JPH06280085A - Galvanized aluminum and aluminum alloy excellent in adhesion and production thereof - Google Patents
Galvanized aluminum and aluminum alloy excellent in adhesion and production thereofInfo
- Publication number
- JPH06280085A JPH06280085A JP6585493A JP6585493A JPH06280085A JP H06280085 A JPH06280085 A JP H06280085A JP 6585493 A JP6585493 A JP 6585493A JP 6585493 A JP6585493 A JP 6585493A JP H06280085 A JPH06280085 A JP H06280085A
- Authority
- JP
- Japan
- Prior art keywords
- plating
- aluminum
- zinc
- iron
- aluminum alloy
- 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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- Electroplating Methods And Accessories (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は自動車,車両,建築材
料,船舶,航空機などに用いられる、密着性の優れた亜
鉛系めっきアルミニウムおよびアルミニウム合金の板お
よび帯に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to zinc-plated aluminum and aluminum alloy plates and strips having excellent adhesion, which are used in automobiles, vehicles, building materials, ships, aircraft and the like.
【0002】[0002]
【従来の技術】近年アルミニウムおよびアルミニウム合
金が軽量化などの目的で自動車等に用いられるようにな
ってきたが、コストや材料強度などの点で全部が従来材
から置換るまでに至らず、薄鋼板あるいは亜鉛系めっき
鋼板と共用される場合が多い。この場合には、塗装前処
理であるりん酸塩処理や電着塗装、トップコートなどは
鋼板と全く同じ処理工程で処理されることになるが、工
程適性や塗装後の特性に関しては鋼板と同等あるいはそ
れ以上の特性が要求される。2. Description of the Related Art In recent years, aluminum and aluminum alloys have come to be used in automobiles and the like for the purpose of weight reduction. However, in terms of cost and material strength, all of them cannot be replaced with conventional materials, and they are thin. It is often shared with steel sheets or zinc-based plated steel sheets. In this case, the pre-coating treatment such as phosphate treatment, electrodeposition coating, and topcoat are processed in exactly the same process as the steel plate, but the process suitability and the properties after coating are equivalent to those of the steel plate. Or even higher characteristics are required.
【0003】このようにアルミニウムあるいはアルミニ
ウム合金を鋼板と同時処理する場合には亜鉛系めっきを
行うとよいことがわかっているが、アルミニウムおよび
アルミニウム合金は亜鉛系めっきを施すのが難しく、最
新表面処理技術総覧(昭和63年4月産業技術サービス
センター発行)に記述のような置換めっき方法、あるい
は特開昭51−1332号公報、特開昭51−4754
9号公報、あるいは特開平4−350195号公報のよ
うに、アノード処理して酸化皮膜を生成させたあと、そ
の上に亜鉛系めっきを行う方法などが試みられてきた。
とくにアノード処理を行ってからめっきする方法は生産
性において優れており、アルミニウムおよびアルミニウ
ム合金を連続的短時間に処理することが可能であった。It has been found that zinc-based plating is preferably applied when simultaneously treating aluminum or an aluminum alloy with a steel sheet as described above, but it is difficult to apply zinc-based plating to aluminum and aluminum alloys, and the latest surface treatment is required. The displacement plating method as described in Technical Guide (published by the Industrial Technology Service Center in April 1988), or JP-A-51-1332 and JP-A-51-4754.
As disclosed in Japanese Patent Laid-Open No. 9-35095 or Japanese Patent Laid-Open No. 4-350195, there have been attempts such as a method in which an oxide film is formed by anodizing and then zinc-based plating is performed thereon.
In particular, the method of plating after the anode treatment was excellent in productivity, and it was possible to treat aluminum and aluminum alloys continuously in a short time.
【0004】[0004]
【発明が解決しようとする課題】このような従来技術に
対して、より生産性に優れ、高速で安価に処理ができ
ること。品質特性が塗装下地として適性であって、鋼
板あるいは亜鉛めっき鋼板と同時に処理しても塗装後の
特性は鋼板あるいは亜鉛めっき鋼板と同じかあるいは優
れていることが望まれている。そのためには、今までよ
りもさらに密着性の優れた亜鉛系めっき層を有するアル
ミニウムおよびアルミニウム合金が必要とされている。In comparison with such a conventional technique, it is possible to perform processing at a higher productivity and at a higher speed and at a lower cost. It is desired that the quality characteristics are suitable as a coating base, and that the characteristics after coating are the same as or superior to those of a steel sheet or a galvanized steel sheet even if they are treated simultaneously with the steel sheet or the galvanized steel sheet. For that purpose, aluminum and aluminum alloys having a zinc-based plating layer with more excellent adhesion than ever are required.
【0005】[0005]
【課題を解決するための手段】そこで本発明者は、鋭意
検討を続けた結果、亜鉛系めっきとアルミニウムおよび
アルミニウム合金との密着性をよくするには、アルミニ
ウムおよびアルミニウム合金の表面に鉄含有量の多い鉄
−亜鉛フラッシュめっきを施し、その上に所定のめっき
を施すことによって優れた密着性が得られることを見い
だし、本発明に至った。すなわち本発明は、下層表面に
鉄の割合が50〜100%の鉄−亜鉛フラッシュめっき
層を厚みで0.01〜7g/m2 有し、その上に亜鉛系
めっき層を有する密着性の優れたアルミニウムおよびア
ルミニウム合金。あるいは、表面にアルミ酸化膜を生成
させ、その上に鉄の割合が50〜100%の鉄−亜鉛フ
ラッシュめっき層を厚みで0.01〜7g/m2 有し、
その上に亜鉛系めっき層を有する密着性の優れたアルミ
ニウムおよびアルミニウム合金。Therefore, as a result of continuous studies, the present inventor has found that in order to improve the adhesion between zinc-based plating and aluminum and aluminum alloys, the iron content on the surface of aluminum and aluminum alloys should be improved. It was found that excellent adhesion can be obtained by performing iron-zinc flash plating, which is often used, and then performing a predetermined plating thereon, and has reached the present invention. That is, the present invention has an iron-zinc flash plating layer having a ratio of iron of 50 to 100% on the lower layer surface in a thickness of 0.01 to 7 g / m 2 and having a zinc-based plating layer thereon, which is excellent in adhesion. Aluminum and aluminum alloys. Alternatively, an aluminum oxide film is formed on the surface, and an iron-zinc flash plating layer having an iron ratio of 50 to 100% is formed on the surface of 0.01 to 7 g / m 2 in thickness,
Aluminum and aluminum alloys having a zinc-based plating layer thereon and excellent in adhesion.
【0006】さらにはこのようなアルミニウムおよびア
ルミニウム合金を得るために第一鉄イオンを20〜10
0g/l、亜鉛イオンを50g/l以下、遊離酸5〜8
0g/lを含むめっき液で電流密度100〜700A/
dm2 にてフラッシュめっきし、そのあと亜鉛系電気め
っきを行う方法。あるいは、第一鉄イオンを20〜10
0g/l、亜鉛イオンを50g/l以下、遊離酸5〜8
0g/lを含むめっき液でアルミニウムおよびアルミニ
ウム合金をアノードとして電気量10〜200c/dm
2 で電解処理し、そのままカソードとして電流密度50
〜600A/dm2 にてフラッシュめっきし、そのあと
亜鉛系電気めっきを行う方法を要旨とする。Further, in order to obtain such aluminum and aluminum alloys, ferrous ions are added in an amount of 20 to 10
0 g / l, zinc ion 50 g / l or less, free acid 5-8
Current density of 100-700 A / with plating solution containing 0 g / l
Flash plating with dm 2 followed by zinc-based electroplating. Alternatively, the ferrous ion is 20 to 10
0 g / l, zinc ion 50 g / l or less, free acid 5-8
Electricity of 10 to 200 c / dm with a plating solution containing 0 g / l using aluminum and aluminum alloy as an anode
Electrolyzed at 2 , current density 50 as cathode
The gist is a method of performing flash plating at up to 600 A / dm 2 and then performing zinc-based electroplating.
【0007】[0007]
【作用】以下、本発明を詳細に説明する。本発明のめっ
き皮膜の構成図を図1に示す。(a)はアルミニウムお
よびアルミニウム合金1の表面の酸化皮膜を除いて鉄含
有量の多い鉄−亜鉛フラッシュめっき3を施し、その上
に亜鉛系めっき4を行ったもので、(b)はアノード処
理によってアルミニウムおよびアルミニウム合金1の表
面に酸化膜2を付着させ、その上に鉄含有量の多い鉄−
亜鉛フラッシュめっき3を施し、その上に亜鉛系めっき
4を行ったもので、(c)は(b)の鉄−亜鉛フラッシ
ュめっきを施した段階で表面からみた2000倍の拡大
模式図である。The present invention will be described in detail below. A configuration diagram of the plating film of the present invention is shown in FIG. (A) shows an iron-zinc flash plating 3 having a high iron content excluding the oxide film on the surface of aluminum and aluminum alloy 1, and zinc-based plating 4 thereon, and (b) shows anodization. By depositing an oxide film 2 on the surface of aluminum and aluminum alloy 1, and iron with a high iron content on the oxide film 2.
Zinc flash plating 3 is applied, and then zinc-based plating 4 is applied, and (c) is an enlarged schematic view of 2000 times viewed from the surface at the stage of applying iron-zinc flash plating of (b).
【0008】本発明のアルミニウムおよびアルミニウム
合金としては、板厚2.0mm以下の高純度アルミニウ
ムのほかに5000系あるいは6000系などマグネシ
ウムを10%以下含むものや銅を合金化したものも用い
ることができる。表面処理の観点からは合金化金属はで
きるだけ少ないものが望ましい。また、表面は圧延のま
まあるいは熱処理を受けたものでもよいが、酸化膜はで
きるだけ薄く、また防錆油もできるだけ少ない方が望ま
しい。酸化膜および油、汚れの付着状況によってアルカ
リ脱脂と酸洗の処理条件を決め、適性なめっき用表面を
得る必要がある。As the aluminum and aluminum alloy of the present invention, in addition to high-purity aluminum having a plate thickness of 2.0 mm or less, those containing 10% or less of magnesium such as 5000 series or 6000 series and those alloyed with copper can be used. it can. From the viewpoint of surface treatment, it is desirable that the amount of alloying metal is as small as possible. The surface may be as-rolled or subjected to heat treatment, but it is desirable that the oxide film be as thin as possible and the rust preventive oil be as small as possible. It is necessary to determine the processing conditions for alkaline degreasing and pickling depending on the state of adhesion of oxide film, oil and dirt to obtain an appropriate plating surface.
【0009】アルミニウムおよびアルミニウム合金のア
ルカリ脱脂および/あるいは酸洗は、表面調整をも兼ね
るのでかなり慎重に処理条件を選定する必要がある。ま
たこれらの工程で表面の酸化皮膜を除いても処理直後か
ら改めて酸化皮膜が生成しはじめ、めっき性を阻害する
ことになるので、極力早期にめっき工程に移る必要があ
る。通常の表面は、アルミニウムおよびアルミニウム合
金板をアルカリ脱脂あるいはアルカリ脱脂後に常温の5
%硫酸に浸漬酸洗して得られた。また、平滑で完全に酸
化皮膜を除いた良好な表面状態は、アルカリ脱脂あるい
はアルカリ脱脂後酸洗処理したあと、めっき液に少なく
とも1〜30秒浸漬して、その液中でめっきする方法に
よって可能であった。Since alkaline degreasing and / or pickling of aluminum and aluminum alloys also serves as surface adjustment, it is necessary to select treatment conditions fairly carefully. In addition, even if the oxide film on the surface is removed in these steps, an oxide film will start to be formed again immediately after the treatment and the plating property will be impaired, so it is necessary to move to the plating step as early as possible. Ordinary surfaces should be degreased with aluminum or aluminum alloy plates at room temperature or after alkaline degreasing at room temperature.
It was obtained by dipping and pickling in% sulfuric acid. In addition, a good surface condition that is smooth and completely free of oxide film can be obtained by a method of plating with alkali degreasing or after alkali degreasing followed by pickling, dipping in a plating solution for at least 1 to 30 seconds, and plating in that solution. Met.
【0010】鉄−亜鉛フラッシュめっきの密着性に関し
て、まずめっき組成と密着性との関係について調査した
結果、通常の前処理条件では鉄50%以上であれば充分
な密着性が得られることが判明した。めっき後のめっき
液に接触する時間、めっき液の遊離酸濃度、あるいはつ
ぎのめっきのめっき液に対する浸漬時間、遊離酸濃度に
よっても鉄−亜鉛めっきの必要最低鉄比率を決めること
ができた。通常の場合には、鉄の割合が50から100
%になるようにすれば充分であった。このような鉄の組
成比50%以上の鉄−亜鉛フラッシュめっきの付着量
は、平滑な表面の場合には3g/m2 以下あればよく、
さらに平滑で完全に酸化膜を除いた表面状態であれば
0.01g/m2 もあれば充分であった。Regarding the adhesion of iron-zinc flash plating, first, the result of an investigation on the relationship between the plating composition and the adhesion revealed that sufficient adhesion can be obtained if the iron content is 50% or more under normal pretreatment conditions. did. The required minimum iron ratio of iron-zinc plating could be determined by the time of contact with the plating solution after plating, the free acid concentration of the plating solution, the immersion time of the next plating in the plating solution, and the free acid concentration. In the normal case, the proportion of iron is 50 to 100
% Was sufficient. The amount of such iron-zinc flash plating having an iron composition ratio of 50% or more may be 3 g / m 2 or less in the case of a smooth surface,
Further, if the surface condition is smooth and the oxide film is completely removed, 0.01 g / m 2 is sufficient.
【0011】めっき浴の組成としては、第一鉄イオン、
亜鉛イオン,遊離酸が不可欠である。めっき層中に鉄を
50%以上含有させ、効率よく析出させるには、第一鉄
イオン濃度は20g/l以上は必要であった。一方、第
一鉄イオン濃度100g/l以上は溶解しにくかった。
また、鉄−亜鉛めっき中の鉄の組成比率は、一次的に
は、めっき浴中の亜鉛イオンと第一鉄イオンの比率によ
って決まる。そこで、鉄を50%以上含むめっきを行う
場合には、第一鉄イオンと亜鉛イオンに対する第一鉄イ
オンの比率を60%以上にする必要があった。このため
には亜鉛イオンは67g/l以下、望ましくは50g/
l以下にする必要があった。The composition of the plating bath is ferrous ion,
Zinc ion and free acid are indispensable. The ferrous ion concentration was required to be 20 g / l or more in order to cause iron to be contained in the plating layer in an amount of 50% or more and to be efficiently deposited. On the other hand, the ferrous ion concentration of 100 g / l or more was difficult to dissolve.
Further, the composition ratio of iron in the iron-zinc plating is primarily determined by the ratio of zinc ions and ferrous ions in the plating bath. Therefore, when performing plating containing 50% or more of iron, the ratio of ferrous ions to ferrous ions and zinc ions needs to be 60% or more. For this purpose, the zinc ion content is 67 g / l or less, preferably 50 g / l.
It was necessary to make it 1 or less.
【0012】遊離酸濃度については、低すぎると鉄や亜
鉛の水酸化物などが付着し、めっきが黒くなるので5g
/l以上にする必要があった。しかし、あまり高くする
と鉄の組成比が低くなり、電流効率が低下するので80
g/l以下にする必要があった。また、めっきの電流密
度について調査した結果、電流密度が低いとめっきの亜
鉛含有率が高くなり、密着性が悪くなるので、通常の場
合には100A/dm2以上が望ましかった。しかし、
電流密度が高くなりすぎると、めっき量のコントロール
が難しくなるだけでなく、密着性も劣化するので上限を
700A/dm2にする必要があった。鉄の含有率の多
い鉄−亜鉛フラッシュめっきの上のめっきとしては亜鉛
含有率の多い鉄−亜鉛めっきあるいは亜鉛めっきなどを
必要厚みだけ行うことが可能である。Regarding the free acid concentration, if it is too low, hydroxides of iron and zinc, etc. will adhere and the plating will turn black.
It was necessary to make it more than 1 / l. However, if it is too high, the composition ratio of iron will be low, and the current efficiency will be reduced.
It was necessary to make it g / l or less. Further, as a result of investigating the current density of the plating, the zinc content of the plating becomes high when the current density is low, and the adhesion becomes poor. Therefore, 100 A / dm 2 or more was usually desired. But,
If the current density becomes too high, not only the control of the plating amount becomes difficult, but also the adhesiveness deteriorates, so it was necessary to set the upper limit to 700 A / dm 2 . As the plating on the iron-zinc flash plating having a high iron content, it is possible to perform iron-zinc plating having a high zinc content or zinc plating to a required thickness.
【0013】次に、アノード電解処理を行う方法につい
て述べる。本発明においては、アノード処理によって表
面にアルミ酸化膜を生成させる。通常、酸化膜は電気抵
抗が大きいので直接めっきすることはできない。しか
し、本発明の鉄−亜鉛フラッシュめっきを行う場合には
実験の結果、密着性のよい鉄の組成比50%以上の鉄−
亜鉛フラッシュめっきを行いやすくするのに有効である
ことがわかった。図1(c)に示したように、鉄−亜鉛
フラッシュめっきを施した段階で表面からみたアルミ酸
化膜の面積は、めっきの面積の60%以下であれば充分
な密着性を得ることができた。Next, a method of performing anode electrolysis will be described. In the present invention, an aluminum oxide film is formed on the surface by anodic treatment. In general, an oxide film has a high electric resistance and therefore cannot be directly plated. However, when performing the iron-zinc flash plating of the present invention, as a result of an experiment, iron having a good adhesion of a composition ratio of iron of 50% or more-
It has been found to be effective in facilitating zinc flash plating. As shown in FIG. 1 (c), if the area of the aluminum oxide film seen from the surface at the time of iron-zinc flash plating is 60% or less of the plating area, sufficient adhesion can be obtained. It was
【0014】アノード処理は、アルカリ脱脂あるいはア
ルカリ脱脂したあとめっき液中でアルミニウムおよびア
ルミニウム合金をアノードとして電解し酸化皮膜を生成
させることによって行った。アノード処理後は、表面が
変化する前にめっきするため、めっき液中でそのまま極
性をカソードに切り換えてめっきした方がよかった。ア
ノード処理によって生成する酸化皮膜の厚みは、通電電
気量によってコントロールが可能であるが、厚すぎると
不めっきの部分が多く残るので、通電量は200c/d
m2 以下、望ましくは150c/dm2 以下にする必要
があった。酸化膜の平均膜厚は100Å以下が望ましか
った。一方、通電量が低すぎると酸化膜が少なすぎるの
で最低10c/dm2 は通電する必要があった。生成し
た酸化膜は、めっき液を通過中あるいは鉄の含有率の高
い鉄−亜鉛フラッシュめっきの初期の段階に一部は消失
し、その部分にはめっきが生成するらしく、アノード処
理の通電量だけでめっきの最適条件を決めることができ
ない面もあった。The anode treatment was carried out by alkaline degreasing or alkaline degreasing, followed by electrolysis in a plating solution using aluminum and aluminum alloy as an anode to form an oxide film. After the anode treatment, the plating is performed before the surface is changed, so it is better to switch the polarity to the cathode as it is in the plating solution. The thickness of the oxide film formed by the anode treatment can be controlled by the amount of electricity supplied, but if it is too thick, many unplated parts remain, so the amount of electricity supplied is 200 c / d.
m 2 or less, preferably 150 c / dm 2 or less. It was desired that the average film thickness of the oxide film be 100 Å or less. On the other hand, if the energization amount is too low, the oxide film is too small, so it is necessary to energize at least 10 c / dm 2 . The generated oxide film may partially disappear during the passage of the plating solution or in the early stage of iron-zinc flash plating with a high iron content, and plating may be generated in that part. There was also a side where it was not possible to determine the optimum plating conditions.
【0015】アノード処理後のめっき液の条件は、既に
前述した条件と同様でよい。ただ、電流密度について
は、めっき前にアノード処理を行う場合は、50A/d
m2 以上、望ましくは70A/dm2 以上と比較的低い
電流密度から密着のよいめっきが可能であった。これ
は、アノード処理を行うことによって表面のかなりの部
分が電気抵抗の大きな酸化膜によって被われるので、初
期電着時における実質のめっき面積が減少するからアノ
ード処理を行わないものに比べて、めっき電流が小さく
ても実質的には大きな電流密度で電着されていることに
なり、アルミニウムおよびアルミニウム合金との界面付
近のめっきに鉄の含有率の高い鉄−亜鉛めっきが生成し
たためと思われる。実験の結果、鉄−亜鉛めっき中の亜
鉛の割合が高いと、通電後にめっき液に接触している
間、さらにこの上にめっきするような場合にめっき液に
よって亜鉛が優先的に溶解し、めっきの密着性を損なわ
れることもわかった。アノード処理を行った場合にも電
流密度に上限があって600A/dm2 以上になると密
着性に問題が生じた。The conditions of the plating solution after the anode treatment may be the same as the above-mentioned conditions. However, regarding the current density, if the anode treatment is performed before plating, 50 A / d
Plating with good adhesion was possible from a relatively low current density of m 2 or more, preferably 70 A / dm 2 or more. This is because a substantial part of the surface is covered with an oxide film having a large electric resistance by anodizing, so the actual plating area at the time of initial electrodeposition is reduced, so compared with the case where anodizing is not performed, It is considered that the electrodeposition was substantially carried out at a high current density even when the current was small, and the iron-zinc plating having a high iron content was generated in the plating near the interface with aluminum and the aluminum alloy. As a result of the experiment, when the proportion of zinc in the iron-zinc plating is high, the zinc is preferentially dissolved by the plating solution during the contact with the plating solution after energization and further plating on the plating solution. It was also found that the adhesiveness of was impaired. Even when the anode treatment was performed, the current density had an upper limit, and when the current density was 600 A / dm 2 or more, there was a problem in adhesion.
【0016】鉄−亜鉛めっきの付着量は、アノード処理
によって酸化膜を生成させた場合には、酸化膜の厚みに
もよるが2000倍のSEMで検鏡してアルミニウム下
地が見えなくするには7g/m2 必要な場合もあった。
ただアノード処理によって下層のめっきがアルミニウム
あるいはアルミニウム合金の表面全面を被わない場合に
はその上にめっきを行うことは困難であった。もしめっ
きされない面積が極く小さい場合には、その上にめっき
する時電流密度をできるだけ小さく、例えば5A/dm
2 以下にすることによってカバーすることができる場合
もあった。The amount of iron-zinc plating deposited depends on the thickness of the oxide film when an oxide film is formed by anodic treatment, but in order to make the aluminum underlayer invisible under a SEM of 2000 times. In some cases, 7 g / m 2 was required.
However, when the plating of the lower layer does not cover the entire surface of the aluminum or aluminum alloy due to the anode treatment, it is difficult to perform plating on it. If the unplated area is extremely small, the current density should be as small as possible when plating on it, eg 5 A / dm
In some cases, it could be covered by setting it to 2 or less.
【0017】本発明のめっきを行う工程としては、例え
ば図2に示す方法が考えられる。図2(a)はアルミニ
ウムおよびアルミニウム合金帯1を搬送ロール12とシ
ンクロール11を介して搬送しながら、最初のタンク1
0の鉄−亜鉛めっき液13中で対極6を用いて高電流密
度の通電を行い、鉄含有量の多い鉄−亜鉛フラッシュめ
っきを行い、つぎのタンク10中の亜鉛系めっき液14
中で対極7との間で亜鉛系めっきを行う方法である。ま
た図2(b)は最初のタンク10の鉄−亜鉛めっき液1
3の入り側で対極5を用いアノード処理を行い、出側の
対極6を用いて高電流密度で鉄含有量の多い鉄−亜鉛フ
ラッシュめっきを行い、つぎのタンク10の対極7を用
いて亜鉛系のめっきを行う方法である。The method shown in FIG. 2, for example, can be considered as the step of performing the plating of the present invention. FIG. 2A shows the first tank 1 while the aluminum and aluminum alloy strips 1 are being conveyed through the conveying roll 12 and the sink roll 11.
In the iron-zinc plating solution 13 of No. 0, the counter electrode 6 was used to conduct high-current density energization, the iron-zinc flash plating with a large iron content was performed, and the zinc-based plating solution 14 in the next tank 10 was used.
In this method, zinc-based plating is performed with the counter electrode 7. Further, FIG. 2B shows the first iron-zinc plating solution 1 in the tank 10.
Anode treatment is performed using the counter electrode 5 on the inlet side of No. 3, iron-zinc flash plating having a high current density and high iron content is performed using the counter electrode 6 on the outlet side, and zinc is applied using the counter electrode 7 of the next tank 10. This is a method of plating the system.
【0018】上層に鉄−亜鉛めっきを行う場合には鉄含
有量がめっき電流密度に依存することを利用して、例え
ば図2(c)に示すようにアルミニウムおよびアルミニ
ウム合金の帯1に最初対極6との間で高電流密度でフラ
ッシュめっきを行い、絶縁体の隔離板9を挟んで対極8
を設け、所定の亜鉛含有量の鉄−亜鉛めっきを得ること
ができる電流密度の電流を流すことによって2層のめっ
きを行うことも考えられる。さらに図2(d)に示すよ
うに最初のパスに対極5を設けアノード処理を行ってか
ら、図2(c)の処理と同じ処理を行うことも考えられ
る。またさらにアノードを帯に対して斜めに設置し、め
っき初期においてはアノードと帯の間隔を小さく、めっ
き出側で大きくすればめっき組成を断面方向で変化させ
ることも可能である。ただこれらの方法では大幅に組成
の異なるめっきを行うことは困難である。When iron-zinc plating is performed on the upper layer, the fact that the iron content depends on the plating current density is utilized, and for example, as shown in FIG. 2 (c), the band 1 of aluminum and aluminum alloy is first counter electrode. 6 and 6 are flash-plated with a high current density, and a separator 8 of an insulator is sandwiched between the counter electrode 8
It is also conceivable to perform two-layer plating by providing an electric current having a current density capable of obtaining iron-zinc plating having a predetermined zinc content. Further, as shown in FIG. 2D, it is also conceivable to provide the counter electrode 5 in the first pass and perform the anode treatment, and then perform the same treatment as the treatment of FIG. 2C. It is also possible to change the plating composition in the cross-sectional direction by disposing the anode obliquely with respect to the strip, and making the gap between the anode and the strip small at the initial stage of plating and increasing it at the plating outlet side. However, it is difficult for these methods to perform plating with a composition greatly different.
【0019】[0019]
実施例1 自動車の部材として用いられる板厚1.0mmのアルミ
ニウム合金(Al−5.5%Mg)の冷間圧延帯を温度
70℃の60g/lFC315(日本パーカライジング
(株)製、非エッチング型弱アルカリクリーナー)に1
分20秒間浸漬し、水洗後60℃の40g/l硫酸にて
酸洗し、水洗した。この材料をカソードとして60℃の
第一鉄イオン95g/l、亜鉛イオン10g/l、遊離
酸45g/l、に添加剤を含む溶液中で電流密度200
A/dm2 にて0.3秒間電解し、めっき付着量1g/
m2 、めっき中の鉄含有率70%の鉄−亜鉛フラッシュ
めっきしたあと50℃の亜鉛イオン110g/l、遊離
酸50g/lの溶液にて電流密度100A/dm2 にて
4秒間電解し、水洗乾燥した。このようにして得られた
アルミニウム合金板のめっきにセロテープを張り付け、
その上から消しゴムでこすり、中の空気を押し出したあ
と急激にセロテープを剥離し、めっきがセロテープ側に
付着してくるか否かでめっきの密着性を調べたが剥離は
全くなかった。Example 1 A cold-rolled strip of an aluminum alloy (Al-5.5% Mg) having a plate thickness of 1.0 mm used as a member for automobiles was manufactured at a temperature of 70 ° C. of 60 g / l FC315 (Nippon Parkerizing Co., Ltd., non-etching type). 1 for weak alkaline cleaner)
It was immersed for 20 minutes per minute, washed with water, then pickled with 40 g / l sulfuric acid at 60 ° C., and washed with water. Using this material as a cathode, at a temperature of 60 ° C., a ferrous ion 95 g / l, a zinc ion 10 g / l, a free acid 45 g / l, and a current density of 200 in a solution containing additives.
Electrolyze at A / dm 2 for 0.3 seconds and deposit plating amount 1 g /
m 2 and iron-zinc flash plating with an iron content of 70% in the plating, followed by electrolysis for 4 seconds at a current density of 100 A / dm 2 with a solution of zinc ions of 110 g / l and free acid of 50 g / l at 50 ° C. It was washed with water and dried. Stick cellophane tape on the plating of the aluminum alloy plate thus obtained,
After rubbing it with an eraser and pushing out the air inside, the cellophane tape was rapidly peeled off. The adhesion of the plating was examined by checking whether the plating adhered to the side of the cellophane tape, but there was no peeling at all.
【0020】実施例2 自動車の部材として用いられる板厚1.0mmのアルミ
ニウム合金(Al−5.5%Mg)の冷間圧延帯を温度
70℃の60g/lFC315(日本パーカライジング
(株)製、非エッチング型弱アルカリクリーナー)に1
分20秒間浸漬し、水洗した。この材料を60℃の第一
鉄95g/l、亜鉛イオン10g/l、遊離酸45g/
lに添加剤を含む溶液中でまずアノードとして電流密度
3A/dm2 にて18秒電解処理し、そのまま同じ液中
でアルミニウム合金をカソードとして電流密度100A
/dm2 にて0.8秒間電解し、めっき付着量1g/m
2、めっき中の鉄含有率75%の鉄−亜鉛フラッシュめ
っきしたあと、50℃の亜鉛イオン110g/l、遊離
酸50g/lの溶液にて電流密度100A/dm2にて
1秒間電解し、水洗乾燥した。このようにして得られた
アルミニウム合金板のめっきにセロテープを張り付け、
その上から消しゴムでこすり、中の空気を押し出したあ
と急激にセロテープを剥離し、めっきがセロテープ側に
付着してくるか否かでめっきの密着性を調べたが剥離は
全くなかった。Example 2 A cold-rolled strip of an aluminum alloy (Al-5.5% Mg) having a plate thickness of 1.0 mm used as a member for automobiles was manufactured at a temperature of 70 ° C. of 60 g / l FC315 (manufactured by Nippon Parkerizing Co., Ltd.). 1 for non-etching type weak alkaline cleaner)
It was immersed for 20 seconds per minute and washed with water. This material is ferrous iron at 60 ° C. 95 g / l, zinc ion 10 g / l, free acid 45 g / l
First, in a solution containing an additive in 1 liter, an electrolytic treatment was first performed as an anode at a current density of 3 A / dm 2 for 18 seconds, and an aluminum alloy was used as a cathode in the same solution at a current density of 100 A.
Electrolysis at 0.8 psi / dm 2 for 0.8 seconds, coating weight 1g / m
2. After iron-zinc flash plating with an iron content of 75% in the plating, electrolysis was performed for 1 second at a current density of 100 A / dm 2 with a solution of zinc ions of 110 g / l and free acid of 50 g / l at 50 ° C. It was washed with water and dried. Stick cellophane tape on the plating of the aluminum alloy plate thus obtained,
After rubbing it with an eraser and pushing out the air inside, the cellophane tape was rapidly peeled off. The adhesion of the plating was examined by checking whether the plating adhered to the side of the cellophane tape, but there was no peeling at all.
【0021】実施例3 自動車の部材として用いられる板厚1.0mmのアルミ
ニウム合金(Al−5.5%Mg)の冷間圧延帯を温度
70℃の60g/lのファインクリーナー315(日本
パーカライジング(株)製、非エッチング型弱アルカリ
クリーナー)に1分20秒間浸漬し、水洗後60℃の4
0g/l硫酸にて酸洗し、水洗した。この材料をカソー
ドとして60℃の第一鉄イオン81g/l、亜鉛イオン
23g/l、遊離酸52g/lに添加剤を含む溶液中で
電流密度50A/dm2 にて1.3秒間電解し、めっき
付着量1g/m2 、めっき中の鉄含有率40%の鉄−亜
鉛フラッシュめっきしたあと、50℃の亜鉛イオン11
0g/l、遊離酸50g/lの溶液にて電流密度100
A/dm2 にて4秒間電解し、水洗乾燥した。このよう
に鉄−亜鉛フラッシュめっきの電流密度の条件が本発明
の範囲100A/dm2 以上の外で処理し、めっき中の
鉄含有率が50%以上から外れたアルミニウム合金板の
めっきにセロテープを張り付け、その上から消しゴムで
こすり、中の空気を押し出したあと急激にセロテープを
剥離し、めっきがセロテープ側に付着してくるか否かで
めっきの密着性を調べたところ完全に剥離した。Example 3 A cold-rolled strip of an aluminum alloy (Al-5.5% Mg) having a plate thickness of 1.0 mm used as a member for automobiles was treated with 60 g / l of fine cleaner 315 (Nihon Parkerizing ( Co., Ltd., non-etching type weak alkaline cleaner) for 1 minute 20 seconds, washed with water, and then at 60 ° C for 4 minutes.
It was pickled with 0 g / l sulfuric acid and washed with water. Using this material as a cathode, electrolysis is carried out at 60 ° C. in a solution containing 81 g / l of ferrous ions, 23 g / l of zinc ions, 52 g / l of free acid and an additive at a current density of 50 A / dm 2 for 1.3 seconds, After the iron-zinc flash plating with a coating weight of 1 g / m 2 and an iron content rate of 40% in the plating, zinc ions at 50 ° C. 11
Current density of 100 with a solution of 0 g / l and free acid 50 g / l
It was electrolyzed at A / dm 2 for 4 seconds, washed with water and dried. In this way, the condition of the current density of the iron-zinc flash plating is treated outside the range of 100 A / dm 2 or more of the present invention, and the cellophane tape is applied to the plating of the aluminum alloy plate in which the iron content in the plating deviates from 50% or more. After sticking, rubbing with an eraser from above and pushing out the air inside, the cellophane tape was rapidly peeled off. When the adhesion of the plating was examined by checking whether the plating adhered to the side of the cellophane tape, it was completely peeled off.
【0022】実施例4 自動車の部材として用いられる板厚1.0mmのアルミ
ニウム合金(Al−5.5%Mg)の冷間圧延帯を温度
70℃の60g/lのファインクリーナー315(日本
パーカライジング(株)製、非エッチング型弱アルカリ
クリーナー)に1分20秒間浸漬し、水洗した。この材
料を60℃の第一鉄イオン81g/l、亜鉛イオン23
g/l、遊離酸52g/lに添加剤を含む溶液中でまず
対極として鉛電極を設置したパスを通し、電流密度3A
/dm2 にて18秒アノード処理し、つぎに同じ液中で
対極として鉛電極を設置したパスに導き、アルミニウム
合金をカソードとして電流密度40A/dm2 にて1.
5秒間電解し、めっき付着量1g/m2 、めっき中の鉄
含有率40%の鉄−亜鉛フラッシュめっきしたあと、5
0℃の亜鉛イオン110g/l、遊離酸50g/lの溶
液にて電流密度100A/dm2 にて4秒間電解し、水
洗乾燥した。このように鉄−亜鉛フラッシュめっき液中
でアノード処理し、そのままカソードとして鉄−亜鉛フ
ラッシュめっきするときの電流密度の条件が本発明の範
囲50A/dm2 以上の外で処理し、めっき中の鉄含有
率が50%以上から外れたアルミニウム合金板のめっき
にセロテープを張り付け、その上から消しゴムでこす
り、中の空気を押し出したあと急激にセロテープを剥離
し、めっきがセロテープ側に付着してくるか否かでめっ
きの密着性を調べたところ完全に剥離した。Example 4 A cold-rolled strip of an aluminum alloy (Al-5.5% Mg) having a plate thickness of 1.0 mm used as a member for automobiles was treated with a fine cleaner 315 (Nihon Parkerizing Co., Ltd., non-etching type weak alkaline cleaner) was immersed for 1 minute 20 seconds and washed with water. 81 g / l of ferrous ion, zinc ion 23 at 60 ° C
g / l, free acid 52 g / l in a solution containing an additive, first pass through a path in which a lead electrode is installed as a counter electrode, current density 3 A
/ Dm 2 for 18 seconds and then led to a path in the same liquid in which a lead electrode was installed as a counter electrode, and an aluminum alloy was used as a cathode at a current density of 40 A / dm 2 .
Electrolyze for 5 seconds, deposit 1g / m 2 of plating, iron-zinc flash plating with an iron content of 40% in the plating, then 5
Electrolysis was performed for 4 seconds at a current density of 100 A / dm 2 with a solution of zinc ions of 110 g / l and free acid of 50 g / l at 0 ° C., followed by washing with water and drying. In this way, when the anode treatment is performed in the iron-zinc flash plating solution and the iron-zinc flash plating is performed as the cathode as it is, the current density condition is outside the range of 50 A / dm 2 or more of the present invention, and the iron in the plating is applied. Stick a cellophane tape on the plating of the aluminum alloy plate whose content is out of 50% or more, rub it with an eraser from it, push out the air inside, and then suddenly peel off the cellophane tape, and the plating will stick to the cellophane tape side When the adhesion of the plating was examined by whether or not it was completely peeled off.
【0023】[0023]
【発明の効果】本発明の皮膜構成のめっきを行えば従来
難しかったアルミニウムおよびアルミニウム合金の密着
性の優れた亜鉛系めっきが容易にできるようになった。EFFECTS OF THE INVENTION By plating the coating composition of the present invention, zinc-based plating with excellent adhesion to aluminum and aluminum alloy, which has been difficult in the past, can be easily performed.
【図1】(a)はアルミニウムおよびアルミニウム合金
に鉄含有量の多い鉄−亜鉛フラッシュめっきを施した
例、(b)はアルミニウムおよびアルミニウム合金をア
ノード処理し、表面に酸化膜を生成させ、その上に鉄含
有量の多い鉄−亜鉛フラッシュめっきを施し、さらに亜
鉛系めっきを施した例、(c)は(b)の鉄−亜鉛フラ
ッシュめっきを施したところを表面からみた2000倍
の拡大模式図、FIG. 1 (a) is an example of iron-zinc flash plating having a high iron content on aluminum and an aluminum alloy, and FIG. 1 (b) is anodizing aluminum and an aluminum alloy to form an oxide film on the surface. An example in which iron-zinc flash plating with a high iron content is applied on top, and further zinc-based plating is applied, (c) is a 2000 times enlarged view of the surface where iron-zinc flash plating in (b) is applied. Figure,
【図2】本発明のアルミニウムおよびアルミニウム合金
帯に密着性の優れた鉄含有量の多い鉄−亜鉛合金フラッ
シュめっきと亜鉛系めっきを施す装置の一例、(a)は
直接鉄含有量の多い鉄−亜鉛合金フラッシュめっきと亜
鉛系めっきを施す装置の例、(b)はアノード処理後鉄
含有量の多い鉄−亜鉛合金フラッシュめっきと亜鉛系め
っきを施す装置の例、(c)は直接鉄含有量の多い鉄−
亜鉛合金フラッシュめっきと亜鉛含有率のより多い亜鉛
系めっきを施す装置の例、(d)はアノード処理後鉄含
有量の多い鉄−亜鉛合金フラッシュめっきと亜鉛含有率
のより多い亜鉛系めっきを施す装置の例を示す図であ
る。FIG. 2 is an example of an apparatus for performing iron-zinc alloy flash plating having a high iron content and excellent zinc-based plating having excellent adhesion to aluminum and aluminum alloy strips of the present invention, (a) is an iron having a high iron content -Example of an apparatus for performing zinc alloy flash plating and zinc-based plating, (b) is an example of an apparatus for performing iron-zinc alloy flash plating and zinc-based plating after anodization, and (c) is direct iron-containing High amount of iron
An example of an apparatus for performing zinc alloy flash plating and zinc-based plating with a higher zinc content, (d) shows iron-zinc alloy flash plating with a higher iron content and zinc-based plating with a higher zinc content after anodizing It is a figure which shows the example of an apparatus.
1 アルミニウム,アルミニウム合金帯 2 酸化膜 3 鉄含有量の多い鉄−亜鉛フラッシュめっき 4 亜鉛系めっき 5 アノード処理用対極 6 鉄含有量の多い鉄−亜鉛合金フラッシュめっきを施
す対極 7 亜鉛系めっき用対極 8 亜鉛含有率のより多い鉄−亜鉛系めっきを施す対極 9 絶縁性隔壁 10 処理タンク 11 シンクロール 12 搬送ロール 13 鉄−亜鉛めっき浴 14 亜鉛系めっき浴1 Aluminum, aluminum alloy band 2 Oxide film 3 Iron-zinc flash plating with high iron content 4 Zinc-based plating 5 Counter electrode for anode treatment 6 Counter electrode for iron-zinc alloy flash plating with high iron content 7 Zinc-based plating counter electrode 8 Counter electrode on which iron-zinc system plating having a higher zinc content is applied 9 Insulating partition wall 10 Processing tank 11 Sink roll 12 Conveying roll 13 Iron-zinc plating bath 14 Zinc system plating bath
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成5年5月25日[Submission date] May 25, 1993
【手続補正1】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】請求項1[Name of item to be corrected] Claim 1
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【手続補正2】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】0003[Name of item to be corrected] 0003
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【0003】このようにアルミニウムあるいはアルミニ
ウム合金を鋼板と同時処理する場合には亜鉛系めっきを
行うとよいことがわかっているが、アルミニウムおよび
アルミニウム合金は亜鉛系めっきを施すのが難しく、最
新表面処理技術総覧(昭和63年4月産業技術サービス
センター発行)に記述のような置換めっき方法、あるい
は特開昭51−1332号公報、特開昭51−4754
9号公報、あるいは特開平4−35019号公報のよう
に、アノード処理して酸化皮膜を生成させたあと、その
上に亜鉛系めっきを行う方法などが試みられてきた。と
くにアノード処理を行ってからめっきする方法は生産性
において優れており、アルミニウムおよびアルミニウム
合金を連続的短時間に処理することが可能であった。It has been found that zinc-based plating is preferably applied when simultaneously treating aluminum or an aluminum alloy with a steel sheet as described above, but it is difficult to apply zinc-based plating to aluminum and aluminum alloys, and the latest surface treatment is required. The displacement plating method as described in Technical Guide (published by the Industrial Technology Service Center in April 1988), or JP-A-51-1332 and JP-A-51-4754.
No. 9, or JP-A-4-35019 , there have been attempts such as a method in which an oxide film is formed by anodic treatment and then zinc-based plating is performed thereon. In particular, the method of plating after the anode treatment was excellent in productivity, and it was possible to treat aluminum and aluminum alloys continuously in a short time.
【手続補正3】[Procedure 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】0004[Correction target item name] 0004
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【0004】[0004]
【発明が解決しようとする課題】このような従来技術に
対して、より生産性に優れ、高速で安価に処理ができ
ること。品質特性が塗装下地として適正であって、鋼
板あるいは亜鉛めっき鋼板と同時に処理しても塗装後の
特性は鋼板あるいは亜鉛めっき鋼板と同じかあるいは優
れていることが望まれている。そのためには、今までよ
りもさらに密着性の優れた亜鉛系めっき層を有するアル
ミニウムおよびアルミニウム合金が必要とされている。In comparison with such a conventional technique, it is possible to perform processing at a higher productivity and at a higher speed and at a lower cost. It is desired that the quality characteristics are appropriate as a coating base and that the characteristics after coating are the same as or superior to those of a steel sheet or a galvanized steel sheet even when treated simultaneously with a steel sheet or a galvanized steel sheet. For that purpose, aluminum and aluminum alloys having a zinc-based plating layer with more excellent adhesion than ever are required.
【手続補正4】[Procedure amendment 4]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】0008[Correction target item name] 0008
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【0008】本発明のアルミニウムおよびアルミニウム
合金としては、板厚2.0mm以下の高純度アルミニウ
ムのほかに5000系あるいは6000系などマグネシ
ウムを10%以下含むものや銅を合金化したものも用い
ることができる。表面処理の観点からは合金化金属はで
きるだけ少ないものが望ましい。また、表面は圧延のま
まあるいは熱処理を受けたものでもよいが、酸化膜はで
きるだけ薄く、また防錆油もできるだけ少ない方が望ま
しい。酸化膜および油、汚れの付着状況によってアルカ
リ脱脂と酸洗の処理条件を決め、適性なめっき用表面を
得る必要がある。As the aluminum and aluminum alloy of the present invention, in addition to high-purity aluminum having a plate thickness of 2.0 mm or less, those containing 10% or less of magnesium such as 5000 series or 6000 series and those alloyed with copper can be used. it can. From the viewpoint of surface treatment, it is desirable that the amount of alloying metal is as small as possible. The surface may be as-rolled or subjected to heat treatment, but it is desirable that the oxide film be as thin as possible and the rust preventive oil be as small as possible. It is necessary to determine the processing conditions for alkaline degreasing and pickling depending on the state of adhesion of oxide film, oil and dirt to obtain an appropriate plating surface.
【手続補正5】[Procedure Amendment 5]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】0013[Correction target item name] 0013
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【0013】次に、アノード電解処理を行う方法につい
て述べる。本発明においては、アノード処理によって表
面にアルミ酸化膜を生成させる。通常、酸化膜は電気抵
抗が大きいので直接めっきすることはできない。しか
し、本発明の鉄−亜鉛フラッシュめっきを行う場合に
は、実験の結果、密着性のよい鉄の組成比50%以上の
鉄−亜鉛フラッシュめっきを行いやすくするのに有効で
あることがわかった。図1(c)に示したように、鉄−
亜鉛フラッシュめっきを施した段階で表面からみたアル
ミ酸化膜の面積は、めっきの面積の60%以下であれば
充分な密着性を得ることができた。Next, a method of performing anode electrolysis will be described. In the present invention, an aluminum oxide film is formed on the surface by anodic treatment. In general, an oxide film has a high electric resistance and therefore cannot be directly plated. However, when performing the iron-zinc flash plating of the present invention,
As a result of the experiment, good adhesion iron composition ratio of 50% or more of iron - has been found to be effective to facilitate the zinc flash plating. As shown in FIG. 1 (c), iron-
If the area of the aluminum oxide film viewed from the surface at the stage of zinc flash plating was 60% or less of the area of plating, sufficient adhesion could be obtained.
Claims (4)
上層表面に鉄の割合が50〜100%(以下重量%を意
味する。)の鉄−亜鉛フラッシュめっき層を厚みで0.
01〜7g/m2 有し、その上に亜鉛系めっき層を有す
る密着性の優れたアルミニウムおよびアルミニウム合
金。1. An iron-zinc flash plating layer having an iron content of 50 to 100% (hereinafter referred to as "weight%") having a thickness of 0.
Aluminum and aluminum alloy having an excellent adhesiveness, which has a zinc-based plating layer on the surface of the aluminum alloy and has an amount of 01 to 7 g / m 2 .
表面にアルミ酸化膜を生成させ、その上に鉄の割合が5
0〜100%の鉄−亜鉛フラッシュめっき層を厚みで
0.01〜7g/m2 有し、その上に亜鉛系めっき層を
有する密着性の優れたアルミニウムおよびアルミニウム
合金。2. An aluminum oxide film is formed on the surface of aluminum and an aluminum alloy, and the ratio of iron is 5 on the aluminum oxide film.
Aluminum and aluminum alloys having a 0 to 100% iron-zinc flash plating layer with a thickness of 0.01 to 7 g / m 2 and having a zinc-based plating layer thereon and having excellent adhesion.
アルミニウム合金を製造するため、第一鉄イオンを20
〜100g/l、亜鉛イオンを50g/l以下、遊離酸
5〜80g/lを含むめっき液で電流密度100〜70
0A/dm2以上にてフラッシュめっきし、そのあと亜
鉛系電気めっきを行う方法。3. To produce the aluminum and aluminum alloys according to claim 1, ferrous ions are added to 20
~ 100 g / l, zinc ion 50 g / l or less, current density 100-70 with plating solution containing 5-80 g / l free acid
Flash plating at 0 A / dm 2 or higher, followed by zinc-based electroplating.
アルミニウム合金を製造するため、第一鉄イオンを20
〜100g/l、亜鉛イオンを50g/l以下、遊離酸
5〜80g/lを含むめっき液でアルミニウムおよびア
ルミニウム合金をアノードとして電気量10〜200c
/dm2 で電解処理し、そのままカソードとして電流密
度50〜600A/dm2 以上にてフラッシュめっき
し、そのあと亜鉛系電気めっきを行う方法。4. Ferrous ions are added in an amount of 20 to produce the aluminum and aluminum alloys of claim 2.
~ 100 g / l, zinc ion 50 g / l or less, a plating solution containing 5-80 g / l of a free acid, and an electric quantity of 10-200 c using aluminum and an aluminum alloy as an anode.
/ Dm 2 , electrolysis treatment is performed, and then the cathode is directly subjected to flash plating at a current density of 50 to 600 A / dm 2 or more, and then zinc-based electroplating.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6585493A JPH06280085A (en) | 1993-03-25 | 1993-03-25 | Galvanized aluminum and aluminum alloy excellent in adhesion and production thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6585493A JPH06280085A (en) | 1993-03-25 | 1993-03-25 | Galvanized aluminum and aluminum alloy excellent in adhesion and production thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH06280085A true JPH06280085A (en) | 1994-10-04 |
Family
ID=13299022
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP6585493A Withdrawn JPH06280085A (en) | 1993-03-25 | 1993-03-25 | Galvanized aluminum and aluminum alloy excellent in adhesion and production thereof |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH06280085A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101288085B1 (en) * | 2012-10-11 | 2013-08-07 | 남동화학(주) | Zinc plated steel having iron flash plating film thereon and bath of iron flash plating and method for manufacturing the zinc plated steel |
-
1993
- 1993-03-25 JP JP6585493A patent/JPH06280085A/en not_active Withdrawn
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101288085B1 (en) * | 2012-10-11 | 2013-08-07 | 남동화학(주) | Zinc plated steel having iron flash plating film thereon and bath of iron flash plating and method for manufacturing the zinc plated steel |
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