EP1881090B1 - Electrolyte composition und process for the deposition of a zinc-nickel alloy layer on a cast iron or steel substrate - Google Patents

Electrolyte composition und process for the deposition of a zinc-nickel alloy layer on a cast iron or steel substrate Download PDF

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Publication number
EP1881090B1
EP1881090B1 EP06014519.0A EP06014519A EP1881090B1 EP 1881090 B1 EP1881090 B1 EP 1881090B1 EP 06014519 A EP06014519 A EP 06014519A EP 1881090 B1 EP1881090 B1 EP 1881090B1
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Prior art keywords
electrolyte composition
zinc
substrate
nickel
deposition
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German (de)
French (fr)
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EP1881090A1 (en
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Dieter Harald Dr. Gollan
Gerard Patron
Thomas Helden
Andreas Heinz Dr. Kirchhof
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MacDermid Enthone Inc
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Enthone Inc
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Priority to ES06014519.0T priority Critical patent/ES2553730T3/en
Priority to HUE06014519A priority patent/HUE026918T2/en
Priority to PL06014519T priority patent/PL1881090T3/en
Priority to EP06014519.0A priority patent/EP1881090B1/en
Priority to PT60145190T priority patent/PT1881090E/en
Priority to US11/778,011 priority patent/US8435398B2/en
Publication of EP1881090A1 publication Critical patent/EP1881090A1/en
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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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/48—Coating with alloys
    • C23C18/50—Coating with alloys with alloys based on iron, cobalt or nickel

Definitions

  • the present invention relates to an electrolyte composition for depositing a zinc-nickel alloy layer on a substrate, particularly a cast iron or steel substrate.
  • ammonium chloride-containing, low-acid baths for the deposition of zinc-nickel alloy layers allow the deposition of corrosion-resistant layers with nickel incorporation rates in the range of 10 to 15 mass%, but have the typical disadvantage of acidic electrolytes, often to produce uneven metal distributions in the layers.
  • the ammonium ions present in the electrolyte are environmentally relevant and pollute the waste water strongly.
  • the ammonium concentration in the waste water of electroplating plants are strictly regulated and subject to constant control. In order to comply with the regulatory requirements therefore expensive and expensive wastewater treatment must be made.
  • Ammonium chloride-containing zinc-nickel electrolytes for depositing corresponding alloy layers are known, for example, from the US patents US 4388160 and US 4765871 known.
  • ammonium chloride-containing electrolyte based on nickel chloride or nickel sulfate as a nickel metal salt carrier.
  • the aforementioned electrolytes typically have ammonium chloride in a concentration of up to 300 g / l, which necessitates extensive wastewater treatment.
  • the zinc-nickel alloy layers deposited from such alkaline zinc-nickel electrolytes typically exhibit incorporation rates of 10 to 15 mass% nickel.
  • a typical electrolyte of this kind as in the US 4765871 6 to 17 g / l of zinc, 0.8 to 2.3 g / l of nickel and 112 to 186 g / l of sodium or potassium hydroxide.
  • EP1295967 and SU524866 disclose electrolytes for depositing zinc-nickel alloys on metallic surfaces, the electrolytes including, inter alia, an aminoacetic acid.
  • the electrolyte compositions according to the invention are based on an alkali metal halide, preferably a potassium halide, more preferably potassium chloride as conductive salt and furthermore have an acetate of the group consisting of sodium acetate, potassium acetate or ammonium acetate or mixtures thereof.
  • an alkali metal halide preferably a potassium halide, more preferably potassium chloride as conductive salt and furthermore have an acetate of the group consisting of sodium acetate, potassium acetate or ammonium acetate or mixtures thereof.
  • the electrolyte composition of the present invention has a molar acetate: aminoacetic acid ratio of about 0.35 to about 0.91.
  • the electrolyte composition according to the invention preferably comprises boric acid and a brightener system consisting of saccharin, benzalacetone, orthochlorobenzaldehyde, octanol ethoxylate and a potassium salt of a sulfopropylated polyalkoxylated naphthol.
  • a brightener system consisting of saccharin, benzalacetone, orthochlorobenzaldehyde, octanol ethoxylate and a potassium salt of a sulfopropylated polyalkoxylated naphthol.
  • the brightener system preferably used comprises between 2 to 4 g / l of sodium saccharin, 0.025 to 0.2 g / l of benzalacetone, 0.006 to 0.01 g / l of orthochlorobenzaldehyde, 0.8 to 1.2 g / l of octanol ethoxylate and 2.5 to 3.2 g / l of potassium salt of the sulfopropylated polyalkoxylated naphthol.
  • the brightener system may have 0.5 to 1.0 g / L pyridine sulfonic acid.
  • the potassium chloride preferably used as the conductive salt in the electrolyte composition may be contained in the composition at a concentration of about 190 to 220 g / L.
  • the aminoacetic acid added according to the invention may be present in a concentration of between 10 and 50 g / l, preferably approximately 30 g / l, in the electrolyte composition.
  • the object is achieved by a method for depositing a zinc-nickel alloy layer on a substrate, in particular a cast iron or steel substrate, in which the substrate to be coated, in particular a cast iron or iron substrate under application of a current with the electrolyte composition according to the invention will be contacted.
  • the temperature of the electrolyte composition between about 20 ° C and about 60 ° C, preferably between 30 ° C and 40 ° C.
  • the current density to be set for the deposition of the layer can be adjusted between about 0.5 and about 5 A / dm 2 , preferably between 1.0 and 3.5 A / dm 2 .
  • the pH of the electrolyte composition described herein is between 5 and 6.
  • the pH of the electrolyte composition described herein is between 5 and 6.
  • a current density between 0.5 and 1.0 A / dm 2 was set.
  • the pH of the electrolyte composition was between 5 and 6.

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

Description

Die vorliegende Erfindung betrifft eine Elektrolytzusammensetzung zur Abscheidung einer Zink-Nickel-Legierungsschicht auf einem Substrat, insbesondere einem Gußeisen- oder Stahlsubstrat.The present invention relates to an electrolyte composition for depositing a zinc-nickel alloy layer on a substrate, particularly a cast iron or steel substrate.

Zur Verbesserung der Oberflächeneigenschaften von Substraten insbesondere hinsichtlich ihres Korrosionswiderstandes werden diese mit galvanischen Überzügen beschichtet. Aus dem Stand der Technik sind eine Vielzahl von unterschiedlichen Beschichtungsverfahren zur Abscheidung unterschiedlichster Metallschichten auf Substratoberflächen bekannt. Aufgrund der Tatsache, daß Zink-Nickel-Legierungen einen verbesserten Korrosionsschutz gegenüber reinen Zinkschichten aufweisen, besteht ein starkes Interesse daran, Zink-Nickel-Legierungen zur Verbesserung des Korrosionswiderstandes auf Substratoberflächen abzuscheiden.To improve the surface properties of substrates, in particular with regard to their corrosion resistance, they are coated with galvanic coatings. The prior art discloses a multiplicity of different coating methods for depositing a wide variety of metal layers on substrate surfaces. Due to the fact that zinc-nickel alloys have improved corrosion protection over pure zinc layers, there is a strong interest in depositing zinc-nickel alloys on substrate surfaces to improve corrosion resistance.

Insbesondere um den gesteigerten Korrosionsschutzanforderungen auf Gußeisen- und Stahloberflächen und dem seitens der Automobil- und Flugzeugindustrie geforderten Verzicht auf Kadmium nachzukommen, wurden in den letzten Jahren unterschiedliche Verfahren zur Abscheidung von Zink-Nickel-Legierungsschichten auf solchen Substratoberflächen entwickelt. Gemeinsames Ziel dieser Entwicklungen war es, Zink-Nickel-Legierungen mit einem definierten Nickelanteil abzuscheiden. Mit den aus dem Stand der Technik bekannten Verfahren werden in der Regel Nickelanteile zwischen 10 bis 15% abgeschieden, was einen größtmöglichen Korrosionsschutz bietet.In particular, in order to meet the increased corrosion protection requirements for cast iron and steel surfaces and the waiver of cadmium demanded by the automotive and aircraft industries, different methods have been developed in recent years for the deposition of zinc-nickel alloy layers on such substrate surfaces. The common goal of these developments was to deposit zinc-nickel alloys with a defined nickel content. With the methods known from the prior art usually deposited nickel shares between 10 to 15%, which offers the greatest possible corrosion protection.

Um solche Zink-Nickel-Legierungen abzuscheiden, werden nach dem Stand der Technik im wesentlichen zwei unterschiedliche Elektrolyten verwendet. Diese sind zum einen alkalische Zink-Nickel-Legierungsbäder und zum anderen leichtsaure ammoniumchloridhaltige Bäder. Beide Badtypen weisen jedoch erhebliche Nachteile auf.In order to deposit such zinc-nickel alloys, essentially two different electrolytes are used in the prior art. These are on the one hand alkaline zinc-nickel alloy baths and on the other hand acidic ammonium chloride-containing baths. Both bath types, however, have significant disadvantages.

Bei der Anwendung alkalischer Bäder lassen sich nur niedrige Abscheidegeschwindigkeiten erreichen und es ergeben sich insbesondere Schwierigkeiten bei der Abscheidung auf Gußeisen- oder Stahlsubstraten. Ein weiterer Nachteil besteht darin, daß diese Bäder hohe Konzentrationen an stark komplexbildenden Stoffen enthalten, was zu einer Belastung der Abwässer mit diesen oftmals organischen Komplexbildnern führt und somit zusätzliche Abwasseraufbereitungsschritte erfordert.When using alkaline baths only low deposition rates can be achieved and there are difficulties especially in the deposition on cast iron or steel substrates. Another disadvantage is that these baths contain high concentrations of highly complexing substances, which leads to a pollution of the waste water with these often organic complexing agents and thus requires additional wastewater treatment steps.

Ammoniumchloridhaltige, leichtsaure Bäder zur Abscheidung von Zink-Nickel-Legierungsschichten ermöglichen zwar die Abscheidung korrosionsfester Schichten mit Nickeleinbauraten im Bereich von 10 bis 15 Massen-%, weisen aber den typischen Nachteil saurer Elektrolyten auf, oftmals ungleichmäßige Metallverteilungen in den Schichten zu erzeugen. Darüber hinaus sind die in den Elektrolyten befindlichen Ammoniumionen umweltrelevant und belasten die Abwässer stark. Die Ammoniumkonzentration in den Abwässern von Galvanobetrieben sind streng reguliert und unterliegen steter Kontrolle. Um den behördlichen Vorgaben Genüge zu leisten müssen daher aufwendige und teure Abwasserreinigungen vorgenommen werden. Ammoniumchloridhaltige Zink-Nickel-Elektrolyten zur Abscheidung entsprechender Legierungsschichten sind beispielsweise aus den US-Patenten US 4388160 und US 4765871 bekannt. Darüber hinaus ist aus der US 4832802 ein auf Nickelchlorid oder Nickelsulfat als Nickelmetallsalzträger basierender ammoniumchloridhaltiger Elektrolyt bekannt. Die zuvor genannten Elektrolyten weisen typischerweise Ammomiumchlorid in einer Konzentration bis 300 g/l auf, was eine aufwendige Abwasseraufbereitung notwendig macht.Although ammonium chloride-containing, low-acid baths for the deposition of zinc-nickel alloy layers allow the deposition of corrosion-resistant layers with nickel incorporation rates in the range of 10 to 15 mass%, but have the typical disadvantage of acidic electrolytes, often to produce uneven metal distributions in the layers. In addition, the ammonium ions present in the electrolyte are environmentally relevant and pollute the waste water strongly. The ammonium concentration in the waste water of electroplating plants are strictly regulated and subject to constant control. In order to comply with the regulatory requirements therefore expensive and expensive wastewater treatment must be made. Ammonium chloride-containing zinc-nickel electrolytes for depositing corresponding alloy layers are known, for example, from the US patents US 4388160 and US 4765871 known. In addition, from the US 4832802 a ammonium chloride-containing electrolyte based on nickel chloride or nickel sulfate as a nickel metal salt carrier. The aforementioned electrolytes typically have ammonium chloride in a concentration of up to 300 g / l, which necessitates extensive wastewater treatment.

Aufgrund der allgemeinen schlechten Schichtdicken- und Legierungselementverteilung, die beim Einsatz solcher ammoniumchloridhaltiger Elektrolyten erzielt werden und der mit dem Einsatz von Ammoniumchlorid einhergehenden Abwasserproblematik, wurden alkalisch arbeitende Zink-Nickel-Elektrolyte entwickelt.Due to the general poor Schichtdicken- and alloy element distribution, which are achieved in the use of such ammonium chloride-containing electrolytes and associated with the use of ammonium chloride wastewater problem, alkaline zinc-nickel electrolytes have been developed.

Die aus solchen alkalischen Zink-Nickel-Elektrolyten abgeschiedenen Zink-Nickel-Legierungsschichten zeigen typischerweise Einbauraten von 10 bis 15 Massen-% Nickel.The zinc-nickel alloy layers deposited from such alkaline zinc-nickel electrolytes typically exhibit incorporation rates of 10 to 15 mass% nickel.

Ein typischer Elektrolyt dieser Art, wie er auch in der US 4765871 offenbart wird weist 6 bis 17 g/l Zink, 0,8 bis 2,3 g/l Nickel und 112 bis 186 g/l Natrium- oder Kaliumhydroxid auf.A typical electrolyte of this kind, as in the US 4765871 6 to 17 g / l of zinc, 0.8 to 2.3 g / l of nickel and 112 to 186 g / l of sodium or potassium hydroxide.

Solche Elektrolyten erweisen sich jedoch als wenig geeignet für die Beschichtung von Gußeisen oder hochfesten Stählen, wie sie beispielsweise als Konstruktionsmaterialien für Bremssättel in der Automobilindustrie eingesetzt werden. Nur nach aufwendigen Oberflächenaktivierungsmaßnahmen und/oder vorgeschalteten Zinkabscheidungen lassen sich solche Materialien in hinreichender Qualität mit einer Zink-Nickel-Legierungsschicht aus einem alkalischen Elektrolyten abgeschieden beschichten. Neben diesen Problemen verringert aber auch die geringe Abscheidegeschwindigkeit das ökonomische Ergebnis solcher Beschichtungsverfahren.However, such electrolytes prove to be less suitable for the coating of cast iron or high strength steels, such as are used as construction materials for calipers in the automotive industry. Only after elaborate surface activation measures and / or upstream zinc deposits can such materials be deposited in sufficient quality with a zinc-nickel alloy layer deposited from an alkaline electrolyte. In addition to these problems, however, the low deposition rate also reduces the economic result of such coating processes.

Aus der deutschen Offenlegungsschrift DE 101 46 559 ist ein Elektrolyt auf Basis von Kaliumchlorid und Natriumacetat bekannt, welcher darüber hinaus Salicylsäure und Nikotinsäure aufweist. Als Glanzbildnersystem weist der dort beschriebene Elektrolyt ein aus Saccharin, einem Kaliumsalz eines sulfopropylierten polyalkoxylierten Naphthols und Oktanolethoxylat bestehendes System auf. Die hieraus abgeschiedenen Zink-Nickel-Legierungsschichten sind korrosionsbeständig und hochglänzend, weisen jedoch eine hohe innere Spannung auf.From the German patent application DE 101 46 559 is known an electrolyte based on potassium chloride and sodium acetate, which also has salicylic acid and nicotinic acid. As a brightener system, the electrolyte described there has a system consisting of saccharin, a potassium salt of a sulfopropylated polyalkoxylated naphthol and octanol ethoxylate. The zinc-nickel alloy layers deposited therefrom are corrosion-resistant and high-gloss, but have a high internal stress.

EP1295967 und SU524866 offenbaren Elektrolyten zur Abscheidung von Zink-Nickel-Legierungen auf metallischen Oberflächen, wobei die Elektrolyten unter anderem eine Aminoessigsäure enthalten. EP1295967 and SU524866 disclose electrolytes for depositing zinc-nickel alloys on metallic surfaces, the electrolytes including, inter alia, an aminoacetic acid.

Unter Berücksichtigung des zuvor Ausgeführten ist es daher die Aufgabe der vorliegenden Erfindung, eine Elektrolytzusammensetzung sowie ein Verfahren zur Abscheidung einer Zink-Nickel-Legierungsschicht auf einem Substrat, insbesondere einem Gußeisen- oder Stahlsubstrat, zur Verfügung zu stellen, welches die aus dem Stand der Technik bekannten Probleme zu überwinden vermag.In view of the above, it is therefore an object of the present invention to provide an electrolyte composition and a method for depositing a zinc-nickel alloy layer on a substrate, in particular a cast iron or steel substrate, which can overcome the problems known from the prior art.

Gelöst wird diese Aufgabe hinsichtlich der Elektrolytzusammensetzung durch eine Elektrolytzusammensetzung gemäß Anspruch 1 zur Abscheidung einer Zink-Nickel-Legierungsschicht auf einem Substrat welche dadurch gekennzeichnet ist, daß die Elektrolytzusammensetzung Aminoessigsäure aufweist.This object is achieved with respect to the electrolyte composition by an electrolyte composition according to claim 1 for depositing a zinc-nickel alloy layer on a substrate which is characterized in that the electrolyte composition comprises aminoacetic acid.

Der Zusatz von Aminoessigsäure zu einem Zink und Nickel aufweisenden Elektrolyten führt überraschenderweise zur Abscheidung von Zink-Nickel-Legierungsschichten, welche einen Nickel-Anteil von 10 bis 18 Massen-% aufweisen und nahezu keine innere Spannung besitzen.The addition of aminoacetic acid to a zinc and nickel-containing electrolyte surprisingly leads to the deposition of zinc-nickel alloy layers, which have a nickel content of 10 to 18 mass% and have almost no internal stress.

Die erfindungsgemäßen Elektrolytzusammensetzungen basieren auf einem Alkalihalogenit, vorzugsweise einem Kaliumhalogenit, besonders bevorzugt Kaliumchlorid als Leitsalz und weisen darüber hinaus ein Acetat der Gruppe bestehend aus Natriumacetat, Kaliumacetat oder Ammoniumacetat oder Mischungen derselben auf.The electrolyte compositions according to the invention are based on an alkali metal halide, preferably a potassium halide, more preferably potassium chloride as conductive salt and furthermore have an acetate of the group consisting of sodium acetate, potassium acetate or ammonium acetate or mixtures thereof.

Die erfindungsgemäße Elektrolytzusammensetzung weist ein molares Acetat: Aminoessigsäureverhältnis von etwa 0,35 bis etwa 0,91 auf.The electrolyte composition of the present invention has a molar acetate: aminoacetic acid ratio of about 0.35 to about 0.91.

Bevorzugt weist die erfindungsgemäße Elektrolytzusammensetzung Borsäure und ein Glanzbildnersystem bestehend aus Saccharin, Benzalaceton, Orthochlorbenzaldehyd, Oktanolethoxylat sowie einem Kaliumsalz eines sulfopropylierten polyalkoxylierten Naphtols auf.The electrolyte composition according to the invention preferably comprises boric acid and a brightener system consisting of saccharin, benzalacetone, orthochlorobenzaldehyde, octanol ethoxylate and a potassium salt of a sulfopropylated polyalkoxylated naphthol.

Hierbei kann die Konzentration der Borsäure in einem Bereich zwischen ungefähr 10 und 30, bevorzugt zwischen 15 bis 20 g/l liegen.Here, the concentration of boric acid in a range between about 10 and 30, preferably between 15 to 20 g / l.

Das bevorzugt eingesetzte Glanzbildnersystem weist zwischen 2 bis 4 g/l Natriumsaccharin, 0,025 bis 0,2 g/l Benzalaceton, 0,006 bis 0,01 g/l Orthochlorbenzaldehyd, 0,8 - 1,2 g/l Oktanolethoxylat sowie 2,5 bis 3,2 g/l Kaliumsalz des sulfopropylierten polyalkoxylierten Naphthols auf. Darüber hinaus kann das Glanzbildnersystem 0,5 bis 1,0 g/l Pyridinsulfonsäure aufweisen.The brightener system preferably used comprises between 2 to 4 g / l of sodium saccharin, 0.025 to 0.2 g / l of benzalacetone, 0.006 to 0.01 g / l of orthochlorobenzaldehyde, 0.8 to 1.2 g / l of octanol ethoxylate and 2.5 to 3.2 g / l of potassium salt of the sulfopropylated polyalkoxylated naphthol. In addition, the brightener system may have 0.5 to 1.0 g / L pyridine sulfonic acid.

Das bevorzugt als Leitsalz in der Elektrolytzusammensetzung eingesetzte Kaliumchlorid kann in einer Konzentration zwischen ungefähr 190 bis 220 g/l in der Zusammensetzung enthalten sein.The potassium chloride preferably used as the conductive salt in the electrolyte composition may be contained in the composition at a concentration of about 190 to 220 g / L.

Die erfindungsgemäß zugesetzte Aminoessigsäure kann in Abhängigkeit des Elektrolytsystems in einer Konzentration zwischen 10 bis 50 g/l, bevorzugt ca. 30 g/l in der Elektrolytzusammensetzung enthalten sein.Depending on the electrolyte system, the aminoacetic acid added according to the invention may be present in a concentration of between 10 and 50 g / l, preferably approximately 30 g / l, in the electrolyte composition.

Hinsichtlich des Verfahrens wird die Aufgabe durch ein Verfahren zur Abscheidung einer Zink-Nickel-Legierungsschicht auf einem Substrat, insbesondere einem Gußeisen- oder Stahlsubstrat gelöst, bei welchem das zu beschichtende Substrat, insbesondere ein Gußeisen- oder Eisensubstrat unter Anlegung eines Stroms mit der erfindungsgemäßen Elektrolytzusammensetzung kontaktiert wird.With regard to the method, the object is achieved by a method for depositing a zinc-nickel alloy layer on a substrate, in particular a cast iron or steel substrate, in which the substrate to be coated, in particular a cast iron or iron substrate under application of a current with the electrolyte composition according to the invention will be contacted.

Hierbei kann die Temperatur der Elektrolytzusammensetzung zwischen ca. 20°C und ca. 60°C, bevorzugt zwischen 30°C und 40°C betragen.Here, the temperature of the electrolyte composition between about 20 ° C and about 60 ° C, preferably between 30 ° C and 40 ° C.

Die zur Abscheidung der Schicht einzustellende Stromdichte kann zwischen ca. 0,5 und ca. 5 A/dm2, bevorzugt zwischen 1,0 und 3,5 A/dm2 eingestellt werden.The current density to be set for the deposition of the layer can be adjusted between about 0.5 and about 5 A / dm 2 , preferably between 1.0 and 3.5 A / dm 2 .

Die Erfindung soll beispielhaft anhand der nachfolgenden Ausführungsbeispiele erläutert werden, ohne daß sich die Erfindung jedoch auf diese beschränken läßt.The invention will be explained by way of example with reference to the following embodiments, but without the invention can be limited to this.

Ausführungsbeispiel 1:Embodiment 1

Ein Gußeisensubstrat wird bei einer Temperatur zwischen 33 und 36° C und bei einer eingestellten Stromdichte von 1,0 bis 3,5 A/dm2 mit einer Elektrolytzusammensetzung der nachfolgenden Art kontaktiert:

Zinkchlorid:
60-70 g/l
Nickelchlorid x 6 H20:
100 - 130 g/l
Kaliumchlorid:
190 - 220 g/l
Borsäure:
15 - 20 g/l
Natriumacetat * 3H2O:
25 g/l
Aminoessigsäure:
30 g/l
Natriumsaccharin:
2 - 4 g/l
Benzalaceton:
0,025 - 0,20 g/l
Orthochlorbenzaldehyd:
0,006 - 0,01 g/l
Oktanolethoxylat:
0,8 - 1,2 g/l
Kaliumsalz des sulfopropylierten polyalkoxylierten Naphtols: 2,5 - 3,2 g/lA cast iron substrate is contacted with an electrolyte composition of the following type at a temperature between 33 and 36 ° C and at a set current density of 1.0 to 3.5 A / dm 2 :
Zinc chloride:
60-70 g / l
Nickel chloride x 6 H20:
100-130 g / l
Potassium chloride:
190-220 g / l
boric acid:
15-20 g / l
Sodium acetate * 3H 2 O:
25 g / l
aminoacetic:
30 g / l
sodium:
2 - 4 g / l
benzalacetone:
0.025-0.20 g / l
Orthochlorbenzaldehyd:
0.006 - 0.01 g / l
Oktanolethoxylat:
0.8-1.2 g / l
Potassium salt of sulfopropylated polyalkoxylated naphthol: 2.5-3.2 g / l

Der pH-Wert der hier beschriebenen Elektrolytzusammensetzung liegt zwischen 5 und 6.The pH of the electrolyte composition described herein is between 5 and 6.

Ausführungsbeispiel 2:Embodiment 2:

Ein Gußeisensubstrat wird bei einer Temperatur zwischen 33 und 36° C und bei einer eingestellten Stromdichte von 1,0 bis 3,5 A/dm2 mit einer Elektrolytzusammensetzung der nachfolgenden Art kontaktiert:

Zinkchlorid:
60 - 70 g/l
Nickelchlorid x 6 H20:
100 - 130 g/l
Kaliumchlorid:
190 - 220 g/l
Borsäure:
15 - 20 g/l
Natriumacetat * 3H2O:
25 g/l
Aminoessigsäure:
30 g/l
Natriumsaccharin:
2 - 4 g/l
Benzalacetone:
0,025 - 0,050 g/l
Pyridinsulfonsäure:
0,5- 1,0 g/l
Oktanolethoxylate:
0,8 - 1,2 g/l
Kaliumsalz des sulfopropylierten polyalkoxylierten Naphtols: 2,5 - 3,2 g/lA cast iron substrate is contacted with an electrolyte composition of the following type at a temperature between 33 and 36 ° C and at a set current density of 1.0 to 3.5 A / dm 2 :
Zinc chloride:
60 - 70 g / l
Nickel chloride x 6 H20:
100-130 g / l
Potassium chloride:
190-220 g / l
boric acid:
15-20 g / l
Sodium acetate * 3H 2 O:
25 g / l
aminoacetic:
30 g / l
sodium:
2 - 4 g / l
Benzalacetone:
0.025-0.050 g / l
pyridinesulfonic:
0.5-1.0 g / l
Oktanolethoxylate:
0.8-1.2 g / l
Potassium salt of sulfopropylated polyalkoxylated naphthol: 2.5-3.2 g / l

Der pH-Wert der hier beschriebenen Elektrolytzusammensetzung liegt zwischen 5 und 6.The pH of the electrolyte composition described herein is between 5 and 6.

Ausführungsbeispiel 3:Embodiment 3

Stahlsubstrate und Stahlsubstrate für das Trommelgalvanisieren wurden bei einer Temperatur zwischen 33 und 35°C mit einer Elektrolytzusammensetzung der nachfolgenden Art kontaktiert.

Zinkchlorid:
60 - 76 g/l
Nickelchlorid x 6 H20:
100 - 130 g/l
Kaliumchlorid:
190 - 220 g/l
Borsäure:
15 - 20 g/l
Kaliumacetat:
25 g/l
Aminoessigsäure:
30 g/l
Natriumsaccharin:
2 - 4 g/l
Benzalacetone:
0,025 - 0,050 g/l
Orthochlorbenzaldehyd:
0,008 - 0,012 g/l
Oktanolethoxylate:
0,8 - 1,2 g/l
Kaliumsalz des sulfopropylierten polyalkoxylierten Naphtols: 2,5 - 3,2 g/lSteel substrates and steel substrates for barrel plating were contacted at a temperature between 33 and 35 ° C with an electrolyte composition of the following type.
Zinc chloride:
60 - 76 g / l
Nickel chloride x 6 H20:
100-130 g / l
Potassium chloride:
190-220 g / l
boric acid:
15-20 g / l
potassium acetate:
25 g / l
aminoacetic:
30 g / l
sodium:
2 - 4 g / l
Benzalacetone:
0.025-0.050 g / l
Orthochlorbenzaldehyd:
0.008-0.012 g / l
Oktanolethoxylate:
0.8-1.2 g / l
Potassium salt of sulfopropylated polyalkoxylated naphthol: 2.5-3.2 g / l

Hierbei wurde eine Stromdichte zwischen 0,5 und 1,0 A/dm2 eingestellt. Der pH-Wert der Elektrolytzusammensetzung lag zwischen 5 und 6.Here, a current density between 0.5 and 1.0 A / dm 2 was set. The pH of the electrolyte composition was between 5 and 6.

Claims (7)

  1. Electrolyte composition for depositing a zinc nickel alloy layer comprising a nickel content of 10 to 18 mass-% onto a substrate, wherein the electrolyte composition includes zinc and nickel ions, characterized in that the electrolyte composition comprises amino acetic acid and an acetate of the group consisting of sodium acetate, potassium acetate, ammonium acetate or mixtures thereof in a molar acetate : amino acetic acid ratio of about 0.35 to about 0.91.
  2. Electrolyte composition according to claim 1, further comprising at least one alkali halide, preferably a potassium halide, more preferably potassium chloride.
  3. Electrolyte composition according to any one of the preceding claims, further comprising boric acid.
  4. Electrolyte composition according to any one of the preceding claims, further comprising a brightening system.
  5. Method of depositing a zinc nickel alloy layer comprising a nickel content of 10 to 18 mass-% onto a substrate, in particular a cast iron or steel substrate, characterized in that for the deposition the substrate is brought into contact with an electrolyte composition according to any one of claims 1 to 4 under current supply.
  6. Method according to claim 5, characterized in that the substrate is brought into contact with the electrolyte composition at a temperature between 20°C and 60°C, preferably between 30°C and 40°C.
  7. Method according claim 5 or 6, characterized in that for the deposition of the layer a current density between 0.5 and 5 A/dm2, preferably between 1.0 and 3.5 A/dm2 is set.
EP06014519.0A 2006-07-13 2006-07-13 Electrolyte composition und process for the deposition of a zinc-nickel alloy layer on a cast iron or steel substrate Active EP1881090B1 (en)

Priority Applications (6)

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ES06014519.0T ES2553730T3 (en) 2006-07-13 2006-07-13 Electrolyte composition and procedure for the deposition of a layer of zinc-nickel alloy on a cast iron or cast steel substrate
HUE06014519A HUE026918T2 (en) 2006-07-13 2006-07-13 Electrolyte composition und process for the deposition of a zinc-nickel alloy layer on a cast iron or steel substrate
PL06014519T PL1881090T3 (en) 2006-07-13 2006-07-13 Electrolyte composition und process for the deposition of a zinc-nickel alloy layer on a cast iron or steel substrate
EP06014519.0A EP1881090B1 (en) 2006-07-13 2006-07-13 Electrolyte composition und process for the deposition of a zinc-nickel alloy layer on a cast iron or steel substrate
PT60145190T PT1881090E (en) 2006-07-13 2006-07-13 Electrolyte composition und process for the deposition of a zinc-nickel alloy layer on a cast iron or steel substrate
US11/778,011 US8435398B2 (en) 2006-07-13 2007-07-13 Electrolyte composition and method for the deposition of a zinc-nickel alloy layer on a cast iron or steel substrate

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DE102008007133A1 (en) * 2008-01-31 2009-08-06 Metallveredelung Huber Gmbh Coating for galvanically applying on fittings as corrosion support, comprises a first alkaline zinc layer applied on raw material, a second acid zinc-nickel layer applied on the zinc layer, and a transparent passivation
FR2956123B1 (en) * 2010-02-08 2017-10-27 Dalic METHOD FOR PROTECTING A METAL SUBSTRATE AGAINST CORROSION AND ABRASION, AND METAL SUBSTRATE OBTAINED BY THIS METHOD.
ES2543789T5 (en) * 2013-03-26 2018-07-05 Atotech Deutschland Gmbh Process for corrosion protection of iron-containing materials
CN104651888B (en) * 2015-03-04 2017-03-22 武汉风帆电化科技股份有限公司 High corrosion resistance zinc-nickel alloy electroplating additive with weak acidity to neutrality and electroplating liquid

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3930965A (en) * 1974-03-18 1976-01-06 Mcgean Chemical Company, Inc. Zinc-copper alloy electroplating baths
SU524866A1 (en) * 1975-04-10 1976-08-15 Предприятие П/Я А-7697 Electrolyte for deposition of zinc-nickel alloys
US4146441A (en) * 1977-10-06 1979-03-27 R. O. Hull & Company, Inc. Additive compositions, baths, and methods for electrodepositing bright zinc deposits
US4388160A (en) 1980-02-20 1983-06-14 Rynne George B Zinc-nickel alloy electroplating process
US4765871A (en) 1981-12-28 1988-08-23 The Boeing Company Zinc-nickel electroplated article and method for producing the same
US4543166A (en) 1984-10-01 1985-09-24 Omi International Corporation Zinc-alloy electrolyte and process
US4825009A (en) * 1985-12-23 1989-04-25 Shell Oil Company Preparation of nonionic surfactants
JPH01219188A (en) * 1988-02-26 1989-09-01 Okuno Seiyaku Kogyo Kk Zinc-nickel alloy plating bath
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
JP2901523B2 (en) * 1995-08-09 1999-06-07 日本カニゼン株式会社 Electroless black plating bath composition and film formation method
US6238542B1 (en) 1998-09-15 2001-05-29 Thomas Helden Water soluble brighteners for zinc and zinc alloy electrolytes
DE10146559A1 (en) * 2001-09-21 2003-04-10 Enthone Omi Deutschland Gmbh Process for the deposition of a zinc-nickel alloy from an electrolyte
US20060283715A1 (en) * 2005-06-20 2006-12-21 Pavco, Inc. Zinc-nickel alloy electroplating system

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ES2553730T3 (en) 2015-12-11
US20080110762A1 (en) 2008-05-15
EP1881090A1 (en) 2008-01-23
PT1881090E (en) 2015-12-01
US8435398B2 (en) 2013-05-07
HUE026918T2 (en) 2016-07-28

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