JP2001170460A - Hydrogen separating material and producing method therefor - Google Patents
Hydrogen separating material and producing method thereforInfo
- Publication number
- JP2001170460A JP2001170460A JP35843199A JP35843199A JP2001170460A JP 2001170460 A JP2001170460 A JP 2001170460A JP 35843199 A JP35843199 A JP 35843199A JP 35843199 A JP35843199 A JP 35843199A JP 2001170460 A JP2001170460 A JP 2001170460A
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- Japan
- Prior art keywords
- film
- alloy
- palladium
- hydrogen
- thickness
- Prior art date
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- Separation Using Semi-Permeable Membranes (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、水素を含む混合ガ
スから水素を分離するときに用いる水素透過性に優れた
水素分離材料及びその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrogen separation material having excellent hydrogen permeability and used for separating hydrogen from a mixed gas containing hydrogen, and a method for producing the same.
【０００２】[0002]
【従来の技術】高純度水素は、薬品の原料、半導体の製
造、燃料電池の高効率化などに、多くの用途がある。今
後も、燃料電池自動車、家庭用コジェネレーション等に
使用され、高純度水素の製造方法にはより高効率化が求
められる。2. Description of the Related Art High-purity hydrogen has many uses for producing chemicals, manufacturing semiconductors, and improving the efficiency of fuel cells. In the future, it will be used for fuel cell vehicles, home cogeneration, etc., and the method for producing high-purity hydrogen will require higher efficiency.
【０００３】高純度水素を作り出す方法として、吸収
法、深冷分離法、吸着法、拡散法がある。最も高純度の
水素を得られるのは、膜を使用する拡散法である。拡散
法は、膜表面で水素原子に解離し、膜中を拡散して高純
度の水素を得る方法である。現在、この拡散法で実用化
されている膜として、パラジウムと銀の合金膜がある。As methods for producing high-purity hydrogen, there are an absorption method, a cryogenic separation method, an adsorption method, and a diffusion method. The highest purity hydrogen can be obtained by a diffusion method using a membrane. The diffusion method is a method in which high-purity hydrogen is obtained by dissociation into hydrogen atoms on the film surface and diffusion in the film. At present, there is an alloy film of palladium and silver as a film practically used by this diffusion method.
【０００４】パラジウムと銀の合金膜を形成する方法と
して、特開昭６３−２９４９２５号公報には、多数の小
孔を有する耐熱性多孔体の表面にパラジウム薄膜を、該
パラジウム薄膜上に銅薄膜を、それぞれ化学メッキ法に
よって形成させ、次いで熱処理温度３００〜５４０℃、
好ましくは４００〜５００℃、処理時間５〜４０時間、
望ましくは１２〜１６時間の条件下で、熱処理を行うこ
とにより得られる水素分離用膜が開示されている。As a method of forming an alloy film of palladium and silver, JP-A-63-294925 discloses a palladium thin film on the surface of a heat-resistant porous body having a large number of small holes, and a copper thin film on the palladium thin film. Are respectively formed by a chemical plating method, and then a heat treatment temperature of 300 to 540 ° C.
Preferably 400 to 500 ° C, treatment time 5 to 40 hours,
A membrane for hydrogen separation obtained by performing a heat treatment under a condition of preferably 12 to 16 hours is disclosed.
【０００５】また、特開平１−１６４４１９号公報に
は、多数の小孔を有する耐熱性多孔体の表面にパラジウ
ム薄膜を、該パラジウム薄膜上に銀薄膜を、それぞれ化
学メッキ法によって形成させ、次いで熱処理温度４５０
〜６００℃、処理時間８〜１６時間の条件下で、熱処理
を行うことにより得られる水素分離用膜が開示されてい
る。Japanese Patent Application Laid-Open No. 1-164419 discloses that a palladium thin film is formed on a surface of a heat-resistant porous body having a large number of small holes, and a silver thin film is formed on the palladium thin film by a chemical plating method. Heat treatment temperature 450
Disclosed is a hydrogen separation membrane obtained by performing a heat treatment under the conditions of -600 ° C and a treatment time of 8 to 16 hours.
【０００６】また、特開平３−１４６１２２号公報に
は、耐熱性多孔質体の表面にパラジウム薄膜を、該パラ
ジウム薄膜上に銀薄膜を、それぞれ化学メッキ法により
形成し、次いで熱処理温度８００〜１３００℃、処理時
間３〜１６時間の条件下で、熱処理を行うことにより得
られる水素分離膜が開示されている。Japanese Patent Application Laid-Open No. 3-146122 discloses that a palladium thin film is formed on the surface of a heat-resistant porous body and a silver thin film is formed on the palladium thin film by a chemical plating method. A hydrogen separation membrane obtained by performing a heat treatment at a temperature of 3 ° C. for 3 to 16 hours is disclosed.
【０００７】また、特開平５−１２３５４８号公報に
は、金属多孔体を基材とし、この基材表面に、第一層と
して電気Ｎｉメッキ、第二層として電気パラジウムメッ
キを行った後、金属多孔体の裏面から真空吸引しながら
無電解パラジウムメッキを行うことにより得られる水素
分離膜が開示されている。Japanese Patent Application Laid-Open No. 5-123548 discloses that a porous metal body is used as a base material, and the surface of the base material is subjected to electric Ni plating as a first layer and electric palladium plating as a second layer. A hydrogen separation membrane obtained by performing electroless palladium plating while vacuum-sucking from the back surface of a porous body is disclosed.
【０００８】また、特開平１１−１０４４７１号公報に
は、基板にパラジウム−銀合金を主成分とし、Ｇｄおよ
びＹを３％以上含有させ、その上にパラジウム−銀を電
気メッキで形成して得られる水素分離膜が開示されてい
る。Japanese Patent Application Laid-Open No. 11-104471 discloses that a substrate contains a palladium-silver alloy as a main component, contains 3% or more of Gd and Y, and forms palladium-silver thereon by electroplating. The disclosed hydrogen separation membrane is disclosed.
【０００９】水素分離用膜に要求されるのは、水素透過
度が大きいことと、他のガスと反応して酸化物、窒化
物、炭化物等を生成しないことと、水素透過性を低下さ
せる材料を含まないことが重要である。さらに、基材が
水素脆化を起こさないことが必要である。また、広い温
度範囲で高い水素透過性を有することが必要である。[0009] The hydrogen separation membrane is required to have a high hydrogen permeability, not to react with other gases to form oxides, nitrides, carbides, etc., and to be made of a material which reduces hydrogen permeability. It is important not to include Furthermore, it is necessary that the substrate does not undergo hydrogen embrittlement. Further, it is necessary to have high hydrogen permeability in a wide temperature range.
【００１０】上記の特開昭６３−２９４９２５号公報、
特開平１−１６４４１９号公報、特開平３−１４６１２
２号公報では、膜としてパラジウムを化学メッキで形成
し、該パラジウムの上にさらに銅、銀をめっきした後、
合金化するために長時間の熱処理を行っている。しか
し、パラジウムおよびパラジウム合金の水素透過性は、
Ｎｂ、Ｖ、およびＴａより低く、特に、温度が４７３Ｋ
以下ではさらに低下するという欠点がある。さらに、使
用する材料が貴金属で高価であり、また、合金にするた
め高温で長時間の熱処理を行うので製作費が高価にな
る。The above-mentioned JP-A-63-294925,
JP-A-1-164419, JP-A-3-14612
In Japanese Patent Publication No. 2, palladium is formed as a film by chemical plating, and copper and silver are further plated on the palladium.
Long-term heat treatment is performed for alloying. However, the hydrogen permeability of palladium and palladium alloys is
Lower than Nb, V, and Ta, especially at temperatures of 473K
In the following, there is a disadvantage that it is further reduced. Further, the material used is a precious metal and is expensive, and the heat treatment is performed at a high temperature for a long time to form an alloy, so that the production cost is high.
【００１１】上記の特開平５−１２３５４８号公報で
は、一層目としてＮｉメッキ、二層目としてパラジウム
メッキを行いており、パラジウムを用いることによる欠
点を解消していない。無電解メッキや電気メッキで、パ
ラジウムもしくはパラジウム合金を形成すると、メッキ
液の不純物が膜中に取り込まれ、これが水素透過性を低
下させる一因にもなっている。さらに、メッキ特有の廃
水処理の問題があり、環境性に劣る処理である。In the above-mentioned Japanese Patent Application Laid-Open No. 5-123548, Ni plating is performed as the first layer and palladium plating is performed as the second layer, and the drawbacks caused by using palladium are not solved. When palladium or a palladium alloy is formed by electroless plating or electroplating, impurities of a plating solution are taken into the film, which also causes a reduction in hydrogen permeability. Furthermore, there is a problem of wastewater treatment peculiar to plating, and the treatment is inferior in environmental properties.
【００１２】上記の特開平１１−１０４４７１号公報に
は、基材にもパラジウム合金を使用し、膜にもパラジウ
ム合金を用いることで、高温強度に優れた膜を得ている
が、パラジウムを使用する限り、水素透過性に限界があ
り、全体に厚さが増し、水素透過性が劣化する。さら
に、コストが上がり、広く使用されない可能性がある。In Japanese Patent Application Laid-Open No. 11-104471, a film excellent in high-temperature strength is obtained by using a palladium alloy for the base material and a palladium alloy for the film. As far as possible, the hydrogen permeability is limited, the thickness increases as a whole, and the hydrogen permeability deteriorates. In addition, costs may increase and may not be widely used.
【００１３】また、Ｎｂ、Ｔａ、Ｖの金属膜は、化学メ
ッキが不可能もしくは大変形成困難であり、Ｎｂ、Ｔ
ａ、Ｖを基とする合金膜は、脆く、箔にしずらく、圧延
などの一般的な手法では薄膜が得られなかった。The metal films of Nb, Ta, and V cannot be chemically plated or are very difficult to form.
The alloy films based on a and V were brittle and hard to be made into foil, and a thin film could not be obtained by a general method such as rolling.
【００１４】[0014]
【発明が解決しようとする課題】本発明は、上記従来の
問題を解決し、パラジウム合金より優れた水素透過性を
有し、安価に製造できる水素透過膜を、多孔体基材の表
面に備えた水素分離材料およびその製造方法を提供する
ことを目的とする。SUMMARY OF THE INVENTION The present invention solves the above-mentioned conventional problems and provides a hydrogen-permeable membrane having hydrogen permeability superior to that of a palladium alloy and which can be produced at low cost on the surface of a porous substrate. And a method for producing the same.
【００１５】[0015]
【課題を解決するための手段】上記課題を解決するため
の本発明の水素分離材料は、金属粉もしくはセラミック
粉を焼結して得た多孔体の表面に、Ｖ、Ｎｂ、Ｔａ、Ｖ
と５〜２０ｗｔ％Ｎｉとの合金、Ｖと５〜２０ｗｔ％Ｃ
ｏとの合金、Ｖと５〜２０ｗｔ％Ｍｏとの合金、Ｎｂと
５〜２０ｗｔ％Ｎｉとの合金、Ｎｂと５〜２０ｗｔ％Ｃ
ｏとの合金、Ｎｂと５〜２０ｗｔ％Ｍｏとの合金、Ｔａ
と５〜２０ｗｔ％Ｎｉとの合金、Ｔａと５〜２０ｗｔ％
Ｃｏとの合金、およびＴａと５〜２０ｗｔ％Ｍｏとの合
金からなる群より選ばれた１種からなる膜が形成され
る。The hydrogen separating material of the present invention for solving the above-mentioned problems is characterized in that V, Nb, Ta, V, V, Nb, Ta are applied to the surface of a porous body obtained by sintering metal powder or ceramic powder.
Alloy of V and 5 to 20 wt% Ni, V and 5 to 20 wt% C
alloy with o, alloy with V and 5 to 20 wt% Mo, alloy with Nb and 5 to 20 wt% Ni, Nb and 5 to 20 wt% C
alloy with N, alloy with Nb and 5 to 20 wt% Mo, Ta
Of 5-20 wt% Ni, Ta and 5-20 wt%
A film made of one type selected from the group consisting of an alloy with Co and an alloy of Ta and 5 to 20 wt% Mo is formed.
【００１６】前記膜の膜厚は、１〜７０μｍの範囲内で
あることが望ましい。The thickness of the film is desirably in the range of 1 to 70 μm.
【００１７】また、前記膜の上に、パラジウムまたはパ
ラジウム−銀系合金からなる酸化防止膜が形成されるこ
とが望ましい。Preferably, an antioxidant film made of palladium or a palladium-silver alloy is formed on the film.
【００１８】上記酸化防止膜の膜厚は、０．１〜７．０
μｍ範囲内であることが望ましく、さらに好ましくは
０．１〜２．０μｍの範囲内であることが望ましい。The thickness of the antioxidant film is 0.1 to 7.0.
It is desirably in the range of μm, and more desirably in the range of 0.1 to 2.0 μm.
【００１９】また、本発明の水素分離材料の製造方法
は、金属粉もしくはセラミック粉を円筒形状に焼結して
多孔体とし、この多孔体の表面に、カソードアーク式イ
オンプレーティング法で、Ｖ、Ｎｂ、Ｔａ、Ｖと５〜２
０ｗｔ％Ｎｉとの合金、Ｖと５〜２０ｗｔ％Ｃｏとの合
金、Ｖと５〜２０ｗｔ％Ｍｏとの合金、Ｎｂと５〜２０
ｗｔ％Ｎｉとの合金、Ｎｂと５〜２０ｗｔ％Ｃｏとの合
金、Ｎｂと５〜２０ｗｔ％Ｍｏとの合金、Ｔａと５〜２
０ｗｔ％Ｎｉとの合金、Ｔａと５〜２０ｗｔ％Ｃｏとの
合金、およびＴａと５〜２０ｗｔ％Ｍｏとの合金からな
る群より選ばれた１種からなる膜を、膜厚が１〜７０μ
ｍの範囲内で形成する。In the method for producing a hydrogen separation material according to the present invention, a metal powder or a ceramic powder is sintered into a cylindrical shape to form a porous body, and the surface of the porous body is coated with V by a cathode arc ion plating method. , Nb, Ta, V and 5-2
Alloy with 0 wt% Ni, alloy with V and 5-20 wt% Co, alloy with V and 5-20 wt% Mo, Nb with 5-20
alloy with wt% Ni, alloy with Nb and 5-20 wt% Co, alloy with Nb and 5-20 wt% Mo, Ta with 5-2
A film made of one kind selected from the group consisting of an alloy of 0 wt% Ni, an alloy of Ta and 5 to 20 wt% Co, and an alloy of Ta and 5 to 20 wt% Mo is formed by a film having a thickness of 1 to 70 μm.
m.
【００２０】さらに、その上に、パラジウムまたはパラ
ジウム−銀系合金からなる酸化防止膜を、イオンプレー
ティング法または化学メッキ法で、膜厚が０．１〜７．
０μｍの範囲内で形成するのが望ましく、さらに好まし
くは０．１〜２．０μｍの範囲内で形成するのが望まし
い。Further, an antioxidant film made of palladium or a palladium-silver alloy is formed thereon by ion plating or chemical plating to a thickness of 0.1 to 7.
It is desirable to form within a range of 0 μm, more preferably within a range of 0.1 to 2.0 μm.
【００２１】前記酸化防止膜を形成する前に、洗浄のた
めに、真空中でアルゴンガスによるイオンボンバードを
行うのが望ましい。また、前記膜または前記酸化防止膜
の表面に、平滑化のために、径４０〜２００μｍの硬質
ショット球を高速で噴射衝突させるのが望ましい。Before forming the antioxidant film, it is preferable to perform ion bombardment with argon gas in vacuum for cleaning. In addition, it is desirable that a hard shot ball having a diameter of 40 to 200 μm be blasted at high speed onto the surface of the film or the antioxidant film for smoothing.
【００２２】前記合金の膜の形成は、合金組成の金属を
溶解し、焼結法で作製したターゲットを用いることがで
きる。例えば、ＮｂとＭｏの２種類のターゲットを、真
空装置に設けることで作製できる。For forming the alloy film, a target prepared by dissolving a metal having an alloy composition and sintering can be used. For example, it can be manufactured by providing two types of targets, Nb and Mo, in a vacuum device.
【００２３】前記のように、Ｖ、Ｎｂ、Ｔａ等の金属の
膜、及び、それらにＮｉ、Ｃｏ、Ｍｏを添加した合金の
膜の膜厚を、１〜７０μｍの範囲内とするのは、ピンポ
ールの数や膜応力の増大を考慮するからである。As described above, the film thickness of a metal film such as V, Nb, Ta, and the like and the alloy film obtained by adding Ni, Co, and Mo to the film is in the range of 1 to 70 μm. This is because the number of pin poles and the increase in film stress are taken into consideration.
【００２４】[0024]
【発明の実施の形態】本発明の基材には、耐熱性と耐食
性に優れたステンレス基材やアルミナのようなセラミッ
クスが適している。ガスから膜を通して水素を分離する
ため、多孔体を使用する。孔径が大きいと、イオンプレ
ーティング膜が不連続になり、ピンホールを生じる可能
性があるので、１〜１０μｍ程度の孔径が望ましい。そ
れらの基材の上に、パラジウムやパラジウム合金より水
素拡散速度が速く、水素の固溶度も大きいＶ、Ｎｂ、Ｔ
ａ等の金属や合金の膜を、カソードアーク式イオンプレ
ーティング法で形成する。BEST MODE FOR CARRYING OUT THE INVENTION As the substrate of the present invention, a stainless steel substrate excellent in heat resistance and corrosion resistance and ceramics such as alumina are suitable. A porous body is used to separate hydrogen from the gas through the membrane. If the pore size is large, the ion plating film becomes discontinuous and pinholes may be generated. Therefore, a pore size of about 1 to 10 μm is desirable. V, Nb, T have a higher hydrogen diffusion rate and a higher solid solubility of hydrogen than palladium or a palladium alloy on those substrates.
A film of a metal or alloy such as a is formed by a cathodic arc ion plating method.
【００２５】このカソードアーク式イオンプレーティン
グ法は、真空容器を正、金属ターゲットおよび基板を負
に印加し、金属ターゲット表面でアーク放電を起こさせ
る。そのアーク放電によって直接、金属を瞬時に蒸気化
し、それをプラズマ化して、イオン化する方法である。
よって、単一成分のターゲットを用いて成膜しても、合
金成分のターゲットを用いて成膜しても、ターゲット組
成に近い組成の膜が形成される。このとき、イオン化率
は８０％以上に達し、イオン化された蒸発粒子は、負に
印加された基板に引き付けられ、緻密で良質な膜が形成
される。In the cathodic arc ion plating method, a vacuum vessel is applied positively, and a metal target and a substrate are applied negatively to cause arc discharge on the surface of the metal target. In this method, the metal is instantaneously vaporized directly by the arc discharge, and the metal is turned into plasma and ionized.
Therefore, a film having a composition close to the target composition is formed regardless of whether a film is formed using a single-component target or a film formed using an alloy-component target. At this time, the ionization rate reaches 80% or more, and the ionized evaporated particles are attracted to the negatively applied substrate, and a dense and high quality film is formed.
【００２６】前記膜の耐水素脆化性を向上させるため
に、Ｖ、Ｎｂ、Ｔａ等に対し、Ｎｉ、Ｃｏ、Ｍｏを５〜
２０ｗｔ％添加した合金が適している。この場合は、カ
ソードアーク式イオンプレーティング装置に合金組成を
形成するターゲットを設置するか、２種類のターゲット
を配置してコーティングすることで、任意の比率の合金
膜が作製できる。Ｎｉ、Ｃｏ、Ｍｏを適当量添加すると
水素化物が生成し難くなり、耐水素脆化性を向上させる
ことができる。しかし、添加元素を入れすぎると、水素
透過度と拡散係数が低下してくるので、添加量は５〜２
０ｗｔ％が適量である。In order to improve the hydrogen embrittlement resistance of the film, Ni, Co and Mo are added to V, Nb, Ta and the like in an amount of 5 to 5%.
An alloy containing 20 wt% is suitable. In this case, an alloy film having an arbitrary ratio can be produced by installing a target for forming an alloy composition in the cathode arc ion plating apparatus or by arranging and coating two kinds of targets. When an appropriate amount of Ni, Co, or Mo is added, hydrides are hardly generated, and the hydrogen embrittlement resistance can be improved. However, if the added element is added too much, the hydrogen permeability and the diffusion coefficient decrease, so the addition amount is 5 to 2%.
0 wt% is an appropriate amount.
【００２７】前記膜の膜厚は１〜７０μｍの範囲内が良
い。１μｍ以下ではピンホールが多くなり、水素以外の
ガスが混入してくる。また７０μｍ以上では膜の応力が
大きくなりすぎ、基材と膜で剥離する可能性がある。The thickness of the film is preferably in the range of 1 to 70 μm. If it is 1 μm or less, pinholes increase and gases other than hydrogen are mixed. If it is 70 μm or more, the stress of the film becomes too large, and there is a possibility that the film is separated from the substrate.
【００２８】これらの膜は実製品になり、高温で長期間
使用されると酸化する可能性がある。酸化した膜は水素
透過性を低下させる。そのため、高温大気中で膜表面が
酸化されないように、高温酸化特性に優れるパラジウム
膜、すなわち、パラジウムやパラジウム−銀系合金の膜
を形成させる。このパラジウム膜は、カソードアーク式
イオンプレーティング法で、前記膜を形成した後、同じ
装置でパラジウムターゲットを用いて成膜する。These films become actual products and may be oxidized when used at high temperatures for a long period of time. Oxidized membranes reduce hydrogen permeability. Therefore, a palladium film having excellent high-temperature oxidation characteristics, that is, a film of palladium or a palladium-silver alloy is formed so that the film surface is not oxidized in a high-temperature atmosphere. This palladium film is formed by using a palladium target in the same apparatus after forming the film by a cathode arc ion plating method.
【００２９】また、前記膜を、カソードアーク式イオン
プレーティング装置で形成し、大気中に取り出し、別の
イオンプレーティング装置でパラジウム膜を形成するこ
とも可能である。その時は、アルゴンイオンをバイアス
電圧で加速させ、膜の表面の酸化膜を除去し、当該膜と
パラジウム膜との密着力を向上させる。パラジウム膜
は、膜厚が０．１〜２．０μｍの範囲内で作製する。
０．１μｍより膜厚が薄いと、酸化防止膜としての機能
が低下する。２．０μｍより厚くすると、水素透過性が
低下し、また、製造コストが上昇する。Further, it is also possible to form the film by a cathode arc type ion plating apparatus, take out the film into the atmosphere, and form a palladium film by another ion plating apparatus. At that time, argon ions are accelerated by a bias voltage to remove an oxide film on the surface of the film, thereby improving the adhesion between the film and the palladium film. The palladium film is formed with a thickness in the range of 0.1 to 2.0 μm.
If the thickness is less than 0.1 μm, the function as an antioxidant film is reduced. When the thickness is more than 2.0 μm, the hydrogen permeability decreases and the manufacturing cost increases.
【００３０】長時間、大気雰囲気の高温下で使用される
場合は、さらに化学メッキでパラジウム膜を、膜厚が１
〜５μｍの範囲内で形成する。１μｍより膜厚が薄い
と、長時間の酸化防止膜としての機能が低下し、５μｍ
より厚いと、水素透過性が低下し、また、製造コストが
上昇する。化学メッキを施すことにより、イオンプレー
ティング装置で形成したパラジウム膜の微少な凹凸、欠
陥などが無くなるか、もしくは減少する。When used for a long time at a high temperature in the air atmosphere, a palladium film is further formed by chemical plating to form
It is formed within a range of ５5 μm. When the thickness is less than 1 μm, the function as a long-time antioxidant film is reduced,
If it is thicker, the hydrogen permeability decreases and the production cost increases. By performing the chemical plating, fine irregularities, defects, and the like of the palladium film formed by the ion plating apparatus are eliminated or reduced.
【００３１】[0031]
【実施例】（実施例１）ＳＵＳ３１６の微粉末を用い
て、圧力１ｔ、焼結温度１０００℃、１時間で焼結して
得た相対密度６６％の多孔体を、基材として用いた。基
材をエタノールで超音波洗浄し、乾燥させた。膜形成に
は、マルチアーク社製カソードアーク式イオンプレーテ
ィング装置を用いた。この装置のターゲットとしてのカ
ソードに、Ｎｂを取り付けた。基材を真空チャンバーに
セットし、チャンバー内を２×１０ -5Ｔｏｒｒ以下まで
排気した。EXAMPLES (Example 1) Using fine powder of SUS316
Sintering at pressure 1t, sintering temperature 1000 ° C for 1 hour
The obtained porous body having a relative density of 66% was used as a substrate. Base
The material was ultrasonically cleaned with ethanol and dried. For film formation
Is a multi-arc cathode arc ion plate
A printing device was used. Power as a target for this device
Nb was attached to the sword. Substrate in vacuum chamber
Set, 2 × 10 inside the chamber -FiveUp to Torr
Exhausted.
【００３２】次に、アルゴンガスを３ｍＴｏｒｒ導入
し、基材に−１０００Ｖのバイアス電圧を印加し、１８
０Ａのカソード電流を流し、Ｎｂ金属ボンバードを２分
間、行った。この処理は、基材表面を洗浄し、基材温度
を５００℃付近まで上げるために行われる。Next, argon gas was introduced at 3 mTorr, a bias voltage of -1000 V was applied to the substrate,
A cathode current of 0 A was passed, and Nb metal bombardment was performed for 2 minutes. This treatment is performed to clean the surface of the substrate and increase the substrate temperature to around 500 ° C.
【００３３】次に、バイアス電圧を−５０Ｖ、カソード
電流１８０Ａ、アルゴンガス圧３０ｍＴｏｒｒで、１５
０分間、成膜して、膜厚が３０μｍのＮｂ膜を形成する
ことによって、水素透過膜を作製した。Next, at a bias voltage of -50 V, a cathode current of 180 A and an argon gas pressure of 30 mTorr,
A hydrogen-permeable film was formed by forming a film for 30 minutes to form an Nb film having a thickness of 30 μm.
【００３４】表面と膜断面を走査電子顕微鏡で２０００
倍まで拡大し観察したが、割れ、クラック、ピンホール
は観察されなかった。The surface and the cross section of the film were examined with a scanning electron microscope by 2000.
Although observed at a magnification of × 2, no cracks, cracks or pinholes were observed.
【００３５】（実施例２）実施例１で形成したＮｂ膜
に、３５０メッシュアンダー、粒径４０〜７４μｍのハ
イスピード鋼ビーズのショットを、基材から１５ｃｍ離
して、４ｋｇｆ／ｃｍ2のエアー圧力で照射した。Example 2 A shot of high-speed steel beads having a mesh size of 350 mesh and a particle size of 40 to 74 μm was placed on the Nb film formed in Example 1 at a distance of 15 cm from the base material and an air pressure of 4 kgf / cm 2 . Irradiation.
【００３６】表面と膜断面を走査電子顕微鏡で２０００
倍まで拡大して観察したが、割れ、クラック、ピンホー
ルは観察されなかった。The surface and the cross section of the film were examined with a scanning electron microscope by 2000.
When observed at a magnification of × 2, no cracks, cracks or pinholes were observed.
【００３７】（実施例３）実施例１と同様の基材に、同
様の処理を行い、膜厚が３０μｍのＮｂ膜を形成した。
この基材を真空装置から取り出し、電子ビーム方式のイ
オンプレーティング装置に取り付け、２×１０-5Ｔｏｒ
ｒまで排気した。Example 3 The same process was performed on the same substrate as in Example 1 to form an Nb film having a thickness of 30 μm.
The substrate was taken out of the vacuum apparatus and attached to an electron beam type ion plating apparatus, and 2 × 10 −5 Torr
e.
【００３８】次に、４０ｍＴｏｒｒまでアルゴンガスを
導入し、バイアス電圧−８００Ｖで１０分間、Ｎｂ膜に
アルゴンイオンを打ち付けた。この処理により、Ｎｂ膜
表面の酸化膜除去と基材温度を上昇させた。Next, argon gas was introduced to 40 mTorr, and argon ions were bombarded on the Nb film at a bias voltage of -800 V for 10 minutes. By this treatment, the oxide film on the surface of the Nb film was removed and the temperature of the substrate was increased.
【００３９】次に、電子ビーム出力１０ｋＶ、電流３０
０ｍＡを流し、１０分間、成膜し、膜厚が１．０μｍの
パラジウム膜を形成することによって、水素透過膜を作
製した。Next, an electron beam output of 10 kV and a current of 30 kV were used.
A hydrogen permeable film was produced by flowing a 0 mA current and forming the film for 10 minutes to form a palladium film having a thickness of 1.0 μm.
【００４０】表面と膜断面を走査電子顕微鏡で２０００
倍まで拡大して観察しても、割れ、クラック、ピンホー
ルは観察されなかった。The surface and the cross section of the film were examined with a scanning electron microscope by 2000.
No cracks, cracks, or pinholes were observed even when observed at a magnification of × 2.
【００４１】（実施例４）実施例３で形成したＮｂ膜
に、３５０メッシュアンダー、粒径４０〜７４μｍのハ
イスピード鋼ビーズのショットを、基材から１５ｃｍ離
して、４ｋｇｆ／ｃｍ2のエアー圧力で照射した。(Example 4) A shot of high-speed steel beads having a mesh size of 350 mesh and a particle size of 40 to 74 µm was placed on the Nb film formed in Example 3 at a distance of 15 cm from the base material and an air pressure of 4 kgf / cm 2 . Irradiation.
【００４２】表面と膜断面を走査電子顕微鏡で２０００
倍まで拡大して観察したが、割れ、クラック、ピンホー
ルは観察されなかった。The surface and the cross section of the film were examined with a scanning electron microscope by 2000.
When observed at a magnification of × 2, no cracks, cracks or pinholes were observed.
【００４３】（実施例５）実施例１と同様の基材を、エ
タノールで超音波洗浄し、乾燥させた。実施例１と同じ
装置の、ターゲットとしてのカソードに、Ｔａを取り付
けた。この基材を真空チャンバーにセットし、チャンバ
ー内を２×１０-5Ｔｏｒｒ以下まで排気した。Example 5 The same substrate as in Example 1 was ultrasonically washed with ethanol and dried. Ta was attached to the cathode as a target of the same apparatus as in Example 1. The substrate was set in a vacuum chamber, and the inside of the chamber was evacuated to 2 × 10 −5 Torr or less.
【００４４】次に、アルゴンガスを３ｍＴｏｒｒ導入
し、基材に−１０００Ｖのバイアス電圧を印加し、１８
０Ａのカソード電流を流し、Ｔａ金属ボンバードを２分
間、行った。この処理は、基材表面を洗浄し、基材温度
を５００℃付近まで上げるために行われる。Next, argon gas was introduced at 3 mTorr, a bias voltage of -1000 V was applied to the substrate,
A cathode current of 0 A was passed, and Ta metal bombardment was performed for 2 minutes. This treatment is performed to clean the surface of the substrate and increase the substrate temperature to around 500 ° C.
【００４５】次に、バイアス電圧を−５０Ｖ、カソード
電流２００Ａ、アルゴンガス圧３０ｍＴｏｒｒで、１５
０分間、成膜して、膜厚が３０μｍのＴａ膜を形成し
た。この基材を真空装置から取り出し、電子ビーム方式
のイオンプレーティング装置に取り付け、２×１０-5Ｔ
ｏｒｒまで排気した。Next, at a bias voltage of -50 V, a cathode current of 200 A and an argon gas pressure of 30 mTorr,
The film was formed for 0 minute to form a Ta film having a thickness of 30 μm. The substrate is taken out of the vacuum device and attached to an electron beam type ion plating device, and 2 × 10 −5 T
evacuated to orr.
【００４６】次に、４０ｍＴｏｒｒまでアルゴンガスを
導入し、バイアス電圧−８００Ｖで１０分間、Ｔａ膜に
アルゴンイオンを打ち付けた。この処理により、Ｔａ膜
表面の酸化膜除去と基材温度を上昇させた。Next, argon gas was introduced up to 40 mTorr, and argon ions were applied to the Ta film at a bias voltage of -800 V for 10 minutes. By this treatment, the oxide film on the surface of the Ta film was removed and the temperature of the substrate was increased.
【００４７】次に、電子ビーム出力１０ｋＶ、電流３０
０ｍＡを流し、１０分間、成膜し、膜厚が１．０μｍの
パラジウム膜を剥離なく形成することにより、水素透過
膜が作製できた。Next, an electron beam output of 10 kV and a current of 30 kV were used.
A hydrogen permeable film was produced by flowing 0 mA, forming a film for 10 minutes, and forming a palladium film having a thickness of 1.0 μm without peeling.
【００４８】表面と膜断面を走査電子顕微鏡で２０００
倍まで拡大して観察しても、割れ、クラック、ピンホー
ルは観察されなかった。The surface and the cross section of the film were examined with a scanning electron microscope by 2000.
No cracks, cracks, or pinholes were observed even when observed at a magnification of × 2.
【００４９】（実施例６）実施例５で形成したパラジウ
ム膜に、３５０メッシュアンダー、粒径４０〜７４μｍ
のハイスピード鋼ビーズのショットを、基材から１５ｃ
ｍ離して、４ｋｇｆ／ｃｍ2のエアー圧力で照射した。(Example 6) The palladium film formed in Example 5 was replaced with a 350 mesh under, particle size of 40 to 74 µm.
Shot of high speed steel beads from
Irradiated at an air pressure of 4 kgf / cm 2 .
【００５０】表面と膜断面を走査電子顕微鏡で２０００
倍まで拡大して観察したが、割れ、クラック、ピンホー
ルは観察されなかった。The surface and the cross section of the film were examined with a scanning electron microscope by 2000.
When observed at a magnification of × 2, no cracks, cracks or pinholes were observed.
【００５１】（実施例７）実施例１と同様の基材を、エ
タノールで超音波洗浄し、乾燥させた。実施例１と同じ
装置の、ターゲットとしてのカソードに、ＮｂとＭｏの
焼結ターゲットを取り付けた。Ｍｏは全体量の１０ｗｔ
％である。この基材を真空チャンバーにセットし、チャ
ンバー内を２×１０-5Ｔｏｒｒ以下まで排気した。Example 7 The same substrate as in Example 1 was ultrasonically washed with ethanol and dried. A sintered target of Nb and Mo was attached to a cathode as a target of the same apparatus as in Example 1. Mo is the total amount of 10wt
%. The substrate was set in a vacuum chamber, and the inside of the chamber was evacuated to 2 × 10 −5 Torr or less.
【００５２】次に、アルゴンガスを３ｍＴｏｒｒ導入
し、基材に−１０００Ｖのバイアス電圧を印加し、１８
０Ａのカソード電流を流し、Ｎｂ−Ｍｏ（１０ｗｔ％）
金属ボンバードを２分間、行った。この処理は、基材表
面を洗浄し、基材温度を５００℃付近まで上げるために
行われる。Next, 3 mTorr of argon gas was introduced, a bias voltage of -1000 V was applied to the substrate,
A cathode current of 0 A flows, and Nb-Mo (10 wt%)
A metal bombard was performed for 2 minutes. This treatment is performed to clean the surface of the substrate and increase the substrate temperature to around 500 ° C.
【００５３】次に、バイアス電圧を−５０Ｖ、カソード
電流１８０Ａ、アルゴンガス圧３０ｍＴｏｒｒで１３０
分間、成膜して、膜厚が３０μｍのＮｂ−Ｍｏ（１０ｗ
ｔ％）膜を形成した。この基材を真空装置から取り出
し、電子ビーム方式のイオンプレーティング装置に取り
付け、２×１０-5Ｔｏｒｒまで排気した。Next, at a bias voltage of -50 V, a cathode current of 180 A, and an argon gas pressure of 30 mTorr, a bias voltage of 130 mTorr was applied.
Nb-Mo (10 w
t%) film was formed. The substrate was taken out of the vacuum apparatus, attached to an electron beam type ion plating apparatus, and evacuated to 2 × 10 −5 Torr.
【００５４】次に、４０ｍＴｏｒｒまでアルゴンガスを
導入し、バイアス電圧−８００Ｖで１０分間、Ｎｂ−Ｍ
ｏ（１０ｗｔ％）膜にアルゴンイオンを打ち付けた。こ
の処理により、Ｎｂ−Ｍｏ（１０ｗｔ％）膜表面の酸化
膜除去と基材温度の上昇を行った。Next, an argon gas was introduced up to 40 mTorr, and Nb-M was applied at a bias voltage of -800 V for 10 minutes.
Argon ions were applied to the o (10 wt%) film. By this treatment, the oxide film on the surface of the Nb-Mo (10 wt%) film was removed and the temperature of the base material was increased.
【００５５】次に、電子ビーム出力１０ｋＶ、電流３０
０ｍＡを流し、１０分間、成膜して、膜厚が１．０μｍ
のパラジウム膜を形成することによって、水素透過膜が
形成できた。Next, an electron beam output of 10 kV and a current of 30 kV were used.
0 mA was flowed and a film was formed for 10 minutes,
By forming the palladium film, a hydrogen permeable film could be formed.
【００５６】表面と膜断面を走査電子顕微鏡で２０００
倍まで拡大して観察しても、割れ、クラック、ピンホー
ルは観察されなかった。The surface and the cross section of the film were examined with a scanning electron microscope for 2000 times.
No cracks, cracks, or pinholes were observed even when observed at a magnification of × 2.
【００５７】（実施例８）実施例７で形成したパラジウ
ム膜に、３５０メッシュアンダー、粒径４０〜７４μｍ
のハイスピード鋼ビーズのショットを、基材から１５ｃ
ｍ離して、４ｋｇｆ／ｃｍ2のエアー圧力で照射した。(Embodiment 8) The palladium film formed in the embodiment 7 was overlaid with a 350 mesh under, a particle size of 40 to 74 μm.
Shot of high speed steel beads from
Irradiated at an air pressure of 4 kgf / cm 2 .
【００５８】表面と膜断面を走査電子顕微鏡で２０００
倍まで拡大して観察したが、割れ、クラック、ピンホー
ルは観察されなかった。The surface and the cross section of the film were examined with a scanning electron microscope by 2000.
When observed at a magnification of × 2, no cracks, cracks or pinholes were observed.
【００５９】（実施例９）実施例１と同様の基材を、エ
タノールで超音波洗浄し、乾燥させた。実施例１と同じ
装置の、ターゲットとしてのカソードに、ＴａとＭｏの
焼結ターゲットを取り付けた。Ｍｏは全体量の５ｗｔ％
である。さらに、パラジウムターゲットを取り付けた。
この基材を真空チャンバーにセットし、チャンバー内を
２×１０-5Ｔｏｒｒ以下まで排気した。(Example 9) The same substrate as in Example 1 was subjected to ultrasonic cleaning with ethanol and dried. A sintered target of Ta and Mo was attached to a cathode as a target of the same apparatus as in Example 1. Mo is 5wt% of the total amount
It is. Further, a palladium target was attached.
The substrate was set in a vacuum chamber, and the inside of the chamber was evacuated to 2 × 10 −5 Torr or less.
【００６０】次に、アルゴンガスを３ｍＴｏｒｒ導入
し、基材に−１０００Ｖのバイアス電圧を印加し、１８
０Ａのカソード電流を流し、Ｔａ−Ｍｏ（５ｗｔ％）金
属ボンバードを２分間、行った。この処理は、基材表面
を洗浄し、基材温度を５００℃付近まで上げるために行
われる。Next, argon gas was introduced at 3 mTorr, a bias voltage of -1000 V was applied to the substrate,
A cathode current of 0 A was passed, and Ta-Mo (5 wt%) metal bombardment was performed for 2 minutes. This treatment is performed to clean the surface of the substrate and increase the substrate temperature to around 500 ° C.
【００６１】次に、バイアス電圧を−５０Ｖ、カソード
電流１８０Ａ、アルゴンガス圧３０ｍＴｏｒｒで１３０
分間、成膜し、膜厚が２５μｍのＴａ−Ｍｏ（５ｗｔ
％）膜を形成した。Next, at a bias voltage of -50 V, a cathode current of 180 A and an argon gas pressure of 30 mTorr,
For 25 minutes, and a Ta-Mo (5 wt.
%) A film was formed.
【００６２】次に、３０ｍＴｏｒｒまでアルゴンガスを
導入し、バイアス電圧−５０Ｖ、カソード電流９０Ａで
２０分間、成膜して、Ｔａ−Ｍｏ（５ｗｔ％）膜に２．
０μｍのパラジウム膜を成膜することによって、水素脆
化しない水素透過膜が形成できた。Next, an argon gas is introduced up to 30 mTorr, a film is formed at a bias voltage of −50 V and a cathode current of 90 A for 20 minutes, and a film is formed on a Ta—Mo (5 wt%) film.
By forming a 0 μm palladium film, a hydrogen permeable film that did not become hydrogen embrittled could be formed.
【００６３】表面と膜断面を走査電子顕微鏡で２０００
倍まで拡大して観察しても、割れ、クラック、ピンホー
ルは観察されなかった。The surface and the cross section of the film were examined with a scanning electron microscope for 2000 times.
No cracks, cracks, or pinholes were observed even when observed at a magnification of × 2.
【００６４】（実施例１０）実施例１と同様の基材を、
エタノールで超音波洗浄し、乾燥させた。実施例１と同
じ装置の、ターゲットとしてのカソードに、ＴａとＭｏ
の焼結ターゲットを取り付けた。Ｍｏは全体量の５ｗｔ
％である。さらに、パラジウムターゲットを取り付け
た。この基材を真空チャンバーにセットし、チャンバー
内を２×１０-5Ｔｏｒｒ以下まで排気した。Example 10 The same base material as in Example 1 was used.
Ultrasonic cleaning with ethanol and drying. In the same apparatus as in Example 1, Ta and Mo were applied to the cathode as a target.
Was attached. Mo is 5wt of the total amount
%. Further, a palladium target was attached. The substrate was set in a vacuum chamber, and the inside of the chamber was evacuated to 2 × 10 −5 Torr or less.
【００６５】次に、アルゴンガスを３ｍＴｏｒｒ導入
し、基材に−１０００Ｖのバイアス電圧を印加し、１８
０Ａのカソード電流を流し、Ｔａ−Ｍｏ（５ｗｔ％）金
属ボンバードを２分間、行った。この処理は、基材表面
を洗浄し、基材温度を５００℃付近まで上げるために行
われた。Next, 3 mTorr of argon gas was introduced, and a bias voltage of -1000 V was applied to the base material.
A cathode current of 0 A was passed, and Ta-Mo (5 wt%) metal bombardment was performed for 2 minutes. This treatment was performed to clean the surface of the substrate and increase the substrate temperature to around 500 ° C.
【００６６】次に、バイアス電圧を−５０Ｖ、カソード
電流１８０Ａ、アルゴンガス圧３０ｍＴｏｒｒで１３０
分間、成膜することによって、膜厚が２５μｍのＴａ−
Ｍｏ（５ｗｔ％）膜を形成した。さらに、「Ｐｄ（ＮＨ
3）4」Ｃｌ2・Ｈ2Ｏ，ＥＤＴＡ・２Ｎａ，ＮＨ3，Ｈ2Ｎ
ＮＨ2・Ｈ2Ｏよりなるメッキ液に、温度５０℃にて５時
間浸漬して、膜厚が２μｍの酸化防止膜を得た。Next, at a bias voltage of −50 V, a cathode current of 180 A, and an argon gas pressure of 30 mTorr, a bias voltage of 130 mTorr was applied.
For 25 minutes to form a Ta-
An Mo (5 wt%) film was formed. Further, “Pd (NH
3 ) 4 "Cl 2 · H 2 O, EDTA · 2Na, NH 3 , H 2 N
It was immersed in a plating solution of NH 2 · H 2 O at a temperature of 50 ° C. for 5 hours to obtain an antioxidant film having a thickness of 2 μm.
【００６７】表面と膜断面を走査電子顕微鏡で２０００
倍まで拡大して観察しても、割れ、クラック、ピンホー
ルは観察されなかった。The surface and the cross section of the film were examined with a scanning electron microscope for 2000 times.
No cracks, cracks, or pinholes were observed even when observed at a magnification of × 2.
【００６８】（実施例１１）実施例１０で形成したパラ
ジウム膜に、３５０メッシュアンダー、粒径４０〜７４
μｍのハイスピード鋼ビーズのショットを、基材から１
５ｃｍ離して、４ｋｇｆ／ｃｍ2のエアー圧力で照射し
た。(Embodiment 11) The palladium film formed in the embodiment 10 was overlaid with 350 mesh and the particle size was 40-74.
1 μm high speed steel bead shot from substrate
Irradiation was performed at an air pressure of 4 kgf / cm 2 at a distance of 5 cm.
【００６９】表面と膜断面を走査電子顕微鏡で２０００
倍まで拡大して観察したが、割れ、クラック、ピンホー
ルは観察されなかった。The surface and the cross section of the film were examined with a scanning electron microscope for 2000 times.
When observed at a magnification of × 2, no cracks, cracks or pinholes were observed.
【００７０】（実施例１２）材料にＡｌ2Ｏ3の微粉末を
用いて、圧力１．５ｔ、焼結温度１２００℃、２時間で
焼結して得た孔径２μｍのアルミナの焼結体を用いた。
基材をエタノールで超音波洗浄し、乾燥させた。実施例
１と同じ装置の、ターゲットとしてのカソードに、Ｔａ
とＭｏの焼結ターゲットを取り付けた。Ｍｏは全体量の
５ｗｔ％である。基材を真空チャンバーにセットし、チ
ャンバー内を２×１０-5Ｔｏｒｒ以下まで排気した。Example 12 A sintered body of alumina having a pore diameter of 2 μm obtained by sintering a fine powder of Al 2 O 3 as a material at a pressure of 1.5 t and a sintering temperature of 1200 ° C. for 2 hours was used. Using.
The substrate was ultrasonically cleaned with ethanol and dried. In the same apparatus as in Example 1, Ta was used as a target as a cathode.
And a sintered target of Mo. Mo is 5 wt% of the total amount. The substrate was set in a vacuum chamber, and the inside of the chamber was evacuated to 2 × 10 −5 Torr or less.
【００７１】次に、アルゴンガスを３ｍＴｏｒｒ導入
し、基材にバイアス電圧を印加せず、１８０Ａのカソー
ド電流を流し、Ｔａ−Ｍｏ（５ｗｔ％）金属を１分間、
成膜した。この処理で、基材に導通をとり、続いて基材
に−１０００Ｖのバイアス電圧を印加して、Ｔａ−Ｍｏ
（５ｗｔ％）金属の金属ボンバードを２分間、行った。
この処理は、基材表面を洗浄し、基材温度を５００℃付
近まで上げるために行われた。Next, argon gas was introduced at 3 mTorr, a cathode current of 180 A was passed without applying a bias voltage to the substrate, and Ta-Mo (5 wt%) metal was applied for 1 minute.
A film was formed. In this process, the substrate is brought into conduction, and subsequently, a bias voltage of -1000 V is applied to the substrate to obtain Ta-Mo.
(5 wt%) metal bombarding was performed for 2 minutes.
This treatment was performed to clean the surface of the substrate and increase the substrate temperature to around 500 ° C.
【００７２】次に、バイアス電圧を−５０Ｖ、カソード
電流１８０Ａ、アルゴンガス圧３０ｍＴｏｒｒで１３０
分間、成膜して、膜厚が２５μｍのＴａ−Ｍｏ（５ｗｔ
％）膜を形成した。この基材を真空装置から取り出し、
電子ビーム方式のイオンプレーティング装置に取り付
け、２×１０-5Ｔｏｒｒまで排気した。Next, at a bias voltage of -50 V, a cathode current of 180 A, and an argon gas pressure of 30 mTorr, a bias voltage of 130 mTorr was applied.
For 25 minutes, and a Ta-Mo (5 wt.
%) A film was formed. Take this substrate out of the vacuum device,
It was attached to an electron beam type ion plating apparatus and evacuated to 2 × 10 −5 Torr.
【００７３】次に、４０ｍＴｏｒｒまでアルゴンガスを
導入し、バイアス電圧−８００Ｖで１０分間、Ｔａ−Ｍ
ｏ（５ｗｔ％）膜にアルゴンイオンを打ち付けた。この
処理により、Ｔａ−Ｍｏ（５ｗｔ％）膜表面の酸化膜除
去と基材温度の上昇を行った。Next, argon gas was introduced up to 40 mTorr, and Ta-M was applied at a bias voltage of -800 V for 10 minutes.
Argon ions were applied to the o (5 wt%) film. By this treatment, the oxide film on the Ta-Mo (5 wt%) film surface was removed and the temperature of the base material was increased.
【００７４】次に、電子ビーム出力１０ｋＶ、電流３０
０ｍＡを流し、１０分間、成膜し、膜厚が１．０μｍの
パラジウム膜を形成することによって、水素透過膜が形
成できた。Next, an electron beam output of 10 kV and a current of 30 kV were used.
By flowing 0 mA and forming a film for 10 minutes to form a palladium film having a thickness of 1.0 μm, a hydrogen permeable film could be formed.
【００７５】表面と膜断面を走査電子顕微鏡で２０００
倍まで拡大して観察しても、割れ、クラック、ピンホー
ルは観察されなかった。The surface and the cross section of the film were examined with a scanning electron microscope for 2000 times.
No cracks, cracks, or pinholes were observed even when observed at a magnification of × 2.
【００７６】（実施例１３）実施例１と同様の基材を、
エタノールで超音波洗浄し、乾燥させた。実施例１と同
じ装置の、ターゲットとしてのカソードに、ＴａとＭｏ
の焼結ターゲットを取り付けた。Ｍｏは全体量の５ｗｔ
％である。さらに、パラジウムターゲットを取り付け
た。この基材を真空チャンバーにセットし、チャンバー
内を２×１０-5Ｔｏｒｒ以下まで排気した。(Example 13) The same base material as in Example 1 was used.
Ultrasonic cleaning with ethanol and drying. In the same apparatus as in Example 1, Ta and Mo were applied to the cathode as a target.
Was attached. Mo is 5wt of the total amount
%. Further, a palladium target was attached. The substrate was set in a vacuum chamber, and the inside of the chamber was evacuated to 2 × 10 −5 Torr or less.
【００７７】次に、アルゴンガスを３ｍＴｏｒｒ導入
し、基材に−１０００Ｖのバイアス電圧を印加し、１８
０Ａのカソード電流を流し、Ｔａ−Ｍｏ（５ｗｔ％）金
属ボンバードを２分間、行った。この処理は、基材表面
を洗浄し、基材温度を５００℃付近まで上げるために行
われる。Next, argon gas was introduced at 3 mTorr, a bias voltage of -1000 V was applied to the substrate,
A cathode current of 0 A was passed, and Ta-Mo (5 wt%) metal bombardment was performed for 2 minutes. This treatment is performed to clean the surface of the substrate and increase the substrate temperature to around 500 ° C.
【００７８】次に、バイアス電圧を−５０Ｖ、カソード
電流１８０Ａ、アルゴンガス圧３０ｍＴｏｒｒで１３０
分間、成膜し、膜厚が２５μｍのＴａ−Ｍｏ（５ｗｔ
％）膜を形成した。Next, at a bias voltage of -50 V, a cathode current of 180 A, and an argon gas pressure of 30 mTorr, a bias voltage of 130 mTorr was applied.
For 25 minutes, and a Ta-Mo (5 wt.
%) A film was formed.
【００７９】次に、３０ｍＴｏｒｒまでアルゴンガスを
導入し、バイアス電圧−５０Ｖ，カソード電流９０Ａで
２０分間、成膜することによって、Ｔａ−Ｍｏ（５ｗｔ
％）膜の上に、２．０μｍのパラジウム膜を成膜した。
さらに、「Ｐｄ（ＮＨ3）4」Ｃｌ2・Ｈ2Ｏ，ＥＤＴＡ・
２Ｎａ，ＮＨ3，Ｈ2ＮＮＨ2・Ｈ2Ｏよりなるメッキ液
に、温度５０℃にて５時間、浸漬して、膜厚が２μｍの
酸化防止膜を得た。Next, an argon gas was introduced up to 30 mTorr, and a film was formed at a bias voltage of −50 V and a cathode current of 90 A for 20 minutes to form a Ta—Mo (5 wt.
%) A 2.0 μm palladium film was formed on the film.
Further, “Pd (NH 3 ) 4 ” Cl 2 .H 2 O, EDTA.
2Na, in NH 3, H 2 NNH 2 · H 2 O consisting of plating solution, for 5 hours at a temperature 50 ° C., was dipped, the film thickness was obtained antioxidant film of 2 [mu] m.
【００８０】表面と膜断面を走査電子顕微鏡で２０００
倍まで拡大して観察しても、割れ、クラック、ピンホー
ルは観察されなかった。The surface and the cross section of the film were examined with a scanning electron microscope for 2000 times.
No cracks, cracks, or pinholes were observed even when observed at a magnification of × 2.
【００８１】（比較例１）従来のパラジウム合金膜は、
温度５００℃、膜にかかる圧力差２ｋｇ／ｃｍ2・Ｇの
条件で、水素ガスの透過試験を行ったところ、水素透過
量が３０〜７０ｃｍ3／ｃｍ2／ｍｉｎであった。(Comparative Example 1) A conventional palladium alloy membrane
When a hydrogen gas permeation test was performed under the conditions of a temperature of 500 ° C. and a pressure difference of 2 kg / cm 2 · G applied to the membrane, the hydrogen permeation amount was 30 to 70 cm 3 / cm 2 / min.
【００８２】実施例１〜１３の本発明の水素分離膜の水
素透過量は、前記と同一条件で、３００〜４００ｃｍ3
／ｃｍ2／ｍｉｎの値を得たように、いずれも十分な水
素透過性を示した。The hydrogen permeation amounts of the hydrogen separation membranes of the present invention in Examples 1 to 13 were 300 to 400 cm 3 under the same conditions as described above.
/ Cm 2 / min showed sufficient hydrogen permeability as obtained.
【００８３】[0083]
【発明の効果】従来は、水素透過膜として、パラジウム
及びパラジウム合金を化学メッキ法により長時間かけて
製造していたが、本発明により、より水素透過性に優れ
た材料を、安価に良い密着性で基材に成形でき、廃液処
理がいらず、無公害で製造できる水素透過膜の製造方法
を提供できた。Conventionally, palladium and a palladium alloy have been manufactured as a hydrogen permeable film by chemical plating for a long time. However, according to the present invention, a material having more excellent hydrogen permeability can be inexpensively and well adhered. Thus, a method for producing a hydrogen-permeable membrane that can be formed into a base material with a high degree of conductivity, does not require waste liquid treatment, and can be manufactured without pollution can be provided.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ２２Ｃ 27/02 １０２ Ｃ２２Ｃ 27/02 １０２Ｚ １０３ １０３ (72)発明者 塚田 由貴 千葉県市川市中国分３−18−５ 住友金属 鉱山株式会社中央研究所内 Ｆターム(参考） 4D006 GA41 KE16Q KE16R MA02 MA03 MA06 MA31 MB04 MC02 MC03 NA31 NA62 NA63 NA64 PB66 PC01 PC80 4G040 FA06 FC01 FE01 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C22C 27/02 102 C22C 27/02 102Z 103 103 (72) Inventor Yuki Tsukada 3-Chugoku, Ichikawa, Chiba 18-5 Sumitomo Metal Mining Co., Ltd. Central Research Laboratory F term (reference) 4D006 GA41 KE16Q KE16R MA02 MA03 MA06 MA31 MB04 MC02 MC03 NA31 NA62 NA63 NA64 PB66 PC01 PC80 4G040 FA06 FC01 FE01
Claims (10)
得た多孔体の表面に、Ｖ、Ｎｂ、Ｔａ、Ｖと５〜２０ｗ
ｔ％Ｎｉとの合金、Ｖと５〜２０ｗｔ％Ｃｏとの合金、
Ｖと５〜２０ｗｔ％Ｍｏとの合金、Ｎｂと５〜２０ｗｔ
％Ｎｉとの合金、Ｎｂと５〜２０ｗｔ％Ｃｏとの合金、
Ｎｂと５〜２０ｗｔ％Ｍｏとの合金、Ｔａと５〜２０ｗ
ｔ％Ｎｉとの合金、Ｔａと５〜２０ｗｔ％Ｃｏとの合
金、およびＴａと５〜２０ｗｔ％Ｍｏとの合金からなる
群より選ばれた１種からなる膜が形成された水素分離材
料。1. V, Nb, Ta, V and 5 to 20 watts on the surface of a porous body obtained by sintering a metal powder or a ceramic powder.
alloy with t% Ni, alloy with V and 5-20 wt% Co,
Alloy of V and 5 to 20 wt% Mo, Nb and 5 to 20 wt%
% Ni, an alloy of Nb and 5 to 20 wt% Co,
Alloy of Nb and 5 to 20 wt% Mo, Ta and 5 to 20 w
A hydrogen separation material formed with a film made of one selected from the group consisting of an alloy of t% Ni, an alloy of Ta and 5 to 20 wt% Co, and an alloy of Ta and 5 to 20 wt% Mo.
である請求項１に記載の水素分離材料。2. The hydrogen separation material according to claim 1, wherein the thickness of the membrane is in the range of 1 to 70 μm.
ウム−銀系合金からなる酸化防止膜が形成された請求項
１または２に記載の水素分離材料。3. The hydrogen separation material according to claim 1, wherein an antioxidant film made of palladium or a palladium-silver alloy is formed on the film.
０μｍの範囲内である請求項３に記載の水素分離材料。4. The antioxidant film has a thickness of 0.1 to 7.
The hydrogen separation material according to claim 3, which is within a range of 0 µm.
０μｍの範囲内である請求項３に記載の水素分離材料。5. An antioxidant film having a thickness of 0.1 to 2.
The hydrogen separation material according to claim 3, which is within a range of 0 µm.
に焼結して多孔体とし、この多孔体の表面に、カソード
アーク式イオンプレーティング法で、Ｖ、Ｎｂ、Ｔａ、
Ｖと５〜２０ｗｔ％Ｎｉとの合金、Ｖと５〜２０ｗｔ％
Ｃｏとの合金、Ｖと５〜２０ｗｔ％Ｍｏとの合金、Ｎｂ
と５〜２０ｗｔ％Ｎｉとの合金、Ｎｂと５〜２０ｗｔ％
Ｃｏとの合金、Ｎｂと５〜２０ｗｔ％Ｍｏとの合金、Ｔ
ａと５〜２０ｗｔ％Ｎｉとの合金、Ｔａと５〜２０ｗｔ
％Ｃｏとの合金、およびＴａと５〜２０ｗｔ％Ｍｏとの
合金からなる群より選ばれた１種からなる膜を、膜厚が
１〜７０μｍの範囲内で形成する水素分離材料の製造方
法。6. A porous body obtained by sintering a metal powder or a ceramic powder into a cylindrical shape, and applying V, Nb, Ta,
Alloy of V and 5 to 20 wt% Ni, V and 5 to 20 wt%
Alloy with Co, alloy with V and 5 to 20 wt% Mo, Nb
Of Ni and 5 to 20 wt% Ni, Nb and 5 to 20 wt%
Alloy with Co, alloy with Nb and 5 to 20 wt% Mo, T
alloy of a and 5 to 20 wt% Ni, Ta and 5 to 20 wt%
A method for producing a hydrogen separation material, wherein a film made of one kind selected from the group consisting of an alloy with% Co and an alloy with Ta and 5 to 20 wt% Mo is formed in a thickness of 1 to 70 μm.
に焼結して多孔体とし、この多孔体の表面に、カソード
アーク式イオンプレーティング法で、Ｖ、Ｎｂ、Ｔａ、
Ｖと５〜２０ｗｔ％Ｎｉとの合金、Ｖと５〜２０ｗｔ％
Ｃｏとの合金、Ｖと５〜２０ｗｔ％Ｍｏとの合金、Ｎｂ
と５〜２０ｗｔ％Ｎｉとの合金、Ｎｂと５〜２０ｗｔ％
Ｃｏとの合金、Ｎｂと５〜２０ｗｔ％Ｍｏとの合金、Ｔ
ａと５〜２０ｗｔ％Ｎｉとの合金、Ｔａと５〜２０ｗｔ
％Ｃｏとの合金、およびＴａと５〜２０ｗｔ％Ｍｏとの
合金からなる群より選ばれた１種からなる膜を、膜厚が
１〜７０μｍの範囲内で形成し、その上に、パラジウム
またはパラジウム−銀系合金からなる酸化防止膜を、イ
オンプレーティング法または化学メッキ法で、膜厚が
０．１〜７．０μｍの範囲内で形成する水素分離材料の
製造方法。7. A porous body obtained by sintering a metal powder or a ceramic powder into a cylindrical shape, and applying V, Nb, Ta,
Alloy of V and 5 to 20 wt% Ni, V and 5 to 20 wt%
Alloy with Co, alloy with V and 5 to 20 wt% Mo, Nb
Of Ni and 5 to 20 wt% Ni, Nb and 5 to 20 wt%
Alloy with Co, alloy with Nb and 5 to 20 wt% Mo, T
alloy of a and 5 to 20 wt% Ni, Ta and 5 to 20 wt%
% Co, and a film selected from the group consisting of Ta and an alloy of 5 to 20 wt% Mo in a thickness of 1 to 70 μm, and palladium or A method for producing a hydrogen separation material in which an antioxidant film made of a palladium-silver alloy is formed by an ion plating method or a chemical plating method so as to have a thickness in the range of 0.1 to 7.0 μm.
０μｍの範囲内である請求項７に記載の水素分離材料の
製造方法。8. The antioxidant film having a thickness of 0.1 to 2.
The method for producing a hydrogen separation material according to claim 7, wherein the thickness is within a range of 0 µm.
でアルゴンガスによるイオンボンバードを行うことを特
徴とする請求項７または８に記載の水素分離材料の製造
方法。9. The method for producing a hydrogen separation material according to claim 7, wherein ion bombardment with an argon gas is performed in a vacuum before forming the oxidation preventing film.
に、径４０〜２００μｍの硬質ショット球を、高速で噴
射衝突させる請求項７から９のいずれかに記載の水素分
離材料の製造方法。10. The method for producing a hydrogen separation material according to claim 7, wherein a hard shot sphere having a diameter of 40 to 200 μm is injected and collided at a high speed onto the surface of the film or the antioxidant film.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003034506A (en) * | 2001-07-23 | 2003-02-07 | Toyota Motor Corp | Hydrogen extractor |
| JP2003095616A (en) * | 2001-09-19 | 2003-04-03 | National Institute For Materials Science | Hydrogen separating purifier |
| JP2003305346A (en) * | 2002-04-11 | 2003-10-28 | Toyo Kohan Co Ltd | Separation film laminate and production method for component using the same |
| US6702878B2 (en) | 2001-10-02 | 2004-03-09 | Toyota Jidosha Kabushiki Kaisha | Hydrogen-permeable membrane, manufacturing method of the same, and hydrogen gas separator using the same |
| JP2006181568A (en) * | 2004-12-01 | 2006-07-13 | Ngk Insulators Ltd | Hydrogen separating body and manufacturing method of the same |
| JP2008200558A (en) * | 2007-02-16 | 2008-09-04 | National Institute Of Advanced Industrial & Technology | Hydrogen permeable film manufacturing apparatus using chemical vapor deposition method |
| WO2011030902A1 (en) * | 2009-09-14 | 2011-03-17 | 東京瓦斯株式会社 | Hydrogen separation membrane and method for separating hydrogen |
| US7923105B2 (en) | 2004-12-01 | 2011-04-12 | Ngk Insulators, Ltd. | Hydrogen separator and process for production thereof |
-
1999
- 1999-12-17 JP JP35843199A patent/JP2001170460A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003034506A (en) * | 2001-07-23 | 2003-02-07 | Toyota Motor Corp | Hydrogen extractor |
| JP2003095616A (en) * | 2001-09-19 | 2003-04-03 | National Institute For Materials Science | Hydrogen separating purifier |
| US6702878B2 (en) | 2001-10-02 | 2004-03-09 | Toyota Jidosha Kabushiki Kaisha | Hydrogen-permeable membrane, manufacturing method of the same, and hydrogen gas separator using the same |
| EP1300188A3 (en) * | 2001-10-02 | 2005-02-02 | Toyota Jidosha Kabushiki Kaisha | Hydrogen-permeable membrane, manufacturing method of the same, and hydrogen gas separator using the same |
| JP2003305346A (en) * | 2002-04-11 | 2003-10-28 | Toyo Kohan Co Ltd | Separation film laminate and production method for component using the same |
| JP2006181568A (en) * | 2004-12-01 | 2006-07-13 | Ngk Insulators Ltd | Hydrogen separating body and manufacturing method of the same |
| US7923105B2 (en) | 2004-12-01 | 2011-04-12 | Ngk Insulators, Ltd. | Hydrogen separator and process for production thereof |
| US8211539B2 (en) | 2004-12-01 | 2012-07-03 | Ngk Insulators, Ltd. | Hydrogen separator and process for production thereof |
| JP2008200558A (en) * | 2007-02-16 | 2008-09-04 | National Institute Of Advanced Industrial & Technology | Hydrogen permeable film manufacturing apparatus using chemical vapor deposition method |
| WO2011030902A1 (en) * | 2009-09-14 | 2011-03-17 | 東京瓦斯株式会社 | Hydrogen separation membrane and method for separating hydrogen |
| US8728199B2 (en) | 2009-09-14 | 2014-05-20 | Tokyo Gas Co., Ltd. | Hydrogen separation membrane and method for separating hydrogen |
| JP5597852B2 (en) * | 2009-09-14 | 2014-10-01 | 東京瓦斯株式会社 | Hydrogen separation membrane and hydrogen separation method |
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