EP1344850A1 - Alkaline zinc-nickel bath - Google Patents

Alkaline zinc-nickel bath Download PDF

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Publication number
EP1344850A1
EP1344850A1 EP03003890A EP03003890A EP1344850A1 EP 1344850 A1 EP1344850 A1 EP 1344850A1 EP 03003890 A EP03003890 A EP 03003890A EP 03003890 A EP03003890 A EP 03003890A EP 1344850 A1 EP1344850 A1 EP 1344850A1
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Prior art keywords
anode
nickel
zinc
alkaline
bath
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Granted
Application number
EP03003890A
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German (de)
French (fr)
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EP1344850B1 (en
Inventor
Ernst-Walter Hillebrand
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Hillebrand Walter GmbH and Co KG
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Hillebrand Walter GmbH and Co KG
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Application filed by Hillebrand Walter GmbH and Co KG filed Critical Hillebrand Walter GmbH and Co KG
Priority to DE29924530U priority Critical patent/DE29924530U1/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 proposes the anode of the to separate alkaline electrolyte through an ion exchange membrane.
  • a cation exchange membrane has proven to be particularly advantageous exposed from a perfluorinated polymer because this negligible electrical resistance, but high chemical resistance 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 present invention is based on that shown in the drawing Embodiment explained in more detail.
  • the drawing shows:
  • Fig. 1 shows the schematic structure of an electroplating bath according to the invention.
  • an electroplating cell 1 is shown, the anode 2 and a cathode 3, which is the workpiece to be coated.
  • the catholyte 4 surrounding the cathode is alkaline and consists of a zinc-nickel electroplating bath of known composition, in which as Complexing agents for the nickel ion amines are used.
  • the the anode 2 surrounding anolyte 5 can, for example, from sulfuric or phosphoric acid consist.
  • Anolyte 5 and catholyte 4 are through a perfluorinated cation exchange membrane 6 separated from each other. This membrane 6 enables an unimpeded flow of electricity through the bath, but prevents that the catholyte 4, especially the amines contained therein, with the anode 2 comes into contact, which in detail in the introduction reactions outlined 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 Auf/bringen von Zink-Nickel-Überzügen mit einer Anode, einer Kathode und einem alkalischen Elektrolyten.The invention relates to an electroplating bath for applying / 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 will 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 on the material to be coated is very complex in terms of control technology and mostly 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 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 This coloring intensifies weeks 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 cyanide exposure requires regular Renew the bath and a special wastewater treatment that has a significant impact on the operating costs of the bathroom. This applies all the more more than the waste water has a very high organic concentration and cyanide detoxification with a COD value of approx. 15,000 to 20,000 mg / l difficult. Compliance with the wastewater values specified by the legislator (Nickel 0.5 ppm and zinc 2 ppm) is then only 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 must also continuously add new complexing agents to the bath become what 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 these 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.Through this separation, the reaction of the amines at the nickel anode avoided, which has the consequence that no undesirable side reactions expire, the disposal problems or to a second phase lead reaction products on the bath and the quality of the Adversely affect zinc-nickel coating. The elaborate skimming this layer as well as the renewal of the bath is through the invention 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 exposed from a perfluorinated polymer because this negligible electrical resistance, but high chemical resistance 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:The present invention is based on that shown in the drawing Embodiment explained in more detail. The drawing shows:

Fig. 1 den schematischen Aufbau eines erfindungsgemäßen Galvanikbades. 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.In Fig. 1, an electroplating cell 1 is shown, the anode 2 and a cathode 3, which is the workpiece to be coated. The catholyte 4 surrounding the cathode is alkaline and consists of a zinc-nickel electroplating bath of known composition, in which as Complexing agents for the nickel ion amines are used. The the anode 2 surrounding anolyte 5 can, for example, from sulfuric or phosphoric acid consist. Anolyte 5 and catholyte 4 are through a perfluorinated cation exchange membrane 6 separated from each other. This membrane 6 enables an unimpeded flow of electricity through the bath, but prevents that the catholyte 4, especially the amines contained therein, with the anode 2 comes into contact, which in detail in the introduction reactions outlined including their adverse effects be avoided.

Claims (4)

Alkalisches Galvanikbad (1) zum Aufbringen von Zink-Nickel-Überzügen mit einer Anode (2) und einer Kathode (3), dadurch gekennzeichnet, daß die Anode von dem alkalischen Elektrolyten durch eine lonenaustauschermembran (6) getrennt ist.Alkaline electroplating bath (1) for applying zinc-nickel coatings with an anode (2) and a cathode (3), characterized in that the anode is separated from the alkaline electrolyte by an ion exchange membrane (6). Galvanikbad nach Anspruch 1, dadurch gekennzeichnet, daß die Anode (2) durch eine perfluorierte Kationenaustauschermembran (6) von dem alkalischen Elektrolyten (4) getrennt ist.Electroplating bath according to claim 1, characterized in that the anode (2) is separated from the alkaline electrolyte (4) by a perfluorinated cation exchange membrane (6). Galvanikbad nach Anspruch 1 oder 2, gekennzeichnet durch Schwefelsäure, Phosphorsäure, Methansulfonsäure, Amidosulfonsäure und/oder Phosphonsäure als Anolyt (5).Electroplating bath according to claim 1 or 2, characterized by sulfuric acid, phosphoric acid, methanesulfonic acid, amidosulfonic acid and / or phosphonic acid as anolyte (5). Galvanikbad nach einem der Ansprüche 1 bis 3, gekennzeichnet durch eine platinierte Titananode.Electroplating bath according to one of Claims 1 to 3, characterized by a platinized titanium anode.
EP03003890A 1998-07-30 1999-07-29 Alkaline zinc-nickel bath Expired - Lifetime EP1344850B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE29924530U DE29924530U1 (en) 1998-07-30 1999-07-29 Alkaline zinc-nickel galvanic bath for producing zinc-nickel coatings has an ion exchange membrane separating the anode from the alkaline electrolyte

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
EP99940077A EP1102875B1 (en) 1998-07-30 1999-07-29 Alkali zinc nickel bath

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EP99940077A Division EP1102875B1 (en) 1998-07-30 1999-07-29 Alkali zinc nickel bath
EP99940077.3 Division 1999-07-29

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EP1344850B1 EP1344850B1 (en) 2006-11-22

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EP99940077A Revoked EP1102875B1 (en) 1998-07-30 1999-07-29 Alkali 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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DE102008058086A1 (en) 2008-11-18 2010-05-27 Atotech Deutschland Gmbh Method and device for cleaning electroplating baths for the deposition of metals
EP2384800A1 (en) 2010-05-07 2011-11-09 Dr.Ing. Max Schlötter GmbH & Co. KG Regeneration of alkaline zinc electrolytes by removing cyanidiones
DE102010044551A1 (en) 2010-09-07 2012-03-08 Coventya Gmbh Anode and their use in an alkaline electroplating bath
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DE202015002289U1 (en) 2015-03-25 2015-05-06 Hartmut Trenkner Two-chamber electrodialysis cell with anion and cation exchange membrane for use as an anode in alkaline zinc and zinc alloy electrolytes for the purpose of metal deposition in electroplating plants
DE102015009379A1 (en) 2015-03-25 2016-09-29 Coventya International Gmbh Two-compartment electrodialysis cell with anion and cation exchange membrane for use as an anode in alkaline zinc and zinc alloy electrolytes for the purpose of metal deposition in galvanic plants
US10738391B2 (en) 2015-03-25 2020-08-11 Coventya International Gmbh Two-chamber electrodialysis cell with anion and cation exchange membrane for use as an anode in alkaline zinc electrolytes and zinc alloy electrolytes for the purpose of deposition of metal in electroplating systems
EP3358045A1 (en) 2017-02-07 2018-08-08 Dr.Ing. Max Schlötter GmbH & Co. KG Method for the galvanic deposition of zinc and zinc alloy layers from an alkaline coating bath with reduced degradation of organic bath additives
WO2018146041A1 (en) 2017-02-07 2018-08-16 Dr.-Ing. Max Schlötter Gmbh & Co. Kg Method for electrodepositing zinc and zinc alloy coatings from an alkaline coating bath with reduced depletion of organic bath additives
US11339492B2 (en) 2017-02-07 2022-05-24 Dr.-Ing. Max Schlötter Gmbh & Co. Kg Method for electrodepositing zinc and zinc alloy coatings from an alkaline coating bath with reduced depletion of organic bath additives
EP3415665A1 (en) 2017-06-14 2018-12-19 Dr.Ing. Max Schlötter GmbH & Co. KG Method for the galvanic deposition of zinc-nickel alloy layers from an alkaline zinc-nickel alloy bath with reduced degradation of additives

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