US20060137991A1 - Method for bronze galvanic coating - Google Patents
Method for bronze galvanic coating Download PDFInfo
- Publication number
- US20060137991A1 US20060137991A1 US10/531,142 US53114205A US2006137991A1 US 20060137991 A1 US20060137991 A1 US 20060137991A1 US 53114205 A US53114205 A US 53114205A US 2006137991 A1 US2006137991 A1 US 2006137991A1
- Authority
- US
- United States
- Prior art keywords
- electrolyte
- concentration
- wetting agent
- tin
- aromatic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 238000000034 method Methods 0.000 title claims abstract description 52
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 title claims description 14
- 229910000906 Bronze Inorganic materials 0.000 title claims description 13
- 239000010974 bronze Substances 0.000 title claims description 13
- 238000000576 coating method Methods 0.000 title description 28
- 239000011248 coating agent Substances 0.000 title description 8
- 239000003792 electrolyte Substances 0.000 claims abstract description 117
- 239000000080 wetting agent Substances 0.000 claims abstract description 36
- 239000002253 acid Substances 0.000 claims abstract description 35
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 10
- 229910001432 tin ion Inorganic materials 0.000 claims abstract description 9
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 30
- 230000008021 deposition Effects 0.000 claims description 25
- 125000003118 aryl group Chemical group 0.000 claims description 22
- 230000003647 oxidation Effects 0.000 claims description 20
- 238000007254 oxidation reaction Methods 0.000 claims description 20
- 239000003112 inhibitor Substances 0.000 claims description 18
- 239000010949 copper Substances 0.000 claims description 17
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 15
- 239000008139 complexing agent Substances 0.000 claims description 13
- 239000003381 stabilizer Substances 0.000 claims description 12
- 125000001931 aliphatic group Chemical group 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 125000000129 anionic group Chemical group 0.000 claims description 6
- -1 dihydroxybenzene compound Chemical class 0.000 claims description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001728 carbonyl compounds Chemical class 0.000 claims description 2
- BSXVKCJAIJZTAV-UHFFFAOYSA-L copper;methanesulfonate Chemical compound [Cu+2].CS([O-])(=O)=O.CS([O-])(=O)=O BSXVKCJAIJZTAV-UHFFFAOYSA-L 0.000 claims description 2
- AICMYQIGFPHNCY-UHFFFAOYSA-J methanesulfonate;tin(4+) Chemical compound [Sn+4].CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O AICMYQIGFPHNCY-UHFFFAOYSA-J 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims 3
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 claims 1
- 229940050410 gluconate Drugs 0.000 claims 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 22
- 238000004070 electrodeposition Methods 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 description 24
- 239000011135 tin Substances 0.000 description 21
- 229910052718 tin Inorganic materials 0.000 description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 16
- 229910052802 copper Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 8
- 229910001128 Sn alloy Inorganic materials 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 229910052797 bismuth Inorganic materials 0.000 description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-M methanesulfonate group Chemical class CS(=O)(=O)[O-] AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 239000011686 zinc sulphate Substances 0.000 description 2
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 1
- IEORSVTYLWZQJQ-UHFFFAOYSA-N 2-(2-nonylphenoxy)ethanol Chemical compound CCCCCCCCCC1=CC=CC=C1OCCO IEORSVTYLWZQJQ-UHFFFAOYSA-N 0.000 description 1
- VDBJCDWTNCKRTF-UHFFFAOYSA-N 6'-hydroxyspiro[2-benzofuran-3,9'-9ah-xanthene]-1,3'-dione Chemical compound O1C(=O)C2=CC=CC=C2C21C1C=CC(=O)C=C1OC1=CC(O)=CC=C21 VDBJCDWTNCKRTF-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical class [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 description 1
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 208000026935 allergic disease Diseases 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 150000001621 bismuth Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- OIQPTROHQCGFEF-UHFFFAOYSA-L chembl1371409 Chemical compound [Na+].[Na+].OC1=CC=C2C=C(S([O-])(=O)=O)C=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 OIQPTROHQCGFEF-UHFFFAOYSA-L 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- LFEBAVXLPLPXCX-UHFFFAOYSA-H dibismuth methane trisulfate Chemical compound C.[Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LFEBAVXLPLPXCX-UHFFFAOYSA-H 0.000 description 1
- 150000005205 dihydroxybenzenes Chemical class 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000011089 mechanical engineering Methods 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229910001112 rose gold Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910000597 tin-copper alloy Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910001097 yellow gold Inorganic materials 0.000 description 1
- 239000010930 yellow gold Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Classifications
-
- 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
- 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
Definitions
- This invention concerns a method for electrodeposition of bronzes, with which the substrate to be coated is plated in an acid electrolyte that contains at least tin and copper ions, an alkylsulfonic acid and a wetting agent, and the preparation of such an electrolyte.
- acid electrolytes and methods for deposition of qualitatively high grade tin or tin alloys with a higher deposition rate are known from EP 1 111 097 A2 and U.S. Pat. No. 6,176,996 B1. These are electrolytes that contain at least two divalent metal salts of an organic sulfonic acid and from which are deposited solderable and corrosion resistant coatings that can be used, for example, as substitutes for lead-containing solderable coatings in electronics for manufacture of circuit boards, etc.
- bronze coatings are used in the jewelry industry as a substitute for expensive silver or allergy-triggering nickel.
- methods for electrodeposition of bronzes are also gaining importance in some technical fields, for example in electronics for coating electronic components or in mechanical engineering and/or in process technology for coating bearing overlays and friction layers.
- chiefly white bronzes or the so-called “false bronzes,” whose copper content can be kept quite low due to process conditions, are deposited as nickel substitutes.
- the invention is based on the task of providing a method for deposition of bronzes that, in contrast to the methods known from the prior art, enables uniform deposition of at least tin and copper side by side from an acid electrolyte at considerably higher deposition rates. Moreover, with this method firmly bonding and pore-free bronze coatings with high copper contents as well as various decorative and mechanical properties are said to be deposited.
- an acid electrolyte that can have a high content of divalent copper ions, is stable with respect to oxidation-caused sludge formation, and is both economical and environmentally friendly when used over a long period of time, is to be made available.
- the task is solved in accordance with the invention by a method of the kind mentioned at the start, which is characterized by the fact that an aromatic, nonionic wetting agent is added to the electrolyte.
- a method for electrodeposition of bronzes is made available, where an anode of a copper-tin alloy and a cathode are connected to the substrate that is to be coated by means of an electrolyte, and coating takes place by passing a direct current through them.
- an electrolyte that is usable in particular for this method and the coatings that are obtainable by this method are made available.
- the disadvantages known in the prior art are remedied with the offering of a new electrolyte composition and in this way considerably better deposition results are achieved.
- the conduct of the method is made to be simpler and more economical.
- This, too, is chiefly based on the advantageous composition of the electrolyte.
- the method is carried out at room temperature, or between 17 and 25° C., and the substrate to be coated is plated in a highly acid environment at a pH ⁇ 1.
- the electrolyte is particularly stable in this temperature range.
- there are no longer any costs for heating the electrolyte and the plated substrates also do not have to be cooled very much, with large expenditures of time and money.
- deposition rates of 0.25 im/min at a current density of 1 A/dm 2 are achieved due to, among other things, the pH value and the advantageous addition of at least one aromatic non-ionic wetting agent.
- this rate can be raised up to 7 A/dm 2 in rack operation and even up to 120 A/dm 2 for continuous plants.
- usable current densities in a range from 0.1-120 A/dm 2 are reached in each case according to plant type.
- the wetting of the surfaces to be plated is considerably improved in particular through the addition of at least one aromatic nonionic wetting agent to the electrolyte.
- Another advantage of the aromatic nonionic wetting agent that is used is that because of the advantageous wetting properties the electrolyte and/or the substrate in the electrolyte need to be agitated only a little or even not at all, in order to achieve the desired deposition results, so that additional devices for agitation of the electrolyte can be omitted.
- electrolyte residues drain from the plated substrate better when it is removed from the electrolyte, which leads to reduced entrainment losses and thus to lower process costs.
- the proposed method is therefore advantageously economical and environmentally friendly compared to the cyanide processes.
- anionic and/or aliphatic nonionic wetting agent that is known from the prior art is also optionally possible, provided these wetting agents support or even enhance the advantageous effects of the aromatic nonionic wetting agent.
- polyethylene glycols and/or anionic surfactants are preferably added to the electrolyte as anionic and/or aliphatic nonionic wetting agents.
- the method in accordance with the invention is characterized in particular by the special composition of the electrolyte. It contains essentially tin and copper ions, an alkylsulfonic acid and an aromatic nonionic wetting agent.
- stabilizers and/or complexing agents, anionic and/or nonionic, aliphatic wetting agents, oxidation inhibitors, brighteners, and other metal salts can optionally be contained in the electrolyte.
- Tin methanesulfonate is especially preferably used as tin salt in the electrolyte preferably in an amount of 5-195 g/L of electrolyte, preferably 11-175 g/L of electrolyte. This corresponds to a use of 2-75 g/L, preferably 4-57 g/L divalent tin ions.
- Copper methanesulfonate is especially preferably used in the electrolyte as the copper salt, which is advantageously added to the electrolyte in an amount of 8-280 g/L of electrolyte, preferably 16-260 g/L of electrolyte. This corresponds to the use of 2-70 g/L, preferably 4-65 g/L divalent copper ions.
- an acid preferably a mineral and/or an alkylsulfonic acid
- an acid is added to the electrolyte in amounts of 140-382 g/L of electrolyte, preferably 175-245 g/L of electrolyte.
- methanesulfonic acid turned out to be especially advantageous, since for one thing this produces advantageous solubility of metal salts and for another, because of its acid strength, it produces or facilitates the adjustment of the pH needed for the process.
- methanesulfonic acid has the advantageous property of contributing considerably to the stability of the bath.
- At least one additional metal and/or chloride is added to the electrolyte.
- the metals are in the form of their soluble salts.
- the addition of zinc and/or bismuth has a considerable effect on the properties of the deposited coatings.
- the metals zinc and/or bismuth added to the electrolyte can namely be in the form of salts of alkylsulfonic acids, preferably as methanesulfonates or as salts of mineral acids, preferably as sulfates.
- Zinc sulfate is especially preferably uses in the electrolytes as zinc salt, and is advantageously added in an amount of 0-25 g/L of electrolyte, preferably 15-20 g/L of electrolyte.
- Bismuth methane sulfate is especially preferably used in the electrolyte as bismuth salt and is advantageously added to the electrolyte in an amount of 0-5 g/L of electrolyte, preferably 0.05-0.2 g/L of electrolyte.
- additives for example stabilizers and/or complexing agents, oxidation inhibitors and brighteners, that are usually used in acid electrolytes for deposition of tin alloys can be added to the electrolyte.
- Gluconates are advantageously added to the electrolyte and stabilizers and/or complexing agents.
- the concentration of the stabilizers and/or complexing agents is 0-50 g/L of electrolyte, preferably 20-30 g/L of electrolyte.
- Compounds from the class of the dihydroxybenzenes, for example mono- or polyhydroxyphenyl compounds like pyrocatechol or phenolsulfonic acid are preferably used as oxidation inhibitors.
- the concentration of oxidation inhibitors is 0-5 g/L of electrolyte.
- the electrolyte contains hydroquinone as oxidation inhibitor.
- the conduct of the method in accordance with the invention enables the deposition of bronzes onto various substrates.
- all of the usual methods for making electronic components can be used.
- especially hard and wear-resistant bronze coatings can be deposited on materials like bearings, etc., to the method in accordance with the invention.
- the method in accordance with the invention is advantageously also used in the fields of decorative coating of, for example, fixtures and jewelry, etc., where the deposition of multi-component alloys that contain tin, copper, zinc and bismuth is particularly advantageous in these areas.
- a really special advantage is that the so-called “true” bronzes that have a copper content >60% can be deposited with the method in accordance with the invention, where the copper content can be up to 95 wt % in each according to the desired properties.
- the ratio of the amount of copper to the amount of tin in the electrolyte has a considerable effect of properties like hardness and color of the bronze coatings. For instance, at a tin/copper ratio of 40/60 silver-colored coatings, the so-called white bronzes, which are relatively soft, are deposited. At a tin/copper ratio of 20/80 yellow gold colored coatings result, the so-called yellow bronzes, and at a tin/copper ratio of 10/90 red gold colored coatings are formed, the so-called red bronzes.
- the electrolyte contains brighteners from the class of the aromatic carbonyl compounds and/or á,â-unsaturated carbonyl compounds.
- the concentration of brighteners is 0-5 g/L of electrolyte.
- the base electrolyte of the highly acid electrolyte in accordance with the invention contains essentially (per liter of electrolyte)
- electrolyte per liter of electrolyte
- the electrolyte is prepared by varying the individual components, as given below as a matter of example. Additional information about the corresponding process conditions as well as other properties of the individual coatings can be seen in Table 1.
- Coating/Amounts Example in wt % Properties of coating No. Sn Cu Zn Bi Hardness Ductility Gloss Color 1 10 90 — — 180 HV 50 ++ Yes Red 2a 20 80 — — 283 Hv 50 ⁇ Yes Yellow 2b 20 80 — — 317 HV 50 ⁇ Yes Yellow 3 40 60 — — 360 HV 50 ⁇ Yes White 4 90 10 — — — ⁇ No White 5 20 80 ⁇ 1 — — +++ Yes Yellow 6 20 80 — ⁇ 1 345 HV 50 ⁇ Yes Yellow 7 20 80 ⁇ 1 — — ++ Yes Yellow
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Chemically Coating (AREA)
- Electroplating Methods And Accessories (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP02022718.7A EP1408141B1 (fr) | 2002-10-11 | 2002-10-11 | Methode et électrolyte pour la deposition galvanique des bronzes |
| EP020227187 | 2002-10-11 | ||
| PCT/EP2003/011229 WO2004035875A2 (fr) | 2002-10-11 | 2003-10-10 | Procede de depot galvanique de bronzes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US20060137991A1 true US20060137991A1 (en) | 2006-06-29 |
Family
ID=32010957
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US10/531,142 Abandoned US20060137991A1 (en) | 2002-10-11 | 2003-10-10 | Method for bronze galvanic coating |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20060137991A1 (fr) |
| EP (1) | EP1408141B1 (fr) |
| JP (1) | JP4675626B2 (fr) |
| KR (1) | KR100684818B1 (fr) |
| CN (1) | CN1703540B (fr) |
| ES (1) | ES2531163T3 (fr) |
| WO (1) | WO2004035875A2 (fr) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050263403A1 (en) * | 2002-10-11 | 2005-12-01 | Enthone Inc. | Method for electrodeposition of bronzes |
| EP2071057A2 (fr) | 2007-12-12 | 2009-06-17 | Rohm and Haas Electronic Materials LLC | Bronze d'électrodéposition |
| US20090205714A1 (en) * | 2006-05-24 | 2009-08-20 | Kuehnlein Holger | Metal Plating Composition and Method for the Deposition of Copper-Zinc-Tin Suitable for Manufacturing Thin Film Solar Cell |
| US20110089043A1 (en) * | 2008-05-08 | 2011-04-21 | Umicore Galvanotechnik Gmbh | Modified copper-tin electrolyte and process for the deposition of bronze layers |
| US20110174631A1 (en) * | 2008-07-10 | 2011-07-21 | Umicore Galvanotechnik Gmbh | Copper-tin electrolyte and process for the deposition of bronze layers |
| US8426241B2 (en) | 2010-09-09 | 2013-04-23 | International Business Machines Corporation | Structure and method of fabricating a CZTS photovoltaic device by electrodeposition |
| US9145617B2 (en) | 2011-08-30 | 2015-09-29 | Rohm And Haas Electronic Materials Llc | Adhesion promotion of cyanide-free white bronze |
| US20200071140A1 (en) * | 2018-09-05 | 2020-03-05 | Vis, Llc | Power unit for a floor jack |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102004041701A1 (de) * | 2004-08-28 | 2006-03-02 | Enthone Inc., West Haven | Verfahren zur elektrolytischen Abscheidung von Metallen |
| WO2006036479A1 (fr) * | 2004-09-24 | 2006-04-06 | Jarden Zinc Products, Inc. | Metaux deposes par electrodeposition presentant un aspect blanc argente et procede de production |
| US7296370B2 (en) * | 2004-09-24 | 2007-11-20 | Jarden Zinc Products, Inc. | Electroplated metals with silvery-white appearance and method of making |
| CN100368924C (zh) * | 2005-05-31 | 2008-02-13 | 西北工业大学 | 一种非周期性红外波段负磁导率材料 |
| ES2698205T5 (en) | 2005-11-25 | 2025-02-27 | Macdermid Enthone Inc | Process for cleaning of processing solutions |
| ATE453740T1 (de) | 2007-02-14 | 2010-01-15 | Umicore Galvanotechnik Gmbh | Kupfer-zinn-elektrolyt und verfahren zur abscheidung von bronzeschichten |
| DE102011008836B4 (de) * | 2010-08-17 | 2013-01-10 | Umicore Galvanotechnik Gmbh | Elektrolyt und Verfahren zur Abscheidung von Kupfer-Zinn-Legierungsschichten |
| CN102605394B (zh) * | 2012-03-07 | 2015-02-18 | 深圳市华傲创表面技术有限公司 | 一种无氰酸性白铜锡电镀液 |
| JP6101510B2 (ja) * | 2013-02-18 | 2017-03-22 | 株式会社シミズ | 非シアン銅−錫合金めっき浴 |
| CA2957587C (fr) * | 2014-08-08 | 2019-03-05 | Okuno Chemical Industries Co., Ltd. | Bain de placage d'alliage de cuivre-etain |
| US11597637B2 (en) | 2018-02-22 | 2023-03-07 | Vis, Llc | Under hoist support stand |
| EP3540097A1 (fr) | 2018-03-13 | 2019-09-18 | COVENTYA S.p.A. | Produits galvanisés et bain électrolytique approprié pour fournir de tels produits |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2854388A (en) * | 1955-03-14 | 1958-09-30 | City Auto Stamping Co | Electrodeposition of copper-tin alloys |
| US4565608A (en) * | 1983-11-02 | 1986-01-21 | Degussa Aktiengesellschaft | Alkaline cyanide bath for electrolytic deposition of copper-tin-alloy coatings |
| US5176957A (en) * | 1989-12-05 | 1993-01-05 | Sumitomo Rubber Industries, Ltd. | Bead wire for tire, rubber-coated bead wire for tire and tire using the same |
| US5385661A (en) * | 1993-09-17 | 1995-01-31 | International Business Machines Corporation | Acid electrolyte solution and process for the electrodeposition of copper-rich alloys exploiting the phenomenon of underpotential deposition |
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- 2003-10-10 CN CN2003801012538A patent/CN1703540B/zh not_active Expired - Lifetime
- 2003-10-10 US US10/531,142 patent/US20060137991A1/en not_active Abandoned
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050263403A1 (en) * | 2002-10-11 | 2005-12-01 | Enthone Inc. | Method for electrodeposition of bronzes |
| US20060260948A2 (en) * | 2005-04-14 | 2006-11-23 | Enthone Inc. | Method for electrodeposition of bronzes |
| US9263609B2 (en) | 2006-05-24 | 2016-02-16 | Atotech Deutschland Gmbh | Metal plating composition and method for the deposition of copper—zinc—tin suitable for manufacturing thin film solar cell |
| US20090205714A1 (en) * | 2006-05-24 | 2009-08-20 | Kuehnlein Holger | Metal Plating Composition and Method for the Deposition of Copper-Zinc-Tin Suitable for Manufacturing Thin Film Solar Cell |
| EP2071057A2 (fr) | 2007-12-12 | 2009-06-17 | Rohm and Haas Electronic Materials LLC | Bronze d'électrodéposition |
| US20110089043A1 (en) * | 2008-05-08 | 2011-04-21 | Umicore Galvanotechnik Gmbh | Modified copper-tin electrolyte and process for the deposition of bronze layers |
| US20110174631A1 (en) * | 2008-07-10 | 2011-07-21 | Umicore Galvanotechnik Gmbh | Copper-tin electrolyte and process for the deposition of bronze layers |
| US8426241B2 (en) | 2010-09-09 | 2013-04-23 | International Business Machines Corporation | Structure and method of fabricating a CZTS photovoltaic device by electrodeposition |
| US9041141B2 (en) | 2010-09-09 | 2015-05-26 | International Business Machines Corporation | Structure and method of fabricating a CZTS photovoltaic device by electrodeposition |
| US8790956B2 (en) | 2010-09-09 | 2014-07-29 | International Business Machines Corporation | Structure and method of fabricating a CZTS photovoltaic device by electrodeposition |
| US9145617B2 (en) | 2011-08-30 | 2015-09-29 | Rohm And Haas Electronic Materials Llc | Adhesion promotion of cyanide-free white bronze |
| US20200071140A1 (en) * | 2018-09-05 | 2020-03-05 | Vis, Llc | Power unit for a floor jack |
| WO2020050961A1 (fr) * | 2018-09-05 | 2020-03-12 | Vis, Llc | Unité d'énergie pour un cric rouleur |
| US10906789B2 (en) * | 2018-09-05 | 2021-02-02 | Vis, Llc | Power unit for a floor jack |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005537394A (ja) | 2005-12-08 |
| ES2531163T3 (es) | 2015-03-11 |
| KR100684818B1 (ko) | 2007-02-22 |
| EP1408141B1 (fr) | 2014-12-17 |
| JP4675626B2 (ja) | 2011-04-27 |
| EP1408141A1 (fr) | 2004-04-14 |
| WO2004035875A3 (fr) | 2005-04-14 |
| CN1703540B (zh) | 2010-10-06 |
| WO2004035875A2 (fr) | 2004-04-29 |
| KR20050059174A (ko) | 2005-06-17 |
| CN1703540A (zh) | 2005-11-30 |
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