JP6407879B2 - パッケージング用途のための鋼基材に適用されるクロム−酸化クロムコーティング及び前記コーティングを製造する方法 - Google Patents
パッケージング用途のための鋼基材に適用されるクロム−酸化クロムコーティング及び前記コーティングを製造する方法 Download PDFInfo
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- JP6407879B2 JP6407879B2 JP2015543420A JP2015543420A JP6407879B2 JP 6407879 B2 JP6407879 B2 JP 6407879B2 JP 2015543420 A JP2015543420 A JP 2015543420A JP 2015543420 A JP2015543420 A JP 2015543420A JP 6407879 B2 JP6407879 B2 JP 6407879B2
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- chromium
- tin
- coating
- electrodeposited
- metal
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/04—Electroplating: Baths therefor from solutions of chromium
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/04—Electroplating: Baths therefor from solutions of chromium
- C25D3/06—Electroplating: Baths therefor from solutions of chromium from solutions of trivalent chromium
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/38—Chromatising
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- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
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- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
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- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
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- C25D9/00—Electrolytic coating other than with metals
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- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
- C25D9/10—Electrolytic coating other than with metals with inorganic materials by cathodic processes on iron or steel
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Description
1.従来の不動態化されていない電着された、場合により流動溶融されたブリキ(即ち、ETP)、又は
2.冷間圧延されて回復焼き鈍しされ電着された、場合により流動溶融されたブリキ
を含み、基材の片側又は両側が3価クロムの電気メッキ法を使用することにより、単一のメッキステップで製造された金属クロム−酸化クロム(Cr−CrOx)コーティング層でコートされたパッケージング用鋼基材を提供することにより達せられる。
両側に2.8gSn/m2のスズコーティング重量を有する従来の不動態化されていない、流動溶融されたブリキのシート(通常の鋼規格及び含炭量)を、酸化スズ層厚さを極小化するために電解前処理した。これは、上記シートを炭酸ナトリウム溶液(3.1g/lのNa2CO3、温度50℃)中に浸漬して、0.8A/dm2の陰極電流密度を2秒間適用することにより行った。脱イオン水ですすいだ後、試料を120g/lの塩基性硫酸クロム、250g/lの塩化カリウム、15g/lの臭化カリウム及び51.2g/lのギ酸カリウムで構成される50℃に保たれた3価クロム電解質中に浸漬した。この溶液のpHを、硫酸添加により、25℃で測定して2.3に調節した。白金化されたチタン陽極を対極に使用して、21〜25mgCr/m2(XRFにより測定)の間を含有するCr−CrOxコーティングを、10A/dm2の陰極電流密度を約1秒間適用することにより、表面に堆積させた。そのように製造された試料は、輝く金属的外観を示した。
両側に2.8gSn/m2のスズコーティング重量を有する従来の、不動態化されていない、流動溶融されたブリキのシート(通常の鋼規格及び炭素含有率)を、最初に電解前処理して酸化スズ層厚さを最小化した。これは、シートを炭酸ナトリウム溶液(3.1g/lのNa2CO3、温度50℃)中に浸漬して、0.8A/dm2の陰極電流密度を2秒間適用することにより行った。脱イオン水ですすいだ後、試料を120g/lの塩基性硫酸クロム、250g/lの塩化カリウム、15g/lの臭化カリウム及び51.2g/lのギ酸カリウムで構成される50℃に保たれた3価クロム電解質中に浸漬した。この溶液のpHを、硫酸を添加することにより、25℃で測定して2.3に調節した。白金化されたチタン陽極を対極に使用して、15A/dm2の陰極電流密度を約1秒間適用することにより、65〜75mgCr/m2(XRFにより測定)の間を含有するCr−CrOxコーティングを表面に堆積させた。そのように製造された全ての試料は、輝く金属的外観を示した。典型的なSEM像を図1及び図2に示すが、それらの図はスズ表面における金属クロム−酸化クロムの非常に微細な粒子の堆積を示す。
どのような金属コーティングも含まないブリキ原板のコイル(通常の鋼規格及び炭素含有率)を、20m/分のライン速度で走る加工処理ラインで処理した。加工処理配列は、ストリップを約10秒間、60℃に保った30ml/1の市販の清浄化剤(Percy P3)及び40g/lのNaOHを含有する溶液を通して走らせることによる鋼のアルカリ清浄化で開始した。ストリップの清浄化中に、1.3A/dm2の陽極電流密度を適用した。脱イオン水ですすいだ後、帯鋼を酸溶液に約10秒間通して、表面を活性化した。酸溶液は50g/l H2SO4からなり、25℃に保った。脱イオン水ですすいだ後、帯鋼を、50℃に保たれた3価クロムを主成分とする電解質を含む電気メッキ槽中に通した。この電解質は、120g/lの塩基性硫酸クロム、250g/lの塩化カリウム、15g/lの臭化カリウム及び51.2g/lのギ酸カリウムからなった。この溶液のpHを、硫酸を添加することにより、25℃で測定して2.3に調節した。電気メッキ槽は、1組の白金化されたチタンからなる陽極を含んだ。ストリップの加工処理中に、約17A/dm2の陰極電流密度を丁度1秒かけて適用し、60〜70mgCr/m2のクロム−酸化クロムコーティングを(XRFにより測定)ブリキ原板表面に電着した。そのように製造された全ての試料は、輝く金属的外観を示した。典型的なSEM像を図1及び2に示すが、それらは、鋼表面に金属クロム−酸化クロムの非常に微細な粒子の堆積を示す。
引っかき傷のあるDRD缶に関する。
どのような金属コーティングも含まないブリキ原板のコイル(通常の鋼規格及び炭素含有率)を、先行実施例に記載したのと同一の加工処理ラインで処理してCr−CrOxコーティングを適用した。
2 電流コレクター
3 多孔質ガス拡散輸送層
4 親水性反応層
5 プロトン交換膜
Claims (10)
- 金属クロム−酸化クロムのコーティングを、
1a.不動態化されていない電着されたブリキ、
1b.不動態化されていない電着され、流動溶融されたブリキ、
2a.冷間圧延されて回復焼き鈍しされ電着されたブリキ、または
2b.冷間圧延されて回復焼き鈍しされ電着され、流動溶融されたブリキを含有する、パッケージング用途のための基材上に堆積させることによって、パッケージング用途のためのコートされた鋼基材を製造する方法であって、
3価クロム化合物、ギ酸アニオンを含むキレート剤の混合物を含み、酸又は塩基がpHを調節するために添加されたメッキ溶液から、単一工程のステップで、前記基材上に前記金属クロム−酸化クロムコーティングを電着させることを含んでなり、
前記メッキ溶液は緩衝剤を含有せず、及び
前記基材を、外部電源の陰極に接続し、十分に高い電流密度となるよう電圧を印加する、方法。 - 前記メッキ溶液が、伝導性強化塩、臭化物を含有する塩を含む復極剤および界面活性剤の少なくとも1以上をさらに含む、請求項1に記載の方法。
- 前記キレート剤が、ギ酸アニオンを含み、前記伝導性強化塩はアルカリ金属カチオンを含有し、及び前記復極剤は臭化物含有金属塩を含む、請求項2に記載の方法。
- 前記キレート剤、前記伝導性強化塩及び前記復極剤におけるカチオン種が、カリウムである、請求項2又は3に記載の方法。
- 前記コートされた基材が、片側又は両側に、ラッカー塗りステップによる熱硬化性有機コーティング、又は熱可塑性の単層ポリマー、又は膜ラミネート化ステップ若しくは直接押出ステップによる熱可塑性の多層ポリマーからなる有機コーティングをさらに備える、請求項1から4までのいずれか一項に記載の方法。
- 陽極が、メッキステップ中におけるCr(III)イオンのCr(VI)イオンへの酸化を減少させるか又は排除するように選択される、請求項1から5までのいずれか一項に記載の方法。
- 電着により、金属クロム−酸化クロム層を、少なくとも2.0mg/m2の全クロム含有量を有する不動態化されていないブリキ上に堆積させる、請求項1から6までのいずれか一項に記載の方法。
- 電着により、金属クロム−酸化クロム層を、全クロム含有量の上限が、140mg/m2の、不動態化されていないブリキ上に堆積させる、請求項1から7までのいずれか一項に記載の方法。
- 電着により、金属クロム−酸化クロム層を、冷間圧延されて回復焼き鈍しされ電着されたブリキ、または冷間圧延されて回復焼き鈍しされ電着され、流動溶融されたブリキであって、少なくとも20mg/m2の全クロム含有量を有するブリキ上に堆積させる、請求項1から8のいずれか一項に記載の方法。
- 電着により、金属クロム−酸化クロム層を、冷間圧延されて回復焼き鈍しされ電着されたブリキ、または冷間圧延されて回復焼き鈍しされ電着され、流動溶融されたブリキであって、最大で140mg/m2の全クロム含有量を有するブリキ上に堆積させる、請求項1から9のいずれか一項に記載の方法。
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PCT/EP2013/074337 WO2014079909A1 (en) | 2012-11-21 | 2013-11-21 | Chromium-chromium oxide coatings applied to steel substrates for packaging applications and a method for producing said coatings |
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