CN103069054A - Electrolyte and process for the deposition of copper-tin alloy layers - Google Patents
Electrolyte and process for the deposition of copper-tin alloy layers Download PDFInfo
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- CN103069054A CN103069054A CN2011800387288A CN201180038728A CN103069054A CN 103069054 A CN103069054 A CN 103069054A CN 2011800387288 A CN2011800387288 A CN 2011800387288A CN 201180038728 A CN201180038728 A CN 201180038728A CN 103069054 A CN103069054 A CN 103069054A
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- tin
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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
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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
- C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/16—Apparatus for electrolytic coating of small objects in bulk
Abstract
The present invention relates to an electrolyte and a process for depositing bronze alloys on consumer goods and industrial articles. The electrolyte of the invention comprises, in addition to the metals to be deposited and additives such as wetting agents, complexing agents and brighteners, in particular sulfur compounds which have a positive effect in the corresponding process for the deposition of the bronzes.
Description
The present invention relates to a kind of ionogen and a kind of for the method at the consumer's goods and industrial article deposition bell metal.Metal and the additive of ionogen of the present invention except remaining to be deposited for example outside wetting agent, complexing agent and the brightener, also comprises the sulfide derivative that has active effect in the respective process for the deposition of this bronze particularly.
The consumer's goods or goods for consumption as in the goods for consumption rules, define, upgrade by thin, oxidation-stabilized metal level for ornamental reason and in order to prevent from corroding.These layers should be mechanically stable and should in long-term use, not show tarnishing or wear phenomenon.From calendar year 2001, no longer allowed in European market with the consumer's goods of nickeliferous upgrading alloy-coated or only to follow stringent condition just possible, because nickel and nickeliferous metal level are the contact allergens according to the guide 94/27/EC of European Union.Particularly, bell metal has been established as the surrogate for nickeliferous upgrading layer, and the mass-produced consumer's goods can upgrade to come by these production without allergen, attractive product with electrochemistry barrel plating or rack plating process at an easy rate.
In the production of the bronze layer of electron trade, the weldability of resulting layer and (suitable words) its mechanical adhesion are the key properties that layer to be produced is arranged.For the purposes in this field, the outward appearance of these layers is important not as its function generally.For producing bronze layer at the consumer's goods, on the other hand, it is important target component that the decorative effect of gained layer (gloss and brightness) and weather resistance combine with ideally constant outward appearance.
The known method for the production of bronze layer comprise conventional use contain the process of prussiate and therefore highly toxic alkaline bath process and also have various electrolytic processes, these processes can be designated as one of following two main groups of noticing in the prior art usually according to electrolytical composition: use based on the electrolytical process of organic sulfonic acid or use process based on the bath of bisphosphate (tetra-sodium).
For example, EP1111097A2 has described a kind of ionogen, and the ion that this ionogen comprises a kind of organic sulfonic acid and tin and copper is together with dispersion agent and brightener and also have randomly antioxidant.
EP1146148A2 has described a kind of copper-tin electrolyte of cyanide-free, this ionogen be based on bisphosphate and comprise amine and epoxy chloropropane with the reaction product of the mol ratio of 1:1 together with a kind of cats product.This amine can be vulkacit H.It is with 0.5,1.5,2.5 and 3.0A/dm
2Current density in electrolytic deposition, use.
WO2004/005528 relates to a kind of bisphosphate-copper of cyanide-free-tin electrolyte, and this ionogen comprises additive, epoxy chloropropane and the glycidyl ether compound that is comprised of sulfonamide derivatives, and mol ratio is 1:0.5-2:0.1-5.A purpose of the document is the scope that increases current density, wherein can be implemented in uniform deposition metal in one shinny (shiny) layer.Pointed out that clearly this kind deposition only can be realized by above mentioning when all three kinds of component form at the additive that adds.
The acid bronze ionogen of cyanide-free is known equally.Because this kind bath often comprises one or more alkylsulphonic acids, often with other additive, for example wetting agent, complexing agent, brightener, etc. combination.
EP1408141A1 has described a kind of method for the electrochemical deposition bronze, has wherein used a kind of stanniferous and cupric ion together with the acidic electrolyte bath of alkylsulphonic acid and aromatic nonionic wetting agent.
EP1874982A1 has described from a kind of copper and tin ion of comprising together with the electrolyte deposition bronze of alkylsulphonic acid and wetting agent.Exist in the ionogen that sulphur compound also can advantageously propose herein.Yet they are combined with non-ionic aromatic series wetting agent at this.
EP1325175B1 advise equally in the bronze ionogen of acidity existing have general formula-R-Z-R '-specific sulphur compound.Purpose is to realize the equalization of standard C u (II) and Sn (II) ionic potential by copper complexing action optionally.Although used thio-compounds in this document, the interpolation of antioxidant is seemingly indispensable to prevent damaging Sn (II) oxidation.
In electroplating industry, usually use different coating procedures along with the variation of the type that part to be coated is arranged and character.These methods except other things, are different with regard to operable current density.Can mention in fact 3 kinds of different coating procedures.
1. the barrel plating that is used for loose material and mass-produced part:
In this electroplating process, used the lower working current density (order of magnitude: 0.025-0.5A/dm
2)
2. the rack plating that is used for individual part:
In this electroplating process, used the working current density (order of magnitude: 0.2-5A/dm of moderate
2)
3. the high speed electrodeposition that in continuous device, is used for band and wire rod:
In this field, used the very high working current density (order of magnitude: 5-100A/dm
2)
For the coating of using copper-Xi, front two kinds of processes (barrel plating and rack plating) are most important.Depend on different ionogen types, barrel plating (lower current density) also or rack plating (moderate current density) be possible (referring to " practical electroplating technology (Praktische Galvanotechnik) ", Eugen G.Leuze Verlag1997, the 74ff page or leaf).
In view of above-mentioned prior art can be determined, especially use for barrel plating, particularly advantageous is following deposition process, and this process has been guaranteed metal uniform deposition and used with regard to composition more uncomplicated and particularly for the oxidation-stabilized ionogen of Sn (II) in the whole range of current of usually considering.
Therefore an object of the present invention is to provide a kind of deposition process and a kind of other ionogen, compare with the ionogen that discloses in the prior art, this ionogen is favourable from ecological and economy viewpoint.What should arouse attention especially is with low current density scope deposit perfect ground white, shinny bronze layer by stable and ionogen with simple composition.
These purposes and other this do not mention, but the purpose that can be drawn in obvious mode from prior art by those of ordinary skill in the art, respectively by will be according to claim 1 realizing with a kind of ionogen that is used for the deposition bronze and the corresponding method of claim 10.Quote the preferred embodiment that the dependent claims of getting back to claim 1 and claim 10 represents respectively this ionogen or method.
A kind of cyanide-free ionogen for deposited copper-tinbronze on the consumer's goods and industrial article that proposes, this ionogen comprise the metal that remains to be deposited that is in the water-soluble salt form (for example copper, tin and randomly zinc) and are characterised in that
This ionogen comprises following other component:
A) one or more alkylsulphonic acids;
B) a kind of ionic wetting agent that is in salt form sulfonation or Sulfated aromatic series alkylaryl ether compound;
C) a kind of complexing agent; And
D) a kind of compound that is selected from the group that is formed by the dialkyl sulfide derivative,
However extremely beneficial ground still but unexpectedly make described purpose realize.This ionogen makes it might be on the consumer's goods and industrial article, the copper of especially producing very uniformly with the low current density scope and extremely becoming clear-tinbronze settling.Employed ionogen has satisfactory stability, particularly with regard to Sn (IV) throw out.This has fully unexpectedly caused release that other antioxidant is joined in this ionogen.Therefore in a preferred embodiment, in ionogen of the present invention, do not exist other antioxidant, particularly quinhydrones, pyrocatechol, Resorcinol, sulfocarbolic acid, cresol sulfonic acid, etc.This is that those of ordinary skill in the art does not anticipate with regard to prior art.
In ionogen of the present invention, the metallic copper that remains to be deposited and tin or copper, tin and zinc exist in solution as its ion.Give preferably following embodiment, wherein metal ion exists as salt, and wherein there has been or can caused by the other metal-salt of introducing correspondence any increase of the concentration of the anionic group in this ionogen in negatively charged ion in ionogen.Therefore they are most preferably introduced with the form of water-soluble salt, these salt preferably are selected from lower group, and this group is comprised of the following: alkylsulfonate, carbonate, subcarbonate, supercarbonate, oxyhydroxide, hydroxide oxide compound, oxide compound or its combination.Can point out that in a preferred embodiment these metals can also be incorporated into the form of soluble anode in this ionogen.In this regard, can with reference to correspondingly referred in this embodiment of method of the present invention as favourable scheme.
The type of the salt of introducing in these ionogen and value can be conclusive and can require to set according to the human consumer for the color of resulting ornamental bronze layer.The metal that deposits as noted, shows the form of the ionic formula dissolving of the ionogen of using at the ornamental bronze layer that is used on the consumer's goods and the industrial article.The ionic concn of copper can be set in 0.2 to 10g/l electrolytical scope, preferably in 0.3 to 4g/l scope, the ionic concn of tin can be set in 1.0 to 30g/l electrolytical scopes, preferably in the scope of 2-20g/l, and the ionic concn of zinc can be set in 0.5 to 20g/l electrolytical scope if present, preferably in the scope of 1-3g/l.
Ionogen of the present invention is based on the acidic electrolyte bath of one or more alkylsulphonic acids.Acid concentration in this ionogen can change in the 100-300ml/l scope, preferred 150-250ml/l and very particularly preferably about 200ml/l.As the alkylsulphonic acid in the ionogen, might use those that considered for this kind purpose by those of ordinary skill in the art.In situation of the present invention, the term alkyl refers to the alkyl of the side chain of a kind of straight chain or any type, and these alkyl have from 1 to 10, preferably from 1 to 5 and from 1 to 3 carbon atom very particularly preferably.Give very particularly preferably be to use to be selected from lower group alkylsulphonic acid, this group by methylsulfonic acid, ethyl sulfonic acid and just propanesulfonic acid form.The above-mentioned metal that remains to be deposited advantageously uses with the form of water-soluble alkyl sulfonate.For the consumer's goods of upgrading, give very particularly preferably be that these metals that remain to be deposited are introduced in such a way as the salt of methylsulfonic acid, so that resulting ionic concn is that every liter ionogen restrains in the scope of copper from 0.3 to 4 in each case, from 2 to 20 gram tin and from 0 to 3 gram zinc.
As mentioned above, employed ionogen comprises the wetting agent/brightener of ionic.These wetting agents are by the salt formation of aromatic series alkylaryl ether compound a kind of sulfonation or Sulfated.This kind wetting agent is (" electroplating deposition of zinc and zinc alloy (the Die galvanische Abscheidung von Zinn und Zinnlegierungen) " that fully know for those of ordinary skills, Manfred Jordan, Eugen G.Leuze Verlag, Bad Saulgau).Aromatic series alkylaryl ether compound employed sulfonation or Sulfated comprises one and is connected to alkyl group on the aromatic yl group by oxo bridge.For purposes of the present invention, the term alkyl refers to a kind of group straight chain or the branched-chain alkyl type that comprises in situation of the present invention, and these alkyl have from 1 to 10, preferably from 1 to 5 and from 1 to 3 carbon atom very particularly preferably.As aromatic yl group, those of ordinary skill in the art might select those can be considered to meet the group of following chemical formula: (C
7-C
19)-alkaryl, (C
6-C
18)-aryl, (C
7-C
19)-aralkyl, (C
3-C
18)-heteroaryl, (C
4-C
19)-miscellaneous alkyl aryl, (C
4-C
19)-heteroaralkyl.Particularly preferably be to use and be selected from those of lower group, this group is comprised of phenol, naphthols, benzene,toluene,xylene, isopropyl benzene, phenylmethylether, aniline.Very particularly advantageous is to use to be selected from lower group alkylaryl ether compound, and this organize by the aryl ethoxylate, 2-Naphthol ethoxylate particularly, nonyl phenol ethoxylate composition.Position sulfonation or Sulfated can exist in part fragrance or fat of this compound.Preferably the part at the fragrance of this compound exists.As counterion, all positively charged ions that might select those of ordinary skills will can take into account for this purpose.Give preferably to use the ammonium ion of an alkali metal salt or corresponding acid.These particularly advantageously are to be selected from the group that is comprised of sodium and potassium.This additive (for example, the sodium salt of aryl ethoxylate sulfonation or Sulfated, Na salt sulfonation or Sulfated alkylphenol ethoxylate particularly) increased the brightness of the layer that deposits, widened current density range and will increase about 2L unit according to the whiteness of the layer that deposits in the combination of the present invention to the high current density direction.Simultaneously, this brightener works as wetting agent.Mentioned wetting agent advantageously is used for ionogen by following concentration, that is: the ionogen of 0.01-10ml/l, and selection of land is the ionogen of 0.2-5ml/l, and particularly preferably is the ionogen of 0.5-1ml/l.
Should in this ionogen, there be complexing agent equally.This complexing agent has the effect that prevents any Sn (IV) ion formation tindioxide precipitation except other things.Do not add complexing agent, then ionogen is owing to formed tindioxide after short period of time only becomes muddy.This bronze settling of result little by little becomes dumb light.SnO by fine dispersion
2The turbidity that causes has increased the consumption of other organic additives significantly.Adding rate of utilization that constant quality ground that complexing agent reduced the degree of electrolysis qualitative change muddiness and bronze layer significantly keeps good (gloss and whiteness) to increase simultaneously bathing and the consumption of organic additive is minimized.
As complexing agent, those compounds that might select those of ordinary skills will can take into account for this purpose.Preferred compound is based on (hydroxyl) dicarboxylic acid or tricarboxylic acid.Particularly preferably be the complexing agent that use is selected from lower group, this group is comprised of the following: oxalic acid, propanedioic acid, Succinic Acid, tartrate, oxysuccinic acid, citric acid, toxilic acid, pentanedioic acid, hexanodioic acid.Under this background, give very particularly preferably be oxysuccinic acid.Mentioned complexing agent advantageously uses by following concentration, that is: the ionogen of 1-300g/l, and selection of land is the ionogen of 20-200g/l, particularly preferably is the ionogen of 50-150g/l.
As mentioned above, ionogen of the present invention also mixes with one or more dialkyl sulfide derivatives.These reagent have caused the improved deposition of bell metal, particularly in the scope of low current density.Under this background, the dialkyl sulfide derivative that symmetry replaces, for example Thiodiglycol propoxylated glycerine or Thiodiglycol ethoxylate are favourable.As alkyl group, again might use above-mentioned those.These alkyl groups can be replaced by other functional group.The latter can preferably be selected from by hydroxyl, carboxylic acid (ester), mercaptan, the amino group that forms.Under this background, give very particularly preferably be for example to be selected from lower group compound, this group is comprised of the following: the Thiodiglycol propoxylated glycerine, Thiodiglycol, sulfo-two glycerine, the Thiodiglycol ethoxylate, thio-diethylene glycol is two, and (3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester), 2-amino-4-(methylthio group) butyric acid, 2,2 '-sulfo-diethyl mercaptan, 3,3 '-sulfo-dipropyl mercaptan, 2,2 '-thiodiglycolic acid, 3,3 '-thio-2 acid, 2,2 '-thiodiglycolic acid diethyl ester, 2,2 '-thiodiglycolic acid dimethyl esters, 2,2 '-thiodiglycolic acid dioctyl ester, 2, the two dodecyl esters of 2 '-thiodiglycolic acid, 3, the two dodecyl esters of 3 '-thio-2 acid, 3,3 '-thio-2 acid dimethyl esters, 3,3 '-thio-2 acid diethyl ester, 3,3 '-thio-2 acid dioctyl ester, 3,3 '-sulfo-, two propyl alcohol, 2,2 '-thiodiethanol, 4,4 '-sulfo-, two butanols, 1,1 '-(sulfo-two-2,1-ethane two bases) 2-propionic ester, 3, the two stearyl of 3 '-thio-2 acid wherein demonstrate very preferably 2-amino-4-(methylthio group) butyric acid.
Above-mentioned dialkyl sulfide derivative advantageously uses by following concentration, that is: the ionogen of 0.01-20g/l, and selection of land is the ionogen of 0.1-5g/l, particularly preferably is the ionogen of 0.3-1g/l.
Because the interpolation of acid, electrolytical pH is in the strong acid scope.It is set to produce from-1 to 4 scope, preferably from-0.5 to 2 scope and particularly preferably about 1 pH.
In addition, the present invention proposes a kind of electrolyte deposition method for bell metal layer electrochemistry being administered on the consumer's goods and the industrial article, wherein will have substrate to be coated to be immersed in according in the ionogen of the present invention and a suitable current flow is provided.Electrolytical preferred embodiment discussed above is applicable to shown herein method similarly.
Preferably, this ionogen is heated to the temperature in the scope of from 20 to 40 ° of C, preferred about 30 ° of C.Current density might be set in from 0.01 to 100 ampere of/square decimeter [A/dm
2] scope in, and depend on the type of electroplating facility.Therefore, in the barrel plating process, from 0.01 to 0.75A/dm
2Scope in current density be preferred, from 0.025 to 0.5A/dm
2Current density be preferred and about 0.1-0.3A/dm
2Current density be very particularly preferred.In the rack plating process, preferably be chosen in from 0.2 to 10.0A/dm
2Scope in current density, particularly preferably from 0.2 to 5.0A/dm
2And very particularly preferably from 0.25-1.0A/dm
2Yet barrel plating (referring to foreword and " practical electroplating technology ", Eugen G.Leuze Verlag1997,74ff page or leaf) is preferred.
When using ionogen of the present invention, might adopt various anodes.Soluble anode is particularly advantageous.As soluble anode, give preferably to use the anode that is formed by the material that is selected from lower group, this group is comprised of the following: the copper of electrolysis, phosphorous copper, tin, copper-tin alloy, copper-zinc alloy and copper-tin-zinc alloy.Particularly preferably be the combination of using the different soluble anodes that formed by these materials.
In this electrolyte system, can also use pure copper anode.Yet, the preferred anodes that is used for this copper-tin electrolyte based on alkylsulphonic acid is copper-tin alloy anode, and the copper content that these anodes have is from by weight＜90% to by weight〉50% and tin content be from by weight 10% to by weight＜50%.These anodes more preferably comprise the copper of 85%-60% by weight and the tin of 40%-15% by weight.The copper content of this anode most preferably is about 4 times of this tin content.In other elements situation that for example (preferably) zinc randomly exists in this soluble anode, it also is this kind situation.
This ionogen does not also contain the material of any insalubrity, and this is another advantage that surmounts other copper based on methylsulfonic acid-tin electrolyte system.In copper methane sulfonate-tin electrolyte, antioxidant is commonly used to prevent the oxidation of tin except other things.As antioxidant, often use quinhydrones (carcinogens), pyrocatechol and Resorcinol (all insalubrity).Above-mentioned chemicals all do not use in electrolyte system of the present invention.This ionogen is sufficiently stable, can not add other antioxidant.
For the purposes of the present invention, (C
6-C
18)-aryl is a kind of aromatic series system, and this system is comprised of from 6 to 18 carbon atoms fully.Particularly, this system is selected from the group that is comprised of phenyl, naphthyl, anthryl etc.
(C
7-C
19)-alkaryl is at (C
6-C
18On the)-aromatic yl group with (a C
1-C
8The group of)-alkyl group.
(C
7-C
19)-aralkyl is at (C
1-C
8On the)-alkyl group with (a C
6-C
18The group of)-aromatic yl group, this group is by being somebody's turn to do (C
1-C
8)-alkyl group is connected on the molecule of considering.
For the purposes of the present invention, (C
3-C
18)-heteroaryl groups is the aromatic series system with at least three carbon atoms.The heteroatoms that in this aromatic series system, has in addition other.They are nitrogen and/or sulphur preferably.This type of heteroaromatic compound can be at Bayer-Walter, organic chemistry textbook (Lehrbuch der Organischen Chemie), and S.Hirzel Verlag, finds in the 703ff page or leaf by the 22nd edition.
For the purposes of the present invention, (C
4-C
19)-miscellaneous alkyl aryl is to be supplemented with a C
1-C
8(the C of)-alkyl substituent
3-C
18)-heteroaryl groups.Be attached on the molecule of considering by heteroaromatics.
On the other hand, (C
4-C
19)-heteroaralkyl is by (a C
1-C
8)-alkyl substituent is attached to the (C that considers
3-C
18)-heteroaryl groups.
Example:
According to ionogen preparation of the present invention
The methylsulfonic acid of 180ml/l (70%)
The oxysuccinic acid of 60g/l
Cu in the copper methane sulfonate solution (100g/l) of 20ml/l=2g/l ionogen
Sn in the tin methane sulfonate of 20ml/l (300g/l)=6g/l ionogen
2-amino-4-(methylthio group) butyric acid of 1g/l
The brightener of 1ml/l (sulfonation with sodium salt Sulfated alkylphenol ethoxylate)
1. the deionized water of 200ml/l is placed the glass beaker of a 1L.
2. the methylsulfonic acid (70%) that then under violent stirring, adds lentamente 180ml/l.
3. then under violent stirring, the oxysuccinic acid of 60g/l is dissolved in the methylsulfonic acid of dilution.After dissolving fully,
4. add 20ml/l copper methane sulfonate solution and 20ml/l tin methane sulfonate and volume is added to 950ml with deionized water.
5. 2-amino-4-(methylthio group) butyric acid that then adds 1g/l.After it dissolves fully,
6. in this ionogen, add the brightener of 1ml/l and use deionized water that this ionogen is added to final volume (1000ml).
Deposition parameter:
Temperature: electrolyte temperature: 30 ° of C
pH:pH<1
The current density that barrel plating is used:
The optimum current density range of using for barrel plating is to 0.3A/dm from 0.1
2
Anode:
The anode that is used for this copper-tin electrolyte based on alkylsulphonic acid is copper-tin alloy anode, the copper content that these anodes have be by weight 80% and tin content be by weight 20%[to take German company (Goodfellow GmbH) from Gu Te commercially available].
The ionogen characteristic:
The characteristic of coating:
Coating: copper-Xi
The Cu of alloy composition: 70%-55%, the Sn(of 30%-45% depends on working conditions)
The density of coating: about 8.2g/cm
3(calculating)
Color: white, the L* value is at 0.1A/dm
2Lower about 82-85
Use the experiment of the surrogate that is used for the dialkyl sulfide derivative
The electrolytical compound method of 1L:
Referring to the experiment of using 2-amino-4-(methylthio group) butyric acid
Working parameter:
Temperature: 30 ° of C
Anode: Cu-Sn80/20
Magnetic stirring bar/kinds of goods of glass beaker/200rpm/6cm of 1 liter move
Experiment is deposited on 0.5dm
2Copper coin on 0.2A/dm
2/ 10min and 0.5A/dm
2/ 5min carries out.
In these experiments, use following material (seeing table) to replace the dialkyl sulfide derivative.
The result: these materials of testing all can not look like the dialkyl sulfide derivative, and particularly 2-amino-4-(methylthio group) butyric acid carries out work like that well.
Claims (14)
1. cyanide-free ionogen that is used for deposited copper-tinbronze on the consumer's goods and industrial article, this ionogen comprises the metal that remains to be deposited that is in the water-soluble salt form,
It is characterized in that
This ionogen comprises following other component:
A) one or more alkylsulphonic acids;
B) a kind of ionic wetting agent, this wetting agent is in the salt form of aromatic series alkylaryl ether compound sulfonation or Sulfated;
C) a kind of complexing agent; And
D) a kind of compound that is selected from the group that is formed by the dialkyl sulfide derivative.
2. ionogen as claimed in claim 1 is characterized in that this ionogen comprises copper and tin or copper, tin and zinc as the metal that remains to be deposited.
3. such as claim 1 and/or 2 described ionogen, it is characterized in that these metals that remain to be deposited exist with the form of ionic formula dissolving, wherein the ionic concn of copper is in 0.2 to 10g/l electrolytical scope, the ionic concn of tin is in 1.0 to 20g/l electrolytical scopes, if present, the ionic concn of zinc is in 1.0 to 20g/l electrolytical scopes.
4. such as one or more described ionogen in the claims 1 to 3, it is characterized in that alkylsulphonic acid is to be selected from lower group, this group is comprised of the following: methylsulfonic acid, ethyl sulfonic acid and positive propanesulfonic acid.
5. such as one or more described ionogen in the claim 1 to 4, it is characterized in that the alkyl sulfonate of the metal that these remain to be deposited is used as water-soluble salt.
6. such as one or more described ionogen in the claim 1 to 5, it is characterized in that using a kind of alkylaryl ether compound that is selected from lower group, this group is comprised of the following: 2-Naphthol ethoxylate, nonyl phenol ethoxylate.
7. such as one or more described ionogen in the claim 1 to 6, it is characterized in that using an alkali metal salt of the acid of these correspondences.
8. such as one or more described ionogen in the claim 1 to 7, it is characterized in that using being selected from lower group complexing agent, this group is comprised of the following: oxalic acid, propanedioic acid, Succinic Acid, tartrate, oxysuccinic acid, citric acid, toxilic acid, pentanedioic acid, hexanodioic acid.
9. such as one or more described ionogen in the claim 1 to 8, it is characterized in that using a kind of dialkyl sulfide derivative that is selected from lower group, this group is comprised of the following: the Thiodiglycol propoxylated glycerine, Thiodiglycol, sulfo-two glycerine, the Thiodiglycol ethoxylate, thio-diethylene glycol is two, and (3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester), 2-amino-4-(methylthio group) butyric acid, 2,2 '-sulfo-diethyl mercaptan, 3,3 '-sulfo-dipropyl mercaptan, 2,2 '-thiodiglycolic acid, 3,3 '-thio-2 acid, 2,2 '-thiodiglycolic acid diethyl ester, 2,2 '-thiodiglycolic acid dimethyl esters, 2,2 '-thiodiglycolic acid dioctyl ester, 2, the two dodecyl esters of 2 '-thiodiglycolic acid, 3, the two dodecyl esters of 3 '-thio-2 acid, 3,3 '-thio-2 acid dimethyl esters, 3,3 '-thio-2 acid diethyl ester, 3,3 '-thio-2 acid dioctyl ester, 3,3 '-sulfo-, two propyl alcohol, 2,2 '-thiodiethanol, 4,4 '-sulfo-, two butanols, 1,1 '-(sulfo-two-2,1-ethane two bases) 2-propionic ester, 3, the two stearyl of 3 '-thio-2 acid.
10. such as one or more described ionogen in the claim 1 to 9, it is characterized in that this electrolytical pH is in from-1 to 4 scope.
11. method that is used for electrochemically depositing copper-tinbronze on the consumer's goods and industrial article, comprise the metal that remains to be deposited that is in the water-soluble salt form, wherein these there is substrate to be coated to be immersed in a kind of ionogen and the electric current of a suitable flow is provided, it is characterized in that using such as the one or more described ionogen of claim 1 to 10.
12. method as claimed in claim 11 is characterized in that in the deposition process of these metals this ionogen is heated to the temperature in 20 ° C to the 40 ° C scope.
13. such as claim 11 and/or 12 described methods, it is characterized in that a current density is set in from 0.01 to 100 ampere/square decimeter the scope.
14. such as one or more described method among the claim 11-13, it is characterized in that using the soluble anode that is comprised of the material that is selected from lower group, this group is comprised of the following: the copper of electrolysis, phosphorous copper, tin, copper-tin alloy, copper-zinc alloy and copper-tin-zinc alloy; Or the combination of these anodes.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102010034646 | 2010-08-17 | ||
| DE102010034646.2 | 2010-08-17 | ||
| PCT/EP2011/063923 WO2012022689A1 (en) | 2010-08-17 | 2011-08-12 | Electrolyte and process for the deposition of copper-tin alloy layers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103069054A true CN103069054A (en) | 2013-04-24 |
| CN103069054B CN103069054B (en) | 2016-08-10 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201180038728.8A Active CN103069054B (en) | 2010-08-17 | 2011-08-12 | For depositing electrolyte and the method for copper-tin alloy layers |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20130140185A1 (en) |
| EP (1) | EP2606164A1 (en) |
| JP (1) | JP2013534276A (en) |
| KR (1) | KR20130098304A (en) |
| CN (1) | CN103069054B (en) |
| DE (1) | DE102011008836B4 (en) |
| WO (1) | WO2012022689A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105220189A (en) * | 2015-10-30 | 2016-01-06 | 无锡市嘉邦电力管道厂 | A kind of samarium-tin-copper alloy electroplating liquid and electro-plating method thereof |
| 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 |
| CN107922324A (en) * | 2015-05-22 | 2018-04-17 | 巴斯夫欧洲公司 | Beta Naphthol 99MIN ether sulfonate, its preparation method and its purposes as brightness improvement agent |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102012008544A1 (en) | 2012-05-02 | 2013-11-07 | Umicore Galvanotechnik Gmbh | Chromed composites without nickel coating |
| EP2735627A1 (en) * | 2012-11-26 | 2014-05-28 | ATOTECH Deutschland GmbH | Copper plating bath composition |
| DE102021117095A1 (en) | 2021-07-02 | 2023-01-05 | Umicore Galvanotechnik Gmbh | Bronze layers as a substitute for precious metals |
| DE202021004169U1 (en) | 2021-07-02 | 2022-12-07 | Umicore Galvanotechnik Gmbh | Bronze layer as a substitute for precious metals in smart cards |
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- 2011-08-12 US US13/816,623 patent/US20130140185A1/en not_active Abandoned
- 2011-08-12 EP EP11749145.6A patent/EP2606164A1/en not_active Withdrawn
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Also Published As
| Publication number | Publication date |
|---|---|
| EP2606164A1 (en) | 2013-06-26 |
| KR20130098304A (en) | 2013-09-04 |
| US20130140185A1 (en) | 2013-06-06 |
| WO2012022689A1 (en) | 2012-02-23 |
| CN103069054B (en) | 2016-08-10 |
| DE102011008836A1 (en) | 2012-02-23 |
| DE102011008836B4 (en) | 2013-01-10 |
| JP2013534276A (en) | 2013-09-02 |
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