JPH0375395A - Method and electrolytic cell for electrolytically plating metal surface - Google Patents
Method and electrolytic cell for electrolytically plating metal surfaceInfo
- Publication number
- JPH0375395A JPH0375395A JP2197576A JP19757690A JPH0375395A JP H0375395 A JPH0375395 A JP H0375395A JP 2197576 A JP2197576 A JP 2197576A JP 19757690 A JP19757690 A JP 19757690A JP H0375395 A JPH0375395 A JP H0375395A
- Authority
- JP
- Japan
- Prior art keywords
- anode
- cathode
- compartment
- electrolytic cell
- anode unit
- 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
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 14
- 239000002184 metal Substances 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims description 14
- 238000007747 plating Methods 0.000 title description 3
- 239000012528 membrane Substances 0.000 claims abstract description 24
- 238000005341 cation exchange Methods 0.000 claims abstract description 23
- 238000000576 coating method Methods 0.000 claims abstract description 16
- 239000003792 electrolyte Substances 0.000 claims abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 18
- 239000011248 coating agent Substances 0.000 claims description 14
- 239000011701 zinc Substances 0.000 claims description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 229910052725 zinc Inorganic materials 0.000 claims description 12
- 229910000831 Steel Inorganic materials 0.000 claims description 7
- 239000010959 steel Substances 0.000 claims description 7
- 238000013508 migration Methods 0.000 claims description 5
- 230000005012 migration Effects 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 3
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 claims description 3
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 claims description 3
- 238000009713 electroplating Methods 0.000 claims description 2
- 239000007769 metal material Substances 0.000 claims description 2
- 238000005192 partition Methods 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims 2
- 239000000155 melt Substances 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 230000008021 deposition Effects 0.000 abstract description 3
- 230000005484 gravity Effects 0.000 abstract description 2
- 230000008018 melting Effects 0.000 abstract description 2
- 238000002844 melting Methods 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract 1
- 238000004070 electrodeposition Methods 0.000 description 10
- 239000004020 conductor Substances 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
- C25D7/065—Diaphragms
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/002—Cell separation, e.g. membranes, diaphragms
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
- C25D17/12—Shape or form
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating Methods And Accessories (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、メッキ、特に、鋼板への鉄−亜鉛およびニッ
ケル−亜鉛の電着に関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to plating, in particular to the electrodeposition of iron-zinc and nickel-zinc onto steel sheets.
従来の技術
本出願人名で第２．６１７．５０９号として公表された
フランス国実用証出願には、陽イオン交換膜を用いた電
着方法が開示されている。この方法では、陰極電解液（
陰極液と呼ぶ）の組成とは異なる陽極電解液（陽極液と
呼ぶ〉組成が選択され、陰極電流密度を一定値に調節し
て、各陰極反応のファラデー効率を一定に維持し、それ
によって陽極電解液および陰極電解液の組成、ならびに
得られる被覆の組成をほぼ一定に維持している。BACKGROUND OF THE INVENTION French utility certificate application number 2.617.509 published in the name of the present applicant discloses an electrodeposition process using a cation exchange membrane. In this method, the catholyte (
A different composition of the anolyte (referred to as the anolyte) than that of the anolyte (referred to as the catholyte) is selected, and the cathode current density is adjusted to a constant value to maintain a constant faradaic efficiency for each cathode reaction, thereby The composition of the electrolyte and catholyte, as well as the composition of the resulting coating, are kept approximately constant.
発明が解決しようとする課題
しかし、１つまたは複数の可溶性陽極から供給されて溶
液中に存在する多数の元素を陰極上に電着させる場合に
、化学的な置換現象が電解液の組成に不均衡をもたらす
可能性がある。従って、長時間にわたって設備動作の定
常状態を維持するのは不可能である。さらに、可溶性陽
極の段階的消耗が、電解槽の幾何学的形状の変化を起こ
し、動作に影響を及ぼすことになる。Problem to be Solved by the Invention However, when a large number of elements present in solution are electrodeposited onto a cathode, provided by one or more soluble anodes, chemical displacement phenomena may occur that are inconsistent with the composition of the electrolyte. It has the potential to bring about equilibrium. Therefore, it is impossible to maintain a steady state of equipment operation for long periods of time. Furthermore, the gradual depletion of the soluble anode will cause changes in the electrolyzer geometry and affect its operation.
本発明の目的は、陽極液および陰極液の両方の組成の定
常状態を実現すると共に、電解槽の主な幾何学的特徴を
一定に維持することにより、製品の被覆の組成を一定に
維持することにある。更に、本発明の別の目的は、付着
させる被覆の性質の急速な変化を可能にすることである
。The aim of the invention is to achieve a steady state of the composition of both the anolyte and catholyte and to keep the composition of the product coating constant by keeping the main geometrical features of the electrolytic cell constant. There is a particular thing. Furthermore, another object of the invention is to enable rapid changes in the properties of the coating being deposited.
課題を解決するための手段
このため、本発明は、鋼板等の金属表面を連続的に被覆
するための電解槽の陽極ユニットであって、その陰極は
被覆すべき金属表面から成り、上記電解槽は、陽極区画
と陰極区画とを画定する陽イオン交換膜を備える形式で
あり、上記陽極ユニットが、少なくとも１つの陽極バス
ケットを備えるケースにより構成されて、上記電解槽の
上記陽極区画を形成しており、上記陽イオン交換膜は、
被覆すべき金属表面と向き合って位置するよう陽極ユニ
ットの面の少なくとも一部を形成しており、上記陽極バ
スケットは、陽極ユニットの電気的接続を確保するため
に不溶性の導電材料から構成されており、上記陽極ユニ
ットは更に、電解液中で溶けて陰極上に析出すべき金属
（１つまたは複数）の少なくとも１つのブロックに上記
陽極バスケットが常時接触している状態を確保する接触
確保手段と、上記ブロックを上記陽極バスケットに導入
するための導入手段とを備えていることを特徴とする陽
極ユニットを提供する。Means for Solving the Problems Therefore, the present invention provides an anode unit for an electrolytic cell for continuously coating a metal surface such as a steel plate, the cathode of which consists of the metal surface to be coated, is of the type comprising a cation exchange membrane defining an anode compartment and a cathode compartment, the anode unit being constituted by a case comprising at least one anode basket to form the anode compartment of the electrolytic cell. The above cation exchange membrane is
forming at least a part of the surface of the anode unit to be positioned facing the metal surface to be coated, said anode basket being constructed of an insoluble conductive material to ensure electrical connection of the anode unit; , the anode unit further comprises contact ensuring means for ensuring that the anode basket is always in contact with at least one block of metal(s) to be dissolved in the electrolyte and deposited on the cathode; and introduction means for introducing the block into the anode basket.
上記陽極バスケットは、上記ケースの内壁を形成するこ
とが望ましい。Preferably, the anode basket forms an inner wall of the case.
本発明はまた、１より大きいｎ個の元素Ｍ １（ｉ＝１
〜ｎ）から構成される被覆を形成するために、陽極ユニ
ットが上記した形式である電解槽を用いて実施すること
のできる金属材料の連続電解メッキ方法であって、
陽極区画と陰極区画を画定する陽イオン交換膜を各々備
え、陽極区画内で元素Ｍ＋を溶解させることのできるｎ
個の電解槽を、電気的に互いに並列に接続して使用し、
各電解槽の陽極区画には個別に陽極液を供給し、陰極区
画には直列に陰極液を供給して、それらの共通の陰極を
被覆すべき製品により構成し、
陰極液、陽極液ならびに製品表面上に付着される被覆の
組成を一定に維持するため、陽極液および陰極液の組成
を選択し、ならびに回路の各分路中の電流密度Ｊｌを
ただし、ｒ＝１は元素Ｍｉの陰極への析出のファラデー
効率を示し、Ｒ１１ｌは陽イオン交換膜を介した元素Ｍ
ｌの泳動効率を示す
となるように選択することを特徴とする方法を提供する
。The present invention also provides n elements M 1 (i=1
~n) A continuous electrolytic plating method for metallic materials that can be carried out using an electrolytic cell in which the anode unit is of the type described above, defining an anode compartment and a cathode compartment. each with a cation exchange membrane capable of dissolving element M+ in the anode compartment.
electrolytic cells electrically connected in parallel to each other,
The anode compartment of each electrolytic cell is supplied with anolyte individually, the catholyte compartment is supplied with catholyte in series, and the common cathode is composed of the product to be coated, the catholyte, the anolyte and the product. In order to keep the composition of the coating deposited on the surface constant, the compositions of the anolyte and catholyte are selected, and the current density Jl in each branch of the circuit, where r=1 to the cathode of element Mi, is R111 represents the faradaic efficiency of the precipitation of element M through the cation exchange membrane.
Provided is a method characterized in that the method is characterized in that the method is selected so as to exhibit a migration efficiency of 1.
後述するように、本発明による電解槽は、第一に、「陽
極バスケット」という名称で知られる構成による電解液
の再発生を確実にする可溶性陽極を備え、第二に、析出
層の組成を一定に維持することに寄与する陽イオン交換
膜を備える。As will be explained below, the electrolytic cell according to the invention firstly comprises a soluble anode that ensures the regeneration of the electrolyte by means of an arrangement known under the name "anode basket" and, secondly, the composition of the deposited layer is Equipped with a cation exchange membrane that contributes to maintaining a constant temperature.
前述の実用証出願に開示されたような電着装置において
、イオンＳ○、−をベースとする電解液と亜鉛または鉄
の可溶性陽極が使用されている場合には、化学的な置換
の問題が生じる。即ち、電解液中のＺｎ”／Ｆｅ”の比
が不均衡となり、動作時ｐＨが変化する。この問題は、
一方は亜鉛電極を備え、他方が鉄電極を備える２つの電
解槽を組み合わせることにより解決される。これら２つ
の電解槽は電気回路内に並列に接続される。２つの電解
槽のそれぞれの陽極区画は互いに通じていないのに対し
、陰極区画は互いに通じている。Chemical displacement problems arise when electrolytes based on ions S○,- and soluble zinc or iron anodes are used in electrodeposition devices such as those disclosed in the above-mentioned utility application. arise. That is, the ratio of Zn''/Fe'' in the electrolyte becomes unbalanced, and the pH changes during operation. This problem,
The solution is to combine two electrolytic cells, one with a zinc electrode and the other with an iron electrode. These two electrolyzers are connected in parallel in an electrical circuit. The anode compartments of each of the two electrolytic cells do not communicate with each other, whereas the cathode compartments communicate with each other.
以下に行う添付の図面を参照にした説明から、本発明は
さらによく理解されることであろう。The present invention will be better understood from the description given below with reference to the accompanying drawings.
実施例
第１図は、被覆すべき対象物に一定比率で鉄および亜鉛
の複合被覆をメッキすることのできる、２つの組合され
た電解槽を備える形式の、電着により鋼板等の金属対象
物を被覆する装置の原理図を示す。Embodiment FIG. 1 shows a metal object, such as a steel plate, by electrodeposition, in a type comprising two combined electrolytic cells, which makes it possible to plate the object to be coated with a composite coating of iron and zinc in a fixed ratio. The principle diagram of the device for coating is shown.
電解槽１および１°は、電着装置の電気回路において並
列に接続された２つのチャンバ中に配置される。合計電
流密度はＪで表す。電解槽１は、鉄陽極２を備え、密度
Ｊ７の電流が供給される。Electrolyzers 1 and 1° are arranged in two chambers connected in parallel in the electrical circuit of the electrodeposition device. The total current density is expressed in J. The electrolytic cell 1 includes an iron anode 2 and is supplied with a current having a density J7.
電解槽ｌ′は、亜鉛陽極２°を備え、密度Ｊ２．．の電
流が供給される。これら２つの陽極は、共通端これら２
つの電解槽の陰極は、共通であり、被覆される製品、例
えば、移動する鋼板３で構成される。これらの電解槽の
各々は、電解槽を２つの区画、即ち、陽極区画５２％５
’ａおよび陰極区画６ａ１６°ａにそれぞれ分割する陽
イオン交換膜４．４’ａを備える。これら電解槽は必ず
しも互いに同一とは限らない。陽イオン交換膜（ＣＥＭ
） は、同じ形式（例えば、デュポン ドウ ヌムー
ル（ＤＵＦＯＮＴ ＯＢ ＮＥＭＯＵＲ５）社により商
品名ナフィオン（ＮＡＦＩＯＮ）で販売されている膜）
であり、各電解槽の陰極区画６ａ１６°ａに向かう陽極
区画５ａ、５’ａ内の鉄および亜鉛の泳動効率Ｒ１゜お
よびＲＺ ｎによって特徴付けられる。陽極区画５ａ、
５°ａは互いに独立しているのに対し、陰極区画６ａ１
６”ａは互いに通じている。従って、２つの区画の陰極
液は同じ組成である。陽極液および陰極液の組成は一般
的には異なる。The electrolytic cell l' is equipped with a zinc anode 2° and has a density J2. ．． current is supplied. These two anodes have a common end
The cathodes of the two electrolyzers are common and consist of the product to be coated, for example a moving steel plate 3. Each of these electrolyzers divides the electrolyzer into two compartments, namely the anode compartment.
It is provided with a cation exchange membrane 4.4'a which is divided into a cation exchange membrane 4.4'a and a cathode compartment 6a16°a, respectively. These electrolytic cells are not necessarily identical to each other. Cation exchange membrane (CEM)
) are of the same type (e.g. membranes sold under the trade name NAFION by the company DUFONT OB NEMOUR5)
and is characterized by the migration efficiency R1° and RZ n of iron and zinc in the anode compartments 5a, 5′a towards the cathode compartments 6a16°a of each electrolytic cell. anode section 5a,
5°a are independent of each other, whereas the cathode compartments 6a1
6"a are in communication with each other. Therefore, the catholyte of the two compartments is of the same composition. The compositions of the anolyte and catholyte are generally different.
前述の実用証出願の説明によれば、これらの組成は、陰
極液の組成が一定に維持されるように選択される。この
目的のための条件（、′！、鉄の陰極への析出のファラ
デー効率（ｒＦａで表す）と、亜鉛の陰極への析出のフ
ァラデー効率（ｒＺｈで表す〉（ただし、ｒ：、＋ ｒ
’ｚ、＝ ｌ ）が、それぞれ陽イオン交換膜４ａおよ
び４”ａを介した鉄及び亜鉛の泳動効率Ｒ７およびＲ２
ｌ１に等しくなることである。According to the description in the aforementioned utility certificate application, these compositions are selected such that the composition of the catholyte remains constant. The conditions for this purpose (,′!, Faradic efficiency of the deposition of iron on the cathode (denoted rFa) and Faradic efficiency of the deposition of zinc on the cathode (denoted rZh)〉 (where r:, + r
'z, = l) are the migration efficiencies R7 and R2 of iron and zinc through the cation exchange membranes 4a and 4''a, respectively.
It is to be equal to l1.
システムが完全に定常状態で作動すること、即ち、陽極
液の組成が常に一定であることを確実にするためには、
陽極の鉄および亜鉛の開始陽極効率を泳動効率Ｒ８およ
びＲ２，、にそれぞれ等しくなるように調整するだけで
必要・充分である。このとなるようにすることにより達
成される。To ensure that the system operates completely in steady state, i.e. that the composition of the anolyte remains constant at all times,
It is necessary and sufficient to adjust the starting anodic efficiencies of the iron and zinc anodes to be equal to the migration efficiencies R8 and R2, respectively. This is achieved by making this happen.
この平衡条件は、所与の動作条件において、被覆すべき
製品上での鉄および亜鉛の被覆の安定した組成を実現す
るのに必要な、陽極液ならびに陰極液の一定した組成を
保証する。This equilibrium condition ensures, at given operating conditions, a constant composition of the anolyte and catholyte, which is necessary to achieve a stable composition of the iron and zinc coating on the product to be coated.
陰極上への被覆の組成の安定性を得るのに必要なもう１
つの条件は、陰極と陽イオン源と間の距離を一定の値に
維持することである。可溶性陽極を有するが陽イオン交
換膜はない通常の電解槽の場合には、陽極と陰極の間の
距離は、陽極が段階的に消耗する過程において機械的手
段によって一定に維持しなければならない。可溶性陽極
と陽イオン交換膜を有する電解槽の場合には、陽イオン
交換膜と陰極との間の距離が電解槽の動作を決定する。Another necessary step is to obtain stability of the coating composition on the cathode.
One condition is to maintain the distance between the cathode and the cation source at a constant value. In the case of conventional electrolytic cells with a soluble anode but without a cation exchange membrane, the distance between the anode and the cathode must be kept constant by mechanical means in the process of gradual consumption of the anode. In the case of electrolytic cells with a soluble anode and a cation exchange membrane, the distance between the cation exchange membrane and the cathode determines the operation of the electrolytic cell.
この距離を構造上一定に維持するのは容易である。It is easy to maintain this distance constant structurally.
ここに開示する実施例は、陰極として作用する製品上に
ｎ個の元素Ｍから成る被覆をメッキさせる場合に数行す
ることができる。このとき、ｎ個の電解槽が電気的に並
列に接続されて使用され、各電解槽の陽極区画は普通に
互いに独立し、全電解槽の陰極区画は互いに連通させら
れる。電解槽は、移動する被覆すべき製品の通路に順次
並べられ、各電解槽ｌは要素Ｍｌから構成される陽極を
備える。The embodiments disclosed here can be carried out in several cases when plating a coating of n elements M onto a product that acts as a cathode. In this case, n electrolytic cells are used electrically connected in parallel, the anode compartments of each electrolytic cell being generally independent of each other, and the cathode compartments of all electrolytic cells communicating with each other. The electrolytic cells are arranged one after the other in the path of the moving product to be coated, each electrolytic cell l being provided with an anode consisting of an element Ml.
一般的に、電着装置の回路の各分路の電流密度Ｊｌは、
式：
％式％
さらに、このような電着装置では、陽極区画中の溶液に
置かれる金属（１つまたは複数）の性質を急速に変える
ことが可能な電解槽を使用することもできる。In general, the current density Jl in each branch of the circuit of the electrodeposition device is:
Formula: %Formula % Furthermore, in such electrodeposition devices it is also possible to use electrolytic cells that are capable of rapidly changing the properties of the metal(s) placed in solution in the anode compartment.
この条件は、第２図に示したような「陽極バスケット」
を陽極区画に使用することにより満たすことができる。This condition is based on the “anode basket” shown in Figure 2.
can be met by using it in the anode compartment.
この陽極バスケット７は、チタン、白金、ジルコニウム
等のような不溶性の導電材料製の容器８から戊る。この
容器は、供給された陽極液を保持し、電流密度Ｊｌの電
流が供給され、すでに説明した電解槽の１つと同様な陽
極区画５ｂを懲戒する。陽極区画５ｂは、陽イオン交換
膜４ｂにより陰極区画６ｂから分離されている。陽イオ
ン交換膜を介して不可逆的に泳動する析出元素Ｍｌの補
充は、単純に重力により容器８の壁と接触して陽極バス
ケット内に置かれて可溶性陽極の機能を果たす元素の少
なくとも１つの消耗ブロック９が溶解することにより確
保される。陽極バスケットの下方部分には、消耗ブロッ
ク９を受けるくぼんだ底部が設けられ、これによって陽
極バスケラトと消耗ブロックとの接触を最良の方法で確
実にすると共に、消耗ブロックを陽イオン交換膜から離
している。容器は、電気絶縁性カバー１０で覆われてい
るのが望ましい。陽極バスケットの上部には、消耗ブロ
ック９を連続的または非連続的に供給するため開けるこ
とが可能な上部延長部１３が備えられている。陽イオン
交換膜４ｂの前に硬質材料製の格子乃至網１４が配置さ
れ、消耗ブロック９を供給する際に陽イオン交換膜を保
護している。振り開くことが可能な底部１５により、陽
極波の排出後、処理の終了時点で溶解されないまま残っ
たブロック９を除去することができる。陰極区画６ｂに
関しては、その底部は、−船釣場合の同様に、陰極とし
て作用する被覆すべき移動製品３で構成される。The anode basket 7 is removed from a container 8 made of an insoluble conductive material such as titanium, platinum, zirconium, etc. This vessel holds the supplied anolyte and is supplied with a current of current density Jl, discharging the anolyte compartment 5b similar to one of the electrolytic cells already described. The anode compartment 5b is separated from the cathode compartment 6b by a cation exchange membrane 4b. The replenishment of the precipitated element Ml, which migrates irreversibly through the cation exchange membrane, is simply due to the depletion of at least one of the elements placed in the anode basket in contact with the wall of the vessel 8 by gravity and acting as a soluble anode. This is secured by melting the block 9. The lower part of the anode basket is provided with a recessed bottom for receiving the consumable block 9, which ensures the best possible contact between the anode basket and the consumable block and also keeps the consumable block away from the cation exchange membrane. There is. Preferably, the container is covered with an electrically insulating cover 10. The upper part of the anode basket is provided with an upper extension 13 which can be opened for continuous or discontinuous supply of consumable blocks 9. A grid or mesh 14 made of hard material is arranged in front of the cation exchange membrane 4b to protect it when feeding the consumable block 9. The swing-open bottom part 15 makes it possible to remove the blocks 9 remaining undissolved at the end of the process after the discharge of the anodic wave. As for the cathode compartment 6b, its bottom is constituted by the moving product 3 to be coated, which acts as a cathode - as in the case of boat fishing.
この゛ように、電極の構造を変えることなく、消耗ブロ
ック９の性質を変えるだけで、析出させる金属の性質を
変えることができる。可溶性陽極が電極の構造と一体で
あるとき必要な大掛かりな操作はこのようにして避けら
れる。同様に、ＳＯ２−をベースとする電解液とＣｌ１
−をベースとする電解液とを、鉄と亜鉛の間の化学的な
置換がなく、電解液の交換以外に電着装置に変更を施す
必要がなく、交互に使用することが可能である。In this way, the properties of the metal to be deposited can be changed simply by changing the properties of the consumable block 9 without changing the structure of the electrode. The extensive manipulation required when the soluble anode is integral to the structure of the electrode is thus avoided. Similarly, SO2− based electrolytes and Cl1
- based electrolytes can be used alternately without any chemical substitution between iron and zinc and without the need to make any changes to the electrodeposition apparatus other than replacing the electrolyte.
同じ陽極バスケットには、異なる種類の消耗ブロックを
入れてもよい。化学的な置換を避けなければならない場
合には、すでに見てきたように、電気的に並列に接続さ
れた複数の電解槽を使用することができる。その場合、
陽極バスケットは各々異なる元素を収容している。The same anode basket may contain different types of consumable blocks. If chemical displacement is to be avoided, as we have already seen, it is possible to use several electrolytic cells electrically connected in parallel. In that case,
Each anode basket contains a different element.
本発明の範囲は、以上図示し、説明した実施例に制限さ
れるものではない。特に、１つの電解槽において、溶解
すべきブロック（１つまたは複数〉と接触する不溶性で
導電性の材料から構成される要素は、内壁を構成するこ
となく陽極区画中に単純に浸される簡単な仕切りあるい
は容器により構成することができる。The scope of the invention is not limited to the embodiments shown and described above. In particular, in one electrolytic cell, the elements consisting of insoluble and electrically conductive material in contact with the block(s) to be melted are simply immersed into the anode compartment without forming an inner wall. It can be composed of partitions or containers.
本発明は、鋼板等の金属製品を複数の元素、例えば、鉄
−亜鉛またはニッケル−亜鉛の合金で連続的に電解メッ
キする場合に適用することができる。INDUSTRIAL APPLICATION This invention can be applied when metal products, such as a steel plate, are electrolytically plated continuously with several elements, for example, iron-zinc or nickel-zinc alloy.
第１図は、本発明に従う電着装置の原理を概略的に示し
、第２図は、第１図に示す電着装置に望ましく使用され
る形式の電解槽を概略的に示す。
（主な参照番号）
１．１′・・電解槽、 ２・・鉄陽極、２”・・亜鉛
陽極、 ３・・鋼板、４ａ、４ａ’、４ｂ・・陽イ
オン交換膜、５ａ、５ａ’、５ ｂ ・・ｌｉ極区画、
６ａｓ６ａ”、６ ｂ ・・ｌｔ極区画、７・・陽極バ
スケット、
８・・容器 ９・・消耗ブロック、１０・・被
覆、 １３・・上部延長部、１４・・格子、
１５・・底部
陰楊衰FIG. 1 schematically shows the principle of an electrodeposition apparatus according to the invention, and FIG. 2 schematically shows an electrolytic cell of the type preferably used in the electrodeposition apparatus shown in FIG. (Main reference numbers) 1.1'... Electrolytic cell, 2... Iron anode, 2"... Zinc anode, 3... Steel plate, 4a, 4a', 4b... Cation exchange membrane, 5a, 5a' , 5 b...li polar section,
6as6a'', 6 b...lt electrode compartment, 7...anode basket, 8...container 9...consumable block, 10...coating, 13...upper extension, 14...grid,
15. Bottom Yin Yang Decline
Claims (8)
槽の陽極ユニットであって、その陰極は被覆すべき金属
表面から成り、上記電解槽は、陽極区画と陰極区画とを
画定する陽イオン交換膜を備える形式であり、上記陽極
ユニットが、少なくとも１つの陽極バスケットを備える
ケースにより構成されて、上記電解槽の上記陽極区画を
形成しており、上記陽イオン交換膜は、被覆すべき金属
表面と向き合って位置するよう陽極ユニットの面の少な
くとも一部を形成しており、上記陽極バスケットは、陽
極ユニットの電気的接続を確保するために不溶性の導電
材料から構成されており、上記陽極ユニットは更に、電
解液中で溶けて陰極上に析出すべき金属（１つまたは複
数）の少なくとも１つのブロックに上記陽極バスケット
が常時接触している状態を確保する接触確保手段と、上
記ブロックを上記陽極バスケットに導入するための導入
手段とを備えていることを特徴とする陽極ユニット。(1) An anode unit of an electrolytic cell for continuously coating a metal surface such as a steel plate, the cathode of which consists of the metal surface to be coated, and the electrolytic cell defines an anode compartment and a cathode compartment. the anode unit is constituted by a case comprising at least one anode basket to form the anode compartment of the electrolytic cell, the cation exchange membrane comprising a coating. forming at least a portion of the surface of the anode unit so as to be positioned facing the metal surface to which the anode unit is to be attached; The anode unit further comprises contact ensuring means for ensuring that said anode basket is in constant contact with at least one block of metal(s) to be dissolved in the electrolyte and deposited on the cathode, and said block. and introducing means for introducing the anode basket into the anode basket.
していることを特徴とする請求項１記載の陽極ユニット
。(2) The anode unit according to claim 1, wherein the anode basket forms an inner wall of the case.
素が、上記ケース内に位置する仕切りを構成することを
特徴とする請求項１記載の陽極ユニット。(3) The anode unit according to claim 1, wherein the conductive element ensuring electrical connection of the anode unit constitutes a partition located within the case.
から構成されていることを特徴とする請求項１記載の陽
極ユニット。(4) The anode unit according to claim 1, wherein the contact ensuring means is constituted by a concave bottom portion of the case.
蓋により構成されていることを特徴とする請求項１記載
の陽極ユニット。(5) The anode unit according to claim 1, wherein the introduction means is constituted by an openable and closable lid on the upper part of the case.
ら構成される被覆を形成するための金属材料の連続電解
メッキ方法であって、 陽極区画と陰極区画を画定する陽イオン交換膜を各々備
え、陽極区画内で元素Ｍ＿ｉを溶解させることのできる
ｎ個の電解槽を、電気的に互いに並列に接続して使用し
、上記陽極区画を請求項１記載の陽極ユニット内に設け
、各電解槽の陽極区画には個別に陽極液を供給し、陰極
区画には直列に陰極液を供給して、それらの共通の陰極
を被覆すべき製品により構成し、 陰極液、陽極液ならびに製品表面上に付着される被覆の
組成を一定に維持するため、陽極液および陰極液の組成
を選択し、ならびに回路の各分路中の電流密度Ｊ＿ｉを ▲数式、化学式、表等があります▼ ただし、ｒ■＿ｉは元素Ｍｉの陰極への析出のファラデ
ー効率を示し、Ｒ＿Ｍ＿ｉは陽イオン交換膜を介した元
素Ｍｉの泳動効率を示す となるように選択することを特徴とする方法。(6) A continuous electrolytic plating method of a metallic material to form a coating composed of n elements M_i (i=1 to n) greater than 1, the method comprising cation exchange defining an anode compartment and a cathode compartment. n electrolytic cells each comprising a membrane and capable of dissolving element M_i in an anode compartment are used electrically connected in parallel to each other, said anode compartment being provided in an anode unit according to claim 1; , the anode compartment of each electrolytic cell is supplied with an anolyte individually, the cathode compartment is supplied with a catholyte in series, and their common cathode is constituted by the product to be coated, the catholyte, the anolyte and In order to maintain a constant composition of the coating deposited on the product surface, the composition of the anolyte and catholyte is selected, as well as the current density J_i in each branch of the circuit ▲Mathematical formulas, chemical formulas, tables, etc.▼ However, the method is characterized in that r_i represents the faradic efficiency of precipitation of element Mi onto the cathode, and R_M_i represents the migration efficiency of element Mi through the cation exchange membrane.
金で被覆するため、一方が鉄またはニッケルを溶解し、
他方が亜鉛を溶解する２つの電解槽を使用することを特
徴とする請求項６記載の方法。(7) To coat the product with iron-zinc alloy or nickel-zinc alloy, one side melts the iron or nickel,
7. Process according to claim 6, characterized in that two electrolytic cells are used, the other dissolving the zinc.
された形式であることを特徴とする請求項６または７の
いずれか一項に記載の方法を実施するための装置。(8) An apparatus for carrying out the method according to claim 6 or 7, characterized in that the anode unit of the electrolytic cell is of the type described in claim 1 or 2.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8910117A FR2650304B1 (en) | 1989-07-25 | 1989-07-25 | METHOD OF ELECTROLYTIC COATING OF A METAL SURFACE, AND ELECTROLYSIS CELL FOR IMPLEMENTING IT |
| FR8910117 | 1989-07-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0375395A true JPH0375395A (en) | 1991-03-29 |
Family
ID=9384185
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2197576A Pending JPH0375395A (en) | 1989-07-25 | 1990-07-25 | Method and electrolytic cell for electrolytically plating metal surface |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0410919A1 (en) |
| JP (1) | JPH0375395A (en) |
| KR (1) | KR920002827A (en) |
| BR (1) | BR9003582A (en) |
| CA (1) | CA2021242A1 (en) |
| DD (1) | DD295730A5 (en) |
| FR (1) | FR2650304B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013011011A (en) * | 2011-05-30 | 2013-01-17 | Ebara Corp | Plating apparatus |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19834353C2 (en) * | 1998-07-30 | 2000-08-17 | Hillebrand Walter Gmbh & Co Kg | Alkaline zinc-nickel bath |
| DE19848467C5 (en) * | 1998-10-21 | 2006-04-27 | Walter Hillebrand Gmbh & Co. Kg Galvanotechnik | Alkaline zinc-nickel bath |
| FR2821627B1 (en) * | 2001-03-05 | 2003-09-12 | Lorilleux | METHOD AND DEVICE FOR ELECTROLYTICALLY PREPARING A SELECTIVE THICK DEPOSIT OF NICKEL ON A WORKPIECE |
| FR3020642B1 (en) | 2014-04-30 | 2021-07-02 | Turbomeca | DEVICE INTENDED FOR IMPLEMENTING AN ANODIZATION TREATMENT |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62199800A (en) * | 1986-02-27 | 1987-09-03 | Kawasaki Steel Corp | Method and apparatus for supplying metallic particle for plating in electroplating |
| FR2617509B3 (en) * | 1987-07-02 | 1989-06-30 | Siderurgie Fse Inst Rech | METHOD OF CONTINUOUS ELECTROLYTIC COATING, IN PARTICULAR OF IRON-ZINC, ON A STEEL SHEET, USING AN ION-EXCHANGING MEMBRANE |
-
1989
- 1989-07-25 FR FR8910117A patent/FR2650304B1/en not_active Expired - Fee Related
-
1990
- 1990-07-16 EP EP90470044A patent/EP0410919A1/en not_active Withdrawn
- 1990-07-16 CA CA002021242A patent/CA2021242A1/en not_active Abandoned
- 1990-07-23 KR KR1019900011188A patent/KR920002827A/en not_active Application Discontinuation
- 1990-07-24 DD DD90343032A patent/DD295730A5/en not_active IP Right Cessation
- 1990-07-24 BR BR909003582A patent/BR9003582A/en unknown
- 1990-07-25 JP JP2197576A patent/JPH0375395A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013011011A (en) * | 2011-05-30 | 2013-01-17 | Ebara Corp | Plating apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| BR9003582A (en) | 1991-08-27 |
| EP0410919A1 (en) | 1991-01-30 |
| FR2650304A1 (en) | 1991-02-01 |
| KR920002827A (en) | 1992-02-28 |
| FR2650304B1 (en) | 1991-10-04 |
| CA2021242A1 (en) | 1991-01-26 |
| DD295730A5 (en) | 1991-11-07 |
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