JPH09157856A - Metallic porous body and its production - Google Patents
Metallic porous body and its productionInfo
- Publication number
- JPH09157856A JPH09157856A JP32144695A JP32144695A JPH09157856A JP H09157856 A JPH09157856 A JP H09157856A JP 32144695 A JP32144695 A JP 32144695A JP 32144695 A JP32144695 A JP 32144695A JP H09157856 A JPH09157856 A JP H09157856A
- Authority
- JP
- Japan
- Prior art keywords
- chemical plating
- porous body
- metal
- resin
- porous
- 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.)
- Pending
Links
Landscapes
- Chemically Coating (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、電池用電極やフィルタ
ー等に用いられる金属多孔体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 metal porous body used for battery electrodes, filters and the like, and a method for producing the same.
【０００２】[0002]
【従来の技術】一般に金属多孔体の製造方法は、電気導
電性のない樹脂多孔体に導電処理を施し、この上に電気
メッキにより所定の金属量を付加し必要に応じて内部に
残存する樹脂分を焼却除去する手段を取っている。その
ほか、金属粉を焼結することにより得る手段もあるが、
含有気孔率等で不安定なため、好まれない。樹脂多孔体
には、樹脂発泡体、不織布、フェルト、織布などがあ
り、必要によってはこれらを組み合わせても用いられ
る。素材として特に指定されるものではないが、金属を
メッキした後焼却処理により除去できるものが好まれ
る。2. Description of the Related Art Generally, a method for producing a metal porous body is such that a resin porous body having no electrical conductivity is subjected to a conductive treatment, a predetermined amount of metal is added by electroplating on the resin, and a resin remaining inside as necessary. The means to incinerate and remove the minutes is taken. In addition, although there is a means to obtain it by sintering metal powder,
It is not preferred because it is unstable due to the content of porosity. The resin porous body includes a resin foam, a non-woven fabric, a felt, a woven fabric, and the like, and if necessary, they may be used in combination. Although not particularly specified as a material, a material that can be removed by incineration after plating metal is preferred.
【０００３】また、樹脂多孔体の取扱い上、特にシート
状のものにおいては剛性が高いと折れるのでしなやかな
状況を付与するために素材が高分子であると好ましい。
樹脂多孔体に導電性を付与する手段としては、金属粉
や、カーボン等を塗布することによる方法のほか、ドラ
イメッキと称されるカソードスパッタリング、イオンプ
レーティング、蒸着、プラズマコーティング等による手
法、また、化学メッキといわれる無電解メッキによる金
属コーティング等がある。本発明は、この化学メッキ法
を改善し、金属多孔体の品質を大幅に向上させるもので
ある。Further, in handling the porous resin body, particularly in the case of a sheet-like material, it is preferable that the material is a polymer in order to impart a supple condition since it breaks when the rigidity is high.
As a means for imparting conductivity to the resin porous body, in addition to a method of applying metal powder, carbon, etc., a method such as cathode sputtering called dry plating, ion plating, vapor deposition, plasma coating, or the like, , Metal plating by electroless plating called chemical plating. The present invention improves the chemical plating method and significantly improves the quality of the porous metal body.
【０００４】化学メッキ法は、樹脂多孔体のような導電
性のない素材に対しては、あらかじめ樹脂表面を活性化
させる必要がある。一般に用いられている方法として
は、樹脂多孔体を界面活性剤により親水化させ、水洗後
触媒を付着させ、さらに水洗してから触媒の活性化処理
をした後、化学メッキする手段が取られている。In the chemical plating method, it is necessary to activate the resin surface in advance for a non-conductive material such as a resin porous body. As a generally used method, a method of hydrophilizing a resin porous body with a surfactant, washing with water to attach a catalyst, further washing with water, activating the catalyst, and then performing chemical plating is taken. There is.
【０００５】[0005]
【発明が解決しようとする課題】ところが、触媒を付着
させる相手である樹脂多孔体は、その骨格が細く、コロ
イド状の触媒が付着し、乾燥すると樹脂表面でひび割れ
等が発生し、そのまま化学メッキすると化学メッキ槽中
で触媒の脱落等がおこり、均一な化学メッキができなく
なる。特に、化学メッキ槽ではメッキスピードを早める
ために、攪拌等の機械的動作を加え、拡散層をへらすこ
とを行っている。このため、槽内で触媒の付着した樹脂
多孔体は液の振動を加えられ、触媒の脱落をおこし易く
なる。However, the resin porous body to which the catalyst is attached has a thin skeleton and has a colloidal catalyst attached, and when dried, cracks or the like occur on the resin surface, and chemical plating is performed as it is. Then, the catalyst may fall off in the chemical plating tank and uniform chemical plating cannot be performed. In particular, in the chemical plating tank, in order to accelerate the plating speed, mechanical operations such as stirring are added to reduce the diffusion layer. For this reason, the resin porous body to which the catalyst adheres in the tank is liable to be vibrated by the liquid, and the catalyst is likely to drop off.
【０００６】触媒の脱落した部分は、化学メッキが進行
せず、ピンホール状にのこり、その後の電気メッキにお
いてもそのままメッキされない状態となる。出来上がっ
た金属多孔体はピンホールにより応力の集中等で欠陥の
原因となる。In the portion where the catalyst has fallen off, the chemical plating does not proceed, but remains in the shape of a pinhole, and is not directly plated in the subsequent electroplating. The completed metal porous body causes defects such as stress concentration due to pinholes.
【０００７】[0007]
【課題を解決するための手段】本発明は、上記のような
欠陥を残さない金属多孔体及びその製造方法を与えるも
のである。すなわち、樹脂多孔体を骨格としてこれに金
属メッキを施してなる金属多孔体の製造方法において、
該樹脂多孔体を導電処理するための化学メッキの前に化
学メッキ液をあらかじめ塗布した後に化学メッキを施
し、その後電気メッキを施すものである。その化学メッ
キ液を化学メッキする２０〜１２０秒前に塗布するのが
よく、その塗布の仕方は、シャワー、トラバース、ディ
ップ、フローの中から選ばれる。このようにして化学メ
ッキをすることにより、ピンホールのない金属多孔体を
得ることができる。The present invention provides a metal porous body which does not leave the above defects and a method for producing the same. That is, in the method for producing a metal porous body having a resin porous body as a skeleton and subjecting this to metal plating,
Prior to chemical plating for conducting a conductive treatment on the resin porous body, a chemical plating solution is applied in advance, chemical plating is performed, and then electroplating is performed. It is preferable to apply the chemical plating solution 20 to 120 seconds before the chemical plating, and the application method is selected from shower, traverse, dip and flow. By performing the chemical plating in this manner, a pinhole-free metal porous body can be obtained.
【０００８】[0008]
【作用】上記改善による金属多孔体の製造方法は、化学
メッキにおける工程の弱点を解決したものである。樹脂
多孔体に付着したコロイド状触媒は、化学メッキ槽に入
る前に付着効果を高めるために乾燥されるが、その結
果、表面にひび割れ等が発生し、その後の機械的操作
（曲げ、引っ張りなど）により拡大する。このような状
態で化学メッキ槽に入り、液の振動が加わることにより
一部が脱落する。脱落した部分は化学的活性を失うこと
で化学メッキに関与せず、その部分は化学メッキされず
にピンホール状に残る。その後の電気メッキにおいて、
金属でおおわれた部分がメッキされるのに対し、未メッ
キ部分となって残る。その結果、金属多孔体を曲げた
り、引っ張ったりして用いるとき、その部分に応力集中
し、割れや亀裂の原因になる。The method for producing a metal porous body by the above improvement solves the weak point of the process in chemical plating. The colloidal catalyst adhering to the resin porous body is dried before entering the chemical plating bath to enhance the adhering effect, but as a result, cracks etc. occur on the surface and subsequent mechanical operations (bending, pulling, etc.). ) To enlarge. In such a state, a part of the chemical plating bath falls off due to vibration of the liquid. The part that has fallen off does not participate in chemical plating because it loses its chemical activity, and that part remains as a pinhole without being chemically plated. In subsequent electroplating,
The metal-covered part is plated, while the unplated part remains. As a result, when the porous metal body is bent or pulled and used, stress concentrates on that portion, causing cracks or cracks.
【０００９】ところが、本発明のように化学メッキする
前に同じ化学メッキ液を触媒の付いた樹脂多孔体に塗布
しておくと、その時点で化学メッキの一部反応が進むと
共に表面がウエット状態となりひび割れが改善され、か
つ一部メッキの進行により触媒の脱落が防止されるので
前記のような欠陥部分がなくなる。但し、化学メッキす
る前の処理時間において、直前であると樹脂多孔体のウ
エット状態が進んでおらず、長すぎると化学メッキが一
旦停止してしまい、化学メッキ槽にはいってからメッキ
層の積み上げがなくなるので好ましくない。約１分前が
適当であり、２０〜１２０秒の範囲が好ましい。However, when the same chemical plating solution is applied to the porous resin body with the catalyst before the chemical plating as in the present invention, a partial reaction of the chemical plating proceeds and the surface is in a wet state at that time. The cracks are improved and the catalyst is prevented from falling off due to the progress of partial plating, so that the above-mentioned defective portions are eliminated. However, in the processing time before chemical plating, the wet state of the resin porous body has not progressed immediately before, and if it is too long, the chemical plating will stop temporarily and the plating layer will be piled up after entering the chemical plating tank. It is not preferable because it disappears. About 1 minute before is suitable, and the range of 20 to 120 seconds is preferable.
【００１０】また、樹脂多孔体にメッキ液を塗布する手
段であるが、メッキ槽入り口におけるシャワーによる方
法、ノズルを樹脂多孔体シートの幅に合わせて左右に振
るトラバース方法、メッキ槽に入る前に一旦シートをた
るませ、メッキ液に漬け込むディップ方法、シートをガ
イドに通した上でそのガイド中にメッキ液を流すことに
よりシートを湿らすフロー方法等がある。いずれも液を
強くかけると触媒を脱落させる恐れがあるから、おだや
かにかけることが肝要である。また、使ったメッキ液は
化学メッキ槽に回収するのが無駄を省くと同時に、塗布
するメッキ液は化学メッキ槽の補給液として用いられ
る。The means for applying the plating solution to the porous resin body includes a shower method at the entrance of the plating tank, a traverse method in which the nozzle is swung to the left and right according to the width of the porous resin sheet, and before entering the plating tank. There are a dipping method in which the sheet is once slackened and immersed in the plating solution, a flow method in which the sheet is passed through a guide and then the plating solution is flown into the guide to moisten the sheet. In either case, if the solution is strongly applied, the catalyst may fall off, so it is important to apply gently. In addition, it is wasteful to collect the used plating solution in the chemical plating tank, and at the same time, the plating solution to be applied is used as a replenishing solution for the chemical plating tank.
【００１１】このようにして樹脂多孔体に化学メッキを
行うことにより、触媒の脱落を防止し、かつ化学メッキ
を先行して進められるので、短時間で化学メッキを行え
る。その結果として、電気メッキにおけるピンホールの
ような欠陥を作らず品質の良い金属多孔体を得ることが
できる。By performing the chemical plating on the porous resin body in this manner, it is possible to prevent the catalyst from falling off and to proceed with the chemical plating in advance, so that the chemical plating can be performed in a short time. As a result, it is possible to obtain a high-quality metal porous body without producing defects such as pinholes in electroplating.
【００１２】[0012]
【実施例】図１に実施例の概要図を示す。触媒を付着し
た樹脂多孔体シート１にはポリウレタン製の発泡体で２
ｍｍ厚みのものを用い、化学メッキ槽に入る前にシャワ
ー２で化学メッキ液（ＮｉＳＯ4)をかけられ、化学メッ
キの進行と同時に乾燥したシートをウエットにし、触媒
の脱落を押さえる。シートのスピードを調節し、シャワ
ーから化学メッキ槽の液面に到達する時間を１分にし
た。シャワーに用いたメッキ液は化学メッキ槽３に流れ
込むようにした。EXAMPLE FIG. 1 shows a schematic diagram of an example. Polyurethane foam is used for the porous resin sheet 1 to which the catalyst is attached.
Using a sheet having a thickness of mm, a chemical plating solution (NiSO 4 ) is applied in the shower 2 before entering the chemical plating tank, and the dry sheet is wetted at the same time as the progress of the chemical plating to prevent the catalyst from falling off. The speed of the sheet was adjusted, and the time required to reach the liquid surface of the chemical plating tank from the shower was set to 1 minute. The plating solution used for the shower was made to flow into the chemical plating tank 3.
【００１３】化学メッキ槽３の中を約１０分で通過した
後、シートは水洗槽４で水洗され、ドライヤー５で水切
りした後、乾燥炉６で乾燥される。乾燥炉６の代わりに
直接電気メッキに送ることもできる。電気メッキにサプ
ライする化学メッキ完了後のＮｉ金属厚みは０．４５ミク
ロンであった。電気メッキによりシートはＮｉ金属厚みを
２０ミクロンまで付着させ、その後焼却炉で樹脂分の除去及
び還元炉でＮｉ金属の還元を行い、Ｎｉ金属多孔体を得
た。その目付け量は１０００ｇ／ｍ2であった。After passing through the chemical plating tank 3 in about 10 minutes, the sheet is washed in a water washing tank 4, drained by a dryer 5, and then dried in a drying furnace 6. Instead of the drying furnace 6, it is also possible to directly send to electroplating. The Ni metal thickness after the completion of the chemical plating supplied to the electroplating was 0.45 μm. By electroplating, the sheet was made to adhere to a Ni metal thickness of 20 μm, and then the resin component was removed in an incinerator and the Ni metal was reduced in a reducing furnace to obtain a Ni metal porous body. The basis weight was 1000 g / m 2 .
【００１４】（比較例） 実施例と同じ樹脂多孔体シー
ト１を用い、シートのスピードも同一にした。実施例と
違うところはシャワー２による化学メッキ液をかけなか
った。化学メッキ槽３及び水洗槽４また乾燥炉６を経て
化学メッキ完了後のＮｉ金属厚みは０．４ミクロンであっ
た。実施例に比べやや厚みが小さいのはシャワーの効果
である。その後、電気メッキによりＮｉ金属厚みを実施
例と同じ厚み２０ミクロンに調整し、焼却及び還元は実施例
と同様にした。目付け量は１０００ｇ／ｍ2であり、ほ
ぼ実施例と同じとなった。(Comparative Example) The same resin porous sheet 1 as in the example was used, and the speed of the sheet was the same. The difference from the example was that the chemical plating solution by the shower 2 was not applied. The thickness of the Ni metal after completion of the chemical plating through the chemical plating tank 3, the water washing tank 4 and the drying furnace 6 was 0.4 μm. The effect of the shower is that the thickness is slightly smaller than in the examples. Thereafter, the Ni metal thickness was adjusted to the same thickness of 20 μm as in the example by electroplating, and incineration and reduction were performed in the same manner as in the example. The basis weight was 1000 g / m 2 , which was almost the same as in the example.
【００１５】実施例と比較例の金属多孔体シートを１０
０ｍｍ角に切り出し、電池用極板と同様に樹脂の不織布
シートを挟み、渦巻状に丸めた後、実体顕微鏡（８倍）
で金属多孔体の表面を観察した。ひび割れの数を見たと
ころ実施例では見られないひび割れが比較例では５カ所
見つかった。これは実施例の品質の安定性を示してい
る。10 porous metal sheets of Examples and Comparative Examples were prepared.
Cut into 0 mm square, sandwich a non-woven fabric sheet of resin in the same manner as a battery electrode plate, and roll it into a spiral shape, then use a stereomicroscope (8x)
The surface of the metal porous body was observed with. When the number of cracks was checked, five cracks which were not seen in the example were found in the comparative example. This shows the stability of the quality of the examples.
【００１６】[0016]
【発明の効果】本願発明によれば、品質の安定な金属多
孔体を得ることができ、かつ電気メッキの前処理が短時
間で品質良く行われ、その結果、電気メッキの時間が短
くできることになり、経済的にも適した製造方法をあた
えるものである。According to the present invention, it is possible to obtain a porous metal body of stable quality, and pretreatment of electroplating is performed in a short time with good quality, and as a result, electroplating time can be shortened. Therefore, the manufacturing method is economically suitable.
【図１】本願発明の実施例の１例を示す構成図である。FIG. 1 is a configuration diagram showing an example of an embodiment of the present invention.
１：触媒を付着した樹脂多孔体 ２：塗布装置（シャワー） ３：化学メッキ槽 ４：水洗槽 ５：ドライヤー ６：乾燥炉 1: Porous resin with catalyst attached 2: Coating device (shower) 3: Chemical plating tank 4: Washing tank 5: Dryer 6: Drying furnace
Claims (4)
キを施してなる金属多孔体の製造方法において、前記樹
脂多孔体を導電処理するための化学メッキの前に化学メ
ッキ液をあらかじめ塗布した後に化学メッキを施し、そ
の後電気メッキを施すことを特徴とする金属多孔体の製
造方法。1. A method for producing a metal porous body having a resin porous body as a skeleton and subjecting the resin porous body to metal plating, after applying a chemical plating solution in advance before chemical plating for conducting the conductive treatment of the resin porous body. A method for producing a porous metal body, which comprises performing chemical plating and then electroplating.
ッキするまでの時間が２０〜１２０秒である請求項１記
載の金属多孔体の製造方法。2. The method for producing a porous metal body according to claim 1, wherein the time from the application of the chemical plating solution to the chemical plating is 20 to 120 seconds.
ャワー、トラバース、ディップ、フローの方法から選ば
れるいずれかによるものである請求項１または請求項２
記載の金属多孔体の製造方法。3. The method for applying the chemical plating solution according to any one of shower, traverse, dip, and flow methods.
The method for producing a porous metal body described.
記載の製造方法により製造された金属多孔体。4. A metallic porous body manufactured by the manufacturing method according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32144695A JPH09157856A (en) | 1995-12-11 | 1995-12-11 | Metallic porous body and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32144695A JPH09157856A (en) | 1995-12-11 | 1995-12-11 | Metallic porous body and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09157856A true JPH09157856A (en) | 1997-06-17 |
Family
ID=18132656
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32144695A Pending JPH09157856A (en) | 1995-12-11 | 1995-12-11 | Metallic porous body and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09157856A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007197753A (en) * | 2006-01-25 | 2007-08-09 | Hokkaido Univ | Metallic thin film and method for producing the same |
-
1995
- 1995-12-11 JP JP32144695A patent/JPH09157856A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007197753A (en) * | 2006-01-25 | 2007-08-09 | Hokkaido Univ | Metallic thin film and method for producing the same |
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