JPH08225986A - Electrodeposition method and device therefor - Google Patents
Electrodeposition method and device thereforInfo
- Publication number
- JPH08225986A JPH08225986A JP7034111A JP3411195A JPH08225986A JP H08225986 A JPH08225986 A JP H08225986A JP 7034111 A JP7034111 A JP 7034111A JP 3411195 A JP3411195 A JP 3411195A JP H08225986 A JPH08225986 A JP H08225986A
- Authority
- JP
- Japan
- Prior art keywords
- base material
- electrodeposition
- plating
- metal
- preliminary
- 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
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 120
- 238000000034 method Methods 0.000 title claims description 35
- 239000000463 material Substances 0.000 claims abstract description 110
- 238000007747 plating Methods 0.000 claims abstract description 76
- 229910052751 metal Inorganic materials 0.000 claims abstract description 69
- 239000002184 metal Substances 0.000 claims abstract description 69
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 13
- 238000012546 transfer Methods 0.000 claims description 7
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 5
- 239000006260 foam Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 230000003313 weakening effect Effects 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Electroplating Methods And Accessories (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ニッケルカドミウム電
池，リチウム電池，ニッケル水素電池，燃料電池などの
各種電池の電極や、フィルタなどの用途に用いる金属多
孔体の製造に用いる電着方法とその装置に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrodeposition method for producing a metal porous body for use in electrodes such as electrodes of various batteries such as nickel-cadmium batteries, lithium batteries, nickel-hydrogen batteries and fuel cells, and filters, and the like. Regarding the device.
【０００２】[0002]
【従来の技術】上記目的に用いられる金属多孔体には、
基材としてスライスされたウレタンフォームシート，不
織布などが用いられる。例えばウレタンフォームシート
は、三次元網状組織の骨格を有しており、金属多孔体
は、ウレタンフォームシートの網状組織に予め導電化処
理を施し、その骨格表面に所定厚みの金属メッキを施す
ことによって得られる。不織布を基材に用いたときもそ
の要領は同じである。2. Description of the Related Art The metal porous body used for the above purpose is
Sliced urethane foam sheet, non-woven fabric, etc. are used as the base material. For example, a urethane foam sheet has a skeleton of a three-dimensional network structure, and the metal porous body is obtained by subjecting the network structure of the urethane foam sheet to electrical conductivity treatment in advance, and by plating the skeleton surface with a metal having a predetermined thickness. can get. The procedure is the same when a nonwoven fabric is used as the substrate.
【０００３】ところで、金属メッキ処理は、基材の網状
組織を骨格とし、組織に隙間を残してその表面全面にわ
たり均一に金属を電着する処理であり、単に平面上にメ
ッキを施す場合とは異なり、内部へメッキ液を浸透させ
て三次元の網状組織に金属メッキを行うものであるた
め、高度の技術が必要とされる。By the way, the metal plating treatment is a treatment in which the network structure of the base material is used as a skeleton and a metal is electrodeposited uniformly over the entire surface leaving a gap in the structure. Differently, since a plating solution is permeated into the inside to perform metal plating on a three-dimensional network structure, a high level of technology is required.
【０００４】導電化処理は、誘電体である基材に導電剤
を塗布又は含浸させ、あるいは無電解メッキを施して基
材表面に金属を析出させる処理である。この導電化処理
によって基材の抵抗値が減少し、基材への金属メッキが
可能となる。次いで、基材に金属メッキ処理が施される
と、基材の三次元網状組織の網を骨格としてその周囲に
メッキ金属が付着して金属多孔体が得られ、後処理とし
て必要により基材を焼却処理すると、メッキ金属のみの
三次元網状組織の金属多孔体が得られる。The electroconductivity treatment is a treatment for coating or impregnating a base material which is a dielectric with a conductive agent, or electroless plating to deposit a metal on the surface of the base material. This conductivity treatment reduces the resistance value of the base material and enables metal plating on the base material. Then, when the base material is subjected to metal plating treatment, the metal of the three-dimensional network of the base material is used as a skeleton to deposit the plated metal around the periphery to obtain a metal porous body, and the base material is subjected to post-treatment as necessary. When incinerated, a metal porous body having a three-dimensional network structure containing only plated metal is obtained.
【０００５】[0005]
【発明が解決しようとする課題】しかし、基材の金属メ
ッキ処理に際し、前述の導電化処理を行ったのみでは、
基材の表層部と、内層部とでは電流密度のばらつきが起
り、これが三次元網状組織への均一な電着の妨げとなる
ことを指摘し、導電化処理後、二次の導電化処理とし
て、第１槽内で金属メッキ処理を施して基材の骨格表面
に０．１〜数μｍの厚みにメッキ金属を電着させ、次い
で第２槽内で予定厚みまで基材の両表面から本来の金属
メッキ処理を行う方法が提案された（特公昭５７−３９
３１７号公報参照）。However, when the metal plating treatment of the base material is performed only by the above-mentioned conductive treatment,
It was pointed out that the current density varies between the surface layer and the inner layer of the substrate, which hinders uniform electrodeposition on the three-dimensional network structure. , Metal plating is performed in the first tank to electrodeposit the plated metal on the skeleton surface of the base material to a thickness of 0.1 to several μm, and then in the second tank to the planned thickness from both surfaces of the base material. Has been proposed (Japanese Patent Publication No. 57-39).
317).
【０００６】この方法は、要するに、メッキ条件を改善
し、一般のメッキとほぼ同程度の電流密度の使用を可能
とし、メッキ液に浸潤した基材の総ての部分が同時に電
着を開始するようにし、あわせて、メッキ金属の電着速
度を向上させ、均一性のある金属多孔体を得ようとする
ものである。This method, in short, improves the plating conditions and enables the use of a current density almost equal to that of ordinary plating, and all parts of the base material soaked in the plating solution start electrodeposition at the same time. In addition, the electrodeposition rate of the plated metal is improved and a uniform metal porous body is obtained.
【０００７】ところが、この方法に関しては次のような
問題点が指摘されている。すなわち、上記方法では、第
１槽で二次導電化処理を低電流密度（数Ａ／ｄｍ2）で
行った後、第２槽で高電流密度（１０Ａ／ｄｍ2）にて
金属メッキ処理を行うと、低電流密度でメッキした金属
粒度に差異が生じ、粒界に歪みを発生するため、粒界強
度が弱くなり、多孔体の強度も弱く、形状が不安定とな
って、第２槽における両面のメッキ厚の不均一や局部的
な不均一を助長する結果となり、ひいては、シート状の
金属多孔体をコイル状に巻き取ることは不可能である、
というのである（特開平１−２９０７９２号参照）。However, the following problems have been pointed out regarding this method. That is, in the above method, after the secondary conductivity treatment is performed in the first tank at a low current density (several A / dm 2 ), the metal plating treatment is performed in the second tank at a high current density (10 A / dm 2 ). When this is done, differences occur in the grain size of the metal plated at a low current density, and distortion occurs at the grain boundaries, weakening the grain boundary strength, weakening the strength of the porous body, and making the shape unstable. In the result, it promotes non-uniformity or local non-uniformity of the plating thickness on both surfaces, and it is impossible to wind the sheet-shaped metal porous body into a coil.
(See Japanese Patent Application Laid-Open No. 1-290792).
【０００８】たしかに、得られた金属多孔体には局部的
にメッキ厚の不均一が生ずるのは事実のようである。発
明者らの実験によっても得られた金属多孔体には、基材
を横切ってクラックが生ずることを確認している。しか
し、電流密度の大小によるメッキ金属粒度の差異が原因
で粒界強度が低下するという事実は認められなかった。Certainly, it seems to be the case that the obtained porous metal body locally has a nonuniform plating thickness. It has been confirmed by the inventors' experiments that the metal porous body obtained also has cracks across the substrate. However, the fact that the grain boundary strength decreases due to the difference in the grain size of the plated metal depending on the magnitude of the current density was not recognized.
【０００９】メッキ厚に不均一が生ずる原因は、必ずし
も明らかではないが、特開平１−２９０７９２号が指摘
するようなメッキ条件の問題ではなく、原因は、メッキ
処理の方法にあるようである。つまり、特公昭５７−３
９３１７号公報に記載された金属多孔体の連続製造方法
において、二次の導電化処理は、図５に示すように、第
１槽中で給電ロール２０の円周面に接して転回する基材
Ｍの曲面に対して行われ、メッキ金属が基材Ｍの網状組
織に付着すると、組織が固定され、強度が増大する。し
かし、メッキ金属の付着量は給電ロール２０に接する基
材Ｍの内面側と、電極板２１に面する外面側とでは異な
り、外面側のメッキ金属の付着量が多いため、外面側が
硬くなり、基材Ｍは給電ロール２０の形状に沿って曲面
に賦型され、次いで給電ロール２０から離れて平坦面に
戻されると、メッキ金属の付着量が少ない内側の面が強
制的に引き伸されることになって、図６に示すように基
材Ｍの内側の面には基材を横切って細かい間隔で筋状の
クラック２２が平行に生ずる。The cause of non-uniformity in the plating thickness is not always clear, but it is not the problem of the plating conditions pointed out in JP-A-1-290792, but the cause seems to be the plating method. That is, Japanese Examined Japanese Patent Publication Sho 57-3
In the continuous method for producing a porous metal body described in Japanese Patent No. 9317, the secondary electroconductivity treatment is, as shown in FIG. 5, a base material that turns in contact with the circumferential surface of the power supply roll 20 in the first tank. When applied to the curved surface of M and the plated metal adheres to the network structure of the base material M, the structure is fixed and the strength is increased. However, the adhesion amount of the plating metal is different between the inner surface side of the base material M contacting the power supply roll 20 and the outer surface side facing the electrode plate 21, and since the adhesion amount of the plating metal on the outer surface side is large, the outer surface side becomes hard, When the base material M is shaped into a curved surface along the shape of the power feeding roll 20 and then returned from the power feeding roll 20 to a flat surface, the inner surface having a small amount of the deposited metal is forcibly stretched. As a result, as shown in FIG. 6, streaky cracks 22 are formed in parallel on the inner surface of the base material M across the base material at fine intervals.
【００１０】このようなクラック２２が生じたままの基
材Ｍが次に第２槽中に送り込まれ、高電流密度をもって
その両面から電着が行われると、クラック２２の部分が
断線状態となり、電極として使用するときに導電不良と
なるのではないかと思われる。When the base material M in which the cracks 22 have been generated as described above is then fed into the second tank and electrodeposition is performed with a high current density from both sides of the base material M, the cracks 22 are broken. It seems that conductivity may be poor when used as an electrode.
【００１１】本発明の目的は、基材の二次導電化処理と
しての予備電着処理において、基材にクラックを生じさ
せずに均一に金属メッキを行う方法とその装置を提供す
ることにある。An object of the present invention is to provide a method and apparatus for uniformly plating metal in a pre-electrodeposition treatment as a secondary electroconductivity treatment of a substrate without causing cracks in the substrate. .
【００１２】[0012]
【課題を解決するための手段】上記目的を達成するた
め、本発明による電着方法においては、予備電着工程
と、本電着工程とを有し、基材に連続送りを与えつつ基
材の三次元網状組織に金属をメッキする電着方法であっ
て、予備電着工程は、導電化処理が施された基材をメッ
キ液中に浸漬して金属メッキを行い、基材の組織表面に
金属イオンを析出させる工程であり、本電着工程は、基
材に析出したメッキ金属を核として基材の網状組織の表
面に所定厚みまで金属メッキを施す工程であり、予備電
着工程及び本電着工程中は、基材に直線方向の移動送り
を与えるものである。In order to achieve the above object, the electrodeposition method according to the present invention comprises a preliminary electrodeposition step and a main electrodeposition step, and the base material is provided while continuously feeding the base material. In the electrodeposition method of plating a metal on the three-dimensional network structure, the preliminary electrodeposition step is performed by immersing the base material subjected to the electroconductivity treatment in the plating solution to perform metal plating, and the surface of the base material structure Is a step of precipitating metal ions, the present electrodeposition step is a step of performing metal plating to a predetermined thickness on the surface of the network structure of the base material using the plated metal deposited on the base material as a nucleus, and the preliminary electrodeposition step and During the electrodeposition step, the base material is moved and fed in a linear direction.
【００１３】また、予備電着工程は、メッキ浴槽中で処
理を行い、予備電着処理を終了した基材をメッキ浴槽よ
り斜上方に引き上げ、次いで水平方向に誘導して本電着
工程に導入するものである。In the pre-electrodeposition step, the treatment is carried out in the plating bath, and the base material after the pre-electrodeposition treatment is pulled up obliquely above the plating bath and then guided horizontally to be introduced into the main electro-deposition step. To do.
【００１４】また、本発明による電着装置においては、
予備電着装置と、本電着装置とを有する電着装置であっ
て、予備電着装置は、２以上の給電ロールと、電極板と
をメッキ浴槽内に有し、各給電ロールは、陰極に印加さ
れ、ガイドロールと組合せて直列に配置されたものであ
り、各給電ロールとガイドロールとの組は、基材の搬送
ラインを形成し、メッキ浴槽内に導入された基材を支え
てメッキ浴槽内を直線方向に搬送するものであり、電極
板は、陽極に印加され、基材に電着すべき金属イオンの
供給源として各給電ロール間に跨って基材の搬送ライン
と向き合わせに配設されたものであり、本電着装置は、
２以上の給電ロールと、電着ユニットとを有し、２以上
の給電ロールは陰極に印加され、ガイドロールと組合せ
て直列に配列されたものであり、各給電ロールとガイド
ロールとの組は、基材の搬送ラインを形成し、予備電着
装置から送り出された基材を支えて直線方向に搬送する
ものであり、電着ユニットは、液溜めと、電極板とを有
し、給電ロールの列間に配置され、液溜めは、常時メッ
キ液を噴出させつつ基材と電極板とをメッキ液の噴流中
に浸漬させるものであり、電極板は、基材に電着すべき
金属イオンの供給源として基材の搬送ラインを挾んでそ
の両側に配置されたものである。In the electrodeposition apparatus according to the present invention,
An electrodeposition apparatus having a preliminary electrodeposition apparatus and the present electrodeposition apparatus, wherein the preliminary electrodeposition apparatus has two or more power feed rolls and an electrode plate in a plating bath, and each power feed roll is a cathode. Applied to the guide rolls and arranged in series in combination with the guide rolls, and each pair of the power feed rolls and the guide rolls forms a base material transport line and supports the base material introduced into the plating bath. It conveys in the plating bath in a straight line direction.The electrode plate is applied to the anode and faces the conveyance line of the base material across each power supply roll as a supply source of metal ions to be electrodeposited on the base material. The electrodeposition device is
Two or more power feeding rolls and an electrodeposition unit are provided, and the two or more power feeding rolls are applied to the cathode and are arranged in series in combination with the guide rolls. , A carrier line is formed, and the carrier sent from the preliminary electrodeposition device is supported and conveyed in a linear direction. The electrodeposition unit has a liquid reservoir and an electrode plate, and a power supply roll. The liquid reservoir is arranged between the columns to immerse the base material and the electrode plate in the jet of the plating solution while constantly ejecting the plating solution, and the electrode plate is a metal ion to be electrodeposited on the base material. It is arranged on both sides of the base material transport line as a supply source of the.
【００１５】[0015]
【作用】導電化処理された基材は、予備電着工程，本電
着工程を経て基材の三次元網状組織に予定厚みにメッキ
金属が電着される。予備電着工程においては、基材はメ
ッキ浴中に浸漬され、複数の給電ロール間を跨って直線
方向に移動送りが与えられる間に電極板から金属イオン
が供給され、基材の組織の表面にメッキ金属が均等に付
着する。予備電着工程を経た基材は、緩やかな角度で上
方に引き上げられ、次いで本電着工程に導入され、給電
ロールの列上を直線方向に移動し、メッキ液の噴流を受
けながら、対の電極板間を移動する間にメッキ金属が所
定厚みに電着される。In the electroconductive substrate, the plating metal is electrodeposited to the predetermined thickness on the three-dimensional network structure of the substrate through the preliminary electrodeposition process and the main electrodeposition process. In the pre-electrodeposition process, the base material is immersed in a plating bath, metal ions are supplied from the electrode plate while being fed in a linear direction across a plurality of power supply rolls, and the surface of the base material structure is supplied. The plated metal adheres evenly to the. The base material that has undergone the preliminary electrodeposition process is pulled upward at a gentle angle, then introduced into the main electrodeposition process, moves linearly on the row of the power supply rolls, receives the jet of the plating solution, and The plating metal is electrodeposited to a predetermined thickness while moving between the electrode plates.
【００１６】予備電着工程では、基材を曲面に変形させ
ないため、表面の電着密度に疎密の差が生ぜず、基材全
面に均一に予備電着が行われ、予備電着工程終了後は、
僅かに上傾方向に引出されて引き続き直線移動しつつ本
電着処理が行われ、本電着工程では予備電着処理によっ
て析出したメッキ金属を核として基材の三次元網状組織
の全表面に均等に所定厚みにメッキ金属を電着できる。In the pre-electrodeposition step, since the base material is not deformed into a curved surface, there is no difference in the density of electrodeposition on the surface, and the pre-electrodeposition is uniformly performed on the entire surface of the base material. Is
The main electrodeposition treatment is performed while being pulled out slightly in the upward tilt direction and continuously moving linearly.In the main electrodeposition process, the plating metal deposited by the pre-electrodeposition treatment is used as a nucleus to cover the entire surface of the three-dimensional network structure of the base material. The plated metal can be evenly electrodeposited to a predetermined thickness.
【００１７】[0017]
【実施例】以下に本発明の実施例を図によって説明す
る。図１において、本発明装置は、予備電着装置１と、
本電着装置２との組合せからなっているものである。Embodiments of the present invention will be described below with reference to the drawings. In FIG. 1, the device of the present invention comprises a preliminary electrodeposition device 1 and
It is a combination with the present electrodeposition apparatus 2.
【００１８】予備電着装置１は、図２のようにメッキ浴
槽３内に形成する基材の搬送ラインＬに沿って、直列に
配列された複数の給電ロール４と電極板５とを有するも
のである。各給電ロール４は一方向に回転駆動され、そ
の下周面には、基材Ｍを支えて送り方向に誘導するガイ
ドローラ６を配設している。電極板５は、両給電ロール
４，４間に跨って、搬送ラインＬの下方に配置されたも
のである。The preliminary electrodeposition apparatus 1 has a plurality of power supply rolls 4 and an electrode plate 5 which are arranged in series along a substrate transfer line L formed in the plating bath 3 as shown in FIG. Is. Each power feeding roll 4 is driven to rotate in one direction, and a guide roller 6 that supports the base material M and guides it in the feeding direction is disposed on the lower peripheral surface thereof. The electrode plate 5 is arranged below the transport line L across the power feeding rolls 4 and 4.
【００１９】本電着装置２は、給電ロール７と、電着ユ
ニット８との組合せである。給電ロール７は、メッキ浴
槽３から引き出された基材Ｍの搬送ラインＬに沿って一
定間隔毎に直列に配列され、各々の給電ロール７はその
上周面に、基材Ｍを支えて送り方向に誘導するガイドロ
ーラ９を配設している。The present electrodeposition apparatus 2 is a combination of a power supply roll 7 and an electrodeposition unit 8. The power supply rolls 7 are arranged in series at regular intervals along the transfer line L of the base material M drawn from the plating bath 3, and each of the power supply rolls 7 supports the base material M and feeds the upper peripheral surface thereof. A guide roller 9 that guides in the direction is arranged.
【００２０】電着ユニット８は、図３のように液溜め１
０と、対の電極板１１とを有している。液溜め１０は、
容器１２と容器１２上の搬送ラインＬの前後対向壁の上
下段に設置した対のローラ１３，１３との組合せからな
り、容器１２内には、メッキ液槽１５内のメッキ液をポ
ンプ１６で汲み上げて常時供給され、メッキ液は、容器
１２上に噴流し、その液面を上段ロール１３の高さに保
っている。基材の搬送ラインＬは、その液面の範囲内に
形成するものである。対のローラ１３，１３は、基材Ｍ
の搬送用ガイドローラを兼ねている。また、対の電極板
１１は、液溜め１０に充満させたメッキ液の液面の厚さ
の範囲内で基材Ｍの搬送ラインＬを挾んでその上下に配
置されたものである。前後の上段ローラ１３及び容器１
２の両側縁から溢流するメッキ液は、メッキ液槽１５中
に返還している。The electrodeposition unit 8 has a liquid reservoir 1 as shown in FIG.
It has 0 and a pair of electrode plates 11. The liquid reservoir 10 is
It is composed of a container 12 and a pair of rollers 13, 13 installed at the upper and lower stages of the front and rear facing walls of the transfer line L on the container 12. Inside the container 12, a plating solution in a plating solution tank 15 is pumped by a pump 16. The plating liquid is pumped up and constantly supplied, and the plating liquid is jetted onto the container 12 to keep the liquid surface at the height of the upper roll 13. The transfer line L for the base material is formed within the range of the liquid surface thereof. The pair of rollers 13, 13 is a base material M.
Also serves as a guide roller for conveyance. In addition, the pair of electrode plates 11 are arranged above and below the transport line L of the base material M within the range of the thickness of the liquid surface of the plating liquid filled in the liquid reservoir 10. Front and rear upper rollers 13 and container 1
The plating liquid overflowing from both side edges of No. 2 is returned to the plating liquid tank 15.
【００２１】電着ユニット８は、図１のように給電ロー
ル７，７，…間に配置されている。実施例では４個の給
電ロールを用い、各ロール間に３基の電着ユニットを配
置した例を示している。The electrodeposition unit 8 is arranged between the power feeding rolls 7, 7, ... As shown in FIG. In the embodiment, four power feed rolls are used, and three electrodeposition units are arranged between the rolls.
【００２２】実施例において、予め導電化処理を施した
三次元網状組織をなすウレタンフォーム，不織布などを
基材Ｍとし、その一端をメッキ液が充填された予備電着
装置１のメッキ浴槽３内に浸漬し、各ガイドローラ６で
支え、水平姿勢を保たせて両給電ロール４，４間に直線
状に張り渡し、さらに、本電着装置２の給電ロール７と
ガイドローラ６，６間及び電着ユニット８を通し、水平
姿勢に張り渡して巻取り器１４に導く。この状態で各給
電ロール４及び７を回転駆動し、電極板５及び１１を陽
極，各給電ロールを陰極に印加して電着処理を開始す
る。In the embodiment, in the plating bath 3 of the preliminary electrodeposition apparatus 1 in which a urethane foam, a non-woven fabric or the like having a three-dimensional network structure which has been subjected to a conductivity treatment in advance is used as a base material M, and one end of which is filled with a plating solution. It is soaked in, and supported by each guide roller 6 and stretched linearly between both power feeding rolls 4 and 4 while maintaining a horizontal posture, and further between the power feeding roll 7 and the guide rollers 6 and 6 of the present electrodeposition device 2 and It passes through the electrodeposition unit 8 and is stretched horizontally to guide it to the winder 14. In this state, the power feed rolls 4 and 7 are rotationally driven to apply the electrode plates 5 and 11 to the anode and the power feed rolls to the cathode to start the electrodeposition process.
【００２３】予備電着工程において、導電化処理された
基材Ｍは、給電ロール４を通じて陰極となり、両給電ロ
ール４，４間を直線状に移動する間に電極板５から溶出
した金属イオン１７が図２のように基材Ｍの網状組織の
表面に電着する。予備電着工程で基材Ｍに付着する金属
イオンの電着量は０．１〜数μｍ程度の極く僅かであ
る。両給電ロール４，４間を経由した基材Ｍは、メッキ
浴槽３上に引き上げられ、次いで本電着装置２に導入さ
れ、給電ロール７とガイドローラ９間を直線状に送ら
れ、各電着ユニット８に順次導入される。電着ユニット
８においては、常時メッキ液が液溜め１０上に吹き上げ
られて液面が一定高さを保っており、基材Ｍはその液面
下を潜り抜ける際に、予備電着処理で基材Ｍの表面に析
出した金属を核として上下の電極板１１，１１から液中
に溶出した金属イオンが電着する。特にメッキ液は、噴
流を続けるため、その噴出圧を受けて金属イオンが基材
Ｍの三次元網状組織内へ強制的に導入され、基材Ｍ内に
深く浸透して三次元網状組織全体に電着が進行して金属
イオンが付着する。In the preliminary electrodeposition process, the electroconductive base material M becomes a cathode through the power feed roll 4, and metal ions 17 eluted from the electrode plate 5 while linearly moving between the power feed rolls 4 and 4. Is electrodeposited on the surface of the network of the base material M as shown in FIG. The electrodeposition amount of the metal ions attached to the base material M in the preliminary electrodeposition step is as small as about 0.1 to several μm. The base material M that has passed through between the power feeding rolls 4 and 4 is pulled up onto the plating bath 3 and then introduced into the electro-deposition apparatus 2, and is fed linearly between the power feeding roll 7 and the guide roller 9 for each electrode. It is sequentially introduced into the receiving unit 8. In the electrodeposition unit 8, the plating liquid is constantly blown up onto the liquid reservoir 10 to keep the liquid surface at a constant height, and when the base material M passes under the liquid surface, the base electrode is subjected to preliminary electrodeposition treatment. Using the metal deposited on the surface of the material M as nuclei, metal ions eluted in the liquid from the upper and lower electrode plates 11, 11 are electrodeposited. In particular, since the plating liquid continues to jet, metal ions are forcibly introduced into the three-dimensional network of the base material M under the jet pressure of the plating solution and penetrate deeply into the three-dimensional network of the base material M. Electrodeposition proceeds and metal ions adhere.
【００２４】本電着装置２では、基材Ｍが２以上の電着
ユニット８内を繰返し通過する間にその三次元網状組織
の全表面が均等に、且つ所要厚さに金属メッキされ、三
次元網状組織を骨格とする金属多孔体となる。本電着工
程を終了して得られた金属多孔体のシートは、巻取り器
１４にロール状に巻き取って電着処理を完了する。In the present electrodeposition apparatus 2, while the substrate M repeatedly passes through the two or more electrodeposition units 8, the entire surface of the three-dimensional network is uniformly and metal-plated to a required thickness, It becomes a metal porous body having a skeleton of the original network. The sheet of the metal porous body obtained after the completion of the electrodeposition step is wound into a roll on the winder 14 to complete the electrodeposition process.
【００２５】得られた金属多孔体は、次に空気中で加熱
し、基材を焼却すると三次元網状構造の金属のみの多孔
体となる。もっとも、基材の焼却は、電池の電極として
使用するときに必要とされる処理であり、フィルターな
どの用途に使用するときにはあえて基材を焼却する必要
はない。The metal porous body thus obtained is then heated in air to incinerate the base material to form a metal-only porous body having a three-dimensional network structure. However, the incineration of the base material is a treatment required when it is used as an electrode of a battery, and it is not necessary to incinerate the base material when it is used for applications such as a filter.
【００２６】本発明において、予備電着工程では、複数
の給電ロール間に渡って基材が直線方向に移動する間
に、少なくとも基材の組織の表面にメッキ金属の電着が
行われ、予備電着処理における基材の電着面の条件は同
じであるため、基材の表面にクラックが生ぜず、さらに
本電着工程においても、基材を直線方向に搬送しつつそ
の両面から所定厚みにメッキ金属を電着させるため、電
着量に不同が生ぜず、得られた金属多孔体に断線状態は
生じない。In the present invention, in the preliminary electrodeposition step, the plating metal is electrodeposited at least on the surface of the texture of the base material while the base material moves linearly across the plurality of power supply rolls, and the preliminary electrodeposition step is performed. Since the conditions of the electrodeposition surface of the base material in the electrodeposition treatment are the same, no cracks occur on the surface of the base material, and even in the main electrodeposition process, the base material is conveyed in a straight line direction while the predetermined thickness is applied from both sides. Since the plated metal is electrodeposited on the plate, the electrodeposition amount does not differ, and the obtained metal porous body is not broken.
【００２７】予備電着工程において、基材の組織に僅か
であってもメッキ金属が付着することにより、基材の表
面抵抗値が大幅に減少し、基材を本電着工程に導入した
ときには、予備電着処理によって基材面に形成されたメ
ッキ金属の僅かの電着膜が引き金となり、その電着膜を
核として比較的高い電流密度の下でメッキ金属が析出
し、三次元網状構造の基材の内部の組織にまで及んで均
一にメッキ金属を電着することができる。In the preliminary electrodeposition step, the surface resistance value of the base material is greatly reduced due to the adhesion of the plating metal to the structure of the base material even if it is slight, and when the base material is introduced into the main electrodeposition step. , A slight electrodeposition film of the plated metal formed on the surface of the base material by the preliminary electrodeposition treatment triggers, and the plated metal is deposited at a relatively high current density with the electrodeposited film as the nucleus, and the three-dimensional network structure is formed. The plated metal can be electrodeposited evenly over the internal structure of the base material.
【００２８】ウレタンフォーム（厚み１．６ｍｍ，幅４
００ｍｍ）を３００ｍｍφの給電ロール（送り速度１０
ｍ／ｈ）に沿わせ、電流密度１５Ａ／ｄｍ2で予備電着
処理（二次導電化処理）を行い、次いで電流密度２５Ａ
／ｄｍ2で本電着処理を行って、目付量５００〜６００
ｇ／ｍ2の金属多孔体を製造したところ、得られた金属
多孔体には約１ｃｍの間隔で基材を横切る方向のクラッ
ク（亀裂）が発生したが、本発明の方法によれば同一の
条件の下で得られた金属多孔体には目視では全くクラッ
ク（亀裂）の発生は認められなかった。Urethane foam (thickness 1.6 mm, width 4
00mm) 300mmφ power supply roll (feed speed 10
m / h), a pre-electrodeposition treatment (secondary conductivity treatment) is performed at a current density of 15 A / dm 2 , and then a current density of 25 A
This electrodeposition treatment is performed at / dm 2 , and the basis weight is 500 to 600.
When a porous metal body of g / m 2 was produced, cracks were generated in the obtained porous metal body in the direction crossing the substrate at intervals of about 1 cm, but the same method was used according to the method of the present invention. No cracks were visually observed in the porous metal body obtained under the conditions.
【００２９】この結果によって、本発明によれば、予備
電着工程においても大きな電流密度で電着が可能とな
り、したがって高速で電着処理ができることが分かる。From these results, it can be seen that according to the present invention, electrodeposition can be performed with a large current density even in the preliminary electrodeposition process, and therefore the electrodeposition process can be performed at high speed.
【００３０】以上実施例においては、基材Ｍの搬送ライ
ンＬの下方にのみ電極板５を設置した例を示したが、あ
るいは図４のように両給電ロール４，４間にも電極板５
を追加し、搬送ラインＬを挾んで基材Ｍの両面に電極板
５，５を設置して予備電着処理を行えば、基材Ｍの両面
にメッキ金属が析出して、後の本電着工程によって基材
の組織の全体に対して有効に電着処理を行うことができ
る。In the above embodiment, the electrode plate 5 is installed only below the conveying line L of the base material M, but as shown in FIG.
If the electrode plates 5 and 5 are installed on both sides of the base material M by sandwiching the transport line L and pre-electrodeposition treatment is performed, plated metal is deposited on both sides of the base material M and the subsequent main electrode The electrodeposition process can be effectively performed on the entire structure of the base material.
【００３１】[0031]
【発明の効果】以上のように本発明によるときには、基
材の三次元網状構造を変形させずに正規の形態である水
平姿勢を保たせて予備電着処理を行うため、メッキ金属
は基材組織表面に均等に付着し、基材にクラックが生ぜ
ず、本電着処理においても基材に直線方向に搬送しつつ
水平姿勢を保たせて電着するため、予備電着処理によっ
て析出したメッキ金属を引き金として三次元網状組織の
全表面にむらなくメッキ金属を所要厚みに析出して均一
で強度の大きい金属多孔体を製造できる。As described above, according to the present invention, the pre-electrodeposition treatment is carried out while maintaining the normal horizontal posture without deforming the three-dimensional network structure of the base material. It adheres evenly to the tissue surface and does not cause cracks in the base material.Even in this electrodeposition process, the plate is deposited in the pre-electrodeposition process because it is transported in a straight line direction to the base material and electrodeposited while maintaining a horizontal posture. It is possible to manufacture a metal porous body that is uniform and has high strength by uniformly depositing plated metal to a required thickness on the entire surface of the three-dimensional network by using metal as a trigger.
【００３２】また、本発明によるときには、予備電着工
程における基材の搬送ラインを直線状に設定したため、
直方形又は直方体の電極板を使用でき、メッキ浴槽内へ
の電極板の設置並びに浴槽内からの取り外しが容易とな
り、また、基材は２以上の給電ロール間に跨って直線状
に配置すればよいため、基材のセッティング並びに処理
中に基材が切れたときでも切断個所の発見，修復を容易
に行うことができる。また、本電着工程においても、処
理期間中は基材を平坦に保ち、メッキ液の噴流中で電着
させるため、基材内へ強制的にメッキ液を混入させて電
着効率を高めることができ、しかも、２以上の電着ユニ
ットを通してメッキ浴槽外で行うため、メッキ浴槽内に
基材を浸漬して処理を行う場合に比してそのメンテナン
スが容易である。Further, according to the present invention, since the carrier line for the base material in the preliminary electrodeposition step is set to be linear,
A rectangular or rectangular parallelepiped electrode plate can be used, which facilitates installation and removal of the electrode plate in the plating bath, and when the base material is linearly arranged across two or more power supply rolls. Therefore, even if the base material is cut during setting and processing of the base material, it is possible to easily find and repair the cut portion. Also in this electrodeposition process, the base material is kept flat during the treatment period and electrodeposition is carried out in the jet of the plating solution. Therefore, the plating solution is forcibly mixed into the base material to improve the electrodeposition efficiency. Moreover, since the treatment is performed outside the plating bath through two or more electrodeposition units, the maintenance is easier than when the substrate is immersed in the plating bath for the treatment.
【図１】本発明の一実施例を示す装置の断面図である。FIG. 1 is a sectional view of an apparatus showing an embodiment of the present invention.
【図２】予備電着処理によって、基材に析出したメッキ
金属の付着要領を示す図である。FIG. 2 is a diagram showing an adhesion procedure of a plating metal deposited on a base material by a preliminary electrodeposition process.
【図３】電着ユニットの拡大図である。FIG. 3 is an enlarged view of an electrodeposition unit.
【図４】予備電着処理の他の実施例を示す図である。FIG. 4 is a diagram showing another embodiment of the preliminary electrodeposition process.
【図５】従来技術の問題点を示す図である。FIG. 5 is a diagram showing a problem of the related art.
【図６】クラックが発生した基材を示す図である。FIG. 6 is a diagram showing a base material in which cracks have occurred.
１ 予備電着装置 ２ 本電着装置 ３ メッキ浴槽 ４ 給電ロール ５ 電極板 ６ ガイドローラ ７ 給電ロール ８ 電着ユニット ９ ガイドローラ １０ 液溜め １１ 電極板 １２ 容器 １３ ローラ １４ 巻取り器 １５ メッキ液槽 １６ ポンプ １７ 金属イオン 1 Preliminary electrodeposition device 2 Main electrodeposition device 3 Plating bath 4 Feed roll 5 Electrode plate 6 Guide roller 7 Feed roll 8 Electroplating unit 9 Guide roller 10 Liquid reservoir 11 Electrode plate 12 Container 13 Roller 14 Winder 15 Plating liquid tank 16 pumps 17 metal ions
Claims (3)
基材に連続送りを与えつつ基材の三次元網状組織に金属
をメッキする電着方法であって、 予備電着工程は、導電化処理が施された基材をメッキ液
中に浸漬して金属メッキを行い、基材の組織表面に金属
イオンを析出させる工程であり、 本電着工程は、基材に析出したメッキ金属を核として基
材の網状組織の表面に所定厚みまで金属メッキを施す工
程であり、 予備電着工程及び本電着工程中は、基材に直線方向の移
動送りを与えることを特徴とする電着方法。1. A preliminary electrodeposition process and a main electrodeposition process are provided.
An electrodeposition method for plating a metal on a three-dimensional network of a base material while continuously feeding the base material, wherein the pre-electrodeposition step is performed by immersing the base material subjected to a conductive treatment in a plating solution. This is a step of performing metal plating to deposit metal ions on the tissue surface of the base material.This electrodeposition step uses the plated metal deposited on the base material as a nucleus to perform metal plating on the surface of the network structure of the base material to a predetermined thickness. The electrodeposition method is a step of applying, and during the preliminary electrodeposition step and the main electrodeposition step, the substrate is fed by linear movement.
行い、予備電着処理を終了した基材をメッキ浴槽より斜
上方に引き上げ、次いで水平方向に誘導して本電着工程
に導入することを特徴とする請求項１に記載の電着方
法。2. The preliminary electrodeposition step is performed in a plating bath, and the base material after the preliminary electrodeposition treatment is pulled up obliquely above the plating bath and then guided horizontally to be introduced into the main electrodeposition step. The electrodeposition method according to claim 1, wherein
電着装置であって、 予備電着装置は、２以上の給電ロールと、電極板とをメ
ッキ浴槽内に有し、 各給電ロールは、陰極に印加され、ガイドロールと組合
せて直列に配置されたものであり、 各給電ロールとガイドロールとの組は、基材の搬送ライ
ンを形成し、メッキ浴槽内に導入された基材を支えてメ
ッキ浴槽内を直線方向に搬送するものであり、 電極板は、陽極に印加され、基材に電着すべき金属イオ
ンの供給源として各給電ロール間に跨って基材の搬送ラ
インと向き合わせに配設されたものであり、 本電着装置は、２以上の給電ロールと、電着ユニットと
を有し、 ２以上の給電ロールは陰極に印加され、ガイドロールと
組合せて直列に配列されたものであり、 各給電ロールとガイドロールとの組は、基材の搬送ライ
ンを形成し、予備電着装置から送り出された基材を支え
て直線方向に搬送するものであり、 電着ユニットは、液溜めと、電極板とを有し、給電ロー
ルの列間に配置され、 液溜めは、常時メッキ液を噴出させつつ基材と電極板と
をメッキ液の噴流中に浸漬させるものであり、 電極板は、基材に電着すべき金属イオンの供給源として
基材の搬送ラインを挾んでその両側に配置されたもので
あることを特徴とする電着装置。3. An electrodeposition apparatus having a preliminary electrodeposition apparatus and the present electrodeposition apparatus, wherein the preliminary electrodeposition apparatus has two or more power supply rolls and an electrode plate in a plating bath. The power supply roll was applied to the cathode and was arranged in series in combination with the guide roll, and each power supply roll and guide roll pair formed a substrate transfer line and was introduced into the plating bath. It supports the base material and conveys it linearly in the plating bath.The electrode plate is a source of metal ions that are applied to the anode and should be electrodeposited on the base material. The electro-deposition apparatus has two or more power feed rolls and an electrodeposition unit, and the two or more power feed rolls are applied to a cathode and are combined with a guide roll. The power supply rolls and guides are arranged in series. The pair with the roll forms a base material transfer line, and supports the base material sent from the preliminary electrodeposition device to transfer the base material in a linear direction.The electrodeposition unit connects the liquid reservoir and the electrode plate. It is provided between the rows of the power supply rolls, and the liquid reservoir is for constantly ejecting the plating solution and immersing the base material and the electrode plate in the jet flow of the plating solution. An electrodeposition device characterized in that it is arranged on both sides of a carrier line of a base material as a supply source of metal ions to be deposited.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7034111A JPH08225986A (en) | 1995-02-22 | 1995-02-22 | Electrodeposition method and device therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7034111A JPH08225986A (en) | 1995-02-22 | 1995-02-22 | Electrodeposition method and device therefor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08225986A true JPH08225986A (en) | 1996-09-03 |
Family
ID=12405169
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7034111A Pending JPH08225986A (en) | 1995-02-22 | 1995-02-22 | Electrodeposition method and device therefor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08225986A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005108647A1 (en) * | 2004-05-06 | 2005-11-17 | Mitsui Mining & Smelting Co., Ltd. | Porous metal foil with carrier foil and process for producing the same |
| JP2014516121A (en) * | 2011-06-09 | 2014-07-07 | ユニヴェルシテ・ドゥ・レンヌ・１ | Processing method of felt element percolation by electrodeposition |
| JP2015137378A (en) * | 2014-01-21 | 2015-07-30 | 住友電気工業株式会社 | Method and apparatus for producing aluminum film |
-
1995
- 1995-02-22 JP JP7034111A patent/JPH08225986A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005108647A1 (en) * | 2004-05-06 | 2005-11-17 | Mitsui Mining & Smelting Co., Ltd. | Porous metal foil with carrier foil and process for producing the same |
| JP2014516121A (en) * | 2011-06-09 | 2014-07-07 | ユニヴェルシテ・ドゥ・レンヌ・１ | Processing method of felt element percolation by electrodeposition |
| JP2015137378A (en) * | 2014-01-21 | 2015-07-30 | 住友電気工業株式会社 | Method and apparatus for producing aluminum film |
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