JPH0688282A - Production of al-cr alloy plated steel sheet - Google Patents
Production of al-cr alloy plated steel sheetInfo
- Publication number
- JPH0688282A JPH0688282A JP24018092A JP24018092A JPH0688282A JP H0688282 A JPH0688282 A JP H0688282A JP 24018092 A JP24018092 A JP 24018092A JP 24018092 A JP24018092 A JP 24018092A JP H0688282 A JPH0688282 A JP H0688282A
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- plating
- halide
- plated steel
- corrosion resistance
- 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.)
- Withdrawn
Links
Landscapes
- Electroplating Methods And Accessories (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はＡｌとＣｒを含有する新
規な溶融塩めっき浴を用いて電気めっきによる効率的な
Ａｌ−Ｃｒ合金めっき鋼板の製造法に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an efficient method for producing an Al-Cr alloy plated steel sheet by electroplating using a novel molten salt plating bath containing Al and Cr.
【０００２】[0002]
【従来の技術】近年、排気系材料や自動車用外板あるい
は建材を中心として、これまで以上の耐食性を有する表
面処理鋼板の要求が非常に強くなっている。現在、これ
らの要求に対して、特開昭６１−１４７８６５号公報、
特開昭６２−２７４０６０号公報などのごときＣｒ含有
鋼板に溶融Ａｌめっきを行ったステンレスＡｌめっき鋼
板で対応されている。ステンレスＡｌめっき鋼板が使用
されている理由は、めっき原板中のＣｒが溶融Ａｌめっ
き時にめっき原板からめっき層中に拡散し、Ａｌ−Ｃｒ
合金めっき層を形成することによりめっき層の耐食性が
Ａｌ単独より飛躍的に向上するからである。しかし、ス
テンレスＡｌ鋼板はめっき時にＡｌ−Ｃｒ合金めっき層
を形成するだけでなく、Ａｌと鋼板が合金化反応を生
じ、硬くて脆いＡｌ−Ｆｅ合金層を生成するため、曲げ
あるいは絞り等の成形部で合金層にミクロクラックを生
じ、耐食性の著しい低下や最悪の場合めっき剥離を生じ
るなど問題があった。したがって、Ａｌ−Ｃｒ合金めっ
きでは合金層の抑制が技術的な課題となっていた。ま
た、近年著しく発展した真空蒸着法等のドライプロセス
を用いれば確かにＡｌ−Ｆｅ合金層の無いＡｌ−Ｃｒ合
金めっき鋼板を製造できるがＣｒの融点がＡｌに比べて
非常に高いため生産性が低く経済的に不利である。2. Description of the Related Art In recent years, there has been a strong demand for surface-treated steel sheets having more corrosion resistance than ever, centering on exhaust system materials, automobile outer panels or building materials. Currently, in order to meet these demands, Japanese Patent Laid-Open No. 61-147865,
A stainless steel Al-plated steel sheet obtained by performing hot-dip Al plating on a Cr-containing steel sheet, such as Japanese Patent Laid-Open No. 62-274060, is applicable. The reason why the stainless Al-plated steel sheet is used is that the Cr in the plating original plate diffuses from the plating original plate into the plating layer during hot Al plating, and Al-Cr
By forming the alloy plating layer, the corrosion resistance of the plating layer is dramatically improved as compared with Al alone. However, a stainless Al steel plate not only forms an Al-Cr alloy plating layer at the time of plating but also causes an alloying reaction between Al and the steel plate to form a hard and brittle Al-Fe alloy layer. There was a problem that micro-cracks were generated in the alloy layer at the part, the corrosion resistance was remarkably reduced, and in the worst case, plating peeling occurred. Therefore, suppression of the alloy layer has been a technical issue in Al-Cr alloy plating. Further, if a dry process such as a vacuum vapor deposition method which has been remarkably developed in recent years is used, an Al-Cr alloy plated steel sheet without an Al-Fe alloy layer can be certainly manufactured, but since the melting point of Cr is much higher than that of Al, productivity is high. Low and economically disadvantageous.
【０００３】[0003]
【発明が解決しようとする課題】本発明はＡｌとＣｒを
含有する新規な溶融塩めっき浴を用いて電気めっきによ
る効率的なＡｌ−Ｃｒ合金めっき鋼板の製造法に関する
ものである。DISCLOSURE OF THE INVENTION The present invention relates to an efficient method for producing an Al--Cr alloy plated steel sheet by electroplating using a novel molten salt plating bath containing Al and Cr.
【０００４】[0004]
【課題を解決するための手段】即ち、本発明の要旨とす
るところは、５０モル％を越えたハロゲン化アルミニウ
ム（ＡｌＸ3 、但しＸはＦ、Ｃｌ、Ｂｒ、Ｉ）とハロゲ
ン化クロム（ＣｒＸ2、但しＸはＦ、Ｃｌ、Ｂｒ、Ｉ）
の混合物と５０モル％を下回る１−メチル−３−エチル
イミダゾリウムハロゲン化物（以下ＭＥＩＸと記す）That is, the gist of the present invention is that aluminum halide (AlX 3 , where X is F, Cl, Br, I) exceeding 50 mol% and chromium halide (CrX) are used. 2 , where X is F, Cl, Br, I)
And less than 50 mol% of 1-methyl-3-ethylimidazolium halide (hereinafter referred to as MEIX)
【０００５】[0005]
【化２】 [Chemical 2]
【０００６】[0006]
【作用】以下に本発明について詳細に説明する。本発明
で使用するめっき浴はＡｌイオンまたはＣｒイオンがＭ
ＥＩＸと錯体を形成した溶融塩である。ＡｌまたはＣｒ
はＭＥＩＸと１：１または２：１の錯体を形成すること
は出来るが、１：１の錯体からはＡｌが電析しにくいた
め、めっき浴中には２：１の錯体を存在させることが重
要である。そのためには、浴中のＡｌ量とＣｒ量の混合
和とＭＥＩＸの比が１：１を越えれば良く、したがっ
て、ハロゲン化アルミニウムとハロゲン化クロムの混合
量は５０モル％を越えなければならない。そのため、Ｍ
ＥＩＸ量は５０モル％を下回る事になる。The present invention will be described in detail below. In the plating bath used in the present invention, Al ions or Cr ions are M
It is a molten salt that forms a complex with EIX. Al or Cr
Can form a 1: 1 or 2: 1 complex with MEIX, but since Al is less likely to be electrodeposited from a 1: 1 complex, a 2: 1 complex may be present in the plating bath. is important. For that purpose, the ratio of MEIX and the mixed amount of Al and Cr in the bath should exceed 1: 1. Therefore, the mixed amount of aluminum halide and chromium halide must exceed 50 mol%. Therefore, M
The amount of EIX will be less than 50 mol%.
【０００７】また、浴中のＣｒイオンは２価の陽イオン
にする必要がある。すなわち、２価以外（３〜６価）の
Ｃｒイオンからは、めっき浴からＡｌ−Ｃｒ合金めっき
の析出を効率的に行うことが出来ないため浴中のＣｒイ
オンは２価が望ましい。また、２価以外のＣｒを還元剤
や電解法を用いて２価に還元した後、めっきを行うこと
は本発明の本質と異なるものではない。このようなめっ
き浴からめっきを行うには、２価のＣｒイオンを安定に
保つために浴中の酸素あるいは水分を除去する必要があ
る。浴中の酸素や水分は２価のＣｒイオンを酸化し３価
あるいは６価のイオンにするため、浴中の酸素や水分を
除去する必要がある。したがって、めっきは無水無酸素
雰囲気でする必要がある。また、上記めっき浴は浴中あ
るいは空気中の水分や酸素に触れると劣化するため、め
っき雰囲気あるいは浴保存雰囲気を無水無酸素にするこ
とが不可欠である。The Cr ions in the bath must be divalent cations. That is, it is desirable that the Cr ions in the bath be divalent, because the precipitation of Al-Cr alloy plating from the plating bath cannot be efficiently performed from Cr ions other than divalent (3 to 6 valent). Further, it is not different from the essence of the present invention to perform plating after reducing Cr other than divalent to divalent using a reducing agent or an electrolytic method. In order to carry out plating from such a plating bath, it is necessary to remove oxygen or water in the bath in order to keep divalent Cr ions stable. Since oxygen and water in the bath oxidize divalent Cr ions into trivalent or hexavalent ions, it is necessary to remove oxygen and water in the bath. Therefore, the plating needs to be performed in an anhydrous oxygen-free atmosphere. Further, since the plating bath deteriorates when exposed to water or oxygen in the bath or in the air, it is indispensable to make the plating atmosphere or the bath storage atmosphere anhydrous and oxygen-free.
【０００８】さらに、めっき層中に含有するＣｒの重量
％はめっき浴中のＣｒ量あるいは浴温、電流密度などで
制御できる。電気めっき方法は通常行われている陰極電
解法でよく特に規制するものではない。イオンの供給方
法については、Ａｌは塩化アルミあるいは金属Ａｌを陽
極にした可溶性電極でも良く、Ｃｒは塩化クロムあるい
は金属Ｃｒを陽極にした可溶性電極で供給してもよい。
また、本発明において、めっき原板としては自動車用、
排気系用あるいは容器用鋼板として用途に応じた材質を
有するめっき原板を使用する。めっき原板の製造法は特
に規制されるものではなく、通常の鋼片製造工程から熱
間圧延、酸洗、冷間圧延、焼鈍、調質圧延などの工程を
経て製造される。Further, the weight% of Cr contained in the plating layer can be controlled by the amount of Cr in the plating bath, the bath temperature, the current density and the like. The electroplating method is a commonly used cathodic electrolysis method and is not particularly limited. Regarding the method of supplying ions, Al may be supplied by a soluble electrode having aluminum chloride or metal Al as an anode, and Cr may be supplied by a soluble electrode having chromium chloride or metal Cr as an anode.
Further, in the present invention, the plating base plate is for an automobile,
As a steel plate for an exhaust system or a container, a plated original plate having a material suitable for the application is used. The method for producing the plated original sheet is not particularly limited, and it is produced from the ordinary billet producing step through steps such as hot rolling, pickling, cold rolling, annealing, and temper rolling.
【０００９】[0009]
【実施例】以下に本発明の実施例について述べ、その結
果を表１に示す。冷間圧延、焼鈍工程により、用途に応
じた材質と板厚に調整しためっき原板を５％苛性ソーダ
中で電解脱脂水洗後、１０％硫酸中で電解酸洗し表面活
性化後、（１）−（イ）、（ロ）、（ハ）、（ニ）に示
す条件でＡｌめっきを行った。また、Ａｌめっき鋼板の
評価は（２）−（イ）、（ロ）に示す耐食性試験を行っ
た。EXAMPLES Examples of the present invention will be described below, and the results are shown in Table 1. After cold-rolling and annealing processes, the plating base plate adjusted to the material and plate thickness according to the application is electrolytically degreased and washed in 5% caustic soda, and electrolytically pickled in 10% sulfuric acid to activate the surface, and then (1)- Al plating was performed under the conditions shown in (a), (b), (c), and (d). The evaluation of the Al-plated steel sheet was performed by the corrosion resistance test shown in (2)-(a) and (b).
【００１０】（１）Ａｌ−Ｃｒ合金めっき条件 （イ）めっき浴組成 ・塩化アルミ（ＡｌＣｌ3 ） ・塩化クロム（ＣｒＣｌ2 ） ・１−メチル−３−エチルイミダゾリウム塩化物 めっき浴温 １０〜８０℃ 電流密度 １〜３０Ａ／ｄｍ2 （電解時間はめっき量
に応じて調整）[0010] (1) Al-Cr alloy plating condition (b) plating bath composition, aluminum chloride (AlCl 3), chromium chloride (CrCl 2), 1-methyl-3-ethyl imidazolium chloride plating bath temperature 10 to 80 C current density 1 to 30 A / dm 2 (electrolysis time is adjusted according to plating amount)
【００１１】（ロ）めっき浴組成 ・臭化アルミ（ＡｌＢｒ3 ） ・塩化クロム（ＣｒＢｒ2 ） ・１−メチル−３−エチルイミダゾリウム臭化物 めっき浴温 １０〜１２０℃ 電流密度 １〜３０Ａ／ｄｍ2 （電解時間はめっき量
に応じて調整）[0011] (ii) Plating bath composition & aluminum bromide (AlBr 3), chromium chloride (CrBr 2) · 1- methyl-3-ethyl imidazolium bromide plating temperature 10 to 120 ° C. The current density 1~30A / dm 2 (Electrolysis time is adjusted according to plating amount)
【００１２】（ハ）めっき浴組成 ・ヨウ化アルミ（ＡｌＩ3 ） ・塩化クロム（ＣｒＩ2 ) ・１−メチル−３−エチルイミダゾリウムヨウ化物 めっき浴温 ４０〜１６０℃ 電流密度 １〜３０Ａ／ｄｍ2 （電解時間はめっき量
に応じて調整）(C) Plating bath composition-Aluminum iodide (AlI 3 ) -Chromium chloride (CrI 2 ) -1-Methyl-3-ethylimidazolium iodide Plating bath temperature 40-160 ° C Current density 1-30 A / dm 2 (Electrolysis time is adjusted according to the plating amount)
【００１３】（ニ）めっき浴組成 ・フッ化アルミ（ＡｌＦ3) ・フッ化クロム（ＣｒＦ2) ・１−メチル−３−エチルイミダゾリウム臭化物 めっき浴温 １０〜１２０℃ 電流密度 １〜３０Ａ／ｄｍ2 （電解時間はめっき量
に応じて調整）[0013] (d) plating bath composition, aluminum fluoride (AlF 3), chromium fluoride (CrF 2) - 1-methyl-3-ethyl imidazolium bromide plating temperature 10 to 120 ° C. The current density 1~30A / dm 2 (Electrolysis time is adjusted according to the plating amount)
【００１４】（２）耐食性試験 （イ）塩水噴霧試験（平板） 平板に５％塩水を５０００時間噴霧し赤錆発生率で耐食
性を評価した。尚、評価基準は以下の基準で判定した。 ◎；赤錆発生が無く耐食性は極めて良好。 ○；赤錆発生率３０％。 △；赤錆発生率５０％。 ×；ほぼ全面に赤錆が発生し耐食性に劣る。(2) Corrosion resistance test (a) Salt spray test (flat plate) A flat plate was sprayed with 5% salt water for 5000 hours to evaluate the corrosion resistance by the red rust occurrence rate. The evaluation criteria are as follows. ⊚: Red rust is not generated and corrosion resistance is extremely good. ◯: Red rust occurrence rate is 30%. Δ: Red rust occurrence rate is 50%. X: Corrosion resistance is poor because red rust occurs on almost the entire surface.
【００１５】（ロ）加工部の耐食性 ＯＴ曲げを行った試料に５％塩水を５０００時間噴霧し
曲げ加工部の赤錆発生率で耐食性を評価した。 ◎；赤錆発生が無く耐食性は極めて良好。 ○；赤錆発生率３０％。 △；赤錆発生率５０％。 ×；ほぼ全面に赤錆が発生し耐食性に劣る。 上記の実験結果から明らかなように、本発明法は本発明
から逸脱した比較法に較べめっき層中にＣｒを含有し、
優れた耐食性を示す。(B) Corrosion resistance of the processed portion The OT-bent sample was sprayed with 5% salt water for 5000 hours, and the corrosion resistance was evaluated by the red rust occurrence rate of the bent portion. ⊚: Red rust is not generated and corrosion resistance is extremely good. ◯: Red rust occurrence rate is 30%. Δ: Red rust occurrence rate is 50%. X: Corrosion resistance is poor because red rust occurs on almost the entire surface. As is apparent from the above experimental results, the method of the present invention contains Cr in the plating layer as compared with the comparative method which deviates from the present invention,
Shows excellent corrosion resistance.
【００１６】[0016]
【表１】 [Table 1]
【００１７】[0017]
【発明の効果】以上述べたように、本発明によるめっき
層中にＣｒを含有せしめることで比較法に比べ極めて優
れた耐食性を有するめっき鋼板を製造することが出来
た。As described above, by including Cr in the plating layer according to the present invention, it is possible to manufacture a plated steel sheet having extremely excellent corrosion resistance as compared with the comparative method.
Claims (1)
ウム（ＡｌＸ3 、但しＸはＦ、Ｃｌ、Ｂｒ、Ｉ）とハロ
ゲン化クロム（ＣｒＸ2 、但しＸはＦ、Ｃｌ、Ｂｒ、
Ｉ）の混合物と、５０モル％を下回る１−メチル−３−
エチルイミダゾリウムハロゲン化物（次式） 【化１】 からなる浴を用いて、無水無酸素雰囲気下で被めっき鋼
板を電気めっきすることを特徴とするＡｌ−Ｃｒ合金め
っき鋼板の製造法。1. An aluminum halide (AlX 3 , wherein X is F, Cl, Br, I) exceeding 50 mol% and a chromium halide (CrX 2 , wherein X is F, Cl, Br,
I) with a mixture of less than 50 mol% of 1-methyl-3-
Ethylimidazolium halide (the following formula) A method for producing an Al-Cr alloy-plated steel sheet, which comprises electroplating a steel sheet to be plated in an anhydrous oxygen-free atmosphere using a bath consisting of
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24018092A JPH0688282A (en) | 1992-09-09 | 1992-09-09 | Production of al-cr alloy plated steel sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24018092A JPH0688282A (en) | 1992-09-09 | 1992-09-09 | Production of al-cr alloy plated steel sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0688282A true JPH0688282A (en) | 1994-03-29 |
Family
ID=17055664
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24018092A Withdrawn JPH0688282A (en) | 1992-09-09 | 1992-09-09 | Production of al-cr alloy plated steel sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0688282A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012093668A1 (en) * | 2011-01-05 | 2012-07-12 | ディップソール株式会社 | Electrical aluminium or aluminium alloy fused salt plating bath having good throwing power, and electroplating method and pretreatment method using same |
-
1992
- 1992-09-09 JP JP24018092A patent/JPH0688282A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012093668A1 (en) * | 2011-01-05 | 2012-07-12 | ディップソール株式会社 | Electrical aluminium or aluminium alloy fused salt plating bath having good throwing power, and electroplating method and pretreatment method using same |
| CN103298979A (en) * | 2011-01-05 | 2013-09-11 | 迪普索尔化学株式会社 | Electrical aluminium or aluminium alloy fused salt plating bath having good throwing power, and electroplating method and pretreatment method using same |
| JP5914954B2 (en) * | 2011-01-05 | 2016-05-11 | ディップソール株式会社 | Electroaluminum or aluminum alloy molten salt plating bath with good throwing power, and electroplating method and pretreatment method using the same |
| US9926638B2 (en) | 2011-01-05 | 2018-03-27 | Dipsol Chemicals Co., Ltd. | Aluminum or aluminum alloy molten salt electroplating bath having good throwing power, electroplating method using the bath, and pretreatment method of the bath |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 19991130 |