JP3316417B2 - Method for producing Pd alloy foil - Google Patents
Method for producing Pd alloy foilInfo
- Publication number
- JP3316417B2 JP3316417B2 JP14565997A JP14565997A JP3316417B2 JP 3316417 B2 JP3316417 B2 JP 3316417B2 JP 14565997 A JP14565997 A JP 14565997A JP 14565997 A JP14565997 A JP 14565997A JP 3316417 B2 JP3316417 B2 JP 3316417B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- plating
- alloy foil
- alloy
- producing
- 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 - Lifetime
Links
- 239000011888 foil Substances 0.000 title claims description 24
- 229910001252 Pd alloy Inorganic materials 0.000 title claims description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 238000007747 plating Methods 0.000 claims description 41
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 229910045601 alloy Inorganic materials 0.000 claims description 9
- 239000000956 alloy Substances 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000010408 film Substances 0.000 description 81
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 66
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 16
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 14
- 229910001316 Ag alloy Inorganic materials 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 238000004506 ultrasonic cleaning Methods 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 238000005097 cold rolling Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- LFAGQMCIGQNPJG-UHFFFAOYSA-N silver cyanide Chemical compound [Ag+].N#[C-] LFAGQMCIGQNPJG-UHFFFAOYSA-N 0.000 description 1
- 229940098221 silver cyanide Drugs 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Electroplating Methods And Accessories (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、Ｐｄ合金箔の製造
方法、特にＰｄ−Ａｇ合金からなる水素透過性箔の製造
方法に関する。The present invention relates to a method for producing a Pd alloy foil, and more particularly to a method for producing a hydrogen-permeable foil made of a Pd-Ag alloy.
【０００２】[0002]
【従来の技術】水素混合ガスから高純度の水素ガスを分
離、回収する手段として、水素を選択的に透過する金属
箔（または金属膜）を用いる方法が、既に実用化されて
いる。例えば、Ｐｄ（パラジウム）系合金膜は、極めて
高い水素透過性を示すため、現在、半導体製造用水素の
分離、精製に用いられ、また、石油化学工業への使用の
拡大も進展している。2. Description of the Related Art As a means for separating and recovering high-purity hydrogen gas from a hydrogen mixed gas, a method using a metal foil (or metal film) that selectively transmits hydrogen has already been put to practical use. For example, Pd (palladium) -based alloy membranes exhibit extremely high hydrogen permeability, and are currently used for separating and purifying hydrogen for semiconductor production, and their use in the petrochemical industry is also expanding.
【０００３】Ｐｄ系合金膜の水素選択透過性は、水素混
合ガスがＰｄ合金膜に接触したとき、水素分子がＰｄ膜
に吸着されて原子状態になり、更にイオン化して膜の反
対側に拡散し、再結合して再び水素ガスになる現象と説
明されている。工業的には、Ｐｄ膜に接触する混合ガス
圧力を、該膜の反対側面の圧力よりもやや高くして、水
素透過の推進力を付加し、透過する水素を集めることに
よって水素製造または水素精製装置として利用すること
ができる。[0003] The hydrogen selective permeability of a Pd-based alloy film is such that when a hydrogen mixed gas comes into contact with the Pd alloy film, hydrogen molecules are adsorbed on the Pd film to be in an atomic state, and further ionized and diffused to the opposite side of the film. It is described as a phenomenon in which hydrogen gas is recombined and becomes hydrogen gas again. Industrially, the pressure of the mixed gas in contact with the Pd membrane is slightly higher than the pressure on the opposite side of the membrane to add a driving force for hydrogen permeation and collect the permeating hydrogen to produce or produce hydrogen. It can be used as a device.
【０００４】水素透過膜として用いられるＰｄ合金膜の
製造に際しては、（１）高価な金属であるＰｄの使用量
を可能な限り削減して、製造コストを低減すること、及
び、（２）高い水素透過性能を得るために、水素透過に
対する抵抗の大きさに関係を有する膜厚を可能な限り小
さくすると共に、膜欠陥のない安定した膜を製造するこ
と、が要求される。In manufacturing a Pd alloy film used as a hydrogen permeable film, (1) the use amount of Pd, which is an expensive metal, is reduced as much as possible to reduce the manufacturing cost, and (2) the cost is high. In order to obtain hydrogen permeation performance, it is required that the film thickness related to the magnitude of resistance to hydrogen permeation be as small as possible and that a stable film free of film defects be manufactured.
【０００５】従来、Ｐｄ合金膜は、ＰｄやＰｄ−Ａｇ合
金の素材金属のインゴットを焼鈍した後、冷間圧延して
薄い箔とする方法によって製造している。また、最近で
は、例えば特開平３−１４６１２２号公報に記載されて
いるように、Ｐｄ膜の支持体となる多孔質体の表面に、
メッキまたは蒸着操作によって薄膜を形成させる方法も
開発されている。これらの金属膜の製造法は、いずれ
も、バッチ操作によるものである。Conventionally, a Pd alloy film is manufactured by a method of annealing an ingot of a material metal such as Pd or a Pd-Ag alloy, followed by cold rolling to a thin foil. Recently, as described in, for example, JP-A-3-146122, the surface of a porous body serving as a support for a Pd film is
Methods for forming thin films by plating or vapor deposition operations have also been developed. All of these methods for producing a metal film are based on a batch operation.
【０００６】[0006]
【発明が解決しようとする課題】従来の製造法では、バ
ッチ製法が主体であるため、膜の厚さが不均一になり易
く、また、膜欠陥の発生を防止するために、膜厚に下限
を設ける必要があった。すなわち、バッチ製法であるた
めに、膜の特性が不揃いになる傾向があり、生産性が低
くて、大量の膜の需要に応ずることができず、さらに生
産コストも高い等の問題があった。In the conventional manufacturing method, since the batch manufacturing method is mainly used, the thickness of the film tends to be non-uniform, and in order to prevent the occurrence of film defects, a lower limit is imposed on the film thickness. It was necessary to provide. That is, because of the batch production method, there is a tendency that the characteristics of the film tend to be uneven, the productivity is low, the demand for a large amount of film cannot be met, and the production cost is high.
【０００７】例えば、冷間圧延法を用いた場合には、膜
厚を１５μｍ以下にすることが難しく、製膜の歩留まり
も、７０％程度であり、良好ではない。多孔質の支持体
の上に膜を形成させる方法を用いた場合でも、該支持体
の表面の粗さが関係して、冷間圧延法で製造する場合と
同程度の膜しか製造することができない。したがって、
本発明の目的は、水素透過性Ｐｄ合金箔（または合金
膜）を製造するに際し、薄くて欠陥のない安定した性能
の膜を、低コストでしかも高い生産性を持って製造する
ことにある。For example, when the cold rolling method is used, it is difficult to reduce the film thickness to 15 μm or less, and the yield of film formation is about 70%, which is not good. Even when using a method of forming a film on a porous support, it is possible to produce only a film of the same degree as that produced by the cold rolling method due to the surface roughness of the support. Can not. Therefore,
An object of the present invention is to produce a thin, defect-free and stable-performance film at low cost and with high productivity when producing a hydrogen-permeable Pd alloy foil (or alloy film).
【０００８】[0008]
【課題を解決するための手段】本発明のＰｄ合金箔の製
造方法は、めっき法によって支持体上にＰｄ膜を連続的
に形成させる工程と、該Ｐｄ膜を該支持体から剥離させ
た後、めっき法によって該Ｐｄ膜の両面にＡｇ膜を形成
させる工程と、Ａｇ膜を両面に形成させた該Ｐｄ膜を、
真空または不活性ガス雰囲気下で加熱処理して、Ｐｄ合
金箔を生成させる工程とを含むことを特徴とする。According to the present invention, there is provided a method for producing a Pd alloy foil, comprising the steps of continuously forming a Pd film on a support by plating, and removing the Pd film from the support. Forming an Ag film on both sides of the Pd film by plating, and forming the Ag film on both sides of the Pd film by:
Heat-treating in a vacuum or an inert gas atmosphere to produce a Pd alloy foil.
【０００９】[0009]
【発明の実施の形態】本発明のＰｄ合金箔の製造方法
を、各工程毎に以下、説明する。（１）第１工程 ：第１工程は、めっき法によって支持体
上にＰｄ膜を連続的に形成させる工程である。本発明で
用いる支持体としては、例えば、ＳＵＳ材等の材質から
なる幅１０〜１００ｃｍ程度のベルト状ダミーシート環
等が用いられる。支持体上にＰｄ膜を連続的に形成させ
るには、例えば、Ｐｄめっき槽のめっき浴中に下半分を
浸漬させた直径０．５〜１ｍ、幅１０〜１００ｃｍ程度
のドラム等の回転体の表面に、支持体（ベルト状ダミー
シート環）を巻き付かせて、めっき浴中に支持体が一定
時間浸漬されるようにする。DESCRIPTION OF THE PREFERRED EMBODIMENTS The method for producing a Pd alloy foil according to the present invention will be described below for each step. (1) First step : The first step is a step of continuously forming a Pd film on a support by a plating method. As the support used in the present invention, for example, a belt-shaped dummy sheet ring having a width of about 10 to 100 cm made of a material such as a SUS material is used. In order to continuously form a Pd film on a support, for example, a rotating body such as a drum having a diameter of 0.5 to 1 m and a width of about 10 to 100 cm, in which a lower half is immersed in a plating bath of a Pd plating tank, is used. A support (belt-shaped dummy sheet ring) is wound around the surface so that the support is immersed in the plating bath for a certain period of time.
【００１０】形成されるＰｄ膜の厚みは、３〜１０μｍ
程度である。支持体（ダミーシート環）は、めっき浴に
浸漬させる直前に、王水等の前処理剤を用いて、表面の
酸化物を除去し、表面を活性化させておく。この前処理
によって、後に、支持体上に形成させたＰｄめっき膜を
容易に剥がすことができ、連続したＰｄ膜（帯状膜）を
得ることができる。The thickness of the formed Pd film is 3 to 10 μm
It is about. Immediately before the support (dummy sheet ring) is immersed in the plating bath, the surface oxide is removed using a pretreatment agent such as aqua regia to activate the surface. By this pretreatment, the Pd plating film formed on the support can be easily peeled off later, and a continuous Pd film (strip-like film) can be obtained.
【００１１】本発明においては、ベルト状ダミーシート
環を必須とするものではなく、ドラム等の回転体の表面
を適正に前処理する手段を設けることによって、ダミー
シート環を省略することができる。この場合、表面にＰ
ｄ膜を形成させる支持体は、ドラム等の回転体である。In the present invention, the belt-shaped dummy sheet ring is not essential, but the dummy sheet ring can be omitted by providing a means for appropriately pre-treating the surface of the rotating body such as a drum. In this case, P
The support on which the d film is formed is a rotating body such as a drum.
【００１２】（２）第２工程：第２工程は、Ｐｄ膜を支
持体から剥離させた後、めっき法によって該Ｐｄ膜の両
面にＡｇ膜を形成させる工程である。Ｐｄ膜を支持体か
ら剥離させるには、例えば、Ｐｄめっき浴内を通過し
た、表面にＰｄ膜が付着した支持体に、剥がしロール等
の剥離手段を接触させればよい。剥離させたＰｄ膜は、
その表面を洗浄するために、超音波洗浄等を施すのが望
ましい。なお、超音波洗浄によれば、Ｐｄ膜の両面に破
損を与えることがなく、好都合である。 (2) Second step : The second step is a step of peeling off the Pd film from the support and then forming an Ag film on both sides of the Pd film by a plating method. In order to peel the Pd film from the support, for example, a peeling means such as a peeling roll may be brought into contact with the support having passed through the Pd plating bath and having the Pd film adhered to the surface. The peeled Pd film is
In order to clean the surface, it is desirable to perform ultrasonic cleaning or the like. Note that ultrasonic cleaning is advantageous because it does not damage both surfaces of the Pd film.
【００１３】めっき法によってＰｄ膜の両面にＡｇ膜を
形成させるには、Ｐｄ膜をＡｇめっき槽のＡｇめっき浴
内に浸漬させる。Ｐｄ膜を一定時間、Ａｇめっき槽内に
浸漬させるには、例えば、Ａｇめっき槽内に回転ローラ
ーを設け、該回転ローラーの表面にＰｄ膜を巻き付けれ
ばよい。Ａｇめっき後のＰｄ膜は、その表面を洗浄する
ために、超音波洗浄等を施すのが望ましい。形成される
Ａｇ膜の厚みは、片面当たり０．２〜１．０μｍ程度で
ある。In order to form an Ag film on both sides of a Pd film by plating, the Pd film is immersed in an Ag plating bath of an Ag plating tank. In order to immerse the Pd film in the Ag plating tank for a certain period of time, for example, a rotating roller may be provided in the Ag plating tank, and the Pd film may be wound around the surface of the rotating roller. The Pd film after the Ag plating is desirably subjected to ultrasonic cleaning or the like in order to clean the surface. The thickness of the formed Ag film is about 0.2 to 1.0 μm per one side.
【００１４】（３）第３工程：第３工程は、Ａｇ膜を両
面に形成させたＰｄ膜を、真空または不活性ガス雰囲気
下で加熱処理して、Ｐｄ合金箔を生成させる工程であ
る。不活性ガスとしては、例えば、Ａｒ、Ｎ2 等を挙げ
ることができる。加熱温度及び加熱時間は、Ｐｄ膜厚５
μｍ、Ａｇ膜厚１μｍ（片面）の場合、５００℃では５
０時間程度であり、９００℃では２分程度である。温度
が５００℃未満であると、合金化するまでの時間が長く
なる欠点があり、９００℃を越えると、Ｐｄ結晶が粗大
化する欠点がある。生成するＰｄ合金箔の厚みは、３．
４〜１２μｍである。製造速度は、０．１〜１ｍ／分で
ある。以上の各工程において、Ｐｄ膜の移動の際の破断
を防止するため、必要に応じ、各所で張力制御を行な
う。 (3) Third Step : The third step is a step in which a Pd film having an Ag film formed on both sides is heat-treated in a vacuum or an inert gas atmosphere to generate a Pd alloy foil. Examples of the inert gas include Ar and N 2 . The heating temperature and heating time are as follows.
μm, Ag film thickness of 1 μm (one side)
It takes about 0 hours and at 900 ° C. takes about 2 minutes. If the temperature is lower than 500 ° C., there is a disadvantage that the time until alloying becomes long, and if it exceeds 900 ° C., there is a disadvantage that the Pd crystal becomes coarse. The thickness of the Pd alloy foil to be generated is 3.
4 to 12 μm. The production speed is between 0.1 and 1 m / min. In each of the above steps, tension control is performed at various points as necessary to prevent breakage during movement of the Pd film.
【００１５】本発明に基づくＰｄ合金箔の製造工程の例
を図１及び図２に示す。図１において、ダミーシート前
処理装置１は、Ｐｄ膜をめっきするベルト状ダミーシー
ト２を前処理液によって前処理するために設けられてい
る。ダミーシート２は、Ｐｄめっき装置３と前処理装置
１の間を移動している。前処理されたダミーシート２
は、Ｐｄめっき装置３内に入り、ダミーシート２の表面
には、電気めっき法によってＰｄめっき膜が連続的に形
成される。ダミーシート２上のＰｄめっき膜は、めっき
浴から出た後、剥がしロール４によって剥がされ、Ｐｄ
膜連続シート５になる。Ｐｄ膜連続シート５は、洗浄槽
６内で、超音波洗浄によるＰｄ膜の表面の清浄化を受け
た後、Ａｇめっき槽７に入る。FIGS. 1 and 2 show an example of a manufacturing process of a Pd alloy foil according to the present invention. In FIG. 1, a dummy sheet pretreatment apparatus 1 is provided for pretreating a belt-shaped dummy sheet 2 for plating a Pd film with a pretreatment liquid. The dummy sheet 2 is moving between the Pd plating device 3 and the pretreatment device 1. Pre-processed dummy sheet 2
Enters the Pd plating apparatus 3, and a Pd plating film is continuously formed on the surface of the dummy sheet 2 by an electroplating method. After leaving the plating bath, the Pd plating film on the dummy sheet 2 is peeled off by the peeling roll 4, and the Pd plating film is removed.
It becomes the film continuous sheet 5. The Pd film continuous sheet 5 enters the Ag plating tank 7 after the surface of the Pd film is cleaned by ultrasonic cleaning in the cleaning tank 6.
【００１６】Ａｇめっき槽７に導入されたＰｄ膜連続シ
ート５の両面には、コンダクタロール８からの通電によ
ってＡｇがめっきされ、ＡｇでめっきされたＰｄ膜（以
下、「ＡｇめっきＰｄ膜」という。）の連続シート９と
なる。続いて、ＡｇめっきＰｄ膜の連続シート９は、洗
浄槽１０に導かれ、超音波洗浄された後に、連続式加熱
処理炉１１に導入され、真空または不活性雰囲気中で加
熱される。加熱によって、ＡｇはＰｄ中に拡散し、Ｐｄ
−Ａｇ合金膜シート１２が生成する。Ｐｄ−Ａｇ合金膜
シート１２は、巻き取りロール１３によって連続的に巻
き取られ、製品となる。Ag is plated on both sides of the Pd film continuous sheet 5 introduced into the Ag plating tank 7 by energization from the conductor roll 8, and a Pd film plated with Ag (hereinafter referred to as “Ag-plated Pd film”). )). Subsequently, the continuous sheet 9 of the Ag-plated Pd film is guided to a cleaning tank 10 and, after being subjected to ultrasonic cleaning, introduced into a continuous heating furnace 11 and heated in a vacuum or an inert atmosphere. By heating, Ag diffuses into Pd and Pd
-Ag alloy film sheet 12 is generated. The Pd-Ag alloy film sheet 12 is continuously wound by the winding roll 13 to be a product.
【００１７】以上、全工程が連続的に行われる例を説明
したが、場合によっては、図２に示すように、洗浄槽１
０を出たＡｇめっきＰｄ膜の連続シート９を乾燥後、巻
き取りロール１３で巻き取り、この巻き取られたＡｇめ
っきＰｄ膜のコイル９’を、バッチタイプ加熱処理炉１
１’内に入れ、真空または不活性雰囲気中で加熱しても
よい。加熱によって、ＡｇがＰｄ中に拡散し、Ｐｄ−Ａ
ｇ合金膜１２が生成する。In the above, an example in which all the steps are performed continuously has been described. In some cases, as shown in FIG.
After drying the continuous sheet 9 of the Ag-plated Pd film that has come out of the winding 9, it is taken up by a take-up roll 13, and the wound coil 9 ′ of the Ag-plated Pd film is placed in a batch-type heat treatment furnace 1.
1 ′ and heated in a vacuum or inert atmosphere. By heating, Ag diffuses into Pd and Pd-A
The g alloy film 12 is generated.
【００１８】[0018]
【実施例】実施例１ 図１に示すフローの試験装置を作り、Ｐｄ合金膜を試作
した。製造する合金箔連続シートの幅は、１００ｍｍと
し、製造速度は、０．１ｍ／ｓとした。ＳＵＳ３０４製
ダミーシートの前処理のために、室温下で３０秒間、王
水中に浸漬させた。図１のＰｄめっき装置３におけるＰ
ｄめっき浴の組成は、パラジウム４ｇ／Ｌ、硝酸アンモ
ニウム９０ｇ／Ｌ、亜硝酸ナトリウム１０ｇ／Ｌとし、
アンモニア水でｐＨ９に調整した。Ｐｄめっきの条件と
して、浴温を４５〜５０℃、電流密度を３Ａ／ｄｍ2 と
し、陽極をＰｔとした。Ａｇめっき槽７におけるＡｇめ
っき浴の組成は、シアン化銀４０ｇ／Ｌ、シアン化カリ
ウム６０ｇ／Ｌ、炭酸カリウム５０ｇ／Ｌとした。Ａｇ
めっきの条件として、浴温を２５℃、電流密度を１．０
Ａ／ｄｍ2 とし、陽極をＰｔとした。 EXAMPLE 1 A test device having the flow shown in FIG. 1 was made, and a Pd alloy film was trial-produced. The width of the alloy foil continuous sheet to be manufactured was 100 mm, and the manufacturing speed was 0.1 m / s. For pretreatment of the SUS304 dummy sheet, it was immersed in aqua regia at room temperature for 30 seconds. P in the Pd plating apparatus 3 of FIG.
d The composition of the plating bath was 4 g / L of palladium, 90 g / L of ammonium nitrate, and 10 g / L of sodium nitrite.
The pH was adjusted to 9 with aqueous ammonia. As conditions for Pd plating, the bath temperature was 45 to 50 ° C., the current density was 3 A / dm 2 , and the anode was Pt. The composition of the Ag plating bath in the Ag plating tank 7 was 40 g / L of silver cyanide, 60 g / L of potassium cyanide, and 50 g / L of potassium carbonate. Ag
The plating conditions were as follows: a bath temperature of 25 ° C. and a current density of 1.0
A / dm 2 and the anode was Pt.
【００１９】形成されたＰｄめっきの膜厚は、５μｍで
あり、また、Ｐｄめっきの上にめっきされたＡｇめっき
の膜厚は、１μｍであった。加熱処理炉１１での加熱条
件は、Ａｒガス雰囲気中で９００℃、２分間とした。製
造されたＰｄ合金箔の特性を調査したところ、水素透過
性能は、５００℃で２ｋｇｆ／ｃｍ2 であり、差圧を設
けた条件下では、Ｈ2 流量は４５ｍ3 Ｎ／ｍ 2 ｈであっ
た。このように、製造されたＰｄ合金箔は、十分に実用
可能な水素透過性を有することがわかった。また、Ｐｄ
合金箔の製造歩留まりは、約９０％であり、製造コスト
は、合金箔の単位面積当たりで、従来の冷間圧延法の１
／２程度と推定された。The thickness of the formed Pd plating is 5 μm.
Yes, and Ag plating plated on Pd plating
Was 1 μm. Heating strip in heating furnace 11
The condition was 900 ° C. for 2 minutes in an Ar gas atmosphere. Made
The characteristics of the produced Pd alloy foil were investigated,
Performance is 2kgf / cm at 500 ℃TwoAnd set the differential pressure
Under girder conditions, HTwoFlow rate is 45mThreeN / m Twoh
Was. Thus, the manufactured Pd alloy foil is sufficiently practical.
It has been found to have a possible hydrogen permeability. Also, Pd
The production yield of alloy foil is about 90%, and the production cost
Per unit area of the alloy foil is one of the conventional cold rolling method.
/ 2 was estimated.
【００２０】実施例２ ダミーシートの前処理に用いる処理液として、フッ酸と
硝酸の混合液を用いたこと、及び、ＡｇめっきＰｄ膜の
連続シートの加熱処理の方法として、図２に示すよう
に、洗浄槽１０を出た連続シート９を乾燥させ、巻き取
りロール１３によってロール状にした後、バッチタイプ
加熱処理炉１１’内で加熱する方法を採用したことを除
いては、実施例１と同様にして、Ｐｄ合金箔を製造し
た。なお、硝フッ酸（ＨＮＯ3 ＋１％ＨＦ）を用いたダ
ミーシートの前処理は、室温で３０秒間行ない、Ａｇめ
っきＰｄ膜のコイル９’の加熱処理条件は、Ａｒガス雰
囲気中で７００℃、３時間とした。得られた合金箔の特
性は、実施例１とほとんど変わらないものであった。 Example 2 FIG. 2 shows that a mixed solution of hydrofluoric acid and nitric acid was used as a treatment liquid used for pretreatment of a dummy sheet, and a method of heating a continuous sheet of an Ag-plated Pd film was as shown in FIG. Example 1 was repeated except that the continuous sheet 9 exiting the cleaning tank 10 was dried, rolled by a take-up roll 13, and then heated in a batch-type heat treatment furnace 11 '. In the same manner as in the above, a Pd alloy foil was manufactured. The pretreatment of the dummy sheet using nitric hydrofluoric acid (HNO 3 + 1% HF) was performed at room temperature for 30 seconds, and the heat treatment conditions for the Ag-plated Pd film coil 9 ′ were 700 ° C. in an Ar gas atmosphere. 3 hours. The properties of the obtained alloy foil were almost the same as those of Example 1.
【００２１】[0021]
【発明の効果】本発明によれば、薄くて欠陥のない安定
した品質の膜を製造することができる。また、連続シー
トとしてＰｄ箔（Ｐｄ膜）を製造するため、それに引き
続く作業の連続化が容易になり、Ｐｄ合金膜の生産性が
向上し、大幅なコストダウンが可能となる。According to the present invention, it is possible to produce a thin, defect-free and stable quality film. Further, since a Pd foil (Pd film) is manufactured as a continuous sheet, subsequent operations can be easily performed continuously, the productivity of the Pd alloy film can be improved, and a significant cost reduction can be achieved.
【図１】本発明のＰｄ合金箔の製造方法を実施するため
に用いる装置全体の一例を示す図である。FIG. 1 is a diagram showing an example of an entire apparatus used for carrying out a method for producing a Pd alloy foil of the present invention.
【図２】本発明のＰｄ合金箔の製造方法を実施するため
に用いる装置全体の一例を示す図である。FIG. 2 is a view showing an example of an entire apparatus used for carrying out the method for producing a Pd alloy foil of the present invention.
１ ダミーシート前処理装置 ２ ダミーシート ３ Ｐｄめっき装置 ４ 剥がしロール ５ Ｐｄ膜連続シート ６ 洗浄槽 ７ Ａｇめっき槽 ８ コンダクタロール ９ ＡｇめっきＰｄ膜の連続シート ９’ＡｇめっきＰｄ膜のコイル １０ 洗浄槽 １１ 連続式加熱処理炉 １１’バッチタイプ加熱処理炉 １２ Ｐｄ−Ａｇ合金膜シート １３ 巻き取りロール DESCRIPTION OF SYMBOLS 1 Dummy sheet pre-processing apparatus 2 Dummy sheet 3 Pd plating apparatus 4 Peeling roll 5 Pd film continuous sheet 6 Cleaning tank 7 Ag plating tank 8 Conductor roll 9 Continuous sheet of Ag plating Pd film 9 'Ag plating Pd film coil 10 Cleaning tank Reference Signs List 11 continuous heat treatment furnace 11 'batch type heat treatment furnace 12 Pd-Ag alloy film sheet 13 take-up roll
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平８−266876（ＪＰ，Ａ) 特開 平７−124453（ＪＰ，Ａ) 特開 平５−317662（ＪＰ，Ａ) 特開 平５−171487（ＪＰ，Ａ) 特開 平２−182889（ＪＰ，Ａ) 特開 平７−300689（ＪＰ，Ａ) 特開 平３−146122（ＪＰ，Ａ) 特開 昭47−33036（ＪＰ，Ａ) 特開 昭54−91781（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C25D 7/06 C25D 1/04 C25D 5/50 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-8-266876 (JP, A) JP-A-7-124453 (JP, A) JP-A-5-317662 (JP, A) 171487 (JP, A) JP-A-2-182889 (JP, A) JP-A-7-300689 (JP, A) JP-A-3-146122 (JP, A) JP-A-47-33036 (JP, A) JP-A-54-91781 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C25D 7/06 C25D 1/04 C25D 5/50
Claims (2)
続的に形成させる工程と、該Ｐｄ膜を該支持体から剥離
させた後、めっき法によって該Ｐｄ膜の両面にＡｇ膜を
形成させる工程と、Ａｇ膜を両面に形成させた該Ｐｄ膜
を、真空または不活性ガス雰囲気下で加熱処理して、Ｐ
ｄ合金箔を生成させる工程とを含むＰｄ合金箔の製造方
法。1. A step of continuously forming a Pd film on a support by a plating method, and forming an Ag film on both sides of the Pd film by a plating method after peeling the Pd film from the support. And heating the Pd film having the Ag film formed on both sides thereof in a vacuum or an inert gas atmosphere to obtain a Pd film.
producing a d-alloy foil.
成させたＰｄ膜を連続的に加熱処理することを特徴とす
る請求項１に記載のＰｄ合金箔の製造方法。 2. The heat treatment forms the Ag film on both sides.
Characterized by continuously heating the formed Pd film.
The method for producing a Pd alloy foil according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14565997A JP3316417B2 (en) | 1997-06-04 | 1997-06-04 | Method for producing Pd alloy foil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14565997A JP3316417B2 (en) | 1997-06-04 | 1997-06-04 | Method for producing Pd alloy foil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10330992A JPH10330992A (en) | 1998-12-15 |
| JP3316417B2 true JP3316417B2 (en) | 2002-08-19 |
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|---|---|---|---|
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| US7527661B2 (en) | 2005-04-18 | 2009-05-05 | Intelligent Energy, Inc. | Compact devices for generating pure hydrogen |
| JP2008062213A (en) * | 2006-09-11 | 2008-03-21 | Okuno Chem Ind Co Ltd | Method for producing hydrogen permeable membrane structure |
| JP5229503B2 (en) * | 2007-02-19 | 2013-07-03 | 三菱瓦斯化学株式会社 | Hydrogen purification method, hydrogen separation membrane, and hydrogen purification apparatus |
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