JPH0754188A - Production of aluminum-chromium alloy plated steel sheet - Google Patents
Production of aluminum-chromium alloy plated steel sheetInfo
- Publication number
- JPH0754188A JPH0754188A JP19570193A JP19570193A JPH0754188A JP H0754188 A JPH0754188 A JP H0754188A JP 19570193 A JP19570193 A JP 19570193A JP 19570193 A JP19570193 A JP 19570193A JP H0754188 A JPH0754188 A JP H0754188A
- Authority
- JP
- Japan
- Prior art keywords
- aluminum
- chromium
- halide
- steel sheet
- plating
- 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- Withdrawn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 And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はアルミとクロムを含有す
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
的なアルミ−クロム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 a method for efficiently producing an aluminum-chromium alloy plated steel sheet by electroplating using a novel molten salt plating bath containing aluminum and chromium.
【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、クロム含有鋼板に溶融アルミめっき
を行ったステンレスアルミめっき鋼板で対応されてい
る。ステンレスアルミめっき鋼板が使用される理由は、
めっき原板中のクロムが溶融アルミめっき時にめっき原
板からめっき層中に拡散し、アルミ−クロム合金めっき
層を形成することによりめっき層の耐食性がアルミ単独
より飛躍的に向上するからである。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. At present, these requirements are met by a stainless aluminized steel sheet obtained by plating a chromium-containing steel sheet with hot dip aluminum. The reason why stainless aluminized steel sheet is used is
This is because the chromium in the plating original plate diffuses from the plating original plate into the plating layer during hot dipping of aluminum to form an aluminum-chromium alloy plating layer, so that the corrosion resistance of the plating layer is dramatically improved as compared with aluminum alone.
【０００３】[0003]
【発明が解決しようとする課題】しかし、ステンレスア
ルミ鋼板はめっき時にアルミ−クロム合金めっき層を形
成するだけでなく、アルミと鋼板が合金化反応を生じ、
硬くて脆いアルミ−鉄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。従って、アルミ−クロム合金めっきで
は合金層の抑制が技術的な課題となっていた。However, not only does a stainless-aluminum steel plate form an aluminum-chromium alloy plating layer at the time of plating, but aluminum and a steel plate cause an alloying reaction,
In order to produce a hard and brittle aluminum-iron alloy layer, micro cracks are generated in the alloy layer at the forming part such as bending or drawing,
There have been problems such as a significant decrease in corrosion resistance and, in the worst case, plating peeling. Therefore, suppression of the alloy layer has been a technical issue in aluminum-chromium alloy plating.
【０００４】一方、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アルミ−鉄合金層の無
いアルミ−クロム合金めっき鋼板を製造できる。しか
し、クロムの融点がアルミに比べて非常に高いため、ド
ライプロセスでは生産性が低く経済的に不利である。本
発明はアルミとクロム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アルミ−クロム合金
めっき鋼板の製造法を提供せんとするものである。On the other hand, if a dry process such as a vacuum deposition method which has been remarkably developed in recent years is used, an aluminum-chromium alloy plated steel sheet without an aluminum-iron alloy layer can be certainly manufactured. However, since the melting point of chromium is much higher than that of aluminum, productivity is low and it is economically disadvantageous in the dry process. The present invention is to provide an efficient method for producing an aluminum-chromium alloy plated steel sheet by electroplating using a novel molten salt plating bath containing aluminum and chromium.
【０００５】[0005]
【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、被めっき鋼板を５０モル％を越えたハロゲ
ン化アルミニウム（ＡｌＸ3 、但しＸはハロゲン原子）
とハロゲン化クロム（ＣｒＸ2 、但しＸはハロゲン原
子）の混合物と、５０モル％を下回る下記化学式１，３
−ジアルキルイミダゾリウムハロゲン化物からなる浴を
用いて電気めっき法により、めっき層中にＣｒを０．０
０１〜６０重量％含有したアルミ−クロム合金めっき層
を施すアルミ−クロム合金めっき鋼板の製造法を提供す
るものである。That is, the gist of the present invention is that an aluminum halide containing more than 50 mol% of the steel sheet to be plated (AlX 3 , where X is a halogen atom).
And a chromium halide (CrX 2 , where X is a halogen atom), and the following chemical formulas 1 and 3 below 50 mol%.
-Cr in the plating layer to 0.0 by electroplating using a bath of dialkyl imidazolium halide.
It is intended to provide a method for producing an aluminum-chromium alloy-plated steel sheet on which an aluminum-chromium alloy plating layer containing 01 to 60% by weight is applied.
【０００６】[0006]
【化２】 [Chemical 2]
【０００７】[0007]
【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アルミイオンまたはクロムイオン
がジアルキルイミダゾリウムハロゲン化物と錯体を形成
した溶融塩である。アルミまたはクロムはジアルキルイ
ミダゾリウムハロゲン化物と１：１または２：１の錯体
を形成することが出来るが、１：１の錯体からはアルミ
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、浴中のアル
ミ量とクロム量の混合和とジアルキルイミダゾリウムハ
ロゲン化物の比が１：１を越えれば良く、従って、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、ジアルキル
イミダゾリウムハロゲン化物量は５０モル％を下回る事
になる。The present invention will be described in detail below. The plating bath used in the present invention is a molten salt in which aluminum ions or chromium ions form a complex with a dialkylimidazolium halide. Aluminum or chromium can form a 1: 1 or 2: 1 complex with a dialkyl imidazolium halide, but aluminum is less likely to be electrodeposited from a 1: 1 complex, so 2: 1 in a plating bath. The presence of the complex of is important. For that purpose, the ratio of the mixed amount of aluminum and chromium in the bath and the ratio of the dialkylimidazolium halide exceeds 1: 1. Therefore, the mixed amount of aluminum halide and chromium halide is 50.
Must exceed mol%. Therefore, the amount of dialkyl imidazolium halide is less than 50 mol%.
【０００８】また、浴中のクロムイオンは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）
のクロムイオンからは、めっき浴からアルミ−クロム合
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
のクロムイオンは２価が望ましい。また、２価以外のク
ロム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価のクロム
イオンを安定に保つために浴中の酸素あるいは水分を十
分に除去する必要がある。浴中の酸素や水分は２価のク
ロムイオンを酸化し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十分に除去する事が望ましい。Further, the chromium ions in the bath must be divalent cations. That is, other than divalent (3 to 6)
It is desirable that the chromium ions in the bath be divalent, since the aluminum-chromium alloy plating cannot be efficiently deposited from the plating ions. Further, it is not different from the essence of the present invention to perform plating after reducing chromium other than divalent to divalent using a reducing agent or an electrolytic method. To perform plating from such a plating bath, it is necessary to sufficiently remove oxygen or water in the bath in order to keep divalent chromium ions stable. Since oxygen and water in the bath oxidize divalent chromium ions into trivalent or hexavalent ions, it is desirable to sufficiently remove oxygen and water in the bath.
【０００９】更に、めっき層中に含有するクロムの重量
％はめっき浴中のクロム量あるいは浴温、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、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、アルミは塩化アルミあるいは金属アルミ
を陽極にした可溶性電極でも良く、クロムは塩化クロム
あるいは金属クロムを陽極にした可溶性電極で供給して
もよい。Further, the weight% of chromium contained in the plating layer can be controlled by the amount of chromium 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 ion supply method, aluminum may be supplied by a soluble electrode having aluminum chloride or metal aluminum as an anode, and chromium may be supplied by a soluble electrode having chromium chloride or metal chromium as an anode.
【００１０】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, in the present invention, as the plating original plate, a plating original plate having a material suitable for use as a steel plate for automobiles, exhaust systems or containers 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.
【００１１】[0011]
【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
す条件でアルミめっきを行った。また、アルミめっき鋼
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)- Aluminum plating was performed under the conditions shown in (a), (b), (c), and (d). Further, the evaluation of the aluminum-plated steel sheet was performed by the corrosion resistance test shown in (2)-(a) and (b).
【００１２】[0012]
【表１】 [Table 1]
【００１３】（１）アルミ−クロム合金めっき条件 （イ）めっき浴組成 塩化アルミ（ＡｌＣｌ3 ） 塩化クロム（ＣｒＣｌ2 ） １，３−ジメチルイミダゾリウムクロリド 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）[0013] (1) Aluminum - chromium alloy plating condition (b) plating bath composition of aluminum chloride (AlCl 3) Chromium chloride (CrCl 2) 1,3-dimethyl-imidazolium chloride plating bath temperature 10 to 80 ° C. Current density 1~30A / Dm 2 (electrolysis time is adjusted according to the plating amount)
【００１４】（ロ）めっき浴組成 臭化アルミ（ＡｌＢｒ3 ） 塩化クロム（ＣｒＣｌ2 ） １−エチル−３−メチルイミダゾリウムブロミド 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）(B) Plating bath composition Aluminum bromide (AlBr 3 ) Chromium chloride (CrCl 2 ) 1-Ethyl-3-methylimidazolium bromide Plating bath temperature 10 to 120 ° C. Current density 1 to 30 A / dm 2 (electrolysis time Is adjusted according to the plating amount)
【００１５】（ハ）めっき浴組成 ヨウ化アルミ（ＡｌＩ3 ） 塩化クロム（ＣｒＣｌ2 ) １，３−ジエチルイミダゾリウムクロリド 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 (CrCl 2 ) 1,3-Diethylimidazolium chloride Plating bath temperature 40 to 160 ° C. Current density 1 to 30 A / dm 2 (electrolysis time is plating (Adjust according to the amount)
【００１６】（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−ブチルイミダゾリウムフルオリド 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）(D) Plating bath composition Aluminum fluoride (AlF 3 ) Chromium fluoride (CrF 2 ) 1-Methyl-3-butylimidazolium fluoride Plating bath temperature 10 to 120 ° C. Current density 1 to 30 A / dm 2 ( (Electrolysis time is adjusted according to the plating amount)
【００１７】（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.
【００１８】（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。(B) Corrosion resistance of the processed part The sample subjected to OT bending was sprayed with 5% salt water for 5000 hours, and the corrosion resistance was evaluated by the red rust occurrence rate of the bent part. ⊚: 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.
【００１９】[0019]
【発明の効果】以上述べたように、本発明によって平板
及び加工部での耐食性の極めて良好で、しかも電気めっ
きによる効率的なアルミ−クロム合金めっき鋼板を製造
することが出来る極めて優れた効果を奏するものであ
る。As described above, according to the present invention, it is possible to produce an aluminum-chromium alloy-plated steel sheet which has excellent corrosion resistance on a flat plate and a machined portion and is efficient by electroplating. It plays.
Claims (1)
ゲン化アルミニウム（ＡｌＸ3 、但しＸはハロゲン原
子）とハロゲン化クロム（ＣｒＸ2 、但しＸはハロゲン
原子）の混合物と、５０モル％を下回る下記化学式１，
３−ジアルキルイミダゾリウムハロゲン化物からなる浴
を使用して電気めっき法により、めっき層中にＣｒを
０．００１〜６０重量％含有したアルミ−クロム合金め
っき層を施すことを特徴とするアルミ−クロム合金めっ
き鋼板の製造法。 【化１】 1. A mixture of aluminum halide (AlX 3 , where X is a halogen atom) and chromium halide (CrX 2 , where X is a halogen atom) in an amount of more than 50 mol% and 50 mol% to a plated steel sheet. Below formula 1,
Aluminum-chromium characterized by applying an aluminum-chromium alloy plating layer containing 0.001 to 60% by weight of Cr in the plating layer by electroplating using a bath of 3-dialkylimidazolium halide. Manufacturing method of alloy plated steel sheet. [Chemical 1]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19570193A JPH0754188A (en) | 1993-08-06 | 1993-08-06 | Production of aluminum-chromium alloy plated steel sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19570193A JPH0754188A (en) | 1993-08-06 | 1993-08-06 | Production of aluminum-chromium alloy plated steel sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0754188A true JPH0754188A (en) | 1995-02-28 |
Family
ID=16345547
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19570193A Withdrawn JPH0754188A (en) | 1993-08-06 | 1993-08-06 | Production of aluminum-chromium alloy plated steel sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0754188A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005063661A1 (en) * | 2003-12-25 | 2005-07-14 | Sumitomo Chemical Company, Limited | Fluorinating agent and method for producing fluorine-containing compound using same |
| JP2005289970A (en) * | 2003-12-25 | 2005-10-20 | Sumitomo Chemical Co Ltd | Fluorinating agent and method for producing fluorine-containing compound |
| WO2011151785A1 (en) * | 2010-06-01 | 2011-12-08 | Basf Se | Composition for metal electroplating comprising leveling agent |
-
1993
- 1993-08-06 JP JP19570193A patent/JPH0754188A/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005063661A1 (en) * | 2003-12-25 | 2005-07-14 | Sumitomo Chemical Company, Limited | Fluorinating agent and method for producing fluorine-containing compound using same |
| JP2005289970A (en) * | 2003-12-25 | 2005-10-20 | Sumitomo Chemical Co Ltd | Fluorinating agent and method for producing fluorine-containing compound |
| WO2011151785A1 (en) * | 2010-06-01 | 2011-12-08 | Basf Se | Composition for metal electroplating comprising leveling agent |
| CN102939339A (en) * | 2010-06-01 | 2013-02-20 | 巴斯夫欧洲公司 | Composition for metal electroplating comprising leveling agent |
| US9683302B2 (en) | 2010-06-01 | 2017-06-20 | Basf Se | Composition for metal electroplating comprising leveling agent |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH07157891A (en) | Production of al-cr alloy plated steel sheet | |
| JPH0754188A (en) | Production of aluminum-chromium alloy plated steel sheet | |
| JPH0688282A (en) | Production of al-cr alloy plated steel sheet | |
| JP3670857B2 (en) | Chemical treatment of nickel-plated steel sheet | |
| JPH05156416A (en) | Galvanizing method for si-containing steel sheet | |
| US3898139A (en) | Process for surface treatment of zinc-plated steel plates | |
| JPH0158276B2 (en) | ||
| JPS6027757B2 (en) | Highly corrosion resistant electrogalvanized steel sheet and its manufacturing method | |
| JPS59162294A (en) | Steel sheet having two-layered zn plating provided with superior workability and its manufacture | |
| JP2726144B2 (en) | Manufacturing method of high corrosion resistance Pb-Sn alloy plated Cr-containing steel sheet with excellent coverage and adhesion | |
| JP2724045B2 (en) | Method for producing chromium-containing steel sheet plated with hot-dip zinc or zinc alloy | |
| JPS6379994A (en) | Production of steel sheet for welded can | |
| JPH01108396A (en) | Production of galvannealed steel sheet for coating by cationic electrodeposition | |
| JPS6254099A (en) | Composite-plated steel sheet having superior spot welability and corrosion resistance and its manufacture | |
| JP2827709B2 (en) | Surface treated steel sheet with multiple plating layers, excellent in filiform rust resistance, corrosion resistance and weldability | |
| JPS61119694A (en) | Production of electroplated steel plate | |
| JPH04289187A (en) | A1 alloy plated material | |
| KR960005026B1 (en) | Method for manufacturing zn-cr alloy two layer coating steel plate with a high corrosion resistance | |
| KR0146874B1 (en) | Method for manufacturing zn-cr/zn alloy coated steel sheet with 2-layers | |
| JPS59159987A (en) | Surface-treated steel sheet with superior suitability to chemical conversion treatment | |
| JPS59185792A (en) | Method for forming highly corrosion resistant zinc-nickel alloy film | |
| JP2000087298A (en) | Surface treated steel sheet excellent in high speed seam weldability adhesion and corrosion resistance and its production | |
| JPH04224666A (en) | Production of hot-dip galvanized stainless steel strip excellent in adhesive strength of plating and corrosion resistance | |
| JPH0790610A (en) | Production of glavanized steel sheet excellent in resistance to blackening and corrosion and coating film adhesion | |
| JPH0438837B2 (en) |
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: 20001031 |