initial activity |
| JPH11130401A (en) * | 1997-10-29 | 1999-05-18 | Toyota Central Res & Dev Lab Inc | High activation treatment of hydrogen storage alloy |
| JP2000256002A (en) * | 1999-03-09 | 2000-09-19 | Agency Of Ind Science & Technol | Amorphous zirconium-nickel alloy based hydrogen separation dissociation membrane, its production and activating method thereof |
| JP2000319733A (en) * | 1999-04-30 | 2000-11-21 | Agency Of Ind Science & Technol | AMORPHOUS HfNi ALLOY BASED FILM FOR SEPARATING AND DISSOCIATING HYDROGEN, ITS PRODUCTION AND METHOD OF ACTIVATING TREATMENT THEREFOR |
-
2002
- 2002-08-19 JP JP2002238245A patent/JP4029123B2/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS634829A (en) * | 1986-06-24 | 1988-01-09 | Matsushita Electric Ind Co Ltd | Production of hydrogen-permeable medium |
| JPH08291391A (en) * | 1995-02-22 | 1996-11-05 | Toyota Central Res & Dev Lab Inc | Surface treatment of hydrogen occlusion alloy material, activation treatment of hydrogen occlusion alloy electrode, activating solution, and hydrogen occlusion alloy electrode having excellent initial activity |
| JPH11130401A (en) * | 1997-10-29 | 1999-05-18 | Toyota Central Res & Dev Lab Inc | High activation treatment of hydrogen storage alloy |
| JP2000256002A (en) * | 1999-03-09 | 2000-09-19 | Agency Of Ind Science & Technol | Amorphous zirconium-nickel alloy based hydrogen separation dissociation membrane, its production and activating method thereof |
| JP2000319733A (en) * | 1999-04-30 | 2000-11-21 | Agency Of Ind Science & Technol | AMORPHOUS HfNi ALLOY BASED FILM FOR SEPARATING AND DISSOCIATING HYDROGEN, ITS PRODUCTION AND METHOD OF ACTIVATING TREATMENT THEREFOR |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006055831A (en) * | 2004-07-21 | 2006-03-02 | Iwatani Internatl Corp | Hydrogen separation membrane and its manufacturing method |
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