CN102605394B - Cyanogen-free acidic cupronickel-tin plating solution - Google Patents
Cyanogen-free acidic cupronickel-tin plating solution Download PDFInfo
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- CN102605394B CN102605394B CN201210058349.1A CN201210058349A CN102605394B CN 102605394 B CN102605394 B CN 102605394B CN 201210058349 A CN201210058349 A CN 201210058349A CN 102605394 B CN102605394 B CN 102605394B
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Abstract
The invention discloses a cyanogen-free acidic cupronickel-tin plating solution. The cyanogen-free acidic cupronickel-tin plating solution comprises the following formulation components: 150 to 400 g/L of organic acid, 10 to 60 g/L of copper methanesulfonate, 5 to 25 g/L of tin methanesulfonate, 0.1 to 5 g/L of brightening agent, 1.0 to 10 g/L of wetting agent, and 0.5 to 10 g/L stabilizing agent. The operating conditions of the plating solution are that a copper-tin alloy anode is adopted; and the current density is 0.3 to 2.0A/dm<2>. The cyanogen-free acidic cupronickel-tin plating solution disclosed by the invention has high stability and plating efficiency, has no cyanogen or heavy metal additives, and is safe and environment-friendly. The obtained copper-tin alloy clad layer in uniform and luculent in appearance, is bright silver-white, high in malleability, corrosion resistance, discoloration preventing capacity and hardness; the thickness of the clad layer can reach over 10 mu m; therefore, the copper-tin alloy clad layer is an ideal substitute for a nickel clad layer.
Description
Technical field
The invention belongs to technical field of surface, be specifically related to a kind of without cyanic acid copper-nickel alloy tin bath solution.
Background technology
Nickel coating is widely used due to its excellent decoration protective, but along with quality of life raising and to human body cause illness because of further investigation, nickel plating has gone out of use and has eliminated in many fields of decorative electroplating.It is reported, European Union stops import in July, 2000 and produces nickeliferous gadget, forbids commercialization after July calendar year 2001.Along with European Union, western countries are to the enforcement of the daily necessities nickel plating import prohibition decrees such as jewellery, glasses, dress ornament, toy for children, case and bag, the copper nickel chromium triangle technique always accounting for protected decoration dominant position is progressively weakened, and industry is opened up always diligently and new is prohibited nickel tide without nickel or for nickel system to tackle the consequent.
As for nickel coating, the luminance brightness close to nickel must be had, and can certain thickness be reached, could effectively stop underlying metal to be diffused into precious metal surface (as gold) like this, precious metal plating diffuses to bottom, thus prevents the precious metal of surface layer from fading and variable color; When doing surface layer for nickel dam, need extremely strong Anti-tarnishing ability and suitable hardness; Certainly also moderate cost is required.
The nickel-free electroplating technology of current comparative maturity has cyanide copper tin alloy, cyaniding Kalchoids and without cyanogen tin cobalt, tin zinc cobalt ternary-alloy and red brass electroplating technology.Tin cobalt and tin zinc cobalt ternary-alloy be not containing prussiate, but coating luminance brightness and technology stability are all not so good as gunmetal.Therefore in the market still based on cyanide copper tin/Albaloy technique.
Above nickel substitute plating technique is the alloy plating of tin, and electroplating copper tin alloy is one of alloy plating grown up the earliest, particularly after practical cyanide bath in 1934 occurs, electroplating copper tin alloy in a large number for the production of.Nineteen fifties, as nickel coating, gunmetal once obtained fairly large application in China to the seventies.Wherein, stanniferous amount is the high tin gunmetal of 40% ~ 55%, has beautiful silvery white gloss, also known as silver mirror alloy or copper-nickel alloy tin.Copper-nickel alloy tin has many excellent performances: its surface finish back reflection rate is high, and scale resistance is strong in atmosphere, also not easy to change in the air of sulfur-bearing; Good solidity to corrosion is had to weak acid, weak base and organic acid; There is good solderability and electroconductibility; Hardness is between nickel chromium triangle, and wear resistance is strong, therefore applies widely.Not only can be used as nickel coating, also can be used as Dai Yin, nickel-base alloy coating, the decorative coating of reflecting coating and instrument, daily necessities, tableware, light fixture and musical instrument etc.Although technical maturity, to be widely used, everything is all based on the huge cyanide bath of toxicity.The lethal quantity of prussiate is only 5 milligrams, and the cyanide content tens grams at least in prussiate electroplate liquid, nearly more than 100 gram, liquid measure a few decaliter at least of work nest, nearly a few kilolitre liter even up to ten thousand, contains cyanogen root and to environment in the draining that these electroplates.And along with the change of China's industrial structure and the transfer of international processing industry, make the consumption of China's prussiate plating increasing.Serious threat is constituted to the ecotope of China.Along with entering 21st century, the requirement of people to Environmental Safety is also more and more higher, and cyanide bath will be eliminated gradually, as the plating of the main copper-nickel alloy tin for nickel technique also to low cyanogen without cyanogen future development.
Based on the demand in market, at present existing fewer companies develops new for cyamelide copper tin electroplating technology.Domestic Ye You company has dropped into the research and development without cyamelide copper tin, as Meidisi New Material Co., Ltd., Guangzhou just develops a kind of FCS without the plating of cyamelide copper tin plating replacement nickel, based on potassium pyrophosphate, cupric pyrophosphate, stannous pyrophosphate solution, adopt a kind of novel brightening agent, achieve completely without the requirement of cyanogen, coating color gloss can match in excellence or beauty bright nickel, welding property is good, and shortcoming is cannot any thick plating, and hardness is relatively low, wear resistance is slightly poor, need Continual Improvement.In addition, Biyadi Co Ltd (patent No. CN 101096769, CN101618616,101899664A etc.), Shanghai Mint Co., Ltd (patent No. CN 102108533A) and University of Fuzhou (patent No. CN 102220610A) the also successively just patent without the application of cyanogen gunmetal electro-plating method, same, these patents are all based on pyrophosphate salt, have similar relative merits.Japan and the U.S. have about the patent of electroplating without cyanogen copper tin: JP2000-328285, JP2001-40498, US6416571B1 etc.
It is novel without cyanic acid copper-nickel alloy tin bath solution and electroplating technology that the present invention researches and develops, and adopts methylsulphonic acid salt system, select novel brightening agent and stablizer, completely without cyanogen and without any heavy metal additive, meets all standards of ROHS-WEEE; Bath stability is high, safety simple to operate.Gained copper-nickel alloy tin coating appearance uniform light, anti-corrosion capability is good, and Anti-tarnishing ability is strong, and the similar nickel dam of hardness, plates thick more than 10 μm, can effectively prevent bottom to the diffusion of precious metal surface layer, is desirable for nickel product.
Summary of the invention
The object of the invention is to the above-mentioned deficiency overcoming prior art, there is provided a kind of cu-sn alloy coating of appearance uniform light, and its protection against corrosion, Anti-tarnishing ability are strong, hardness is high, thickness of coating can reach more than 10 μm, and simple to operate without cyanic acid copper-nickel alloy tin bath solution.
In order to realize foregoing invention object, technical scheme of the present invention is as follows:
A kind of without cyanic acid copper-nickel alloy tin bath solution, comprise following recipe ingredient:
Above-mentioned without cyanic acid copper-nickel alloy tin bath solution employing methylsulphonic acid salt system, under the synergy of brightening agent, wetting agent and stablizer, electroplate liquid good stability, electroplating efficiency is higher containing cyanogen process than alkalescence.Meanwhile, this does not contain cyanogen and lead completely without cyanic acid copper-nickel alloy tin bath solution, and without other heavy metal additive, meets all standards of ROHS-WEEE, effectively prevent the harm to ecotope.Gained cu-sn alloy coating of the present invention is containing the copper of 55 ~ 60% and the tin of 40 ~ 45%, appearance uniform light, in bright silvery white, ductility is good, solidity to corrosion and Anti-tarnishing ability strong, hardness reaches 300 ~ 400Vickers, and coating can replace nickel as bottom that is gold-plated, silver-plated, plating palladium, to prevent " nickel itch "; Also can be used as the final complexion of product, be applicable to high-grade electronic product.Compare pyrophosphate salt copper-nickel alloy tin plating system, thickness of coating can reach more than 10 μm and do not affect coating performance, can effectively prevent bottom from spreading to precious metal surface layer.The present invention is simple to operate, and condition is easily controlled, and is applicable to suitability for industrialized production.
Embodiment
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearly understand, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The embodiment of the present invention provides a kind of even light, solidity to corrosion and Anti-tarnishing ability is strong, hardness is high, thickness of coating can reach the gunmetal of more than 10 μm without cyanic acid copper-nickel alloy tin bath solution.This comprises following recipe ingredient without cyanic acid copper-nickel alloy tin bath solution:
Like this, above-described embodiment adopt methylsulphonic acid salt system without cyanic acid copper-nickel alloy tin bath solution, under the synergy of brightening agent, wetting agent and stablizer, make this have excellent stability and the electroplating efficiency of Geng Gao without cyanic acid copper-nickel alloy tin bath solution.Meanwhile, this is completely unleaded without cyanogen without cyanic acid copper-nickel alloy tin bath solution, and without other heavy metal additive, meets ROHS-WEEE standard, safety and environmental protection, effectively prevent its harm to ecotope.The Deposit appearance using this to obtain without the plating of cyanic acid copper-nickel alloy tin bath solution is evenly bright, and in bright silvery white, anti-corrosion capability is good, and Anti-tarnishing ability is strong.Coating is gunmetal, and hardness reaches 300 ~ 400Vickers, the similar nickel dam of hardness, and thickness of coating can up to more than 10 μm, can effectively prevent bottom to the diffusion of precious metal surface layer, is desirable for nickel product.
Preferably, as embodiments of the invention, above-mentioned organic acid is methylsulphonic acid or ethylsulfonic acid, and content is 200 ~ 350g/L.Contriver finds under study for action, organic acid concentration to without the stability of cyanic acid copper-nickel alloy tin bath solution and electroconductibility very important.This organic acid composition, as solvent and ionogen, provides sour environment and the conductivity improved without cyanic acid copper-nickel alloy tin bath solution.The organic acid of this preferred content and kind thereof can improve stability without cyanic acid copper-nickel alloy tin bath solution and electroconductibility significantly.
Preferably, as embodiments of the invention, brightening agent is 3,5-dithia-1,7-heptanediol, and its content is 0.5 ~ 1.5g/L.This preferred brightening agent can make coating brighter, even.Certainly, brightening agent also can adopt 3,6-dithia-1,8-ethohexadiol or 3,7-dithia-1,9-nonanediol, but learns through experiment, adds the light of brightening agent to coating of the type, homogeneity improves effect not as 3,5-dithia-1,7-heptanediol.The brightening agent of this preferred content and the main salt system of sulfonate act synergistically, coating is bright and homogeneity is better, hardness is higher, its hardness can up to 300 ~ 400Vickers, thickness can arrive more than 10 μm, nickel can be replaced as bottom that is gold-plated, silver-plated, plating palladium, to prevent " nickel itch ", also can be used as the final complexion of product, be applicable to high-grade electronic product.
Preferably, as embodiments of the invention, copper methanesulfonate content is 10 ~ 35g/L, and stannous methanesulfonate content is 5 ~ 15g/L.The copper methanesulfonate of this preferred content, stannous methanesulfonate are main salt, cupric ion, stannous ion are provided respectively, and the ratio of copper and Theil indices is relatively stable in guarantee electroplate liquid, coating is made to be gunmetal layer, the further degree of uniformity improving copper, tin composition in coating, and the hardness of coating simultaneously and ductility reach necessary requirement.
Preferably, as embodiments of the invention, wetting agent is sulfonate, and its content is 1.0 ~ 10g/L.Wherein, sulfonate can be
f11-13,
the anion surfactants such as NAPE14-90.This wetting agent plays the solvent of brightening agent and the effect of carrier at this without cyanic acid copper-nickel alloy tin bath solution, can ensure the copper tin coating forming light from high current density region to low current density district, and makes coating even, and still, hardness is high.This preferred wetting agent content and kind can make coating bright property, homogeneity better, and hardness is higher.
Preferably, as embodiments of the invention, stablizer is Resorcinol, and its content is 0.5 ~ 10g/L.This stablizer plays and prevents stannous ion to be oxidized, thus it is stable to ensure that without cyanic acid copper-nickel alloy tin bath solution, ensures even, luminance brightness and the high ductibility of coating, makes the thickness that coating can reach enough simultaneously.
From the above mentioned, preferably, as embodiments of the invention, following recipe ingredient is comprised without cyanic acid copper-nickel alloy tin bath solution:
This screening formulation better without cyanic acid copper-nickel alloy tin bath solution stability, electroplating efficiency is higher, the even bright property of Deposit appearance, solidity to corrosion and the Anti-tarnishing ability that use this to obtain without the plating of cyanic acid copper-nickel alloy tin bath solution are better, hardness is higher is 300 ~ 400Vickers, plates thickly to reach more than 10 μm.
Operational condition without cyanic acid copper-nickel alloy tin bath solution of the present invention is: adopt soluble copper tin alloy to be anode, current density is 0.3A/dm
2~ 2.0A/dm
2.
Preferably, as embodiments of the invention, electric current is preferably 0.5 ~ 1.5A/dm
2, suitable current density has impact to coating performance, plating speed and electroplating efficiency.Contriver finds, when cathode current density is 1.3A/dm through experiment
2time, every 2.5 ~ 5min can plate 1 μm of thick coating, and this electroplating efficiency is higher containing cyanogen process electroplating efficiency than existing alkalescence.
Applying the operation steps without cyanic acid copper-nickel alloy tin bath solution of the present invention is: in the organic acid aqueous solution, add copper methanesulfonate, brightening agent, wetting agent and stablizer while stirring successively to dissolving completely; Then stannous methanesulfonate is added while stirring and the constant volume that adds water can prepare required electroplate liquid; Finally, gunmetal anode and the metal base negative electrode handled well are put into electroplate liquid, selects suitable current density and electroplating time to carry out electroplating operations as required.
This electro-plating method technique is simple, and condition is easily controlled, and plating solution is without the need to heating or cooling, and at room temperature electroplate, energy consumption is low; This electroplating efficiency is higher containing cyanogen process electroplating efficiency than existing alkalescence.And because plating solution is not containing cyanogen and lead, improve the safety performance of production, after plating, the waste liquid of plating is all pollution-free to air, water resources, reduces environmental protection treatment cost.
The embodiment of the present invention adopts above-mentioned without cyanic acid copper-nickel alloy tin bath solution, and the cu-sn alloy coating adopting aforesaid operations step to be formed on plated item surface is even, in bright silvery white, solidity to corrosion and ductility good, hardness reaches high 300 ~ 400Vickers, in this cu-sn alloy coating, the weight percentage of copper is 55 ~ 60%, and tin is 45 ~ 40%.
In order to be further elaborated to the present invention, more preferred examples are as follows:
Use following when electroplating without cyanic acid copper-nickel alloy tin bath solution, adopting weight percentage to be the gunmetal of 60% bronze medal and 40% tin is anode, and copper sheet is negative electrode, operates under current density is 0.5A/dm2 ~ 1.5A/dm2.
Embodiment 1
A kind of without cyanic acid copper-nickel alloy tin bath solution, comprise following recipe ingredient:
Preparing this without cyanic acid copper-nickel alloy tin bath solution according to the electroplating operations step in embodiment uses this electroplate liquid to carry out electroplating operations, and current density is 1.0A/dm
2, electroplating time is 10min, and result plates the copper-nickel alloy tin alloy of evenly light on copper sheet, and recording thickness of coating is 3.0 μm.
Embodiment 2
A kind of without cyanic acid copper-nickel alloy tin bath solution, comprise following recipe ingredient:
Preparing this without cyanic acid copper-nickel alloy tin bath solution according to the electroplating operations step in embodiment uses this electroplate liquid to carry out electroplating operations, and current density is 0.6A/dm
2, electroplating time is 10min, and result plates bright argenteous copper-nickel alloy tin alloy on copper sheet, and in alloy, copper tin component accounts for 59% and 41% respectively.
Embodiment 3
A kind of without cyanic acid copper-nickel alloy tin bath solution, comprise following recipe ingredient:
Preparing this without cyanic acid copper-nickel alloy tin bath solution according to the electroplating operations step in embodiment uses this electroplate liquid to carry out electroplating operations, and current density is 1.5A/dm
2, electroplating time is 25min, and result plates the copper-nickel alloy tin alloy of evenly light on copper sheet, and thickness of coating reaches 10.5 μm, and hardness reaches 380Vickers.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (2)
1., without a cyanic acid copper-nickel alloy tin bath solution, be made up of following recipe ingredient:
2. according to claim 1 without cyanic acid copper-nickel alloy tin bath solution, it is characterized in that: the described operational condition without cyanic acid copper-nickel alloy tin bath solution is: adopt soluble copper tin alloy anode, current density is 0.3A/dm
2~ 2.0A/dm
2.
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| CN102605394B true CN102605394B (en) | 2015-02-18 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102912390A (en) * | 2012-10-30 | 2013-02-06 | 南通博远合金铸件有限公司 | Ag-Cu-Sn alloy solution |
| US20160298249A1 (en) * | 2014-09-30 | 2016-10-13 | Rohm And Haas Electronic Materials Llc | Cyanide-free electroplating baths for white bronze based on copper (i) ions |
| CN105755512B (en) * | 2016-03-04 | 2018-01-05 | 昆山艾森半导体材料有限公司 | A kind of tin methane sulfonate antioxidant and preparation method thereof and application method |
| CN108203837A (en) * | 2018-04-04 | 2018-06-26 | 临海市伟星电镀有限公司 | A kind of no cyamelide copper and tin electroplate liquid and its preparation method |
| CN115305537A (en) * | 2022-09-06 | 2022-11-08 | 蔡杰 | Copper-tin alloy environment-friendly electroplating process |
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