WO2020166062A1 - 亜鉛又は亜鉛合金電気めっき方法及びシステム - Google Patents

亜鉛又は亜鉛合金電気めっき方法及びシステム Download PDF

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WO2020166062A1
WO2020166062A1 PCT/JP2019/005548 JP2019005548W WO2020166062A1 WO 2020166062 A1 WO2020166062 A1 WO 2020166062A1 JP 2019005548 W JP2019005548 W JP 2019005548W WO 2020166062 A1 WO2020166062 A1 WO 2020166062A1
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zinc
alloy electroplating
zinc alloy
alkaline
anode
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PCT/JP2019/005548
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English (en)
French (fr)
Japanese (ja)
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俊寛 新鞍
章 橋本
井上　学
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ディップソール株式会社
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Priority to PCT/JP2019/005548 priority Critical patent/WO2020166062A1/ja
Priority to EP19766159.8A priority patent/EP3715506A4/de
Priority to JP2019508981A priority patent/JP6582353B1/ja
Priority to CN201980001581.1A priority patent/CN110462107A/zh
Priority to US16/577,895 priority patent/US20200263314A1/en
Publication of WO2020166062A1 publication Critical patent/WO2020166062A1/ja

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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 a zinc or zinc alloy electroplating method and system. Specifically, when applying zinc or zinc alloy electroplating with excellent anticorrosion property to a steel member using an alkaline zinc or zinc alloy electroplating bath, a state in which the alkali resistant ceramics can conduct electricity on the conductive base material.
  • the present invention relates to an electroplating method and system that can be used for a long period of time while maintaining plating bath performance by using an anode coated with.
  • Zinc plating has been used as an inexpensive rust preventive plating that uses a bath containing a cyanide compound and hardly contains an organic compound.
  • a zinc plating bath that does not use a highly toxic cyanide compound has been studied, and a zinc plating bath containing an organic compound such as a quaternary amine polymer has been widely used.
  • this organic compound decomposes and disappears by anodic oxidation, dendrite deposition with poor adhesion results and good zinc rust preventive plating cannot be performed.
  • Zinc alloy plating is more widely used for automobile parts and the like because it has better corrosion resistance than zinc plating.
  • alkaline zinc nickel alloy plating baths are used for fuel parts that require high corrosion resistance and engine parts that are placed in high temperature environments.
  • the alkaline zinc-nickel alloy plating bath is a plating bath in which an amine-based chelating agent suitable for the eutectoid ratio of Ni is selected to dissolve nickel, and zinc and nickel are co-deposited on the plating film.
  • an amine-based chelating agent suitable for the eutectoid ratio of Ni is selected to dissolve nickel, and zinc and nickel are co-deposited on the plating film.
  • Japanese Patent Publication No. 2002-521572 discloses a method of separating an alkaline zinc nickel alloy plating bath (catholyte) and an acidic anolyte with a cation exchange membrane made of a perfluoropolymer.
  • an acidic solution is used as the anolyte
  • an expensive corrosion-resistant member such as platinum-plated titanium must be used for the anode.
  • the diaphragm is damaged, there is a possibility that an acidic solution on the anode side and an alkaline solution on the cathode side are mixed with each other to cause a rapid chemical reaction.
  • Japanese Unexamined Patent Publication No. 2007-2274 describes a method of solving the above-mentioned problems by using a cation exchange membrane and additionally supplying an alkaline component to an alkaline anolyte.
  • this method requires additional equipment, liquid management, etc., and the operation becomes complicated.
  • a cathode region including a cathode and an anode region including an anode are separated by an anion exchange membrane, and an alkaline zinc alloy plating solution is used as a catholyte contained in the cathode region
  • a method for performing zinc alloy electroplating using an alkaline aqueous solution as an anolyte contained in the anode region is described. According to this method, the oxidative decomposition of the amine-based chelating agent in the bath at the anode is suppressed, but anions move from the plating solution to the anode electrolyte, and sodium carbonate, sodium sulfate, and sodium oxalate rapidly increase.
  • Japanese Patent Publication No. 2008-539329 discloses a zinc alloy plating bath in which electrodes of a cathode and an anode are separated by a filtration membrane.
  • the present inventors have confirmed that the disclosed filtration membrane cannot prevent the migration of the catholyte and the anolyte, and cannot prevent the decomposition of the chelating agent at the anode. Further, since the zinc alloy plating solution is used as the anolyte, the decomposition of the anolyte is greatly promoted. Therefore, it is necessary to replace the anolyte, and if not replaced, the decomposed product moves into the cathode plating solution. Therefore, it has been found that the liquid life is not substantially extended.
  • the present invention suppresses oxidative decomposition of chelating agents and brighteners on the anode surface without using a special device such as an expensive anode cell, maintains zinc or zinc alloy plating bath performance, and achieves long life.
  • An object is to provide an inexpensive and economical plating method that can be performed.
  • the present invention uses an anode in which a conductive base material is coated with an alkali-resistant ceramic in a current-carrying state, whereby oxidative decomposition does not occur on the anode surface of the amine-based chelating agent in the bath, and plating bath performance is improved. It is based on the knowledge that it will be maintained. That is, the present invention provides the following zinc or zinc alloy electroplating method and system.
  • a zinc or zinc alloy electroplating method comprising energizing in an alkaline zinc or zinc alloy electroplating bath comprising a cathode and an anode,
  • the anode is an anode coated on a conductive base material in a state in which alkali resistant ceramics can conduct electricity
  • the alkaline zinc or zinc alloy electroplating bath is an alkaline zinc plating bath containing an organic compound additive, or an alkaline zinc alloy electroplating bath containing an amine chelating agent and an organic compound additive, Oxidative decomposition of the organic compound additive in the alkaline zinc plating bath or the amine-based chelating agent and organic compound additive in the alkaline zinc alloy electroplating bath caused by oxidative decomposition on the surface of the anode is coated with alkali resistant ceramics.
  • the alkali resistant ceramic contains at least one selected from the group consisting of tantalum oxide, aluminum oxide, tantalum nitride, aluminum nitride, silicon nitride, boron nitride, silicon carbide, and boron carbide.
  • the alkaline zinc or zinc alloy electroplating bath is an alkaline zinc alloy electroplating bath containing at least zinc ions, metal ions, caustic, amine-based chelating agents, and organic compound additives, and the metal ions are nickel ions.
  • a zinc or zinc alloy electroplating system comprising an alkaline zinc or zinc alloy electroplating bath comprising a cathode and an anode,
  • the anode is an anode coated on a conductive base material in a state in which alkali resistant ceramics can conduct electricity
  • the alkaline zinc or zinc alloy electroplating bath is an alkaline zinc plating bath containing an organic compound additive, or an alkaline zinc alloy electroplating bath containing an amine chelating agent and an organic compound additive, Oxidative decomposition of the organic compound additive in the alkaline zinc plating bath or the amine-based chelating agent and organic compound additive in the alkaline zinc alloy electroplating bath caused by oxidative decomposition on the surface of the anode is coated with alkali resistant ceramics.
  • the zinc or zinc alloy electroplating system is suppressed compared to when the same conductive substrate is not used as the anode.
  • the zinc or zinc alloy electroplating system according to the above [8], wherein the anode in which the alkali-resistant ceramic is coated on the conductive substrate in a conductive state comprises the conductive substrate and the alkali-resistant ceramic coating.
  • the alkali-resistant ceramic contains at least one selected from the group consisting of tantalum oxide, aluminum oxide, tantalum nitride, aluminum nitride, silicon nitride, boron nitride, silicon carbide, and boron carbide.
  • the alkaline zinc or zinc alloy electroplating bath is an alkaline zinc alloy electroplating bath containing at least zinc ions, metal ions, caustic, amine-based chelating agents, and organic compound additives, and the metal ions are nickel ions.
  • the result of the plating test (plating appearance) according to the Hull cell test of Example 1 is shown.
  • the result of the plating test (plating appearance) based on the Hull cell test of Example 2 is shown.
  • the result of the plating test (plating appearance) according to the Hull cell test of Example 3 is shown.
  • the result (plating appearance) of the plating test based on the Hull cell test of Comparative Example 1 is shown.
  • the result (plating appearance) of the plating test based on the Hull cell test of Comparative Example 2 is shown.
  • the result (film thickness distribution) of the plating test based on the Hull cell test of Example 1 is shown.
  • the result (Ni eutectoid rate distribution) of the plating test based on the Hull cell test of Example 1 is shown.
  • the result (film thickness distribution) of the plating test based on the Hull cell test of Example 2 is shown.
  • the result (Ni eutectoid rate distribution) of the plating test based on the Hull cell test of Example 2 is shown.
  • the result (film thickness distribution) of the plating test based on the Hull cell test of Example 3 is shown.
  • the result (Ni eutectoid distribution) of a plating test based on the Hull cell test of Example 3 is shown.
  • the result (film thickness distribution) of the plating test based on the Hull cell test of Comparative Example 1 is shown.
  • the result of the plating test (Ni eutectoid distribution) according to the Hull cell test of Comparative Example 1 is shown.
  • the result (film thickness distribution) of the plating test based on the Hull cell test of Comparative Example 2 is shown.
  • the result (Ni eutectoid rate distribution) of the plating test based on the Hull cell test of Comparative Example 2 is shown.
  • the zinc or zinc alloy electroplating method of the present invention includes energizing in an alkaline zinc alloy electroplating bath having a cathode and an anode.
  • the metal to be combined with zinc in the zinc alloy plating include one or more metals selected from nickel, iron, cobalt, tin and manganese. Specific examples include zinc-nickel alloy plating, zinc-iron alloy plating, zinc-cobalt alloy plating, zinc-manganese alloy plating, zinc-tin alloy plating, zinc-nickel-cobalt alloy plating, but not limited to these alloy platings. Absent.
  • the zinc alloy plating is zinc nickel alloy plating.
  • the cathode is an object to be plated that is electroplated with zinc or zinc alloy.
  • an anode in which an alkali-resistant ceramic is coated on a conductive base material in a state in which current can flow is used.
  • alkali-resistant ceramics include, but are not limited to, tantalum oxide, aluminum oxide, tantalum nitride, aluminum nitride, silicon nitride, boron nitride, silicon carbide, boron carbide, and the like.
  • the alkali-resistant ceramic preferably contains at least one selected from the group consisting of tantalum oxide, aluminum oxide, tantalum nitride, aluminum nitride, silicon nitride, boron nitride, silicon carbide, and boron carbide.
  • the coating film of alkali-resistant ceramics can be prepared on the conductive base material by, but not limited to, sintering, vapor phase plating, or a combination of vapor phase plating and anodization.
  • a suitable pretreatment such as etching can be performed on the conductive base material in order to obtain adhesion due to the anchor effect.
  • the arithmetic average roughness (Ra) of the surface is preferably 3 to 4 ⁇ m.
  • An ion exchange resin or the like may be top-coated on the coating film of the alkali-resistant ceramics.
  • the thickness of the alkali-resistant ceramic coating film is preferably about 0.1 to 50 ⁇ m. Particularly preferably, it is 0.5 to 1 ⁇ m.
  • the coating film of the alkali-resistant ceramics may be obtained by performing the above-described manufacturing method a plurality of times so that the total film thickness thereof falls within the above range.
  • the pore diameter in the alkali-resistant ceramic coating film is preferably about 0.1 to 5 ⁇ m. More preferably, it is 0.1 to 1 ⁇ m. If the pore size exceeds 5 ⁇ m, the effect of suppressing decomposition is reduced.
  • the state in which electricity can be applied means a state in which ions and the like can move due to the above-described holes and cracks.
  • the conductive base material is preferably iron, nickel, stainless steel, carbon, titanium, zirconium, niobium, tantalum, platinum, platinum-plated titanium, palladium-tin alloy or those coated with these, but if energizable, these It is not limited to.
  • the conductive substrate more preferably contains at least one of nickel and iron.
  • the anode in which the alkali resistant ceramic is coated on the conductive base material in a conductive state is preferably an anode composed of the conductive base material and the alkali resistant ceramic coating.
  • the alkaline zinc electroplating bath used in the present invention is an alkaline zinc plating bath containing an organic compound additive.
  • the alkaline zinc electroplating bath contains one or more organic compound additives selected from the group consisting of brightening agents, auxiliary additives such as leveling agents, and defoaming agents.
  • the alkaline zinc electroplating bath preferably contains a brightener.
  • the alkaline zinc alloy electroplating bath used in the present invention is an alkaline zinc alloy electroplating bath containing an amine-based chelating agent and an organic compound additive.
  • the alkaline zinc alloy electroplating bath is an amine-based chelating agent, an organic compound additive, and one or more selected from the group consisting of auxiliary additives such as brighteners and leveling agents, and defoaming agents. Contains organic compound additives.
  • the alkaline zinc alloy electroplating bath preferably contains a brightener.
  • the brightening agent is not particularly limited as long as it is a known brightening agent in a zinc-based plating bath.
  • Anionic surfactants such as polyoxyethylene lauryl ether sulfate and alkyldiphenyl ether disulfonate; (2) polyallylamine such as copolymers of diallyldimethylammonium chloride and sulfur dioxide; condensation polymers of ethylenediamine and epichlorohydrin, dimethyl Condensation polymer of aminopropylamine and epichlorohydrin, condensation polymer of imidazole and epichlorohydrin, condensation polymer of imidazole derivative such as 1-methylimidazole and 2-methylimidazole and epichlorohydrin, triazine derivative of acetoguanamine, benzoguanamine, etc.
  • Polyepoxypolyamines such as condensation polymers of heterocyclic amines and epichlorohydrin; condensation polymers of 3-dimethylaminopropylurea and epichlorohydrin, condensation polymers of bis(N,N-dimethylaminopropyl)urea and epichlorohydrin
  • Polyamine polyurea resin such as, Polyamide polyamine such as water-soluble nylon resin such as condensation polymer of N,N-dimethylaminopropylamine, alkylenedicarboxylic acid and epichlorohydrin; Diethylenetriamine, dimethylaminopropylamine and 2,2'- Condensation polymer with dichlorodiethyl ether, condensation polymer with dimethylaminopropylamine and 1,3-dichloropropane, N,N,N',N'-tetramethyl-1,3-diaminopropane and 1, Polyalkylene polyamines such as condensation polymers with 4-dichlorobutane, condensation poly
  • quaternary ammonium salts and aromatic aldehydes are preferable.
  • These brighteners may be used alone or in combination of two or more.
  • the concentration of the brightener in the alkaline zinc or zinc alloy electroplating bath is preferably 1 to 500 mg/L, more preferably 5 to 100 mg/L in the case of aromatic aldehydes, benzoic acid or salts thereof. In this case, it is preferably 0.01 to 10 g/L, more preferably 0.02 to 5 g/L.
  • the brightener may be a nitrogen-containing heterocyclic quaternary ammonium salt.
  • the nitrogen-containing heterocyclic quaternary ammonium salt brightener is more preferably a carboxy group- and/or hydroxy group-substituted nitrogen-containing heterocyclic quaternary ammonium salt.
  • Examples of the nitrogen-containing heterocycle of the nitrogen-containing heterocycle quaternary ammonium salt include a pyridine ring, a piperidine ring, an imidazole ring, an imidazoline ring, a pyrrolidine ring, a pyrazole ring, a quinoline ring and a morpholine ring, and a pyridine ring is preferable.
  • the carboxy group and/or the hydroxy group may be substituted on the nitrogen-containing heterocycle via a substituent such as a carboxymethyl group.
  • the nitrogen-containing heterocycle may have a substituent such as an alkyl group.
  • the N substituent forming the heterocyclic quaternary ammonium cation is not particularly limited as long as it does not inhibit the effect of containing the brightening agent, and examples thereof include a substituted or unsubstituted alkyl group, aryl group, and alkoxy group.
  • Examples of the counter anion forming a salt include compounds containing a halogen anion, an oxy anion, a borate anion, a sulfonate anion, a phosphate anion, an imide anion, and the like, and a halogen anion is preferable. Since such a quaternary ammonium salt contains both a quaternary ammonium cation and an oxyanion in the molecule, it also behaves as an anion, which is preferable.
  • nitrogen-containing heterocyclic quaternary ammonium salt compound examples include, for example, N-benzyl-3-carboxypyridinium chloride, N-phenethyl-4-carboxypyridinium chloride, N-butyl-3-carboxypyridinium bromide, N-chloro.
  • Methyl-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-carboxyridinium chloride, N-benzyl-3-carboxmethylpyridinium chloride, 1-butyl-3-methyl-4-carboxyimidazololium bromide, 1-butyl-3-methyl-4-carboxymethylimidazololium bromide, 1-Butyl-2-hydroxymethyl-3-methylimidazololium chloride, 1-butyl-1-methyl-3-methylcarboxypyrroli
  • nitrogen-containing heterocyclic quaternary ammonium salts may be used alone or in combination of two or more kinds.
  • concentration of the nitrogen-containing heterocyclic quaternary ammonium salt in the alkaline zinc or zinc alloy electroplating bath is preferably 0.01 to 10 g/L, more preferably 0.02 to 5 g/L.
  • auxiliary additive examples include organic acids, silicates and mercapto compounds. These auxiliary additives may be used alone or in combination of two or more.
  • concentration of the auxiliary additive in the alkaline zinc or zinc alloy electroplating bath is preferably 0.01 to 50 g/L.
  • defoaming agent examples include a surfactant and the like. These antifoaming agents may be used alone or in combination of two or more kinds.
  • concentration of the defoaming agent in the alkaline zinc or zinc alloy electroplating bath is preferably 0.01 to 5 g/L.
  • amine-based chelating agent examples include alkyleneamine compounds such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine; alkylene oxide adducts such as ethylene oxide adducts and propylene oxide adducts of the alkylene amines.
  • Amino alcohols such as ethanolamine, diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, ethylenediaminetetra-2-propanol, N-(2-aminoethyl)ethanolamine, 2-hydroxyethylaminopropylamine; N- (2-hydroxyethyl)-N,N',N'-triethylethylenediamine, N,N'-di(2-hydroxyethyl)-N,N'-diethylethylenediamine, N,N,N',N'-tetrakis Alkanolamine compounds such as (2-hydroxyethyl)propylenediamine, N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine; poly(alkyleneimines obtained from ethyleneimine, 1,2-propyleneimine, etc.
  • the amine-based chelating agent preferably contains at least one selected from the group consisting of alkyleneamine compounds, alkylene oxide adducts thereof, and alkanolamine compounds. These amine-based chelating agents may be used alone or in combination of two or more kinds.
  • the concentration of the amine-based chelating agent in the alkaline zinc or zinc alloy electroplating bath is preferably 5 to 200 g/L, more preferably 30 to 100 g/L.
  • the alkaline zinc or zinc alloy electroplating bath used in the present invention contains zinc ions.
  • the concentration of zinc ions in the alkaline zinc or zinc alloy electroplating bath is preferably 2 to 20 g/L, more preferably 4 to 12 g/L.
  • Examples of the zinc ion source include Na 2 [Zn(OH) 4 ], K 2 [Zn(OH) 4 ] and ZnO. These zinc ion sources may be used alone or in combination of two or more.
  • the alkaline zinc or zinc alloy electroplating bath used in the present invention preferably contains caustic. Examples of the caustic alkali include sodium hydroxide and potassium hydroxide, but sodium hydroxide is preferable.
  • the concentration of caustic alkali in the alkaline zinc or zinc alloy electroplating bath is preferably 60 to 200 g/L, more preferably 100 to 160 g/L.
  • the alkaline zinc alloy electroplating bath used in the present invention contains metal ions other than zinc.
  • the alkaline zinc alloy electroplating bath preferably contains, as the metal ions, one or more metal ions selected from the group consisting of nickel ions, iron ions, cobalt ions, tin ions, and manganese ions.
  • the total concentration of the metal ions in the alkaline zinc alloy electroplating bath is preferably 0.4 to 4 g/L, more preferably 1 to 3 g/L.
  • the metal ion source include nickel sulfate, ferrous sulfate, cobalt sulfate, stannous sulfate, and manganese sulfate. These metal ion sources may be used alone or in combination of two or more.
  • the alkaline zinc alloy electroplating bath used in the present invention is preferably an alkaline zinc nickel alloy electroplating bath containing nickel ions as the metal ions.
  • the alkaline zinc electroplating bath is preferably an alkaline zinc electroplating bath containing at least zinc ions, caustic, and an organic compound additive.
  • the alkaline zinc alloy electroplating bath is preferably an alkaline zinc alloy electroplating bath containing at least zinc ions, metal ions, caustic, an amine chelating agent, and an organic compound additive, and the metal ions are nickel ions. At least one selected from the group consisting of iron ion, cobalt ion, tin ion, and manganese ion.
  • the temperature at which zinc or zinc alloy plating is performed is preferably 15°C to 40°C, more preferably 25 to 35°C.
  • the cathode current density when performing zinc or zinc alloy plating is preferably 0.1 to 20 A/dm 2 , and more preferably 0.2 to 10 A/dm 2 .
  • the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
  • Example 1 An alkaline zinc nickel alloy plating bath shown below was used using an anode plate (surface roughness Ra: 4 ⁇ m, 64 ⁇ 64 ⁇ 2 mm) in which tantalum oxide was coated on Ni to a thickness of 0.5 to 0.8 ⁇ m ( Zinc-nickel alloy plating was carried out by applying a current of 500 mL) and 500 Ah/L.
  • the pore diameter in the coating film was 0.1 to 1 ⁇ m, and the pumping out of the plating bath was 2 mL/Ah.
  • the cathode current density is 4 A/dm 2
  • the anode current density is 9.8 A/dm 2
  • the plating bath temperature is 25°C.
  • the plating bath was cooled and maintained at 25°C.
  • An iron plate was used for the cathode.
  • the iron plate of the cathode was replaced every 16 Ah/L during energization.
  • the zinc ion concentration in the plating bath was kept constant by dipping and dissolving metallic zinc.
  • the nickel ion concentration in the plating bath was maintained constant by supplementing nickel replenisher IZ-250YNi (manufactured by Dipsol).
  • the caustic soda concentration in the plating bath was analyzed periodically and replenished so that the concentration would be constant.
  • polyamine-based IZ-250YR1 manufactured by Dipsol
  • nitrogen-containing heterocyclic quaternary ammonium salt-based IZ-250YR2 manufactured by Dipsol
  • the amine chelating agent IZ-250YB was replenished at a replenishment rate of 80 mL/kAh of IZ-250YB.
  • concentration of the amine-based chelating agent, the concentration of oxalic acid, and the concentration of cyanide in the catholyte were analyzed each time 250 Ah/L was applied.
  • Plating solution composition Zn ion concentration 8 g/L (Zn ion source is Na 2 [Zn(OH) 4 ]) Ni ion concentration 1.6 g / L (Ni ion source NiSO 4 ⁇ 6H 2 O) Caustic soda concentration 130g/L Amine type chelating agent (ethylene oxide adduct of alkylene amine) IZ-250YB (manufactured by Dipsol) 60 g/L Brightener IZ-250YR1 (manufactured by Dipsol) 0.6 mL/L (polyamine 0.1 g/L) Brightener IZ-250YR2 (manufactured by Dipsol) 0.5 mL/L (quaternary ammonium salt of nicotinic acid 0.2 g/L)
  • Example 2 Using an alkaline zinc nickel alloy plating bath shown below, using an anode plate (surface roughness Ra: 4 ⁇ m, 64 ⁇ 64 ⁇ 2 mm) in which Fe is coated with tantalum oxide in a thickness of 0.5 to 0.8 ⁇ m ( Zinc-nickel alloy plating was carried out by applying a current of 500 mL) and 500 Ah/L.
  • the pore diameter in the coating film was 0.1 to 1 ⁇ m, and the pumping out of the plating bath was 2 mL/Ah.
  • the cathode current density is 4 A/dm 2
  • the anode current density is 9.8 A/dm 2
  • the plating bath temperature is 25°C.
  • the plating bath was cooled and maintained at 25°C.
  • An iron plate was used for the cathode.
  • the iron plate of the cathode was replaced every 16 Ah/L during energization.
  • the zinc ion concentration in the plating bath was kept constant by dipping and dissolving metallic zinc.
  • the nickel ion concentration in the plating bath was maintained constant by supplementing nickel replenisher IZ-250YNi (manufactured by Dipsol).
  • the caustic soda concentration in the plating bath was analyzed periodically and replenished so that the concentration would be constant.
  • polyamine-based IZ-250YR1 manufactured by Dipsol
  • nitrogen-containing heterocyclic quaternary ammonium salt-based IZ-250YR2 manufactured by Dipsol
  • the amine chelating agent IZ-250YB was replenished at a replenishment rate of 80 mL/kAh of IZ-250YB.
  • concentration of the amine-based chelating agent, the concentration of oxalic acid, and the concentration of cyanide in the catholyte were analyzed each time 250 Ah/L was applied.
  • Plating solution composition Zn ion concentration 8 g/L (Zn ion source is Na 2 [Zn(OH) 4 ]) Ni ion concentration 1.6 g / L (Ni ion source NiSO 4 ⁇ 6H 2 O) Caustic soda concentration 130g/L Amine type chelating agent (ethylene oxide adduct of alkylene amine) IZ-250YB (manufactured by Dipsol) 60 g/L Brightener IZ-250YR1 (manufactured by Dipsol) 0.6 mL/L (polyamine 0.1 g/L) Brightener IZ-250YR2 (manufactured by Dipsol) 0.5 mL/L (quaternary ammonium salt of nicotinic acid 0.2 g/L)
  • Example 3 An alkaline zinc nickel alloy plating bath shown below was used using an anode plate (surface roughness Ra: 4 ⁇ m, 64 ⁇ 64 ⁇ 2 mm) in which tantalum oxide was coated on Ni to a thickness of 0.5 to 0.8 ⁇ m ( Zinc-nickel alloy plating was carried out by applying a current of 500 mL) and 500 Ah/L.
  • the pore diameter in the coating film was 0.1 to 1 ⁇ m, and the pumping out of the plating bath was 2 mL/Ah.
  • the cathode current density is 2 A/dm 2
  • the anode current density is 4.9 A/dm 2
  • the plating bath temperature is 25° C.
  • the plating bath was cooled and maintained at 25°C.
  • An iron plate was used for the cathode.
  • the iron plate of the cathode was replaced every 16 Ah/L during energization.
  • the zinc ion concentration in the plating bath was kept constant by dipping and dissolving metallic zinc.
  • the nickel ion concentration in the plating bath was maintained constant by supplementing nickel replenisher IZ-250YNi (manufactured by Dipsol).
  • the caustic soda concentration in the plating bath was analyzed periodically and replenished so that the concentration would be constant.
  • polyamine-based IZ-250YR1 manufactured by Dipsol
  • nitrogen-containing heterocyclic quaternary ammonium salt-based IZ-250YR2 manufactured by Dipsol
  • the amine chelating agent tetraethylenepentamine was supplied at a supply rate of 40 mL/kAh.
  • the concentration of the amine-based chelating agent and the concentration of cyan in the catholyte were analyzed every 250 Ah/L energization. In addition, the presence or absence of precipitate was visually confirmed. The results are shown in Table 2.
  • the chelating agent concentration was adjusted to the initial concentration at the time of energizing 500 Ah/L, and a plating test similar to the Hull cell test was conducted using a long cell with a 20 cm iron plate as the cathode, and the plating appearance, film thickness distribution, and Ni eutectoid distribution Was measured. These results are shown in FIGS. 3, 10 and 11, respectively.
  • the conditions of the plating test based on the Hull cell test are 2A-20 minutes and 25°C.
  • Plating solution composition Zn ion concentration 8 g/L (Zn ion source is Na 2 [Zn(OH) 4 ]) Ni ion concentration 1.2 g / L (Ni ion source NiSO 4 ⁇ 6H 2 O) Caustic soda concentration 130g/L Amine type chelating agent (tetraethylene pentamine) 30g/L Brightener IZ-250YR1 (manufactured by Dipsol) 0.6 mL/L (polyamine 0.1 g/L) Brightener IZ-250YR2 (manufactured by Dipsol) 0.5 mL/L (quaternary ammonium salt of nicotinic acid 0.2 g/L)
  • the zinc ion concentration in the plating bath was kept constant by dipping and dissolving metallic zinc.
  • the nickel ion concentration in the plating bath was maintained constant by supplementing nickel replenisher IZ-250YNi (manufactured by Dipsol).
  • the caustic soda concentration in the plating bath was analyzed periodically and replenished so that the concentration would be constant.
  • polyamine-based IZ-250YR1 manufactured by Dipsol
  • nitrogen-containing heterocyclic quaternary ammonium salt-based IZ-250YR2 manufactured by Dipsol were supplied at a replenishment rate of 15 mL/kAh and 15 mL/kAh, respectively. did.
  • the amine chelating agent IZ-250YB was replenished at a replenishment rate of 80 mL/kAh of IZ-250YB.
  • the concentration of the amine-based chelating agent, the concentration of oxalic acid, and the concentration of cyan were analyzed each time 250 Ah/L was applied. In addition, the presence or absence of precipitate was visually confirmed. The results are shown in Table 1. Further, the chelating agent concentration was adjusted to the initial concentration at the time of energizing 500 Ah/L, and a plating test similar to the Hull cell test was conducted using a long cell with a 20 cm iron plate as the cathode, and the plating appearance, film thickness distribution, and Ni eutectoid distribution Was measured.
  • Plating solution composition Zn ion concentration 8 g/L (Zn ion source is Na 2 [Zn(OH) 4 ]) Ni ion concentration 1.6 g / L (Ni ion source NiSO 4 ⁇ 6H 2 O) Caustic soda concentration 130g/L Amine type chelating agent (ethylene oxide adduct of alkylene amine) IZ-250YB (manufactured by Dipsol) 60 g/L Brightener IZ-250YR1 (manufactured by Dipsol) 0.6 mL/L (polyamine 0.1 g/L) Brightener IZ-250YR2 (manufactured by Dipsol) 0.5 mL/L (quaternary ammonium salt of nicotinic acid 0.2 g/L)
  • the plating bath was cooled and maintained at 25°C.
  • An iron plate was used for the cathode.
  • the iron plate of the cathode was replaced every 16 Ah/L during energization.
  • the zinc ion concentration in the plating bath was kept constant by dipping and dissolving metallic zinc.
  • the nickel ion concentration in the plating bath was maintained constant by supplementing nickel replenisher IZ-250YNi (manufactured by Dipsol).
  • the caustic soda concentration in the plating bath was analyzed periodically and replenished so that the concentration would be constant.
  • polyamine-based IZ-250YR1 manufactured by Dipsol
  • nitrogen-containing heterocyclic quaternary ammonium salt-based IZ-250YR2 manufactured by Dipsol
  • the amine chelating agent IZ-250YB was replenished at a replenishment rate of 80 mL/kAh of IZ-250YB.
  • concentration of the amine-based chelating agent, the concentration of oxalic acid, and the concentration of cyanide in the catholyte were analyzed each time 250 Ah/L was applied.
  • Plating solution composition Zn ion concentration 8 g/L (Zn ion source is Na 2 [Zn(OH) 4 ]) Ni ion concentration 1.6 g / L (Ni ion source NiSO 4 ⁇ 6H 2 O) Caustic soda concentration 130g/L Amine type chelating agent (ethylene oxide adduct of alkylene amine) IZ-250YB (manufactured by Dipsol) 60 g/L Brightener IZ-250YR1 (manufactured by Dipsol) 0.6 mL/L (polyamine 0.1 g/L) Brightener IZ-250YR2 (manufactured by Dipsol) 0.5 mL/L (quaternary ammonium salt of nicotinic acid 0.2 g/L)
  • Table 2 Changes in amine-based chelating agent concentration and cyan concentration, and presence or absence of precipitation Examples 1 to 3 have the following effects as compared with Comparative Examples 1 and 2.

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PCT/JP2019/005548 2019-02-15 2019-02-15 亜鉛又は亜鉛合金電気めっき方法及びシステム WO2020166062A1 (ja)

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EP19766159.8A EP3715506A4 (de) 2019-02-15 2019-02-15 Zink- oder zinklegierungen elektropliermethode und -system
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CN201980001581.1A CN110462107A (zh) 2019-02-15 2019-02-15 锌或锌合金电镀方法和系统
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US11661666B2 (en) * 2019-10-10 2023-05-30 The Boeing Company Electrodeposited zinc and iron coatings for corrosion resistance
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CN111826691B (zh) * 2020-08-21 2021-09-21 东北大学 一种溶剂化离子液体制备锌钽合金的方法
CN116670334A (zh) 2020-12-28 2023-08-29 迪普索股份公司 用金属对物品进行电镀的方法和系统
EP4212651A4 (de) * 2021-12-02 2024-08-14 Dipsol Chem Verfahren und system zur elektroplattierung eines artikels mit metall
WO2023100381A1 (ja) 2021-12-02 2023-06-08 ディップソール株式会社 金属で物品を電気めっきする方法及びシステム
JP7442866B1 (ja) 2022-11-25 2024-03-05 ディップソール株式会社 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

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01298192A (ja) * 1988-05-27 1989-12-01 Ebara Yuujiraito Kk 亜鉛−ニッケル合金めっき液
JPH03240987A (ja) * 1990-02-16 1991-10-28 Tdk Corp 有機物電解用電極及びその製造方法
JPH09157879A (ja) * 1995-11-30 1997-06-17 Tdk Corp 電解用電極およびその製造方法
JP2000256898A (ja) * 1999-03-03 2000-09-19 Permelec Electrode Ltd ウェーハの銅めっき方法
JP2002521572A (ja) 1998-07-30 2002-07-16 ヴァルター ヒレブラント ゲーエムベーハー ウント コー． ガルヴァノテヒニーク 亜鉛−ニッケル浴用アルカリ性めっき浴槽
JP2004068153A (ja) * 2002-07-23 2004-03-04 Nippon Hyomen Kagaku Kk ジンケート浴亜鉛めっき方法
JP2006503187A (ja) * 2002-10-18 2006-01-26 エルテック・システムズ・コーポレーション 電気化学的電池における望ましくない酸化を阻害するためのコーティング
JP2007002274A (ja) 2005-06-21 2007-01-11 Nippon Hyomen Kagaku Kk 亜鉛−ニッケル合金めっき方法
JP2008539329A (ja) 2005-04-26 2008-11-13 アトテック・ドイチュラント・ゲーエムベーハー ろ過膜を備えたアルカリ電気めっき浴
JP2013216958A (ja) * 2012-04-11 2013-10-24 Matex Japan Co Ltd 不溶性金属電極、電解装置、および、めっき方法
WO2016075963A1 (ja) 2015-07-22 2016-05-19 ディップソール株式会社 亜鉛合金めっき方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5522484B2 (ja) * 2011-09-13 2014-06-18 学校法人同志社 電解めっき用陽極および該陽極を用いる電解めっき法
US20160024683A1 (en) * 2013-03-21 2016-01-28 Atotech Deutschland Gmbh Apparatus and method for electrolytic deposition of metal layers on workpieces
RU2613826C1 (ru) * 2015-07-22 2017-03-21 Дипсол Кемикалз Ко., Лтд. Способ гальваностегии цинковым сплавом
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

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01298192A (ja) * 1988-05-27 1989-12-01 Ebara Yuujiraito Kk 亜鉛−ニッケル合金めっき液
JPH03240987A (ja) * 1990-02-16 1991-10-28 Tdk Corp 有機物電解用電極及びその製造方法
JPH09157879A (ja) * 1995-11-30 1997-06-17 Tdk Corp 電解用電極およびその製造方法
JP2002521572A (ja) 1998-07-30 2002-07-16 ヴァルター ヒレブラント ゲーエムベーハー ウント コー． ガルヴァノテヒニーク 亜鉛−ニッケル浴用アルカリ性めっき浴槽
JP2000256898A (ja) * 1999-03-03 2000-09-19 Permelec Electrode Ltd ウェーハの銅めっき方法
JP2004068153A (ja) * 2002-07-23 2004-03-04 Nippon Hyomen Kagaku Kk ジンケート浴亜鉛めっき方法
JP2006503187A (ja) * 2002-10-18 2006-01-26 エルテック・システムズ・コーポレーション 電気化学的電池における望ましくない酸化を阻害するためのコーティング
JP2008539329A (ja) 2005-04-26 2008-11-13 アトテック・ドイチュラント・ゲーエムベーハー ろ過膜を備えたアルカリ電気めっき浴
JP2007002274A (ja) 2005-06-21 2007-01-11 Nippon Hyomen Kagaku Kk 亜鉛−ニッケル合金めっき方法
JP2013216958A (ja) * 2012-04-11 2013-10-24 Matex Japan Co Ltd 不溶性金属電極、電解装置、および、めっき方法
WO2016075963A1 (ja) 2015-07-22 2016-05-19 ディップソール株式会社 亜鉛合金めっき方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3715506A4

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