EP4269663A1 - Method and system for electroplating article with metal - Google Patents

Method and system for electroplating article with metal Download PDF

Info

Publication number
EP4269663A1
EP4269663A1 EP21915031.5A EP21915031A EP4269663A1 EP 4269663 A1 EP4269663 A1 EP 4269663A1 EP 21915031 A EP21915031 A EP 21915031A EP 4269663 A1 EP4269663 A1 EP 4269663A1
Authority
EP
European Patent Office
Prior art keywords
nickel
iron
oxide
conductive substrate
layer
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.)
Pending
Application number
EP21915031.5A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP4269663A4 (en
Inventor
Kota Kobayashi
Nobuya SUGAYA
Manabu Inoue
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.)
Dipsol Chemicals Co Ltd
Original Assignee
Dipsol Chemicals Co Ltd
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
Application filed by Dipsol Chemicals Co Ltd filed Critical Dipsol Chemicals Co Ltd
Publication of EP4269663A1 publication Critical patent/EP4269663A1/en
Publication of EP4269663A4 publication Critical patent/EP4269663A4/en
Pending legal-status Critical Current

Links

Images

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
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • 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
    • 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
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • 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
    • C25D5/67—Electroplating to repair workpiece
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils
    • C25D7/0642—Anodes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/12—Process control or regulation
    • C25D21/14—Controlled addition of electrolyte components

Definitions

  • the present invention relates to a method and system for electroplating an article with metal. Specifically, the present invention relates to an electroplating method and system in which decomposition of an organic compound additive added to a plating bath comprising metal ions is suppressed.
  • Zinc plating is used as a relatively inexpensive anti-corrosive plating, and its alkaline plating bath comprises an organic compound such as a quaternary amine polymer as an additive.
  • organic compound such as a quaternary amine polymer as an additive.
  • Zinc alloy plating has corrosion resistance superior to zinc plating and therefore is widely used for automobile parts and so on.
  • alkaline zinc-nickel alloy plating is used for fuel system parts required to have high corrosion resistance and engine parts to be placed under a high temperature environment.
  • An alkaline zinc-nickel alloy plating bath is obtained by dissolving nickel by using an amine-based chelating agent suitable for a nickel co-deposition ratio, and is for forming a plating film in which zinc and nickel are co-deposited.
  • the alkaline zinc-nickel alloy plating bath has a problem that during current application, the amine-based chelating agent is oxidatively decomposed on the surface of the anode to generate oxalic acid and sodium carbonate.
  • Patent Literatures 1 and 2 describe a so-called anode cell system partitioned such that an anolyte is placed in a cell covered with a diaphragm and that a plating bath is out of contact with an anode plate, thereby making it possible to suppressing decomposition of an organic compound additive. Since oxalic acid and sodium carbonate generated in the plating bath migrate from the plating solution into the anode cell in this anode cell system, this system is expected to produce an effect of removing the decomposed products in the plating bath. On the other hand, the anode cell system requires many ancillary facilities such as an anode cell body, piping, and a pump. In addition, it is necessary to control the concentration of the anolyte, and to renew the anolyte every time a certain amount of current is applied.
  • Patent Literature 3 teaches that decomposition of an organic compound additive is suppressed by applying a coating to the surface of a conductive substrate of an anode. In this case, there is no need for ancillary facilities or anolyte control, but the cost for manufacturing the anode is a problem.
  • Patent Literature 4 also teaches that a coating is applied to the surface of a conductive substrate of an anode, but further improvement is required.
  • Patent Literature 5 teaches that a metal oxide film can be formed by heat-treating a metal film formed by electroplating, and an iron oxide film has high water repellency while a nickel oxide film has low water repellency.
  • Patent Literature 6 and Non Patent Literatures 1 and 2 teach that an electrode having a film layer formed of iron nitride or oxide of nickel and iron is used for oxygen generation reaction by water electrolysis.
  • none of Patent Literatures 1 to 6 and Non Patent Literatures 1 and 2 teaches that a conductive substrate having a layer comprising oxide or nitride of nickel and iron formed on a surface thereof is used as an electrode for electroplating.
  • the object of the present invention is to provide a method and system for electroplating without requiring ancillary facilities or anolyte control, while using an anode which can be relatively easily produced without requiring an expensive metal or special metal.
  • the present inventors found that, when electroplating an article with metal, decomposition of an organic compound additive in a plating bath can be suppressed by using, as an anode, a conductive substrate having a layer comprising oxide or nitride of nickel and iron formed on a surface thereof, and completed the present invention.
  • the present invention provides the following method and system for electroplating an article with metal.
  • the present invention it is possible to suppress decomposition of an organic compound additive in a plating bath in electroplating an article with metal by using, as an anode, a conductive substrate having a layer comprising oxide or nitride of nickel and iron formed on a surface thereof.
  • Nickel and iron are metals available at relatively low prices, and no complicated processes are required to form a layer comprising oxide of these metals. Therefore, it is possible to perform metal plating such as zinc plating or zinc alloy plating with low manufacturing cost.
  • the present invention relates to a method for electroplating an article with metal.
  • the metal is not particularly limited as long as it is usable for electroplating.
  • the metal may comprise zinc, nickel, iron, copper, cobalt, tin, manganese, and the like.
  • the metal consists of zinc only, a zinc film is formed on the article.
  • the metal comprises zinc and another metal, a zinc alloy film is formed on the article.
  • the other metal is not particularly limited as long as it can form the zinc alloy film, but may be at least one selected from the group consisting of, for example, nickel, iron, cobalt, tin, manganese, and the like.
  • the zinc alloy film may be, but not particularly limited to, zinc-nickel alloy plating, zinc-iron alloy plating, zinc-cobalt alloy plating, zinc-manganese alloy plating, zinc-tin alloy plating, or the like, and is preferably zinc-nickel alloy plating.
  • the article is an article to be plated, and any article commonly used in this technical field can be employed without particular limitation.
  • the article may be made of any of various metals such as iron, nickel, copper, zinc, and aluminum and alloys of them.
  • its shape is not particularly limited.
  • any of various articles including: plate-shaped articles such as a steel plate and a plated steel plate; and shaped articles such as a rectangular parallelepiped article, a columnar article, a cylindrical article, and a spherical article are exemplified.
  • shaped articles include: fastening parts such as bolts, nuts, and washers; pipe parts such as fuel pipes; cast iron parts such as brake calipers and common rails; and various articles such as connectors, plugs, housings, bases or mouthpieces, and seatbelt anchors.
  • the method of the present invention comprises the step of applying current in a plating bath comprising ions of a metal to be plated and an organic compound additive, wherein the plating bath comprises the article as a cathode, and comprises, as an anode, a conductive substrate having a layer comprising oxide or nitride of nickel and iron on a surface thereof.
  • the plating bath may be, but not particularly limited to, any of acidic or neutral plating baths such as a sulfuric acid bath, a boron fluoride bath, and an organic acid bath, and alkaline plating baths such as a cyanide bath, a zincate bath, and a pyrophosphate bath, and is preferably an alkaline plating bath.
  • the conductive substrate is not particularly limited as long as it can conduct electricity, but may be, for example, an iron, nickel, stainless steel, carbon, titanium, zirconium, niobium, tantalum, platinum, platinum-plated titanium, or palladium-tin alloy substrate, a substrate coated with any of them, or the like, and is preferably a substrate comprising at least one of nickel and iron.
  • the layer comprising the oxide or nitride of nickel and iron is formed on a liquid contact portion of the conductive substrate.
  • the organic compound additive is oxidatively decomposable in the vicinity of the anode, and thus the layer comprising the oxide or nitride of nickel and iron suppresses decomposition of the organic compound additive by functioning as a catalyst for an oxygen evolution reaction due to electrolysis of water, and thereby making the oxygen evolution reaction more dominant than the oxidative decomposition reaction in the vicinity of the anode.
  • a method for forming the layer comprising the oxide or nitride is not particularly limited.
  • the layer comprising the oxide or nitride may be formed by oxidation or nitridation of a conductive substrate having a plating film comprising nickel and iron, a conductive substrate comprising iron and having a plating film comprising nickel, a conductive substrate comprising nickel and having a plating film comprising iron, or a conductive substrate comprising nickel and iron.
  • the conductive substrate may be plated with nickel and iron, and the film comprising nickel and iron may be treated with thermal oxidation to oxidize a part or all of the film.
  • an alloy of nickel and iron may be used as the conductive substrate and the alloy may be treated with thermal oxidation to oxidize the surface of the alloy.
  • the conductive substrate In the case where the conductive substrate is plated with nickel and iron and only the surface of the film is oxidized, the conductive substrate would have, on its surface, two layers, that is, a layer comprising oxide of nickel and iron and a film layer comprising nickel and iron.
  • the plating film comprising nickel and iron, the plating film comprising nickel, and the plating film comprising iron for use to form the layer comprising the oxide or nitride of nickel and iron can be formed by a plating method commonly used in this technical field.
  • the plating film comprising nickel and iron, the plating film comprising nickel, or the plating film comprising iron may be formed by using a plating bath comprising saccharin or a salt thereof, or preferably using a plating bath comprising sodium saccharin.
  • an anode comprising the layer comprising the oxide or nitride of nickel and iron derived from the plating film formed in the plating bath comprising the saccharin or the salt thereof makes it possible to further improve the effect of suppressing decomposition of the organic compound additive.
  • concentration of the saccharin or the salt thereof in the plating bath is not particularly limited, but may be, for example, about 0.1 to about 2.0 g/L, and is preferably about 0.5 to about 1.9 g/L.
  • the amounts of nickel (Ni) and iron (Fe) constituting the layer comprising the oxide are not particularly limited.
  • the atomic percent of Ni in the layer comprising the oxide may be about 0.5% to about 45%, and is preferably about 1% to about 15%
  • the atomic percent of Fe in the oxide-comprising layer may be about 5% to about 45%, and is preferably about 30% to about 40%.
  • the thickness of the layer comprising the oxide is not particularly limited, but may be, for example, about 0.5 ⁇ m to about 10 ⁇ m, and is preferably about 1.5 ⁇ m to about 4 ⁇ m. When the thickness of the layer comprising the oxide is within the above range, it is possible to maintain the good performance of the anode and exert the effect of suppressing the decomposition of the organic compound additive more satisfactorily.
  • the layer comprising the oxide or nitride of nickel and iron further contains phosphorus atoms or boron atoms.
  • a phosphorus compound or a boron compound may be added to the plating bath used therein.
  • organic compound additive refers to an organic compound to be added to a plating bath for electroplating.
  • a type of the organic compound additive is not particularly limited.
  • the organic compound additive may be at least one selected from the group consisting of brightening agents, auxiliary additives (such as smoothing agents), defoamers, and the like.
  • the organic compound additive may be at least one selected from the group consisting of amine-based chelating agents, brightening agents, auxiliary additives (such as smoothing agents), defoamers, and the like.
  • the organic compound additive comprises a brightening agent in a preferred embodiment.
  • any agent commonly used in this technical field may be employed without particular limitation.
  • the brightening agent include: (1) nonionic surfactants such as polyoxyethylene polyoxypropylene block polymer and acetylene glycol EO adduct, and anionic surfactants such as polyoxyethylene lauryl ether sulfate and alkyldiphenyl ether disulfonate; (2) polyamine compounds: such as polyallylamines such as copolymer of diallyldimethylammonium chloride and sulfur dioxide; polyepoxypolyamines such as condensation polymer of ethylenediamine and epichlorohydrin, condensation polymer of dimethylaminopropylamine and epichlorohydrin, condensation polymer of imidazole and epichlorohydrin, condensation polymer of an imidazole derivative such as 1-methylimidazole or 2-methylimidazole with epichlorohydrin, and condensation polymer of epichlorohydrin with heterocyclic amine including a tri
  • the brightening agent comprises a quaternary ammonium salt or an aromatic aldehyde.
  • the above brightening agents may be used alone or used in combination of two or more.
  • the concentration of the brightening agent in the plating bath is not particularly limited.
  • the concentration of the brightening agent may be about 1 to about 500 mg/L, and is preferably about 5 to about 100 mg/L, and in the other cases, the concentration may be about 0.01 to about 10 g/L, and is preferably about 0.02 to about 5 g/L.
  • the brightening agent may comprise a nitrogen-containing heterocycle quaternary ammonium salt in addition to the quaternary ammonium salt not having a nitrogen-containing heterocycle.
  • the nitrogen-containing heterocycle quaternary ammonium salt is a nitrogen-containing heterocycle quaternary ammonium salt having a carboxyl group and/or a hydroxy group.
  • the nitrogen-containing heterocycle in the nitrogen-containing heterocycle quaternary ammonium salt is not particularly limited, but may be, for example, pyridine ring, piperidine ring, imidazole ring, imidazoline ring, pyrrolidine ring, pyrazole ring, quinoline ring, or morpholine ring, and is preferably pyridine ring. More preferably, the nitrogen-containing heterocycle quaternary ammonium salt is a quaternary ammonium salt of nicotinic acid or a derivative thereof.
  • the carboxyl group and/or the hydroxy group may be directly bonded to the nitrogen-containing heterocycle, or may be bonded via another substituent as in a carboxymethyl group.
  • the nitrogen-containing heterocycle quaternary ammonium salt may contain an additional substituent such as, for example, an alkyl group, in addition to the carboxyl group and the hydroxy group.
  • N substituent forming a heterocyclic quaternary ammonium cation is not particularly limited as long as it does not impair the effect as the brightening agent, but may be, for example, a substituted or unsubstituted alkyl, aryl, or alkoxy group.
  • the counter anion forming the salt is not particularly limited, but may be, for example, a compound containing halogen anion, oxyanion, borate anion, sulfonate anion, phosphate anion, imide anion, or the like, and is preferably halogen anion.
  • Such a quaternary ammonium salt is preferable because it contains both a quaternary ammonium cation and an oxyanion in its molecule, and also behaves as an anion.
  • nitrogen-containing heterocycle quaternary ammonium salt is N-benzyl-3-carboxypyridinium chloride, N-phenethyl-4-carboxypyridinium chloride, N-butyl-3-carboxypyridinium bromide, N-chloromethyl-3-carboxypyridinium bromide, N-hexyl-6-hydroxy-3-carboxypyridinium chloride, N-hexyl-6-3-hydroxypropyl-3-carboxypyridinium chloride, N-2-hydroxyethyl-6-methoxy-3-carboxypyridinium chloride, N-methoxy-6-methyl-3-carboxypyridinium chloride, N-propyl-2-methyl-6-phenyl-3-carboxypyridinium chloride, N-propyl-2-methyl-6-phenyl-3-carboxypyridinium chloride, N-propyl-2-methyl-6-phenyl-3-carboxypyridinium chloride, N
  • the nitrogen-containing heterocycle quaternary ammonium salts may be used alone or used in combination of two or more.
  • concentration of the nitrogen-containing heterocycle quaternary ammonium salt in the plating bath is not particularly limited, but may be, for example, about 0.01 to about 10 g/L and is preferably 0.02 to 5 g/L.
  • the auxiliary additive any additive commonly used in this technical field may be employed without particular limitation.
  • the auxiliary additive may comprise organic acid, silicate, or a mercapto compound and these may be used as a smoothing agent.
  • the auxiliary additives may be used alone or used in combination of two or more.
  • the concentration of the auxiliary additive in the plating bath is not particularly limited, but may be, for example, about 0.01 to about 50 g/L.
  • the defoamer any defoamer commonly used in this technical field may be employed without particular limitation.
  • the defoamer may be a surfactant or the like.
  • the defoamers may be used alone or used in combination of two or more.
  • the concentration of the defoamer in the plating bath is not particularly limited, but may be, for example, about 0.01 to about 5 g/L.
  • the amine-based chelating agent may comprise: alkyleneamine compounds such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine; alkylene oxide adducts of the above alkyleneamines such as ethylene oxide adducts and propylene oxide adducts; amino alcohols such as ethanolamine, diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, ethylenediaminetetra-2-propanol, N-(2-aminoethyl)ethanolamine, and 2-hydroxyethylaminopropylamine; alkanolamine compounds such as N-(2-hydroxyethyl)-N,N',N'-triethylethylenediamine, N,N'-di(2-hydroxyethyl)-N
  • the amine-based chelating agent comprises at least one selected from the group consisting of alkyleneamine compounds, their alkylene oxide adducts, and alkanolamine compounds.
  • the amine-based chelating agents may be used alone or used in combination of two or more.
  • the concentration of the amine-based chelating agent in the plating bath is not particularly limited, but may be, for example, about 5 to about 200 g/L, and is preferably about 30 to about 100 g/L.
  • the plating bath particularly the alkaline plating bath, comprises zinc ions.
  • any ion source commonly used in this technical field may be employed without particular limitation.
  • the ion source may be Na 2 [Zn(OH) 4 ], K 2 [Zn(OH) 4 ], or ZnO.
  • the zinc ion sources may be used alone or used in combination of two or more.
  • the concentration of the zinc ions in the alkaline plating bath is not particularly limited, but may be, for example, about 2 to about 20 g/L, and is preferably about 4 to about 12 g/L.
  • the plating bath particularly the alkaline plating bath, further comprises another kind of metal ions for forming the zinc alloy film in addition to the zinc ions.
  • the other kind of metal ions is not particularly limited as long as it can form the zinc alloy film, but may be at least one kind selected from the group consisting of nickel ions, iron ions, cobalt ions, tin ions, manganese ions, and the like, and is preferably nickel ions.
  • An ion source for producing the other kind of metal ions is not particularly limited, but may be, for example, nickel sulfate, iron(II) sulfate, cobalt sulfate, tin(II) sulfate, manganese sulfate, or the like.
  • the ion sources for the other kinds of metal ions may be used alone or used in combination of two or more.
  • the total concentration of the other kinds of metal ions in the alkaline plating bath is not particularly limited, but may be, for example, about 0.4 to about 4 g/L, and is preferably about 1 to about 3 g/L.
  • the plating bath may comprise caustic alkali.
  • the caustic alkali is not particularly limited, but may be, for example, sodium hydroxide, potassium hydroxide, or the like. More specifically, the plating bath may comprise sodium hydroxide when the plating bath is an alkaline plating bath or may comprise potassium hydroxide when the plating bath is an acidic plating bath.
  • the concentration of the caustic alkali in the alkaline plating bath is not particularly limited, but may be, for example, about 60 to about 200 g/L, and is preferably about 100 to about 160 g/L.
  • Conditions for the current application step are not particularly limited as long as zinc or zinc alloy plating can be applied.
  • the current may be applied at a temperature of about 15°C to about 40°C and preferably about 25°C to about 35°C, or the current may be applied with a cathode current density of about 0.1 to 20 A/dm 2 and preferably 0.2 to 10 A/dm 2 .
  • the method of the present invention may further comprise any step commonly used in this technical field as long as the step will not impair the object of the present invention.
  • the method of the present invention may further comprise a step of washing the article before the current application step, a step of washing the article after the current application step, and so on.
  • the present invention relates to a system for electroplating an article with metal.
  • the system of the present invention comprises a plating bath comprising the metal ions and an organic compound additive, and the plating bath comprises the article as a cathode and a conductive substrate having a layer comprising oxide or nitride of nickel and iron on a surface thereof as an anode.
  • the system of the present invention may further comprise any facility commonly used in this technical field as long as the facility will not impair the object of the present invention.
  • the present invention relates to a method for producing an electrode comprising a conductive substrate having a layer comprising oxide or nitride of nickel and iron formed on a surface thereof.
  • the production method of the present invention comprises a step of performing oxidation treatment or nitridation treatment on a conductive substrate having a plating film comprising nickel and iron, a conductive substrate comprising iron and having a plating film comprising nickel, a conductive substrate comprising nickel and having a plating film comprising iron, or a conductive substrate comprising nickel and iron, thereby forming a layer comprising oxide or nitride of nickel and iron on a surface of the conductive substrate.
  • the production method of the present invention may further comprise a step of forming the plating film comprising nickel and iron, the plating film comprising nickel, or the plating film comprising iron by using a plating bath comprising saccharin or a salt thereof.
  • the production method of the present invention may further comprise any step commonly used in this technical field as long as the step will not impair the object of the present invention.
  • the present invention relates to a method for repairing an electrode comprising a conductive substrate with a surface having a layer comprising oxide of nickel and iron formed on a surface thereof, in which electrode the layer comprising the oxide is partly damaged on the surface.
  • the repairing method of the present invention comprises a step of heating the electrode in an ambient atmosphere or oxidizing atmosphere.
  • the conductive substrate has a plating film comprising nickel and iron under the layer comprising the oxide of nickel and iron, or comprises iron and has a plating film comprising nickel under the layer comprising the oxide of nickel and iron, or comprises nickel and has a plating film comprising iron under the layer comprising the oxide of nickel and iron, or contains nickel and iron.
  • An anode having a coating on a surface thereof has been heretofore known, but in the case where the coating is damaged, it is necessary to remove all the coating once and perform the coating process again.
  • the repairing method of the present invention without peeling off the partly damaged layer, it is possible to restore the oxide in the damaged part only by heating the electrode having the layer.
  • a heating unit for the heating step is not particularly limited, and the heating may be performed by, for example, a burner, a muffle furnace such as an electric furnace or gas furnace, a heater such as a ceramic heater or an infrared heater, an electromagnetic induction heater, a laser heating device, or the like.
  • Conditions for the heating step are not particularly limited as long as the oxide in the damaged parts in the layer comprising the oxide can be regenerated, and may be adjusted as appropriate depending on the size of the electrode and the number and size of the damaged parts.
  • the electrode may be repaired by heating with a burner for about 5 to 30 minutes or may be repaired by heating in a muffle furnace for about 30 to 90 minutes.
  • the electrode can be repaired effectively with indirect heating avoiding direct exposure of the damaged parts to the flame, or with heating in an apparatus such as a muffle furnace that does not emit a flame.
  • the electrode can be repaired any number of times by applying the repairing method of the present invention again.
  • An iron plate (64 ⁇ 64 ⁇ 2.3 mm) was degreased and activated with hydrochloric acid by conventional methods. Then, the iron plate was plated under the conditions of 4 A/dm 2 , 50°C, and 20 minutes using a plating bath having each of compositions specified in Table 1 below, thereby fabricating the iron plate with Ni-Fe plating.
  • Table 1 Composition of Plating Bath [g/L] Component
  • Example 1 NiSO 4 ⁇ 6H 2 O 250 250 NiCl 2 ⁇ 6H 2 O 40 40 FeSO 4 ⁇ 7H 2 O 7.2 7.2 H 3 BO 3 30 30 Malonic Acid 5.2 5.2 Saccharin Na 0 0.5
  • the iron plate with Ni-Fe plating was washed, dried in room temperature, and then heated by using a muffle furnace at 650°C for one hour. After that, the iron plate was slowly cooled down to room temperature for about one hour to fabricate an iron plate electrode. A surface and a cross-section of this iron plate electrode were observed with a scanning electron microscope (SEM) and elemental mapping was performed with an energy dispersive X-ray spectrometer (EDS).
  • Figs. 1A to 1D and Fig. 2 show the results of the iron plate electrode in Example 1.
  • Ni-Fe oxide layer a layer comprising oxide of nickel and iron (Ni-Fe oxide layer) was formed on the surface of the iron plate electrode (Table 2).
  • X-ray diffraction analysis of this Ni-Fe oxide layer revealed that NiO, Fe 2 O 3 , and NiFe 2 O 4 were contained in both the electrodes.
  • the element concentrations in the plated part of each of the iron plate electrodes were measured by EDS before and after the heat treatment, the element concentrations of nickel atoms (Ni), iron atoms (Fe), and oxygen atoms (O) were obtained as shown in Table 2 below.
  • Example 2 Ni Fe O Ni Fe O Before Heat Treatment (After Plating) 84.9 15.1 Not Detected 88.4 11.6 Not Detected After Heat Treatment 7.0 35.3 57.7 10.1 34.7 55.2
  • Alkaline zinc-nickel plating using the iron plate electrode with the Ni-Fe oxide layer of Example 1 or 2 as the anode and using an ordinary iron plate electrode (electrode degreased and activated with hydrochloric acid) as a cathode was performed in 500 mL of a plating bath having the composition specified in Table 3 below.
  • Table 3 Composition of Plating Bath Component Concentration ZnO 10 g/L (8 g/L in terms of Zn ions) NiSO 4 ⁇ 6H 2 O 7.3 g/L (1.6 g/L in terms of Ni ions) Caustic Soda 130 g/L IZ-250YB ⁇ 1 60 g/L IZ-250YR1 ⁇ 2 0.6 mL/L (polyamine 0.1 g/L) IZ-250YR2 ⁇ 3 0.5 mL/L (quaternary ammonium salt of nicotinic acid 0.2 g/L) ⁇ 1 Amine-based chelating agent (ethylene oxide adduct of alkyleneamine) manufactured by DIPSOL CHEMICALS Co., Ltd.
  • ZnO 10 g/L 8 g/L in terms of Zn ions
  • NiSO 4 ⁇ 6H 2 O 7.3 g/L (1.6 g/L in terms of Ni ions)
  • Brightening agent (polyamine) manufactured by DIPSOL CHEMICALS Co., Ltd.
  • Brightening agent (quaternary ammonium salt of nicotinic acid) manufactured by DIPSOL CHEMICALS Co., Ltd.
  • the temperature of the plating bath was set to 25°C and controlled by cooling to keep a constant temperature during current application.
  • An anode current density was set to 8 A/dm 2 and a cathode current density was set to 2.56 A/dm 2 .
  • a cathode iron plate was replaced every application of 5.1 Ah/L during the current application.
  • the ion concentrations in the plating bath were maintained during the current application in such a way that metallic zinc was immersed in the plating bath for replenishment of the zinc ion concentration and IZ-250YNi (nickel replenisher manufactured by DIPSOL CHEMICALS Co., Ltd) was added for replenishment of the nickel ion concentration.
  • the concentration of the caustic soda was periodically measured and was kept constant during the current application with replenishment with the caustic soda.
  • IZ-250YB was replenished at 80 mL/kAh.
  • IZ-250YR1 and IZ-250YR2 were replenished at 15 mL/kAh.
  • Table 4 Test Results [g/L] IZ-250YB Oxalic Acid Na 2 CO 3 Before Current application 60 Not Detected Not Detected After Current Application with Anode in Example 1 53 0.2 3.9 After Current Application with Anode in Example 2 60 0.1 3.2
  • Iron plate electrodes with Ni-Fe oxide layers in Examples 3 to 8 were fabricated in the same way as in Preparation Example 1 except that the iron plate was plated under the conditions of 4 A/dm 2 , 50°C, and 20 minutes using a plating bath having each of compositions specified in Table 5 below. Then, a plated portion of each of the iron plate electrodes was measured by EDS and the element concentration of iron atoms (Fe) was checked (Table 6).
  • Table 5 Composition of Plating Bath [g/L] Component Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 NiSO 4 ⁇ 6H 2 O 250 250 250 250 250 250 250 250 NiCl 2 ⁇ 6H 2 O 40 40 40 40 40 40 40 FeSO 4 ⁇ 7H 2 O 1.5 2.3 7.2 4.8 7.2 18 H 3 BO 3 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30
  • the iron plate electrode with the Ni-Fe oxide layer in each of Examples 3 to 8 was set as the anode, a satin steel plate of SPCC was set as the cathode, and 160 mL of an electrolytic liquid with the composition specified in Table 7 below was added. Then, current application was started with a current value of 2.6 A. The anode current density at that time was 8.1 A/dm 2 .
  • Table 7 Composition of Electrolytic Liquid Component Concentration NiSO 4 ⁇ 6H 2 O 7.3 g/L (1.6 g/L in terms of Ni ions) Caustic Soda 130 g/L IZ-250YB ⁇ 1 60 g/L IZ-250YR1 ⁇ 2 0.5 mL/L (polyamine 0.1 g/L) IZ-250YR2 ⁇ 3 1.0 mL/L (quaternary ammonium salt of nicotinic acid 0.4 g/L) ⁇ 1 Amine-based chelating agent (ethylene oxide adduct of alkyleneamine) manufactured by DIPSOL CHEMICALS Co., Ltd.
  • NiSO 4 ⁇ 6H 2 O 7.3 g/L (1.6 g/L in terms of Ni ions)
  • Brightening agent (polyamine) manufactured by DIPSOL CHEMICALS Co., Ltd.
  • Brightening agent (quaternary ammonium salt of nicotinic acid) manufactured by DIPSOL CHEMICALS Co., Ltd.
  • the current application was continued for 7 hours 42 minutes, and the temperature of the electrolytic liquid was adjusted at 25°C during the current application. Then, in the electrolytic liquid before and after the current application, the concentrations of IZ-250YB and the oxalic acid were measured by ion chromatography, the concentration of the quaternary ammonium salt of nicotinic acid was measured by capillary electrophoresis, and the concentration of the sodium carbonate (Na 2 CO 3 ) was measured by titration. The results are shown in Table 8.
  • Table 8 Test Results [g/L] IZ-250YB Quaternary Ammonium Salt of Nicotinic Acid Oxalic Acid Na 2 CO 3 Before Current Application 60 0.4 Not Detected Not Detected After Current Application With Iron Plate Electrode with Ni-Fe Oxide Layer Produced without Using Saccharin Electrode in Example 3 48 0.24 0.1 Not Detected Electrode in Example 4 43 0.2 0.2 4.2 Electrode in Example 5 50 0.24 0.2 3.2 After Current Application With Iron Plate Electrode with Ni-Fe Oxide Layer Produced by Using Saccharin Electrode in Example 6 46 0.2 0.3 5.6 Electrode in Example 7 52 0.24 0.1 Not Detected Electrode in Example 8 55 0.28 0.2 Not Detected
  • the amine-based chelating agent (IZ-250YB) and the brightening agent (IZ-250YR2) are decomposed during current application (see Comparative Test Example below).
  • the iron plate electrode with the Ni-Fe oxide layer was used as the anode, the decomposition of the amine-based chelating agent (IZ-250YB) and the brightening agent (IZ-250YR2) during the current application was suppressed.
  • the oxalic acid and the sodium carbonate that tend to increase along with current application, the increases in their concentrations were suppressed by use of the iron plate electrode with the Ni-Fe oxide layer.
  • Each of a nickel plate (64 ⁇ 64 ⁇ 2.3 mm) and an iron plate (64 ⁇ 64 ⁇ 2.3 mm) was placed in a muffle furnace, was heated at 650°C for 30 minutes, and then was slowly cooled down to room temperature for about one hour, thereby fabricating electrodes for comparison (the nickel plate with a nickel oxide layer and the iron plate with an iron oxide layer).
  • An iron plate electrode with a Ni-Fe oxide layer was fabricated in the same manner as in Example 3 of Preparation Example 2. Using this iron plate electrode as an anode, alkaline zinc-nickel plating was performed according to the method described in Test Example 1 to consume the anode. Then, after 300 hours, the anode was taken out and current application was performed for 7 hours and 42 minutes according to the method described in Test Example 2. The concentrations of the amine-based chelating agent (IZ-250YB), the brightening agent (quaternary ammonium salt of nicotinic acid; IZ-250YR2), the oxalic acid, and the sodium carbonate in the electrolytic liquid were measured.
  • IZ-250YB the amine-based chelating agent
  • the brightening agent quaternary ammonium salt of nicotinic acid
  • oxalic acid oxalic acid
  • the anode consumed by the alkaline zinc-nickel plating was repaired by heating with a gas burner. Specifically, four places on the side of the anode that was unconsumed due to contact with the inner surface of the electrolytic cell during the current application were each heated for 5 minutes, then allowed to stand at room temperature and cooled. Then, for the repaired anode, the current application was also performed for 7 hours and 42 minutes according to the method described in Test Example 2, and the concentrations of the amine-based chelating agent (IZ-250YB), the brightening agent (quaternary ammonium salt of nicotinic acid; IZ-250YR2), the oxalic acid, and the sodium carbonate in the electrolytic liquid were measured.
  • IZ-250YB the amine-based chelating agent
  • the brightening agent quaternary ammonium salt of nicotinic acid
  • oxalic acid oxalic acid
  • the anode repaired after the current application for 300 hours was consumed by being further used for additional current application for 100 hours. Then, this consumed electrode was repaired by heating with the burner in the same manner as in the case of the current application for 300 hours.
  • the current application was also performed for 7 hours and 42 minutes according to the method described in Test Example 2, and the concentrations of the amine-based chelating agent (IZ-250YB), the brightening agent (quaternary ammonium salt of nicotinic acid; IZ-250YR2), the oxalic acid, and the sodium carbonate in the electrolytic liquid were measured. The results of all the measurements are presented in Table 10.
  • Table 10 Test Results [g/L] IZ-250YB Quaternary Ammonium Salt of Nicotinic Acid Oxalic Acid Na 2 CO 3 Before Current Application 60 0.4 Not Detected Not Detected After Current Application with Unconsumed Anode 49 0.24 0.1 Not Detected Consumption with Current Application for 300 Hours After Current Application with Unrepaired Anode 39 0.2 0.6 9.3 After Current Application with Repaired Anode 49 0.24 0.2 Not Detected Consumption with Additional Current Application for 100 Hours After Current Application with Unrepaired Anode 45 0.24 0.4 6.6 After Current Application with Repaired Anode 48 0.36 0.2 2.0
  • the anode As the time of the current application was increased, the anode was consumed more, and the effects of suppressing the decomposition of the organic compound additive and suppressing the increases in the electrolyte aging products in the plating bath were decreased. On the other hand, these effects were recovered by heating the consumed anodes. The same recovery effect was also confirmed by heating the consumed anode in the muffle furnace at 650°C for one hour. In addition, even when the repaired anode was consumed, the effects of suppressing the decomposition of the organic compound additive and suppressing the increases in the electrolyte aging products in the plating bath were recovered by heating the anode again.

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)
  • Electroplating Methods And Accessories (AREA)
EP21915031.5A 2020-12-28 2021-12-02 METHOD AND SYSTEM FOR ELECTROPLATING AN ARTICLE WITH METAL Pending EP4269663A4 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2020219501 2020-12-28
PCT/JP2021/044238 WO2022145170A1 (ja) 2020-12-28 2021-12-02 金属で物品を電気めっきする方法及びシステム

Publications (2)

Publication Number Publication Date
EP4269663A1 true EP4269663A1 (en) 2023-11-01
EP4269663A4 EP4269663A4 (en) 2024-09-18

Family

ID=82260376

Family Applications (1)

Application Number Title Priority Date Filing Date
EP21915031.5A Pending EP4269663A4 (en) 2020-12-28 2021-12-02 METHOD AND SYSTEM FOR ELECTROPLATING AN ARTICLE WITH METAL

Country Status (5)

Country Link
EP (1) EP4269663A4 (ja)
JP (1) JPWO2022145170A1 (ja)
CN (1) CN116670334A (ja)
TW (1) TW202233528A (ja)
WO (1) WO2022145170A1 (ja)

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5155781A (en) * 1974-11-12 1976-05-17 Tdk Electronics Co Ltd Kinzokusankabutsuhifukudenkyoku
JPS5640852Y2 (ja) * 1976-08-20 1981-09-24
JPS5974291A (ja) * 1982-10-21 1984-04-26 インステイチユ−ツ・ポ・フイジコチミア 光沢ニツケル−鉄合金電析用浴
US8377283B2 (en) * 2002-11-25 2013-02-19 Coventya, Inc. Zinc and zinc-alloy electroplating
JP6222121B2 (ja) 2015-01-21 2017-11-01 株式会社豊田中央研究所 不溶性電極の製造方法
US10156020B2 (en) 2015-07-22 2018-12-18 Dipsol Chemicals Co., Ltd. Zinc alloy plating method
RU2613826C1 (ru) 2015-07-22 2017-03-21 Дипсол Кемикалз Ко., Лтд. Способ гальваностегии цинковым сплавом
CN108699718B (zh) 2016-02-25 2021-03-02 株式会社丰田中央研究所 金属氧化物膜及其制造方法
EP3358045A1 (de) 2017-02-07 2018-08-08 Dr.Ing. Max Schlötter GmbH & Co. KG Verfahren zur galvanischen abscheidung von zink- und zinklegierungsüberzügen aus einem alkalischen beschichtungsbad mit reduziertem abbau von organischen badzusätzen
CN110462107A (zh) 2019-02-15 2019-11-15 迪普索股份公司 锌或锌合金电镀方法和系统

Also Published As

Publication number Publication date
EP4269663A4 (en) 2024-09-18
WO2022145170A1 (ja) 2022-07-07
JPWO2022145170A1 (ja) 2022-07-07
CN116670334A (zh) 2023-08-29
TW202233528A (zh) 2022-09-01

Similar Documents

Publication Publication Date Title
KR101622527B1 (ko) 아연 합금 도금 방법
JP6582353B1 (ja) 亜鉛又は亜鉛合金電気めっき方法及びシステム
KR101622528B1 (ko) 아연 합금 도금 방법
US6755960B1 (en) Zinc-nickel electroplating
EP1292724B1 (en) Zinc-nickel electroplating
EP4269663A1 (en) Method and system for electroplating article with metal
JP7442866B1 (ja) 電気めっき用陽極並びに金属で物品を電気めっきする方法及びシステム
JP4570738B2 (ja) 電気亜鉛めっき浴及びめっき方法
JP7233793B1 (ja) 金属で物品を電気めっきする方法及びシステム
TWI826912B (zh) 以金屬電鍍物品的方法及系統
JPH06346273A (ja) 錫めっき硫酸浴用スラッジ抑制剤および錫めっき方法
TW202430730A (zh) 電鍍用陽極以及以金屬將物品電鍍的方法及系統
JP2024067618A (ja) 電気めっき用光沢剤及びそれを含む電気めっき浴並びに金属で物品を電気めっきする方法
KR19990084931A (ko) 내 흑색무늬성이 우수한 전기아연 도금강판 제조방법

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

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

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

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20230713

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Free format text: PREVIOUS MAIN CLASS: C25D0017120000

Ipc: C25D0003560000

RIC1 Information provided on ipc code assigned before grant

Ipc: C25D 21/14 20060101ALN20240517BHEP

Ipc: C25D 7/06 20060101ALI20240517BHEP

Ipc: C25D 5/50 20060101ALI20240517BHEP

Ipc: C25D 21/00 20060101ALI20240517BHEP

Ipc: C25D 17/10 20060101ALI20240517BHEP

Ipc: C25D 5/00 20060101ALI20240517BHEP

Ipc: C25D 3/56 20060101AFI20240517BHEP

A4 Supplementary search report drawn up and despatched

Effective date: 20240816

RIC1 Information provided on ipc code assigned before grant

Ipc: C25D 21/14 20060101ALN20240809BHEP

Ipc: C25D 7/06 20060101ALI20240809BHEP

Ipc: C25D 5/50 20060101ALI20240809BHEP

Ipc: C25D 21/00 20060101ALI20240809BHEP

Ipc: C25D 17/10 20060101ALI20240809BHEP

Ipc: C25D 5/00 20060101ALI20240809BHEP

Ipc: C25D 3/56 20060101AFI20240809BHEP