US3440151A - Electrodeposition of copper-tin alloys - Google Patents
Electrodeposition of copper-tin alloys Download PDFInfo
- Publication number
- US3440151A US3440151A US460852A US3440151DA US3440151A US 3440151 A US3440151 A US 3440151A US 460852 A US460852 A US 460852A US 3440151D A US3440151D A US 3440151DA US 3440151 A US3440151 A US 3440151A
- Authority
- US
- United States
- Prior art keywords
- bath
- copper
- tin
- alkali
- cyanide
- 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
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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
Definitions
- This invention relates to an improved process .of electroplating copper-tin alloys, i.e. bronzes and to electrolytic compositions for plating such alloys.
- aqueous electrolytic bath composition containing tin and copper in which the tendency for tin to sludge out is nullified.
- This invention is based on the discovery that the tendency of tin to sludge out of a copper-tin bath can be prevented by incorporating considerable quantities of the salts of acetic acid substituted aliphatic amines, such as the salts of ethylenediaminetetracetic acid (EDTA) and diethylenetriaminepentaacetate, into the plating bath.
- EDTA ethylenediaminetetracetic acid
- the addition of small quantities of EDTA and similar compounds in acid-tin baths has been described to function as a brightener, and such addition has also been disclosed for extending the bright range of brass solutions but the discovery of the effectiveness of relatively large quantities of this material as a sludge inhibitor was totally unexpected.
- aqueous electrolytic bath composition for plating bright bronze in which the tendency for tin to sludgeout is nullified.
- This the bath of the invention comprises the following ingredients:
- Copper cyanide (g./l.) Alkali Stannate (g./l.) Alkali cyanide (g./l.) Alkali hydroxide (g./l.) Agali aminoaeetates (g p
- the copper cyanide is at least partially present in said bath as the double cyanide of copper and alkali and the copper may be added in the form of said double cyanide.
- Potassium and sodium are the usual alkalis re ferred in the table but ammonium and lithium compounds can also be employed.
- alkali amino acetates will be understood to include the ammonium compounds, and to include such amines carrying acetate groups having a pK value between about 12 and 22.
- the acid amino acetates (instead of salts) can be added and the tin can be added as the stannic oxide provided the additional alkali hydroxide necessary to form the corresponding salts is taken into account to provide the required pH.
- the deposits obtained from this bath are smooth, but not fully bright.
- the bath is operated above room temperature (approx. 110-160 F.) preferably at a current density of 1 to 10 amp/dm.
- the pH is higher than 12.5 as stated above.
- Example 1 A bath is made of the following components:
- Example 2 The process was conducted as in Example 1 except that 0.1 g./l. of lead as lead acetate was added to the bath. The panels obtained were fully bright. The bath has the same stability as that of Example 1.
- Copper cyanide -70 Alkali metal stannate -90 Alkali cyanide -1 60-120 Alkali hydroxide (to pH l2.5) 10-80 Alkali metal alkylene aminoacetates selected from the group consisting of alkali metal alkylene diamino tetra acetate and alkali metal alkylene triamino penta acetate 25-200 3.
- An aqueous electrolytic bath for co-electrodepositing copper and tin containing the following ingredients:
- Alkali metal alkylene aminoacetates selected from the group consisting of alkali metal alkylene diamino tetra acetate and alkali metal alkylene triamino penta acetate 725-200 5.
- An aqueous electrolytic bath according to claim 4 containing in addition a lead compound in the amount of about 0.05 to 0.75 g./l. calculated as lead.
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)
Description
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US46085265A | 1965-06-02 | 1965-06-02 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3440151A true US3440151A (en) | 1969-04-22 |
Family
ID=23830322
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US460852A Expired - Lifetime US3440151A (en) | 1965-06-02 | 1965-06-02 | Electrodeposition of copper-tin alloys |
Country Status (1)
Country | Link |
---|---|
US (1) | US3440151A (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3769181A (en) * | 1971-07-21 | 1973-10-30 | Richardson Chemical Co | Method of simultaneously electroplating and machining a metal surface |
FR2244832A1 (en) * | 1973-09-25 | 1975-04-18 | Richardson Chemical Co | Electroplating and machining process - using tool as anode |
US4223826A (en) * | 1979-01-29 | 1980-09-23 | Usui Kokusai Sangyo Kabushiki Kaisha | Method of brazing stainless steels |
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 |
US4565608A (en) * | 1983-11-02 | 1986-01-21 | Degussa Aktiengesellschaft | Alkaline cyanide bath for electrolytic deposition of copper-tin-alloy coatings |
FR2688234A1 (en) * | 1992-03-03 | 1993-09-10 | Sarrel | Process for protecting a silver or silver-coated article |
WO1997021852A1 (en) * | 1995-12-09 | 1997-06-19 | Metallveredlung Gmbh & Co. Kg | Method of forming an alloy layer |
US20100323115A1 (en) * | 2005-12-05 | 2010-12-23 | Rohm And Haas Electronic Materials Llc | Metallization of dielectrics |
CN108138346A (en) * | 2015-09-30 | 2018-06-08 | 科文特亚股份公司 | The purposes of the electrochemical deposition method of electroplating bath, the alloy for electrochemical deposition Cu-Sn-Zn-Pd alloys, the base material comprising the alloy and base material |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2436316A (en) * | 1946-04-25 | 1948-02-17 | Westinghouse Electric Corp | Bright alloy plating |
US2658032A (en) * | 1949-06-11 | 1953-11-03 | City Auto Stamping Co | Electrodeposition of bright copper-tin alloy |
US2854388A (en) * | 1955-03-14 | 1958-09-30 | City Auto Stamping Co | Electrodeposition of copper-tin alloys |
US2886500A (en) * | 1956-11-01 | 1959-05-12 | Battelle Development Corp | Electroplating of copper alloys |
US2989448A (en) * | 1959-04-08 | 1961-06-20 | Daniel R France | Brass, copper-tin, and copper plating bath brightener |
CA655356A (en) * | 1963-01-08 | Flack Arnold | Electrodeposition of metals having two valences and alloys thereof | |
US3108006A (en) * | 1959-07-13 | 1963-10-22 | M & T Chemicals Inc | Plating on aluminum |
US3120550A (en) * | 1960-05-27 | 1964-02-04 | Dow Chemical Co | Organo-tin and lead chelates |
US3152155A (en) * | 1960-01-04 | 1964-10-06 | Dow Chemical Co | Insoluble chelates of divalent tin, germanium, and lead |
-
1965
- 1965-06-02 US US460852A patent/US3440151A/en not_active Expired - Lifetime
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA655356A (en) * | 1963-01-08 | Flack Arnold | Electrodeposition of metals having two valences and alloys thereof | |
US2436316A (en) * | 1946-04-25 | 1948-02-17 | Westinghouse Electric Corp | Bright alloy plating |
US2658032A (en) * | 1949-06-11 | 1953-11-03 | City Auto Stamping Co | Electrodeposition of bright copper-tin alloy |
US2854388A (en) * | 1955-03-14 | 1958-09-30 | City Auto Stamping Co | Electrodeposition of copper-tin alloys |
US2886500A (en) * | 1956-11-01 | 1959-05-12 | Battelle Development Corp | Electroplating of copper alloys |
US2989448A (en) * | 1959-04-08 | 1961-06-20 | Daniel R France | Brass, copper-tin, and copper plating bath brightener |
US3108006A (en) * | 1959-07-13 | 1963-10-22 | M & T Chemicals Inc | Plating on aluminum |
US3152155A (en) * | 1960-01-04 | 1964-10-06 | Dow Chemical Co | Insoluble chelates of divalent tin, germanium, and lead |
US3120550A (en) * | 1960-05-27 | 1964-02-04 | Dow Chemical Co | Organo-tin and lead chelates |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3769181A (en) * | 1971-07-21 | 1973-10-30 | Richardson Chemical Co | Method of simultaneously electroplating and machining a metal surface |
FR2244832A1 (en) * | 1973-09-25 | 1975-04-18 | Richardson Chemical Co | Electroplating and machining process - using tool as anode |
US4223826A (en) * | 1979-01-29 | 1980-09-23 | Usui Kokusai Sangyo Kabushiki Kaisha | Method of brazing stainless steels |
US4565608A (en) * | 1983-11-02 | 1986-01-21 | Degussa Aktiengesellschaft | Alkaline cyanide bath for electrolytic deposition of copper-tin-alloy coatings |
US4605474A (en) * | 1983-11-02 | 1986-08-12 | Gerd Hoffacker | Alkaline cyanide bath for electrolytic deposition of copper-tin-alloy coatings |
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 |
FR2688234A1 (en) * | 1992-03-03 | 1993-09-10 | Sarrel | Process for protecting a silver or silver-coated article |
WO1997021852A1 (en) * | 1995-12-09 | 1997-06-19 | Metallveredlung Gmbh & Co. Kg | Method of forming an alloy layer |
US20100323115A1 (en) * | 2005-12-05 | 2010-12-23 | Rohm And Haas Electronic Materials Llc | Metallization of dielectrics |
CN108138346A (en) * | 2015-09-30 | 2018-06-08 | 科文特亚股份公司 | The purposes of the electrochemical deposition method of electroplating bath, the alloy for electrochemical deposition Cu-Sn-Zn-Pd alloys, the base material comprising the alloy and base material |
EP3150744B1 (en) | 2015-09-30 | 2020-02-12 | COVENTYA S.p.A. | Electroplating bath for electrochemical deposition of a cu-sn-zn-pd alloy layer, method for electrochemical deposition of said alloy layer, substrate comprising said alloy layer and uses of the coated substrate |
CN108138346B (en) * | 2015-09-30 | 2021-03-05 | 科文特亚股份公司 | Electroplating bath for the electrochemical deposition of a Cu-Sn-Zn-Pd alloy, method for the electrochemical deposition of said alloy, substrate comprising said alloy and use of the substrate |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: OXY METAL INDUSTRIES CORPORATION Free format text: CHANGE OF NAME;ASSIGNOR:OXY METAL FINISHING CORPORATION;REEL/FRAME:003967/0084 Effective date: 19741220 |
|
AS | Assignment |
Owner name: HOOKER CHEMICALS & PLASTICS CORP. Free format text: MERGER;ASSIGNOR:OXY METAL INDUSTRIES CORPORATION;REEL/FRAME:004075/0885 Effective date: 19801222 |
|
AS | Assignment |
Owner name: OCCIDENTAL CHEMICAL CORPORATION Free format text: CHANGE OF NAME;ASSIGNOR:HOOKER CHEMICAS & PLASTICS CORP.;REEL/FRAME:004126/0054 Effective date: 19820330 |
|
AS | Assignment |
Owner name: OMI INTERNATIONAL CORPORATION, 21441 HOOVER ROAD, Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:OCCIDENTAL CHEMICAL CORPORATION;REEL/FRAME:004190/0827 Effective date: 19830915 |
|
AS | Assignment |
Owner name: MANUFACTURERS HANOVER TRUST COMPANY, A CORP OF NY Free format text: SECURITY INTEREST;ASSIGNOR:INTERNATIONAL CORPORATION, A CORP OF DE;REEL/FRAME:004201/0733 Effective date: 19830930 |