EP1639155B1 - Galvanische abscheidung von zink und zinklegierungen - Google Patents

Galvanische abscheidung von zink und zinklegierungen Download PDF

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Publication number
EP1639155B1
EP1639155B1 EP03734340.7A EP03734340A EP1639155B1 EP 1639155 B1 EP1639155 B1 EP 1639155B1 EP 03734340 A EP03734340 A EP 03734340A EP 1639155 B1 EP1639155 B1 EP 1639155B1
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EP
European Patent Office
Prior art keywords
anode
anolyte
nickel
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.)
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EP03734340.7A
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English (en)
French (fr)
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EP1639155A1 (de
EP1639155A4 (de
Inventor
William E. Eckles
Robert E. Frischauf
Frederic Raulin
Lionel Thiery
Jean-Jacques Duprat
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Coventya SAS
Coventya Inc
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Coventya SAS
Coventya Inc
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/22—Electroplating: Baths therefor from solutions 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
    • 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 and zinc alloy electroplating.
  • US 5,162,079 A 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 electric 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. Accumulated acid is periodically flushed from the enclosure.
  • One purpose of the apparatus of the '079 patent is to inhibit the increase in concentration of dissolved metal in the electroplating bath due to a cathode efficiency which is less than anode efficiency.
  • US 4,778,572 A discloses an electroplating apparatus for plating nickel onto a workpiece.
  • a nickel-plating 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 in an ion exchange membrane that allows electric current to flow from the anodes to the cathode workpiece while at the same time shielding the anodes from organics, such as Coumarin within the bath.
  • the nickel plate anodes are immersed in dilute sulfuric acid contained within the ion exchange membrane enclosure.
  • DE 19834353A1 discloses an apparatus for applying a zinc-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 zinc-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 electric current to flow from the anode to the cathode, but at the same time shields the anode from the alkaline zinc-nickel electroplating bath.
  • WO 01/96631 A 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 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 is positioned in the bath.
  • An anode assembly is also positioned in the bath.
  • the anode assembly comprises an enclosure defining an anolyte compartment, at least a portion of the enclosure 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.
  • 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.
  • the present invention relates to an apparatus for applying a zinc or zinc-alloy electroplate to a workpiece, as set forth in claim 1. Preferred embodiments of the present invention may be gathered from the dependent claims.
  • the anode assembly can comprise an enclosure defining an anolyte compartment. At least a portion of the enclosure can be an ion exchange membrane.
  • the anolyte can be disposed in the compartment and the insoluble metal anode can be immersed in the anolyte.
  • the electroplating bath further comprises additional metal ions, which can be electroplated onto the workpiece with the zinc and iron ions.
  • the additional metal ions can include manganese ions, cobalt ions, and combinations thereof.
  • the additional metal ions can be free of nickel ions.
  • the additive can be potentially oxidizable to cyanide upon contact with the anode.
  • the anode can comprise any metal or metalloid that can serve as an anode in a caustic solution.
  • the anolyte can be a sodium or potassium hydroxide solution.
  • the present invention relates to an electroplating apparatus for applying a zinc-iron alloy electroplate to a workpiece.
  • zinc-alloy it is meant a mixture of zinc and iron optionally and at least one other metal, for example, cobalt-iron, and manganese. Other metals not listed in these examples can also be used.
  • the electroplating apparatus includes an alkaline, cyanide-free, zinc electroplating bath.
  • the electroplating apparatus of the present invention can inhibit the electrolytic breakdown of electroplating bath additives in the electroplating bath.
  • Fig. 1 illustrates an electroplating apparatus in accordance with one aspect of the invention.
  • the electroplating apparatus 12 comprises a tank 14.
  • the tank 14 contains the 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 can be closed by the enclosure 22 on all sides and the bottom.
  • At least one wall 26 of the enclosure 22 can be an ion exchange membrane.
  • the anolyte compartment 24 contains an anolyte 28.
  • An anode 30 can be immersed in the anolyte 28.
  • Fig. 1 shows that 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 can face the cathode workpiece 18. This allows electric 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 electric current flow causes plating of the cathode workpiece 18.
  • an enclosure 42 can comprise a pliable bag 44 that is suspended in a catholyte 46 of a tank 48. At least a portion of the bag 44 and, preferably, substantially all of the bag 44 comprises an ion exchange membrane 50.
  • a cathode workpiece 52 is disposed in the catholyte 46.
  • a metal anode 54 is disposed in the anolyte 56, which is contained within the bag 44.
  • an enclosure 60 can comprise a wall or partition 62 extending cross-wise in a tank 64 dividing the tank 64 into a catholyte compartment 66 and an anolyte compartment 68. At least a portion of the wall 62 and, preferably, substantially all of the wall comprises an ion exchange membrane 70.
  • a cathode workpiece 72 is disposed in the catholyte 74 and a metal anode 76 is disposed in the anolyte 78.
  • an enclosure 80 can comprise a cylindrical member 82.
  • the cylindrical member 82 can have a first end 84 and a second end 86.
  • the second end 86 can be positioned in a catholyte 88 contained within a tank 90. At least a portion of the second end 86, and preferably, substantially all of the second end 86 can comprise an ion exchange membrane 92.
  • the first end 84 can include an anolyte inlet 94 and anolyte outlet 96.
  • the anolyte inlet 94 and anolyte outlet 96 allow anolyte (not shown) to flow into the enclosure 80, about an anode 98 disposed in the enclosure 80, and out of the enclosure.
  • a cathode workpiece 100 is disposed in the catholyte 88.
  • the cathode workpiece can be any workpiece typically used in electroplating.
  • a steel plate can be used.
  • the enclosure of the anode assembly can be made of any suitable plastic resistant to the electroplating bath and the anolyte, for instance, polyethylene.
  • the ion exchange membrane of the enclosure can be any ion exchange membrane used in an electroplating bath, such as a perfluorosulfonic acid ion exchange membrane marketed by E.I. Dupont de Nemours under the trademark NAFION.
  • NAFION is a copolymer of tetrafluorethylene and perfluro-3,6-dioxa-4-methyl-7-octanesulfonic acid.
  • Preferred NAFION membranes used in accordance with the present invention include a NAFION 324 membrane or a NAFION 424 membrane.
  • ion exchange membranes that can also be used include membranes made from sulfonated styrene-divinylbenzene dispersed in a matrix of polyethylene and membranes made by the graft polymerization of the polyethylene and styrene followed by sulfonation.
  • the anolyte in the anolyte compartment can comprise a conductive salt or base solution, such as an aqueous solution of sodium sulfate or an alkaline solution of potassium hydroxide or sodium hydroxide.
  • a conductive salt or base solution such as 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 hydroxide.
  • a preferred anolyte can comprise about 50 g/liter sodium hydroxide to about 760 g/liter sodium hydroxide.
  • the anode of the anode assembly can comprise a metal or metalloid that is capable of functioning as an anode in an electroplating bath and that is stable in a caustic solution.
  • stable in a caustic solution it is meant that the anode does not decompose, deteriorate, or erode in a caustic solution.
  • metals that can be used include nickel, cobalt, iron, chromium, and alloys thereof, such as steel and ferrous alloys. Other metals or metalloids can also be used as long as they are capable of functioning as an anode and are stable in a caustic solution.
  • the anode can be a solid metal or metalloid or a metal coated on a substrate.
  • the anode can be nickel, a nickel alloy, or nickel 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 can be cobalt or cobalt coated onto a substrate, and alloys thereof.
  • the anode can also be a mild steel, a steel alloy, ferrous alloy, or an iron chromium alloy, such as stainless steel.
  • the material construction of the anode is not restricted.
  • either an electrolytic coating or an electroless coating can be effectively employed on the anode.
  • Practical considerations, such as cost and stability in a caustic solution will dictate the most suitable material for the anode.
  • the electroplating bath can be an aqueous solution that is alkaline, having a pH that is preferably about 14.
  • the bath contains an inorganic alkaline component in an amount effective to achieve this pH. Based on the electroplating bath of the alkaline component, amounts from about 50 g/liter to about 200 g/liter, can be used.
  • suitable alkaline components are alkali metal derivatives, such as sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
  • the electroplating bath can also contain a controlled amount of zinc ions.
  • the source for the zinc ions for the electroplating bath 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 zinc salt, such as zinc sulfate, zinc carbonate, zinc sulfamate, and zinc acetate.
  • the concentration of zinc ions in the electroplating bath can be from about 1 to 100 g/liter (about 1,000 ppm to about 100,000 ppm), preferably about 4 to about 50 g/liter (about 4,000 to about 50,000 ppm). At a pH about 14, the predominant zinc species in the bath is zincate ion.
  • the bath can further contain a controlled amount additional metal ions, which are not zinc or iron ions.
  • these additional metal ions can include any metal ion that can be effectively electroplated with the zinc ions onto the workpiece in an alkaline electroplating bath.
  • these metal ions can include transition metal ions, such as manganese ions, cobalt ions, and combinations thereof.
  • Other metal ions not listed, which can be electroplated with the zinc ions onto the workpiece in an alkaline electroplating bath can also be used and are within the scope of the present invention.
  • 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 inorganic and organic acid salts of nickel, such as nickel sulfate, nickel carbonate, nickel acetate, nickel sulfamate, and nickel formate.
  • the concentratipn of nickel ions in the electroplating bath can be from about 0.1 to about 10 g/liter (about 100 to 10,000 ppm), more preferably in the range from about 0.1 gram per liter to about 3 g/liter (about 100 ppm to about 3,000 ppm).
  • the additional metal ions can include any metal ion except that nickel ions cannot be used as the sole additional metal ions.
  • the electroplating bath can comprise, for example, a mixture of zinc ions and iron ions, a mixture of zinc ions, and iron ions, but not a mixture of zinc ions and nickel ions.
  • the source for these additional metal ions for the electroplating bath can be any suitable metal compound, which can be made soluble in an aqueous alkaline solution.
  • the concentration of metal ions in the electroplating bath can be from about 0.1 to about 10 g/liter (about 100 to 10,000 ppm), more preferably in the range from about 0.1 g/liter to about 3 g/liter (about 100 ppm to about 3,000 ppm).
  • the electroplating bath can also contain, in addition to the zinc and the additional metal ions, at least one additive commonly used in a zinc or zinc alloy electroplating bath that improves an aspect of the electroplating process.
  • aspects of the electroplating process that can be improved include the physical properties of the electroplate and the metal complexing properties of the bath.
  • the additive can be any type of additive, which is potentially capable of electrolytically breaking down at the anode (i.e., reacting at the anode) to produce a breakdown product (i.e., a reaction product), which would detrimentally affect the electroplating process.
  • a breakdown product i.e., a reaction product
  • These breakdown products can detrimentally affect the electroplating process by, for example, inhibiting the plating rates, producing a dull deposit, increasing the toxicity of the electroplating bath, precipitating from solution insoluble breakdown products.
  • the additives in accordance with the present invention can potentially electrolytically breakdown upon contact with an anode
  • the additives when used with the anode assembly of the present invention do not undergo electrolytic breakdown.
  • the anode assembly of the present invention inhibits electrolytic breakdown by minimizing contact of the additives with the anode.
  • One type of additive which is capable of potentially electrolytically breaking down at the anode, can comprise an amine.
  • Amines can potentially be oxidizable to cyanides upon contact with the anode.
  • Examples of amines that are oxidizable to cyanides include alphatic amines, such as ethyleneimine, 1,2-propyleneimine, 1,2-butyleneimine, and 1,1-dimethylethyleneimine as well as polyamines, such as poly(alkyleneimine).
  • 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 designation 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.
  • TEPA tetraethylenepentamine
  • PEHA pentaethylenehexamine
  • EPOMIN 003 heptaethylene octamine
  • Another type of additive which is capable of potentially electrolytically breaking down at the anode, is the reaction product of imidazole and an electrophylic difunctional monomer, such as epichlorohydrin. These polymers can break down to produce cyanide at levels of about 3 ppm. While this is not a very high amount of cyanide, the cost of treatment of the electroplating bath can increase many times because of the presence of cyanide even at trace levels.
  • polyquaternium-2 Yet another type of additive, which is capable of potentially electrolytically breaking down at the anode, is polyquaternium-2.
  • Polyquaternium-2 upon contact with the anode can breakdown causing slow plating rates and dull deposits. In certain cases, these effects become so severe that the bath must be dumped after as little as six months.
  • Still yet another type of additive which is capable of potentially electrolytically breaking down at the anode, is a chelating agent, such as gluconate or tartrate. These additives can be oxidized at the anode to produce oxalate, in accordance with the present invention.
  • the electroplating bath may also contain other additives such as other brighteners, and metal complexing agents, which may or may not electrolytically breakdown upon contact with the anode.
  • metal complexing agent is QUADROL from BASF. QUADROL is N,N,N',N'-tetrakis(2-hydroxypropyl)-ethylenediamine.
  • An alkaline zinc-nickel bath contained 10 g/liter of zinc, 1.5 g/liter of nickel, 20 g/liter of tetraethylenepentamine (TEPA) and 10 g/liter QUADROL.
  • An anode box (disclosed in Figure 1 ) having a NAFION 450 membrane on one side, containing 500 mL of a solution of 150 g of sodium hydroxide was placed in a 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 amperes of current were passed through the 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.
  • the anode box was filled with a solution of 150 g/liter of sodium hydroxide in water.
  • the metal anode in the box was made of nickel metal.
  • a 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 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 that contained 8%P.
  • the bath was analyzed for cyanide and was found to contain no detectable cyanide. There was no metal anode weight loss.
  • a 2-liter alkaline zinc-nickel plating bath containing 30 g/liter of 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 filled with a solution of 150 g/liter of potassium hydroxide.
  • the metal anode in the anolyte was 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 150 g/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 ampere-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.
  • the metal anode in the anode box 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 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 alkaline non-cyanide zinc plating bath was prepared containing 10 g/liter of zinc, 130 g/liter of sodium hydroxide, 8 ml/liter of a brightener and about 5 g/liter of sodium tartrate. After extended periods of electrolysis, a white precipitate formed in the plating bath. This precipitate was sodium oxalate, produced by anodic oxidation. The precipitated oxalate interfered with the brighteners, causing dull and rough zinc plate.
  • the anodic oxidation of the TEA produced breakdown products, which interfered with waste treatment.
  • Two test cells containing alkaline zinc-nickel plating baths were electrolyzed for 40 ampere-hours.
  • One cell had a nickel anode without an anode enclosure and the other cell had an anode enclosure containing a nickel anode.
  • the electrolyte in each cell was composed of 10 g/liter of zinc, 1,500 ppm of nickel, 25 g/liter of tetraethylenepentamine, and a brightener.
  • the membrane anode enclosure contained 1 liter of a 25% solution of 50% liquid caustic in water.
  • the cell with the direct anode was plating with 6.5% lower efficiency than the cell with the membrane enclosed anode. After two months of continuous operation, the cell with the direct anode was plating with about 40% lower efficiency than the cell with the membrane enclosed anode.
  • An alkaline zinc plating bath containing 10 g/liter of zinc, 130 g/liter of sodium hydroxide and maintained with 2 g/liter of Mirapol WT, was operated until the anodic breakdown products from the anodic oxidation of the Mirapol reduced the cathodic efficiency by about 50% of the initial level of efficiency, which took about 1 year.
  • Using membrane enclosed anodes eliminates this decrease in cathodic efficiency, because the Mirapol WT is prevented from undergoing anodic oxidation.
  • an apparatus and process are provided by which zinc and a zinc-alloy can be safely plated onto a substrate using an electroplating bath containing an additive, especially poly(alkyleneimines). This is accomplished without anode corrosion or generating cyanides in the electroplating bath.
  • a commercial apparatus and process will employ a electroplating bath comprising additives in addition to additives described in above.
  • a commercial bath typically can employ a 4000 liter tank and the cathode workpiece can be positioned between arrays of compartmentalized anodes on opposite sides of the cathode along the sides of the tank.

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Claims (7)

  1. Vorrichtung (12) zum Aufbringen eines galvanischen Überzugs aus einer Zink-Eisen-Legierung auf ein Werkstück, wobei die Vorrichtung Folgendes aufweist:
    ein Galvanisierbad (16) mit einem pH-Wert von mehr als ungefähr 14, wobei das Galvanisierbad (16) Zink-Ionen und einen Zusatzstoff aufweist;
    ein Kathoden-Werkstück (18) in dem Bad (16);
    eine Anodenanordnung (20), die das Bad (16) kontaktiert, wobei die Anodenanordnung (20) einen Anolyt (28) und eine unlösliche Metall-Anode (30) in dem Anolyt (28) aufweist;
    wobei der Zusatzstoff imstande ist, elektrolytisch beim Kontakt mit der Anode (30) zu zerfallen;
    wobei die Anodenanordnung (20) den elektrolytischen Zerfall des Zusatzstoffs inhibiert;
    dadurch gekennzeichnet, dass
    das Galvanisierbad (16) ein Nicht-Zyanid-Galvanisierbad (16) ist, das ferner einen Glanzbildner bzw. Aufheller aufweist,
    wobei der Zusatzstoff ein Komplex- bzw. Chelatbildner ist, der imstande ist, beim Kontakt mit der Anode (30) zu zerfallen, um ein Oxalat zu bilden,
    wobei das Galvanisierbad (16) ferner zusätzliche Eisen-Ionen aufweist, die auf das Werkstück mit den Zink-Ionen galvanisiert werden können, und die zusätzlichen Metallionen frei von Nickel-Ionen sind.
  2. Vorrichtung gemäß Anspruch 1, wobei die Anodenanordnung (20) eine Einfassung (22) aufweist, die eine Anolytkammer (24) definiert, wobei zumindest ein Teil der Einfassung (22) eine Ionenaustauschmembran (26) ist, wobei der Anolyt (28) in der Anolytkammer (24) angeordnet ist und die unlösliche Metall-Anode (30) in den Anolyt (28) eingetaucht ist.
  3. Vorrichtung gemäß Anspruch 2, wobei die Einfassung (42) einen Beutel (44) aufweist, wobei der Beutel (44) in dem Galvanisierbad (46) angeordnet ist, wobei zumindest ein Teil des Beutels (44) eine Ionenaustauschmembran (50) ist.
  4. Vorrichtung gemäß Anspruch 2, wobei die Einfassung (60) eine Wand (62) aufweist, wobei die Wand (62) einen Behälter (64) in eine erste Kammer (66) und eine zweite Kammer (68) unterteilt, wobei zumindest ein Teil der Wand (62) eine Ionenaustauschmembran (70) ist.
  5. Vorrichtung gemäß Anspruch 2, wobei die Einfassung (80) ein Glied (82) aufweist, wobei das Glied (82) ein erstes Ende (84) und ein zweites Ende (86) aufweist, wobei das zweite Ende (86) in dem Galvanisierbad (88) ange-ordnet ist, wobei das erste Ende (84) einen Anolyteinlass (94) und einen Anolytauslass (96) aufweist, wobei es der Anolyteinlass (94) und der Anolytauslass (96) einem Anolyt ermöglichen, durch die Einfassung (80) zu fließen.
  6. Vorrichtung gemäß einem der vorangehenden Ansprüche, wobei die Anode (30) Folgendes aufweist: Nickel, eine Nickel-Legierung, eine Nickel-Beschichtung, eine Nickel-Legierungsbeschichtung, Kobalt, eine KobaltLegierung, eine Kobalt-Legierungsbeschichtung, unlegierten Stahl, eine Stahl-Legierung, eine Eisen-Legierung, und
    der Anolyt (28) eine Natrium- oder Kaliumhydroxidlösung ist, die 50 bis ungefähr 760 Gramm pro Liter Natrium oder Kaliumhydroxid aufweist.
  7. Vorrichtung gemäß einem der vorangehenden Ansprüche,
    wobei der Anolyt (28) eine leitende Salz- oder Basenlösung ist, und
    der Zusatzstoff ein Gluconat oder Tartrat ist, das imstande ist, beim Kontakt mit der Anode (30) elektrolytisch zu zerfallen, um ein Oxalat zu bilden.
EP03734340.7A 2003-06-03 2003-06-03 Galvanische abscheidung von zink und zinklegierungen Expired - Lifetime EP1639155B1 (de)

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EP1712660A1 (de) 2005-04-12 2006-10-18 Enthone Inc. Unlösliche Anode
ATE429528T1 (de) 2005-04-26 2009-05-15 Atotech Deutschland Gmbh Alkalisches galvanikbad mit einer filtrationsmembran
DE102005051632B4 (de) 2005-10-28 2009-02-19 Enthone Inc., West Haven Verfahren zum Beizen von nicht leitenden Substratoberflächen und zur Metallisierung von Kunststoffoberflächen
DE102007002321B4 (de) * 2007-01-16 2018-07-05 Volkswagen Ag Schraubenfeder mit Korrosionsschutz
DE102010044551A1 (de) * 2010-09-07 2012-03-08 Coventya Gmbh Anode sowie deren Verwendung in einem alkalischen Galvanikbad
DE202015002289U1 (de) 2015-03-25 2015-05-06 Hartmut Trenkner Zweikammer - Elektrodialysezelle mit Anionen- und Kationenaustauschermembran zur Verwendung als Anode in alkalischen Zink- und Zinklegierungselektrolyten zum Zweck der Metallabscheidung in galvanischen Anlagen
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JP7256042B2 (ja) * 2019-03-20 2023-04-11 株式会社ユアサメンブレンシステム 隔膜部材
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EP1639155A1 (de) 2006-03-29
BR0318331A (pt) 2006-07-11
EP1639155A4 (de) 2007-04-25

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