WO2003100136A2 - Bain de zinc-nickel alcalique a rendement en courant accru - Google Patents

Bain de zinc-nickel alcalique a rendement en courant accru Download PDF

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Publication number
WO2003100136A2
WO2003100136A2 PCT/EP2003/005394 EP0305394W WO03100136A2 WO 2003100136 A2 WO2003100136 A2 WO 2003100136A2 EP 0305394 W EP0305394 W EP 0305394W WO 03100136 A2 WO03100136 A2 WO 03100136A2
Authority
WO
WIPO (PCT)
Prior art keywords
bath
zinc
alkaline
deposition
nickel
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.)
Ceased
Application number
PCT/EP2003/005394
Other languages
German (de)
English (en)
Other versions
WO2003100136A3 (fr
Inventor
Ernst-Walter Hillebrand
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.)
Hillebrand Walter GmbH and Co KG
Original Assignee
Hillebrand Walter GmbH and Co KG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hillebrand Walter GmbH and Co KG filed Critical Hillebrand Walter GmbH and Co KG
Priority to AU2003238380A priority Critical patent/AU2003238380A1/en
Publication of WO2003100136A2 publication Critical patent/WO2003100136A2/fr
Publication of WO2003100136A3 publication Critical patent/WO2003100136A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
    • 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 invention relates to a method and a composition for the galvanic coating of metals by applying zinc-nickel layers in an alkaline bath.
  • Zinc-nickel coatings are used extensively on metallic surfaces to improve the corrosion properties and to achieve a certain appearance.
  • alkaline baths which also enable a more homogeneous metal distribution, has become common practice.
  • a bath is described as a zinc-nickel bath in US Pat. No. 3,681,211.
  • An aqueous zinc-nickel solution is adjusted to a pH between 10 and 13, for example with NaOH.
  • Zinc and nickel are largely present in such solutions as hydroxides or hydroxide precipitates in the solution and, especially in the case of nickel, must be kept in solution at the given pH by adding complexing agents.
  • Polyethylene amines are used as preferred complexing agents; in particular diethylenetriamine, triethylenetetramine, tetraethylene pentamine (TEPA), pentaethylene hexamine or N, N, N ', N , -Tetrakis (2-hydroxypropyl) ethylenediamine (Quadrol L). Furthermore, sheen can be added; In addition to the polyethylene amines, which also act as gloss substances, N-benzyl nicotinate betaine (BN betaine) is used as the preferred gloss substance.
  • alkaline zinc-nickel baths allow the formation of homogeneous protective layers, they have the considerable disadvantage of only allowing a low cathodic current yield, which is around 10-30% (see Fig. 1). The usual cathodic current densities that are used in these processes are approximately in the range from 0.1 to 8 A / dm 2 .
  • the time for applying a layer with a layer thickness of 8 ⁇ m is approximately 40 minutes in a common alkaline electroplating bath, as described for example in DE-198 48467 A1, with an average current density of 2.5 A / dm2.
  • An increase in the current density is only possible to a limited extent in alkaline electroplating baths, since the quality, in particular the homogeneity, of the coating decreases rapidly with increasing current density.
  • the invention is therefore based on the object of providing a process principle and a reaction solution for the galvanic zinc-nickel coating which, with an increase in the current efficiency, enables a considerably faster deposition of a homogeneous galvanic alloy coating.
  • the invention is based on the knowledge that the difficulties prevailing in the prior art in alkaline electroplating baths for the cathodic deposition of zinc-nickel alloy coatings can be attributed to deposition, in particular oiling out of the polyethylene amine or comparable complexing agents in the cathode film.
  • deposition in particular oiling out of the polyethylene amine or comparable complexing agents in the cathode film.
  • oiling out a film forms on the cathode surface, which hinders the further deposition of metal.
  • this problem is solved by reducing the deposition or oiling out of the polyethylene amine or comparable complexing agents. Such a reduction can be achieved with the help of solubilizers between polar and non-polar phases.
  • One way of realizing the teaching according to the invention is to add a substance in baths which contain at least one polyethylene amine. Add the solubility of the polyethylene amine. Substances with polar groups such as aryl sulfonates are particularly effective substances for achieving this purpose.
  • Aryl sulfonates used for this purpose are cumene sulfonate and xylene sulfonate, which have a comparable effect.
  • a particularly effective reduction in the deposition of the complexing agents on the cathode can be achieved using cumene sulfonate or xylene sulfonate, which allows an increased current efficiency of more than 50% and consequently a significant reduction in the coating time when a homogeneous protective layer is formed (see Fig. 2).
  • This embodiment according to the invention represents a particularly advantageous and further surprising result using known substances, which has hitherto been used in the field of galvanic coating, but for completely different purposes in other baths.
  • Cumene sulfonate in particular is found in the prior art, in addition to a gene use in solvents and bleaches, in acidic electroplating baths, especially for phosphating use. Such use is described in German Offenlegungsschrift 19956 383 A1.
  • the bath contains diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine or N, N, N ⁇ N'-tetrakis (2-hydroxypropyl) ethylenediamine (Quadrol L) as polyethylene amines.
  • diethylene triamine (DETA) or tetraethylene pentamine (TEPA) is contained.
  • compositions of cumene sulfonate or xylene sulfonate are 0.1 to 50 g / l.
  • the zinc concentration is 6-15 g / l.
  • the nickel concentration depends on the zinc concentration and must be such that an alloy of 12-15% Ni is obtained.
  • Preferred concentrations of the polyethylene amines are 1-100 g / l, advantageous NaOH concentrations are 60-200 g / l.
  • Tetraethylene pentamine is preferably used in a concentration of 40 g / l.
  • the bath according to the invention is preferably operated with insoluble nickel anodes. Furthermore, the use of an ion exchange membrane can be advantageous in order to avoid undesired side reactions and to separate the anode from the electrolyte.
  • the following bath is used:
  • Nickel 1.8 g / l
  • BN betaine 0.1 g / l Cumolsulf. 1.6 g / l bath temperature: 32 ° C anodes: nickel anodes cathodic current density: 2.1 A / dm 2 cathodic current yield: 60% (see also Fig. 2)
  • the coating metals were added by dissolving zinc oxide and adding nickel sulfate.
  • a current yield of 60% is achieved using tetraethylene pentamine at a cumene sulfonate concentration of 1.6 g / l.
  • the working time for the deposition of an 8 ⁇ m thick alloy layer is 20 minutes.
  • the formed zinc-nickel layer is characterized by a homogeneous nickel distribution.

Landscapes

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

Abstract

L'invention concerne un bain de galvanisation ainsi qu'un procédé de dépôt cathodique de revêtement d'alliage zinc-nickel. Selon ledit procédé, le bain contient, comme agent complexant, au moins une polyéthylènamine. Par addition d'un arylsulfonate tel que du cumolsulfonate ou du xylènesulfonate, on augmente la solubilité de l'agent complexant, ou bien on réduit son dépôt local au niveau de la cathode. On obtient ainsi une augmentation de la densité de courant utilisable et du rendement en courant par dépôt de couches de galvanisation homogènes et la durée de travail nécessaire est réduite.
PCT/EP2003/005394 2002-05-28 2003-05-23 Bain de zinc-nickel alcalique a rendement en courant accru Ceased WO2003100136A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003238380A AU2003238380A1 (en) 2002-05-28 2003-05-23 Alkaline zinc-nickel bath with increased current efficiency

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2002123622 DE10223622B4 (de) 2002-05-28 2002-05-28 Alkalisches Zink-Nickelbad sowie entsprechende Galvanisierungsverfahren mit erhöhter Stromausbeute
DE10223622.4 2002-05-28

Publications (2)

Publication Number Publication Date
WO2003100136A2 true WO2003100136A2 (fr) 2003-12-04
WO2003100136A3 WO2003100136A3 (fr) 2004-03-25

Family

ID=29557338

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2003/005394 Ceased WO2003100136A2 (fr) 2002-05-28 2003-05-23 Bain de zinc-nickel alcalique a rendement en courant accru

Country Status (3)

Country Link
AU (1) AU2003238380A1 (fr)
DE (1) DE10223622B4 (fr)
WO (1) WO2003100136A2 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105239115A (zh) * 2015-10-22 2016-01-13 广州超邦化工有限公司 一种高稳定性的碱性锌-镍合金电镀溶液
DE102007002321B4 (de) * 2007-01-16 2018-07-05 Volkswagen Ag Schraubenfeder mit Korrosionsschutz

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3681211A (en) * 1970-11-23 1972-08-01 Enequist Chem Co Inc The Electroplating a black nickel-zinc alloy deposit
DE3712511C3 (de) * 1986-04-14 1995-06-29 Dipsol Chem Alkalisches cyanidfreies Elektroplattierungsbad und Verwendung dieses Bades
US4699696A (en) * 1986-04-15 1987-10-13 Omi International Corporation Zinc-nickel alloy electrolyte and process
US4832802A (en) * 1988-06-10 1989-05-23 Mcgean-Rohco, Inc. Acid zinc-nickel plating baths and methods for electrodepositing bright and ductile zinc-nickel alloys and additive composition therefor
US5417840A (en) * 1993-10-21 1995-05-23 Mcgean-Rohco, Inc. Alkaline zinc-nickel alloy plating baths
DE19834353C2 (de) * 1998-07-30 2000-08-17 Hillebrand Walter Gmbh & Co Kg Alkalisches Zink-Nickelbad
DE19848467C5 (de) * 1998-10-21 2006-04-27 Walter Hillebrand Gmbh & Co. Kg Galvanotechnik Alkalisches Zink-Nickelbad
DE19956383A1 (de) * 1999-11-24 2001-05-31 Henkel Kgaa Verfahren zur Phospatierung mit metallhaltiger Nachspülung

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007002321B4 (de) * 2007-01-16 2018-07-05 Volkswagen Ag Schraubenfeder mit Korrosionsschutz
CN105239115A (zh) * 2015-10-22 2016-01-13 广州超邦化工有限公司 一种高稳定性的碱性锌-镍合金电镀溶液

Also Published As

Publication number Publication date
AU2003238380A8 (en) 2003-12-12
WO2003100136A3 (fr) 2004-03-25
DE10223622B4 (de) 2005-12-08
DE10223622A1 (de) 2003-12-18
AU2003238380A1 (en) 2003-12-12

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