CN102016130B - Modified copper-tin electrolyte and method of depositing bronze layers - Google Patents
Modified copper-tin electrolyte and method of depositing bronze layers Download PDFInfo
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- CN102016130B CN102016130B CN2009801164345A CN200980116434A CN102016130B CN 102016130 B CN102016130 B CN 102016130B CN 2009801164345 A CN2009801164345 A CN 2009801164345A CN 200980116434 A CN200980116434 A CN 200980116434A CN 102016130 B CN102016130 B CN 102016130B
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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
- C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
-
- 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
- C25D17/002—Cell separation, e.g. membranes, diaphragms
-
- 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
- C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin
Abstract
The invention relates to a modified copper-tin electrolyte which is free of toxic constituents such as cyanides or thio compounds. The invention further relates to a process for the deposition of decorative bronze layers on consumer goods and industrial articles using the electrolyte of the invention. The electrolyte comprises an additive formed from epichlorohydrin and hexamethylenetetramine and contains carbonate or hydrogencarbonate ions.
Description
The present invention relates to a kind of copper that contains pyrophosphate salt of modification-Xi electrolytic solution, it does not contain toxic component for example prussiate or sulfur-bearing (thio) compound.The invention still further relates to and use electrolytic solution of the present invention that ornamental bronze layer is deposited on method on the consumer's goods and the mechanicals.
With daily necessities or daily goods, such as its institute's definition in daily goods regulation, for the decoration reason and for stop corrode and by thin, oxidation-stabilized metal level is made with extra care (upgrade).These layers must mechanically be stablized and should not show any variable color or the wear phenomenon that causes because of dimization in the situation that longer-term uses.Since two thousand one, according to EUDirective 94/27/EC, sell that the daily necessities be coated with nickeliferous refining alloy no longer are allowed in Europe or only just possible under strict condition, reason is that nickel and nickeliferous metal level are Contact hyper sensitizations.Especially, bell metal has been asserted now the surrogate of nickeliferous refining layer, and these allow will so a large amount of generations daily necessities in electrolysis barrel plating (barrel plating) or rack plating (rack plating) at an easy rate refining with generation do not contain anaphylactogen, have mark can follow the goods of (tracked).
In the production of the bronze layer that is used for electrolytic industry, the key property of the layer that make is the solderability of gained layer and possible mechanical adhesion intensity thereof.For the use in this area, the outward appearance of layer does not generally have its function important.On the other hand, for the production of bronze layer on the consumer's goods, the decorative effect of gained layer is important target component with the long durability of the layer with the outward appearance that substantially remains unchanged.
For the preparation of the currently known methods of bronze layer except comprise use contain prussiate from but the ordinary method of highly toxic alkaline body lotion, comprise that also its composition according to their electrolytic solution can be classified as the different electromechanical means of one of two large classes of belonging to prior art usually: use based on the method for the electrolytic solution of organic sulfonic acid or the use bath method based on tetra-sodium.For the purpose of this paper, " nontoxic " means, and the regulation that does not contain the with good grounds processing hazardous substance that come into force in Europe and objectionable impurities in the electrolytic solution of the present invention of so appointment is classified as " poisonous " (T) or " very malicious " (T
+) any material.
For example, EP1111097A2 has described a kind of electrolytic solution, and it also comprises dispersion agent and brightening agent and optional antioxidant except organic sulfonic acid and tin ion and cupric ion.EP 1 408141 A1 have described the method for electrochemical deposition bronze, wherein use acid electrolyte, and described electrolytic solution contains tin ion and cupric ion and alkylsulphonic acid and aromatics, nonionic wetting agent.DE
100 46 600 A1 have described the body lotion that contains alkylsulphonic acid or alkanol sulfonic acids (alkanolsulfonic acid) and solubility pink salt and mantoquita and organosulfur compound, and the method for using this body lotion.
EP1146148A2 has described based on copper tetra-sodium, that do not contain prussiate-Xi electrolytic solution, and it contains reaction product and the cats product of 1: 1 amine of mol ratio and epoxy chloropropane.Amine is vulkacit H.In electrolytic deposition, use 0.5,1.5,2.5 and 3.0A/dm
2Current density.
WO2004/005528 has described tetra-sodium-copper of not containing prussiate-Xi electrolytic solution, and it comprises by sulfonamide derivatives, epoxy chloropropionate ring and glycidyl ether compound take mol ratio as 1: the additive that 0.5-2: 0.1-5 forms.The purpose of this paper is in order to obtain the more current density range of broadening, wherein can to obtain metal with the uniform deposition of bright layer.Need to explicitly point out, only have when the additive that adds is comprised of all three kinds of said components to obtain this deposition.
According to function type and the character of parts to be coated, usually in electroplating industry, use different coating methods.Especially, method is according to spendable current density and difference.Also can mention basically three kinds of different solution and coating method.
1. the barrel plating that is used for loose material and mass-produced parts:
In this coating method, use the relatively low working current density (order of magnitude: 0.05-0.5A/dm
2).
2. the rack plating that is used for particular:
In this coating method, use the medium working current density (order of magnitude: 0.2-5A/dm
2).
3. the high speed plating that is used for band and wire rod in the continuous device:
In this field of electroplating, use the very high working current density (order of magnitude: 5-100A/dm
2).
For using copper-Xi to electroplate, front two kinds of solution and coating method (barrel plating and rack plating) are most important.Depend on dissimilar electrolytic solution, roll and cross (relatively low current density) or rack plating (medium current density) is possible.
In view of above-mentioned prior art, can determine, especially for the application of rack plating, such deposition method is particularly advantageous: its guarantee to exceed common consideration current density range the metal uniform deposition and use and aspect composition, demonstrate more uncomplicated electrolytic solution.
Therefore the purpose of this invention is to provide a kind of electrolytic solution and the deposition method that can satisfy these demands.Especially, this electrolytic solution even should use under the favourable current density and with uniform mode deposit bright, luminous layer using for rack plating.As if its ratio of components prior art should be simple, because this has special advantage from economy and ecological viewpoint.
NM but other purpose that can from prior art, obtain significantly of these purposes and the present invention, by provide electrolytic solution with claim 1 feature of the present invention and as claim 11 of the present invention described in deposition method purposes realize.Returning the preferred embodiment of drawing these claims can find in claim 2 to 10 and 12 to 16.
Be used for containing daily goods and the ornamental bell metal layer of industrial goods deposition nontoxic the providing of electrolytic solution of pyrophosphate salt, very surprising but still realized described purpose, described electrolytic solution contains treating metal refining and comprising the brightening agent system that the reaction product by epoxy chloropropane and vulkacit H and carbanion or bicarbonate ion forms with the water-soluble salt form with being conducive to.Its composition is different from the electrolytic solution of the present invention of prior art, even makes the excellent electrolytic deposition at medium current density range acquisition bell metal become possibility.Alloy composition keeps approximately constant in wide current density range, this uses particularly favourable for rack plating and relative prior art is non-obvious.
Electrolytic solution among the present invention comprises the reaction product as epoxy chloropropane and the vulkacit H of brightening agent composition.According to the present invention, this additive reaction product or compositions of mixtures by vulkacit H and epoxy chloropropane.Vulkacit H in the reaction product and the mol ratio of epoxy chloropropane are preferably 1:＞1-10.Be particularly preferably 1: 1.5-5 ratio and more preferably 1: the ratio of 2-3.Especially preferred 1: about 2.7 ratio.Such product can be commercially available with the name (Cat.No.33786) of J146 from URSA Chemie GmbH.
To 5.0ml/l, more preferably 0.1ml/l particularly preferably 0.5 arrives 2.0ml/l to 3.0ml/l with 0.01ml/l, and especially preferred 1.0ml/l joins reaction product in the electrolytic solution to the amount of 1.5ml/l, based on total solution meter.
Electrolytic solution of the present invention has certain density carbonate or bicarbonate ion.Can add the form of these soluble salts with alkali and alkaline earth metal ions (the especially carbonate of sodium or potassium or supercarbonate) to electrolytic solution.Yet, preferred such embodiment: wherein also with adding in the electrolytic solution with the form of carbonate or supercarbonate whole or in part with metal to be deposited of using.The interpolation of above-mentioned salt advantageously makes it possible to adjust carbonate in the electrolytic solution or the concentration of bicarbonate ion, and it is 1-50g/l electrolytic solution.This concentration is particularly preferably 5-40g/l, is preferably very especially 15-25g/l.
In electrolytic solution of the present invention, metallic copper to be deposited and tin or copper, tin and zinc all exist with the form of its ion.Preferably with the form of water-soluble salt they are introduced, described salt preferably is selected from pyrophosphate salt, carbonate, subcarbonate (hydroxidecarbonate), supercarbonate, sulphite, vitriol, phosphoric acid salt, nitrite, nitrate, halogenide, oxyhydroxide, oxide hydroxide (oxidehydroxide), oxide compound and their composition.Such embodiment particularly preferably: wherein metal uses with the form of salt with ion, and this salt is selected from pyrophosphate salt, carbonate, subcarbonate, oxide hydroxide, oxyhydroxide and supercarbonate.Introduce the type of the salt in the electrolytic solution and the color that quantity can determine the ornamental bronze layer of gained, and can answer the customer requirement adjustment.As described, metal to be deposited is present in electrolytic solution with the form of ion dissolving, is used for applying ornamental bronze layer at the consumer's goods and industrial goods.The ionic concn of copper is 0.2-10g/l electrolytic solution, preferred 0.3-4g/l electrolytic solution, and the ionic concn of tin is 1.0-20g/l electrolytic solution, preferred 2-10g/l electrolytic solution, and, if exist, then the ionic concn of zinc can be 1.0-20g/l electrolytic solution, preferred 0-3g/l electrolytic solution.In daily necessities refining, preferably, take the form of pyrophosphate salt, carbonate or subcarbonate introduce metal to be deposited in case the ionic concn that makes generation in every liter of electrolytic solution: copper 0.3-4 gram, tin 2-10 gram and zinc 0-3 restrain, in each situation.
As described, in electrochemical method, by using electrolytic solution according to the present invention ornamental bronze layer is applied on daily necessities and the industrial goods.Herein importantly, metal to be deposited remains on during processing in the solution always, no matter carries out electrochemical coating with continuation method or batch processes.In order to ensure this point, electrolytic solution of the present invention comprises that pyrophosphate salt is as complexing agent.
Those skilled in the art according to target mode adjusts the amount of pyrophosphate ions.It is subject to the restriction of the following fact: the concentration in the electrolytic solution should be higher than minimum value in order to bring expected effect with satisfied degree.On the other hand, the amount of tetra-sodium to be used is guided by economic aspect also.About this point, can be with reference to EP1146148 and the information that provides thereof.The preferred 50-400g/l of the amount of pyrophosphate salt to be used in the electrolytic solution.Particularly preferably be and use 250-350g/l electrolytic solution, very particularly preferably the amount of about 300g/l electrolytic solution.If pyrophosphate salt is not introduced as the salt component for the treatment of metal refining, then it can be as the diphosphate of basic metal or alkaline-earth metal or as H
2P
2O
7Be used in combination with the carbonate/bicarbonate of basic metal or alkaline-earth metal.For this purpose, preferably use K
2P
2O
7
The scope of the pH value of electrolytic solution is 6-13, and this is that the plating purposes is desired.Be preferably 6-12, very preferably 6-10.Especially preferably, under the pH of 7.9-8.1 value, implement the method.
Described electrolytic solution can also comprise the organic additive that serves as brightening agent, wetting agent or stablizer except the brightening agent system that contains the metal that remains to be deposited, the pyrophosphate salt that is used as complexing agent and use.Electrolytic solution of the present invention also can need not to use cats product.Only when the outward appearance of ornamental bronze layer to be deposited must satisfy particular requirement, the interpolation of other brightening agent and wetting agent was only preferably.Except the bronze layer color of the ratio that depends primarily on metal to be deposited, these are also so that be that whole grades between unglazed silk (matt silk) and the high gloss become possibility with the brightness adjustment of layer.One or more are selected from monocarboxylic acid or di-carboxylic acid, alkansulfonic acid, trimethyl-glycine and aromatic nitro compound preferred adding.These compounds serve as the stablizer of electrolysis bath of liquid.Particularly preferably use oxalic acid, alkansulfonic acid, particularly methylsulfonic acid, or oil of mirbane triazole or their mixture.Suitable alkansulfonic acid can find in EP1001054.For example, possible carboxylic acid is citric acid (Jordan, Manfred, Die galvanische Abscheidung von Zinn und Zinnlegierungen, 1993,156 pages of Saulgau).The trimethyl-glycine that uses preferably can be at WO2004/005528 or at Jordan, those that find among the Manfred (Diegalvanische Abscheidung von Zinn und Zinnlegierungen, Saulgau1993,156 pages).Particularly preferably in put down in writing among the EP636713 those.About this point, preferably use very especially 1-(3-sulfopropyl) pyridine betaine or 1-(3-sulfopropyl)-2-vinyl pyridine trimethyl-glycine.This external additive can find in document (Jordan, Manfred, Die galvanische Abscheidung von Zinn und Zinnlegierungen, Saulgau1993).
Electrolytic solution of the present invention does not contain the toxic substance that is classified as poisonous (T) and very malicious (T+).Cyanide-free, without thiourea derivative and without the existence of thiol derivative.The electrochemistry that nontoxic electrolytic solution according to the present invention is highly suitable on daily goods and the industrial goods applies ornamental bronze layer.The plating equipment that can use it for barrel plating, rack plating, band (belt) plating or carry continuously.Yet, preferably in the rack plating method, use (referring to prefatory note and " PraktischeGalvanotechnik ", 1997,74 pages of Eugen G.Leutze Verlag).
And, the present invention proposes and a kind ofly apply the electrolytic solution deposition method of ornamental bell metal layer for electrochemistry on daily goods and industrial goods, wherein base material to be coated is immersed according in the electrolytic solution of the present invention.In the method that the preferred embodiment of electrolytic solution discussed above is applied to present similarly herein.
Operation method of the present invention under the temperature that can those skilled in the art will select based on its routine techniques knowledge.Preferred 20 ℃ to 60 ℃, wherein during electrolysis, keep the electrolysis bath of liquid.More preferably select 30 to 50 ℃ scope.Particularly preferably in implementing the method under about 40 ℃ temperature.
A significant advantage of the present invention is in the wide current density range of being deposited on of alloy composite obvious change not to occur.Even under the relatively high current density of using for rack plating, this still causes the surface quality that seems full and uniform.When at 0.2A/dm
2-5A/dm
2When implementing deposition in the scope, can obtain the intermetallic Cu/Sn phase (η+δ phase of special alloy composition and expectation; Referring to: E.Raub, F.Sautter; Der Aufbau galvanischer
XII,
11., No. 19578).Current density in the deposition is preferably 0.5A/dm
2To 2A/dm
2, 0.75A/dm particularly preferably
2To 1.8A/dm
2
When using nontoxic electrolytic solution of the present invention, can use different anodes.Solvable or insoluble anode all is fit to, and the combination of solvable and soluble anode also is fit to.
As soluble anode, preferably use such anode: this anode is comprised of the material that is selected from electrolytic copper, phosphorous copper, tin, tin-copper alloy, zinc-copper alloy and zinc-tin-copper alloy.Particularly preferably be the combination of the different soluble anodes that formed by these materials, and the combination of solubility tin anode and soluble anode.
As insoluble anode, preferably use such anode: (" diamond-like carbon ", material DLC) forms this anode, or the combination of these anodes by the titanium that is selected from platinum plating, graphite, iridium-transition metal mixed oxide and specific carbon material.Particularly preferably be, by iridium-ruthenium mixed oxide, the mixing oxide anode that iridium-ruthenium-titanium mixed oxide or iridium-tantalum mixed oxidization consists of.In addition, can be at Cobley, A.J. etc. (The use of insoluble Anodes in AcidSulphate Copper Electrodeposition Solutions, Trans IMF, 2001,79 (3), 113 and 114 pages) in find other material.
When using the anode of solubility, when the base material that ornamental bronze layer is arranged and represent negative electrode to be supplied is separated so that when forming cathode space and anode chamber from insoluble anode by ion-exchange membrane, obtained the particularly preferred embodiment of the method.In this case, only cathode space is filled with nontoxic electrolytic solution of the present invention.Anode chamber preferably contains the aqueous solution, and this solution only contains electrolytic salt, such as potassium pyrophosphate, salt of wormwood, potassium hydroxide, saleratus or their mixture.It is tin (IV) ion that this configuration has stoped the anodic oxidation of tin (II) ion, and this has detrimental action in coating procedure.As ion-exchange membrane, can use negatively charged ion or cationic exchange membrane.The preferred film that is comprised of Nafion that uses, this film has the thickness of 50 to 200 μ m.
Similarly, can realize the exemplary currents density that rack plating is used by the electrolytic solution that contains pyrophosphate salt of routine.Yet, be not with flawless quality metal refining visually.This electrolytic solution trends towards forming (in the custom scope of rack plating operation) settling dark, striated.
Only when using electrolytic solution of the present invention, just so that being deposited in the whole current density range that is used for habitually the rack plating application of light and luminescent layer becomes possibility.The formation of dark fringe is suppressed significantly.
Therefore, by using the additive that is combined to form by the carbonate that exists in vulkacit H and epoxy chloropropane and the electrolytic solution or bicarbonate ion to make electrolytic solution of the present invention and present method uniqueness.In this way control the luminance brightness of alloy composite and settled layer: carry out to use desirable mode for rack plating.In rack plating was used, the medium current density range was important.First, the combination of additive so that under the relatively high current density that surpasses wide current density range alloy composite can keep approximately constant (to contain the 40-70 % by weight, the copper of preferred 50-60 % by weight, and 60-30 % by weight, the bell metal of the tin of preferred 50-40 % by weight is useful), the second, can obtain satisfied light and luminous layer.During the combination of this additive, required alloy compositions only can not obtain in very narrow current density window, and this is obsolete in industrial operation.In most practical application, when not having the combination of additive, gloss and the luminance brightness of layer are not satisfied.
By electrolytic solution according to the present invention, the acquisition of these advantages is non-obvious with respect to prior art.
Embodiment
The plating of test sheet material:
Base material: 0.5 and 0.75dm
2Brass sheet material.
Apply:
0.5-2 copper-Xi of μ m is in different current densities (0.5,1.0,1.5 and 2.0A/dm
2) under.
Experiment mechanism:
Will be in the specified 4l water of components dissolved in having the 5l glass beaker of magnetic stirrer of embodiment electrolytic solution and mobile article.Subsequently shown in condition under process goods to be coated.
Embodiment electrolytic solution
The electrolytic solution that is used for white bronze rack plating deposition can have following composition:
The first embodiment electrolytic solution
The potassium pyrophosphate of 300g/l
The methylsulfonic acid of 20ml/l, 70%
The salt of wormwood of 20g/l
5.21g/l copper carbonate (II)
8.66g/l stannous pyrophosphate
5.55g/l zinc pyrophosphate
1.25ml/l vulkacit H and the reaction product of epoxy chloropropane
Temperature: 40 ℃
pH：7.4
The second embodiment electrolytic solution
The potassium pyrophosphate of 300g/l
The methylsulfonic acid of 20ml/l
The salt of wormwood of 20g/l
5.21g/l copper carbonate (II)
8.66g/l stannous pyrophosphate
5.55g/l zinc pyrophosphate
0.125ml/l reaction product (J146)
Temperature: 40 ℃
pH：8.0
The 3rd embodiment electrolytic solution
The 100g/l potassium pyrophosphate
The 50ml/l methylsulfonic acid
The salt of wormwood of 50g/l
2.0g/l copper sulfate
The tin sulphate of 20g/l
5.0ml/l reaction product (J146)
pH：9.0
Temperature: 30 ℃
The 4th embodiment electrolytic solution
The potassium pyrophosphate of 160g/l
The 20ml/l methylsulfonic acid
The yellow soda ash of 5g/l
The 4g/l ventilation breather
The stannous pyrophosphate of 5g/l
0.5ml/l the reaction product of vulkacit H and epoxy chloropropane
pH：7.5
Temperature: 45 ℃
The 5th embodiment electrolytic solution
The potassium pyrophosphate of 200g/l
The 30ml/l ethyl sulfonic acid
The citric acid of 50g/l
5g/l basic carbonate potassium
The copper sulfate of 3g/l
The tin sulphate of 15g/l
The reaction product of 1ml/l vulkacit H and epoxy chloropropane
Temperature: 45 ℃
pH：8.5
By following layer is estimated:
A) visual appearance
B) measurement of gloss and luminance brightness
C) measurement of alloy composition (content of copper is higher, and layer is darker)
D) darkening test, corrosion test
The result:
A) visual appearance:
Settled layer is luminous and bright equably.
B) brightness values (L
*Value; Test by CIE LAB method; Http:// www.cielab.de/)
The contrast of " embodiment electrolytic solution 2 " and " prior art "
C) alloy composition
The contrast of " embodiment electrolytic solution 2 " and " prior art "
Higher copper content in the layer causes the darker color of coating and is tending towards producing relatively poor darkening behavior.
Claims (16)
- One kind nontoxic, the electrolytic solution that contains pyrophosphate salt, it is used at daily necessities and the ornamental bell metal layer of mechanicals deposition, it contains the metal refining for the treatment of with the form of water-soluble cpds, wherein this electrolytic solution comprises brightening agent system and carbanion or bicarbonate ion, wherein this brightening agent system is comprised of the reaction product of epoxy chloropropane and vulkacit H, and wherein said water-soluble cpds is selected from pyrophosphate salt, carbonate, subcarbonate, supercarbonate, sulphite, vitriol, phosphoric acid salt, nitrite, nitrate, halogenide, oxyhydroxide, oxide hydroxide, oxide compound and their mixture.
- 2. electrolytic solution as claimed in claim 1, wherein reaction product had 1: 1 to 1: 10 but got rid of the mol ratio of 1: 1 vulkacit H and epoxy chloropropane.
- 3. electrolytic solution as claimed in claim 2, the amount of use therein reaction product is 0.01-5ml/l.
- 4. electrolytic solution as claimed in claim 1, wherein the amount of carbonate or bicarbonate ion is 1-50g/l.
- 5. such as each described electrolytic solution of claim 1 to 4, wherein electrolytic solution comprises that copper and tin or copper, tin and zinc are as metal to be deposited.
- 6. electrolytic solution claimed in claim 5, wherein metal to be deposited exists with the ion solubilized form, and the ionic concn of copper is 0.2-10g/l, and the ionic concn of tin is 1.0-20g/l.
- 7. electrolytic solution claimed in claim 5, wherein metal to be deposited exists with the ion solubilized form, and the ionic concn of copper is 0.2-10g/l, and the ionic concn of tin is 1.0-20g/l, and the ionic concn of zinc is 1.0-20g/l.
- 8. electrolytic solution as claimed in claim 1, wherein the amount of pyrophosphate salt is 50-400g/l in the electrolytic solution.
- 9. electrolytic solution as claimed in claim 1, wherein the pH of electrolytic solution is 6-13.
- 10. wherein there are one or more compounds with stabilization in electrolytic solution as claimed in claim 1, and described compound is selected from monocarboxylic acid and di-carboxylic acid, alkansulfonic acid, trimethyl-glycine and aromatic nitro compound.
- 11. a method for electrodeposition is used for ornamental bell metal layer electrochemically is applied to daily necessities and mechanicals, wherein substrate to be coated is immersed in each the described electrolytic solution such as claim 1 to 9.
- 12. method as claimed in claim 11 wherein remains on electrolytic solution in 20 to 60 ℃ the temperature range.
- 13. method as claimed in claim 11, wherein adjusting current density is 0.2 to 5 ampere/square decimeter.
- 14. method as claimed in claim 11 is wherein used soluble anode, this anode is comprised of the material that is selected from electrolytic copper, phosphorous copper, tin, tin-copper alloy, zinc-copper alloy and zinc-tin-copper alloy, or the combination of these anodes.
- 15. method is wherein used insoluble anode as claimed in claim 11, this anode is comprised of the material of the titanium that is selected from platinum plating, graphite, iridium-transition metal mixed oxide and diamond-like carbon, or the combination of these anodes.
- 16. method as claimed in claim 11, wherein, negative electrode and insoluble anode are spaced apart from each other to form cathode space and anode chamber by ion-exchange membrane, and only cathode space comprises nontoxic electrolytic solution, so that Sn 2+To Sn 4+Anodic oxidation be suppressed.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP08008637.4 | 2008-05-08 | ||
| EP08008637A EP2116634B1 (en) | 2008-05-08 | 2008-05-08 | Modified copper-tin electrolyte and method of depositing bronze layers |
| PCT/EP2009/002323 WO2009135572A2 (en) | 2008-05-08 | 2009-03-31 | Modified copper-tin electrolyte and process for the deposition of bronze layers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102016130A CN102016130A (en) | 2011-04-13 |
| CN102016130B true CN102016130B (en) | 2013-03-13 |
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ID=39639007
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009801164345A Expired - Fee Related CN102016130B (en) | 2008-05-08 | 2009-03-31 | Modified copper-tin electrolyte and method of depositing bronze layers |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US20110089043A1 (en) |
| EP (1) | EP2116634B1 (en) |
| JP (1) | JP2011520037A (en) |
| KR (1) | KR20110011613A (en) |
| CN (1) | CN102016130B (en) |
| AT (1) | ATE486157T1 (en) |
| DE (1) | DE502008001647D1 (en) |
| HK (1) | HK1152352A1 (en) |
| MX (1) | MX2010012041A (en) |
| PL (1) | PL2116634T3 (en) |
| TW (1) | TW201005129A (en) |
| WO (1) | WO2009135572A2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5569718B2 (en) * | 2009-08-21 | 2014-08-13 | キザイ株式会社 | Cyan-free bright copper-tin alloy plating bath |
| KR101236165B1 (en) * | 2011-02-15 | 2013-02-22 | (주)지오데코 | Environmental friendly three element alloys plating solution and method for treating metal surface using the same |
| DE102011121799B4 (en) | 2011-12-21 | 2013-08-29 | Umicore Galvanotechnik Gmbh | An electrolyte and a method for the electrodeposition of Cu-Zn-Sn alloy layers and a method for producing a thin-film solar cell |
| DE102011121798B4 (en) | 2011-12-21 | 2013-08-29 | Umicore Galvanotechnik Gmbh | An electrolyte and a method for the electrodeposition of Cu-Zn-Sn alloy layers and a method for producing a thin-film solar cell |
| JP5952093B2 (en) * | 2012-05-31 | 2016-07-13 | ローム・アンド・ハース電子材料株式会社 | Electrolytic copper plating solution and electrolytic copper plating method |
| JP6093143B2 (en) * | 2012-10-19 | 2017-03-08 | 株式会社シミズ | Non-cyanide copper-tin alloy plating bath |
| 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 |
| AR100422A1 (en) * | 2014-05-15 | 2016-10-05 | Nippon Steel & Sumitomo Metal Corp | SOLUTION FOR DEPOSITION FOR THREADED CONNECTION FOR A PIPE OR PIPE AND PRODUCTION METHOD OF THE THREADED CONNECTION FOR A PIPE OR PIPE |
| CN104152955A (en) * | 2014-07-17 | 2014-11-19 | 广东致卓精密金属科技有限公司 | Plating solution and process for electroplating and brightening white copper-tin by using alkaline solution |
| CN111276725B (en) * | 2017-11-19 | 2021-10-08 | 湖南辰砾新材料有限公司 | Anion exchange membrane fuel cell |
| BE1027099B1 (en) * | 2019-03-08 | 2020-10-05 | Umicore Nv | PROCEDURE FOR ELECTROLYTIC BUYER EXECUTION |
| DE202021004169U1 (en) | 2021-07-02 | 2022-12-07 | Umicore Galvanotechnik Gmbh | Bronze layer as a substitute for precious metals in smart cards |
| DE102021117095A1 (en) | 2021-07-02 | 2023-01-05 | Umicore Galvanotechnik Gmbh | Bronze layers as a substitute for precious metals |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1146148A2 (en) * | 2000-04-14 | 2001-10-17 | Nihon New Chrome Co. Ltd. | Cyanide-free pyrophosphoric acid bath for use in copper-tin alloy plating |
| CN1665965A (en) * | 2002-07-05 | 2005-09-07 | 日本新铬电镀株式会社 | Pyrophosphoric acid bath for use in copper-tin alloy plating |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2198365A (en) * | 1938-06-29 | 1940-04-23 | Special Chemicals Corp | Electroplating |
| US3227638A (en) * | 1961-06-16 | 1966-01-04 | Robert H Burnson | Alkali cyanide bath and process for electroplating therewith |
| DE3346721A1 (en) * | 1983-12-23 | 1985-06-27 | Fa. Karl-Wilh. Hen, 5820 Gevelsberg | Alkaline bath for depositing a high-lustre electroplated coating on a substrate |
| JPH02175894A (en) * | 1988-12-28 | 1990-07-09 | Kosaku:Kk | Method and device for tin or tin alloy electroplating |
| US5194140A (en) * | 1991-11-27 | 1993-03-16 | Macdermid, Incorporated | Electroplating composition and process |
| DE4324995C2 (en) | 1993-07-26 | 1995-12-21 | Demetron Gmbh | Cyanide-alkaline baths for the galvanic deposition of copper-tin alloy coatings |
| JP3674887B2 (en) * | 1996-09-30 | 2005-07-27 | 日本ニュークローム株式会社 | Pyrophosphate bath for copper-tin alloy plating |
| US6176996B1 (en) * | 1997-10-30 | 2001-01-23 | Sungsoo Moon | Tin alloy plating compositions |
| TW577938B (en) | 1998-11-05 | 2004-03-01 | Uyemura C & Co Ltd | Tin-copper alloy electroplating bath and plating process therewith |
| JP2001181889A (en) | 1999-12-22 | 2001-07-03 | Nippon Macdermid Kk | Bright tin-copper alloy electroplating bath |
| DE10046600C2 (en) | 2000-09-20 | 2003-02-20 | Schloetter Fa Dr Ing Max | Electrolyte and process for the deposition of tin-copper alloy layers and use of the electrolyte |
| ES2531163T3 (en) * | 2002-10-11 | 2015-03-11 | Enthone | Procedure and electrolyte for galvanic deposition of bronzes |
-
2008
- 2008-05-08 EP EP08008637A patent/EP2116634B1/en not_active Not-in-force
- 2008-05-08 DE DE502008001647T patent/DE502008001647D1/en active Active
- 2008-05-08 AT AT08008637T patent/ATE486157T1/en active
- 2008-05-08 PL PL08008637T patent/PL2116634T3/en unknown
-
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- 2009-03-31 JP JP2011507800A patent/JP2011520037A/en active Pending
- 2009-03-31 WO PCT/EP2009/002323 patent/WO2009135572A2/en active Application Filing
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- 2009-03-31 KR KR1020107024999A patent/KR20110011613A/en not_active Application Discontinuation
- 2009-03-31 CN CN2009801164345A patent/CN102016130B/en not_active Expired - Fee Related
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1146148A2 (en) * | 2000-04-14 | 2001-10-17 | Nihon New Chrome Co. Ltd. | Cyanide-free pyrophosphoric acid bath for use in copper-tin alloy plating |
| CN1665965A (en) * | 2002-07-05 | 2005-09-07 | 日本新铬电镀株式会社 | Pyrophosphoric acid bath for use in copper-tin alloy plating |
Non-Patent Citations (1)
| Title |
|---|
| 刘建平.无氰电镀高锡铜锡合金工艺.《电镀与涂饰》.2008,第27卷(第3期),9-11. * |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2009135572A2 (en) | 2009-11-12 |
| KR20110011613A (en) | 2011-02-08 |
| HK1152352A1 (en) | 2012-02-24 |
| MX2010012041A (en) | 2011-03-04 |
| PL2116634T3 (en) | 2011-04-29 |
| EP2116634B1 (en) | 2010-10-27 |
| ATE486157T1 (en) | 2010-11-15 |
| TW201005129A (en) | 2010-02-01 |
| CN102016130A (en) | 2011-04-13 |
| WO2009135572A3 (en) | 2009-12-30 |
| JP2011520037A (en) | 2011-07-14 |
| US20110089043A1 (en) | 2011-04-21 |
| DE502008001647D1 (en) | 2010-12-09 |
| EP2116634A1 (en) | 2009-11-11 |
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