CN110462107A - Zinc or Zinc alloy electroplating method and system - Google Patents
Zinc or Zinc alloy electroplating method and system Download PDFInfo
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- CN110462107A CN110462107A CN201980001581.1A CN201980001581A CN110462107A CN 110462107 A CN110462107 A CN 110462107A CN 201980001581 A CN201980001581 A CN 201980001581A CN 110462107 A CN110462107 A CN 110462107A
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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
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
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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
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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
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Abstract
The present invention provides a kind of zinc or Zinc alloy electroplating method, it is included in the Alkaline Zinc for having cathode and anode or the zinc being powered in Zinc alloy electroplating bath or Zinc alloy electroplating method, anode is the anode for being coated with alkali resistance ceramics with the state that can be powered on conductive substrate, Alkaline Zinc or Zinc alloy electroplating bath are the Alkaline Zinc plating bath containing organic compound additive, it or is the Alkaline Zinc alloy electroplating bath containing amine system chelating agent and organic compound additive, with use compared with the case where identical conductive substrate for not being coated with alkali resistance ceramics is as anode, the oxygenolysis in above-mentioned anode surface caused by being powered of the amine system chelating agent and organic compound additive in organic compound additive or Alkaline Zinc alloy electroplating bath in Alkaline Zinc plating bath is suppressed.
Description
Technical field
The present invention relates to zinc or Zinc alloy electroplating method and systems.Specifically, it is related to using Alkaline Zinc or kirsite
Electroplating bath to steel part etc. implement excellent corrosion resistance zinc or Zinc alloy electroplating when, by using on conductive substrate with energy
The state being enough powered is coated with the anode of alkali resistance ceramics, the electro-plating method that can be used for a long time while maintaining and plating bath performance
And system.
Background technique
Zinc plating is used as being practically free of the cheap antirust plating of organic compound using the bath containing cyanide.
But Recent study is without using the zinc plating bath of the cyanide of strong toxicity, zinc containing organic compounds such as quaternary ammonium polymers
Plating bath starts to popularize.But if the organic compound decomposes disappearance, the skeleton analysis of adaptation difference because of anodic oxidation
Out, good antirust zinc plating can not be carried out.
Kirsite plating has excellent corrosion resistance compared with zinc plating, therefore be widely used in automobile component etc..Especially
It is the engine portion that alkaline zinc-nickel alloy plating bath be used to require the fuel part of highly corrosion resistant, be placed under hot environment
Part.Alkaline zinc-nickel alloy plating bath is to select the amine system chelating agent of suitable Ni eutectoid rate and dissolve nickel, makes zinc and nickel eutectoid to plating
Cover the plating bath on epithelium.But when implementing to be electroplated using alkaline zinc-nickel alloy plating bath, the amine system chelating of anode surface when energization
The oxygenolysis of agent becomes problem.When the Ferrious materials ion such as nickel ion or iron ion coexists, they become oxidation catalyst and
Further promote the oxygenolysis of amine system chelating agent.Alkaline zinc-nickel alloy plating bath and amine system chelating agent when positive contact are fast as a result,
Speed is decomposed, and plating performance declines rapidly.Cause because of the savings of the decomposition product reduction for current efficiency occur, bath voltage it is upper
Liter, the reduction of plating film thickness, the reduction of nickel containing ratio in plating epithelium, the diminution of current density range for capableing of plating, light
Many problems such as the damp rising of reduction, COD.Therefore, it is impossible to which plating bath is used for a long time, it is necessary to replace plating bath.
As the method for improving the above problem, it is known so far there is several methods that.For example, in Japanese Unexamined Patent Application Publication
It is disclosed in 2002-521572 bulletin and gathers the anolyte of alkaline zinc-nickel alloy plating bath (catholyte) and acidity with by perfluor
The method for closing the cation-exchange membrane separation that object is constituted.However, anode must be used through platinum plating when anolyte uses Acidic Liquid
The expensive corrosion-resistant member such as titanium.In addition, there are also the alkalinity of the acid solution of anode-side and cathode side is molten when diaphragm breakage
A possibility that liquid mixes and the accident of violent chemical reaction occurs.On the other hand, the inventors of the present invention are clear by plating tests
When anolyte replaces Acidic Liquid using alkalies, cause anolyte sharp mobile to catholyte because of energization, anolyte
Liquid level reduce and catholyte liquid level rise and meanwhile occur.
In Japanese Unexamined Patent Publication 2007-2274 bulletin, as the method to solve the above problems a little, describe using sun from
Proton exchange, the method for additional supply alkaline components in the anolyte of alkalinity.However, this method needs additional equipment, liquid
Body management etc., operation become cumbersome.
In addition, describing in International Publication No. 2016/075963 by the cathode zone comprising cathode and comprising anode
Anode region anion exchange UF membrane, use alkaline zinc alloy bath as the catholyte contained in cathode zone, make
Use alkaline aqueous solution as the anolyte contained in anode region, the method for carrying out Zinc alloy electroplating.According to this method, in bath
Amine system chelating agent is suppressed in the oxygenolysis of anode, but there are anion from plating solution to anolyte mobile, sodium carbonate, sulphur
Sour sodium, sodium oxalate sharply increase, and the problem of precipitating on film, being precipitated and destroy film, this point, needs the miscellaneous of anolyte in order to prevent
The update of matter concentration management and frequent anolyte.In addition, the importing of anode unit needs the very equipment investment of great number and sun
The setting place of the spaciousness such as circulating tank, piping of pole liquid, it is also necessary to the maintenance of anode unit, regularly film replacement etc., it is uneconomical.
In addition, in Japanese Unexamined Patent Application Publication 2008-539329 bulletin, disclose the electricity of cathode and anode using filter membrane
The zinc alloy coating bath of interpolar separation.But the inventors of the present invention carried out confirmation, as a result having distinguished disclosed filter membrane can not prevent
The movement of catholyte and anolyte can not prevent the chelating agent of anode from decomposing.In addition, since anolyte is also plated using kirsite
Liquid, so promoting very much the decomposition of anolyte.Therefore, it is necessary to the replacement of anolyte, decomposition product is to cathode in the case where being changed without
Plating solution in move.Therefore bath life can not substantially be extended by recognizing.
Summary of the invention
The issue of the present invention is to provide be also able to suppress anode table without using the special device such as expensive anode unit
The chelating agent in face or the oxygenolysis of gloss agent are able to maintain that zinc or zinc alloy coating bath performance and realize the cheap warp of long lifetime
The coating method of Ji.
The present invention is the invention of completion based on following cognitions: by using the shape on conductive substrate can be powered
State is coated with the anode of alkali resistance ceramics, thus do not cause bath in amine system chelating agent anode surface oxygenolysis and maintain
Plate bath performance.That is, the present invention provides zinc or Zinc alloy electroplating method and system as shown below.
〔1〕
A kind of zinc or Zinc alloy electroplating method, including leading in Alkaline Zinc or the Zinc alloy electroplating bath for having cathode and anode
The step of electricity,
Anode is the anode for being coated with alkali resistance ceramics with the state that can be powered on conductive substrate,
Alkaline Zinc or Zinc alloy electroplating bath are the Alkaline Zinc plating bath containing organic compound additive or are to contain amine system
The Alkaline Zinc alloy electroplating bath of chelating agent and organic compound additive,
With use compared with the case where identical conductive substrate for not being coated with alkali resistance ceramics is as anode, Alkaline Zinc
The amine system chelating agent and organic compound additive in organic compound additive or Alkaline Zinc alloy electroplating bath in plating bath
By be powered caused by the oxygenolysis in above-mentioned anode surface be suppressed.
〔2〕
According to zinc described in above-mentioned (1) or Zinc alloy electroplating method, wherein the shape on conductive substrate can be powered
The anode that state is coated with alkali resistance ceramics is made of conductive substrate and alkali resistance ceramic coating.
〔3〕
According to zinc described in above-mentioned (1) or (2) or Zinc alloy electroplating method, wherein above-mentioned conductive substrate contain nickel and
It is at least one kind of in iron.
〔4〕
Zinc or Zinc alloy electroplating method according to any one of above-mentioned (1)~(3), wherein above-mentioned alkali resistance ceramics
Containing at least one kind of in tantalum oxide, aluminium oxide, tantalum nitride, aluminium nitride, silicon nitride, boron nitride, silicon carbide and boron carbide.
〔5〕
Zinc or Zinc alloy electroplating method according to any one of above-mentioned (1)~(4), wherein above-mentioned Alkaline Zinc or zinc
Alloy electroplating bath is at least Alkaline Zinc electroplating bath containing zinc ion, caustic alkali and organic compound additive.
〔6〕
Zinc or Zinc alloy electroplating method according to any one of above-mentioned (1)~(4), wherein above-mentioned Alkaline Zinc or zinc
Alloy electroplating bath is at least alkalinity containing zinc ion, metal ion, caustic alkali, amine system chelating agent and organic compound additive
Zinc alloy electroplating bath, above-mentioned metal ion contain at least 1 in nickel ion, iron ion, cobalt ions, tin ion and manganese ion
Kind.
〔7〕
According to zinc described in above-mentioned (6) or Zinc alloy electroplating method, wherein amine system chelating agent contains selected from alkylidene amination
It closes at least one kind of in object, its alkylene oxide addition product and chain triacontanol amine compound.
〔8〕
A kind of zinc or Zinc alloy electroplating system, including having the Alkaline Zinc of cathode and anode or Zinc alloy electroplating bath,
Anode is the anode for being coated with alkali resistance ceramics with the state that can be powered on conductive substrate, Alkaline Zinc or zinc
Alloy electroplating bath is the Alkaline Zinc plating bath containing organic compound additive or is to contain amine system chelating agent and organic compound
The Alkaline Zinc alloy electroplating bath of additive,
With use compared with the case where identical conductive substrate for not being coated with alkali resistance ceramics is as anode, Alkaline Zinc
The amine system chelating agent and organic compound additive in organic compound additive or Alkaline Zinc alloy electroplating bath in plating bath
By be powered caused by the oxygenolysis in above-mentioned anode surface be suppressed.
〔9〕
According to zinc described in above-mentioned (8) or Zinc alloy electroplating system, wherein the shape on conductive substrate can be powered
The anode that state is coated with alkali resistance ceramics is made of conductive substrate and alkali resistance ceramic coating.
〔10〕
According to zinc described in above-mentioned (8) or (9) or Zinc alloy electroplating system, wherein above-mentioned conductive substrate contain nickel and
It is at least one kind of in iron.
〔11〕
Zinc or Zinc alloy electroplating method according to any one of above-mentioned (8)~(10), wherein above-mentioned alkali resistance ceramics
Containing at least one kind of in tantalum oxide, aluminium oxide, tantalum nitride, aluminium nitride, silicon nitride, boron nitride, silicon carbide and boron carbide.
〔12〕
Zinc or Zinc alloy electroplating method according to any one of above-mentioned (8)~(11), wherein above-mentioned Alkaline Zinc or zinc
Alloy electroplating bath is at least Alkaline Zinc electroplating bath containing zinc ion, caustic alkali and organic compound additive.
〔13〕
Zinc or Zinc alloy electroplating method according to any one of above-mentioned (8)~(11), wherein above-mentioned Alkaline Zinc or zinc
Alloy electroplating bath is at least alkalinity containing zinc ion, metal ion, caustic alkali, amine system chelating agent and organic compound additive
Zinc alloy electroplating bath, above-mentioned metal ion contain at least 1 in nickel ion, iron ion, cobalt ions, tin ion and manganese ion
Kind.
〔14〕
According to zinc described in above-mentioned (13) or Zinc alloy electroplating method, wherein amine system chelating agent contains selected from alkylene amines
It is at least one kind of in compound, its alkylene oxide addition product and chain triacontanol amine compound.
According to the present invention, it is possible to provide economical and be able to maintain that zinc or Zinc alloy electroplating bath performance and realize the plating of long lifetime
Coating method and system.
Detailed description of the invention
Fig. 1 shows the results (plating appearance) of the plating tests of the Kazakhstan slot test based on embodiment 1.
Fig. 2 indicates the result (plating appearance) of the plating tests of the Kazakhstan slot test based on embodiment 2.
Fig. 3 indicates the result (plating appearance) of the plating tests of the Kazakhstan slot test based on embodiment 3.
Fig. 4 indicates the result (plating appearance) of the plating tests of the Kazakhstan slot test based on comparative example 1.
Fig. 5 indicates the result (plating appearance) of the plating tests of the Kazakhstan slot test based on comparative example 2.
Fig. 6 indicates the result (film thickness distribution) of the plating tests of the Kazakhstan slot test based on embodiment 1.
Fig. 7 indicates the result (distribution of Ni eutectoid rate) of the plating tests of the Kazakhstan slot test based on embodiment 1.
Fig. 8 shows the results (film thickness distribution) of the plating tests of the Kazakhstan slot test based on embodiment 2.
Fig. 9 indicates the result (distribution of Ni eutectoid rate) of the plating tests of the Kazakhstan slot test based on embodiment 2.
Figure 10 indicates the result (film thickness distribution) of the plating tests of the Kazakhstan slot test based on embodiment 3.
Figure 11 indicates the result (distribution of Ni eutectoid rate) of the plating tests of the Kazakhstan slot test based on embodiment 3.
Figure 12 indicates the result (film thickness distribution) of the plating tests of the Kazakhstan slot test based on comparative example 1.
Figure 13 indicates the result (distribution of Ni eutectoid rate) of the plating tests of the Kazakhstan slot test based on comparative example 1.
Figure 14 indicates the result (film thickness distribution) of the plating tests of the Kazakhstan slot test based on comparative example 2.
Figure 15 indicates the result (distribution of Ni eutectoid rate) of the plating tests of the Kazakhstan slot test based on comparative example 2.
Specific embodiment
Zinc or Zinc alloy electroplating method of the invention includes leading in the Alkaline Zinc alloy electroplating bath for having cathode and anode
The step of electricity.
As the metal combined with zinc as kirsite plating, such as a kind in nickel, iron, cobalt, tin, manganese can be enumerated
Above metal.Specifically, having admiro plating, zinc-iron alloy plating, zinc-cobalt alloy plating, manganese alloy plating, zinc
Tin alloy plating, zinc-nickel cobalt alloy plating etc., but it is not limited to these alloy platings.Kirsite plating is preferably admiro plating
It covers.
Cathode is the plated body for being carried out zinc or Zinc alloy electroplating.As plated body, the various gold such as iron, nickel, copper can be enumerated
Belong to and their alloy, or the metals such as aluminium for implementing zinc replacement Treatment, the plate object of alloy, cube, cylinder, cylinder,
The substance of various shapes such as sphere.
Anode uses the anode for being coated with alkali resistance ceramics with the state that can be powered on conductive substrate.As alkaline-resisting
Property ceramics, tantalum oxide, aluminium oxide, tantalum nitride, aluminium nitride, silicon nitride, boron nitride, silicon carbide, boron carbide etc. can be enumerated, but not
It is confined to this.Alkali resistance ceramics are preferably comprised selected from tantalum oxide, aluminium oxide, tantalum nitride, aluminium nitride, silicon nitride, boron nitride, carbonization
It is at least one kind of in silicon and boron carbide.The coating epithelium of alkali resistance ceramics can pass through sintering, vapor deposition, vapor deposition and sun
Pole oxidation etc. combination and be produced on conductive substrate, however, it is not limited to this.In addition, utilizing anchoring effect in order to obtain
Adaptation such as can be etched at the pre-treatment appropriate to conductive substrate.At this point, the arithmetic average roughness on such as surface
It (Ra) is preferably 3~4 μm.It should be noted that can on the coating epithelium of alkali resistance ceramics outside apply ion exchange resin etc..
The film thickness of the coating epithelium of alkali resistance ceramics is preferably from about 0.1~50 μm.Particularly preferably 0.5~1 μm.On if
It is blocked up to state film thickness, then powered reduces, if excessively thin, the effect decomposed is inhibited to reduce.For the coating skin of alkali resistance ceramics
For film, repeatedly above-mentioned production method can be carried out and make its total film thickness above range.The coating skin of alkali resistance ceramics
Emptying aperture diameter in film is preferably from about 0.1~5 μm.Further preferably 0.1~1 μm.If emptying aperture diameter is greater than 5 μm, press down
The effect that system is decomposed reduces.Here, the state that can be powered refers to that ion etc. can be moved using above-mentioned emptying aperture or crackle etc.
State.
Conductive substrate be preferably iron, nickel, stainless steel, carbon, titanium, zirconium, niobium, tantalum, platinum, the titanium of platinum plating, palladium-tin alloy or
The substrate that person is coated with by them, but as long as can be powered just is not limited to these.In conductive substrate further preferably nickel and iron
It is at least one kind of.
The anode of alkali resistance ceramics is coated with preferably by electric conductivity base with the state that can be powered on conductive substrate
The anode that material and alkali resistance ceramic coating are constituted.
Alkaline Zinc electroplating bath used in the present invention is the Alkaline Zinc plating bath containing organic compound additive.It is preferred that alkalinity
Zinc electroplating bath contains the organic compound addition selected from one or more of the auxiliary additives such as gloss agent, smooth agent and defoaming agent
Agent.Alkaline Zinc electroplating bath preferably comprises gloss agent.
Alkaline Zinc alloy electroplating bath used in the present invention is the alkali containing amine system chelating agent and organic compound additive
Property Zinc alloy electroplating bath.It is preferred that Alkaline Zinc alloy electroplating bath contains amine system chelating agent and organic compound additive, that is, it is selected from light
The organic compound additive of one or more of the auxiliary additives such as damp agent, smooth agent and defoaming agent.It is preferred that alkaline kirsite electricity
Plating bath contains gloss agent.
As gloss agent, as long as to be not particularly limited as long as well known gloss agent in the plating bath of zinc system, such as (1) can be enumerated
The nonionic surfactants, polyoxyethylene laurel ether such as polyoxyethylene polyoxypropylene block polymer, acetylenic glycols EO addition body
The anionic surfactants such as sulfate, alkyl diphenyl base ether disulfonate；(2) diallyldimethylammonium chloride and dioxy
Change the polyallylamines such as the copolymer of sulphur；The condensation polymer of ethylenediamine and epichlorohydrin, the condensation polymer of dimethylaminopropylamine and epichlorohydrin, miaow
The condensation polymer of the imdazole derivatives such as the condensation polymer of azoles and epichlorohydrin, 1- methylimidazole or 2-methylimidazole and epichlorohydrin contains
The polycyclics oxygen polyamines such as the condensation polymer of the miscellaneous cyclic amines of the pyrrolotriazine derivatives such as acetylguanamine, benzoguanamine etc. and epichlorohydrin；3- diformazan
The polyamines polyureas such as the condensation polymer of the condensation polymer of aminopropyl urea and epichlorohydrin, bis- (N, N- dimethylamino-propyl) ureas and epichlorohydrin
The polyamide such as the water-soluble nylons resins such as the condensation polymer of resin, N, N- dimethylaminopropylamine and alkylene dicarboxylic acids and epichlorohydrin
Polyamines；The condensation polymer of diethylenetriamine, dimethylaminopropylamine etc. and 2,2 '-dichlorodiethyl ethers, dimethylaminopropylamine and 1,3-
Condensation polymer, the N of dichloropropane, N, N ', condensation polymer, the N of N '-tetramethyl -1,3- diaminopropanes and 1,4- dichloroetane,
N, N ', the polyalkylene polyamines such as condensation polymer of N '-tetramethyl -1,3- diaminopropanes and 1,3- dichloropropane -2- alcohol
Equal polyamine compounds class；(3) condensation polymer of dimethylamine etc. and dichloroether；(4) aromatic series such as veratraldehyde, vanillic aldehyde, anisaldehyde
Aldehydes, benzoic acid or its salt；(5) hexadecyltrimethylammonium chloride, 3- carbamoyl benzyl chloride, pyridineEqual quaternary ammonium salts
Class etc..Wherein, preferably quaternary ammonium salt and aromatic series aldehydes.These gloss agents can be used alone, or be applied in combination 2 kinds with
On.Concentration of the gloss agent in Alkaline Zinc or Zinc alloy electroplating bath is excellent for aromatic series aldehydes, benzoic acid or its salt
It is selected as 1~500mg/L, further preferably 5~100mg/L, in other cases, preferably 0.01~10g/L is further excellent
It is selected as 0.02~5g/L.
In addition, gloss agent can be nitrogen-containing heterocycle quaternary ammonium salt.Above-mentioned nitrogen-containing heterocycle quaternary ammonium salt gloss agent is more preferably carboxyl
And/or hydroxyl substituted nitrogen-containing heterocyclic quaternary ammonium salt.As the nitrogen-containing heterocycle of above-mentioned nitrogen-containing heterocycle quaternary ammonium salt, such as pyridine can be enumerated
Ring, piperidine ring, imidazole ring, imidazoline ring, pyrrolidine ring, pyrazole ring, quinoline ring, morpholine ring etc., preferably pyridine ring, it is especially excellent
It is selected as the quaternary ammonium salt of niacin or derivatives thereof.Carboxyl and/or hydroxyl are for example in the form of carboxymethyl in above-mentioned quarternary ammonium salt compound
Nitrogen-containing heterocycle is replaced via substituent group.In addition, above-mentioned nitrogen-containing heterocycle is in addition to carboxyl and/or hydroxyl, such as also
It can have the substituent groups such as alkyl.As long as forming the N of heterocyclic quaternary ammonium cation in addition, not hindering the effect containing gloss agent
Substituent group is not particularly limited, such as substitution, unsubstituted alkyl, aryl, alkoxy can be enumerated etc..In addition, as forming salt
Counter anion, such as can enumerate containing halide anion, oxo-anions, borate anion, azochlorosulfonate acid anion, phosphorus
The compound of acid radical anion, imide anion etc., preferably halide anion.Such quaternary ammonium salt is because in the molecule simultaneously
Containing quaternary ammonium cation and oxo-anions, so also show that the behavior as anion, so it is preferred that.As nitrogen-containing heterocycle
The concrete example of quarternary ammonium salt compound, for example, N- benzyl -3- carboxyl pyridine can be enumeratedChloride, N- phenethyl -4-
Carboxyl pyridineChloride, N- butyl -3- carboxyl pyridineBromide, N- chloromethyl -3- carboxyl pyridineBromination
Object, N- hexyl -6- hydroxyl -3- carboxyl pyridineChloride, N- hexyl -6-3- hydroxypropyl -3- carboxyl pyridineChloride, N-2- ethoxy -6- methoxyl group -3- carboxyl pyridineChloride, N- methoxyl group -6- methyl -
3- carboxyl pyridineChloride, N- propyl -2- methyl -6- phenyl -3- carboxyl pyridineChloride, N- propyl-
2- methyl -6- phenyl -3- carboxyl pyridineChloride, N- benzyl -3- carboxymethyl pyridineChloride, 1- fourth
Base -3- methyl -4- carboxyl imidazolesBromide, 1- butyl -3- methyl -4- carboxymethyl imidazolesBromide, 1-
Butyl -2- methylol -3- methylimidazoleChloride, 1- butyl -1- methyl -3- methyl carboxy pyrrole alkaneChlorine
Compound, 1- butyl -1- methyl -4- methyl carboxypiperidinChloride etc..These nitrogen-containing heterocycle quaternary ammonium salts can be independent
It uses, or two or more use can be combined.Concentration of the nitrogen-containing heterocycle quaternary ammonium salt in Alkaline Zinc or Zinc alloy electroplating bath is preferred
For 0.01~10g/L, further preferably 0.02~5g/L.
As auxiliary additive, such as organic acid, silicate, sulfhydryl compound can be enumerated etc..These auxiliary additives
It can be used alone, or two or more use can be combined.Concentration of the auxiliary additive in Alkaline Zinc or Zinc alloy electroplating bath
Preferably 0.01~50g/L.
As defoaming agent, such as surfactant can be enumerated etc..These defoaming agents can be used alone, or can combine
Two or more is used.Concentration of the defoaming agent in Alkaline Zinc or Zinc alloy electroplating bath is preferably 0.01~5g/L.
As amine system chelating agent, such as ethylenediamine, diethylenetriamine, triethylene tetramine, tetraethylenepentamine, five second can be enumerated
The alkylidene amine compounds such as alkene hexamine；The alkylene oxides such as ethylene oxide adduct, the propylene oxide adduct of above-mentioned alkylene amines add
At object；Ethanol amine, diethanol amine, triethanolamine, diisopropanolamine (DIPA), triisopropanolamine, ethylenediamine tetraacetic -2- propyl alcohol, N- (2-
Aminoethyl) amino alcohols such as ethanol amine, 2- hydroxyethylamino propylamine；N- (2- ethoxy)-N, N ', N '-triethyl group second two
Amine, N, N '-two (2- ethoxy)-N, N '-diethyl ethylenediamine, N, N, N ', N '-four (2- ethoxy) propane diamine, N,
N, N ', the chain triacontanol amine compounds such as N '-four (2- hydroxypropyl) ethylenediamine；It is obtained by aziridine, 1,2- propyleneimine etc.
Poly- (alkyleneimines)；Poly- (alkylene amines) etc. obtained by ethylenediamine, triethylene tetramine etc..Amine system chelating agent preferably comprises choosing
From one or more of alkylidene amine compound, its alkylene oxide addition product and chain triacontanol amine compound.These amine system chelating agents can be with
It is used alone, or two or more use can be combined.Alkaline Zinc or the concentration of the amine system chelating agent in Zinc alloy electroplating bath are preferred
For 5~200g/L, more preferably 30~100g/L.
Alkaline Zinc used in the present invention or Zinc alloy electroplating bath contain zinc ion.In Alkaline Zinc or Zinc alloy electroplating bath
The concentration of zinc ion is preferably 2~20g/L, more preferably 4~12g/L.As zinc ion source, Na can be enumerated2[Zn(OH)4]、K2
[Zn(OH)4], ZnO etc..These zinc ion sources can be used alone, or can combine two or more use.
Alkaline Zinc used in the present invention or Zinc alloy electroplating bath preferably comprise caustic alkali.As caustic alkali, hydrogen can be enumerated
Sodium oxide molybdena, potassium hydroxide etc., preferably sodium hydroxide.Alkaline Zinc or the concentration of the caustic alkali in Zinc alloy electroplating bath are preferably 60
~200g/L, more preferably 100~160g/L.
Alkaline Zinc alloy electroplating bath used in the present invention contains the metal ion in addition to zinc.Alkaline Zinc alloy electroplating bath
In, as above-mentioned metal ion, preferably comprise a kind in nickel ion, iron ion, cobalt ions, tin ion and manganese ion with
On metal ion.The total concentration of above-mentioned metal ion in Alkaline Zinc alloy electroplating bath is preferably 0.4~4g/L, more preferably
1~3g/L.As metal ion source, nickel sulfate, ferrous sulfate, cobaltous sulfate, stannous sulfate, manganese sulfate etc. can be enumerated.These gold
Belonging to ion source can be used alone, or can combine two or more use.Alkaline Zinc alloy electroplating bath used in the present invention is excellent
It is selected as the Electrodeposition of Zn-ni Alloy In Alkaline Bath bath for containing nickel ion as above-mentioned metal ion.
Alkaline Zinc electroplating bath is preferably at least the Alkaline Zinc plating containing zinc ion, caustic alkali and organic compound additive
Bath.
Alkaline Zinc alloy electroplating bath more preferably at least contains zinc ion, metal ion, caustic alkali, amine system chelating agent and has
The Alkaline Zinc alloy electroplating bath of machine compound additive, above-mentioned metal ion contain selected from nickel ion, iron ion, cobalt ions, tin
It is at least one kind of in ion and manganese ion.
Temperature when implementing zinc or kirsite plating is preferably 15 DEG C~40 DEG C, further preferably 25~35 DEG C.Implement
Cathode-current density when zinc or kirsite plating is preferably 0.1~20A/dm2, further preferably 0.2~10A/dm2。
Next, by embodiment and comparative example, the present invention will be described, but the present invention is not restricted to these.
Embodiment
(embodiment 1)
Using on Ni with 0.5~0.8 μm of thickness be coated with tantalum oxide anode plate (surface roughness Ra: 4 μm, 64
× 64 × 2mm), and using alkaline zinc-nickel alloy plating bath (500mL) shown in following, implement zinc-nickel using 500Ah/L energization
Alloy plating.The emptying aperture diameter being coated in epithelium is 0.1~1 μm, and plating bath drains out as 2mL/Ah.Cathode-current density is 4A/
dm2, anodic current density 9.8A/dm2, plating bath is 25 DEG C.By plating bath cooling and maintain 25 DEG C.Cathode uses iron plate.It answers
Explanation is given, every 16Ah/L just replaces the iron plate of cathode in energization.The zinc ion concentration of plating bath by make metallic zinc dipping dissolution come
Remain constant.The nickel ion concentration of plating bath feeds the IZ-250YNi (DIPSOL corporation) of agent by supply nickel to remain permanent
It is fixed.The naoh concentration of periodic analysis plating bath, and carrying out supply makes concentration remain constant.Gloss agent is by the IZ- of polyamines system
250YR1 (DIPSOL corporation) and the IZ-250YR2 (DIPSOL corporation) of nitrogen-containing heterocycle quaternary ammonium salt system are respectively with recharge rate
15mL/kAh and 15mL/kAh supply.Amine system chelating agent IZ-250YB is fed with the recharge rate 80mL/kAh of IZ-250YB.
Every energization 250Ah/L just analyzes amine system chelating agent concentrations, concentration of oxalic acid and concentration of cyanide in catholyte.In addition, passing through mesh
There is deposit-free depending on observing to confirm.These results are shown in table 1.In turn, 500Ah/L be powered when by chelating agent concentrations and just
Beginning concentration merges, and uses the plating for carrying out testing using the iron plate of 20cm as the long battery (long cell) of cathode based on Kazakhstan slot
Test, measurement plating appearance, film thickness distribution and the distribution of Ni eutectoid rate.These results are shown in Fig. 1, Fig. 6 and Fig. 7.It should
Illustrate, the condition of the plating tests based on the test of Kazakhstan slot is 4A-20 minutes, 25 DEG C.In addition, the surface of observation anode, confirmation
Whether there is or not epithelium removings.Show the result in table 1.
Plating solution composition:
(Zn ion source is Na to Zn ion concentration 8g/L2[Zn(OH)4])
(Ni ion source is NiSO to Ni ion concentration 1.6g/L4·6H2O)
Naoh concentration 130g/L
Amine system chelating agent (ethylene oxide adducts of alkylene amines) IZ-250YB (DIPSOL corporation) 60g/L
Gloss agent IZ-250YR1 (DIPSOL corporation) 0.6mL/L (polyamines 0.1g/L)
Gloss agent IZ-250YR2 (DIPSOL corporation) 0.5mL/L (the quaternary ammonium salt 0.2g/L of niacin)
(embodiment 2)
Using on Fe with 0.5~0.8 μm of thickness be coated with tantalum oxide anode plate (surface roughness Ra: 4 μm, 64
× 64 × 2mm), and using alkaline zinc-nickel alloy plating bath (500mL) shown in following, implement zinc-nickel using 500Ah/L energization
Alloy plating.The emptying aperture diameter being coated in epithelium is 0.1~1 μm, and plating bath drains out as 2mL/Ah.Cathode-current density is 4A/
dm2, anodic current density 9.8A/dm2, plating bath is 25 DEG C.By plating bath cooling and maintain 25 DEG C.Cathode uses iron plate.
It should be noted that every 16Ah/L just replaces the iron plate of cathode in being powered.The zinc ion concentration of plating bath is by making metallic zinc dipping dissolution
To remain constant.The nickel ion concentration of plating bath feeds the IZ-250YNi (DIPSOL corporation) of agent by supply nickel to remain permanent
It is fixed.The naoh concentration of periodic analysis plating bath, and carrying out supply makes concentration remain constant.Gloss agent is by the IZ- of polyamines system
250YR1 (DIPSOL corporation) and the IZ-250YR2 (DIPSOL corporation) of nitrogen-containing heterocycle quaternary ammonium salt system are respectively with recharge rate
15mL/kAh and 15mL/kAh supply.Amine system chelating agent IZ-250YB is fed with the recharge rate 80mL/kAh of IZ-250YB.
Every energization 250Ah/L just analyzes amine system chelating agent concentrations, concentration of oxalic acid and concentration of cyanide in catholyte.In addition, passing through mesh
There is deposit-free depending on observing to confirm.These results are shown in table 1.In turn, 500Ah/L be powered when by chelating agent concentrations and just
Beginning concentration merges, and uses the plating tests for carrying out testing using the iron plate of 20cm as the long battery of cathode based on Kazakhstan slot, measurement plating
Cover appearance, film thickness distribution and the distribution of Ni eutectoid rate.These results are shown in Fig. 2, Fig. 8 and Fig. 9.It should be noted that based on breathing out
The condition of the plating tests of family name's slot test is 4A-20 minutes, 25 DEG C.In addition, the surface of observation anode, whether there is or not epithelium strippings for confirmation
From.Show the result in table 1.
Plating solution composition:
(Zn ion source is Na to Zn ion concentration 8g/L2[Zn(OH)4])
(Ni ion source is NiSO to Ni ion concentration 1.6g/L4·6H2O)
Naoh concentration 130g/L
Amine system chelating agent (ethylene oxide adducts of alkylene amines) IZ-250YB (DIPSOL corporation) 60g/L
Gloss agent IZ-250YR1 (DIPSOL corporation) 0.6mL/L (polyamines 0.1g/L) gloss agent IZ-250YR2
(DIPSOL corporation) 0.5mL/L (the quaternary ammonium salt 0.2g/L of niacin)
(embodiment 3)
Using on Ni with 0.5~0.8 μm of thickness be coated with tantalum oxide anode plate (surface roughness Ra: 4 μm, 64
× 64 × 2mm), and using alkaline zinc-nickel alloy plating bath (500mL) shown in following, implement zinc-nickel using 500Ah/L energization
Alloy plating.The emptying aperture diameter being coated in epithelium is 0.1~1 μm, and plating bath drains out as 2mL/Ah.Cathode-current density is 2A/
dm2, anodic current density 4.9A/dm2, plating bath is 25 DEG C.By plating bath cooling and maintain 25 DEG C.Cathode uses iron plate.
It should be noted that every 16Ah/L just replaces the iron plate of cathode in being powered.The zinc ion concentration of plating bath is by making metallic zinc dipping dissolution
To remain constant.The nickel ion concentration of plating bath feeds the IZ-250YNi (DIPSOL corporation) of agent by supply nickel to remain permanent
It is fixed.The naoh concentration of periodic analysis plating bath, and carrying out supply makes concentration remain constant.Gloss agent is by the IZ- of polyamines system
250YR1 (DIPSOL corporation) and the IZ-250YR2 (DIPSOL corporation) of nitrogen-containing heterocycle quaternary ammonium salt system are respectively with recharge rate
15mL/kAh and 15mL/kAh supply.Amine system chelating agent tetraethylenepentamine is with recharge rate 40mL/kAh supply.Every energization
250Ah/L just analyzes amine system chelating agent concentrations and concentration of cyanide in catholyte.In addition, by visual observation observe confirm whether there is or not
Sediment.These results are shown in table 2.In turn, chelating agent concentrations are merged when 500Ah/L is powered with initial concentration, is used
Using the iron plate of 20cm as the long battery of cathode, the plating tests tested based on Kazakhstan slot are carried out, measure plating appearance, film thickness distribution
It is distributed with Ni eutectoid rate.These results are shown in Fig. 3, Figure 10 and Figure 11.It should be noted that the plating based on the test of Kazakhstan slot
The condition of test is 2A-20 minutes, 25 DEG C.
Plating solution composition:
(Zn ion source is Na to Zn ion concentration 8g/L2[Zn(OH)4])
(Ni ion source is NiSO to Ni ion concentration 1.2g/L4·6H2O)
Naoh concentration 130g/L
Amine system chelating agent (tetraethylenepentamine) 30g/L
Gloss agent IZ-250YR1 (DIPSOL corporation) 0.6mL/L (polyamines 0.1g/L)
Gloss agent IZ-250YR2 (DIPSOL corporation) 0.5mL/L (the quaternary ammonium salt 0.2g/L of niacin)
(comparative example 1)
Using alkaline zinc-nickel alloy plating bath (500mL) shown in following, implement admiro plating using 500Ah/L energization
It covers.Plating bath drains out as 2mL/Ah.Cathode-current density is 4A/dm2, anodic current density 9.8A/dm2, plating bath 25
℃.By plating solution cooling and maintain 25 DEG C.Cathode uses iron plate, and anode uses nickel plate.It should be noted that be powered in every 16Ah/L just
Replace the iron plate of cathode.The zinc ion concentration of plating bath remains constant by making the dissolution of metallic zinc dipping.The nickel ion of plating bath is dense
Degree feeds the IZ-250YNi (DIPSOL corporation) of agent by supply nickel to remain constant.The sodium hydroxide of periodic analysis plating bath
Concentration, and carrying out supply makes concentration remain constant.Gloss agent is the IZ-250YR1 (DIPSOL corporation) by polyamines system and contains
The IZ-250YR2 (DIPSOL corporation) of azacyclo- quaternary ammonium salt system is respectively with recharge rate 15mL/kAh and 15mL/kAh supply.Amine
It is that chelating agent IZ-250YB is fed with the recharge rate 80mL/kAh of IZ-250YB.Every energization 250Ah/L just analyzes amine system chela
Mixture concentration, concentration of oxalic acid and concentration of cyanide.In addition, observe has deposit-free to confirm by visual observation.These results are shown
In table 1.Also, chelating agent concentrations are merged with initial concentration when 500Ah/L is powered, are used using the iron plate of 20cm as cathode
Long battery carries out the plating tests tested based on Kazakhstan slot, measurement plating appearance, film thickness distribution and the distribution of Ni eutectoid rate.By this
A little results are shown in Fig. 4, Figure 12 and Figure 13.It should be noted that the condition of the plating tests based on the test of Kazakhstan slot is 4A-20
Minute, 25 DEG C.
Plating solution composition:
(Zn ion source is Na to Zn ion concentration 8g/L2[Zn(OH)4])
(Ni ion source is NiSO to Ni ion concentration 1.6g/L4·6H2O)
Naoh concentration 130g/L
Amine system chelating agent (ethylene oxide adducts of alkylene amines) IZ-250YB (DIPSOL corporation) 60g/L
Gloss agent IZ-250YR1 (DIPSOL corporation) 0.6mL/L (polyamines 0.1g/L)
Gloss agent IZ-250YR2 (DIPSOL corporation) 0.5mL/L (the quaternary ammonium salt 0.2g/L of niacin)
(comparative example 2)
Using on Pt/Ti with 0.5~0.8 μm of thickness be coated with yttrium oxide anode plate (surface roughness Ra: 4 μm,
64 × 64 × 2mm), and using alkaline zinc-nickel alloy plating bath (500mL) shown in following, implement zinc using 500Ah/L energization
Nickel alloy plating.The emptying aperture diameter being coated in epithelium is 0.1~1 μm, and plating bath drains out as 2mL/Ah.Cathode-current density is
4A/dm2, anodic current density 9.8A/dm2, plating bath is 25 DEG C.By plating bath cooling and maintain 25 DEG C.Cathode uses iron
Plate.It should be noted that every 16Ah/L just replaces the iron plate of cathode in being powered.The zinc ion concentration of plating bath is molten by impregnating metallic zinc
Solution remains constant.The nickel ion concentration of plating bath feeds the IZ-250YNi (DIPSOL corporation) of agent by supply nickel to maintain
It is constant.The naoh concentration of periodic analysis plating bath, and carrying out supply makes concentration remain constant.Gloss agent is by polyamines system
IZ-250YR1 (DIPSOL corporation) and the IZ-250YR2 (DIPSOL corporation) of nitrogen-containing heterocycle quaternary ammonium salt system is respectively to mend
It is fed to rate 15mL/kAh and 15mL/kAh.Amine system chelating agent IZ-250YB is mended with the recharge rate 80mL/kAh of IZ-250YB
It gives.Every energization 250Ah/L just analyzes amine system chelating agent concentrations, concentration of oxalic acid and concentration of cyanide in catholyte.In addition, passing through
Visually observation has deposit-free to confirm.These results are shown in table 1.In turn, 500Ah/L be powered when by chelating agent concentrations with
Initial concentration merges, and uses the plating tests for carrying out testing using the iron plate of 20cm as the long battery of cathode based on Kazakhstan slot, measurement
Plating appearance, film thickness distribution and the distribution of Ni eutectoid rate.These results are shown in Fig. 5, Figure 14 and Figure 15.It should be noted that base
In Kazakhstan slot test plating tests condition be 4A-20 minutes, 25 DEG C.In addition, the surface of observation anode, whether there is or not skins for confirmation
Film stripping.Show the result in table 1.
Plating solution composition:
(Zn ion source is Na to Zn ion concentration 8g/L2[Zn(OH)4])
(Ni ion source is NiSO to Ni ion concentration 1.6g/L4·6H2O)
Naoh concentration 130g/L
Amine system chelating agent (ethylene oxide adducts of alkylene amines) IZ-250YB (DIPSOL corporation) 60g/L
Gloss agent IZ-250YR1 (DIPSOL corporation) 0.6mL/L (polyamines 0.1g/L)
Gloss agent IZ-250YR2 (DIPSOL corporation) 0.5mL/L (the quaternary ammonium salt 0.2g/L of niacin)
The presence or absence of 1 amine system chelating agent concentrations of table, the differentiation of concentration of oxalic acid and concentration of cyanide and precipitating and epithelium removing
[table 1]
The presence or absence of the differentiation of 2 amine system chelating agent concentrations of table and concentration of cyanide and precipitating
[table 2]
Examples 1 to 3 is compared with comparative example 1 and 2, it can be seen that effect below.
(1) decomposition of amine system chelating agent is inhibited.
(2) inhibit the reduction of plating appearance.
(3) inhibit the reduction of plating rate.
(4) inhibit the reduction of Ni eutectoid rate.
By means of the invention it is possible to realize the long-life of Alkaline Zinc or zinc alloy coating bath, particularly alkaline zinc-nickel alloy plating bath
Change.In addition, can be realized plating by Alkaline Zinc or zinc alloy coating bath, particularly the long lifetime of alkaline zinc-nickel alloy plating bath
Stabilisation, the shortening of Plating times, the burden mitigationization of drainage sunk well of quality.
Claims (14)
1. a kind of zinc or Zinc alloy electroplating method, including being powered in Alkaline Zinc or the Zinc alloy electroplating bath for having cathode and anode
The step of,
Anode is the anode for being coated with alkali resistance ceramics with the state that can be powered on conductive substrate,
Alkaline Zinc or Zinc alloy electroplating bath are the Alkaline Zinc plating bath containing organic compound additive or are to chelate containing amine system
The Alkaline Zinc alloy electroplating bath of agent and organic compound additive,
With use compared with the case where identical conductive substrate for not being coated with alkali resistance ceramics is as anode, Alkaline Zinc plating bath
In organic compound additive or Alkaline Zinc alloy electroplating bath in amine system chelating agent and organic compound additive by
The oxygenolysis in the anode surface caused by being powered is suppressed.
2. zinc according to claim 1 or Zinc alloy electroplating method, wherein the shape on conductive substrate can be powered
The anode that state is coated with alkali resistance ceramics is made of conductive substrate and alkali resistance ceramic coating.
3. zinc according to claim 1 or 2 or Zinc alloy electroplating method, wherein the conductive substrate contains nickel and iron
In it is at least one kind of.
4. zinc described in any one of claim 1 to 3 or Zinc alloy electroplating method, wherein the alkali resistance ceramics contain
Have at least one kind of in tantalum oxide, aluminium oxide, tantalum nitride, aluminium nitride, silicon nitride, boron nitride, silicon carbide and boron carbide.
5. zinc according to any one of claims 1 to 4 or Zinc alloy electroplating method, wherein the Alkaline Zinc or zinc close
Gold electroplating bath is at least Alkaline Zinc electroplating bath containing zinc ion, caustic alkali and organic compound additive.
6. zinc according to any one of claims 1 to 4 or Zinc alloy electroplating method, wherein the Alkaline Zinc or zinc close
Gold electroplating bath is at least Alkaline Zinc containing zinc ion, metal ion, caustic alkali, amine system chelating agent and organic compound additive
Alloy electroplating bath, the metal ion contain at least 1 in nickel ion, iron ion, cobalt ions, tin ion and manganese ion
Kind.
7. zinc according to claim 6 or Zinc alloy electroplating method, wherein amine system chelating agent contains selected from alkylidene amination
It closes at least one kind of in object, its alkylene oxide addition product and chain triacontanol amine compound.
8. a kind of zinc or Zinc alloy electroplating system, including having the Alkaline Zinc of cathode and anode or Zinc alloy electroplating bath,
Anode is the anode for being coated with alkali resistance ceramics with the state that can be powered on conductive substrate,
Alkaline Zinc or Zinc alloy electroplating bath are the Alkaline Zinc plating bath containing organic compound additive or are to chelate containing amine system
The Alkaline Zinc alloy electroplating bath of agent and organic compound additive,
With use compared with the case where identical conductive substrate for not being coated with alkali resistance ceramics is as anode, Alkaline Zinc plating bath
In organic compound additive or Alkaline Zinc alloy electroplating bath in amine system chelating agent and organic compound additive by
The oxygenolysis in the anode surface caused by being powered is suppressed.
9. zinc according to claim 8 or Zinc alloy electroplating system, wherein the shape on conductive substrate can be powered
The anode that state is coated with alkali resistance ceramics is made of conductive substrate and alkali resistance ceramic coating.
10. zinc or Zinc alloy electroplating system according to claim 8 or claim 9, wherein the conductive substrate contains nickel and iron
In it is at least one kind of.
11. zinc according to any one of claims 8 to 10 or Zinc alloy electroplating method, wherein the alkali resistance ceramics
Containing at least one kind of in tantalum oxide, aluminium oxide, tantalum nitride, aluminium nitride, silicon nitride, boron nitride, silicon carbide and boron carbide.
12. the zinc according to any one of claim 8~11 or Zinc alloy electroplating method, wherein the Alkaline Zinc or zinc
Alloy electroplating bath is at least Alkaline Zinc electroplating bath containing zinc ion, caustic alkali and organic compound additive.
13. the zinc according to any one of claim 8~11 or Zinc alloy electroplating method, wherein the Alkaline Zinc or zinc
Alloy electroplating bath is at least alkalinity containing zinc ion, metal ion, caustic alkali, amine system chelating agent and organic compound additive
Zinc alloy electroplating bath, the metal ion contain at least 1 in nickel ion, iron ion, cobalt ions, tin ion and manganese ion
Kind.
14. zinc according to claim 13 or Zinc alloy electroplating method, wherein amine system chelating agent contains selected from alkylene amination
It closes at least one kind of in object, its alkylene oxide addition product and chain triacontanol amine compound.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2019/005548 WO2020166062A1 (en) | 2019-02-15 | 2019-02-15 | Zinc or zinc alloy electroplating method and system |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110462107A true CN110462107A (en) | 2019-11-15 |
Family
ID=68095230
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201980001581.1A Pending CN110462107A (en) | 2019-02-15 | 2019-02-15 | Zinc or Zinc alloy electroplating method and system |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20200263314A1 (en) |
| EP (1) | EP3715506A4 (en) |
| JP (1) | JP6582353B1 (en) |
| CN (1) | CN110462107A (en) |
| WO (1) | WO2020166062A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111826691A (en) * | 2020-08-21 | 2020-10-27 | 东北大学 | Method for preparing zinc-tantalum alloy by using solvated ionic liquid |
| CN116406432A (en) * | 2021-12-02 | 2023-07-07 | 迪普索股份公司 | Method and system for electroplating articles with metal |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021131340A1 (en) * | 2019-12-23 | 2021-07-01 | ディップソール株式会社 | Zinc nickel plating bath and plating method using same |
| CN116670334A (en) | 2020-12-28 | 2023-08-29 | 迪普索股份公司 | Method and system for electroplating articles with metal |
| WO2023100381A1 (en) | 2021-12-02 | 2023-06-08 | ディップソール株式会社 | Method and system for electroplating article with metal |
| JP7442866B1 (en) | 2022-11-25 | 2024-03-05 | ディップソール株式会社 | Electroplating anodes and methods and systems for electroplating articles with metals |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01298192A (en) * | 1988-05-27 | 1989-12-01 | Ebara Yuujiraito Kk | Zinc-nickel alloy plating solution |
| JPH03240987A (en) * | 1990-02-16 | 1991-10-28 | Tdk Corp | Organic matter electrolyzing electrode and its production |
| US6432293B1 (en) * | 1999-03-03 | 2002-08-13 | Permelec Electrode Ltd. | Process for copper-plating a wafer using an anode having an iridium oxide coating |
| JP2004068153A (en) * | 2002-07-23 | 2004-03-04 | Nippon Hyomen Kagaku Kk | Galvanizing method with zincate bath |
| CN103827360A (en) * | 2011-09-13 | 2014-05-28 | 学校法人同志社 | Positive electrode for electrolytic plating and electrolytic plating method using positive electrode |
| CN105189831A (en) * | 2013-03-21 | 2015-12-23 | 安美特德国有限公司 | Apparatus and method for electrolytic deposition of metal layers on workpieces |
| CN106550607A (en) * | 2015-07-22 | 2017-03-29 | 迪普索股份公司 | Kirsite method for plating |
| CN106550606A (en) * | 2015-07-22 | 2017-03-29 | 迪普索股份公司 | Kirsite method for plating |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3658823B2 (en) * | 1995-11-30 | 2005-06-08 | ダイソー株式会社 | Electrode for electrolysis and method for producing the same |
| DE19834353C2 (en) | 1998-07-30 | 2000-08-17 | Hillebrand Walter Gmbh & Co Kg | Alkaline zinc-nickel bath |
| US7247229B2 (en) * | 1999-06-28 | 2007-07-24 | Eltech Systems Corporation | Coatings for the inhibition of undesirable oxidation in an electrochemical cell |
| ES2324169T3 (en) | 2005-04-26 | 2009-07-31 | Atotech Deutschland Gmbh | ALCALINE GALVANIC BATHROOM WITH A FILTRATION MEMBRANE. |
| JP4738910B2 (en) | 2005-06-21 | 2011-08-03 | 日本表面化学株式会社 | Zinc-nickel alloy plating method |
| JP5676515B2 (en) * | 2012-04-11 | 2015-02-25 | マテックス・ジャパン株式会社 | Insoluble metal electrode, electrolysis apparatus, and plating method |
| EP3358045A1 (en) * | 2017-02-07 | 2018-08-08 | Dr.Ing. Max Schlötter GmbH & Co. KG | Method for the galvanic deposition of zinc and zinc alloy layers from an alkaline coating bath with reduced degradation of organic bath additives |
-
2019
- 2019-02-15 CN CN201980001581.1A patent/CN110462107A/en active Pending
- 2019-02-15 JP JP2019508981A patent/JP6582353B1/en active Active
- 2019-02-15 EP EP19766159.8A patent/EP3715506A4/en not_active Withdrawn
- 2019-02-15 WO PCT/JP2019/005548 patent/WO2020166062A1/en unknown
- 2019-09-20 US US16/577,895 patent/US20200263314A1/en not_active Abandoned
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01298192A (en) * | 1988-05-27 | 1989-12-01 | Ebara Yuujiraito Kk | Zinc-nickel alloy plating solution |
| JPH03240987A (en) * | 1990-02-16 | 1991-10-28 | Tdk Corp | Organic matter electrolyzing electrode and its production |
| US6432293B1 (en) * | 1999-03-03 | 2002-08-13 | Permelec Electrode Ltd. | Process for copper-plating a wafer using an anode having an iridium oxide coating |
| JP2004068153A (en) * | 2002-07-23 | 2004-03-04 | Nippon Hyomen Kagaku Kk | Galvanizing method with zincate bath |
| CN103827360A (en) * | 2011-09-13 | 2014-05-28 | 学校法人同志社 | Positive electrode for electrolytic plating and electrolytic plating method using positive electrode |
| CN105189831A (en) * | 2013-03-21 | 2015-12-23 | 安美特德国有限公司 | Apparatus and method for electrolytic deposition of metal layers on workpieces |
| CN106550607A (en) * | 2015-07-22 | 2017-03-29 | 迪普索股份公司 | Kirsite method for plating |
| CN106550606A (en) * | 2015-07-22 | 2017-03-29 | 迪普索股份公司 | Kirsite method for plating |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111826691A (en) * | 2020-08-21 | 2020-10-27 | 东北大学 | Method for preparing zinc-tantalum alloy by using solvated ionic liquid |
| CN111826691B (en) * | 2020-08-21 | 2021-09-21 | 东北大学 | Method for preparing zinc-tantalum alloy by using solvated ionic liquid |
| CN116406432A (en) * | 2021-12-02 | 2023-07-07 | 迪普索股份公司 | Method and system for electroplating articles with metal |
Also Published As
| Publication number | Publication date |
|---|---|
| EP3715506A1 (en) | 2020-09-30 |
| US20200263314A1 (en) | 2020-08-20 |
| WO2020166062A1 (en) | 2020-08-20 |
| JPWO2020166062A1 (en) | 2021-02-25 |
| EP3715506A4 (en) | 2021-04-14 |
| JP6582353B1 (en) | 2019-10-02 |
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