CN109267122A - A kind of non-cyanide alkali Zinc-nickel alloy electroplating liquid and its preparation process - Google Patents

A kind of non-cyanide alkali Zinc-nickel alloy electroplating liquid and its preparation process Download PDF

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Publication number
CN109267122A
CN109267122A CN201811394338.4A CN201811394338A CN109267122A CN 109267122 A CN109267122 A CN 109267122A CN 201811394338 A CN201811394338 A CN 201811394338A CN 109267122 A CN109267122 A CN 109267122A
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nickel
solution
alloy electroplating
nickel alloy
epoxychloropropane
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CN201811394338.4A
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薛家伟
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Shanghai Lixuan Chemical Co
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Shanghai Lixuan Chemical Co
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/56Electroplating: Baths therefor from solutions of alloys

Abstract

The present invention discloses a kind of non-cyanide alkali Zinc-nickel alloy electroplating liquid, and every liter of electroplate liquid includes following components: 7-18g zinc oxide, 120-140g sodium hydroxide, 15-20mL nickel replenishers, 100-140mL nickel complexing agent, 2-10mL brightener M, 2-10mL brightener B, surplus are water.The invention can not only reduce nickel metal resource, secondary coating of withholding is not fallen off after can also guaranteeing product plating simultaneously, and after using electroplate liquid of the present invention carrying out coating, the heat-resisting, corrosion resistance of zinc-nickel alloy coating is preferable, salt spray resistance 1000 hours, coating uniform bright, coating ductility it is preferable;Meanwhile invention additionally discloses a kind of preparation process of non-cyanide alkali Zinc-nickel alloy electroplating liquid, preparation process is simple, easy to operate, at low cost, is suitable for large-scale production and uses.

Description

A kind of non-cyanide alkali Zinc-nickel alloy electroplating liquid and its preparation process
Technical field
The invention belongs to electroplate liquid technical fields, and in particular to a kind of non-cyanide alkali Zinc-nickel alloy electroplating liquid and its preparation work Skill.
Background technique
Zn-ni alloy deposits are a kind of novel excellent protective coatings, be mainly used in aerospace, auto industry and In mechano-electronic product.In electric field component surface anti-corrosion and protection, admiro film layer is as final protecting film Layer, it is desirable that it has excellent corrosion resistance, wearability and hardness etc..
With the fast development of modern industry and science and technology, material surface antiseptic property also proposed higher and higher It is required that.Currently, higher by the content that nickel in the coating formed is electroplated in non-cyanide alkali Zinc-nickel alloy electroplating liquid, nickel contains in general coating Amount is 12-15%.As patent of invention (notification number CN104120465B) discloses a kind of Electroplate liquid of alkaline zinc-nickel alloy and its system Preparation Method and application, every liter of electroplate liquid include following components: 100.0~150.0g of sodium hydroxide, 10.0~16.0g of zinc oxide, 6.0~12.0g of nickel sulfate, 6.0~15.0ml of tetraethylenepentamine, complexing agent 10.0~30.0g, A agent 2.5~3.5g, B agent 4.0 ~7.0g, surplus are water;Wherein, A agent is by being benzylideneacetone: sodium benzoate: pyridine according to mass ratio: cinnamic acid=(1.1~ 1.3): (0.55~0.65): (0.35~0.45): (0.55~0.65);B agent is by being anisic aldehyde: alcohol: benzene according to mass ratio Sodium formate: o-chlorobenzaldehyde=(3.4~3.6): (0.75~0.85): (1.1~1.3): the group of (1.1~1.3) is grouped as.To the greatest extent It manages in the invention that corrosion resistance of coating is good, assivation property is good, but its nickel content is higher, the secondary of product is withheld by molding brings centainly Influence and its it is secondary withhold molding after, coating is easy to fall off.Therefore, the lower no cyanogen alkali of nickel content in a kind of coating is studied Property Zinc-nickel alloy electroplating liquid and its preparation process are particularly important.
Summary of the invention
The technical problem to be solved by the invention is to provide a kind of non-cyanide alkali Zinc-nickel alloy electroplating liquid and its preparation works It is higher and cause product is secondary to withhold the technical issues of rear coating falls off to solve nickel content in coating in the prior art for skill.
In order to solve the above technical problems, the technical solution adopted by the present invention: a kind of non-cyanide alkali Zinc-nickel alloy electroplating liquid, It is characterized in that, every liter of electroplate liquid includes following components:
The nickel replenishers are nickel salt solution, and nickel ion concentration is 60-100g/L in the nickel salt solution;The nickel complexing The concentration of agent is 10-600g/L;The concentration of the concentration 10-50g/L, the brightener B of the brightener M are 100-500g/L.
Preferably, the nickel replenishers are the aqueous solution of nickel sulfate or nickel sulfamic acid.
Preferably, the nickel complexing agent is water-soluble comprising being configured by the synthetic product of aminated compounds and epoxychloropropane The aqueous solution of liquid or polyamine compound, wherein the mol ratio of aminated compounds and epoxychloropropane is 1~3:1.
Preferably, the aminated compounds includes ethanol amine, diethanol amine, triethanolamine, diethylenetriamine, triethylene four The combination of one or more of amine, tetraethylenepentamine and its derivative.
Preferably, the synthetic product of the aminated compounds and epoxychloropropane the preparation method is as follows:
(51) aminated compounds and epoxychloropropane are weighed according to the proportion;
(52) aminated compounds is put into reaction vessel, stirs and aminated compounds is heated, elevated the temperature To 50-70 DEG C;
(53) epoxychloropropane is added dropwise into aminated compounds, maintaining reaction temperature is 80-90 DEG C;
(54) reaction solution in step (53) is kept the temperature, holding temperature is 100-120 DEG C, soaking time 10- 20min is finally cooled to room temperature, obtains the synthetic product of aminated compounds and epoxychloropropane.
Preferably, the synthetic product concentration of aqueous solution of the aminated compounds and epoxychloropropane is 100-600g/L.
Preferably, the polyamine compound includes one of polyethyleneimine, polypropylene amine or two kinds of combinations.
Preferably, the concentration of aqueous solution of the polyamine compound is 10-50g/L.
Preferably, the brightener M is one of polyethyleneimine, polypropylene amine or two kinds of combinations, brightener B are Propane sulfonic acid pyridinium salt.
A kind of preparation method of non-cyanide alkali Zinc-nickel alloy electroplating liquid, which comprises the following steps:
(101), nickel replenishers, nickel complexing agent, brightener M and brightener B solution are configured first;
(102), part water is added in a reservoir, then zinc oxide and sodium hydroxide are dissolved in the water, are configured to solution;
(103), it is molten that nickel replenishers, nickel complexing agent, brightener M and brightener B are sequentially added in the solution of step (102) Liquid;
(104), remaining water is finally added in step (103).
Beneficial effects of the present invention: the present invention discloses a kind of non-cyanide alkali Zinc-nickel alloy electroplating liquid, is 20- in bath temperature At 25 DEG C, cathode-current density 3-5A/dm2, anodic current density 2-5A/dm2Range under, nickel content in zinc-nickel alloy coating 5-8% is stabilized to, far below the nickel content in existing coating.The invention can not only reduce nickel metal resource, while can be with After secondary coating of withholding is not fallen off after guaranteeing product plating, and use electroplate liquid of the present invention carries out coating, zinc-nickel alloy coating Heat-resisting, corrosion resistance preferably, salt spray resistance 1000 hours, coating uniform bright, coating ductility it is preferable;Meanwhile the present invention also public affairs A kind of preparation process of non-cyanide alkali Zinc-nickel alloy electroplating liquid is opened, preparation process is simple, and it is easy to operate, it is at low cost, it is suitable for big rule Mould production is used.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects It encloses.
Embodiment 1:
A kind of non-cyanide alkali Zinc-nickel alloy electroplating liquid, every liter of electroplate liquid includes following components:
Wherein, nickel ion concentration is 62g/L in nickel sulfate solution, and the solution of diethanol amine and epoxychloropropane synthetic is dense Degree is 280g/L, and the solution concentration of polyethyleneimine is 10g/L, and the solution concentration of propane sulfonic acid pyridinium salt is 500g/L.
In the present embodiment, the synthetic method of diethanol amine and epoxychloropropane synthetic is as follows:
(1), 105g diethanol amine and 92g epoxychloropropane are weighed;
(2), diethanol amine is poured into three-necked flask, three-necked flask is put into magnetic agitation electric jacket and is stirred, simultaneously Diethanol amine is heated to 60 DEG C;
(3), epoxychloropropane is added in separatory funnel, is then slowly added dropwise into diethanol amine, at this time solution meeting It is brought rapidly up, needs to cool down reaction solution in the present embodiment, the type of cooling can use conventional method, maintain reaction temperature Degree is 85 DEG C;
(4), it needs to keep the temperature reaction solution after dripping epoxychloropropane, removes cooling device at this time, and to anti- Solution is answered to heat, so that holding temperature is 110 DEG C, soaking time 15min is finally cooled to room temperature, obtains synthetic product.
The reaction equation of the synthetic product is as follows:
The preparation step of non-cyanide alkali Zinc-nickel alloy electroplating liquid is as follows in the present embodiment:
(1), zinc oxide, sodium hydroxide, nickel sulfate, diethanol amine, epoxychloropropane, the polyethylene of formula ratio are weighed first Imines, propane sulfonic acid pyridinium salt;Nickel sulfate solution is first configured, nickel sulfate is added to the water, heats up 80 DEG C, is sufficiently stirred molten Solution;It is reconfigured the solution of diethanol amine and epoxychloropropane synthetic product, diethanol amine and epoxychloropropane synthetic product are added Enter into water, is dissolved after being sufficiently stirred;It is reconfigured polyethylenimine solution, polyethyleneimine is added to the water, is sufficiently stirred After dissolve;It is reconfigured propane sulfonic acid pyridinium salting liquid, propane sulfonic acid pyridinium salt is added to the water dissolution;
(2), part water is added in a reservoir, then the zinc oxide of formula ratio and sodium hydroxide are dissolved in the water, stirs Solution is configured to after uniformly;
(3), nickel sulfate solution, the diethyl of the formula ratio by configuring in step (1) are sequentially added in the solution of step (2) Hydramine and epoxychloropropane synthetic product solution, polyethylenimine solution, propane sulfonic acid pyridinium salting liquid;
(4), remaining water is finally added in step (3).
Embodiment 2
A kind of non-cyanide alkali Zinc-nickel alloy electroplating liquid, every liter of electroplate liquid includes following components:
Wherein, nickel ion concentration is 62g/L in nickel sulfate solution, and the solution of diethanol amine and epoxychloropropane synthetic is dense Degree is 280g/L, and the solution concentration of polyethyleneimine is 15g/L, and the solution concentration of propane sulfonic acid pyridinium salt is 450g/L.
In the present embodiment, the synthetic method of diethylenetriamine and epoxychloropropane synthetic is as follows:
(1), 103g diethylenetriamine and 92g epoxychloropropane are weighed;
(2), diethylenetriamine is poured into three-necked flask, three-necked flask is put into magnetic agitation electric jacket and is stirred, together When diethylenetriamine is heated to 60 DEG C;
(3), epoxychloropropane is added in separatory funnel, is then slowly added dropwise into diethylenetriamine, at this time solution It can be brought rapidly up, need to cool down reaction solution in the present embodiment, the type of cooling can use conventional method, maintain reaction Temperature is 85 DEG C;
(4), it needs to keep the temperature reaction solution after dripping epoxychloropropane, removes cooling device at this time, and to anti- Solution is answered to heat, so that holding temperature is 110 DEG C, soaking time 15min is finally cooled to room temperature, obtains synthetic product.
The reaction equation of the synthetic product is as follows:
The preparation step of non-cyanide alkali Zinc-nickel alloy electroplating liquid is as follows in the present embodiment:
(1), zinc oxide, sodium hydroxide, nickel sulfate, diethylenetriamine, the epoxychloropropane, poly- second of formula ratio are weighed first Alkene imines, propane sulfonic acid pyridinium salt;Nickel sulfate solution is first configured, nickel sulfate is added to the water, heats up 80 DEG C, is sufficiently stirred molten Solution;It is reconfigured the solution of diethylenetriamine and epoxychloropropane synthetic product, diethylenetriamine is synthesized into production with epoxychloropropane Object is added to the water, and dissolves after being sufficiently stirred;It is reconfigured polyethylenimine solution, polyethyleneimine is added to the water, sufficiently It is dissolved after stirring;It is reconfigured propane sulfonic acid pyridinium salting liquid, propane sulfonic acid pyridinium salt is added to the water dissolution;
(2), part water is added in a reservoir, then the zinc oxide of formula ratio and sodium hydroxide are dissolved in the water, stirs Solution is configured to after uniformly;
(3), nickel sulfate solution, the diethyl of the formula ratio by configuring in step (1) are sequentially added in the solution of step (2) Alkene triamine and epoxychloropropane synthetic product solution, polyethylenimine solution, propane sulfonic acid pyridinium salting liquid;
(4), remaining water is finally added in step (3).
Embodiment 3
A kind of non-cyanide alkali Zinc-nickel alloy electroplating liquid, every liter of electroplate liquid includes following components:
Wherein, nickel ion concentration is 62g/L, the solution of tetraethylenepentamine and epoxychloropropane synthetic in nickel sulfate solution Concentration is 280g/L, and the solution concentration of polypropylene amine is 10g/L, and the solution concentration of propane sulfonic acid pyridinium salt is 300g/L.
In the present embodiment, the synthetic method of tetraethylenepentamine and epoxychloropropane synthetic is as follows:
(1), 189g tetraethylenepentamine and 92g epoxychloropropane are weighed;
(2), tetraethylenepentamine is poured into three-necked flask, three-necked flask is put into magnetic agitation electric jacket and is stirred, together When tetraethylenepentamine is heated to 60 DEG C;
(3), epoxychloropropane is added in separatory funnel, is then slowly added dropwise into tetraethylenepentamine, at this time solution It can be brought rapidly up, need to cool down reaction solution in the present embodiment, the type of cooling can use conventional method, maintain reaction Temperature is 85 DEG C;
(4), it needs to keep the temperature reaction solution after dripping epoxychloropropane, removes cooling device at this time, and to anti- Solution is answered to heat, so that holding temperature is 110 DEG C, soaking time 15min is finally cooled to room temperature, obtains synthetic product.
The reaction equation of the synthetic product is as follows:
The preparation step of non-cyanide alkali Zinc-nickel alloy electroplating liquid is as follows in the present embodiment:
(1), zinc oxide, sodium hydroxide, nickel sulfate, tetraethylenepentamine, the epoxychloropropane, poly- third of formula ratio are weighed first Enamine solution, propane sulfonic acid pyridinium salt;Nickel sulfate solution is first configured, nickel sulfate is added to the water, heats up 80 DEG C, is sufficiently stirred Dissolution;It is reconfigured the solution of tetraethylenepentamine and epoxychloropropane synthetic product, tetraethylenepentamine is synthesized with epoxychloropropane Product is added to the water, and dissolves after being sufficiently stirred;It is reconfigured polypropylene amine solution, polypropylene amine is added to the water, is sufficiently stirred It is dissolved after mixing;It is reconfigured propane sulfonic acid pyridinium salting liquid, propane sulfonic acid pyridinium salt is added to the water dissolution;
(2), part water is added in a reservoir, then the zinc oxide of formula ratio and sodium hydroxide are dissolved in the water, stirs Solution is configured to after uniformly;
(3), nickel sulfate solution, the tetrem of the formula ratio by configuring in step (1) are sequentially added in the solution of step (2) Five amine of alkene and epoxychloropropane synthetic product solution, polypropylene amine solution, propane sulfonic acid pyridinium salting liquid;
(4), remaining water is finally added in step (3).
Embodiment 4
A kind of non-cyanide alkali Zinc-nickel alloy electroplating liquid, every liter of electroplate liquid includes following components:
Wherein, nickel ion concentration is 62g/L, the solution of tetraethylenepentamine and epoxychloropropane synthetic in nickel sulfate solution Concentration 280g/L, the solution concentration of polypropylene amine are 10g/L, and the solution concentration of propane sulfonic acid pyridinium salt is 300g/L.
Embodiment 5
A kind of non-cyanide alkali Zinc-nickel alloy electroplating liquid, every liter of electroplate liquid includes following components:
Wherein, nickel ion concentration is 62g/L, the solution of tetraethylenepentamine and epoxychloropropane synthetic in nickel sulfate solution Concentration is 280g/L, and the solution concentration of polypropylene amine is 10g/L, and the solution concentration of propane sulfonic acid pyridinium salt is 300g/L.
Embodiment 5
A kind of non-cyanide alkali Zinc-nickel alloy electroplating liquid, every liter of electroplate liquid includes following components:
Wherein, nickel ion concentration is 62g/L, the solution of tetraethylenepentamine and epoxychloropropane synthetic in nickel sulfate solution Concentration is 280g/L, and the solution concentration of polypropylene amine is 10g/L, and the solution concentration of propane sulfonic acid pyridinium salt is 300g/L.
Measuring method:
Thickness of coating and nickel content test: test analysis is carried out using Fischerscope calibrator.In Example 1-3 Electroplate liquid, be 10cm with length, width is that the iron plate of 5cm is tested in the slot of Hull.Wherein, test temperature is 25 DEG C, Anode current is 2A/dm2, cathode-current density 4A/dm2, plating rack plating 30min is first passed through, barrel plating 60min is then electroplated, clearly It is passivated after washing, is closed after then cleaning again, finally dried.Using the middle position of iron plate width as test position, iron Piece is divided into 10 sections, i.e. 9 test points along its length, measures the thickness of coating and nickel percentage composition of each test point, simultaneously The dispersion performance (average value of 9 data and the ratio of peak) of thickness of coating and nickel content is calculated, in the market Product ZN80 example as a comparative reference, it should be noted that the electroplating technology of ZN80 is consistent with electroplating technology in embodiment 1-3.
Thickness of coating and nickel content see the table below:
As seen from the above table, compared to ZN80 product in the market, plating layer film thickness is relatively thin in embodiment 1-3, and dispersibility It can be preferably;Simultaneously with nickel content comparison in ZN80 product it is found that nickel content stabilizes to 5-8% or so in coating in embodiment 1-3, And the nickel content of ZN80 is 14-34% or so, much higher than the nickel content in coating of the present invention.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any Those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all contain Lid is within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.

Claims (10)

1. a kind of non-cyanide alkali Zinc-nickel alloy electroplating liquid, which is characterized in that every liter of electroplate liquid includes following components:
The nickel replenishers are nickel salt solution, and nickel ion concentration is 60-100g/L in the nickel salt solution;The nickel complexing agent Concentration is 10-600g/L;The concentration of the concentration 10-50g/L, the brightener B of the brightener M are 100-500g/L.
2. a kind of non-cyanide alkali Zinc-nickel alloy electroplating liquid according to claim 1, it is characterised in that: the nickel replenishers are sulphur The aqueous solution of sour nickel or nickel sulfamic acid.
3. a kind of non-cyanide alkali Zinc-nickel alloy electroplating liquid according to claim 1, it is characterised in that: the nickel complexing agent includes By the aqueous solution of the synthetic product of aminated compounds and epoxychloropropane configuration or the aqueous solution of polyamine compound, wherein The mol ratio of aminated compounds and epoxychloropropane is 1~3:1.
4. a kind of non-cyanide alkali Zinc-nickel alloy electroplating liquid according to claim 3, it is characterised in that: the aminated compounds packet Include one of ethanol amine, diethanol amine, triethanolamine, diethylenetriamine, triethylene tetramine, tetraethylenepentamine and its derivative Or multiple combinations.
5. a kind of non-cyanide alkali Zinc-nickel alloy electroplating liquid according to claim 4, it is characterised in that: the aminated compounds with The synthetic product of epoxychloropropane the preparation method is as follows:
(51) aminated compounds and epoxychloropropane are weighed according to the proportion;
(52) aminated compounds is put into reaction vessel, stirs and aminated compounds is heated, elevated the temperature to 50- 70℃;
(53) epoxychloropropane is added dropwise into aminated compounds, maintaining reaction temperature is 80-90 DEG C;
(54) reaction solution in step (53) is kept the temperature, holding temperature is 100-120 DEG C, soaking time 10- 20min is finally cooled to room temperature, obtains the synthetic product of aminated compounds and epoxychloropropane.
6. a kind of non-cyanide alkali Zinc-nickel alloy electroplating liquid according to claim 5, it is characterised in that: the aminated compounds with The synthetic product concentration of aqueous solution of epoxychloropropane is 100-600g/L.
7. a kind of non-cyanide alkali Zinc-nickel alloy electroplating liquid according to claim 3, it is characterised in that: the polyamine compound It is combined comprising one of polyethyleneimine, polypropylene amine or two kinds.
8. a kind of non-cyanide alkali Zinc-nickel alloy electroplating liquid according to claim 7, it is characterised in that: the polyamine compound Concentration of aqueous solution be 10-50g/L.
9. a kind of non-cyanide alkali Zinc-nickel alloy electroplating liquid according to claim 1, it is characterised in that: the brightener M is poly- One of aziridine, polypropylene amine or two kinds of combinations, brightener B are propane sulfonic acid pyridinium salt.
10. a kind of preparation method of non-cyanide alkali Zinc-nickel alloy electroplating liquid described in a kind of -9 any one according to claim 1, It is characterized in that, comprising the following steps:
(101), nickel replenishers, nickel complexing agent, brightener M and brightener B solution are configured first;
(102), part water is added in a reservoir, then zinc oxide and sodium hydroxide are dissolved in the water, are configured to solution;
(103), nickel replenishers, nickel complexing agent, brightener M and brightener B solution are sequentially added in the solution of step (102);
(104), remaining water is finally added in step (103).
CN201811394338.4A 2018-11-21 2018-11-21 A kind of non-cyanide alkali Zinc-nickel alloy electroplating liquid and its preparation process Pending CN109267122A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110484939A (en) * 2019-09-09 2019-11-22 惠州市鸿润五金家具有限公司 A kind of hardware chromium replacement electroplating method

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CN1094765A (en) * 1994-01-24 1994-11-09 厦门大学 Basic plating method for bright Zn-Ni alloy
CN101240437A (en) * 2008-03-20 2008-08-13 北京航空航天大学 Method for plating zinc-nickel alloy in alkaline electroplate liquid
CN101314862A (en) * 2008-07-16 2008-12-03 杭州东方表面技术有限公司 Method for acquiring complexing agent special for zinc-nickel alloy plating
CN101314861A (en) * 2008-07-16 2008-12-03 杭州东方表面技术有限公司 Plating process for low-nickel non-cyanogen alkalescent zinc-nickel alloy
CN101942684A (en) * 2010-10-09 2011-01-12 济南德锡科技有限公司 Alkaline electroplating Zn-Ni alloy additive, electroplating solution and preparation method
CN105239115A (en) * 2015-10-22 2016-01-13 广州超邦化工有限公司 Alkaline zinc-nickel alloy electroplating solution with high stability
CN107475756A (en) * 2017-07-24 2017-12-15 宁波亚大金属表面处理有限公司 A kind of black zinc-nickel processing technology

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Publication number Priority date Publication date Assignee Title
CN1094765A (en) * 1994-01-24 1994-11-09 厦门大学 Basic plating method for bright Zn-Ni alloy
CN101240437A (en) * 2008-03-20 2008-08-13 北京航空航天大学 Method for plating zinc-nickel alloy in alkaline electroplate liquid
CN101314862A (en) * 2008-07-16 2008-12-03 杭州东方表面技术有限公司 Method for acquiring complexing agent special for zinc-nickel alloy plating
CN101314861A (en) * 2008-07-16 2008-12-03 杭州东方表面技术有限公司 Plating process for low-nickel non-cyanogen alkalescent zinc-nickel alloy
CN101942684A (en) * 2010-10-09 2011-01-12 济南德锡科技有限公司 Alkaline electroplating Zn-Ni alloy additive, electroplating solution and preparation method
CN105239115A (en) * 2015-10-22 2016-01-13 广州超邦化工有限公司 Alkaline zinc-nickel alloy electroplating solution with high stability
CN107475756A (en) * 2017-07-24 2017-12-15 宁波亚大金属表面处理有限公司 A kind of black zinc-nickel processing technology

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110484939A (en) * 2019-09-09 2019-11-22 惠州市鸿润五金家具有限公司 A kind of hardware chromium replacement electroplating method

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Application publication date: 20190125