EP1292724A1 - Zinc-nickel electroplating - Google Patents

Zinc-nickel electroplating

Info

Publication number
EP1292724A1
EP1292724A1 EP00951046A EP00951046A EP1292724A1 EP 1292724 A1 EP1292724 A1 EP 1292724A1 EP 00951046 A EP00951046 A EP 00951046A EP 00951046 A EP00951046 A EP 00951046A EP 1292724 A1 EP1292724 A1 EP 1292724A1
Authority
EP
European Patent Office
Prior art keywords
nickel
anode
bath
anolyte
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
EP00951046A
Other languages
German (de)
French (fr)
Other versions
EP1292724B1 (en
EP1292724A4 (en
EP1292724B2 (en
Inventor
Robert E. Frischauf
William E. Eckles
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.)
Coventya Inc
Original Assignee
Taskem Inc
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
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=21742124&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP1292724(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Taskem Inc filed Critical Taskem Inc
Priority to DE60023190.9T priority Critical patent/DE60023190T3/en
Publication of EP1292724A1 publication Critical patent/EP1292724A1/en
Publication of EP1292724A4 publication Critical patent/EP1292724A4/en
Publication of EP1292724B1 publication Critical patent/EP1292724B1/en
Application granted granted Critical
Publication of EP1292724B2 publication Critical patent/EP1292724B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • C25D17/10—Electrodes, e.g. composition, counter electrode
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc

Definitions

  • the present invention relates to an apparatus and process for zinc-nickel electroplating.
  • U .S. Patent No. 5, 162,079 discloses an apparatus for electroplating metals.
  • the apparatus comprises an electroplating bath which contains a plating solution of a metallic salt, for instance, nickel sulfate.
  • a cathode workpiece is positioned in the bath.
  • An insoluble anode assembly is also provided in the bath.
  • the anode assembly includes an anode which is essentially insoluble during electroplating and an anion exchange membrane enclosure around the anode.
  • An electrically conductive acid solution is contained within the enclosure of the anode assembly.
  • the flow of current in the apparatus causes anions, for instance sulfate ions, in the plating solution to travel through the anion exchange membrane increasing the acid concentration within the anode assembly enclosure.
  • Accu mulated acid is periodically flushed from the enclosure.
  • One purpose of the apparatus of the x 079 patent is to i nhi bit the increase in concentration of dissolved metal in the electroplating bath due to a cathode efficiency which is less than the anode efficiency.
  • U .S. Patent No. 4,778,572 discloses an apparatus similar to that of the "079 patent.
  • An electroplating apparatus for plating nickel onto a workpiece is provided .
  • a nickel-plati ng bath is provided in the apparatus.
  • the bath is a typical Watts nickel low pH acid bath .
  • a cathode workpiece is positioned in the bath .
  • An anode structure is also positioned in the bath .
  • the anode structure comprises a series of nickel plate anodes.
  • the nickel plate anodes are enclosed i n an ion exchange membrane that allows a current flow from the anodes to the cathode workpiece whi le at the same ti me shielding the anodes from organics, such as Cou marin within the bath .
  • the nickel plate anodes are i m mersed in dilute sulfuric acid contained within the ion excha nge membrane enclosure.
  • the apparatus comprises a vessel which is divided by a cation exchange membrane into a cathode compartment containing a catholyte and an anode compartment containing an anolyte.
  • the catholyte is an alkaline zi nc-nickel electroplating bath containing poly(alkyleneimine) additives for complexing and brightening.
  • a cathode workpiece to be plated is positioned in the cathode compartment.
  • the anolyte is an acid such as sulfuric acid or phosphoric acid.
  • a platinum coated titanium anode is immersed in the anolyte.
  • the ion exchange membrane allows the flow of current from the anode to the cathode, but at the same time shields the anode from the alkaline zinc-nickel electroplating bath. Electrolysis of alkaline zinc-nickel baths containing poly(alkyleneimines) produces amine breakdown at the anode into nitriles and cyanides if the anode is exposed to the plating bath . The ion exchange membrane prevents such amine breakdown.
  • an apparatus which comprises an alkaline electroplating bath adjacent to an acid anolyte can be dangerous.
  • a platinum coated titanium anode is expensive.
  • Fig. 1 is a schematic illustration of a zinc-nickel electroplating apparatus in accordance with the present invention
  • Fig . 2 is a schematic illustration of an anode assembly in the apparatus of Fig. 1 Summarv of the Invention
  • the present invention relates to an apparatus for applying a zinc-nickel electroplate to a workpiece.
  • the apparatus comprises a zinc-nickel electroplating bath comprising an amine additive, such as a poly(alkylene- imines) capable of being oxidized in the bath to cyanides.
  • the bath has a pH more than about 14.
  • a cathode workpiece is positioned in said bath.
  • An anode assembly is in contact with the bath.
  • the anode assembly comprises an enclosure defining an anolyte compartment, at least a portion of the enclosure in contact with the bath being an ion exchange membrane.
  • An anolyte is positioned in the compartment.
  • An insoluble metal anode is immersed in the anolyte.
  • the anolyte is a conductive salt or base solution and the anode is a metal or metal coating selected from the group consisting of nickel, cobalt, iron, chromium and alloys thereof.
  • a preferred anolyte is a solution of 50 to about 760 g/liter of sodium hydroxide.
  • a preferred anode is a nickel or a nickel alloy or coating thereof coated onto a substrate.
  • the present invention also resides in a process for applying a zinc-nickel electroplate to a workpiece.
  • a zinc- nickel electroplating bath comprising amine additives and having a pH more than about 14 is provided.
  • a cathode workpiece is positioned in the bath.
  • An anode assembly is in contact with the bath.
  • the anode assembly comprises an enclosure defining an anolyte compartment, at least a portion of the enclosure in contact with the bath being an ion exchange membrane.
  • An anolyte is positioned in the compartment.
  • An insoluble metal anode is immersed in the anolyte.
  • the anolyte is a conductive salt or base solution and the anode is a metal or metal coating selected from the group consisting of nickel, cobalt, iron, chromium and alloys thereof.
  • a potential is applied between the anode and cathode establishing a current flow from the anode to the cathode through the ion exchange membrane.
  • the ion exchange membrane shields the anode from the zinc-nickel electroplating bath preventing amine breakdown into cyanides.
  • the zinc-nickel electroplating apparatus 12 of the present invention comprises a tank 14.
  • the tank 14 contains a zinc-nickel electroplating bath 16 and a cathode workpiece 18.
  • the tank 14 also comprises an anode assembly 20.
  • the anode assembly 20 comprises an enclosure 22 which defines an anolyte compartment 24.
  • the compartment 24 is closed by the enclosure 22 on all sides and the bottom.
  • At least one wall 26 of the enclosure 22 is an ion exchange membrane.
  • the anolyte compartment 24 comprises an anolyte 28.
  • An anode 30 is immersed in the anolyte 28.
  • the enclosure 22 shields the anode 30 from the electroplating bath 16 so that no bath 16 contacts the anode 30.
  • the ion exchange membrane 26 faces the cathode workpiece 18. This allows current to flow from the anode 30 to the cathode workpiece 18 on the application of an electric potential to the anode 30 and the cathode workpiece 18. The current flow causes plating of the cathode workpiece 18.
  • the enclosure 22 and compartment 24 can have many configurations, for instance, a membrane bag suspended in the catholyte, or a membrane containing wall extending cross-wise in the tank 14 dividing the tank 14 into a catholyte compartment or an anolyte compartment.
  • the cathode workpiece 18 is any workpiece typically used in zinc-nickel electroplating.
  • a steel plate was used.
  • the enclosure 22 of the anode assembly 20 can be made of any suitable plastic resistant to the zinc-nickel electroplating bath 16 and the anolyte 28, for instance, polyethylene.
  • the ion exchange membrane 26 of the enclosure 22 can be any ion exchange membrane used in an electroplating bath, for example, an ion exchange membrane, such as a perfluorosulfonic acid ion exchange membrane, marketed by E.I. DuPont de Nemours under the trademark NAFION. In the following Examples, a NAFION 450 membrane was used.
  • the anolyte 28 in the anolyte compartment 24 is a conductive salt or base solution, for example, an aqueous solution of sodium sulfate or an alkaline solution of potassium hydroxide or sodium hydroxide.
  • alkaline solutions can have concentrations, by way of example, in the range of one molar to about 20 molar hydroxide, with a preferred concentration range of 1 to 10 molar.
  • a preferred anolyte is about 50 g/liter sodium hydroxide to about 760 g/liter.
  • the anode 30 of the anode assembly 20 is a metal or a metal coating selected from the group consisting of nickel, cobalt, iron, chromium, and alloys thereof.
  • the anode 30 can be nickel, a nickel alloy, nickel coated onto a substrate, or a nickel alloy coated onto a substrate.
  • the substrate can be metal, such as steel, copper, or aluminum or a plastic.
  • An example of a nickel alloy is Hastelloy, which is 55% nickel and 45% chromium .
  • the nickel or nickel alloy can be electroplated onto a substrate using a Watts type plating bath, or using an electroless nickel or nickel alloy plating process.
  • the anode 30 can be cobalt or cobalt coated onto a substrate, and alloys thereof.
  • the anode can also be a mild steel, a steel alloy, or an iron chromium alloy such as stainless steel.
  • the zinc-nickel electroplating bath is an aqueous solution that is alkaline having a pH which is preferably above about 14.
  • the bath contains an inorganic alkaline component in an effective amount to achieve this pH . Amounts from about 50 grams per liter to about 200 grams per liter, based on the electroplating bath of the alkaline component can be used.
  • suitable alkaline components are alkali metal derivatives such as sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
  • the electroplating bath 16 also contains a controlled amount of zinc ions and a controlled amount of nickel ions.
  • the source for the zinc ions for the electroplating bath 16 can be any zinc compound which is soluble in an alkaline aqueous medium.
  • Examples of zinc compounds which can be added to the electroplating bath are zinc oxide or a soluble salt such as zinc sulfate, zinc carbonate, zinc sulfamate, and zinc acetate.
  • the concentration of zinc ions in the electroplating bath is from about 1 to 100 grams per liter, preferably about 4 to about 50 grams per liter (about 4,000 to about 50,000 ppm). At a pH above about 14, the predominant zinc species in the bath is zincate ion.
  • the source for the nickel ions for the electroplating bath can be any nickel compound which can be made soluble in an aqueous alkaline solution .
  • suitable nickel compounds are an inorganic or organic acid salt of nickel, such as nickel sulfate, nickel carbonate, nickel acetate, nickel sulfamate and nickel formate.
  • the concentration of nickel ions in the electroplating bath can be from about 0.1 to about 10 grams per liter (about 100 to 10,000 ppm), more preferably in the range from about 0.1 gram per liter to about 3 grams per liter (about 100 ppm to about 3,000 ppm).
  • the zinc-nickel electroplating bath also contains an amine compound capable of being oxidized to cyanides in the bath, such as a polymer of an aliphatic amine.
  • Examples of aliphatic amine polymers oxidizable to cyanides in the bath are ethyleneimine, 1,2-propyleneimine, 1,2- butyleneimine and 1,1-dimethylethyleneimine.
  • the poly(alkyleneimines) may have molecular weights from about 100 to about 100,000 and should be soluble in the bath.
  • poly(ethyleneimine) which is useful in the bath can have a molecular weight of from about 150 to above about 2,000.
  • Useful poly(ethyleneimines) are available commercially, for example from BASF under the designations LUGALVAN G-15, LUGALVAN G-20 and LUGALVAN G-35.
  • TEPA tetraethylenepentamine
  • PEHA pentaethylenehexamine
  • EPOMIN 003 heptaethylene octamine
  • One function of the aliphatic poly(alkyleneimines) is to complex nickel ions in the alkaline zinc-nickel bath.
  • the zinc-nickel electroplating bath may also contain other additives such as other brighteners, and metal complexing agents.
  • One useful metal complexing agent is QUADROL from BASF. QUADROL is N,N,N',N'-tetrakis(2- hydroxypropyl)-ethylenediamine.
  • metal anode 30 copper and tin were tested as metal anodes in the anode box, but both dissolved during electrolysis. Zinc was tested but polarized severely. A graphite electrode was also tested. The graphite decomposed, and the anode box became filled with graphite particles. Iridium oxide on titanium was tested, but there was significant deterioration of the coating during electrolysis.
  • the alkaline zinc-nickel bath was one gallon containing 10 g/liter of zinc, 1.5 g/liter of nickel, 20 g/liter of tetraethylenepentamine (TEPA) and lOg/liter of QUADROL.
  • An anode box (disclosed in the Figure) having a NAFION 450 membrane on one side, containing 500 ml of a solution of 150g of sodium hydroxide was placed in the zinc-nickel bath.
  • a metal anode was placed in the anode box.
  • the metal anode was made of a coating of electroless nickel (containing 10%P) on steel. 5.0 Amperes of current were passed through the one-gallon cell for 6 hours.
  • the plating bath was analyzed for cyanide, and no cyanide was detected. There was no erosion of the electroless coated steel anode in the anode box.
  • Example 2 In this Example, the anode box was filled with a solution of 150g/liter of sodium hydroxide in water.
  • the metal anode in the box was made of nickel metal .
  • a one- gallon cell, similar to Example 1, was run at 5 amperes for 6 hours as before.
  • the plating bath was analyzed for cyanide, and no cyanide was detected.
  • the nickel anode had a thin conductive coating of nickel oxide/nickel hydroxide which did not interfere with the plating process. There was no weight loss of nickel anode.
  • the anode box of Example 1 was filled with a 20% solution of 50% liquid caustic.
  • the metal anode was nickel electroplated from a Watts type plating solution, onto a steel base metal.
  • the bath was run at 5 amperes and 6.84 volts for 6 hours.
  • the plating bath was analyzed for cyanide, and no cyanide was detected. There was no metal anode weight loss.
  • a 1-gallon zinc-nickel plating bath similar to the bath in Example 1, was electrolyzed for 100 ampere hours, using a box anode with a NAFION 450 ion exchange membrane covering one side of the box.
  • the anode in the box was steel coated with electroless nickel with contained 8%P.
  • the bath was analyzed for cyanide and was found to contain no detectable cyanide. There was no metal anode weight loss. Comparative Example 5
  • a 2-liter alkaline zinc-nickel plating bath containing 30g/liter of a polyethyleneimine (TEPA) was electrolyzed for 160 ampere hours with a nickel anode placed directly into the plating bath.
  • the bath was found to contain 508 ppm of cyanide.
  • the anode box of Example 1 was filed with a solution of 150g/liter of potassium hydroxide.
  • the metal anode in the anolyte was a mild steel Q-panel.
  • the bath which was similar to the bath of Example 1, was electrolyzed at 5 amperes for 6 hours. There was a slight loss of weight from the steel anode.
  • the electrolyte was analyzed for cyanide, and no cyanide was detected.
  • the anode box of Example 1 is filled with a solution of 150g/liter of sodium hydroxide.
  • the metal anode in the box is cobalt.
  • the alkaline zinc-nickel bath contains 20 g/liter of poly(ethyleneimine) and is electrolyzed for 30 amp-hours.
  • the metal anode in the anode box of Example 1 is steel coated with cobalt.
  • the plating bath is similar to Example 1.
  • the anolyte in the box is a 20% solution of 50% liquid caustic.
  • Example 9 The metal anode in the anode box in this Example, is a cobalt alloy anode.
  • the anolyte is a 20% solution of 50% liquid caustic.
  • the plating bath and apparatus are similar to Example 1.
  • the metal anode in this Example is steel coated with a cobalt alloy coating from an electroless, cobalt-plating bath.
  • the zinc-nickel plating bath and apparatus are similar to Example 1.
  • the anode box contains a 15% solution of 50% liquid caustic.
  • the alkaline zinc-nickel bath is electrolyzed for 6 hours at 5.0 amperes.
  • the metal anode in the anode box was stainless steel .
  • the plating bath and apparatus were similar to Example 1. After 30-ampere hours, there was no detectable cyanide. There was no weight loss from the stainless steel anode.
  • an apparatus and process are provided by which zinc-nickel can be safely plated onto a substrate using an alkaline zinc-nickel electroplating bath containing polyamines, especially poly(alkyleneimines).
  • a commercial apparatus and process will employ a zinc-nickel electroplating bath comprising additives in addition to a poly(alkyleneimine) such as other brighteners and sequestrants.
  • a commercial bath typically can employ a 1000 gallon tank and the cathode workpiece positioned between arrays of compartmentalized anodes on opposite sides of the cathode along the sides of the tank.

Landscapes

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

Abstract

The present invention relates to an apparatus (12) for applying a zinc-nickel electroplate to a workpiece. The apparatus comprises a zinc-nickel electroplating bath (16) comprising an amine additive, such as poly(alkyleneimine), which is capable of being oxidized in the bath to cyanides. The bath has a pH more than about 14. A cathode workpiece (18) is positioned in the bath. An anode assembly (20) is also positioned in the bath. The anode assembly comprises an enclosure (22) defining an anolyte compartment (24), at least a portion of the enclosure being an ion exchange membrane (26). An anolyte (28) is positioned in the compartment. An insoluble metal anode (30) is immersed in the anolyte. The anolyte is a conductive salt or base solution and the anode is a metal or metal coating selected from the group consisting of nickel, cobalt, iron, chromium and alloys thereof.

Description

ZINC-NICKEL ELECTROPLATING
Background of the Invention
Technical Field
The present invention relates to an apparatus and process for zinc-nickel electroplating.
Description of the Prior Art
U .S. Patent No. 5, 162,079 discloses an apparatus for electroplating metals. The apparatus comprises an electroplating bath which contains a plating solution of a metallic salt, for instance, nickel sulfate. A cathode workpiece is positioned in the bath. An insoluble anode assembly is also provided in the bath. The anode assembly includes an anode which is essentially insoluble during electroplating and an anion exchange membrane enclosure around the anode. An electrically conductive acid solution is contained within the enclosure of the anode assembly. The flow of current in the apparatus causes anions, for instance sulfate ions, in the plating solution to travel through the anion exchange membrane increasing the acid concentration within the anode assembly enclosure. Accu mulated acid is periodically flushed from the enclosure. One purpose of the apparatus of the x079 patent is to i nhi bit the increase in concentration of dissolved metal in the electroplating bath due to a cathode efficiency which is less than the anode efficiency.
U .S. Patent No. 4,778,572 discloses an apparatus similar to that of the "079 patent. An electroplating apparatus for plating nickel onto a workpiece is provided . A nickel-plati ng bath is provided in the apparatus. The bath is a typical Watts nickel low pH acid bath . A cathode workpiece is positioned in the bath . An anode structure is also positioned in the bath . The anode structure comprises a series of nickel plate anodes. The nickel plate anodes are enclosed i n an ion exchange membrane that allows a current flow from the anodes to the cathode workpiece whi le at the same ti me shielding the anodes from organics, such as Cou marin within the bath . The nickel plate anodes are i m mersed in dilute sulfuric acid contained within the ion excha nge membrane enclosure. German Patent Publication DE 19834353A1 published
February 3, 2000, discloses an apparatus similar to that of the Λ079 patent for applying a zi nc-nickel coating onto a cathode workpiece. The apparatus comprises a vessel which is divided by a cation exchange membrane into a cathode compartment containing a catholyte and an anode compartment containing an anolyte. The catholyte is an alkaline zi nc-nickel electroplating bath containing poly(alkyleneimine) additives for complexing and brightening. A cathode workpiece to be plated is positioned in the cathode compartment. The anolyte is an acid such as sulfuric acid or phosphoric acid. A platinum coated titanium anode is immersed in the anolyte. The ion exchange membrane allows the flow of current from the anode to the cathode, but at the same time shields the anode from the alkaline zinc-nickel electroplating bath. Electrolysis of alkaline zinc-nickel baths containing poly(alkyleneimines) produces amine breakdown at the anode into nitriles and cyanides if the anode is exposed to the plating bath . The ion exchange membrane prevents such amine breakdown. However, an apparatus which comprises an alkaline electroplating bath adjacent to an acid anolyte can be dangerous. In addition, a platinum coated titanium anode is expensive.
Brief Description of the Drawings
The present invention and advantages thereof will become more apparent upon consideration of the following specification with reference to the accompanying drawings in which :
Fig. 1 is a schematic illustration of a zinc-nickel electroplating apparatus in accordance with the present invention; and Fig . 2 is a schematic illustration of an anode assembly in the apparatus of Fig. 1 Summarv of the Invention
The present invention relates to an apparatus for applying a zinc-nickel electroplate to a workpiece. The apparatus comprises a zinc-nickel electroplating bath comprising an amine additive, such as a poly(alkylene- imines) capable of being oxidized in the bath to cyanides. The bath has a pH more than about 14. A cathode workpiece is positioned in said bath. An anode assembly is in contact with the bath. The anode assembly comprises an enclosure defining an anolyte compartment, at least a portion of the enclosure in contact with the bath being an ion exchange membrane. An anolyte is positioned in the compartment. An insoluble metal anode is immersed in the anolyte. The anolyte is a conductive salt or base solution and the anode is a metal or metal coating selected from the group consisting of nickel, cobalt, iron, chromium and alloys thereof.
A preferred anolyte is a solution of 50 to about 760 g/liter of sodium hydroxide. A preferred anode is a nickel or a nickel alloy or coating thereof coated onto a substrate.
The present invention also resides in a process for applying a zinc-nickel electroplate to a workpiece. A zinc- nickel electroplating bath comprising amine additives and having a pH more than about 14 is provided. A cathode workpiece is positioned in the bath. An anode assembly is in contact with the bath. The anode assembly comprises an enclosure defining an anolyte compartment, at least a portion of the enclosure in contact with the bath being an ion exchange membrane. An anolyte is positioned in the compartment. An insoluble metal anode is immersed in the anolyte. The anolyte is a conductive salt or base solution and the anode is a metal or metal coating selected from the group consisting of nickel, cobalt, iron, chromium and alloys thereof. A potential is applied between the anode and cathode establishing a current flow from the anode to the cathode through the ion exchange membrane. The ion exchange membrane shields the anode from the zinc-nickel electroplating bath preventing amine breakdown into cyanides.
Description of Preferred Embodiments Referring to the Figures, the zinc-nickel electroplating apparatus 12 of the present invention comprises a tank 14. The tank 14 contains a zinc-nickel electroplating bath 16 and a cathode workpiece 18. The tank 14 also comprises an anode assembly 20. The anode assembly 20 comprises an enclosure 22 which defines an anolyte compartment 24. The compartment 24 is closed by the enclosure 22 on all sides and the bottom. At least one wall 26 of the enclosure 22 is an ion exchange membrane. The anolyte compartment 24 comprises an anolyte 28. An anode 30 is immersed in the anolyte 28. The enclosure 22 shields the anode 30 from the electroplating bath 16 so that no bath 16 contacts the anode 30. The ion exchange membrane 26 faces the cathode workpiece 18. This allows current to flow from the anode 30 to the cathode workpiece 18 on the application of an electric potential to the anode 30 and the cathode workpiece 18. The current flow causes plating of the cathode workpiece 18.
It will be understood by those skilled in the art that the enclosure 22 and compartment 24 can have many configurations, for instance, a membrane bag suspended in the catholyte, or a membrane containing wall extending cross-wise in the tank 14 dividing the tank 14 into a catholyte compartment or an anolyte compartment.
In the present invention, the cathode workpiece 18 is any workpiece typically used in zinc-nickel electroplating. In the example of the Figures, a steel plate was used. The enclosure 22 of the anode assembly 20 can be made of any suitable plastic resistant to the zinc-nickel electroplating bath 16 and the anolyte 28, for instance, polyethylene.
The ion exchange membrane 26 of the enclosure 22 can be any ion exchange membrane used in an electroplating bath, for example, an ion exchange membrane, such as a perfluorosulfonic acid ion exchange membrane, marketed by E.I. DuPont de Nemours under the trademark NAFION. In the following Examples, a NAFION 450 membrane was used.
The anolyte 28 in the anolyte compartment 24 is a conductive salt or base solution, for example, an aqueous solution of sodium sulfate or an alkaline solution of potassium hydroxide or sodium hydroxide. These alkaline solutions can have concentrations, by way of example, in the range of one molar to about 20 molar hydroxide, with a preferred concentration range of 1 to 10 molar. A preferred anolyte is about 50 g/liter sodium hydroxide to about 760 g/liter.
The anode 30 of the anode assembly 20 is a metal or a metal coating selected from the group consisting of nickel, cobalt, iron, chromium, and alloys thereof. For instance, the anode 30 can be nickel, a nickel alloy, nickel coated onto a substrate, or a nickel alloy coated onto a substrate. The substrate can be metal, such as steel, copper, or aluminum or a plastic. An example of a nickel alloy is Hastelloy, which is 55% nickel and 45% chromium . The nickel or nickel alloy can be electroplated onto a substrate using a Watts type plating bath, or using an electroless nickel or nickel alloy plating process. Similarly, the anode 30 can be cobalt or cobalt coated onto a substrate, and alloys thereof. The anode can also be a mild steel, a steel alloy, or an iron chromium alloy such as stainless steel.
The zinc-nickel electroplating bath is an aqueous solution that is alkaline having a pH which is preferably above about 14. The bath contains an inorganic alkaline component in an effective amount to achieve this pH . Amounts from about 50 grams per liter to about 200 grams per liter, based on the electroplating bath of the alkaline component can be used. Examples of suitable alkaline components are alkali metal derivatives such as sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
The electroplating bath 16 also contains a controlled amount of zinc ions and a controlled amount of nickel ions. The source for the zinc ions for the electroplating bath 16 can be any zinc compound which is soluble in an alkaline aqueous medium. Examples of zinc compounds which can be added to the electroplating bath are zinc oxide or a soluble salt such as zinc sulfate, zinc carbonate, zinc sulfamate, and zinc acetate. The concentration of zinc ions in the electroplating bath is from about 1 to 100 grams per liter, preferably about 4 to about 50 grams per liter (about 4,000 to about 50,000 ppm). At a pH above about 14, the predominant zinc species in the bath is zincate ion.
The source for the nickel ions for the electroplating bath can be any nickel compound which can be made soluble in an aqueous alkaline solution . Examples of suitable nickel compounds are an inorganic or organic acid salt of nickel, such as nickel sulfate, nickel carbonate, nickel acetate, nickel sulfamate and nickel formate. The concentration of nickel ions in the electroplating bath can be from about 0.1 to about 10 grams per liter (about 100 to 10,000 ppm), more preferably in the range from about 0.1 gram per liter to about 3 grams per liter (about 100 ppm to about 3,000 ppm).
The zinc-nickel electroplating bath also contains an amine compound capable of being oxidized to cyanides in the bath, such as a polymer of an aliphatic amine.
Examples of aliphatic amine polymers oxidizable to cyanides in the bath are ethyleneimine, 1,2-propyleneimine, 1,2- butyleneimine and 1,1-dimethylethyleneimine. The poly(alkyleneimines) may have molecular weights from about 100 to about 100,000 and should be soluble in the bath. By way of example, poly(ethyleneimine) which is useful in the bath can have a molecular weight of from about 150 to above about 2,000. Useful poly(ethyleneimines) are available commercially, for example from BASF under the designations LUGALVAN G-15, LUGALVAN G-20 and LUGALVAN G-35. Examples of other useful poly(alkyleneimines) are tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), and heptaethylene octamine marketed by Nippon Shokubai Co. Ltd. under the trademark EPOMIN 003.
One function of the aliphatic poly(alkyleneimines) is to complex nickel ions in the alkaline zinc-nickel bath.
It will be understood by those skilled in the art that the zinc-nickel electroplating bath may also contain other additives such as other brighteners, and metal complexing agents. One useful metal complexing agent is QUADROL from BASF. QUADROL is N,N,N',N'-tetrakis(2- hydroxypropyl)-ethylenediamine.
With regard to the metal anode 30, copper and tin were tested as metal anodes in the anode box, but both dissolved during electrolysis. Zinc was tested but polarized severely. A graphite electrode was also tested. The graphite decomposed, and the anode box became filled with graphite particles. Iridium oxide on titanium was tested, but there was significant deterioration of the coating during electrolysis.
The following Examples illustrate the present invention.
Example 1
The alkaline zinc-nickel bath was one gallon containing 10 g/liter of zinc, 1.5 g/liter of nickel, 20 g/liter of tetraethylenepentamine (TEPA) and lOg/liter of QUADROL. An anode box (disclosed in the Figure) having a NAFION 450 membrane on one side, containing 500 ml of a solution of 150g of sodium hydroxide was placed in the zinc-nickel bath. A metal anode was placed in the anode box. The metal anode was made of a coating of electroless nickel (containing 10%P) on steel. 5.0 Amperes of current were passed through the one-gallon cell for 6 hours. The plating bath was analyzed for cyanide, and no cyanide was detected. There was no erosion of the electroless coated steel anode in the anode box.
Example 2 In this Example, the anode box was filled with a solution of 150g/liter of sodium hydroxide in water. The metal anode in the box was made of nickel metal . A one- gallon cell, similar to Example 1, was run at 5 amperes for 6 hours as before. The plating bath was analyzed for cyanide, and no cyanide was detected. The nickel anode had a thin conductive coating of nickel oxide/nickel hydroxide which did not interfere with the plating process. There was no weight loss of nickel anode.
Example 3
The anode box of Example 1 was filled with a 20% solution of 50% liquid caustic. The metal anode was nickel electroplated from a Watts type plating solution, onto a steel base metal. The bath was run at 5 amperes and 6.84 volts for 6 hours. The plating bath was analyzed for cyanide, and no cyanide was detected. There was no metal anode weight loss.
Example 4
A 1-gallon zinc-nickel plating bath, similar to the bath in Example 1, was electrolyzed for 100 ampere hours, using a box anode with a NAFION 450 ion exchange membrane covering one side of the box. The anode in the box was steel coated with electroless nickel with contained 8%P. After 100 ampere hours, the bath was analyzed for cyanide and was found to contain no detectable cyanide. There was no metal anode weight loss. Comparative Example 5
A 2-liter alkaline zinc-nickel plating bath containing 30g/liter of a polyethyleneimine (TEPA) was electrolyzed for 160 ampere hours with a nickel anode placed directly into the plating bath. The bath was found to contain 508 ppm of cyanide.
Example 6
The anode box of Example 1 was filed with a solution of 150g/liter of potassium hydroxide. The metal anode in the anolyte was a mild steel Q-panel. The bath, which was similar to the bath of Example 1, was electrolyzed at 5 amperes for 6 hours. There was a slight loss of weight from the steel anode. The electrolyte was analyzed for cyanide, and no cyanide was detected.
Example 7
The anode box of Example 1 is filled with a solution of 150g/liter of sodium hydroxide. The metal anode in the box is cobalt. The alkaline zinc-nickel bath contains 20 g/liter of poly(ethyleneimine) and is electrolyzed for 30 amp-hours.
Example 8
The metal anode in the anode box of Example 1 is steel coated with cobalt. The plating bath is similar to Example 1. The anolyte in the box is a 20% solution of 50% liquid caustic.
Example 9 The metal anode in the anode box in this Example, is a cobalt alloy anode. The anolyte is a 20% solution of 50% liquid caustic. The plating bath and apparatus are similar to Example 1.
Example 10
The metal anode in this Example is steel coated with a cobalt alloy coating from an electroless, cobalt-plating bath. The zinc-nickel plating bath and apparatus are similar to Example 1. The anode box contains a 15% solution of 50% liquid caustic. The alkaline zinc-nickel bath is electrolyzed for 6 hours at 5.0 amperes.
Example 11
In this Example, the metal anode in the anode box was stainless steel . The plating bath and apparatus were similar to Example 1. After 30-ampere hours, there was no detectable cyanide. There was no weight loss from the stainless steel anode.
By the present invention, an apparatus and process are provided by which zinc-nickel can be safely plated onto a substrate using an alkaline zinc-nickel electroplating bath containing polyamines, especially poly(alkyleneimines).
This is accomplished without anode erosion or generating cyanides in the electroplating bath.
It will be understood by those skilled in the art that a commercial apparatus and process will employ a zinc-nickel electroplating bath comprising additives in addition to a poly(alkyleneimine) such as other brighteners and sequestrants. In addition, a commercial bath typically can employ a 1000 gallon tank and the cathode workpiece positioned between arrays of compartmentalized anodes on opposite sides of the cathode along the sides of the tank. From the above description of the invention, those skilled in the art will perceive improvements, changes and modifications. Such improvements, changes and modifications within the skill of the art are intended to be covered by the appended claims.

Claims

Having described the invention, the following is claimed :
1. An apparatus for applying a zinc-nickel electroplate to a workpiece comprising :
(a) a zinc-nickel electroplating bath comprising an amine additive and having a pH more than about 14;
(b) a cathode workpiece in said bath;
(c) an anode assembly in said bath comprising : (i) an enclosure defining an anolyte compartment, at least a portion of the enclosure being an ion exchange membrane;
(ii) an anolyte in said compartment; and (iii) an insoluble metal anode immersed in said anolyte; wherein the anolyte is a conductive salt or base solution and the anode is a metal or metal coating selected from the group consisting of nickel, cobalt, iron, chromium and alloys thereof.
2. The apparatus of claim 1 wherein said amine additive is a poly(alkyleneimine).
3. The apparatus of claim 2 wherein said zinc-nickel bath comprises poly(ethyleneimines).
4. The apparatus of claim 3 wherein said anode is nickel, a nickel alloy, a nickel coating, or a nickel alloy coating and said anolyte is a sodium or potassium hydroxide solution comprising 50 to about 760 grams per liter sodium or potassium hydroxide.
5. The apparatus of claim 4 wherein said anode is electroless nickel or alloy thereof coated on a substrate, or Watts-nickel or alloy thereof coated on a substrate.
6. A process for applying a zinc-nickel electroplate to a workpiece comprising the steps of:
(a) providing the apparatus of claim 1; and
(b) applying a potential to the anode and cathode workpiece of said apparatus to cause a current flow from the anode to the cathode and plating of said workpiece.
7. A process for applying a zinc-nickel electroplate to a workpiece comprising the steps of:
(a) providing a zinc-nickel electroplating bath comprising an amine additive and having a pH more than about 14;
(b) positioning a cathode workpiece in said bath;
(c) providing an anode assembly in said bath comprising :
(i) an enclosure defining an anolyte compartment, at least a portion of said enclosure being an ion exchange membrane;
(ii) an anolyte in said compartment; and (iii) an insoluble metal anode immersed in said anolyte, wherein the anolyte is a conductive salt or base solution and the anode is a metal or metal coating selected from the group consisting of nickel, cobalt, iron, chromium and alloys thereof,
(d) applying a potential to said anode and cathode to cause a current flow from the anode to the cathode through said ion exchange membrane.
8. The process of claim 7 wherein said amine additive is poly(alkyleneimine).
9. The process of claim 8 wherein said zinc-nickel bath comprises poly(ethyleneimine).
10. A process according to claim 9 wherein said anode is nickel, a nickel alloy, a nickel coating, or a nickel alloy coating and said anolyte is a sodium or potassium hydroxide solution comprising 50 to about 760 grams per liter sodium or potassium hydroxide.
11. A process according to claim 10 wherein said anode is electroless nickel or alloy thereof coated on a substrate, or Watts-nickel or alloy thereof coated on a substrate.
EP00951046.2A 2000-06-15 2000-06-15 Zinc-nickel electroplating Expired - Lifetime EP1292724B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE60023190.9T DE60023190T3 (en) 2000-06-15 2000-06-15 ZINC-NICKEL-electroplating

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2000/040208 WO2001096631A1 (en) 2000-06-15 2000-06-15 Zinc-nickel electroplating

Publications (4)

Publication Number Publication Date
EP1292724A1 true EP1292724A1 (en) 2003-03-19
EP1292724A4 EP1292724A4 (en) 2004-09-08
EP1292724B1 EP1292724B1 (en) 2005-10-12
EP1292724B2 EP1292724B2 (en) 2015-12-23

Family

ID=21742124

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00951046.2A Expired - Lifetime EP1292724B2 (en) 2000-06-15 2000-06-15 Zinc-nickel electroplating

Country Status (5)

Country Link
EP (1) EP1292724B2 (en)
AT (1) ATE306572T1 (en)
DE (1) DE60023190T3 (en)
ES (1) ES2250166T5 (en)
WO (1) WO2001096631A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2384800A1 (en) 2010-05-07 2011-11-09 Dr.Ing. Max Schlötter GmbH & Co. KG Regeneration of alkaline zinc electrolytes by removing cyanidiones
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
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

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6755960B1 (en) 2000-06-15 2004-06-29 Taskem Inc. Zinc-nickel electroplating
US8377283B2 (en) 2002-11-25 2013-02-19 Coventya, Inc. Zinc and zinc-alloy electroplating
WO2004108995A1 (en) 2003-06-03 2004-12-16 Taskem Inc. Zinc and zinc-alloy electroplating
DE10261493A1 (en) * 2002-12-23 2004-07-08 METAKEM Gesellschaft für Schichtchemie der Metalle mbH Anode for electroplating
US7368043B2 (en) * 2003-04-10 2008-05-06 Applied Intellectual Capital Configurations and methods of electrochemical lead recovery from contaminated soil
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
ES2574158T3 (en) 2005-04-26 2016-06-15 Atotech Deutschland Gmbh Galvanic alkaline bath with a filtration membrane
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
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
DE102010044551A1 (en) * 2010-09-07 2012-03-08 Coventya Gmbh Anode and their use in an alkaline electroplating 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
WO2016075963A1 (en) 2015-07-22 2016-05-19 ディップソール株式会社 Zinc alloy plating method
CN113383118A (en) * 2019-01-24 2021-09-10 德国艾托特克公司 Membrane anode system for electrolytic zinc-nickel alloy deposition
CN114574860A (en) * 2022-03-08 2022-06-03 南京南微电机有限公司 Local nickel plating process and application thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3712511A1 (en) * 1986-04-14 1987-10-15 Dipsol Chem ELECTRIC PLATING BATH

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3718549A (en) † 1971-06-14 1973-02-27 Kewanee Oil Co Alkaline nickel plating solutions
JPS62240788A (en) * 1986-04-14 1987-10-21 Deitsupusoole Kk Zinc-nickel alloy plating bath
US4889602B1 (en) † 1986-04-14 1995-11-14 Dipsol Chem Electroplating bath and method for forming zinc-nickel alloy coating
JP2769614B2 (en) * 1986-06-04 1998-06-25 ディップソール 株式会社 Zinc-nickel alloy plating bath
US4778572A (en) 1987-09-08 1988-10-18 Eco-Tec Limited Process for electroplating metals
DE4035316C2 (en) † 1990-11-07 1993-11-04 Daimler Benz Ag METHOD FOR ELECTROLYTIC RECOVERY OF NICKEL FROM CHLORIDE-CONTAINING ELECTROLYTIC BATHS
US5162079A (en) 1991-01-28 1992-11-10 Eco-Tec Limited Process and apparatus for control of electroplating bath composition
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
US5417840A (en) * 1993-10-21 1995-05-23 Mcgean-Rohco, Inc. Alkaline zinc-nickel alloy plating baths
JP3348963B2 (en) * 1994-04-14 2002-11-20 ディップソール株式会社 Zinc-cobalt alloy alkaline plating bath and plating method using the plating bath
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

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3712511A1 (en) * 1986-04-14 1987-10-15 Dipsol Chem ELECTRIC PLATING BATH

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 0121, no. 17 (C-487), 13 April 1988 (1988-04-13) & JP 62 240788 A (DEITSUPUSOOLE KK), 21 October 1987 (1987-10-21) *
PATENT ABSTRACTS OF JAPAN vol. 0121, no. 81 (C-499), 27 May 1988 (1988-05-27) & JP 62 287092 A (DEITSUPUSOOLE KK), 12 December 1987 (1987-12-12) *
PATENT ABSTRACTS OF JAPAN vol. 0140, no. 80 (C-0689), 15 February 1990 (1990-02-15) & JP 1 298192 A (EBARA YUUJIRAITO KK), 1 December 1989 (1989-12-01) *
See also references of WO0196631A1 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2384800A1 (en) 2010-05-07 2011-11-09 Dr.Ing. Max Schlötter GmbH & Co. KG Regeneration of alkaline zinc electrolytes by removing cyanidiones
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
CN110325669A (en) * 2017-02-07 2019-10-11 马克斯·施洛特尔股份有限两合公司 Alkaline plating bath electrodepositing zinc and Zinc alloy coated method by the degradation reduction of organic bath additive
JP2019530800A (en) * 2017-02-07 2019-10-24 デーエル．−イーエヌゲー． エムアーイクス シュロッター ゲーエムベーハー ウント コー． カーゲー Method for galvanic deposition of zinc and zinc alloy coatings from alkaline coating baths with reduced degradation 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

Also Published As

Publication number Publication date
EP1292724B1 (en) 2005-10-12
DE60023190T2 (en) 2006-07-13
EP1292724A4 (en) 2004-09-08
EP1292724B2 (en) 2015-12-23
ES2250166T5 (en) 2016-05-20
DE60023190D1 (en) 2006-02-23
ATE306572T1 (en) 2005-10-15
WO2001096631A1 (en) 2001-12-20
DE60023190T3 (en) 2016-03-10
ES2250166T3 (en) 2006-04-16

Similar Documents

Publication Publication Date Title
EP1292724B1 (en) Zinc-nickel electroplating
US6755960B1 (en) Zinc-nickel electroplating
TWI636164B (en) Zinc alloy plating method
EP1639155B1 (en) Zinc and zinc-alloy electroplating
JP6582353B1 (en) Zinc or zinc alloy electroplating method and system
JP5830202B1 (en) Zinc alloy plating method
US5607570A (en) Electroplating solution
KR20100120160A (en) Pyrophosphate-based bath for plating on tin alloy layers
KR20070031442A (en) Tin-zinc alloy electroplating method
US8377283B2 (en) Zinc and zinc-alloy electroplating
US3131134A (en) Electroplating from an organic electrolytic solution
Ramesh Bapu et al. Studies on non-cyanide alkaline zinc electrolytes
JP5005849B2 (en) Alkaline zinc and zinc alloy plating bath
US3475290A (en) Bright gold plating solution and process
JP7442866B1 (en) Electroplating anodes and methods and systems for electroplating articles with metals
WO2024111515A1 (en) Anode for electroplating, and method and system for electroplating article with metal
JP2997072B2 (en) Zinc-nickel alloy plating bath and method for preventing black deposition on plating object
WO1999050479A1 (en) Electroplating solution
WO2013050258A2 (en) Selective hard gold deposition
Matsuoka et al. Electrodeposition of Iron--Chromium--Nickel Alloy
GB1564332A (en) Non-cyanide silver bath
JPH0471999B2 (en)

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20021216

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

RIN1 Information on inventor provided before grant (corrected)

Inventor name: ECKLES, WILLIAM, E.

Inventor name: FRISCHAUF, ROBERT, E.

A4 Supplementary search report drawn up and despatched

Effective date: 20040728

17Q First examination report despatched

Effective date: 20040914

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20051012

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20051012

Ref country code: LI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20051012

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20051012

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20051012

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20051012

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060112

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060112

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060112

REF Corresponds to:

Ref document number: 60023190

Country of ref document: DE

Date of ref document: 20060223

Kind code of ref document: P

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060313

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2250166

Country of ref document: ES

Kind code of ref document: T3

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060615

ET Fr: translation filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060630

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

26 Opposition filed

Opponent name: WALTER HILLEBRAND GMBH & CO. KG GALVANOTECHNIK

Effective date: 20060712

Opponent name: ATOTECH DEUTSCHLAND GMBH

Effective date: 20060712

PLAF Information modified related to communication of a notice of opposition and request to file observations + time limit

Free format text: ORIGINAL CODE: EPIDOSCOBS2

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060615

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20051012

PLBP Opposition withdrawn

Free format text: ORIGINAL CODE: 0009264

RDAF Communication despatched that patent is revoked

Free format text: ORIGINAL CODE: EPIDOSNREV1

APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO

APBM Appeal reference recorded

Free format text: ORIGINAL CODE: EPIDOSNREFNO

APBP Date of receipt of notice of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA2O

APAW Appeal reference deleted

Free format text: ORIGINAL CODE: EPIDOSDREFNO

APAY Date of receipt of notice of appeal deleted

Free format text: ORIGINAL CODE: EPIDOSDNOA2O

APBM Appeal reference recorded

Free format text: ORIGINAL CODE: EPIDOSNREFNO

APBP Date of receipt of notice of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA2O

APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO

APBQ Date of receipt of statement of grounds of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA3O

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: COVENTYA, INC.

APBU Appeal procedure closed

Free format text: ORIGINAL CODE: EPIDOSNNOA9O

PLAY Examination report in opposition despatched + time limit

Free format text: ORIGINAL CODE: EPIDOSNORE2

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

PLBC Reply to examination report in opposition received

Free format text: ORIGINAL CODE: EPIDOSNORE3

R26 Opposition filed (corrected)

Opponent name: ATOTECH DEUTSCHLAND GMBH

Effective date: 20060712

PLAY Examination report in opposition despatched + time limit

Free format text: ORIGINAL CODE: EPIDOSNORE2

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 16

PUAH Patent maintained in amended form

Free format text: ORIGINAL CODE: 0009272

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT MAINTAINED AS AMENDED

27A Patent maintained in amended form

Effective date: 20151223

AK Designated contracting states

Kind code of ref document: B2

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

REG Reference to a national code

Ref country code: DE

Ref legal event code: R102

Ref document number: 60023190

Country of ref document: DE

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 60023190

Country of ref document: DE

Representative=s name: WAGNER & GEYER PARTNERSCHAFT MBB PATENT- UND R, DE

REG Reference to a national code

Ref country code: ES

Ref legal event code: DC2A

Ref document number: 2250166

Country of ref document: ES

Kind code of ref document: T5

Effective date: 20160520

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 17

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

Free format text: REGISTERED BETWEEN 20161006 AND 20161012

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 18

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20190625

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20190627

Year of fee payment: 20

Ref country code: ES

Payment date: 20190701

Year of fee payment: 20

Ref country code: IT

Payment date: 20190726

Year of fee payment: 20

Ref country code: GB

Payment date: 20190627

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 60023190

Country of ref document: DE

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20200614

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20200614

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20200925

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20200616