EP1102875A2 - Alkali zinc nickel bath - Google Patents

Alkali zinc nickel bath

Info

Publication number
EP1102875A2
EP1102875A2 EP99940077A EP99940077A EP1102875A2 EP 1102875 A2 EP1102875 A2 EP 1102875A2 EP 99940077 A EP99940077 A EP 99940077A EP 99940077 A EP99940077 A EP 99940077A EP 1102875 A2 EP1102875 A2 EP 1102875A2
Authority
EP
European Patent Office
Prior art keywords
nickel
anode
bath
electroplating bath
zinc
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.)
Granted
Application number
EP99940077A
Other languages
German (de)
French (fr)
Other versions
EP1102875B1 (en
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.)
Walter Hillebrand & Co GmbH
Original Assignee
Walter Hillebrand & Co GmbH
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
Family has litigation
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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
Application granted granted Critical
Publication of EP1102875B1 publication Critical patent/EP1102875B1/en
Anticipated expiration legal-status Critical
Revoked legal-status Critical Current

Links

Classifications

    • 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 / applying zinc-nickel coatings with an anode, a cathode and an alkaline electrolyte.
  • 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 kept constant by adding zinc and the nickel concentration by adding a nickel solution, for example a nickel sulfate solution.
  • a nickel solution for example a nickel sulfate solution.
  • these baths show a color change from originally blue-violet to brown. This color intensifies after several days or weeks and the bath can be separated into two phases, the upper phase being dark brown.
  • This phase causes considerable disruptions in the coating of the workpieces, such as uneven layer thicknesses or the formation of bubbles.
  • Continuous cleaning of the bath ie continuous skimming of this layer, is therefore essential. However, this is time-consuming and costly.
  • cyanide can be detected in the baths after a few weeks of operation.
  • the cyanide load requires regular renewal of the bath and a special wastewater treatment, which has a significant impact on the operating costs of the bath. This is all the more so since the waste water has a very high organic concentration and with a COD value of approx. 15,000 to 20,000 mg / l complicates cyanide detoxification. Compliance with the waste water values specified by the legislator (nickel 0.5 ppm and zinc 2 ppm) is then only possible by extensive addition of chemicals.
  • the formation of the second phase is due to a reaction of the amines, which are converted in alkaline solution on nickel anodes to nitriles (including cyanide, among others). Due to the decomposition of the amines, new complexing agents must also be continuously added to the bath, which increases the costs of the process.
  • the invention is based on the problem of creating an alkaline zinc-nickel electroplating bath which provides high-quality zinc-nickel coatings at low cost.
  • the invention proposes to separate the anode from the alkaline electrolyte by means of an ion exchange membrane.
  • a cation exchange membrane made of a perfluorinated polymer has proven to be particularly advantageous, since these have negligible electrical resistance but 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.
  • the anode material that can be used in the electroplating cell according to the invention is anode, such as platinum-plated titanium anodes, since they are no longer exposed to the basic zinc-nickel bath.
  • Fig. 1 shows the schematic structure of an electroplating bath according to the invention.
  • the electroplating cell 1 shows an electroplating cell 1 which has an anode 2 and a cathode 3, which is the workpiece to be coated.
  • the catholyte 4 surrounding the anode is alkaline and consists of a zinc-nickel electroplating bath of known composition, in which amines are used as complexing agents for the nickel ions.
  • 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.
  • This membrane 6 enables an unimpeded flow of current through the bath, but prevents the catholyte 4, in particular the amines contained therein, from coming into contact with the anode 2, as a result of which the reactions detailed in the introduction to the description, including their adverse effects, are avoided.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Automation & Control Theory (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)

Abstract

The anode is separated from the alkaline electrode to avoid undesirable secondary reactions in an alkali zinc nickel electroplating bath.

Description

"Alkalisches Zink-Nickelbad" "Alkaline zinc-nickel bath"
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 coat electrically conductive materials with zinc-nickel alloys to improve their corrosion resistance. For this purpose, an acidic electrolyte bath, for example with sulfate, chloride, fluoropromat or sulfamate electrolytes, is used in a conventional manner. With these methods, achieving a uniform thickness of the zinc-nickel coating on the material to be coated is very complex in terms of control technology and is 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: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/I ZnO11.3 g / l ZnO
4,1 g/l NiSO4 *6H2O 120 g/l NaOH4.1 g / l NiSO 4 * 6H 2 O 120 g / l NaOH
5,1 g/l Polyethylenimin.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 Nickel- sulfat-Lösung, konstant gehalten. 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 kostenauf- wendig.The electroplating baths are usually operated with insoluble nickel anodes. The zinc concentration is kept constant by adding zinc and the nickel concentration by adding a nickel solution, for example a nickel sulfate solution. However, after a few hours of operation these baths show a color change from originally blue-violet to brown. This color intensifies after several days or weeks and the bath can be separated into two phases, the upper phase being dark brown. This phase causes considerable disruptions in the coating of the workpieces, such as uneven layer thicknesses or the formation of bubbles. Continuous cleaning of the bath, ie continuous skimming of this layer, is therefore essential. 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 erheb- lieh 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, cyanide can be detected in the baths after a few weeks of operation. The cyanide load requires regular renewal of the bath and a special wastewater treatment, which has a significant impact on the operating costs of the bath. This is all the more so since the waste water has a very high organic concentration and with a COD value of approx. 15,000 to 20,000 mg / l complicates cyanide detoxification. Compliance with the waste water values specified by the legislator (nickel 0.5 ppm and zinc 2 ppm) is then only possible by extensive addition of chemicals.
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, which are converted in alkaline solution on nickel anodes to nitriles (including cyanide, among others). Due to the decomposition of the amines, new complexing agents must also be continuously added to the bath, which increases the costs 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. 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.Anodes other than nickel anodes cannot be used because they dissolve in the alkaline electrolyte, which likewise has an adverse effect on the quality of the coating. Against this background, the invention is based on the problem of creating an alkaline zinc-nickel electroplating bath which provides high-quality zinc-nickel coatings at low cost.
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 to separate the anode from the alkaline electrolyte by means of an ion exchange membrane.
Durch diese Trennung wird die Reaktion der Amine an der Nickelanode vermieden, was zur Folge hat, daß keine unerwünschten Nebenreaktionen ab- laufen, 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.As a result of this separation, the reaction of the amines at the nickel anode is avoided, with the result that no undesirable side reactions occur, cause disposal problems or lead to a second phase of reaction products settling on the bath and adversely affect the quality of the zinc-nickel coating influence. The invention makes the elaborate skimming off of this layer and the renewal of the bath superfluous. There is also a significant improvement in the quality of the coating.
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 made of a perfluorinated polymer has proven to be particularly advantageous, since these have negligible electrical resistance but 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, which considerably simplifies the entire wastewater treatment. In addition, there is no need to fill the electrolyte with complexing agent, since it no longer decomposes and its concentration in the bath remains almost constant. 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. Die vorliegende Erfindung wird anhand des in der Zeichnung dargestellten Ausführungsbeispiels näher erläutert. In der Zeichnung zeigt: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. The anode material that can be used in the electroplating cell according to the invention is anode, such as platinum-plated titanium anodes, since they are no longer exposed to the basic zinc-nickel bath. The present invention is explained in more detail with reference to the embodiment shown in the drawing. 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, auf- weist. Der die Anode 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 Katio- nenaustauschermembran 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 ver- mieden werden. 1 shows an electroplating cell 1 which has an anode 2 and a cathode 3, which is the workpiece to be coated. The catholyte 4 surrounding the anode is alkaline and consists of a zinc-nickel electroplating bath of known composition, in which amines are used as complexing agents for the nickel ions. 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. This membrane 6 enables an unimpeded flow of current through the bath, but prevents the catholyte 4, in particular the amines contained therein, from coming into contact with the anode 2, as a result of which the reactions detailed in the introduction to the description, including their adverse effects, are avoided.

Claims

Patentansprüche: Claims:
1. 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.1. 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).
2. Galvanikbad nach Anspruch 1 , dadurch gekennzeichnet, daß die Kathode (3) durch eine perfluorierte Kationenaustauschermembran (6) von dem alkalischen Elektrolyten (4) getrennt ist.2. Electroplating bath according to claim 1, characterized in that the cathode (3) is separated from the alkaline electrolyte (4) by a perfluorinated cation exchange membrane (6).
3. Galvanikbad nach Anspruch 1 oder 2, gekennzeichnet durch Schwefelsäure, Phosphorsäure, Methansulfonsäure, Amidosulfonsäure und/oder Phosphonsäure als Anolyt (5).3. 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).
4. Galvanikbad nach einem der Ansprüche 1 bis 3, gekennzeichnet durch eine platinierte Titananode. 4. electroplating bath according to one of 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
DE19834353 1998-07-30
DE19834353A DE19834353C2 (en) 1998-07-30 1998-07-30 Alkaline zinc-nickel bath
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

Publications (2)

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

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

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Country Status (22)

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US (4) US6602394B1 (en)
EP (2) EP1102875B1 (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) ES2277624T3 (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)

Families Citing this family (49)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19834353C2 (en) * 1998-07-30 2000-08-17 Hillebrand Walter Gmbh & Co Kg Alkaline zinc-nickel bath
US8236159B2 (en) * 1999-04-13 2012-08-07 Applied Materials Inc. Electrolytic process using cation permeable barrier
US20060157355A1 (en) * 2000-03-21 2006-07-20 Semitool, Inc. Electrolytic process using anion permeable barrier
US8852417B2 (en) 1999-04-13 2014-10-07 Applied Materials, Inc. Electrolytic process using anion permeable barrier
US20060189129A1 (en) * 2000-03-21 2006-08-24 Semitool, Inc. Method for applying metal features onto barrier layers using ion permeable barriers
DE10026956A1 (en) * 2000-05-30 2001-12-13 Walter Hillebrand Galvanotechn Zinc alloy bath
ATE306572T1 (en) † 2000-06-15 2005-10-15 Taskem Inc ZINC-NICKEL ELECTRO PLATING
US6755960B1 (en) 2000-06-15 2004-06-29 Taskem Inc. Zinc-nickel electroplating
US7628898B2 (en) * 2001-03-12 2009-12-08 Semitool, Inc. Method and system for idle state operation
DE10223622B4 (en) * 2002-05-28 2005-12-08 Walter Hillebrand Gmbh & Co. Kg Galvanotechnik Alkaline zinc-nickel bath and corresponding electroplating process with increased current efficiency
US8377283B2 (en) 2002-11-25 2013-02-19 Coventya, Inc. Zinc and zinc-alloy electroplating
DE10261493A1 (en) * 2002-12-23 2004-07-08 METAKEM Gesellschaft für Schichtchemie der Metalle mbH Anode for electroplating
ES2609080T3 (en) * 2003-06-03 2017-04-18 Coventya, Inc. Zinc and zinc alloy electrolytic coating
US20050121332A1 (en) * 2003-10-03 2005-06-09 Kochilla John R. Apparatus and method for treatment of metal surfaces by inorganic electrophoretic passivation
US20050133376A1 (en) * 2003-12-19 2005-06-23 Opaskar Vincent C. Alkaline zinc-nickel alloy plating compositions, processes and articles therefrom
FR2864553B1 (en) * 2003-12-31 2006-09-01 Coventya INSTALLATION OF ZINC DEPOSITION OR ZINC ALLOYS
US7442286B2 (en) * 2004-02-26 2008-10-28 Atotech Deutschland Gmbh Articles with electroplated zinc-nickel ternary and higher alloys, electroplating baths, processes and systems for electroplating such alloys
DE102004061255B4 (en) 2004-12-20 2007-10-31 Atotech Deutschland Gmbh Process for the continuous operation of acidic or alkaline zinc or zinc alloy baths and apparatus for carrying it out
EP1712660A1 (en) 2005-04-12 2006-10-18 Enthone Inc. Insoluble anode
EP1717353B1 (en) * 2005-04-26 2009-04-22 ATOTECH Deutschland GmbH Alkaline galvanizing bath comprising a filtration membrane
EP1717351A1 (en) * 2005-04-27 2006-11-02 Enthone Inc. Galvanic bath
JP4738910B2 (en) * 2005-06-21 2011-08-03 日本表面化学株式会社 Zinc-nickel alloy plating method
US20070043474A1 (en) * 2005-08-17 2007-02-22 Semitool, Inc. Systems and methods for predicting process characteristics of an electrochemical treatment process
DE102005051632B4 (en) * 2005-10-28 2009-02-19 Enthone Inc., West Haven Process for pickling non-conductive substrate surfaces and for metallizing plastic surfaces
JP4819612B2 (en) * 2006-08-07 2011-11-24 ルネサスエレクトロニクス株式会社 Plating apparatus and method for manufacturing semiconductor device
DE102007040005A1 (en) 2007-08-23 2009-02-26 Ewh Industrieanlagen Gmbh & Co. Kg Depositing functional layers from electroplating bath, circulates zinc-nickel electrolyte between bath and regeneration unit providing ozone- and ultraviolet light treatment
DE102007060200A1 (en) 2007-12-14 2009-06-18 Coventya Gmbh Galvanic bath, process for electrodeposition and use of a bipolar membrane for separation in a galvanic bath
TWI384094B (en) * 2008-02-01 2013-02-01 Zhen Ding Technology Co Ltd Anode device for electroplating and electroplating device with the same
EP2096193B1 (en) 2008-02-21 2013-04-03 Atotech Deutschland GmbH Process for the preparation of corrosion resistant zinc and zinc-nickel plated linear or complex shaped parts
DE102008058086B4 (en) 2008-11-18 2013-05-23 Atotech Deutschland Gmbh Method and device for cleaning electroplating baths for the deposition of metals
KR100977068B1 (en) * 2010-01-25 2010-08-19 한용순 Electroplating appartus and Trivalent chromium alloy electroplating solution for amorphous Trivalent chromium alloy electroplating layer
EP2384800B1 (en) 2010-05-07 2013-02-13 Dr.Ing. Max Schlötter GmbH & Co. KG Regeneration of alkaline zinc nickel electrolytes by removing cyanide ions
DE102010044551A1 (en) 2010-09-07 2012-03-08 Coventya Gmbh Anode and their use in an alkaline electroplating bath
EP2738290A1 (en) 2011-08-30 2014-06-04 Rohm and Haas Electronic Materials LLC Adhesion promotion of cyanide-free white bronze
CN103849915B (en) * 2012-12-06 2016-08-31 北大方正集团有限公司 Electroplanting device and pcb board via copper coating
CN103911650B (en) * 2014-04-02 2016-07-06 广东达志环保科技股份有限公司 A kind of anode being applied to Electrodeposition of Zn-ni Alloy In Alkaline Bath
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
BR112015028629A2 (en) 2015-07-22 2017-07-25 Dipsol Chem Zinc Alloy Electroplating Method
EP3042985B1 (en) 2015-07-22 2019-04-10 Dipsol Chemicals Co., Ltd. Zinc alloy plating method
WO2017171113A1 (en) * 2016-03-29 2017-10-05 (주) 테크윈 Electrolytic bath and electrolysis method
CN106987879A (en) * 2016-11-23 2017-07-28 瑞尔太阳能投资有限公司 Electric deposition device and its electro-deposition method
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
HUE065554T2 (en) 2017-06-14 2024-06-28 Dr Ing Max Schloetter 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
TWI841670B (en) * 2019-01-24 2024-05-11 德商德國艾托特克公司 Membrane anode system for electrolytic zinc-nickel alloy deposition
JP6582353B1 (en) 2019-02-15 2019-10-02 ディップソール株式会社 Zinc or zinc alloy electroplating method and system
JP6750186B1 (en) 2019-11-28 2020-09-02 ユケン工業株式会社 Method for suppressing increase in zinc concentration of plating solution and method for producing zinc-based plated member
WO2021123129A1 (en) 2019-12-20 2021-06-24 Atotech Deutschland Gmbh Method and system for depositing a zinc-nickel alloy on a substrate
EP4273303A1 (en) 2022-05-05 2023-11-08 Atotech Deutschland GmbH & Co. KG Method for depositing a zinc-nickel alloy on a substrate, an aqueous zinc-nickel deposition bath, a brightening agent and use thereof
CN115821346A (en) * 2022-11-16 2023-03-21 广州超邦化工有限公司 Method for plating alkaline zinc-nickel alloy on medium-carbon steel machined part

Family Cites Families (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE925264C (en) 1952-11-15 1955-03-17 Hesse & Co Dr Process for nickel plating without nickel anodes
GB1349735A (en) 1969-11-20 1974-04-10 Fulmer Res Inst Ltd Electrodeposited metal coatings
US3660170A (en) * 1970-04-08 1972-05-02 Gen Electric Dendrite-inhibiting additive for battery cell having zinc electrode
US3718549A (en) 1971-06-14 1973-02-27 Kewanee Oil Co Alkaline nickel plating solutions
JPS5128533A (en) * 1974-09-04 1976-03-10 Matsushita Electric Ind Co Ltd Aen nitsukerugokin metsukyodenkaieki
GB1602404A (en) 1978-04-06 1981-11-11 Ibm Electroplating of chromium
US4192908A (en) * 1979-06-15 1980-03-11 The United States Of America As Represented By The Secretary Of The Navy Mass-transport separator for alkaline nickel-zinc cells and cell
JPS5893886A (en) 1981-11-30 1983-06-03 Tokuyama Soda Co Ltd Electroplating method
JPS5893899A (en) 1981-11-30 1983-06-03 Sumitomo Metal Ind Ltd Controlling method for electroplating bath
US4469564A (en) * 1982-08-11 1984-09-04 At&T Bell Laboratories Copper electroplating process
DE3310730A1 (en) 1983-03-24 1984-03-29 Daimler-Benz Ag, 7000 Stuttgart Process for removing excess metal ions from acidic chloride-containing electroplating baths
JPS59193295A (en) 1983-04-15 1984-11-01 Hitachi Ltd Method and apparatus for nickel plating
DE3712511C3 (en) * 1986-04-14 1995-06-29 Dipsol Chem Alkaline cyanide-free electroplating bath and use of this bath
US4889602B1 (en) 1986-04-14 1995-11-14 Dipsol Chem Electroplating bath and method for forming zinc-nickel alloy coating
US4832812A (en) * 1987-09-08 1989-05-23 Eco-Tec Limited Apparatus for electroplating metals
JPH02175894A (en) * 1988-12-28 1990-07-09 Kosaku:Kk Method and device for tin or tin alloy electroplating
FR2650304B1 (en) 1989-07-25 1991-10-04 Siderurgie Fse Inst Rech METHOD OF ELECTROLYTIC COATING OF A METAL SURFACE, AND ELECTROLYSIS CELL FOR IMPLEMENTING IT
JPH049493A (en) * 1990-04-27 1992-01-14 Permelec Electrode Ltd Method for electrolytically tinning steel sheet
JP2764337B2 (en) * 1990-05-10 1998-06-11 新日本製鐵株式会社 Ni or Ni-Zn alloy or Ni-Zn-Co alloy plating method
JPH0444374A (en) 1990-06-12 1992-02-14 Matsushita Electric Ind Co Ltd Excimer laser device
US5310465A (en) * 1990-06-14 1994-05-10 Vaughan Daniel J Electrodialytic oxydation-reduction of metals
JPH0452296A (en) * 1990-06-20 1992-02-20 Permelec Electrode Ltd Copper plating method
JPH08375Y2 (en) * 1990-08-15 1996-01-10 株式会社アルメックス Anode structure of plating equipment
EP0483937A1 (en) 1990-10-24 1992-05-06 ATOTECH Deutschland GmbH Electrolytic cell, process and its use
DE4035316C2 (en) 1990-11-07 1993-11-04 Daimler Benz Ag METHOD FOR ELECTROLYTIC RECOVERY OF NICKEL FROM CHLORIDE-CONTAINING ELECTROLYTIC BATHS
JPH04176893A (en) 1990-11-08 1992-06-24 Kawasaki Steel Corp Sn-ni alloy plating method
US5162079A (en) 1991-01-28 1992-11-10 Eco-Tec Limited Process and apparatus for control of electroplating bath composition
JP2997072B2 (en) * 1991-02-13 2000-01-11 ディップソール株式会社 Zinc-nickel alloy plating bath and method for preventing black deposition on plating object
JPH059776A (en) * 1991-07-01 1993-01-19 Fujitsu Ltd Method of plating print circuit board
JPH059799A (en) 1991-07-05 1993-01-19 Kawasaki Steel Corp Method and device for supplying metal ion in sulfuric acid-bath zn-ni plating
JPH05128533A (en) 1991-11-05 1993-05-25 Nec Eng Ltd Reproducing device of optical disk
FR2686352B1 (en) 1992-01-16 1995-06-16 Framatome Sa APPARATUS AND METHOD FOR ELECTROLYTIC COATING OF NICKEL.
US5417840A (en) * 1993-10-21 1995-05-23 Mcgean-Rohco, Inc. Alkaline zinc-nickel alloy plating baths
US5405523A (en) * 1993-12-15 1995-04-11 Taskem Inc. Zinc alloy plating with quaternary ammonium polymer
JPH10130878A (en) 1996-11-01 1998-05-19 Asahi Glass Co Ltd Electrolytic nickel plating method
US5883762A (en) 1997-03-13 1999-03-16 Calhoun; Robert B. Electroplating apparatus and process for reducing oxidation of oxidizable plating anions and cations
DE19834353C2 (en) 1998-07-30 2000-08-17 Hillebrand Walter Gmbh & Co Kg Alkaline zinc-nickel bath

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0006807A2 *

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