JPH07157891A - Production of al-cr alloy plated steel sheet - Google Patents
Production of al-cr alloy plated steel sheetInfo
- Publication number
- JPH07157891A JPH07157891A JP30765293A JP30765293A JPH07157891A JP H07157891 A JPH07157891 A JP H07157891A JP 30765293 A JP30765293 A JP 30765293A JP 30765293 A JP30765293 A JP 30765293A JP H07157891 A JPH07157891 A JP H07157891A
- Authority
- JP
- Japan
- Prior art keywords
- chromium
- aluminum
- plating
- steel sheet
- halogen atom
- 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- Withdrawn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
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ている理由
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。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。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 the stainless aluminized steel sheet is used is that the chromium in the plating original plate diffuses from the plating original plate into the plating layer during hot-dip aluminum plating, and the aluminum-chromium alloy plating layer is formed so that the corrosion resistance of the plating layer is independent of aluminum. This is because it will be dramatically improved. However, stainless steel plate not only forms an aluminum-chromium alloy plating layer at the time of plating, but also causes an alloying reaction between aluminum and the steel plate to form a hard and brittle aluminum-iron 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 aluminum-chromium alloy plating.
【０００３】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。On the other hand, if a dry process such as a vacuum vapor 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.
【０００４】[0004]
【発明が解決しようとする課題】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。DISCLOSURE OF THE INVENTION The present invention relates to 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】本発明の要旨とするとこ
ろは、被めっき鋼板に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（ＣｒＸ 2 、但しＸはハロゲン原子) の混
合物と、５０モル％を下回るアルキルピリジニウムハロ
ゲン化物（Ｃ5 Ｈ5 Ｎ−ＲＸ、但しＲは炭素数１〜５の
アルキル基、Ｘはハロゲン原子）からなる浴から、電気
めっき法により、めっき層中にクロムを０．００１〜６
０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。The gist of the present invention is as follows.
Roha is a halogenated alloy containing more than 50 mol% of the plated steel.
Luminium (AlX3Where X is a halogen atom) and halo
Chrome Genide (CrX 2, Where X is a halogen atom)
Compound and an alkylpyridinium halo of less than 50 mol%
Genide (CFiveHFiveN-RX, where R has 1 to 5 carbon atoms
Electricity from a bath consisting of an alkyl group, X is a halogen atom)
Chromium in the plating layer is 0.001 to 6 by the plating method.
Applying an aluminum-chromium alloy plating layer containing 0% by weight
It provides a method for manufacturing Lumi-Chromium alloy plated steel sheets.
is there.
【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アルミイオンまたはクロムイオン
がアルキルピリジニ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アルキルピリジニ
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
ロム量の混合和とアルキルピリジニ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、アルキルピリジニウムハ
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 an alkylpyridinium halide. Aluminum or chromium can form a 1: 1 or 2: 1 complex with an alkylpyridinium halide, but aluminum is less likely to be electrodeposited from a 1: 1 complex. The presence of the complex is important. For that purpose, the ratio of the mixture of the amount of aluminum and the amount of chromium in the bath and the amount of alkylpyridinium halide should exceed 1: 1. Therefore, the amount of aluminum halide and chromium halide must exceed 50 mol%. I have to. Therefore, the amount of alkylpyridinium halide is less than 50 mol%.
【０００７】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, 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.
【０００８】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。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 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. Further, in the present invention, as the plating original plate, a plating original plate having a material suitable for a 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.
【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).
【００１０】[0010]
【表１】 [Table 1]
【００１１】（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（ＡｌＣ13） 塩化クロム（ＣｒＣ12） ブチルピリジニウムクロリド 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）(1) Aluminum-chromium alloy plating conditions (a) Plating bath composition Aluminum chloride (AlC 13 ) Chromium chloride (CrC 12 ) Butylpyridinium chloride Plating bath temperature 10-80 ° C Current density 1-30 A / dm 2 (electrolysis (Time is adjusted according to the plating amount)
【００１２】（ロ）めっき浴組成 臭化アルミ（ＡｌＢｒ3 ） 塩化クロム（ＣｒＢｒ2 ） メチルピリジウムクロリド 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）(B) Plating bath composition Aluminum bromide (AlBr 3 ) Chromium chloride (CrBr 2 ) Methylpyridinium chloride Plating bath temperature 10 to 120 ° C. Current density 1 to 30 A / dm 2 (electrolysis time depends on plating amount) Adjustment)
【００１３】（ハ）めっき浴組成 ヨウ化アルミ（ＡｌＩ3 ） 塩化クロム（ＣｒＣ12） ブチルピリジニウムクロリド 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 (CrC 12 ) Butylpyridinium chloride Plating bath temperature 40 to 160 ° C. Current density 1 to 30 A / dm 2 (electrolysis time is adjusted according to the plating amount) )
【００１４】（ニ）めっき浴組成 フッ化アルミ（ＡｌＦ3 ） フッ化クロム（ＣｒＦ2 ） メチルピリジニウムフルオリド 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 ) Methylpyridinium fluoride Plating bath temperature 10 to 120 ° C. Current density 1 to 30 A / dm 2 (electrolysis time depends on the plating amount) Adjust)
【００１５】（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。 〇；赤錆発生率３０％。 △；赤錆発生率の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 generation 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: 50% of red rust occurrence rate. X: Corrosion resistance is poor because red rust occurs on almost the entire surface.
【００１６】（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。 〇；赤錆発生率３０％。 △；赤錆発生率の５０％。 ×；ほぼ全面に赤錆が発生し耐食性に劣る。(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: 50% of red rust occurrence rate. X: Corrosion resistance is poor because red rust occurs on almost the entire surface.
【００１７】[0017]
【発明の効果】以上述べたように本発明によるアルミと
クロムを含有する溶融塩めっき浴を用いての電気めっき
を極めて効率的にアルミ−クロム合金めっき鋼板を製造
することが可能となり、しかも耐食性特に加工部の耐食
性の優れた鋼板を得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, it becomes possible to extremely efficiently produce an aluminum-chromium alloy-plated steel sheet by electroplating using a molten salt plating bath containing aluminum and chromium according to the present invention, and further, corrosion resistance In particular, it has an extremely excellent effect of being able to obtain a steel sheet having excellent corrosion resistance in the processed part.
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％を下回るアルキルピリジ
ニウムハロゲン化物（Ｃ5 Ｈ5 Ｎ−ＲＸ、但しＲは炭素
数１〜５のアルキル基、Ｘはハロゲン原子）からなる浴
を使用して、電気めっき法により、めっき層中にクロム
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。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. Chromium is contained in the plating layer by an electroplating method using a bath of a lower alkylpyridinium halide (C 5 H 5 N-RX, where R is an alkyl group having 1 to 5 carbon atoms and X is a halogen atom). A method for producing an aluminum-chromium alloy plated steel sheet, which comprises applying an aluminum-chromium alloy plated layer containing 0.001 to 60% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30765293A JPH07157891A (en) | 1993-12-08 | 1993-12-08 | Production of al-cr alloy plated steel sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30765293A JPH07157891A (en) | 1993-12-08 | 1993-12-08 | Production of al-cr alloy plated steel sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07157891A true JPH07157891A (en) | 1995-06-20 |
Family
ID=17971624
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30765293A Withdrawn JPH07157891A (en) | 1993-12-08 | 1993-12-08 | Production of al-cr alloy plated steel sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07157891A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012043776A1 (en) * | 2010-09-29 | 2012-04-05 | Ｊｆｅスチール株式会社 | High-strength steel sheet and manufacturing method therefor |
| 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 |
| JP2016190244A (en) * | 2015-03-31 | 2016-11-10 | 日新製鋼株式会社 | Aluminum-coated steel plate |
| US9534270B2 (en) | 2010-09-30 | 2017-01-03 | Jfe Steel Corporation | High strength steel sheet and method for manufacturing the same |
| WO2018148073A1 (en) * | 2017-02-10 | 2018-08-16 | Applied Materials, Inc. | Aluminum plating at low temperature with high efficiency |
| JP2020158802A (en) * | 2019-03-25 | 2020-10-01 | 日鉄日新製鋼株式会社 | Stainless steel material excellent in fingerprint resistance and method for manufacturing the same |
-
1993
- 1993-12-08 JP JP30765293A patent/JPH07157891A/en not_active Withdrawn
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012072447A (en) * | 2010-09-29 | 2012-04-12 | Jfe Steel Corp | High-strength steel sheet and manufacturing method therefor |
| WO2012043776A1 (en) * | 2010-09-29 | 2012-04-05 | Ｊｆｅスチール株式会社 | High-strength steel sheet and manufacturing method therefor |
| CN103124799A (en) * | 2010-09-29 | 2013-05-29 | 杰富意钢铁株式会社 | High-strength steel sheet and manufacturing method therefor |
| US9598743B2 (en) | 2010-09-29 | 2017-03-21 | Jfe Steel Corporation | High strength steel sheet and method for manufacturing the same |
| US9534270B2 (en) | 2010-09-30 | 2017-01-03 | Jfe Steel Corporation | High strength steel sheet and method for manufacturing 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 |
| 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 |
| 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 |
| 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 |
| JP2016190244A (en) * | 2015-03-31 | 2016-11-10 | 日新製鋼株式会社 | Aluminum-coated steel plate |
| WO2018148073A1 (en) * | 2017-02-10 | 2018-08-16 | Applied Materials, Inc. | Aluminum plating at low temperature with high efficiency |
| US11261533B2 (en) | 2017-02-10 | 2022-03-01 | Applied Materials, Inc. | Aluminum plating at low temperature with high efficiency |
| JP2020158802A (en) * | 2019-03-25 | 2020-10-01 | 日鉄日新製鋼株式会社 | Stainless steel material excellent in fingerprint resistance and method for manufacturing the same |
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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: 20010306 |