JPS58197292A - Production of steel plate plated with gamma zinc-nickel alloy in high efficiency - Google Patents
Production of steel plate plated with gamma zinc-nickel alloy in high efficiencyInfo
- Publication number
- JPS58197292A JPS58197292A JP8003282A JP8003282A JPS58197292A JP S58197292 A JPS58197292 A JP S58197292A JP 8003282 A JP8003282 A JP 8003282A JP 8003282 A JP8003282 A JP 8003282A JP S58197292 A JPS58197292 A JP S58197292A
- Authority
- JP
- Japan
- Prior art keywords
- plating
- bath
- zinc
- nickel alloy
- plated
- 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.)
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Abstract
Description
【発明の詳細な説明】
本発明は高効率で品質の良いガンマ−組織のＮｉ −Ｚ
ｎ合金メッキ鋼板を製造する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention provides highly efficient and high quality gamma-structured Ni-Z
The present invention relates to a method of manufacturing an n-alloy plated steel sheet.
電気匪鉛メッキ鋼板は、その優れた特性から家庭電気製
品、建材、ショーケース、自動販売機、等の防錆素材と
して多岐に使用されている。特に近年、自動車々体に対
する社会的要求から車体の耐久性の向上が急速にクロー
ズアップされている。Due to its excellent properties, electrolytic lead-plated steel sheet is used in a wide variety of applications as a rust-preventing material for home appliances, building materials, showcases, vending machines, etc. Particularly in recent years, improvements in the durability of vehicle bodies have been rapidly focused on due to social demands for vehicle bodies.
この要求に答える素材として亜鉛メッキ鋼板の需要が伸
びている。自動車々体の腐食は、内部および外部塗装面
両面に生じており、特に下延シの内部袋構造部、突き合
せ部は腐食が激しく車体に穴明きが生ずる。構造的にこ
の部分は、リン酸塩処理皮膜及び電着塗膜が不充分もし
くは全く未塗装状態が生ずるためである。従って、従来
の亜鉛メッキでは、かなシメツキ厚の高い鋼板が必要で
あった。Demand for galvanized steel sheets is increasing as a material that meets this demand. Corrosion of automobile bodies occurs on both the internal and external painted surfaces, and the corrosion is particularly severe at the inner bag structure and butt parts of the lower part, causing holes in the car body. Structurally, this is because the phosphate treatment film and electrodeposition coating are insufficient or completely unpainted in this area. Therefore, conventional galvanizing requires a steel plate with a high kana plating thickness.
一方、外面部の腐食は小石等の衝撃やその他物理的な作
用で塗膜に傷が入りその傷を発端としてスキャプコロー
ジョン、フィリフォームコロージョン等の外面部が生ず
る。外面部に対しては、亜鉛メッキが有効であるが、鉄
面との接触腐食や、塗装後の性能が不充分である点等か
ら、純亜鉛メッキに代る合金亜鉛メッキ鋼板が要求され
ている。On the other hand, corrosion on the outer surface occurs when the paint film is scratched by impact with pebbles or other physical action, and these scratches cause scap corrosion, filliform corrosion, etc. on the outer surface. Galvanizing is effective for the external surface, but alloy galvanized steel sheets are required as an alternative to pure galvanizing due to corrosion caused by contact with steel surfaces and insufficient performance after painting. There is.
内面部に対しても純亜鉛メッキでは前述した如く厚メッ
キ品になることのため、溶接性、再資源化に悪影響があ
り、又、近年のカチオン電着化の変化で薄メッキ厚の合
金メッキが要求されている。Pure zinc plating on the inner surface also results in a thick plated product as mentioned above, which has a negative impact on weldability and recycling.Also, due to recent changes in cationic electrodeposition, alloy plating with a thinner plating thickness is required. is required.
自動車４体に限らず、従来使用された分野においても品
質の優れた合金亜鉛メッキ思考が急速になされている。The idea of high-quality alloy galvanizing is rapidly being developed not only for automobiles but also in fields where it has been used conventionally.
′
これ等の社会的要求に対処出来る合金亜鉛メッキ鋼板の
具備条件としては、広範囲の腐食環境に対して薄メッキ
で耐食性および塗装後の耐久性に優れ、溶接性、溶着性
が良く、且つ、コストの安い素材でなければならない。' The requirements for alloy galvanized steel sheets that can meet these social demands are that they are thinly plated in a wide range of corrosive environments, have excellent corrosion resistance and durability after painting, have good weldability and weldability, and It must be a low-cost material.
これ等の要求に対処出来る合金メッキ鋼板としてＮｊ−
Ｚｎ系の合金亜鉛メッキ鋼板を挙げることが出来る。Ｎ
ｉ−Ｚｎ合金メッキ鋼板は特にγ組織のＮｉ７〜２０％
好ましくはＮｉ１Ｏ〜１５％の組成は品質的に優れてい
る。Nj- is an alloy plated steel sheet that can meet these demands.
Examples include Zn-based alloy galvanized steel sheets. N
The i-Zn alloy plated steel sheet has 7 to 20% Ni in the γ structure.
Preferably, a composition of Ni1O to 15% is excellent in quality.
亜鉛メッキ系の鋼板の製造方法としては、溶融メッキ法
と電気メツキ法に大別され連続的に大量ｋ
に製造され、その生産量は年間５００万ｔにも及んでい
る。浴融亜鉛メッキプロセスは厚メッキ品の製造に通し
ており、目付量４０ ｙ／ｍ＋以上の純亜鉛メッキ鋼板
、Ｆｅ −Ｚｎ熱拡散合金メッキ鋼板等の製品が建材、
自動車等に使用されている。一方電気亜鉛メツキプロセ
スでは、厚メツキ製品の製造は、電力費の増大、Ｔ／Ｈ
の低下等の理由でコストの高い製品となるため通常は目
付量１０〜２０ｇ汐の薄メツキ製品が製造される。電気
メツキプロセスは溶融メッキプロセスに比べ鋼材の機械
的性質への影響が少ないこと、片面メッキを製造し易い
、広範囲な合金メッキ製品を製造出来る利点を持ってお
り、前述した現代の自動車４体を特徴とする請求に答え
る。素材の製造プロセスとして有利である。しかしなが
ら、基本的に電気的々還元力でメッキするためコスト高
に々る宿命を内含している。従って電力費の安いＴ／ｆ
（の高い高効率な生産力法を開発する必要がある。その
ためには、極間を近接し高い電流密度で電気メッキを行
う製造方法即ち、高効率電解が不可欠である。更に加え
て、前原した”茹＜、自動車４体等を中心した合金メッ
キ鋼板を高効率で製造する方法を確立することが急務で
ある。The manufacturing methods for galvanized steel sheets are broadly divided into hot-dip plating and electroplating, and they are manufactured continuously in large quantities, with the annual production amount reaching 5 million tons. The bath dip galvanizing process is used to manufacture thick plated products, and products such as pure galvanized steel sheets with a basis weight of 40 y/m+ and Fe-Zn heat diffusion alloy plated steel sheets are used as building materials,
Used in automobiles, etc. On the other hand, in the electrogalvanizing process, the production of thickly plated products requires increased electricity costs, T/H
Since the cost of the product is high due to a decrease in the surface area, thin plating products with a basis weight of 10 to 20 g are usually produced. Compared to the hot-dip plating process, the electroplating process has the advantages of having less influence on the mechanical properties of steel materials, making it easy to produce single-sided plating, and being able to produce a wide range of alloy-plated products. Respond to claims that feature. This is advantageous as a material manufacturing process. However, since plating is basically done using electrical reducing power, the cost is high. Therefore, the power cost is low T/f
It is necessary to develop a high-efficiency production method for (highly efficient) production. To this end, a manufacturing method in which electroplating is performed at high current density with adjacent electrodes, that is, high-efficiency electrolysis, is indispensable. There is an urgent need to establish a highly efficient method for producing alloy-plated steel sheets, mainly used for automobiles, etc.
電気メッキにおいて電流密度を上げると電解槽において
は、可溶性アノードの場合の陽極不動態化、不陽性陽極
の場合のガス留り電圧上昇、電流効率確保難などの問題
、品質力面ではメッキやけ、むら、結晶粗大化による表
面粗れ、ピンホール、ヌケ、密着不良更に合金メッキで
は均一組成が得られないなどの問題を慮起し、電流密度
ＤＫ＝２０〜５０ Ａ／ｄｍ’が限界電流密度であった
。Increasing the current density in electroplating causes problems such as anode passivation in the case of a soluble anode, an increase in gas retention voltage in the case of a non-positive anode, difficulty in ensuring current efficiency, and in terms of quality, plating burns, Considering problems such as unevenness, surface roughness due to crystal coarsening, pinholes, missing spots, poor adhesion, and the inability to obtain a uniform composition with alloy plating, the current density DK = 20 to 50 A/dm' is the limit current density. Met.
１）電極とストリップとを近接化出来ること、２）ガス
除去が出来るセルとすること、３）大電流通電法テムの
機能を持たせたこと。1) The electrode and the strip can be placed close to each other, 2) The cell can remove gas, and 3) It has the function of a large current energization system.
々どの条件を満すものを用いて、高電流密度メッキを行
うに際して、■メッキ浴として、１）高伝導度であるこ
と、 ２）流速に依存しない浴であること（むらが生
じたシ）３）電流効率が良いこと、 ４）メッキやけ、
むらのないこと、 ５）合金組成の変動がないこと。When performing high current density plating using a plating bath that satisfies the following conditions: 1) It must have high conductivity, 2) It must be a bath that does not depend on the flow rate (no unevenness occurs). 3) Good current efficiency, 4) Plating burnout,
5) No variation in alloy composition.
など前記高電流密度メッキに対応した亜鉛−二ツケル合
金メッキ浴の開発を目的としてなされたものである。The purpose of this work was to develop a zinc-Nitskel alloy plating bath compatible with the above-mentioned high current density plating.
即ち本発明は電極面と被メッキ面との間に電解液を噴出
せしめて、極面と被メッキ面との間に液を保持しながら
電気亜鉛−ニッケル合金めっきを行う方法において、め
っき浴としてＺｎ５Ｏ，・７Ｈ２０とＮ ｉ Ｓ ０４
＠６ Ｈ２Ｏとの和が４００〜７００り／１゜の相対
速度を１．０ ｍ／／ｓｅｃ、以上でメッキすることを
特徴とする高効率Ｎｉ −Ｚｎ合金メッキ鋼板の製造方
法である。本発明により外観が良く、合金組成分安定し
た亜鉛−ニッケル合金メッキを高効率で製造することが
できる。That is, the present invention provides a method for performing electrolytic zinc-nickel alloy plating by jetting an electrolytic solution between an electrode surface and a surface to be plated and maintaining the liquid between the electrode surface and the surface to be plated. Zn5O, 7H20 and N i S 04
This is a method for producing a highly efficient Ni--Zn alloy plated steel sheet, characterized by plating at a relative speed of 1.0 m//sec or more at a sum of @6 H2O of 400 to 700 r/1°. According to the present invention, zinc-nickel alloy plating with good appearance and stable alloy composition can be manufactured with high efficiency.
次に本発明について更に詳細に説明する。本発明は高電
流密度による亜鉛−Ｎｉ合金メッキが可能になった点に
最も時数を有する。その結果メッキの析出速度が高く厚
メッキが可能となった。従来技術は極間距離が２５〜５
０団： ＤＫ３０〜５０Ａ／ｄｍ’が限度であった。そ
の理由として限度以上に電流密度を上げると六めつきや
け〃、Ａめつきむら〃、Ｎめつき結晶粗大化〃が生じ、
さらに、合金組成が電流密度によって変化するため高電
流密度によるＮｉ−Ｚｎ合金メッキ鋼板の製造は不可能
であった。本発明を実施する場合にはプロセス的には、
例えば本出願人がすでに開発している高電流密度操業可
能なセル（％開昭５６−１２７７８９に開示）を使用し
、メッキ浴としてＺｎＳＯ４・７Ｈ２０とＮ ｉ Ｓ
０４・６Ｈ２０の和が４００〜７００ ｔ／ｌで、且つ
Ｈ２ＳＯ４５〜２０ ｆ／ｌ 、 Ｎｉ／Ｚｎ比１．０
〜２．０から々る浴を使用することで実施できる。即ち
本発明を実施する場合の電解装置の例を第１図で説明す
る。電解装置はストリップ１を電解液３に浸漬すること
なく空間に保持した状態で通板させる電解槽２と、該電
解槽２内の所定位置に、前記ストリップ１面に対向して
近接して配置しかつストリップ面に電解液を噴射すると
共゛に該流体によりストリップ面に静圧を作用せしめる
ノズル孔を形成した電極パッド４とからなる。Next, the present invention will be explained in more detail. The present invention has the greatest advantage in that it has become possible to perform zinc-Ni alloy plating using high current density. As a result, the deposition rate of plating is high and thick plating is possible. In the conventional technology, the distance between poles is 25 to 5.
Group 0: DK 30-50 A/dm' was the limit. The reason for this is that when the current density is increased beyond the limit, six-metal burn, uneven A-metal, and coarse-grained N-metal crystals occur.
Furthermore, since the alloy composition changes depending on the current density, it has been impossible to manufacture Ni-Zn alloy plated steel sheets at high current densities. When carrying out the present invention, for example, a cell capable of high current density operation which has already been developed by the present applicant (disclosed in 1989-127789) is used, and ZnSO4.7H20 is used as a plating bath. and N i S
04・6H20 sum is 400-700 t/l, H2SO45-20 f/l, Ni/Zn ratio 1.0
It can be carried out by using a ~2.0 Karakara bath. That is, an example of an electrolytic apparatus for carrying out the present invention will be explained with reference to FIG. The electrolytic device includes an electrolytic tank 2 in which the strip 1 is passed through the electrolytic solution 3 while being held in a space without being immersed in the electrolytic solution 3, and a predetermined position in the electrolytic tank 2, which is arranged close to and facing the surface of the strip 1. It also comprises an electrode pad 4 formed with a nozzle hole for injecting electrolyte onto the strip surface and applying static pressure to the strip surface using the fluid.
このように電解槽内でのストリップを電解液に浸漬せず
に空間に保持せしめ、しかも槽内の所定位置にストリッ
プ面に対向して配置した静圧パッドとしても機能を併せ
もつ電極パッドにより、ストリップ面に電解メッキ液を
噴射して電解処理を実施することを特色としている。し
たがって、この電解槽は従来の浸漬タイプと全く異質で
あって、電解液が充満しておらず、しかも電解を行左う
ための電極が中空のボックス構造であってそのノズル孔
からストリップに向って電解液を噴出するものであるか
ら、浸漬タイプに見られた種々の不利益が解消されると
共に、下ロールをもコンダクタ−ロールとし７て利用で
き、加えてストリップの振動を防止してかつ形状不良を
矯正して安定した選歌が行々えるメリットが得られる。In this way, the strip in the electrolytic tank is held in space without being immersed in the electrolyte, and the electrode pad also functions as a static pressure pad placed at a predetermined position in the tank facing the strip surface. The feature is that electrolytic treatment is carried out by spraying electrolytic plating solution onto the strip surface. Therefore, this electrolytic cell is completely different from the conventional immersion type, in that it is not filled with electrolyte, and the electrodes for conducting electrolysis have a hollow box structure and extend from the nozzle hole toward the strip. Since the electrolyte is spouted out by the immersion type, various disadvantages seen in the immersion type are eliminated, and the lower roll can also be used as a conductor roll. This has the advantage of correcting shape defects and allowing stable song selection.
以上、本発明で使用できるメッキ装置の１例を、示した
が、本発明はこの例に限定されるものではなく、電極面
と被メッキ面との間に電解液を噴射して電極面と被メッ
キの間にメッキ液を保持しながら、ストリップと電解液
の相対速度を１ 、０ ｒｒ１Ａｅｃ以上にしてメッキ
できる装置であれば良い。Although one example of a plating apparatus that can be used in the present invention has been shown above, the present invention is not limited to this example, and the electrolytic solution is injected between the electrode surface and the surface to be plated. Any device that can perform plating at a relative speed of 1.0 rr1 Aec or more between the strip and the electrolytic solution while holding the plating solution between the plates to be plated may be used.
そのような条件に適合するその他の例として特公昭５０
−８０２０に開示したようにストリップの進向方向と自
流的にストリップと電極間に電解液を噴射する電解メッ
キ装置、又特願昭５５−１７６５１８に開示したように
電極の中央部からストリップ面に電解液を噴射する装置
などがあげられる。さらに本出願・人が特許出願中の特
願昭５７−１８８３６に開示した静圧流体パッドを備え
た水平電解装置があげられる。又本発明においては極間
距離は近接化するほど好ましい。その理由としては例え
ば電流密度を１００ ｋ／ｄｒｒ？又は２６ ｏ Ａ７
ｄｍ’に設定した場合に極間距離が大きいと極間電圧は
２０〜３０Ｖをこえてしまい電力費、整流器の容量が大
きくなり実用的ではない。本発明は極間電圧を少くとも
２０Ｖ未満望ましくはＩＯＶ以下を目標としている。従
って極間距離を近接化するほど（好ましくは１５＋ｏ＋
以下）極間電圧が減少し、結果としてコストを大巾に節
減することができる。Another example that meets such conditions is
As disclosed in Japanese Patent Application No. 8020, there is an electrolytic plating device that injects an electrolytic solution between a strip and an electrode in a self-current manner in the advancing direction of the strip. Examples include devices that spray electrolyte. Further, there is a horizontal electrolyzer equipped with a hydrostatic fluid pad disclosed in Japanese Patent Application No. 57-18836, which is currently pending. Further, in the present invention, it is preferable that the distance between the poles be closer. The reason for this is, for example, if the current density is 100 k/drr? or 26 o A7
dm' and the distance between the electrodes is large, the voltage between the electrodes exceeds 20 to 30 V, which increases the power cost and the capacity of the rectifier, which is not practical. The present invention aims at a voltage between electrodes of at least less than 20V, preferably less than IOV. Therefore, the closer the distance between poles (preferably 15+o+
(below) The inter-electrode voltage is reduced, resulting in significant cost savings.
従って極間距離を小さくするほどコスト的には有利であ
るが極間きよりを極端に小さくするとストリップと電極
が接触するおそれがあるので極間きよりは５配が実用上
の限界といえる。Therefore, the smaller the distance between the electrodes, the more advantageous it is in terms of cost, but if the distance between the electrodes is made too small, there is a risk that the strip and the electrode will come into contact with each other.
なお本発明では前記のように極間距離をなるべく近接化
してメッキを行うが、メッキ中のストリップの振動や位
置変動或はカテナリーを少なくして極間距離をより縮少
するために、前記説明した特開昭５６−１２７７８９と
特願昭５７−１８８３６に示したような静圧流体パッド
を有するメッキ装置を用いて静圧流体でスｌリップを支
持しながらメッキを行うことが最も好ましい。その結果
ストリップは電極間の中心に静圧で自動的にセンターリ
ングされるので極間距離を大巾に短縮できしかも安定し
てメッキを行うことができる。（この場合には最高２５
０Ａ／ｄｒｒ？での電解が可能である）以上説明したよ
う々電解装置を用いて電極面と被メッキ面との間に電解
液を噴出せしめて極間と被メッキ面との間に液を保持し
彦がらメッキを行なう場合にはＮガス溜り〃がなく極間
距離が近接可能であるので通電抵抗が小さくなるため電
圧の上昇を抑制することが可２能となる。さらに相対ス
ピード（ラインスピード−流速）によるイオン供給、液
置換効率がよいこと々どのため高電流密度によるメッキ
が可能となる。以下本発明のメッキ浴について説明する
。In the present invention, as described above, plating is performed by making the distance between the electrodes as close as possible, but in order to further reduce the distance between the electrodes by reducing the vibrations, positional fluctuations, and catenaries of the strip during plating, the distance between the electrodes is reduced as described above. It is most preferable to carry out plating while supporting the slip with a hydrostatic fluid using a plating apparatus having a hydrostatic fluid pad as shown in Japanese Patent Laid-Open No. 56-127789 and Japanese Patent Application No. 57-18836. As a result, the strip is automatically centered between the electrodes by static pressure, making it possible to greatly shorten the distance between the electrodes and to perform stable plating. (In this case up to 25
0A/drr? The electrolysis device described above is used to spray an electrolytic solution between the electrode surface and the surface to be plated, and to maintain the liquid between the electrodes and the surface to be plated. When plating is performed, there is no N gas accumulation and the distance between the poles can be made close, so that the resistance to conduction becomes small and it becomes possible to suppress the rise in voltage. Furthermore, the relative speed (line speed - flow rate) provides good ion supply and liquid replacement efficiency, making it possible to perform plating with high current density. The plating bath of the present invention will be explained below.
本発明者らは前記の高効率が可能な電解槽を開発したが
、実際にＮｉ −Ｚｎ合金メッキを行うと、まだ解決す
べき課題があることが分った。Although the present inventors have developed an electrolytic cell capable of achieving the above-mentioned high efficiency, it has been found that there are still problems to be solved when actually performing Ni--Zn alloy plating.
以下Ｎｉ −Ｚｎ合金メッキの課題と本発明の方法につ
いて詳述する。Below, the problems of Ni-Zn alloy plating and the method of the present invention will be explained in detail.
亜鉛は水素過電圧が高い性質から高い電流効率でメッキ
出来る特性がある。しかし、Ｎ１ は水素過電圧が低
く、合金メッキにおいては電流効率が低くなる。−力メ
ツキヤケ、液抵抗を下げるためには硫酸の添加が効果的
であるが、水素の発生が多くなり電流効率は著しく低下
する欠点がある。Zinc has the property of being able to be plated with high current efficiency due to its high hydrogen overvoltage. However, N1 has a low hydrogen overvoltage, resulting in low current efficiency in alloy plating. -Addition of sulfuric acid is effective in reducing force discoloration and liquid resistance, but has the drawback that hydrogen is generated in large quantities and current efficiency is significantly reduced.
そこで本発明者等は近接高電流密度電解に対応した亜鉛
−ニッケル合金メッキ浴を新規に見い出すことによって
前記の未題を解決することができた。Therefore, the present inventors were able to solve the above-mentioned unsolved problem by discovering a new zinc-nickel alloy plating bath that is compatible with close proximity high current density electrolysis.
本発明においては浴にＨ２ＳＯ，を５〜２０ ｆｌ／Ｌ
ｌ／間時に、金属イオン濃度の上昇を向上せしめている
。一般には低Ｐ Ｒにすると水素が出やすくなシミ流動
室が低下する。特にＮｃが析出するめつきでは水素が発
生し易く、従来ではＰＨの低下は電流効率に対して負効
果をもたらすと考えられていた。しかしながらＰ Ｈを
低くした本発明浴では低電流密度では従来通シであるが
、高電流密度の場合には逆に良ぐ々ることか解った。In the present invention, H2SO is added to the bath at 5 to 20 fl/L.
1/h, the increase in metal ion concentration is improved. Generally, when the PR is set low, the stain flow chamber where hydrogen is likely to come out is reduced. Particularly in plating where Nc is precipitated, hydrogen is likely to be generated, and it was conventionally thought that a decrease in pH would have a negative effect on current efficiency. However, it has been found that the bath of the present invention with a low PH value is conventional at low current densities, but is not good at high current densities.
第２図は本発明浴（曲線１）と従来実施されている高Ｐ
Ｈ１低濃度浴（曲線２）とを使用し、電流効率と電流
密度との関係を比較したものである。Figure 2 shows the present invention bath (curve 1) and the conventional high P bath.
The relationship between current efficiency and current density is compared using H1 low concentration bath (curve 2).
本発明１はＺｎ ８０４ ’ ７Ｈ２０＋Ｎ ｉ ８０
４ ” ６Ｈ２０”’４８０ ？／ｌ （Ｎｉ／Ｚｎ
＝ １．５ ） Ｎａ２５ｏ、＝１００ ？／Ｌ。Invention 1 is Zn 804' 7H20+N i 80
4” 6H20”’480? /l (Ni/Zn
= 1.5) Na25o, = 100? /L.
Ｈ２ＳＯ，１０ｆ／ｌ、 Ｐ Ｈ＝ １の浴を用い温度
６０℃、流速１ ｍ／ｓｅｃでメッキを行った。比較２
はＺ ｎ Ｓ ０！・７Ｈ２０＋ ＮｉＳＯ４・６Ｈ２
０＝ ３００ ？／ｌ （Ｎｉ／Ｚｎ ＝１．５）、Ｎ
ａ２Ｓ、０４１，００ ｆ／７．Ｉ（２８０４２ｆ／Ｌ
Ｐ Ｈ＝２．５の浴を用い浴温６０℃通常の浸漬法
でメッキを行った。本発明１は１００Ｖｄ７７１″以上
の高電流密度でも電流効率は８２％以上を確保できる。Plating was performed using a bath of H2SO, 10 f/l, P H = 1 at a temperature of 60°C and a flow rate of 1 m/sec. Comparison 2
Z n S 0!・7H20+ NiSO4・6H2
0=300? /l (Ni/Zn = 1.5), N
a2S, 041,00 f/7. I (28042f/L
Plating was carried out using a bath having a pH of 2.5 and a bath temperature of 60° C. by a normal dipping method. The present invention 1 can ensure current efficiency of 82% or more even at a high current density of 100Vd771'' or more.
しかしながら電流密度が３００ Ａ／ｄｒｒ？では本発
明浴においても電流効率の低下やメッキむらが生じはじ
めるため、本発明の好ましい電流密度は１００〜２５０
Ａ７ｄ靜、最も好ましくは１５０〜２００Ａ／ｄｒｒ？
である。However, the current density is 300 A/drr? Therefore, the current density of the present invention is preferably 100 to 250.
A7d quiet, most preferably 150-200A/drr?
It is.
更に合金めっきを均一組成にする条件として従来の考え
力は、
■電流密度を一定にする。Furthermore, the conventional thinking is that the conditions for making alloy plating have a uniform composition are: 1. Keep the current density constant.
■浴組成を一定にする（濃度、ＰＨ） ■錯塩を加える。緩衝剤を加える。■Keep the bath composition constant (concentration, pH) ■Add complex salts. Add buffer.
■流速を一定にする。■Keep the flow velocity constant.
■温度も一定にする。■Keep the temperature constant.
などの設定条件が多く非常に生産し難いものであった。It was very difficult to produce because of the many setting conditions such as.
本発明においては錯塩、緩衝剤を添加せず単純組成浴で
低Ｐ Ｈ（Ｈ２ＳＯ，５〜２０ ｔ／ｌ ）温度（６０
℃以上）、流速ニストリップとの相対速度を一定値以上
（１ｍ／ｓ ）、高濃度浴（Ｚｎ ８０４ ” ７Ｈ２
０十Ｎ１５Ｏ＋・６ｌ−１２０＝ ４００〜７００ ？
／ｌ ）で広い浴組成（Ｎｉ／Ｚｎ比＝ １〜２）とい
う広い管理条件下で電流密度て依存したシめつき条件を
見出した。In the present invention, a bath with a simple composition is used without adding complex salts or buffers, at a low pH (H2SO, 5-20 t/l) and a temperature (60 t/l).
℃ or higher), the relative velocity with the Nitrip is higher than a certain value (1 m/s), and the high concentration bath (Zn 804" 7H2
01N15O+・6l-120=400~700?
Under a wide controlled condition of a wide range of bath compositions (Ni/Zn ratio = 1 to 2), the current density-dependent clinching conditions were found.
また高電流密度用電解槽は高流速で、メッキ液噴射を行
なうため、噴出ノズル部における流速とその他の部分の
流速が異なってくる。合金メッキにおいてはこの流速と
メッキ皮膜合金組成とはかなりの相関を示しメッキむら
等が発生する。特に従来用いていた浴条件ではこの傾向
が強く現れてしまい、噴出ノズルの位置設定ノズル形状
が非常にシビアである。しかし本発明の浴条件ではこの
流速と合金組成との関連はあｔｂ見られなくなシ噴出ノ
ズルの位置設定ノズル形状は自在である。Furthermore, since the electrolytic cell for high current density sprays the plating solution at a high flow rate, the flow rate at the jet nozzle portion differs from the flow rate at other parts. In alloy plating, there is a significant correlation between the flow rate and the alloy composition of the plating film, resulting in uneven plating. This tendency is particularly strong under conventional bath conditions, and the nozzle shape for setting the position of the ejection nozzle is very severe. However, under the bath conditions of the present invention, this relationship between flow rate and alloy composition is no longer observed, and the nozzle shape for setting the position of the ejection nozzle can be freely determined.
後述する相対スピードと合わせて本発明の浴条件を用い
ることによって外観の良い合金組成の安定した亜鉛−ニ
ッケル合金メッキを従来浴条件に比べてはるかに広い範
囲の操業条件で容易に製造することが可能である。By using the bath conditions of the present invention in conjunction with the relative speed described below, zinc-nickel alloy plating with a stable alloy composition and good appearance can be easily produced under a much wider range of operating conditions than conventional bath conditions. It is possible.
Ｚｎ −Ｎｉ合金メッキで最も耐食性の良いＮｉ量は１
０〜１５％の範囲である。第３図はメッキ皮膜中のＮ１
％と電解液のＮｉ／Ｚｎ比との関係を示すものである。The most corrosion-resistant Ni amount in Zn-Ni alloy plating is 1.
It ranges from 0 to 15%. Figure 3 shows N1 in the plating film.
% and the Ni/Zn ratio of the electrolytic solution.
これよりメッキ中の斜線で示したＮｉ量１０〜１５％を
満足するためにはＮｉ／Ｚｎ比比を１．０〜２゜Ｏに調
整する必要がある。From this, in order to satisfy the Ni content of 10 to 15% shown by diagonal lines during plating, it is necessary to adjust the Ni/Zn ratio to 1.0 to 2°O.
まだ、第４．５図は合金メッキ層中のＮ１％と電解液−
ストリップ間の相対速度■との関係を示す。第４図は本
発明の条件であり、第５図は比較の浴条件の例である。Still, Figure 4.5 shows the relationship between N1% in the alloy plating layer and the electrolyte.
The relationship between the relative speed between the strips and ■ is shown. FIG. 4 shows the conditions of the present invention, and FIG. 5 shows an example of comparative bath conditions.
（メッキ浴は第２図における場合と同一浴を使用）第５
図より比較浴を用いた場合、電流密度ＤＫ（曲線１は２
００ Ａ／ｄｍ”曲線２は１００Ａ／ｄ７？Ｚ″ ）に
よってＮ１％が犬きぐ変化し、この傾向は相対速度Ｖを
増加してもほとんど安定し々い。従って操業条件によっ
て得られるＮｉ％が変化してしまい製品品質が安定せず
、品質管理が困難である。しかしながら第４図に示すよ
うに本発明の浴条件を用いればＮｉ％はＤＫに対して非
常に良い安定性を示し、特にＶ−１ｒｒｖ／ｓ以上にな
ると電流密度を変えてもＮｉ最適量である１０〜１５％
組成のメッキを安定して行なうことが可能である。(The same plating bath as in Figure 2 is used) 5th
From the figure, when using the comparison bath, the current density DK (curve 1 is 2
00 A/dm'' curve 2 is 100 A/d7? Therefore, the Ni% obtained varies depending on the operating conditions, resulting in unstable product quality and difficulty in quality control. However, as shown in Fig. 4, if the bath conditions of the present invention are used, Ni% exhibits very good stability with respect to DK, and especially when the current density exceeds V-1rrv/s, the optimal amount of Ni is maintained even if the current density is changed. Some 10-15%
It is possible to perform plating with a stable composition.
従って本発明の浴条件はＮｉ −Ｚｎ合金メッキを行な
う上で操業条件範囲が広く実用的である。しかし力から
本発明浴条件でもＶ ＝ １ ｍ／ｓ以下では要求され
るＮｉ％が必ずしも得られない。Therefore, the bath conditions of the present invention have a wide range of operating conditions and are practical for Ni--Zn alloy plating. However, due to the force, even under the bath conditions of the present invention, the required Ni% cannot necessarily be obtained when V = 1 m/s or less.
また浴温については浴の電導度は温度と供に高くなるた
め浴温は高いほど電解電圧は下り、電力費を消滅するこ
とが可能である。またメッキ外観に対しても浴温は高い
方が良ぐ力る傾向にあるため、本発明条件では浴温を６
０℃以上にするのが最も好ましい。Regarding bath temperature, since the conductivity of the bath increases with temperature, the higher the bath temperature, the lower the electrolytic voltage will be, making it possible to eliminate electricity costs. In addition, the higher the bath temperature, the better the appearance of the plating.
Most preferably the temperature is 0°C or higher.
第６図ばＨ２ＳＯ，量と電導度Ｋ及び電流効率７との関
係を示す。これよりＨ２ＳＯ４量の増加とともにＫは直
線的に増加し、電解電圧も下がるが、Ｈ２Ｓ０４が２０
１／／ｌを越えると７が急激に低下してしまい実用的で
はなくなる。FIG. 6 shows the relationship between the amount of H2SO, conductivity K, and current efficiency 7. From this, K increases linearly as the amount of H2SO4 increases, and the electrolytic voltage also decreases, but when H2SO4
If it exceeds 1//l, the value of 7 will drop sharply, making it impractical.
また第７図はＺ ｎ Ｓ ０４ ’ ７Ｈ２０＋ Ｎ
ＩＳ ０４ ” ６Ｉ（２０量とに、７の関係を示すが
、これよシＺ ｎ Ｓ ０４・７Ｈ２゜十Ｎ１５Ｏ，・
６Ｈ２０の増加は電導度を若干減少させ、特に７００
ｙ／を以上になると急激な低下を示す。Also, Figure 7 shows Z n S 04' 7H20+ N
IS 04 ” 6I (20 shows the relationship of 7 with quantity, but this is Z n S 04・7H2゜10N15O,・
An increase in 6H20 slightly decreases the conductivity, especially at 700
When the value exceeds y/, a rapid decrease occurs.
また、７についてはＺｎ ＳＯ４” ７Ｈ２０＋ Ｎ
ｉ ＳＯ４・６Ｈ２０４００９／を以上で８０％以上の
高効率となる。従ッテＺｎＳＯ４” ７Ｈ２０十Ｎ ｉ
８０４ ’ ６Ｈ２０の量は４００〜７００ ｆ／ｌ
の範囲が最適である。Also, for 7, Zn SO4” 7H20+ N
i SO4・6H204009/ or more results in high efficiency of 80% or more. ZnSO4” 7H20N i
The amount of 804' 6H20 is 400-700 f/l
The range of is optimal.
第８図はＨ２ＳＯ４及びＺｎ ８０４ ’ ７Ｈ２０十
Ｎ １８０４ ”６Ｈ２０とメッキ外観の関係を示す。FIG. 8 shows the relationship between H2SO4 and Zn 804'7H201804''6H20 and the plating appearance.
図中にＯで示すものがメッキ外観が良好である。これよ
りＨ２ＳＯ４５？／を以上、且つＺｎＳＯ４＠ ’７Ｉ
（２ｏ ＋ Ｎ１５Ｏ＋ ・６Ｈ２０４００ｆ／／を以
上で良好なメッキ外観が得られる。Those indicated by O in the figure have a good plating appearance. H2SO45 from this? / or more, and ZnSO4@'7I
(2o + N15O+ ・6H20400f// or more will give a good plating appearance.
以上第６．７．８図より本発明浴はＨ２Ｓ０４−５〜２
０７／１１ＺｎＳＯ４・７Ｈ２０＋Ｎｌ５Ｏ４ＩＩ６Ｈ
２０−４００〜７００ ？／ｌに限定される。From the above Figure 6.7.8, the baths of the present invention are H2S04-5 to 2.
07/11ZnSO4・7H20+Nl5O4II6H
20-400~700? /l.
尚、本発明の合金メッキはＺｎ −Ｎｉを主成分とする
高効率製造方法であるが、要求特許等によシ第３、第４
成分として合金成分を添加した場合もしくは不純物とし
て入る場合も同様の条件でＺｎ−Ｎｉを主成分とする合
金メッキを製造可能である。The alloy plating of the present invention is a highly efficient manufacturing method using Zn-Ni as the main component, but according to the requested patents, etc.
Even when an alloy component is added as an ingredient or included as an impurity, alloy plating containing Zn-Ni as a main component can be manufactured under the same conditions.
これらの添加成分としてはＦｅ、 Ｃｏ、 Ｃｒ 等で
ある。許容される含有量としては浴中でＮｉ／Ｚｎ比が
１〜２におけるＺｎ量の１／２以下である。These additional components include Fe, Co, Cr, etc. The permissible content is 1/2 or less of the amount of Zn when the Ni/Zn ratio is 1 to 2 in the bath.
以上本発明について詳細に述べた、以下実施例を上げ本
発明を説明する。The present invention has been described in detail above, and the present invention will be explained below with reference to Examples.
実施例１
第１図に示した電解装置を用いて第１表に示す浴条件、
メッキ条件で合金メッキを行った。その結果第１表に示
す如き結果を得た。本発明例Ｎｌ １．２．３．４、は
γ組織のＮｉ−Ｚｎ合金メッキ皮膜が高効率で得られ、
被膜中のＮｉ含量は安定していた。又皮膜の外観も良好
であった。これに対して従莱の浴を用いた比較例である
Ｎｌ ５、Ｎα６、Ｎα７はいずれも電流効率が悪く、
メッキ皮膜外観もメッキやけが発生して劣っていた。Example 1 Using the electrolyzer shown in FIG. 1, the bath conditions shown in Table 1,
Alloy plating was performed under the plating conditions. As a result, the results shown in Table 1 were obtained. Inventive example Nl 1.2.3.4, a Ni-Zn alloy plating film with a γ structure was obtained with high efficiency,
The Ni content in the coating was stable. The appearance of the film was also good. On the other hand, Nl 5, Nα6, and Nα7, which are comparative examples using Jurai's bath, all have poor current efficiency;
The appearance of the plating film was also poor due to plating burns.
第１図は本発明に用いる流体パッド法による電解セルの
一例である。ス） ＩＪツブに対向配置したパッド３に
設けたスリットよりメッキ液を噴出させ、ストップとパ
ッド間にメッキ液を保持し近接で高電流密度で電解する
。
第２図は本発明条件による１と比較条件２との電流密度
と陰極電流効率の関係を示す。
第３図は電流密度２００ Ａ／ｄｒｒ？相対流速１．５
ｍ／ｓ ｅ Ｃの時の浴中のＮｉ／Ｚｎ比とメッキ被膜
中のＮｉ含有率％を示す図である。
第４図は浴中のＮｉ／Ｚｎ比が１．５電流密度２００に
／ｄｔｒ？の時の相対流速Ｖとメッキ被膜中のＮ１含有
率を示す本発明条件による図である。
第５図は、第４図に対応した本発明条件に入らない浴条
件で行った場合の図である。
第６〜８図は本発明の浴条件の決定を明らかに示した図
である。
第６図は、浴中のＨ２ＳＯ４濃度と電導塵におよび電流
効率Ｎの関係を示す。
第７図は浴中の（Ｚｎ８０４−７Ｈ２０＋’ＮｉＳＯ４
−６Ｈ２０）の濃度と電導塵におよび電流効率Ｎの関係
を示す図である。
又、第８図はＨ２ＳＯ４および（Ｚｎ ８０４ ・７Ｈ
２０十Ｎ ｉ ８０４ ・６Ｈ２０） （１”）濃度と
電流密度２００ Ａ／ｄｎｌ −Ｔ：行った時のメッキ
外観の関係を示す図である。
■ ストリップ
２ 電解槽
３ 電解液
４ 電極パッド
葬 ／ 図
特開昭５８−１９７２９２ （７）
＄ ４ ピ
ート ＼＼ φｌ−，。
策 窄
区
α〕
擬
手続補正書（方式）
％式％
１、事件の表示
昭和５７年特許願第８００３２号
２、発明の名称
高効率ガンマ−亜鉛ニッケル合金めっき鋼板の製造方法
３補正をする者
事件との関係 特許出願人
住 所 東京都千代田区大手町２丁目６番３号名称
（６６５）新日本製鐵株式会社
代表者 武 １） 豊
４代 理 人 〒１０５ 置（５０３）４８７７住
所 東京都港区西新橋１−１２−１第１森ビル８階６
、補正の対象
明細書の発明の名称のオキ
Ｚ補正の内容
明ａ書の発明の名称を「高効率ガンマ−亜鉛ニッケル合
金めっき鋼板の製造方法」と訂正する。
（２）
手続補正書
昭和５７年９月７ 日
特許庁長官 若 杉 和 夫 殿
１事件の表示
昭和５７年特許願第８００３２号
２発明の名称
高効率ガンマ−亜鉛ニッケル合金めっき鋼板の製造方法
６補正をする者
事件との関係 特許出願人
住 所 東京都千代田区大手町２丁目６番３号名称
（６６５）新日本製鐵株式会社
代表者 武 １） 豊
４、代 理 人 〒１０５ 置（５０３）４８７７住
所 東京都港区西新橋１−１２−１ 第１森ビル８
階Ｚ補正の内容
（１）特許請求の範囲を下記の通り補正する。
「電極面と被めっき面との間に電解液を噴出せしめて極
面と被めっき面との間に液を保持しながら電気亜鉛ニッ
ケル合金めっきを行う方法においてめっき浴としてＺｎ
８０４．’７Ｈ２０とＮ ｉ Ｓｏ、争６Ｈ２０との和
が４００〜７ Ｄ Ｏ！Ｖｌ、 Ｎｉ／Ｚｎ比１０〜２
０、Ｈ２ＳＯ４５〜２０ Ｖｌから々る浴を用い、浴温
６０℃以上、ス） ＩＪ ＞プとめつき浴の相対速度が
１ ｙ７Ｈ／ｓｅｃ 以上、電流密度１００〜２５０
Ａ、／ｄｍ２でめっきを行うことを特徴とする高効率ガ
ンマ−亜鉛ニッケル合金めっき鋼板の製造方法。」
（２）FIG. 1 is an example of an electrolysis cell using the fluid pad method used in the present invention. S) Spout the plating solution from the slit provided in the pad 3 placed opposite the IJ tube, hold the plating solution between the stop and the pad, and conduct electrolysis at high current density in close proximity. FIG. 2 shows the relationship between current density and cathode current efficiency under conditions 1 according to the present invention and under comparative conditions 2. Figure 3 shows a current density of 200 A/drr? Relative flow rate 1.5
FIG. 3 is a diagram showing the Ni/Zn ratio in the bath and the Ni content percentage in the plating film at m/s e C. Figure 4 shows that the Ni/Zn ratio in the bath is 1.5 and the current density is 200/dtr? FIG. 3 is a diagram showing the relative flow velocity V and the N1 content in the plating film under the conditions of the present invention. FIG. 5 is a diagram corresponding to FIG. 4 when the bath conditions were not included in the conditions of the present invention. Figures 6-8 clearly illustrate the determination of bath conditions according to the present invention. FIG. 6 shows the relationship between H2SO4 concentration in the bath, conductive dust, and current efficiency N. Figure 7 shows (Zn804-7H20+'NiSO4) in the bath.
-6H20) concentration, conductive dust, and current efficiency N. In addition, Figure 8 shows H2SO4 and (Zn 804 ・7H
200 N i 804 ・6H20) (1") Concentration and current density 200 A/dnl -T: This is a diagram showing the relationship between plating appearance when performed. ■ Strip 2 Electrolytic tank 3 Electrolyte 4 Electrode pad mounting / Figure JP-A-58-197292 (7) $ 4 Pete \\ φl-,. Strategy Narrowing Area α〕 Pseudo-procedural Amendment (Method) % Formula % 1. Indication of Case 1980 Patent Application No. 80032 2. Invention Name of Highly Efficient Gamma-Zinc Nickel Alloy Coated Steel Sheet Production Method 3 Relationship to the Amendment Case Patent Applicant Address 2-6-3 Otemachi, Chiyoda-ku, Tokyo Name
(665) Nippon Steel Corporation Representative Takeshi 1) Yutaka 4th generation Masato Address: (503) 4877, 105
Address: 6th floor, 8th floor, Daiichi Mori Building, 1-12-1 Nishi-Shinbashi, Minato-ku, Tokyo
, the title of the invention in the specification to be amended is corrected; the title of the invention in the statement of contents of the amendment is corrected to "method for manufacturing high-efficiency gamma-zinc-nickel alloy coated steel sheet". (2) Procedural amendment September 7, 1980 Kazuo Wakasugi, Commissioner of the Patent Office 1. Indication of the case 1982 Patent Application No. 80032 2. Name of the invention Method for manufacturing highly efficient gamma-zinc nickel alloy coated steel sheet 6 Relationship with the case of the person making the amendment Patent applicant address 2-6-3 Otemachi, Chiyoda-ku, Tokyo Name
(665) Nippon Steel Corporation Representative Takeshi 1) Yutaka 4, Agent 105 (503) 4877 Address Daiichi Mori Building 8, 1-12-1 Nishi-Shinbashi, Minato-ku, Tokyo
Contents of the Z-level amendment (1) The claims are amended as follows. ``In a method of electrolytic zinc-nickel alloy plating in which an electrolyte is jetted between the electrode surface and the surface to be plated and the liquid is maintained between the electrode surface and the surface to be plated, Zn is used as the plating bath.
804. The sum of '7H20 and N i So, 6H20 is 400-7 DO! Vl, Ni/Zn ratio 10-2
0, H2SO45-20 Vl using a liquid bath, bath temperature 60°C or higher, relative speed of plating bath 1y7H/sec or higher, current density 100-250
A method for producing a highly efficient gamma-zinc-nickel alloy plated steel sheet, characterized in that plating is carried out at A,/dm2. ” (2)
Claims (1)
と被めっき而との間に液を保持しながら電気亜鉛−ニッ
ケル合金めっきを行う方法においてめっき浴としてＺｎ
８０４ ’ ７Ｈ２０とＮ ｉ Ｓｏ、 ・６Ｈ２０
との和が４ｏＯ〜７００ ｆ／ｌ 、 Ｎｉ／Ｚｎ比１
．０〜２．０、Ｈ２ＳＯ４５〜２０７／ｌからなる浴を
用い、浴温６０℃以上、ストリップとめつき浴の相対速
度が１ｍ／ｓｅｃ以上、電流密度１００〜２５０ Ａ７
’ｄｒｒ？でめつきを行うことを特徴とする高効率ガン
マ−亜鉛−ニッケル合金めっき鋼板の製造方法。Zn is used as a plating bath in a method of electrolytic zinc-nickel alloy plating by jetting an electrolytic solution between the electrode surface and the surface to be plated and maintaining the liquid between the electrode surface and the surface to be plated.
804' 7H20 and N i So, ・6H20
The sum is 4oO~700 f/l, Ni/Zn ratio 1
．． 0 to 2.0, using a bath consisting of H2SO45 to 207/l, bath temperature 60°C or higher, relative speed of strip and plating bath 1 m/sec or higher, current density 100 to 250 A7
'drr? 1. A method for producing a highly efficient gamma-zinc-nickel alloy plated steel sheet, the method comprising plating the steel sheet.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8003282A JPS58197292A (en) | 1982-05-14 | 1982-05-14 | Production of steel plate plated with gamma zinc-nickel alloy in high efficiency |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8003282A JPS58197292A (en) | 1982-05-14 | 1982-05-14 | Production of steel plate plated with gamma zinc-nickel alloy in high efficiency |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58197292A true JPS58197292A (en) | 1983-11-16 |
| JPS6119719B2 JPS6119719B2 (en) | 1986-05-19 |
Family
ID=13706920
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8003282A Granted JPS58197292A (en) | 1982-05-14 | 1982-05-14 | Production of steel plate plated with gamma zinc-nickel alloy in high efficiency |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58197292A (en) |
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| JPS58204195A (en) * | 1982-05-25 | 1983-11-28 | Nippon Kokan Kk <Nkk> | Manufacture of steel plate electroplated with ni-zn alloy and provided with superior workability and corrosion resistance |
| JPS62136590A (en) * | 1985-12-10 | 1987-06-19 | Kawasaki Steel Corp | Production of zn-ni alloy plated steel sheet |
| JPH01316490A (en) * | 1988-06-16 | 1989-12-21 | Kawasaki Steel Corp | Production of zn-ni alloy plated steel strip |
| JPH02228492A (en) * | 1989-03-02 | 1990-09-11 | Nkk Corp | Production of zinc alloy electroplated steel sheet |
| JP2009504914A (en) * | 2005-08-12 | 2009-02-05 | アイソトロン コーポレイション | Composition-modulated composite material and method for forming the same |
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| US7101469B2 (en) * | 2004-11-10 | 2006-09-05 | Atotech Deutschland Gmbh | Metal pieces and articles having improved corrosion resistance |
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1982
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Also Published As
| Publication number | Publication date |
|---|---|
| JPS6119719B2 (en) | 1986-05-19 |
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