US20040104123A1 - Alkaline zinc-nickel bath - Google Patents
Alkaline zinc-nickel bath Download PDFInfo
- Publication number
- US20040104123A1 US20040104123A1 US10/618,352 US61835203A US2004104123A1 US 20040104123 A1 US20040104123 A1 US 20040104123A1 US 61835203 A US61835203 A US 61835203A US 2004104123 A1 US2004104123 A1 US 2004104123A1
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- US
- United States
- Prior art keywords
- nickel
- anode
- bath
- electroplating bath
- zinc
- 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.)
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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
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/02—Tanks; Installations therefor
-
- 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
- C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
Definitions
- the invention relates to an electroplating bath for plating zinc-nickel coatings, having an anode, a cathode and an alkaline electrolyte.
- the alkaline zinc-nickel electroplating baths which are disclosed in German patent 37 12 511 have recently been used, having, for example, the following composition: 11.3 g/l ZnO 4.1 g/l NiSO 4 * 6H 2 O 120 g/l NaOH 5.1 g/l polyethyleneimine.
- the amines contained in the electroplating bath serve as complex formers for the nickel ions, which are otherwise insoluble in the alkaline medium.
- the composition of the baths varies depending on the manufacturer.
- the electroplating baths are usually operated with insoluble nickel anodes.
- the zinc concentration is kept constant by the addition of zinc and the nickel concentration is kept constant by the addition of a nickel solution, for example a nickel sulfate solution.
- the formation of the second phase is attributable to a reaction of the amines, which in alkaline solution are converted at the nickel anodes to form nitrites (including to form cyanide). Moreover, on account of the amines being broken down, fresh complex former has to be continuously added to the bath, which increases the costs of the process.
- Anodes other than nickel anodes cannot be used, since they dissolve in the alkaline electrolyte, which also has adverse effects on the quality of the coating.
- the invention is based on the problem of providing an alkaline zinc-nickel electroplating bath which provides high-quality zinc-nickel coatings at low cost.
- the invention proposes separating the anode from the alkaline electrolyte by an ion exchange membrane.
- This separation prevents the amines from reacting at the nickel anode, with the result that there are no undesirable secondary reactions which cause waste disposal problems or lead to a second phase of reaction products being deposited on the bath and adversely affect the quality of the zinc-nickel coating.
- the invention obviates the need for this layer to be skimmed off at high cost and to renew the bath. Furthermore, there is a considerable improvement in the quality of the coating.
- the zinc-nickel bath functions as catholyte.
- the anolyte used may, for example, be sulfuric acid or phosphoric acid.
- customary anodes such as for example platinum-coated titanium anodes, are suitable as anode material, since they are no longer exposed to the basic zinc-nickel bath.
- FIG. 1 shows the diagrammatic structure of an electroplating bath according to the invention.
- FIG. 1 shows an electroplating cell 1 which has an anode 2 and a cathode 3 , which is the workpiece to be coated.
- the catholyte 4 surrounding the anode is alkaline and consists of a zinc-nickel electroplating bath of known composition, in which amines are added as complex formers for the nickel ions.
- the anolyte 5 surrounding the anode 2 may, for example, consist of sulfuric acid or phosphoric acid.
- Anolyte 5 and catholyte 4 are separated from one another by a perfluorinated cation exchange membrane 6 .
- This membrane 6 allows unimpeded flux of current through the bath but prevents the catholyte 4 , in particular the amines contained therein, from coming into contact with the anode 2 , thus preventing the reactions which were extensively described in the introduction to the description, including the adverse effects of these reactions.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Automation & Control Theory (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Electrolytic Production Of Metals (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The anode is separated from the alkaline electrode to avoid undesirable secondary reactions in an alkali zinc nickel electroplating bath.
Description
- The invention relates to an electroplating bath for plating zinc-nickel coatings, having an anode, a cathode and an alkaline electrolyte.
- It is known to coat electrically conductive materials with zinc-nickel alloys in order to improve their resistance to corrosion. To do this, it is customary to use an acidic electrolyte bath, for example with a sulfate, chloride, fluoropromate [sic] or sulfamate electrolyte. In these processes, it is very difficult and, in practice, generally impossible, in terms of control technology, to achieve a uniform thickness of the zinc-nickel coating on the material to be coated.
- For this reason, the alkaline zinc-nickel electroplating baths which are disclosed in German patent 37 12 511 have recently been used, having, for example, the following composition:
11.3 g/l ZnO 4.1 g/l NiSO4 * 6H2O 120 g/l NaOH 5.1 g/l polyethyleneimine. - The amines contained in the electroplating bath serve as complex formers for the nickel ions, which are otherwise insoluble in the alkaline medium. The composition of the baths varies depending on the manufacturer.
- The electroplating baths are usually operated with insoluble nickel anodes. The zinc concentration is kept constant by the addition of zinc and the nickel concentration is kept constant by the addition of a nickel solution, for example a nickel sulfate solution.
- However, after they have been operating for a few hours, the color of these baths changes from what was originally blue-violet to brown. After a few days or weeks, this discoloration becomes more intense and it is possible to detect a separation of the bath into two phases, the upper phase being dark brown. This phase causes considerable disruption to the coating of the workpieces, such as for example nonuniform layer thicknesses or blistering. It is therefore imperative for the bath to be continuously cleaned, i.e. for this layer to be skimmed off continuously. However, this is time-consuming and expensive.
- Furthermore, after a few weeks of operation it is possible to detect cyanide in the baths. Cyanide pollution requires regular cleaning of the bath and special wastewater treatment, which has a considerable effect on the operating costs of the bath. This applies all the more so if the wastewater has a very high concentration of organics and, with a COD value of approx. 15 000 to 20 000 mg/l, makes cyanide detoxification more difficult. It is then only possible to adhere to statutory wastewater parameters (nickel 0.5 ppm and zinc 2 ppm) by the extensive addition of chemicals.
- The formation of the second phase is attributable to a reaction of the amines, which in alkaline solution are converted at the nickel anodes to form nitrites (including to form cyanide). Moreover, on account of the amines being broken down, fresh complex former has to be continuously added to the bath, which increases the costs of the process.
- Anodes other than nickel anodes cannot be used, since they dissolve in the alkaline electrolyte, which also has adverse effects on the quality of the coating.
- In view of this background, the invention is based on the problem of providing an alkaline zinc-nickel electroplating bath which provides high-quality zinc-nickel coatings at low cost.
- To solve this problem, the invention proposes separating the anode from the alkaline electrolyte by an ion exchange membrane.
- This separation prevents the amines from reacting at the nickel anode, with the result that there are no undesirable secondary reactions which cause waste disposal problems or lead to a second phase of reaction products being deposited on the bath and adversely affect the quality of the zinc-nickel coating. The invention obviates the need for this layer to be skimmed off at high cost and to renew the bath. Furthermore, there is a considerable improvement in the quality of the coating.
- The use of a cation exchange membrane made from a perfluorinated polymer has proven particularly advantageous, since such membranes have a negligible electrical resistance but a high chemical and mechanical resistance.
- Furthermore, the cyanide poisoning of the wastewater no longer takes place, thus considerably simplifying the entire wastewater treatment. Furthermore, there is no need to top up the complex former in the electrolyte, since it is no longer broken down and its concentration in the bath remains approximately constant. As a result, the cost of the process becomes considerably less expensive.
- In the solution according to the invention, the zinc-nickel bath functions as catholyte. The anolyte used may, for example, be sulfuric acid or phosphoric acid. In the electroplating cell according to the invention, customary anodes, such as for example platinum-coated titanium anodes, are suitable as anode material, since they are no longer exposed to the basic zinc-nickel bath.
- The present invention is explained in more detail with reference to the exemplary embodiment illustrated in the drawing, in which:
- FIG. 1 shows the diagrammatic structure of an electroplating bath according to the invention.
- FIG. 1 shows an electroplating cell1 which has an anode 2 and a cathode 3, which is the workpiece to be coated. The
catholyte 4 surrounding the anode is alkaline and consists of a zinc-nickel electroplating bath of known composition, in which amines are added as complex formers for the nickel ions. The anolyte 5 surrounding the anode 2 may, for example, consist of sulfuric acid or phosphoric acid. Anolyte 5 andcatholyte 4 are separated from one another by a perfluorinated cation exchange membrane 6. This membrane 6 allows unimpeded flux of current through the bath but prevents thecatholyte 4, in particular the amines contained therein, from coming into contact with the anode 2, thus preventing the reactions which were extensively described in the introduction to the description, including the adverse effects of these reactions.
Claims (4)
1. Alkaline electroplating bath for plating zinc-nickel coatings, having an anode (2) and a cathode (3), characterized in that the anode is separated from the alkaline electrolyte by an ion exchange membrane (6).
2. Electroplating bath according to claim 1 , characterized in that the cathode (3) is separated from the alkaline electrolyte (4) by a perfluorinated cation exchange membrane (6).
3. Electroplating bath according to claim 1 or 2, characterized by sulfuric acid, phosphoric acid, methanesulfonic acid, amidosulfonic acid and/or phosphonic acid as anolyte (5).
4. Electroplating bath according to one of claims 1 to 3 , characterized by a platinum-coated titanium anode.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/618,352 US20040104123A1 (en) | 1998-07-30 | 2003-07-11 | Alkaline zinc-nickel bath |
US12/030,750 US7807035B2 (en) | 1998-07-30 | 2008-02-13 | Methods of plating zinc-containing coatings under alkaline conditions |
US12/896,673 US8486235B2 (en) | 1998-07-30 | 2010-10-01 | Alkaline zinc-nickel bath |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19834353A DE19834353C2 (en) | 1998-07-30 | 1998-07-30 | Alkaline zinc-nickel bath |
DE19834353.1 | 1998-07-30 | ||
US09/744,706 US6602394B1 (en) | 1998-07-30 | 1999-07-24 | Alkali zinc nickel bath |
US10/618,352 US20040104123A1 (en) | 1998-07-30 | 2003-07-11 | Alkaline zinc-nickel bath |
Related Parent Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/744,706 Division US6602394B1 (en) | 1998-07-30 | 1999-07-24 | Alkali zinc nickel bath |
PCT/EP1999/005443 Division WO2000006807A2 (en) | 1998-07-30 | 1999-07-29 | Alkali zinc nickel bath |
US09744706 Division | 1999-07-29 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/030,750 Continuation US7807035B2 (en) | 1998-07-30 | 2008-02-13 | Methods of plating zinc-containing coatings under alkaline conditions |
Publications (1)
Publication Number | Publication Date |
---|---|
US20040104123A1 true US20040104123A1 (en) | 2004-06-03 |
Family
ID=7875843
Family Applications (4)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/744,706 Expired - Lifetime US6602394B1 (en) | 1998-07-30 | 1999-07-24 | Alkali zinc nickel bath |
US10/618,352 Abandoned US20040104123A1 (en) | 1998-07-30 | 2003-07-11 | Alkaline zinc-nickel bath |
US12/030,750 Expired - Lifetime US7807035B2 (en) | 1998-07-30 | 2008-02-13 | Methods of plating zinc-containing coatings under alkaline conditions |
US12/896,673 Expired - Fee Related US8486235B2 (en) | 1998-07-30 | 2010-10-01 | Alkaline zinc-nickel bath |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/744,706 Expired - Lifetime US6602394B1 (en) | 1998-07-30 | 1999-07-24 | Alkali zinc nickel bath |
Family Applications After (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/030,750 Expired - Lifetime US7807035B2 (en) | 1998-07-30 | 2008-02-13 | Methods of plating zinc-containing coatings under alkaline conditions |
US12/896,673 Expired - Fee Related US8486235B2 (en) | 1998-07-30 | 2010-10-01 | Alkaline zinc-nickel bath |
Country Status (22)
Country | Link |
---|---|
US (4) | US6602394B1 (en) |
EP (2) | EP1344850B1 (en) |
JP (2) | JP4716568B2 (en) |
KR (1) | KR20010071074A (en) |
CN (1) | CN1311830A (en) |
AT (2) | ATE346180T1 (en) |
AU (1) | AU5415299A (en) |
BG (1) | BG105184A (en) |
BR (1) | BR9912589A (en) |
CA (1) | CA2339144A1 (en) |
CZ (1) | CZ298904B6 (en) |
DE (3) | DE19834353C2 (en) |
EE (1) | EE200100059A (en) |
ES (2) | ES2201759T3 (en) |
HR (1) | HRP20010044B1 (en) |
HU (1) | HUP0103951A3 (en) |
IL (1) | IL141086A0 (en) |
MX (1) | MXPA01000932A (en) |
PL (1) | PL198149B1 (en) |
SK (1) | SK285453B6 (en) |
TR (1) | TR200100232T2 (en) |
WO (1) | WO2000006807A2 (en) |
Cited By (5)
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---|---|---|---|---|
US20060226002A1 (en) * | 2005-04-12 | 2006-10-12 | Enthone Inc. | Insoluble anode |
US20060272951A1 (en) * | 2005-04-27 | 2006-12-07 | Enthone Inc. | Electroplating process and composition |
US9903038B2 (en) | 2015-07-22 | 2018-02-27 | Dipsol Chemicals Co., Ltd. | Zinc alloy plating method |
US10156020B2 (en) | 2015-07-22 | 2018-12-18 | Dipsol Chemicals Co., Ltd. | Zinc alloy plating method |
US10738391B2 (en) | 2015-03-25 | 2020-08-11 | Coventya International Gmbh | Two-chamber electrodialysis cell with anion and cation exchange membrane for use as an anode in alkaline zinc electrolytes and zinc alloy electrolytes for the purpose of deposition of metal in electroplating systems |
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DE19834353C2 (en) * | 1998-07-30 | 2000-08-17 | Hillebrand Walter Gmbh & Co Kg | Alkaline zinc-nickel bath |
US8236159B2 (en) | 1999-04-13 | 2012-08-07 | Applied Materials Inc. | Electrolytic process using cation permeable barrier |
US8852417B2 (en) | 1999-04-13 | 2014-10-07 | Applied Materials, Inc. | Electrolytic process using anion permeable barrier |
US20060157355A1 (en) * | 2000-03-21 | 2006-07-20 | Semitool, Inc. | Electrolytic process using anion permeable barrier |
US20060189129A1 (en) * | 2000-03-21 | 2006-08-24 | Semitool, Inc. | Method for applying metal features onto barrier layers using ion permeable barriers |
DE10026956A1 (en) * | 2000-05-30 | 2001-12-13 | Walter Hillebrand Galvanotechn | Zinc alloy bath |
ES2250166T5 (en) | 2000-06-15 | 2016-05-20 | Coventya Inc | Zinc-Nickel Electroplating |
US6755960B1 (en) | 2000-06-15 | 2004-06-29 | Taskem Inc. | Zinc-nickel electroplating |
US7628898B2 (en) * | 2001-03-12 | 2009-12-08 | Semitool, Inc. | Method and system for idle state operation |
DE10223622B4 (en) * | 2002-05-28 | 2005-12-08 | Walter Hillebrand Gmbh & Co. Kg Galvanotechnik | Alkaline zinc-nickel bath and corresponding electroplating process with increased current efficiency |
US8377283B2 (en) | 2002-11-25 | 2013-02-19 | Coventya, Inc. | Zinc and zinc-alloy electroplating |
DE10261493A1 (en) * | 2002-12-23 | 2004-07-08 | METAKEM Gesellschaft für Schichtchemie der Metalle mbH | Anode for electroplating |
BR0318331A (en) * | 2003-06-03 | 2006-07-11 | Taskem Inc | apparatus for applying a zinc or zinc alloy electrodeposit to a workpiece |
US20050121332A1 (en) * | 2003-10-03 | 2005-06-09 | Kochilla John R. | Apparatus and method for treatment of metal surfaces by inorganic electrophoretic passivation |
US20050133376A1 (en) * | 2003-12-19 | 2005-06-23 | Opaskar Vincent C. | Alkaline zinc-nickel alloy plating compositions, processes and articles therefrom |
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US7442286B2 (en) * | 2004-02-26 | 2008-10-28 | Atotech Deutschland Gmbh | Articles with electroplated zinc-nickel ternary and higher alloys, electroplating baths, processes and systems for electroplating such alloys |
DE102004061255B4 (en) | 2004-12-20 | 2007-10-31 | Atotech Deutschland Gmbh | Process for the continuous operation of acidic or alkaline zinc or zinc alloy baths and apparatus for carrying it out |
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US20070043474A1 (en) * | 2005-08-17 | 2007-02-22 | Semitool, Inc. | Systems and methods for predicting process characteristics of an electrochemical treatment process |
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JP4819612B2 (en) * | 2006-08-07 | 2011-11-24 | ルネサスエレクトロニクス株式会社 | Plating apparatus and method for manufacturing semiconductor device |
DE102007040005A1 (en) | 2007-08-23 | 2009-02-26 | Ewh Industrieanlagen Gmbh & Co. Kg | Depositing functional layers from electroplating bath, circulates zinc-nickel electrolyte between bath and regeneration unit providing ozone- and ultraviolet light treatment |
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JP6750186B1 (en) | 2019-11-28 | 2020-09-02 | ユケン工業株式会社 | Method for suppressing increase in zinc concentration of plating solution and method for producing zinc-based plated member |
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- 1999-07-29 KR KR1020017001285A patent/KR20010071074A/en not_active Application Discontinuation
- 1999-07-29 CZ CZ20010189A patent/CZ298904B6/en not_active IP Right Cessation
- 1999-07-29 ES ES99940077T patent/ES2201759T3/en not_active Expired - Lifetime
- 1999-07-29 EP EP03003890A patent/EP1344850B1/en not_active Expired - Lifetime
- 1999-07-29 EP EP99940077A patent/EP1102875B1/en not_active Revoked
- 1999-07-29 AU AU54152/99A patent/AU5415299A/en not_active Abandoned
- 1999-07-29 AT AT03003890T patent/ATE346180T1/en active
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- 1999-07-29 BR BR9912589-7A patent/BR9912589A/en not_active Application Discontinuation
- 1999-07-29 CA CA002339144A patent/CA2339144A1/en not_active Abandoned
- 1999-07-29 EE EEP200100059A patent/EE200100059A/en unknown
- 1999-07-29 PL PL345970A patent/PL198149B1/en unknown
- 1999-07-29 JP JP2000562585A patent/JP4716568B2/en not_active Expired - Lifetime
- 1999-07-29 SK SK89-2001A patent/SK285453B6/en not_active IP Right Cessation
- 1999-07-29 IL IL14108699A patent/IL141086A0/en unknown
- 1999-07-29 DE DE59914011T patent/DE59914011D1/en not_active Expired - Lifetime
- 1999-07-29 MX MXPA01000932A patent/MXPA01000932A/en unknown
- 1999-07-29 HU HU0103951A patent/HUP0103951A3/en unknown
- 1999-07-29 CN CN99809138A patent/CN1311830A/en active Pending
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2001
- 2001-01-16 HR HR20010044A patent/HRP20010044B1/en not_active IP Right Cessation
- 2001-01-25 BG BG105184A patent/BG105184A/en unknown
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2003
- 2003-07-11 US US10/618,352 patent/US20040104123A1/en not_active Abandoned
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2008
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US9903038B2 (en) | 2015-07-22 | 2018-02-27 | Dipsol Chemicals Co., Ltd. | Zinc alloy plating method |
US10156020B2 (en) | 2015-07-22 | 2018-12-18 | Dipsol Chemicals Co., Ltd. | Zinc alloy plating method |
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