EP2342370A1 - Novel cyanide-free electroplating process for zinc and zinc alloy die-cast components - Google Patents
Novel cyanide-free electroplating process for zinc and zinc alloy die-cast componentsInfo
- Publication number
- EP2342370A1 EP2342370A1 EP09818155A EP09818155A EP2342370A1 EP 2342370 A1 EP2342370 A1 EP 2342370A1 EP 09818155 A EP09818155 A EP 09818155A EP 09818155 A EP09818155 A EP 09818155A EP 2342370 A1 EP2342370 A1 EP 2342370A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- zinc
- nickel
- copper
- ions
- electroplating
- 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.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/623—Porosity of the layers
-
- 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
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- 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
- C25D3/22—Electroplating: Baths therefor from solutions 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
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
Definitions
- the present invention is directed to a method for covering an article manufactured from zinc or zinc alloy with an adherent metallic coating, said method being substantially free from cyanide ions.
- the coating of the invention renders the article suitable for subsequent electroplating in other metals such as copper, nickel and chromium.
- Zinc and zinc alloy products are generally produced as die castings and are commonly used in applications such as automotive parts or fittings. To enhance the decorative appearance of such articles and to provide them with protection against corrosion, said articles are commonly coated with other metals by the process of electrolytic or electroless plating.
- the most common metals for this application are copper, nickel, chromium and brass. Further enhancements in appearance or corrosion protection may be obtained by the use of organic coatings.
- Zinc and zinc alloy articles are traditionally electroplated with a first coating of copper, which is applied from a process that contains cyanide ions.
- the copper solution is alkaline in order to minimize chemical attack on the substrate and the cyanide ions are necessary to provide a stable complex of copper (I) ions.
- Efforts have been made to replace copper cyanide electroplating solutions in order to eliminate the use of cyanide ions due to their high toxicity.
- U.S. Patent No. 3,928,147 claims a method of immersing the zinc articles in a solution of an organophosphorus chelating agent prior to immersion in the cyanide-free copper(II) electroplating bath in order to inhibit the immersion deposition of copper.
- U.S. Patent No. 4,469,569 and U.S. Patent No. 4,521,282 have described the use of organophosphonate complexing agents in a copper plating bath
- U.S. Patent No. 6,054,037 describes an organophosphonate bath modified by the addition of halogen ions to stabilise copper(I) ions in the cathode film.
- halogen ions to stabilise copper(I) ions in the cathode film.
- immersion deposits are inherently less adherent than electroplated deposits and in addition, any deposit of a different metal needs to be thick enough to provide a non-porous film in order to prevent further immersion deposition of copper from the subsequent copper(II) solution. Immersion deposits are not thick enough to give non-porous layers. Thus this method still suffers from poor adhesion and a general lack of robustness when compared to the current cyanide-based electroplating technique.
- U.S. Patent Application 2006/0096868 describes a mildly acidic near-neutral nickel electroplating bath used to deposit a thick nickel layer on the zinc die-cast article. Although the deposits from this type of bath are thick enough to protect the substrate from attack in subsequent process stages, the electrolyte has poor throw into recesses and therefore some zinc substrate can remain exposed on complex-shaped parts. Additionally the deposits from this electrolyte exhibit very high internal stress and poor ductility.
- the present invention is directed to a method for producing an adherent metallic coating on a zinc or zinc alloy article without the use of cyanide ions in the process.
- the zinc or zinc alloy article is first cleaned in the normal manner and then electroplated with a zinc alloy coating, said zinc alloy coating being preferably a zinc-nickel alloy.
- the said zinc alloy coating has good adhesion to the substrate and provides a metallic layer suitable for subsequent electroplating stages.
- the present invention describes an electroplating bath and method which provide for producing a zinc alloy coating on a zinc die-cast substrate, said coating providing a suitable base for subsequent electroplating, without the use of cyanide ions.
- the zinc alloy coating is a zinc-nickel alloy. The method comprises the following steps;
- This invention describes a method of treating zinc die-cast articles to produce an adherent coating suitable for the application of subsequent electroplated metallic coatings without the use of solutions containing cyanide ions.
- the method of the invention generally includes the steps of:
- the cleaning and activating step is preferred to provide a surface that is suitable for electroplating. Defects such as lack of adhesion, porosity, roughness, dark spots and nonuniform coating are likely to occur on poorly prepared parts.
- the surface preparation process also serves to activate the surface of the part so that it is optimally receptive to the deposition of the metal coating.
- the zinc die-cast articles are first cleaned in a neutral or alkaline degreasing cleaner to remove oils from the surface of the articles and also any residual buffing compound that may be present from post-casting buffing operations.
- the articles are thoroughly rinsed and then activated to remove surface oxides by a short immersion in a weakly acid solution such as 5- 10% sulphuric acid. Thorough rinsing is preferred between all cleaning stages and also prior to electroplating to remove all traces of acid and alkali from any porous areas on the article.
- the zinc die-cast article is electroplated by making it the cathode in an aqueous solution containing zinc ions, alloying metal ions, which are preferably nickel ions, and counter ions.
- the source of zinc and alloying ions in the invention are any water soluble zinc or alloying metal salts.
- zinc are zinc chloride, zinc sulphate, zinc acetate and alkali metal zincates.
- the preferred source of the alloying ions is the chloride, sulphate or acetate salt of the chosen alloying metal, preferably nickel.
- the concentration of zinc ions in the electrolyte is generally between 2 and 100 g/1, and the concentration of alloying metal is generally between 0.2 and 100 g/I.
- the counter ions merely refers to the anions (eg. chloride, sulfate, acetate, etc.) that are associated with the metal ions in the salt chosen.
- Other useful alloying metals include cobalt, copper and iron.
- the solution may contain other salts and additives, for example (i) sources of hydrogen ion or hydroxide ion to adjust the pH of the electrolyte, (ii) buffering compounds such as ammonium ions, borate ions or organic acid species, (iii) complexing agents such as an amine to prevent precipitation of metal hydroxides, (iv) additional inorganic salts to improve the conductivity of the electrolyte, and (v) wetting agents and brightening agents.
- sources of hydrogen ion or hydroxide ion to adjust the pH of the electrolyte
- buffering compounds such as ammonium ions, borate ions or organic acid species
- complexing agents such as an amine to prevent precipitation of metal hydroxides
- additional inorganic salts to improve the conductivity of the electrolyte
- wetting agents and brightening agents for example (i) sources of hydrogen ion or hydroxide ion to adjust the pH of the electrolyte, (ii) buffering compounds such as
- the electrolyte is composed of a water soluble zinc salt providing zinc ions preferably in the concentration range of 10 - 100 g/1, a water soluble alloying metal salt providing alloying metal ions preferably in the concentration range of 10 - 100 g/1, a buffering compound and optionally further inorganic salts, wetting agents and brighteners.
- the zinc salt is zinc chloride
- the alloying metal salt is most preferably nickel chloride or nickel sulphate
- ammonium chloride or boric acid are the preferred buffering agent.
- the electrolyte is operated at a mildly acidic pH in the range 4.5 - 7.0, preferably about 5.0 - 5.5, and can be operated in the temperature range of 10 - 90 0 C but preferably at 20 - 30 0 C.
- the electrolyte is composed of an alkali metal zincate providing zinc ions preferably in the concentration range of 2 - 30 g/1, a water soluble alloying metal salt providing alloying metal ions preferably in the concentration range of 0.2 - 5 g/1, an amine compound to act as a chelating agent for the alloying metal ions, an alkali metal hydroxide, optionally an alkali metal carbonate and optionally wetting and brightening agents.
- the alkali metal zincate is sodium or potassium zincate
- the alloy metal salt is nickel sulphate
- the chelating agent is a polymeric amine or a substituted ethylenediamine compound
- the alkali metal hydroxide is sodium or potassium hydroxide.
- the electroplating solution is operated at a pH of between 10 and 14 and can be operated in the temperature range of 10 - 90 0 C but preferably at 20 - 30 0 C.
- Both embodiments of the invention provide a zinc alloy deposit which normally consists of 70 - 90% zinc and 10 - 30 % of alloying metal, preferably nickel.
- the anode in the electroplating baths may be either metallic zinc, the alloying metal which is preferably nickel, or insoluble anodes for example titanium coated with mixed metal oxides.
- the alloying metal which is preferably nickel, or insoluble anodes for example titanium coated with mixed metal oxides.
- a zinc anode is preferred, and for the second embodiment of the invention an anode of the alloying metal, which is most preferably nickel, or a coated titanium anode is preferred.
- the articles are electroplated in the solutions of the invention at current densities of between 0.1 and 5.0 A/dm2, preferably between 1 and 4 A/dm2, and the plating time is normally 2 - 10 minutes, preferably 4 - 8 minutes. Under these conditions an adherent zinc alloy, preferably a zinc-nickel alloy, is deposited. Typically the deposit contains 10 - 30% of alloying metal with the remainder being zinc. Both embodiments of the invention have minimal or no attack on the zinc die-cast articles and provide for deposits with excellent coverage into the recesses of complex-shaped parts, thereby providing optimum protection during subsequent processing stages.
- the preferred embodiment is the mildly acidic bath described in the first embodiment.
- the articles are subsequently electroplated with any suitable electroplating bath, however due to the coating of the invention being 70 - 90% zinc, processing in alkaline baths is preferred with pyrophosphate copper being most preferred.
- pyrophosphate copper being most preferred.
- Electroplate in chromium (conventional hexavalent chromium bath, 10 A/dm2, 5 mins)
- a zinc die-cast part was pretreated and then electroplated in a conventional alkaline cyanide copper(I) electroplating bath at lA/dm2 for 5 minutes at a temperature of 55°C.
- This example is representative of the conventional established process of the prior art.
- a zinc die-cast part was pretreated and then electroplated in the solution at 3.5A/dm2 for 20 minutes at a temperature of 55°C followed by conventional nickel and chromium plating.
- a zinc die-cast part was pretreated and then electroplated in the solution for 15 minutes at 0.5A/dm2 and a temperature of 55°C.
- a cathodic potential was applied to the part prior to immersion. This electroplating stage was followed by conventional nickel and chromium plating.
- This example is believed to be representative of the prior art of U.S. Patent No. 4,469,569 and U.S. Patent No. 4,521,282.
- Example 4 An electrolyte was prepared as follows; copper(II) ions (added as copper sulphate) 10 g/1
- a zinc die-cast part was pretreated and electroplated in the solution for 15 minutes at 0.5A/dm2 and a temperature of 55°C.
- a cathodic potential was applied to the part prior to immersion. This electroplating stage was followed by conventional nickel and chromium plating. This example is believed to be representative of the prior art of U.S. Patent No. 6,054,037.
- a zinc die-cast part was pretreated and then immersed in the above solution for 1 minute prior to being electroplated in the solution of Example 3 for 15 minutes at 0.5A/dm2 and a temperature of 55°C, followed by conventional nickel and chromium plating.
- This example is believed to be representative of the prior art of U.S. Patent No. 3,928,147.
- An electrolyte was prepared as follows; copper(II) ions (added as copper sulphate) 8 g/1 sodium potassium tartrate 100 g/1 sodium hydroxide 25 g/1 sodium hypophosphite 25 g/1
- a zinc die-cast part was pretreated and immersed in the solution.
- a displacement copper deposit formed immediately upon immersion into the solution.
- the part was electroplated in the solution for 10 minutes at 0.01A/dm2 and a temperature of 30 0 C and subsequently electroplated by conventional pyrophosphate copper, nickel and chromium plating.
- This example is believed to be representative of the prior art of U.S. Patent Application 2008/0156652.
- An electrolyte was prepared as follows;
- a zinc die-cast part was pretreated and electroplated in the solution for 2 minutes at 2.0A/dm2 and a temperature of 55°C. This electroplating stage was followed by conventional pyrophosphate copper, nickel and chromium plating. This example is believed to be representative of the prior art of GB2272001.
- Nickel (II) ions (added as nickel sulphate) 20 g/1 Potassium pyrophosphate 100 g/1
- a zinc die-cast part was pretreated and immersed in the solution for 3 at a temperature of 50 0 C.
- An immersion nickel deposit formed.
- This stage was followed by conventional pyrophosphate copper, nickel and chromium plating.
- This example is believed to be representative of the prior art of U.S. Patent No. 6,827,834.
- a zinc die-cast part was pretreated and electroplated in the solution of example 8 for 10 minutes at 1.0A/dm2 and a temperature of 50 0 C. This electroplating stage was followed by conventional pyrophosphate copper, nickel and chromium plating.
- Salicylic acid 4 g/1 4-acetamido-5-hydroxy-2,7-naphthalene- disulphonic acid, disodium salt l g/1
- a zinc die-cast part was pretreated and electroplated in the solution for 5 minutes at 4,0 A/dm2 and a temperature of 55 0 C and subsequently electroplated in conventional pyrophosphate copper, nickel and chromium plating.
- This example is believed to be representative of the prior art of U.S. Patent Appl. 2006/0096868.
- An electrolyte was prepared as follows; zinc ions (added as zinc chloride) 45 g/l nickel ions (added as nickel chloride) 55 g ⁇ ammonium chloride 30 g/1
- a zinc die-cast part was pretreated and electroplated in the solution for 10 minutes at 2.0 A/dm2 and a temperature of 30 0 C.
- a cathodic potential was applied to the part prior to immersion.
- This electroplating stage was followed by conventional pyrophosphate copper (with a cathodic potential applied prior to immersion), nickel and chromium plating.
- An electrolyte was prepared as follows; zinc ions (added as zinc chloride) 50 g/1 nickel ions (added as nickel sulphate) 50 g/1 boric acid 30 g/1
- a zinc die-cast part was pretreated and electroplated in the solution for 10 minutes at 1.0 A/dm2 and a temperature of 30 0 C.
- a cathodic potential was applied to the part prior to immersion.
- This electroplating stage was followed by conventional pyrophosphate copper (with a cathodic potential applied prior to immersion), nickel and chromium plating.
- Example 13 An electrolyte was prepared as follows; zinc ions (added as zinc chloride) 50 g/I nickel ions (added as nickel chloride) 50 g/1 ammonium chloride 30 g/1
- a zinc die-cast part was pretreated and electroplated in the solution for 5 minutes at 2.0 AJAmI and a temperature of 20 0 C.
- a cathodic potential was applied to the part prior to immersion.
- This electroplating stage was followed by conventional pyrophosphate copper (with a cathodic potential applied prior to immersion), nickel and chromium plating.
- An electrolyte was prepared as follows; zinc ions (added as zinc sulphate) 50 g/1 nickel ions (added as nickel chloride) 50 g/1 potassium chloride 30 g/1 boric acid 30 g/1 sodium acetate 20 g/I
- a zinc die-cast part was pretreated and electroplated in the solution for 5 minutes at 4.0 A/dm2 and a temperature of 25 0 C.
- a cathodic potential was applied to the part prior to immersion.
- This electroplating stage was followed by conventional pyrophosphate copper (with a cathodic potential applied prior to immersion), nickel and chromium plating.
- An electrolyte was prepared as foliows; zinc ions (added as sodium zincate) 8.0 g/1 nickel ions (added as nickel sulphate) 0.8 g/1 sodium hydroxide 110 g/1 tetraethylenepentamine 10 g/1 triethanolamine 2 g/1 N,N 5 N',N'-tetra(3-hydroxypropyl)- ethylenediamine 15 g/1
- a zinc die-cast part was pretreated and electroplated in the solution for 10 minutes at 1.0 A/dm2 and a temperature of 25°C.
- a cathodic potential was applied to the part prior to immersion.
- This electroplating stage was followed by conventional pyrophosphate copper (with a cathodic potential applied prior to immersion), nickel and chromium plating.
- An electrolyte was prepared as follows; zinc ions (added as sodium zincate) 12.0 g/1 nickel ions (added as nickel sulphate) 1.3 g/1 sodium hydroxide 100 g/1 tetraethylenepentamine 15 g/1
- N 5 N 5 N' ,N' -tetra(3-hydroxypropyl)- ethylenediamine 20 g/1 A zinc die-cast part was pretreated and electroplated in the solution for 5 minutes at 2.0 A/dm2 and a temperature of 25 0 C. A cathodic potential was applied to the part prior to immersion. This electroplating stage was followed by conventional pyrophosphate copper (with a cathodic potential applied prior to immersion), nickel and chromium plating.
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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)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/244,156 US20100084278A1 (en) | 2008-10-02 | 2008-10-02 | Novel Cyanide-Free Electroplating Process for Zinc and Zinc Alloy Die-Cast Components |
PCT/US2009/050937 WO2010039323A1 (en) | 2008-10-02 | 2009-07-17 | Novel cyanide-free electroplating process for zinc and zinc alloy die-cast components |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2342370A1 true EP2342370A1 (en) | 2011-07-13 |
EP2342370A4 EP2342370A4 (en) | 2014-09-10 |
Family
ID=42073800
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP09818155.5A Withdrawn EP2342370A4 (en) | 2008-10-02 | 2009-07-17 | Novel cyanide-free electroplating process for zinc and zinc alloy die-cast components |
Country Status (6)
Country | Link |
---|---|
US (1) | US20100084278A1 (en) |
EP (1) | EP2342370A4 (en) |
JP (1) | JP2012504704A (en) |
CN (1) | CN102131960A (en) |
TW (1) | TWI448590B (en) |
WO (1) | WO2010039323A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI482878B (en) * | 2012-11-09 | 2015-05-01 | Ind Tech Res Inst | Acidic electroless copper plating system and copper plating method using the same |
CN107142502A (en) * | 2017-05-15 | 2017-09-08 | 佛山市兴中达化工实业有限公司 | A kind of replacement has the direct plating of cyanogen alkali copper in the non-cyanogen electro-plating method of kirsite matrix |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3691027A (en) * | 1970-06-16 | 1972-09-12 | Allied Chem | Method of producing corrosion resistant chromium plated articles |
US4904354A (en) * | 1987-04-08 | 1990-02-27 | Learonal Inc. | Akaline cyanide-free Cu-Zu strike baths and electrodepositing processes for the use thereof |
JPH03115594A (en) * | 1990-04-25 | 1991-05-16 | Nippon Steel Corp | Restproof steel sheet having superior corrosion resistance |
US20010015321A1 (en) * | 1998-10-26 | 2001-08-23 | Reid Jonathan D. | Electroplating process for avoiding defects in metal features of integrated circuit devices |
WO2006052310A2 (en) * | 2004-11-10 | 2006-05-18 | Macdermid, Incorporated | Nickel electroplating bath designed to replace monovalent copper strike solutions |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2989446A (en) * | 1956-10-29 | 1961-06-20 | Rockwell Standard Co | Electroplating |
US3202589A (en) * | 1963-09-12 | 1965-08-24 | Diamond Alkali Co | Electroplating |
US3928147A (en) * | 1973-10-09 | 1975-12-23 | Monsanto Co | Method for electroplating |
US4462874A (en) * | 1983-11-16 | 1984-07-31 | Omi International Corporation | Cyanide-free copper plating process |
US4469569A (en) * | 1983-01-03 | 1984-09-04 | Omi International Corporation | Cyanide-free copper plating process |
US4488942A (en) * | 1983-08-05 | 1984-12-18 | Omi International Corporation | Zinc and zinc alloy electroplating bath and process |
US4521282A (en) * | 1984-07-11 | 1985-06-04 | Omi International Corporation | Cyanide-free copper electrolyte and process |
JPS6353285A (en) * | 1986-08-22 | 1988-03-07 | Nippon Hyomen Kagaku Kk | Zinc-nickel alloy plating solution |
JPH01219188A (en) * | 1988-02-26 | 1989-09-01 | Okuno Seiyaku Kogyo Kk | Zinc-nickel alloy plating bath |
US5750018A (en) * | 1997-03-18 | 1998-05-12 | Learonal, Inc. | Cyanide-free monovalent copper electroplating solutions |
US6054037A (en) * | 1998-11-11 | 2000-04-25 | Enthone-Omi, Inc. | Halogen additives for alkaline copper use for plating zinc die castings |
JP4864256B2 (en) * | 2001-09-26 | 2012-02-01 | 石原薬品株式会社 | Tin plating bath for preventing whisker and tin plating method |
US6827834B2 (en) * | 2002-03-12 | 2004-12-07 | Ronald Stewart | Non-cyanide copper plating process for zinc and zinc alloys |
US20080156652A1 (en) * | 2006-12-28 | 2008-07-03 | Chang Gung University | Cyanide-free pre-treating solution for electroplating copper coating layer on zinc alloy surface and a pre-treating method thereof |
-
2008
- 2008-10-02 US US12/244,156 patent/US20100084278A1/en not_active Abandoned
-
2009
- 2009-07-17 CN CN2009801329507A patent/CN102131960A/en active Pending
- 2009-07-17 EP EP09818155.5A patent/EP2342370A4/en not_active Withdrawn
- 2009-07-17 JP JP2011530078A patent/JP2012504704A/en active Pending
- 2009-07-17 WO PCT/US2009/050937 patent/WO2010039323A1/en active Application Filing
- 2009-08-12 TW TW098127087A patent/TWI448590B/en not_active IP Right Cessation
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3691027A (en) * | 1970-06-16 | 1972-09-12 | Allied Chem | Method of producing corrosion resistant chromium plated articles |
US4904354A (en) * | 1987-04-08 | 1990-02-27 | Learonal Inc. | Akaline cyanide-free Cu-Zu strike baths and electrodepositing processes for the use thereof |
JPH03115594A (en) * | 1990-04-25 | 1991-05-16 | Nippon Steel Corp | Restproof steel sheet having superior corrosion resistance |
US20010015321A1 (en) * | 1998-10-26 | 2001-08-23 | Reid Jonathan D. | Electroplating process for avoiding defects in metal features of integrated circuit devices |
WO2006052310A2 (en) * | 2004-11-10 | 2006-05-18 | Macdermid, Incorporated | Nickel electroplating bath designed to replace monovalent copper strike solutions |
Non-Patent Citations (1)
Title |
---|
See also references of WO2010039323A1 * |
Also Published As
Publication number | Publication date |
---|---|
US20100084278A1 (en) | 2010-04-08 |
CN102131960A (en) | 2011-07-20 |
WO2010039323A1 (en) | 2010-04-08 |
TWI448590B (en) | 2014-08-11 |
TW201014934A (en) | 2010-04-16 |
JP2012504704A (en) | 2012-02-23 |
EP2342370A4 (en) | 2014-09-10 |
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