US3360447A - Bath for electrolytical separation of copper with high-grade mechanical properties - Google Patents
Bath for electrolytical separation of copper with high-grade mechanical properties Download PDFInfo
- Publication number
- US3360447A US3360447A US436332A US43633265A US3360447A US 3360447 A US3360447 A US 3360447A US 436332 A US436332 A US 436332A US 43633265 A US43633265 A US 43633265A US 3360447 A US3360447 A US 3360447A
- Authority
- US
- United States
- Prior art keywords
- copper
- bath
- acid
- weight percent
- mechanical properties
- 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.)
- Expired - Lifetime
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 36
- 229910052802 copper Inorganic materials 0.000 title description 35
- 239000010949 copper Substances 0.000 title description 35
- 238000000926 separation method Methods 0.000 title description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 238000007747 plating Methods 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 108010010803 Gelatin Proteins 0.000 claims description 9
- 229960000583 acetic acid Drugs 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 9
- 239000005018 casein Substances 0.000 claims description 9
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 claims description 9
- 235000021240 caseins Nutrition 0.000 claims description 9
- 229920000159 gelatin Polymers 0.000 claims description 9
- 239000008273 gelatin Substances 0.000 claims description 9
- 235000019322 gelatine Nutrition 0.000 claims description 9
- 235000011852 gelatine desserts Nutrition 0.000 claims description 9
- 239000012362 glacial acetic acid Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- 239000011260 aqueous acid Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- 238000003466 welding Methods 0.000 description 5
- 238000009713 electroplating Methods 0.000 description 4
- 238000003754 machining Methods 0.000 description 4
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical group [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010892 electric spark Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 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
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions 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
- C25D1/00—Electroforming
Definitions
- Metallic copper of a high hardness is required in such varied uses as the production of galvanoplastic molds for pressure die casting and mold pressing of plastic materials, in the welding technology for producing electrodes for spot and seam welding, in electroerosive machining, and the like.
- welding techniques and technology also require hard electrodes with a high electrical conductivity.
- the use of pure electrolytic copper with a high electrical conducductivity is not convenient because of its low mechanical properties. Therefore, copper alloys containing tungsten, chromium, beryllium and alloying materials are used which raises the hardness up to about 200 H but as a consequence, the electrical conductivity is reduced.
- the increased resistance leads to a rather high local heating of the electrodes and this effect further reduces electrode life.
- the life of commutators, collectors, and other parts of electrical rotatingfield machines is limited by the low mechanical properties of the copper metal.
- Electrolytic copper of high hardness is also required in electric spark machining because the electrodes employed including those of the most complicated shapes can be produced by galvanoplastic methods. Again electrolytically separated copper does not give the required mechanical properties for this machining process, and is particularly deficient as respects hardness.
- Another more specific object of the invention is to obtain copper with very good mechanical properties, particularly with a high hardness from an electrolytic process.
- Still another object of the invention is to obtain copper for electroplating processes which has the necessary hardness together with the necessary electrical conductivity.
- the invention provides an addition agent for an acid copper-plating bath with a pH-value 0.4 to 1.5 causing separation of copper with high mechanical properties, particularly high hardness and resistance to abrasive wear.
- the novel addition agent is a combination of ingredients in critical amounts.
- the components are 40 to 60 percent by weight of absolute ethyl alcohol, 30 to 40 percent by weight of glacial acetic acid, 0.2 to 0.4 percent ICC by weight of gelatin, 0.5 to 0.7 percent by weight of casein, and from 10 to 20 percent by weight of concentrated sulfuric acid.
- the mixture of components which comprises the addition agent is added to an acid copper-plating bath at the ratio of 1,00021 to 25:1 relative to the volume of the bath.
- the addition of the additive agent is done in the customary way and gives no unusual problems.
- the copper which is separated out in the bath has a hardness of up to 250 H and higher and also possesses a high resistance to abrasive wear. Its structure is believed to be essentially microcrystalline, the surface is smooth, and its electrical conductivity is about equivalent to that of standard electrolytic copper. It can be easily machined by standard methods.
- the plating bath prepared in'accordance with the process of the invention may be conveniently used in the production of galvanoplastic molds. Such molds produced by the improved process preserve the general advantages of the galvanoplastic production and in addition, exhibit much longer life.
- the improved electroplating bath may also be used in the production of tools for electroerosive machining. Tools produced in this manner have a very long life and also show high electrical conductivity. The use of the bath also permits the production of hard copper coatings which are resistant to abrasive wear.
- Electrolytic copper with high hardness properties as obtained from the bath comprising the novel addition agent can be readily used for producing welding electrodes for spot and seam welding. Electrodes produced from this hard copper possess properties which are better than the properties of known copper alloy electrodes of highest quality and their electrical conductivity is also much higher.
- the improved properties result in economy in electrical energy as well as in increased electrode life.
- Typical uses include commutators, collectors, components of switches, and the like.
- the life of a commutator using standard copper was tested to be 2,000 hours.
- the same commutator with active surfaces provided with a layer of hard copper obtained in accordance with the invention had a life of at least 20,000 hours when tested under the same conditions.
- Example 1 To each liter of a standard typical acid copper-plating bat-h comprising 220 g./l. of cupric sulphate (CuSO and having a pH-value of 0.4 to 1.5, are added 20 ml. of the premixed addition agent made up to the following composition:
- the hardness of the separated copper is 2001-4 H If the amount of addition agent described above is increased to the ratio 25 :1, the hardness of the separated copper rises proportionally to a value H 250 and higher.
- Example 2 To each liter of an acid copper-plating bath are added 40 ml. of the addition agent of the following composition:
- Example 3 To each liter of an acid copper electrolytic bath are added 5 ml. of an addition agent of the following composition:
- the obtained hardness of the separated copper is very closely related to the amount of the addition agent in the bath. This permits, if desired, the construction of a graph for reading, for example, the appropriate amount of the addition agent to be used in accordance with the invention to obtain a desired product result.
- An improved aqueous acid copper-plating bath having present therein a soluble copper salt and at least 1 part by volume per 1000 parts of acid bath of an additive material consisting essentially of 40 to 60 weight percent of absolute ethyl alcohol, 30 to 40 weight percent of glacial acetic acid, 0.2 to 0.4 weight percent of gelatin, 0.5 to 0.7 weight percent of casein, and 10 to 20 weight percent of concentrated sulfuric acid.
- an additive material consisting essentially of 40 to 60 weight percent of absolute ethyl alcohol, 30 to 40 weight percent of glacial acetic acid, 0.2 to 0.4 weight percent of gelatin, 0.5 to 0.7 weight percent of casein, and 10 to 20 weight percent of concentrated sulfuric acid.
- An improved aqueous acid copper-plating bath as described in claim 1 which contains per liter of acid copper plating bath, about 20 ml. of said additive material consisting essentially of 1000 ml. of absolute ethyl alcohol, 5 g. of gelatin, 10 g. casein, 200 to 300 m1. of concentrated sulfuric acid and 500 ml. of glacial acetic acid.
- An improved aqueous acid copper plating bath as described in claim 1 which contains per liter of acid copper plating bath, about 40 ml. of said additive material consisting essentially Of 1300 ml. of absolute ethyl alcohol, 6 g. of gelatin, 14 g. of casein, 250 ml. of concentrated sulfuric acid and 600 ml. of glacial acetic acid.
- An improved aqueous acid copper plating bath as described in claim 1 which contains per liter of acid copper plating bath, about 5 ml. of said additive material consisting essentially of absolute ethyl alcohol, 8 g. of gelatin, 12 g. of casein, 300 ml. of concentrated sulfuric acid, and 500 ml. of glacial acetic acid.
- An additive for an acid electroplating bath consisting essentially of 40 to weight percent of absolute ethyl alcohol, 30 to 40 weight percent of glacial acetic acid, 0.2 to 0.4 weight percent of gelatin, 0.5 to 0.7 weight percent of casein and 10 to 20 weight percent of concentrated sulfuric acid.
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)
- Motor Or Generator Current Collectors (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CS139164 | 1964-03-11 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3360447A true US3360447A (en) | 1967-12-26 |
Family
ID=5348157
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US436332A Expired - Lifetime US3360447A (en) | 1964-03-11 | 1965-03-01 | Bath for electrolytical separation of copper with high-grade mechanical properties |
Country Status (9)
Country | Link |
---|---|
US (1) | US3360447A (fr) |
AT (1) | AT271128B (fr) |
BE (1) | BE660618A (fr) |
CH (1) | CH464638A (fr) |
DE (1) | DE1236298B (fr) |
FR (1) | FR1426629A (fr) |
GB (1) | GB1064769A (fr) |
NL (1) | NL6503040A (fr) |
SE (1) | SE305348B (fr) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5266212A (en) * | 1992-10-13 | 1993-11-30 | Enthone-Omi, Inc. | Purification of cyanide-free copper plating baths |
CN102418117A (zh) * | 2011-11-29 | 2012-04-18 | 宁波蓝鼎电子科技有限公司 | 一种阴极铜火法炼铜电解精炼的方法 |
CN112144083A (zh) * | 2020-09-22 | 2020-12-29 | 广州三孚新材料科技股份有限公司 | 一种太阳能电池用无氰镀铜电镀液及制备方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2271209A (en) * | 1934-06-05 | 1942-01-27 | United States Steel Corp | Electrodeposited tin and process of electrodeposition |
US2680711A (en) * | 1950-03-10 | 1954-06-08 | Norwitz George | Deposition of copper by immersion |
US2733198A (en) * | 1956-01-31 | Acid copper plating bath | ||
US2888390A (en) * | 1956-11-08 | 1959-05-26 | Anaconda Co | Electrolytic refining of copper |
-
1965
- 1965-02-22 GB GB7514/65A patent/GB1064769A/en not_active Expired
- 1965-03-01 US US436332A patent/US3360447A/en not_active Expired - Lifetime
- 1965-03-01 DE DES95720A patent/DE1236298B/de active Pending
- 1965-03-04 BE BE660618D patent/BE660618A/xx unknown
- 1965-03-09 CH CH323465A patent/CH464638A/de unknown
- 1965-03-10 NL NL6503040A patent/NL6503040A/xx unknown
- 1965-03-10 AT AT214365A patent/AT271128B/de active
- 1965-03-11 FR FR8828A patent/FR1426629A/fr not_active Expired
- 1965-03-11 SE SE3154/65A patent/SE305348B/xx unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2733198A (en) * | 1956-01-31 | Acid copper plating bath | ||
US2271209A (en) * | 1934-06-05 | 1942-01-27 | United States Steel Corp | Electrodeposited tin and process of electrodeposition |
US2680711A (en) * | 1950-03-10 | 1954-06-08 | Norwitz George | Deposition of copper by immersion |
US2888390A (en) * | 1956-11-08 | 1959-05-26 | Anaconda Co | Electrolytic refining of copper |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5266212A (en) * | 1992-10-13 | 1993-11-30 | Enthone-Omi, Inc. | Purification of cyanide-free copper plating baths |
CN102418117A (zh) * | 2011-11-29 | 2012-04-18 | 宁波蓝鼎电子科技有限公司 | 一种阴极铜火法炼铜电解精炼的方法 |
CN102418117B (zh) * | 2011-11-29 | 2014-04-16 | 宁波蓝鼎电子科技有限公司 | 一种阴极铜火法炼铜电解精炼的方法 |
CN112144083A (zh) * | 2020-09-22 | 2020-12-29 | 广州三孚新材料科技股份有限公司 | 一种太阳能电池用无氰镀铜电镀液及制备方法 |
Also Published As
Publication number | Publication date |
---|---|
AT271128B (de) | 1969-05-27 |
BE660618A (fr) | 1965-07-01 |
CH464638A (de) | 1968-10-31 |
FR1426629A (fr) | 1966-01-28 |
GB1064769A (en) | 1967-04-12 |
DE1236298B (de) | 1967-03-09 |
SE305348B (fr) | 1968-10-21 |
NL6503040A (fr) | 1965-09-13 |
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