CN102605394A - Cyanogen-free acidic cupronickel-tin plating solution - Google Patents
Cyanogen-free acidic cupronickel-tin plating solution Download PDFInfo
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- CN102605394A CN102605394A CN2012100583491A CN201210058349A CN102605394A CN 102605394 A CN102605394 A CN 102605394A CN 2012100583491 A CN2012100583491 A CN 2012100583491A CN 201210058349 A CN201210058349 A CN 201210058349A CN 102605394 A CN102605394 A CN 102605394A
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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, concrete relate to a kind of no cyanic acid property copper-nickel alloy tin bath solution.
Background technology
Nickel coatings is owing to its good decoration protective is widely used, but along with the raising of quality of life and to the human body cause illness because of further investigation, nickel plating goes out of use in many fields of decorative electroplating and eliminates.It is reported that European Union stopped import and produces nickeliferous gadget in July, 2000, forbade commercialization after July calendar year 2001.Along with the enforcement of European Union, western countries to daily necessities nickel plating import prohibition decrees such as jewellery, glasses, dress ornament, toy for children, case and bag; The copper nickel chromium triangle technology that always accounts for the protected decoration dominant position is progressively weakened, and industry is opened up new no nickel always diligently or is prohibited the nickel tide for the nickel system with the reply consequent.
As for nickel coatings, must have luminance brightness, and can reach certain thickness near nickel, could stop parent metal to be diffused into precious metal surface (like gold) so effectively, precious metal plating diffuses to bottom, thus the precious metal that prevents surface layer fades and variable color; When doing surface layer, need extremely strong anti-variable color ability and suitable hardness for nickel dam; Certainly also require cost moderate.
The nickel-free electroplating technology of current comparative maturity has cyanide copper tin alloy, cyaniding Kalchoids and does not have cyanogen tin cobalt, tin zinc cobalt ternary-alloy and red brass electroplating technology.Tin cobalt and tin zinc cobalt ternary-alloy do not contain prussiate, but coating luminance brightness and technology stability all are not so good as gunmetal.Therefore be main still in the market with cyanide copper tin/Albaloy technology.
Be the alloy plating of tin with previous generation's nickel electroplating technology, electroplating copper tin alloy is one of alloy plating that grows up the earliest, and particularly after practical prussiate plating bath in 1934 occurred, electroplating copper tin alloy was used for producing in a large number.Nineteen fifties is to the seventies, and as for nickel coatings, gunmetal once obtained fairly large application in China.Wherein, the stanniferous amount is 40%～55% high tin gunmetal, has beautiful silvery white gloss, claims silver mirror alloy or copper-nickel alloy tin again.Copper-nickel alloy tin has many good performances: its surface finish back reflection rate is high, and scale resistance is strong in air, and is also not easy to change in the atmosphere of sulfur-bearing; Weak acid, weak base and organic acid all there is solidity to corrosion preferably; Has good solderability and electroconductibility; Hardness is between nickel chromium triangle, and wear resistance is strong, therefore uses very extensive.Not only can be used as for nickel coatings, 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.Though technical maturity, be widely used, everything all is based on the huge prussiate plating bath of toxicity.The lethal quantity of prussiate only is 5 milligrams; And the cyanide content in the prussiate electroplate liquid tens restrains at least, nearly more than 100 restrains several at least decaliters of the liquid measure of work nest; Reach several kilolitres even liter up to ten thousand, make and contain the cyanogen root in these galvanized drainings and environment is polluted.And, make the galvanized consumption of China's prussiate increasing along with the variation of China's industrial structure and the transfer of international processing industry.Ecotope to China has constituted serious threat.Along with getting into 21st century, people are also increasingly high to the requirement of Environmental Safety, and the prussiate plating bath will be eliminated gradually, do not develop as mainly electroplating also having the cyanogen direction to low cyanogen for the copper-nickel alloy tin of nickel technology.
Based on the demand in market, existing at present fewer companies has been developed new no cyamelide copper tin electroplating technology.The domestic research and development that also have company to drop into no cyamelide copper tin have just been developed a kind of FCS like Meidisi New Material Co., Ltd., Guangzhou and have not been had the plating of cyamelide copper tin plating replacement nickel, are the basis with potassium pyrophosphate, cupric pyrophosphate, stannous pyrophosphate solution; Adopt a kind of novel brightening agent, realized not having fully the requirement of cyanogen, the coating color gloss bright nickel that can match in excellence or beauty; Welding property is good, and shortcoming is can't any thick plating, and hardness is relatively low; Wear resistance is poor slightly, is still waiting Continual Improvement.In addition; (patent No. CN 101096769 in Biyadi Co Ltd; CN101618616,101899664A etc.), Shanghai Mint Co., Ltd (patent No. CN 102108533A) and University of Fuzhou (the patent No. CN 102220610A) patent of also successively just not had the application of cyanogen gunmetal electro-plating method, same; These patents all are to be the basis with the pyrophosphate salt, have similar relative merits.The Japan and the U.S. have about the galvanized patent of no cyanogen copper tin: JP2000-328285, JP2001-40498, US6416571B1 etc.
Novel no cyanic acid property copper-nickel alloy tin bath solution and electroplating technology that the present invention researched and developed adopt the methylsulphonic acid salt system, select novel brightening agent and stablizer for use, do not have cyanogen fully and do not have any heavy metal additive, meet all standards of ROHS-WEEE; Bath stability is high, safety simple to operate.Gained copper-nickel alloy tin coating outward appearance is light evenly, and anti-corrosion capability is good, and anti-variable color ability is strong, and the similar nickel dam of hardness plates more than the thick 10 μ m, can prevent effectively that bottom to the diffusion of precious metal surface layer, being that ideal is for the nickel product.
Summary of the invention
The objective of the invention is to overcome the above-mentioned deficiency of prior art; The evenly cu-sn alloy coating of light of a kind of outward appearance is provided, and its protection against corrosion, anti-variable color ability are strong, hardness is high; Thickness of coating can reach more than the 10 μ m, and no cyanic acid property copper-nickel alloy tin bath solution simple to operate.
In order to realize the foregoing invention purpose, technical scheme of the present invention is following:
A kind of no cyanic acid property copper-nickel alloy tin bath solution comprises following recipe ingredient:
Above-mentioned no cyanic acid property copper-nickel alloy tin bath solution adopts the methylsulphonic acid salt system, under the synergy of brightening agent, wetting agent and stablizer, and the electroplate liquid good stability, it is higher that electroplating efficiency contains cyanogen process than alkalescence.Simultaneously, this no cyanic acid property copper-nickel alloy tin bath solution does not contain cyanogen and lead fully, and does not have other heavy metal additive, meets all standards of ROHS-WEEE, has effectively avoided the harm to ecotope.Gained cu-sn alloy coating of the present invention contains 55～60% copper and 40～45% tin; Outward appearance is light evenly, and it is silvery white to be light, and ductility is good; Solidity to corrosion and anti-variable color ability are strong; Hardness reaches 300～400Vickers, and coating can replace nickel as bottom gold-plated, silver-plated, the 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 and electroplate system, it is above and do not influence coating performance that thickness of coating can reach 10 μ m, can prevent effectively that bottom from spreading to the precious metal surface layer.The present invention is simple to operate, and condition is prone to control, is fit to suitability for industrialized production.
Embodiment
Clearer for technical problem, technical scheme and beneficial effect that the present invention will be solved, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
The no cyanic acid property copper-nickel alloy tin bath solution that a kind of even light, solidity to corrosion are provided the embodiment of the invention and anti-variable color ability is strong, hardness is high, thickness of coating can reach the above gunmetal of 10 μ m.This no cyanic acid property copper-nickel alloy tin bath solution comprises following recipe ingredient:
Like this, the no cyanic acid property copper-nickel alloy tin bath solution of the foregoing description adopts the methylsulphonic acid salt system, under the synergy of brightening agent, wetting agent and stablizer, makes this no cyanic acid property copper-nickel alloy tin bath solution have advantages of excellent stability ability and higher electroplating efficiency.Simultaneously, it is unleaded that this no cyanic acid property copper-nickel alloy tin bath solution does not have cyanogen fully, and do not have other heavy metal additive, meets the ROHS-WEEE standard, and safety and environmental protection has effectively been avoided its harm to ecotope.The coating outward appearance of using this no cyanic acid property copper-nickel alloy tin bath solution plating to obtain is evenly bright, and it is silvery white to be light, and anti-corrosion capability is good, prevents that the variable color ability is strong.Coating is gunmetal, and hardness reaches 300～400Vickers, the similar nickel dam of hardness, and thickness of coating can prevent effectively that bottom to the diffusion of precious metal surface layer, being that ideal is for the nickel product up to more than the 10 μ m.
Preferably, as embodiments of the invention, above-mentioned organic acid is methylsulphonic acid or ethylsulfonic acid, and content is 200～350g/L.The contriver finds that under study for action organic acid concentration is very important to the stability and the electroconductibility of no cyanic acid property copper-nickel alloy tin bath solution.This organic acid composition provides sour environment and the conductivity that improves no cyanic acid property copper-nickel alloy tin bath solution as solvent and ionogen.The organic acid of this preferred content and kind thereof can improve the stability and the electroconductibility of no cyanic acid property copper-nickel alloy tin bath solution significantly.
Preferably, as embodiments of the invention, brightening agent is 3,5-dithia-1, and 7-heptanediol, its content are 0.5～1.5g/L.This preferred brightening agent can make coating bright more, even.Certainly, brightening agent also can adopt 3,6-dithia-1, and 8-ethohexadiol or 3,7-dithia-1, the 9-nonanediol, but learn through experiment, add the brightening agent of the type and light, the homogeneity of coating are improved effect not as 3,5-dithia-1,7-heptanediol.The brightening agent of this preferred content and sulphonate master salt system synergy, coating light and homogeneity are better, and hardness is higher; Its hardness can be up to 300～400Vickers; Thickness can arrive more than the 10 μ m, can replace nickel as bottom gold-plated, silver-plated, the 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 tin content is relatively stable in the assurance electroplate liquid; Make that coating is the gunmetal layer, improve simultaneously further the degree of uniformity of copper, tin composition in the coating, and the hardness of coating and ductility reach necessary requirement.
Preferably, as embodiments of the invention, wetting agent is a sulphonate, and its content is 1.0～10g/L.Wherein, sulphonate can be ASs such as
F11-13,
NAPE14-90.This wetting agent plays the effect of the solvent and the carrier of brightening agent at this no cyanic acid property copper-nickel alloy tin bath solution, can guarantee to form to the low current density district from high current density region the copper tin coating of light, and make coating even, and is still, and hardness is high.This preferred wetting agent content and kind can make coating light property, homogeneity better, and hardness is higher.
Preferably, as embodiments of the invention, stablizer is a Resorcinol, and its content is 0.5～10g/L.This stablizer plays and prevents the stannous ion oxidation, thereby has guaranteed the stable of no cyanic acid property copper-nickel alloy tin bath solution, guarantee coating evenly, luminance brightness and high ductibility, make coating can reach enough thickness simultaneously.
From the above mentioned, preferably, as embodiments of the invention, no cyanic acid property copper-nickel alloy tin bath solution comprises following recipe ingredient:
The no cyanic acid property copper-nickel alloy tin bath solution stability of this screening formulation is better; Electroplating efficiency is higher; The even light property of coating outward appearance, solidity to corrosion and the anti-variable color ability of using this no cyanic acid property copper-nickel alloy tin bath solution plating to obtain are better; Hardness is higher to be 300～400Vickers, plates thick reaching more than the 10 μ m.
The operational condition of no cyanic acid property copper-nickel alloy tin bath solution of the present invention is: adopting the soluble copper tin alloy is anode, and 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 is all influential to coating performance, plating speed and electroplating efficiency.The contriver finds through experiment, when cathode current density is 1.3A/dm
2The time, per 2.5～5min can plate the thick coating of 1 μ m, and it is higher that this electroplating efficiency contains the cyanogen process electroplating efficiency than existing alkalescence.
The operation steps of using no cyanic acid property 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 fully; Add stannous methanesulfonate then while stirring and add the water constant volume and can prepare required electroplate liquid; At last, gunmetal anode and the metal base negative electrode of handling well are put into electroplate liquid, select suitable current density and electroplating time to carry out electroplating operations as required.
This electro-plating method technology is simple, and condition is prone to control, and plating bath need not heating or cooling, at room temperature electroplates, and energy consumption is low; It is high that this electroplating efficiency contains the cyanogen process electroplating efficiency than existing alkalescence.And, having improved the safety performance of producing because plating bath does not contain cyanogen and lead, after plating finished, galvanized discarded liquid was all pollution-free to air, water resources, has reduced the environmental protection treatment cost.
The embodiment of the invention adopts above-mentioned no cyanic acid property copper-nickel alloy tin bath solution; And adopt cu-sn alloy coating that the aforesaid operations step forms on the plated item surface evenly, to be light silvery white; Solidity to corrosion and ductility are good; Hardness reaches high 300～400Vickers, and the weight percentage of copper is 55～60% in this cu-sn alloy coating, and tin is 45～40%.
For the present invention is further elaborated, more preferred instances are following:
When no cyanic acid property copper-nickel alloy tin bath solution was electroplated below using, the employing weight percentage was that the gunmetal of 60% bronze medal and 40% tin is an anode, and copper sheet is a negative electrode, is to operate under 0.5A/dm2～1.5A/dm2 in current density.
Embodiment 1
A kind of no cyanic acid property copper-nickel alloy tin bath solution comprises following recipe ingredient:
Prepare this no cyanic acid property copper-nickel alloy tin bath solution and use this electroplate liquid to carry out electroplating operations according to the electroplating operations step in the embodiment, current density is 1.0A/dm
2, electroplating time is 10min, and the result plates the copper-nickel alloy tin alloy of even light on copper sheet, and recording thickness of coating is 3.0 μ m.
Embodiment 2
A kind of no cyanic acid property copper-nickel alloy tin bath solution comprises following recipe ingredient:
Prepare this no cyanic acid property copper-nickel alloy tin bath solution and use this electroplate liquid to carry out electroplating operations according to the electroplating operations step in the embodiment, current density is 0.6A/dm
2, electroplating time is 10min, and the result plates bright argenteous copper-nickel alloy tin alloy on copper sheet, and copper tin component accounts for 59% and 41% respectively in the alloy.
Embodiment 3
A kind of no cyanic acid property copper-nickel alloy tin bath solution comprises following recipe ingredient:
Prepare this no cyanic acid property copper-nickel alloy tin bath solution and use this electroplate liquid to carry out electroplating operations according to the electroplating operations step in the embodiment, current density is 1.5A/dm
2, electroplating time is 25min, and the result plates the copper-nickel alloy tin alloy of even light on copper sheet, and thickness of coating reaches 10.5 μ m, and hardness reaches 380Vickers.
The above is merely preferred embodiment of the present invention, not in order to restriction the present invention, all any modifications of within spirit of the present invention and principle, being done, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (7)
1. no cyanic acid property copper-nickel alloy tin bath solution comprises following recipe ingredient:
2. no cyanic acid property copper-nickel alloy tin bath solution according to claim 1, it is characterized in that: said brightening agent is 3,5-dithia-1,7-heptanediol, its content are 0.5～1.5g/L.
3. according to the described no cyanic acid property copper-nickel alloy tin bath solution of claim 1～2, it is characterized in that: said copper methanesulfonate content is 10～35g/L; Said stannous methanesulfonate content is 5～15g/L.
4. according to the arbitrary described no cyanic acid property copper-nickel alloy tin bath solution of claim 1～2, it is characterized in that: said organic acid is that methylsulphonic acid is or/and ethylsulfonic acid.
5. according to the arbitrary described no cyanic acid property copper-nickel alloy tin bath solution of claim 1～2, it is characterized in that: said wetting agent is a sulphonate.
6. according to the arbitrary described no cyanic acid property copper-nickel alloy tin bath solution of claim 1～2, it is characterized in that: said stablizer is a Resorcinol.
7. according to the arbitrary described no cyanic acid property copper-nickel alloy tin bath solution of claim 1～2, it is characterized in that: the operational condition of described no cyanic acid property 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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Cited By (5)
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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 |
| CN105463528A (en) * | 2014-09-30 | 2016-04-06 | 罗门哈斯电子材料有限责任公司 | Cyanide-free electroplating baths for white bronze based on copper (I) ions |
| CN105755512A (en) * | 2016-03-04 | 2016-07-13 | 昆山艾森半导体材料有限公司 | Antioxidant for tin methane-sulfonate, preparation method and use method thereof |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105463528A (en) * | 2014-09-30 | 2016-04-06 | 罗门哈斯电子材料有限责任公司 | Cyanide-free electroplating baths for white bronze based on copper (I) ions |
| CN105463528B (en) * | 2014-09-30 | 2017-12-08 | 罗门哈斯电子材料有限责任公司 | The electroplating bath without cyanide for white bronze based on copper (I) ion |
| CN105755512A (en) * | 2016-03-04 | 2016-07-13 | 昆山艾森半导体材料有限公司 | Antioxidant for tin methane-sulfonate, preparation method and use method thereof |
| 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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