EP3415665B1 - Procédé de dépôt galvanique de revêtements d'alliage zinc/nicel à partir d'un bain d'alliage nickel/zinc à élimination réduite des additifs - Google Patents

Procédé de dépôt galvanique de revêtements d'alliage zinc/nicel à partir d'un bain d'alliage nickel/zinc à élimination réduite des additifs Download PDF

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Publication number
EP3415665B1
EP3415665B1 EP17175993.9A EP17175993A EP3415665B1 EP 3415665 B1 EP3415665 B1 EP 3415665B1 EP 17175993 A EP17175993 A EP 17175993A EP 3415665 B1 EP3415665 B1 EP 3415665B1
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EP
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Prior art keywords
zinc
bath
nickel
nickel alloy
chloride
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EP17175993.9A
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German (de)
English (en)
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EP3415665A1 (fr
Inventor
Michael Zöllinger
Oliver Daub
Ralph Krauß
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Dr Ing Max Schloetter GmbH and Co KG
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Dr Ing Max Schloetter GmbH and Co KG
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Priority to DK17175993.9T priority Critical patent/DK3415665T3/da
Priority to ES17175993T priority patent/ES2969188T3/es
Priority to FIEP17175993.9T priority patent/FI3415665T3/fi
Priority to EP17175993.9A priority patent/EP3415665B1/fr
Priority to SI201731476T priority patent/SI3415665T1/sl
Application filed by Dr Ing Max Schloetter GmbH and Co KG filed Critical Dr Ing Max Schloetter GmbH and Co KG
Priority to PT171759939T priority patent/PT3415665T/pt
Priority to PL17175993.9T priority patent/PL3415665T3/pl
Publication of EP3415665A1 publication Critical patent/EP3415665A1/fr
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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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
    • 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
    • C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt

Definitions

  • the iron materials to be coated are not particularly limited, but component materials made of steel, hardened steel, forged cast iron or die-cast zinc are particularly suitable.
  • Such an alkaline zinc-nickel alloy bath for the galvanic deposition of zinc-nickel alloy coatings also contains, in addition to the zinc-nickel alloy electrolyte, organic bath additives such as complexing agents, brightening agents and wetting agents.
  • the anodic oxidation of the organic bath additives can also form undesirable by-products that can have a disruptive effect on the galvanic coating process. This mainly results in an increased formation of cyanides. This is primarily due to the undesirable anodic oxidation of amine-containing additives, in particular of amine-containing complexing agents. These are usually used to dissolve the nickel used. Since this is basically present as a salt in the form of Ni(II), which forms the poorly soluble nickel hydroxide complex with the surrounding hydroxide ions, special complexing agents must be used with which Ni(II) forms a complex more preferably than with the corresponding hydroxide ions. Amine compounds such as triethanolamine, ethylenediamine, diethylenetetramine or homologous compounds of ethylenediamine, such as diethylenetriamine, tetraethylenepentamine, etc. are preferably used.
  • values of up to 1000 mg/l cyanide can occur until an equilibrium between new formation and carry-out is achieved.
  • the formation of cyanides is disadvantageous for several reasons.
  • cyanide concentration of, for example, 350 mg/l in a commercially available alkaline zinc-nickel alloy bath (zinc-nickel alloy bath SLOTOLOY ZN 80, Schlötter) are shown in the following examples in the table below.
  • the accumulation of cyanide in an alkaline zinc-nickel alloy bath can also have a negative effect on the visual appearance of the deposit.
  • a milky, hazy deposition can occur. This can be partially corrected by using higher dosages of shine formers. However, this measure is associated with increased consumption of brighteners and therefore additional costs during deposition.
  • EP 1 344 850 B1 a method is claimed in which the cathode compartment and the anode compartment are separated by an ion exchange membrane. This prevents the complexing agents from reaching the anode from the cathode compartment. This prevents cyanide formation.
  • a platinum-coated titanium anode is used as the anode.
  • the anolyte is acidic and contains sulfuric acid, phosphoric acid, methanesulfonic acid, amidosulfonic acid and/or phosphonic acid.
  • a similar procedure is used in EP 1 292 724 B1 described.
  • the cathode and anode compartments are also separated by an ion exchange membrane.
  • a sodium or potassium hydroxide solution is used as anolyte.
  • a metal or a metal coating is selected from the group consisting of nickel, cobalt, iron, chromium or alloys thereof.
  • EP 1 702 090 B1 claims a process which provides for the separation of the cathode and anode compartments using an open-pored material.
  • the separator is made of polytetrafluoroethylene or polyolefin, such as polypropylene or polyethylene.
  • the pore diameters have a dimension between 10 nm and 50 pm.
  • charge transport through the membrane occurs through the exchange of cations or anions
  • open-pore separators when using open-pore separators it can only occur through electrolyte transport through the separator.
  • a complete separation of the catholyte from the anolyte is not possible. It cannot therefore be completely prevented that amines reach the anode and are oxidized there. Cyanide formation cannot therefore be completely ruled out with this process.
  • the electrolyte temperature should be kept constant in the range of +/- 2°C in order to deposit a constant alloy composition, the electrolyte must be subjected to considerable heat when a higher bath voltage is applied Effort to be cooled.
  • the separator can also have a pore diameter of 50 pm, which may prevent the formation of overvoltage, the relatively large pore diameter in turn allows an almost unhindered exchange of electrolyte between the cathode and anode space and therefore cannot prevent the formation of cyanides.
  • the anode and cathode space is separated there by a filtration membrane.
  • the size of the pores of the filtration membrane is in the range from 0.1 to 300 nm. A certain transfer of electrolyte from the cathode to the anode space is consciously accepted.
  • CN 1 580 325 A corrosion-resistant coatings of magnesium and magnesium alloys, wherein the magnesium-containing substrate comprises a nickel layer on the bottom and a zinc-nickel layer on the top.
  • the JP H07 41964 A deals with the treatment of surfaces of aluminum substrates, which is intended to prevent the aluminum from dissolving in phosphate-containing media.
  • Various alloys containing zinc and nickel are taught as protective coatings.
  • the US 5,417,840 A describes an aqueous alkaline plating bath for electrodepositing a zinc-nickel alloy coating on a substrate.
  • the plating bath generally includes (A) zinc ions; (B) nickel ions; and (C) at least one heterocyclic compound.
  • the object of the present invention is to provide a method for the galvanic deposition of zinc-nickel alloy coatings from an alkaline zinc-nickel alloy bath with a zinc-nickel alloy electrolyte and organic bath additives a reduced degradation of the bath additives, especially the amine-containing additives, as well as a reduced formation of degradation products, especially cyanides.
  • the process according to the invention for the galvanic deposition of zinc-nickel alloy coatings is intended to allow significantly more economical operation compared to conventional processes.
  • the task defined above is achieved by providing a process for the galvanic deposition of zinc-nickel alloy coatings from an alkaline zinc-nickel alloy bath with a zinc-nickel alloy electrolyte in the form of zinc and nickel ions and organic bath additives, in which a zinc -Nickel alloy bath with 80 - 180 g/l NaOH and/or KOH, 5 - 15 g/l zinc, 0.6 - 4 g/l nickel and 5 - 50 g/l chloride and/or bromide is used, and the anodic current density is set to a value in the range of 5 - 30 A/dm 2 .
  • halides such as chloride and/or bromide
  • the alkaline zinc-nickel alloy bath has a very positive effect on reducing the degradation of the bath additives contained in the zinc-nickel alloy bath, in particular the amine-containing additives , which at the same time results in a significantly reduced formation of degradation products, especially cyanide.
  • the zinc-nickel alloy bath with the zinc-nickel alloy electrolyte and organic bath additives is alkaline.
  • NaOH and/or KOH is used to adjust the pH value.
  • Amounts required are generally 80 - 180 g/l NaOH and/or KOH, preferably 85 - 160 g/l NaOH and/or KOH and particularly preferably 90 - 140 g/l NaOH and/or KOH.
  • the zinc-nickel alloy bath is preferably strongly alkaline and has a pH of at least 13 or more.
  • the zinc-nickel alloy bath used in the process according to the invention also contains a zinc-nickel alloy electrolyte in the form of zinc and nickel ions.
  • the zinc ion concentration is in the range of 5 - 15 g/l, preferably 6 - 10 g/l, calculated as zinc, and the nickel ion concentration is in the range of 0.6 - 4 g/l, preferably 0.6 - 2 g/l. l, calculated as nickel.
  • the zinc- and nickel-containing raw materials used for producing the zinc-nickel alloy electrolyte are not specifically limited.
  • the zinc content in the zinc-nickel alloy electrolyte can be adjusted or supplemented by metallic zinc, which is dissolved in a strong alkaline solution in a separate zinc dissolving container and replenished to the extent that the zinc is consumed during deposition.
  • metallic zinc which is dissolved in a strong alkaline solution in a separate zinc dissolving container and replenished to the extent that the zinc is consumed during deposition.
  • nickel-containing starting materials that can be used are nickel sulfate, nickel chloride, nickel bromide, nickel sulfamate, nickel methanesulfonate or combinations thereof. The use of nickel sulfate, nickel chloride and/or nickel bromide is preferred.
  • the alkaline zinc-nickel alloy bath used in the process according to the invention contains organic bath additives, such as complexing agents, brightening agents, wetting agents, etc.
  • a specific anodic current density is set. This is in the range of 5 - 30 A/dm 2 , preferably in the range of 10 - 20 A/dm 2 and particularly preferably 15 A/dm 2 . If the value falls below 5 A/dm 2 , no significant effect can be observed with regard to the maintenance of the bath additives, in particular the amine-containing additives, and in the course of this a reduction in the degradation products, in particular the formation of cyanide. If the value of 30 A/dm 2 is exceeded, undesirable side reactions can occur and the anode is increasingly attacked, ie material from the anode is increasingly removed. In addition, there are economic and technical limits to further increasing the anodic current density in the sense that stronger rectifiers, larger cable cross-sections and stronger cooling are required.
  • a zinc-nickel alloy coating is preferably deposited from a zinc-nickel alloy bath with zinc-nickel alloy electrolytes and organic bath additives, which contains 85 - 160 g / l NaOH and / or KOH and 10 - 30 g / l chloride contains, and in which the anodic current density is set to a value in the range of 10 - 20 A/dm 2 .
  • the deposition is even more preferably carried out from a zinc-nickel alloy bath with zinc-nickel alloy electrolytes and organic bath additives, which contains 90 - 140 g/l NaOH and/or KOH and 20 g/l chloride, and in which the anodic current density is set to 15 A/dm 2 is set.
  • the anodes used in the alkaline zinc-nickel alloy bath are not specifically limited, and any known anodes suitable in an electroplating process for depositing a zinc-nickel alloy coating from an alkaline zinc-nickel alloy bath may be used, provided they are electrically conductive and at least inert towards bases.
  • materials made of steel, stainless steel, nickel-plated steel, solid nickel material, iron, cobalt or alloys of these metals can be used as anode.
  • steel, stainless steel, nickel-plated steel or solid nickel material are particularly preferred.
  • the substrate connected as a cathode in the method of the present invention is not specifically limited, and any known materials suitable for use as a cathode in an electroplating process for depositing a zinc-nickel alloy coating from an alkaline zinc-nickel alloy bath can be used .
  • substrates made of steel, hardened steel, forged cast iron or zinc die cast, for example can therefore be used as cathodes.
  • the method according to the invention does not require that the anode and cathode compartments be separated from one another by membranes and/or separators.
  • the zinc-nickel alloy bath used in the process according to the invention contains 5 - 50 g / l chloride and / or bromide, preferably 10 - 30 g / l chloride and / or bromide and particularly preferably 15 - 25 g / l Chloride and/or bromide.
  • the chloride and/or bromide is in the form of a salt.
  • the type of chloride and/or bromide compounds is not particularly limited.
  • the chloride and/or bromide can be used as sodium, nickel, zinc or potassium chloride and/or as sodium, nickel, zinc or potassium bromide.
  • Chloride is preferably used.
  • the chloride is particularly preferably used in the form of sodium and/or potassium chloride.
  • the zinc-nickel alloy bath is alkaline. NaOH and/or KOH is used to adjust the pH value. Amounts required are generally 80 - 180 g/l NaOH and/or KOH, preferably 85 - 160 g/l NaOH and/or KOH and particularly preferably 90 - 140 g/l NaOH and/or KOH.
  • the zinc-nickel alloy bath is preferably strongly basic and has a pH of at least 13 or more.
  • the alkaline zinc-nickel alloy bath also contains a zinc-nickel alloy electrolyte in the form of zinc and nickel ions.
  • the zinc ion concentration is in the range of 5 - 15 g/l, preferably 6 - 10 g/l, calculated as zinc, and the nickel ion concentration is in the range of 0.6 - 4 g/l, preferably 0.6 - 2 g/l. l, calculated as nickel.
  • the zinc- and nickel-containing raw materials used for producing the zinc-nickel alloy electrolyte are not specifically limited.
  • metallic zinc sodium tetrahydroxozincate, potassium tetrahydroxozincate and/or zinc oxide is preferred.
  • metallic zinc the amphoteric behavior of this metal is exploited, which chemically dissolves in a strongly alkaline solution to form Zn(II).
  • the zinc content in the zinc-nickel alloy electrolyte can be adjusted or supplemented by metallic zinc, which is dissolved in a strong alkaline solution in a separate zinc dissolving container and replenished to the extent that the zinc is consumed during deposition.
  • nickel-containing starting materials examples include nickel sulfate, nickel chloride, nickel bromide, nickel sulfamate, nickel methanesulfonate or combinations thereof.
  • nickel sulfate, nickel chloride and/or nickel bromide is preferred.
  • the alkaline zinc-nickel alloy bath also contains organic bath additives, such as amine-containing complexing agents, brightening agents, wetting agents, etc.
  • the complexing agents are not specifically limited, and any known amine-containing complexing agents such as triethanolamine, ethylenediamine, tetrahydroxopropylethylenediamine (Lutron Q 75), diethylenetetramine or homologous compounds of ethylenediamine such as diethylenetriamine, tetraethylenepentamine, etc. can be used.
  • the complexing agent and/or mixtures of these complexing agents are/are usually used in a concentration in the range of 5 - 100 g/l, preferably in the range of 10 - 70 g/l, particularly preferably in the range of 15 - 60 g/l.
  • Aromatic or heteroaromatic compounds such as benzylpyridinium carboxylate or pyridinium-N-propane-3-sulfonic acid (PPS), are preferably used as shine formers.
  • the comparison basic bath batch 1 (2 liters) (hereinafter defined as “comparison bath 1”) had the following composition: Zn: 7.5 g/l as ZnO Ni: 0.8 g/l as NiCl 2 x 6 H 2 O ( ⁇ 0.24 g/l chloride) KOH: 160g/l SLOTOLOY ZN 81: 40 ml/l (complexing agent mixture) SLOTOLOY ZN 82: 75 ml/l (complexing agent mixture) SLOTOLOY ZN 87: 2.5 ml/l (basic shine additive) SLOTOLOY ZN 83: 2.5 ml/l (basic shine additive) SLOTOLOY ZN 86: 1.0 ml/l (high-gloss agent)
  • the above-mentioned basic bath batch contains: 10.0 g/l DETA (diethylene triamine), 9.4 g/l TEA (85 wt.% triethanolamine), 40.0 g/l Lutron Q 75 (BASF; 75 wt.% tetrahydroxopropylethylenediamine) and 370 mg/l PPS (1-(3-sulfopropyl)-pyridinium betaine.
  • the basic bath batch 1 (2 liters) according to the invention (hereinafter defined as “5-Cl-KOH bath”) had exactly the same composition as the comparison basic bath batch 1, with the only difference that an additional 5.0 g/l chloride was added Form of KCl (10.5 g/l) is contained in the bath.
  • the bath temperature was set to 35°C.
  • the stirring motion during the current yield sheet coating and the load coating was 250 to 300 rpm.
  • the current densities at the anode and cathode were kept constant.
  • Cathode material sheet steel made from cold strip steel in accordance with DIN EN 10139/10140 (quality: DC03 LC MA RL).
  • V4A stainless steel with material number 14571 (composition: C 0.08%; Si 1.0%; Mn 2.0%; P 0.045%; S 0.015%, Cr 16.5-18.5%; Mo 2 .0-2.5%; Ni 10.5-13.5%; Ti 5xC ⁇ 0.70%); commercially available; V2A stainless steel with the material number 14301, (composition: C 0.07%; Si 1.0%; Mn 2.0%; P 0.045%; S 0.015%, Cr 17.0-19.5%; Ni 8.0 -10.5%; N 0.11%); commercially available.
  • the amount of zinc-nickel alloy deposited on the deposition plate was determined by weighing.
  • the total amount of metal missing due to the deposition in the zinc-nickel alloy bath was converted to 85% by weight of zinc and 15% by weight of nickel (for example, for a total amount of metal deposited of 1.0 g of zinc-nickel alloy layer, there are 850 mg of zinc and 150 mg of nickel been dosed).
  • SLOTOLOY ZN 85 CL contains nickel chloride, as well as the amines triethanolamine, diethylene triamine and Lutron Q 75 (1 ml SLOTOLOY ZN 85 CL contains 63 mg nickel).
  • the KOH content was determined after 10 Ah/l by acid-base titration and adjusted to 160 g/l.
  • Comparison bath 1 // 0.24 to 5.0 g/l chloride by adding NiCl 2 anode Chloride content at start Cyanide content at start-up Chloride content after 50 Ah/l Cyanide content after 50 Ah/l V4A (1.4571) 0.24g/l 0 mg/l 5.0g/l 60 mg/l V2A (1.4301) 0.24g/l 0 mg/l 5.0g/l 55 mg/l 5-Cl-KOH bath // 5.0 to 10.0 g/l chloride by adding NiCl 2 anode Chloride content at start Cyanide content at start-up Chloride content after 50 Ah/l Cyanide content after 50 Ah/l V4A (1.4571) 5.0g/l 0 mg/l 10.0g/l 35 mg/l V2A (1.4301) 5.0g/l
  • Zinc-nickel alloy baths are Zinc-nickel alloy baths:
  • the above-mentioned basic bath batch contains: 10.0 g/l DETA (diethylene triamine), 9.4 g/l TEA (85 wt.% triethanolamine), 40.0 g/l Lutron Q 75 (BASF; 75 wt.% tetrahydroxopropylethylenediamine) and 370 mg/l PPS (1-(3-sulfopropyl)-pyridinium betaine).
  • the basic bath batch 4 (2 liters) according to the invention (hereinafter defined as “20-Cl-NaOH bath”) had exactly the same composition as the comparison basic bath batch 2, with the only difference that an additional 20 g/l chloride in the form of NaCl (33 g/l) is contained in the bath.
  • the bath temperature was set to 35°C.
  • the stirring motion during the current yield sheet coating and the load coating was 250 to 300 rpm.
  • the current densities at the anode and cathode were kept constant.
  • Anode material Bright nickel-plated steel; Steel (material number 1.0330) with a layer thickness of 30 pm Bright nickel (coated with SLOTONIK 20 electrolyte from Schlötter); Production: See JN Unruh, Galvanotechnik table book, 7th edition, EUGEN G. LEUZE Verlag, Bad Saulgau, p.515 ).
  • the amount of zinc-nickel alloy deposited on the deposition plate was determined by weighing.
  • the total amount of metal missing due to the deposition in the zinc-nickel alloy bath was converted to 85% by weight of zinc and 15% by weight of nickel (for example, for a total amount of metal deposited of 1.0 g of zinc-nickel alloy layer, there are 850 mg of zinc and 150 mg of nickel been dosed).
  • SLOTOLOY ZN 85 contains nickel sulfate as well as the amines triethanolamine, diethylene triamine and Lutron Q 75 (1 ml SLOTOLOY ZN 85 contains 63 mg nickel).
  • the chloride consumed in the zinc-nickel alloy baths 2-4 according to the invention was analyzed by argentometric determination and kept constant by appropriate additions using NaCl.
  • the NaOH content was determined after 10 Ah/l by acid-base titration and adjusted to 120 g/l.
  • the cyanide was determined using the LCK 319 cuvette test for easily released cyanides from Dr. Lange (today the Hach company). Easily released cyanides are converted into gaseous HCN through a reaction and transferred through a membrane into an indicator cuvette. The color change of the indicator is then evaluated photometrically.
  • Table 4 shows that an additional addition of chloride reduces the formation of cyanide using the same anode material (bright nickel-plated steel) by approximately 30 - 46% lower than without additional chloride (see baths according to the invention 5-Cl-NaOH bath, 10- Cl-NaOH bath and 20-Cl-NaOH bath compared to comparison bath 2).
  • Table 4 also shows that the chloride concentration has an influence on the cyanide content formed. The higher the chloride content, the lower the cyanide concentration.
  • the anodic oxidation of the amine diethylenetriamine (DETA) is inhibited in the presence of 5-20 g/l chloride.
  • Test Example 2.2 was carried out under the same conditions as described in Test Example 2.1.
  • the deposition of the zinc-nickel electrolyte was checked using a Hull cell test according to DIN 50957.
  • the electrolyte temperature was set at 35°C.
  • a 250 ml Hull cell was used.
  • Cold strip steel DIN EN 10139/10140 (quality: DC03 LC MA RL) was used as the cathode sheet.
  • the cell current was 2 A and the coating time was 15 minutes.
  • Scheme 1 shows the result of the test sheet that was coated in comparison bath 2 (without chloride).
  • Scheme 2 shows the result of the test sheet, which was coated with the bath according to the invention (10-Cl-NaOH bath), which contains 10 g/l chloride.
  • the Hull cell sheet which was coated in the 10-Cl-NaOH bath according to the invention (with 10 g / l chloride) (see scheme 2), shows after 100 Ah / l load a uniformly semi-glossy to shiny appearance over the entire current density range, which is a Measurement of the remaining and undestroyed amine-containing bathroom additives.
  • Zinc-nickel alloy baths are Zinc-nickel alloy baths:
  • comparative base bath 1 The same comparative base bath batch 1 (2 liters) as described in Test Example 1 was used (hereinafter defined as "comparison bath 1").
  • the bath temperature was set to 35°C.
  • the stirring motion during the current yield sheet coating and the load coating was 250 to 300 rpm.
  • the current densities at the anode and cathode were kept constant.
  • Cathode material sheet steel made from cold strip steel in accordance with DIN EN 10139/10140 (quality: DC03 LC MA RL).
  • SLOTOLOY ZN 85 CL contains nickel chloride, as well as the amines triethanolamine, diethylene triamine and Lutron Q 75 (1 ml SLOTOLOY ZN 85 CL contains 63 mg nickel).
  • the KOH content was determined after 10 Ah/l by acid-base titration and adjusted to 160 g/l.
  • the cyanide was determined using the LCK 319 cuvette test for easily released cyanides from Dr. Lange (today the Hach company). Easily released cyanides are converted into gaseous HCN through a reaction and transferred through a membrane into an indicator cuvette. The color change of the indicator is then evaluated photometrically.
  • Zinc-nickel alloy baths are Zinc-nickel alloy baths:
  • comparison bath 2 The same comparison base bath batch 2 (2 liters) as described in test example 2.1 was used (hereinafter defined as “comparison bath 2”).
  • the basic bath batch 7 (2 liters) according to the invention (hereinafter defined as “20-Br-NaOH bath”) had exactly the same composition as the comparison basic bath batch 2, with the only difference that an additional 20 g/l bromide in the form of NaBr (25.8 g/l) is contained in the bath.
  • the bath temperature was set to 35°C.
  • the stirring motion during the current yield sheet coating and the load coating was 250 to 300 rpm.
  • the current densities at the anode and cathode were kept constant.
  • Cathode material sheet steel made from cold strip steel in accordance with DIN EN 10139/10140 (quality: DC03 LC MA RL).
  • Anode material Bright nickel-plated steel; Steel (material number 1.0330) with a layer of 30 pm bright nickel (coated with SLOTONIK 20 electrolyte from Schlötter); Production: See JN Unruh, Galvanotechnik table book, 7th edition, EUGEN G. LEUZE Verlag, Bad Saulgau, p.515 ).
  • SLOTOLOY ZN 85 contains nickel sulfate as well as the amines triethanolamine, diethylene triamine and Lutron Q 75 (1 ml SLOTOLOY ZN 85 contains 63 mg nickel).
  • the cyanide was determined using the LCK 319 cuvette test for easily released cyanides from Dr. Lange (today the Hach company). Easily released cyanides are converted into gaseous HCN through a reaction and transferred through a membrane into an indicator cuvette. The color change of the indicator is then evaluated photometrically.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Claims (7)

  1. Procédé de séparation électrolytique de couches d'alliage zinc-nickel d'un bain alcalin d'alliage zinc-nickel avec un électrolyte d'alliage zinc-nickel sous forme d'ions de zinc et de nickel et d'additifs de bain organiques,
    dans lequel on utilise un bain d'alliage zinc-nickel contenant 80 à 180 g/l de NaOH et/ou de KOH, 5 à 15 g/l de zinc et 0,6 à 4 g/l de nickel, caractérisé en ce que,
    le bain d'alliage contient 5 à 50 g/l de chlorure et/ou de bromure, et
    la densité de courant anodique est ajustée à une valeur comprise entre 5 et 30 A/dm2.
  2. Procédé selon la revendication 1, dans lequel le bain d'alliage zinc-nickel contient 10 à 30 g/l de chlorure et/ou de bromure et, de préférence, 15 à 25 g/l de chlorure et/ou de bromure.
  3. Procédé selon la revendication 1 ou la revendication 2, dans lequel le bain d'alliage zinc-nickel contient du chlorure.
  4. Procédé selon l'une quelconque des revendications 1 à 3, dans lequel la densité de courant anodique est ajustée à une valeur comprise entre 10 et 20 A/dm2 et de préférence à 15 A/dm2.
  5. Procédé selon l'une quelconque des revendications 1 à 4, dans lequel l'anode utilisée dans le bain d'alliage zinc-nickel est en acier, en acier inoxydable, en acier nickelé ou en nickel massif.
  6. Procédé selon la revendication 5, dans lequel l'anode est en acier inoxydable V4A, en acier inoxydable V2A ou en acier nickelé.
  7. Procédé selon l'une quelconque des revendications 1 à 6, dans lequel le bain d'alliage zinc-nickel contient 10 à 30 g/l de chlorure, et la densité de courant anodique est ajustée à une valeur comprise entre 10 et 20 A/dm2.
EP17175993.9A 2017-06-14 2017-06-14 Procédé de dépôt galvanique de revêtements d'alliage zinc/nicel à partir d'un bain d'alliage nickel/zinc à élimination réduite des additifs Active EP3415665B1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
ES17175993T ES2969188T3 (es) 2017-06-14 2017-06-14 Procedimiento para la deposición galvánica de revestimientos de aleaciones de cinc-níquel a partir de un baño de aleación de cinc-níquel alcalino con degradación reducida de aditivos
FIEP17175993.9T FI3415665T3 (fi) 2017-06-14 2017-06-14 Menetelmä sinkki-nikkeliseoskerroksien erottamiseksi galvaanisesti emäksisestä sinkki-nikkeliseoskylvystä vähemmällä lisäaineiden hajoamisella
EP17175993.9A EP3415665B1 (fr) 2017-06-14 2017-06-14 Procédé de dépôt galvanique de revêtements d'alliage zinc/nicel à partir d'un bain d'alliage nickel/zinc à élimination réduite des additifs
SI201731476T SI3415665T1 (sl) 2017-06-14 2017-06-14 Postopek za galvansko ločitev prevlek iz zlitine cinka in niklja iz alkalne kopeli zlitine iz cinka in niklja z manjšo razgradnjo aditivov
DK17175993.9T DK3415665T3 (da) 2017-06-14 2017-06-14 Fremgangsmåde til galvanisk udfældning af zink-nikkel-legeringsovertræk ud fra et alkalisk zink-nikkel-legeringsbad med reduceret nedbrydning af tilsætningsstoffer
PT171759939T PT3415665T (pt) 2017-06-14 2017-06-14 Processo para a deposição galvânica de revestimentos de zinco-níquel a partir de um banho alcalino de liga de zinco-alumínio com degradação reduzida de aditivos
PL17175993.9T PL3415665T3 (pl) 2017-06-14 2017-06-14 Sposób osadzania galwanicznego powłok ze stopu cynku i niklu z alkalicznej kąpieli stopu cynku i niklu z ograniczoną degradacją dodatków

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EP17175993.9A EP3415665B1 (fr) 2017-06-14 2017-06-14 Procédé de dépôt galvanique de revêtements d'alliage zinc/nicel à partir d'un bain d'alliage nickel/zinc à élimination réduite des additifs

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EP3415665A1 EP3415665A1 (fr) 2018-12-19
EP3415665B1 true EP3415665B1 (fr) 2023-12-27

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DK (1) DK3415665T3 (fr)
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PL (1) PL3415665T3 (fr)
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WO2023241905A1 (fr) * 2022-06-13 2023-12-21 Basf Se Bain d'électroplacage alcalin stable avec un diacide

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US3681211A (en) * 1970-11-23 1972-08-01 Enequist Chem Co Inc The Electroplating a black nickel-zinc alloy deposit
JP3230626B2 (ja) * 1993-07-29 2001-11-19 三菱アルミニウム株式会社 表面処理Ａｌ材
US5417840A (en) * 1993-10-21 1995-05-23 Mcgean-Rohco, Inc. Alkaline zinc-nickel alloy plating baths
DE19834353C2 (de) 1998-07-30 2000-08-17 Hillebrand Walter Gmbh & Co Kg Alkalisches Zink-Nickelbad
DE60023190T3 (de) 2000-06-15 2016-03-10 Coventya, Inc. Zink-nickel-elektroplattierung
FR2864553B1 (fr) 2003-12-31 2006-09-01 Coventya Installation de depot de zinc ou d'alliages de zinc
CN1281787C (zh) * 2004-05-20 2006-10-25 上海交通大学 镁及镁合金高耐蚀性复合镀层及其制备工艺
ATE429528T1 (de) 2005-04-26 2009-05-15 Atotech Deutschland Gmbh Alkalisches galvanikbad mit einer filtrationsmembran
EP1870495A1 (fr) * 2006-06-21 2007-12-26 Atotech Deutschland Gmbh Bain aqueux alcalin, exempt de cyanide, pour la déposition galvanique de couches de Zinc et alliages de Zinc

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SI3415665T1 (sl) 2024-06-28
DK3415665T3 (da) 2024-02-12
EP3415665A1 (fr) 2018-12-19
ES2969188T3 (es) 2024-05-16
PT3415665T (pt) 2024-01-23
PL3415665T3 (pl) 2024-03-25
FI3415665T3 (fi) 2024-02-06

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