EP1102875B1 - Alkali zinc nickel bath - Google Patents

Alkali zinc nickel bath Download PDF

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Publication number
EP1102875B1
EP1102875B1 EP99940077A EP99940077A EP1102875B1 EP 1102875 B1 EP1102875 B1 EP 1102875B1 EP 99940077 A EP99940077 A EP 99940077A EP 99940077 A EP99940077 A EP 99940077A EP 1102875 B1 EP1102875 B1 EP 1102875B1
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EP
European Patent Office
Prior art keywords
nickel
anode
zinc
bath
alkaline
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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.)
Revoked
Application number
EP99940077A
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German (de)
French (fr)
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EP1102875A2 (en
Inventor
Ernst-Walter Hillebrand
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Walter Hillebrand & Co GmbH
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Walter Hillebrand & Co GmbH
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Application filed by Walter Hillebrand & Co GmbH filed Critical Walter Hillebrand & Co GmbH
Priority to EP03003890A priority Critical patent/EP1344850B1/en
Publication of EP1102875A2 publication Critical patent/EP1102875A2/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
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/02—Tanks; Installations therefor
    • 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
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/12—Process control or regulation

Definitions

  • the invention relates to an electroplating bath for applying zinc-nickel coatings with an anode, a cathode and an alkaline electrolyte.
  • the alkaline zinc-nickel electroplating baths disclosed in German patent specification 37 12 511 have recently been used, which have the following composition, for example: 11.3 g / l ZnO 4.1 g / l NiSO 4 * 6H 2 O 120 g / l NaOH 5.1 g / l polyethyleneimine.
  • the amines contained in the electroplating bath serve as complexing agents for the nickel ions, which are otherwise insoluble in the alkaline medium.
  • the composition of the baths varies depending on the manufacturer.
  • the electroplating baths are usually operated with insoluble nickel anodes.
  • the zinc concentration is determined by adding zinc and the nickel concentration by adding a nickel solution, for example a nickel sulfate solution, kept constant.
  • the formation of the second phase is due to a reaction of the amines, that in alkaline solution on nickel anodes to nitriles (among others can also be converted to cyanide). Due to the decomposition of the amines new complexing agents must also be continuously added to the bath, which drives up the cost of the process.
  • Anodes other than nickel anodes cannot be used because of this dissolve in the alkaline electrolyte, which is also disadvantageous Effects on the quality of the coating.
  • the problem underlying the invention is an alkaline one To create zinc-nickel electroplating bath, which is inexpensive zinc-nickel coatings delivers high quality.
  • the invention proposes the anode of the to separate alkaline electrolyte through an ion exchange membrane.
  • a cation exchange membrane has proven to be particularly advantageous made out of a perfluorinated polymer, since this has negligible electrical resistance, however have a high chemical and mechanical resistance.
  • the zinc-nickel bath acts as a catholyte in the solution according to the invention.
  • sulfuric or phosphoric acid can be used as the anolyte become.
  • the anode material used in the electroplating cell according to the invention usual anodes, e.g. Platinized titanium anodes are eligible because of this are no longer exposed to the basic zinc-nickel bath.
  • the 1 shows an electroplating cell 1, which has an anode 2 and a cathode 3, which is the workpiece to be coated.
  • the the Catholyte 4 surrounding the cathode is alkaline and consists of a zinc-nickel electroplating bath known composition, in which as a complexing agent for Nickel ion amines are used.
  • the anolyte 5 surrounding the anode 2 can consist for example of sulfuric or phosphoric acid.
  • Anolyte 5 and catholyte 4 are separated from one another by a perfluorinated cation exchange membrane 6 Cut. This membrane 6 enables an unimpeded flow of current through the Bad, however, prevents the catholyte 4, especially those contained therein Amines, comes into contact with the anode 2, which results in the introduction to the description detailed reactions including their adverse effects be avoided.

Abstract

The alkaline galvanic bath (1) for production of zinc-nickel coatings, with an anode (2) and a cathode (3), has the anode separated from the alkaline electrolyte (4) by means of an ion exchange membrane (6).

Description

Die Erfindung betrifft ein Galvanikbad zum Aufbringen von Zink-Nickel-Überzügen mit einer Anode, einer Kathode und einem alkalischen Elektrolyten.The invention relates to an electroplating bath for applying zinc-nickel coatings with an anode, a cathode and an alkaline electrolyte.

Es ist bekannt, elektrisch leitende Werkstoffe zur Verbesserung deren Korrosionsbeständigkeit mit Zink-Nickel-Legierungen zu überziehen. Dazu wird in herkömmlicher Weise ein saures Elekrolytbad, beispielsweise mit Sulfat-, Chlorid-, Fluoropromat- oder Sulfamat-Elektrolyten eingesetzt. Bei diesen Verfahren ist die Erzielung einer gleichmäßigen Dicke des Zink-Nickel-Überzuges auf dem zu beschichtenden Werkstoff regelungstechnisch sehr aufwendig und in der Praxis meistens unmöglich.It is known to use electrically conductive materials to improve their corrosion resistance to be coated with zinc-nickel alloys. This is done in an acidic electrolyte bath, for example with sulfate, Chloride, fluoropromat or sulfamate electrolytes used. With these The method is to achieve a uniform thickness of the zinc-nickel coating in terms of control technology on the material to be coated complex and usually impossible in practice.

Aus diesem Grund werden in jüngster Zeit die in der deutschen Patentschrift 37 12 511 offenbarten alkalischen Zink-Nickel-Galvanikbäder eingesetzt, die beispielsweise folgende Zusammensetzung aufweisen: 11,3 g/l ZnO 4,1 g/l NiSO4*6H2O 120 g/l NaOH 5,1 g/l Polyethylenimin. For this reason, the alkaline zinc-nickel electroplating baths disclosed in German patent specification 37 12 511 have recently been used, which have the following composition, for example: 11.3 g / l ZnO 4.1 g / l NiSO 4 * 6H 2 O 120 g / l NaOH 5.1 g / l polyethyleneimine.

Die in dem Galvanikbad enthaltenen Amine dienen als Komplexbildner für die Nickelionen, welche im alkalischen Medium ansonsten unlöslich sind. Die Zusammensetzung der Bäder variiert je nach Hersteller.The amines contained in the electroplating bath serve as complexing agents for the nickel ions, which are otherwise insoluble in the alkaline medium. The The composition of the baths varies depending on the manufacturer.

Betrieben werden die Galvanikbäder gewöhnlich mit unlöslichen Nickelanoden. Die Zinkkonzentration wird durch Zugabe von Zink und die Nickelkonzentration durch Addition einer Nickellösung, zum Beispiel einer Nickelsulfat-Lösung, konstant gehalten. The electroplating baths are usually operated with insoluble nickel anodes. The zinc concentration is determined by adding zinc and the nickel concentration by adding a nickel solution, for example a nickel sulfate solution, kept constant.

Diese Bäder zeigen jedoch nach einigen Stunden Betrieb eine Farbänderung von ursprünglich blau-violett nach braun. Nach mehreren Tagen bzw. Wochen verstärkt sich diese Färbung und es ist eine Trennung des Bades in zwei Phasen feststellbar, wobei die obere Phase dunkelbraun ist. Diese Phase bewirkt erhebliche Störungen der Beschichtung der Werkstücke, wie beispielsweise ungleichmäßige Schichtdicken oder Bläschenbildung. Eine kontinuierliche Reinigung des Bades, d.h. ein kontinuierliches Abschöpfen dieser Schicht, ist somit unumgänglich. Diese ist aber zeit- und kostenaufwendig.However, these baths show a color change after a few hours of operation from originally blue-violet to brown. After several days or weeks this coloring intensifies and there is a separation of the bath in two phases can be identified, the upper phase being dark brown. This Phase causes significant disturbances in the coating of the workpieces, such as for example, uneven layer thicknesses or blistering. A continuous cleaning of the bath, i.e. a continuous skimming this layer is therefore inevitable. However, this is time-consuming and costly.

Des weiteren kann nach einigen Wochen des Betriebs Cyanid in den Bädern nachgewiesen werden. Die Cyanidbelastung erfordert ein regelmäßiges Erneuern des Bades und eine spezielle Abwasserbehandlung, die sich erheblich auf die Betriebskosten des Bades auswirkt. Dies gilt um so mehr, als die Abwässer eine sehr hohe Organikkonzentration aufweisen und mit einem CSB-Wert von ca. 15.000 bis 20.000 mg/l die Cyanidentgiftung erschweren. Das Einhalten der vom Gesetzgeber vorgegebenen Abwasserwerte (Nickel 0,5 ppm und Zink 2 ppm) ist dann nur noch durch umfangreichen Zusatz von Chemikalien möglich.Furthermore, after a few weeks of operation, cyanide in the baths be detected. The exposure to cyanide requires regular renewal of the bath and a special wastewater treatment, which is considerable affects the operating costs of the bathroom. This is all the more true than that Wastewater has a very high organic concentration and with a COD values of approx. 15,000 to 20,000 mg / l make cyanide detoxification more difficult. Compliance with the wastewater values specified by law (nickel 0.5 ppm and zinc 2 ppm) is then only possible through the extensive addition of Chemicals possible.

Die Ausbildung der zweiten Phase ist auf eine Reaktion der Amine zurückzuführen, die in alkalischer Lösung an Nickelanoden zu Nitrilen (unter anderen auch zu Cyanid) umgesetzt werden. Aufgrund der Zersetzung der Amine muß dem Bad zudem kontinuierlich neuer Komplexbildnern zugegeben werden, was die Kosten des Prozesses in die Höhe treibt.The formation of the second phase is due to a reaction of the amines, that in alkaline solution on nickel anodes to nitriles (among others can also be converted to cyanide). Due to the decomposition of the amines new complexing agents must also be continuously added to the bath, which drives up the cost of the process.

Andere Anoden als Nickel-Anoden können nicht eingesetzt werden, weil diese sich in dem alkalischen Elektrolyten auflösen, was ebenfalls nachteilige Auswirkungen auf die Qualität der Beschichtung mit sich bringt. Anodes other than nickel anodes cannot be used because of this dissolve in the alkaline electrolyte, which is also disadvantageous Effects on the quality of the coating.

Vor diesem Hintergrund liegt der Erfindung das Problem zugrunde, ein alkalisches Zink-Nickel-Galvanikbad zu schaffen, welches kostengünstig Zink-Nickel-Beschichtungen von hoher Qualität liefert.Against this background, the problem underlying the invention is an alkaline one To create zinc-nickel electroplating bath, which is inexpensive zinc-nickel coatings delivers high quality.

Zur Lösung dieses Problems schlägt die Erfindung vor, die Anode von dem alkalischen Elektrolyt durch eine lonenaustauschermembran zu trennen.To solve this problem, the invention proposes the anode of the to separate alkaline electrolyte through an ion exchange membrane.

Durch diese Trennung wird die Reaktion der Amine an der Nickelanode vermieden, was zur Folge hat, daß keine unerwünschten Nebenreaktionen ablaufen, die Entsorgungsprobleme bereiten oder zu einer zweiten Phase auf dem Bad absetzenden Reaktionsprodukten führen und die Qualität des Zink-Nickel-Überzuges nachteilig beeinflussen. Das aufwendige Abschöpfen dieser Schicht sowie das Erneuern des Bades wird durch die Erfindung überflüssig. Ferner ist eine erhebliche Qualitätsverbesserung der Beschichtung zu verzeichnen.This separation avoids the reaction of the amines at the nickel anode, which means that there are no undesirable side reactions, the disposal problems or prepare for a second phase lead reaction products to the bath and the quality of the zinc-nickel coating adversely affect. The elaborate skimming of this The invention makes layer and renewal of the bath superfluous. There is also a significant improvement in the quality of the coating to be recorded.

Als besonders vorteilhaft hat sich der Einsatz einer Kationenaustauschermembran aus einem perfluorierten Polymer herausgestellt, da diese einen vernachlässigbaren elektrischen Widerstand, jedoch eine hohe chemische und mechanischer Widerstandsfähigkeit besitzen.The use of a cation exchange membrane has proven to be particularly advantageous made out of a perfluorinated polymer, since this has negligible electrical resistance, however have a high chemical and mechanical resistance.

Des weiteren entfällt die Cyanidvergiftung des Abwassers, wodurch die gesamte Abwasserreinigung erheblich vereinfacht wird. Darüber hinaus wird das Auffüllen des Elektrolyten mit Komplexbildner überflüssig, da dieser sich nicht mehr zersetzt und seine Konzentration im Bad annähernd konstant bleibt. Das Verfahren wir dadurch erheblich kostengünstiger.Furthermore, cyanide poisoning of the wastewater is eliminated, so that the entire Wastewater treatment is significantly simplified. Beyond that the filling of the electrolyte with complexing agent is unnecessary, since this is no longer decomposes and its concentration in the bathroom is almost constant remains. This makes the process considerably cheaper.

Das Zink-Nickelbad fungiert bei der erfindungsgemäßen Lösung als Katholyt. Als Anolyt können beispielsweise Schwefel- oder Phosphorsäure eingesetzt werden. Als Anodenmaterial kommen in der erfindungsgemäßen Galvanikzelle übliche Anoden, wie z.B. platinierte Titan-anoden infrage, da diese nicht mehr dem basischen Zink-Nickelbad ausgesetzt sind. The zinc-nickel bath acts as a catholyte in the solution according to the invention. For example, sulfuric or phosphoric acid can be used as the anolyte become. The anode material used in the electroplating cell according to the invention usual anodes, e.g. Platinized titanium anodes are eligible because of this are no longer exposed to the basic zinc-nickel bath.

Die vorliegende Erfindung wird anhand des in der Zeichnung dargestellten Ausführungsbeispiels näher erläutert. In der Zeichnung zeigt:

  • Fig. 1 den schematischen Aufbau eines erfindungsgemäßen Galvanikbades.
    • The present invention is explained in more detail with reference to the embodiment shown in the drawing. The drawing shows:
  • Fig. 1 shows the schematic structure of an electroplating bath according to the invention.

    • In Fig. 1 ist eine Galvanikzelle 1 dargestellt, die eine Anode 2 und eine Kathode 3, bei der es sich um das zu beschichtende Werkstück handelt, aufweist. Der die Kathode umgebende Katholyt 4 ist alkalisch und besteht aus einem Zink-Nickel-Galvanikbad bekannter Zusammensetzung, bei dem als Komplexbildner für die Nickelionen Amine eingesetzt werden. Der die Anode 2 umgebende Anolyt 5 kann beispielsweise aus Schwefel- oder Phosphorsäure bestehen. Anolyt 5 und Katholyt 4 sind durch eine perfluorierte Kationenaustauschermembran 6 voneinander getrennt. Diese Membran 6 ermöglicht einen ungehinderten Stromfluß durch das Bad, verhindert jedoch, daß der Katholyt 4, insbesondere die darin enthaltenen Amine, mit der Anode 2 in Kontakt kommt, wodurch die in der Beschreibungseinleitung ausführlich dargelegten Reaktionen einschließlich deren nachteiligen Auswirkungen vermieden werden.1 shows an electroplating cell 1, which has an anode 2 and a cathode 3, which is the workpiece to be coated. The the Catholyte 4 surrounding the cathode is alkaline and consists of a zinc-nickel electroplating bath known composition, in which as a complexing agent for Nickel ion amines are used. The anolyte 5 surrounding the anode 2 can consist for example of sulfuric or phosphoric acid. Anolyte 5 and catholyte 4 are separated from one another by a perfluorinated cation exchange membrane 6 Cut. This membrane 6 enables an unimpeded flow of current through the Bad, however, prevents the catholyte 4, especially those contained therein Amines, comes into contact with the anode 2, which results in the introduction to the description detailed reactions including their adverse effects be avoided.

    Claims (4)

    1. Alkaline electroplating bath (1) for applying electroplates of zinc-nickel comprising an anode (2), a cathode (3), and an alkaline catalyst in which amines are used as complexing agents for the nickel-ions, wherein the anode is separated from the catalyst by an ion exchange membrane.
    2. Electroplating bath as claimed in claim 1 wherein the anode (2) is separated from the alkaline catalyst (4) by a perfluorinated cation exchange membrane (6).
    3. Electroplating bath as claimed in 1 or 2 wherein sulfuric acid, phosphoric acid, methane sulfonic acid, amido sulfonic acid and/or phosphonic acid are used as anolyte (5).
    4. Electroplating bath as claimed in one of the claims 1 to 3 characterized by a platinized titanium anode.
    EP99940077A 1998-07-30 1999-07-29 Alkali zinc nickel bath Revoked EP1102875B1 (en)

    Priority Applications (1)

    Application Number Priority Date Filing Date Title
    EP03003890A EP1344850B1 (en) 1998-07-30 1999-07-29 Alkaline zinc-nickel bath

    Applications Claiming Priority (3)

    Application Number Priority Date Filing Date Title
    DE19834353A DE19834353C2 (en) 1998-07-30 1998-07-30 Alkaline zinc-nickel bath
    DE19834353 1998-07-30
    PCT/EP1999/005443 WO2000006807A2 (en) 1998-07-30 1999-07-29 Alkali zinc nickel bath

    Related Child Applications (2)

    Application Number Title Priority Date Filing Date
    EP03003890A Division EP1344850B1 (en) 1998-07-30 1999-07-29 Alkaline zinc-nickel bath
    EP03003890.5 Division-Into 2003-02-21

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    EP1102875A2 EP1102875A2 (en) 2001-05-30
    EP1102875B1 true EP1102875B1 (en) 2003-06-11

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    EP03003890A Expired - Lifetime EP1344850B1 (en) 1998-07-30 1999-07-29 Alkaline zinc-nickel bath
    EP99940077A Revoked EP1102875B1 (en) 1998-07-30 1999-07-29 Alkali zinc nickel bath

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    EP03003890A Expired - Lifetime EP1344850B1 (en) 1998-07-30 1999-07-29 Alkaline zinc-nickel bath

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    US (4) US6602394B1 (en)
    EP (2) EP1344850B1 (en)
    JP (2) JP4716568B2 (en)
    KR (1) KR20010071074A (en)
    CN (1) CN1311830A (en)
    AT (2) ATE242821T1 (en)
    AU (1) AU5415299A (en)
    BG (1) BG105184A (en)
    BR (1) BR9912589A (en)
    CA (1) CA2339144A1 (en)
    CZ (1) CZ298904B6 (en)
    DE (3) DE19834353C2 (en)
    EE (1) EE200100059A (en)
    ES (2) ES2201759T3 (en)
    HR (1) HRP20010044B1 (en)
    HU (1) HUP0103951A3 (en)
    IL (1) IL141086A0 (en)
    MX (1) MXPA01000932A (en)
    PL (1) PL198149B1 (en)
    SK (1) SK285453B6 (en)
    TR (1) TR200100232T2 (en)
    WO (1) WO2000006807A2 (en)

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