EP2096193B1 - Verfahren zur Herstellung von korrosionsresistentem Zink und Zink-Nickel-plattierten linearen oder komplex geformten Teilen - Google Patents

Verfahren zur Herstellung von korrosionsresistentem Zink und Zink-Nickel-plattierten linearen oder komplex geformten Teilen Download PDF

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Publication number
EP2096193B1
EP2096193B1 EP08075132A EP08075132A EP2096193B1 EP 2096193 B1 EP2096193 B1 EP 2096193B1 EP 08075132 A EP08075132 A EP 08075132A EP 08075132 A EP08075132 A EP 08075132A EP 2096193 B1 EP2096193 B1 EP 2096193B1
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EP
European Patent Office
Prior art keywords
zinc
nickel
process according
layer
foregoing
Prior art date
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Not-in-force
Application number
EP08075132A
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English (en)
French (fr)
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EP2096193A1 (de
Inventor
Jörg UNGER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Atotech Deutschland GmbH and Co KG
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Atotech Deutschland GmbH and Co KG
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Priority to EP08075132A priority Critical patent/EP2096193B1/de
Priority to PCT/EP2009/001367 priority patent/WO2009103567A1/en
Publication of EP2096193A1 publication Critical patent/EP2096193A1/de
Application granted granted Critical
Publication of EP2096193B1 publication Critical patent/EP2096193B1/de
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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
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/021—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal alloy layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
    • C23C28/025—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only with at least one zinc-based layer
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/615—Microstructure of the layers, e.g. mixed structure
    • C25D5/617—Crystalline layers
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium
    • 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
    • C25D3/22—Electroplating: Baths therefor from solutions of zinc
    • 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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc

Definitions

  • the present invention relates to a process for the preparation of corrosion resistant zinc and zinc nickel deposits on linear or complex shaped parts, usually made of steel.
  • the deposition according to the present invention consists of a two step deposition, wherein a layer of zinc from an alkaline zinc bath and a layer of zinc nickel alloy deposited from an acid bath is deposited.
  • Such coated substrates possess a similar corrosion protection and similar thickness distribution as zinc nickel coated parts deposited from an alkaline zinc nickel electrolyte with the advantage of not using high concentrations of amines or ammonia as strong complexing agents and not forming cyanide while at the same time providing reasonable post-forming capability.
  • Substrates to be plated either have a linear shape (like window frames) or complex shapes (like lock housings). These kind of parts are preferably plated from an alkaline electrolyte as the current efficiency in the high current density area (on the end of linear parts or at the edges of complex shaped parts) is reduced by using special polymeric inhibitors. Due to this fact the deposited coating exhibits a very homogeneous thickness distribution over the entire component surface and also provides excellent corrosion protection.
  • Such bath usually contain zinc ions, nickel ions and poly(alkyleneimines) obtained from ethyleneimine, 1,2-propyleneimine, 1,2-butyleneimine and 1,1-dimethylethyleneimine.
  • the poly(alkyleneimines) may have molecular weights of from about 100 to about 100,000.
  • US 6,652,728 discloses a zinc and zinc alloy bath which contains zinc ions, hydroxide ions, optionally nickel ions and a polymer having the following formula: Wherein m has a value of 2 or 3, n has a value of at least 2; R 1 , R 2 , R 3 , which may be the same or different, each independently denote methyl, ethyl or hydroxyethyl; p has a value in the range from 3 to 12; and X - denotes chloride, bromide and/or iodide.
  • Such bath is suitable for depositing alkaline zinc deposits.
  • the zinc-nickel coating contains a gamma-phase zinc-nickel alloy. This is realized with a nickel content of an average of 15 %. However, this coating is significantly less ductile than pure zinc coatings.
  • GB 2 294 949 A relates to anti-corrosive multilayer-plated steel materials, e.g. plates, pipes, joints, clamps, bolts and nuts made of two zinc-nickel alloy layers, wherein the first zinc-nickel layer is deposited from an acidic plating bath and the second zinc-nickel layer is deposited from an alkaline plating bath.
  • the disadvantage of using an alkaline zinc-nickel bath as described above cannot be avoided by using such a layer sequence.
  • DE 31 29 129 A1 relates to a method for the multi-stage electrodeposition of very bright, strongly adhering zinc coatings employing alkaline cyanide-free baths for the top layer, characterised in that a zinc, nickel, tin, copper and/or cadmium layer is first deposited, followed by deposition on this layer of a zinc layer.
  • a process is provided wherein the homogeneous coating thickness and ductility is provided by a pure zinc layer also providing corrosion protection and the very high corrosion protection particularly regarding red rust is provided by a subsequent zinc-nickel, which is deposited from an acid electrolyte and which does not contain high concentrations of amines or ammonia.
  • the pure zinc layer is deposited on the metal substrate and the zinc nickel layer is deposited on the zinc layer:
  • Such process for the preparation of corrosion resistant substrate comprises the steps of
  • the thickness of the zinc layer typically is between 1 - 12 ⁇ m, preferably between 2 - 8 ⁇ m, and more preferably 4-6 ⁇ m.
  • the thickness of the zinc nickel layer typically is between 1 - 12 ⁇ m, preferably between 2 - 8 ⁇ m, and more preferably 4-6 ⁇ m.
  • the alkaline zinc electrolyte preferably has the following composition:
  • Brightening additives are used depending on the demand of the optical aspect. Such brightening agents are well known in the art and for example described in US 6,652,728 .
  • Acid zinc nickel electrolytes are known in the art and for example described in US 4,699,696 .
  • Such acid zinc-nickel electrolytes solutions contain zinc ions and nickel Ions, and an additive agent of a class selected from the group consisting of (a) aromatic sulfonic acids, (b) aromatic sulfonamides, sulfonimides and mixed carboxamides/sulfonamides, (c) acetylene alcohols.
  • Solutions for passivating zinc and zinc alloy surfaces are known and for example described in EP 1 484 432 .
  • Such solutions typically contain a water soluble Cr(III)-salt in a concentration of 0.5-80 g/l, preferably 1-40 g/l, more preferably 1-10 g/l.
  • the pH of such solution is 0.8 - 4.0 and the temperature 10-80°C.
  • the passivate solution can contain additional metals such as cobalt, nickel, zinc, iron, zircon, titanium, aluminium, silver, copper, pigments.
  • Optional additional components contain silicates, nitrates, phosphates, fluorides and polymer resins.
  • the zinc plated surface is immersed in the passivation solution, rinsed and thereafter optionally treated at elevated temperatures of 100 to 250°C for 10 to 300 minutes.
  • coatings are obtained by electroplating in zinc and an acid zinc-nickel electrolytes. Thickness distribution was tested according to the following test procedure:
  • Comparative Example 1 Deposition of a pure zinc layer from an alkaline zinc plating bath
  • an alkaline zinc electrolyte which contains zinc ions in an amount of 10 g/l, 120 g/l NaOH, 0.5 g/l polymeric inhibitor according to Example 2.1 of US 6,652,728 and a brightening additive, the composition of which is described in US 6,652,728 , is filled into a Hull cell.
  • Zinc is used as anode material.
  • the cathode steel panel will be deposited for 15 minutes at 1 A. The temperature is 28°C. The panel is rinsed and dried.
  • the thickness distribution is measured at 2 positions on the panel: 3 cm of the lower edge and 2.5 cm of the right and left edge of the panel at high (app. 2.8 A/dm 2 ) and low current density (app 0.5 A/dm 2 ).
  • the thickness of the coating is measured four times at the two positions to avoid measuring mistakes.
  • Comparative Example 2 Deposition of a zinc nickel layer from a commercially available alkaline zinc nickel plating bath
  • composition of the bath acidic zinc nickel plating bath was as follows: ZnCl 2 0.3 M/l NiCl 2 0.5 M/l KCI 2.7 M/l H 3 BO 3 0.3 M/l aromatic sulfonamide 1.1 g/l acetylenic alcohol 0.02 g/l sodium acetate 0.7 M/l alkylene oxide polymer 1.1 g/l sulfosuccinate-alkyl diester 1.1 g/l
  • Plating is with 1 A for 15 minutes plating at a temperature of 35°C in the Hull cell.
  • Table 1 Thickness distribution for different plated layers hcd lcd hcd : lcd Comp.
  • Example 1 4.1 micron 2.8 micron 1.5 Comp.
  • Example 2 5.5 micron 1.8 micron 3
  • Example 3 8.1 micron 2.2 micron 3.7
  • Example 4 (invention) 6.1 micron 2.6 micron 2.4
  • the plated thickness for the same plating time and current clearly shows that higher thicknesses and better thickness distributions - represented by the high current density (hcd) to low current density (lcd) thickness ration - can be achieved with the two layer sequence of the present invention according to Example 4 compared to the alkaline zinc nickel process Reflectalloy ZNA (Comparative Example 2). 20% higher thickness is obtained in the low current density regime.
  • Comparative Example 2 600 Vicker's Hardness at 50 mN
  • Example 4 525 Vicker's Hardness at 50 mN
  • the grain size in the zinc nickel layer also influences the ductility of the coating. With increasing grain size the ductility of the coating is increasing. A good compromise between grain size and current density is observed at a value of 2 A/dm 2 .
  • Corrosion protection of the coatings obtained according to Example 4 was evaluated in DIN 50021 neutral salt spray exposure and found >240 h to first appearance of white corrosion and >1000 h to substrate corrosion.
  • gamma-phase ZnNi from the acid zinc nickel obtained by Example 4 was confirmed by XRD. Such phase exhibits very good corrosion resistance.
  • the deposit shows a homogeneous alloy composition over a wide range of current density.
  • the gamma phase zinc-nickel layer is consistently obtained even on complex shaped parts, as confirmed by X-ray diffraction.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Claims (10)

  1. Verfahren zur Herstellung eines korrosionsbeständigen Substrats, bei dem man
    (i) ein Metallsubstrat bereitstellt,
    (ii) darauf eine Schicht aus Zink aus einem alkalischen Elektrolyten abscheidet,
    (iii) danach eine Schicht aus Zink-Nickel aus einem sauren Elektrolyten abscheidet.
  2. Verfahren nach Anspruch 1, bei dem es sich bei dem Metallsubstrat um ein Stahlsubstrat handelt.
  3. Verfahren nach einem der vorhergehenden Ansprüche, bei dem man den Zinküberzug aus einem alkalischen Zinkelektrolyten, der einen polymeren Inhibitor in einer Konzentration von 0,2-2 g/l enthält, durchführt.
  4. Verfahren nach einem der vorhergehenden Ansprüche, bei dem man die Abscheidung über einen Zeitraum von 5-50 Minuten bei 0,5-5 A/dm2 und einer Temperatur von 18-35°C durchführt.
  5. Verfahren nach einem der vorhergehenden Ansprüche, bei dem die Zinkschicht eine Dicke von 1-12 µm, vorzugsweise 2-8 µm und weiter bevorzugt 4-6 µm aufweist.
  6. Verfahren nach einem der vorhergehenden Ansprüche, bei dem der saure Zink-Nickel-Elektrolyt Zink in einer Menge von 10-60 g/l und Nickel in einer Menge von 10-50 g/l enthält.
  7. Verfahren nach einem der vorhergehenden Ansprüche, bei dem man die Schicht aus Zink-Nickel zusätzlich mit einem Cr(VI)-freien passivierenden Konversionsüberzug behandelt.
  8. Verfahren nach Anspruch 7, wobei das Passivat 1 bis 5 g/l Cr (III) -Ionen enthält.
  9. Verfahren nach einem der vorhergehenden Ansprüche, bei dem man das Substrat abschließend mit einem Versiegelungsmittel behandelt.
  10. Verfahren nach Anspruch 9, bei dem das Versiegelungsmittel sauerstoffhaltige Siliciumverbindungen, Organosiliciumverbindungen, aus Acrylharzen, Polyurethanharzen oder Polyethylenharzen hergestellte Polymerdispersionen oder Mischungen davon enthält.
EP08075132A 2008-02-21 2008-02-21 Verfahren zur Herstellung von korrosionsresistentem Zink und Zink-Nickel-plattierten linearen oder komplex geformten Teilen Not-in-force EP2096193B1 (de)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP08075132A EP2096193B1 (de) 2008-02-21 2008-02-21 Verfahren zur Herstellung von korrosionsresistentem Zink und Zink-Nickel-plattierten linearen oder komplex geformten Teilen
PCT/EP2009/001367 WO2009103567A1 (en) 2008-02-21 2009-02-23 Process for the preparation of corrosion resistant zinc and zinc-nickel plated linear or complex shaped parts

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP08075132A EP2096193B1 (de) 2008-02-21 2008-02-21 Verfahren zur Herstellung von korrosionsresistentem Zink und Zink-Nickel-plattierten linearen oder komplex geformten Teilen

Publications (2)

Publication Number Publication Date
EP2096193A1 EP2096193A1 (de) 2009-09-02
EP2096193B1 true EP2096193B1 (de) 2013-04-03

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WO (1) WO2009103567A1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2468929B1 (de) 2010-12-27 2015-04-08 Fontana Fasteners R.D. S.r.l. Verfahren zur Beschichtung metallischer Teile mit Gewinde

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CN104005063A (zh) * 2014-06-11 2014-08-27 沈阳飞机工业（集团）有限公司 一种钢制件电镀锌镍合金的方法
CN106637315A (zh) * 2015-11-02 2017-05-10 株洲时代新材料科技股份有限公司 一种不含铬离子的锌镍合金自动电镀工艺
DE102016225681A1 (de) * 2016-12-20 2018-06-21 Thyssenkrupp Ag Vergraute Oberfläche zum Zwecke einer verkürzten Aufheizung
CN113463141B (zh) * 2021-06-28 2022-10-25 成都飞机工业（集团）有限责任公司 一种提高镀锌层耐酸性盐雾腐蚀性能的方法

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2468929B1 (de) 2010-12-27 2015-04-08 Fontana Fasteners R.D. S.r.l. Verfahren zur Beschichtung metallischer Teile mit Gewinde

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WO2009103567A1 (en) 2009-08-27

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