EP1190118B1 - Systeme de bain pour depot de metaux par voie galvanique - Google Patents

Systeme de bain pour depot de metaux par voie galvanique Download PDF

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Publication number
EP1190118B1
EP1190118B1 EP00940346A EP00940346A EP1190118B1 EP 1190118 B1 EP1190118 B1 EP 1190118B1 EP 00940346 A EP00940346 A EP 00940346A EP 00940346 A EP00940346 A EP 00940346A EP 1190118 B1 EP1190118 B1 EP 1190118B1
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EP
European Patent Office
Prior art keywords
bath
water soluble
acid
bath system
metals
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
Application number
EP00940346A
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German (de)
English (en)
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EP1190118A1 (fr
Inventor
Gerhard Hoffacker
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Rohm and Haas Electronic Materials LLC
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Hoffacker Gerhard
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Publication date
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Publication of EP1190118A1 publication Critical patent/EP1190118A1/fr
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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
    • C25D3/48—Electroplating: Baths therefor from solutions of gold
    • 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
    • C25D3/46—Electroplating: Baths therefor from solutions of silver

Definitions

  • the invention relates to a bath system for the electrodeposition of metals.
  • Galvanic baths for the deposition of precious metals and precious metal alloys have long been known both for decorative and technical applications.
  • the soluble noble metal compounds which are used predominantly are based on cyanide (potassium cyanide, potassium silver cyanide), sulfite (gold sulfite complexes) or contain ammonium (palladium complexes).
  • cyanide potassium cyanide, potassium silver cyanide
  • sulfite gold sulfite complexes
  • ammonium palladium complexes
  • an aqueous bath system for the electrodeposition of metals which contains inter alia a metal (gold), glycine (fission product of a protein), a nitro-containing substance (trinitrobenzenesulfonic acid) and pyridine at a pH of 7.8.
  • a metal gold
  • glycine glycine
  • a nitro-containing substance trinitrobenzenesulfonic acid
  • pyridine a nitro-containing substance
  • aqueous bath system for the electrodeposition of metals comprising inter alia a metal salt with a nitrate-containing substance (Palladiumdiaminodinitrit), which is reduced under the influence of an acid in the presence of urea to metal compounds (palladium).
  • the known bath also has glycine (cleavage product of a protein) and succinimide.
  • Example 7 of the same document uses nicotinamide (vitamin B 3 ) instead of succinimide.
  • the present invention has the object, aqueous bath systems for electrodeposition of metals, in particular of precious metals and their alloys to develop, which are suitable for stable operation both for decorative and technical application and high quality layers of consistent quality in galvanostatic working processes, the bath system free of harmful substances such as cyanides, sulfites and hard complexing agents. Furthermore, the number of complexing of the individual metal-requiring salt formers should be kept as low as possible.
  • the bath system according to the current main claim also allows the addition of various alloying metals, so that a wide range of alloy compositions can be achieved.
  • the bath system is characterized by a high quality of the deposited layers with the simplest handling.
  • high current yields are possible, so that the energy input quantities can be reduced and therefore the costs.
  • the bath system according to the invention is little dependent on fluctuations in the bath components and can be easily supplemented by appropriate additives depending on the individual requirements.
  • the bath system has a long service life.
  • the mentioned protein amino acids can also have one or more mercapto groups in the molecule in addition to one or more amino groups.
  • Examples of such protein amino acids are glycine, alanine, cysteine and methionine.
  • the sulfonic acids mentioned may contain one or more alkyl groups and / or one or more amino groups in the molecule.
  • Examples of these sulfonic acids are in particular amidosulfonic acid, methanesulfonic acid and ⁇ thansulfonklare.
  • nitro compounds To stabilize and complex the bath system, particularly water-soluble nitro compounds have proved to be favorable as acids and / or their derivatives and / or their salts.
  • the mentioned nitro compounds may have at least one nitro group, a carboxylic acid residue and / or sulfonic acid residue. Examples of these nitro acids are 3-nitrophthalic acid, 4-nitrophthalic acid, m-nitrobenzenesulfonic acids.
  • water-soluble nitrogen compounds can be used as acids and / or their derivatives and / or their salts.
  • the nitrogen compounds used contain at least one amino group and / or a carboxylic acid radical and / or sulfonic acid radical.
  • these nitrogen compounds are nicotinic acid, its derivatives and / or salts and / or succinic acid, their derivatives and / or salts, preferably their amide or sulfo compounds.
  • nicotinamide is used, which is the vitamin B complex, in particular the vitamin B 3 , attributed.
  • Sulphon derivatives which have one or two aromatic radicals on the sulphone group at the core of which partial substitution of the carbon-bonded hydrogen by metal, nitro groups, amino groups and halogens can be present can be used as brighteners.
  • a gold bath designed to remove fine gold according to the invention contains the gold, for example, as a protein amino acid derivative of class a), preferably in the form of a gold cysteine complex, the gold concentration being between 0.5 and 30 g / l bath, preferably between 1 and 10 g / l bath, lies.
  • the pH of the bath can be adjusted between 7 and 14, preferably between 8 and 12, in particular between 9 and 10.
  • the adjustment and stabilization of the pH can be carried out with borate buffer, phosphate buffer, citrate buffer or other conventional buffer systems in electroplating.
  • the working temperature of a pertinent bath is set between 20 ° C and 80 ° C, preferably between 40 ° C and 60 ° C.
  • the applicable cathodic current density is between 0.1 A / dm 2 and 15 A / dm 2 , preferably between 0.5 Ndm 2 and 5 A / dm 2 .
  • the exemplary gold bath designed according to the bath system according to the invention contains an excess of the protein derivative used for depositing the fine gold and may contain, in addition to the mentioned sulfonic acids, one of the indicated nitro acids for stabilization and / or additionally a water-soluble nitrogen compound.
  • This water-soluble nitrogen compound may, in addition to the complexation of the gold in a wide pH range, preferably the complexation optionally take over existing alloy metals.
  • the added water-soluble nitrogen compound is preferably at least one heterocyclic organic compound.
  • This heterocyclic organic compound may preferably consist of aromatic heterocycles.
  • amides of nicotinic acid have proven to be particularly advantageous.
  • additional stabilizing agents it is also possible to add amides of succinic acid.
  • a silver bath for depositing fine silver prepared according to the invention contains the silver, for example, as sulfonate of compound class b), preferably in the form of silver methanesulfonate, the silver concentration being between 0.5 and 60 g / l bath, preferably between 2 and 40 g / l Bath, lies.
  • the bath may contain additional portions of the sulfonate used.
  • at least one water-soluble protein-amino acid compound of compound class a) is added to the bath according to the invention.
  • the water-soluble protein-amino acid compound is present in excess of the stoichiometric ratio to silver.
  • At least one water-soluble organic nitrogen compound may additionally be added to the bath system according to the invention.
  • this water-soluble nitrogen compound can preferably take over the complexing of any alloying metals present.
  • the added water-soluble nitrogen compound is preferably at least one heterocyclic organic compound.
  • This heterocyclic organic compound may preferably be aromatic heterocycles. Particularly advantageous have thereby amides of nicotinic acid proved. As additional stabilization also amides of succinic acid can be added.
  • the pH of the bath can be adjusted between 7 and 14, preferably between 8 and 12, in particular between 9 and 10.
  • the adjustment and stabilization of the pH value can be carried out with borate buffer, phosphate buffer, citrate buffer or other conventional buffer systems in electroplating.
  • the working temperature of a pertinent bath is between 10 ° C and 50 ° C, preferably between 20 ° C and 40 ° C.
  • the applicable cathodic current density can be set between 0.1 A / dm 2 and 15 A / dm 2 , preferably between 0.5 A / dm 2 and 5 A / dm 2 .
  • substrates of brass can be directly coated in the silver baths according to the invention.
  • the previously required pre-silvering of brass substrates in pre-silver baths can therefore be omitted and thus a complete operation can be saved.
  • the baths according to the invention for the deposition of fine coatings of noble metals can be added in a known manner alloying metals.
  • Suitable alloy metals are all known metals of the Periodic Table which can be deposited together with the respective noble metal from an aqueous solution.
  • these are the above-mentioned precious metals gold, silver, palladium and combinations of these precious metals with each other.
  • Other preferred alloy metals for gold are copper, zinc, tin, iron and bismuth.
  • alloying metals for silver, especially tin and bismuth have proved to be advantageous.
  • the individual alloying partners can be electrodeposited by enrichment or depletion in the baths in proportions of between 0 and 100%.
  • the specimens are coated over the entire surface.
  • the color of the metallic coating corresponds to the typical fine gold color.
  • the specimens are coated over the entire surface.
  • the color of the metallic coating corresponds to the typical fine silver color.

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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)

Claims (10)

  1. Système de bain pour le dépôt de métaux par voie galvanique comprenant :
    - au moins un métal, notamment sous la forme d'un métal précieux et/ou d'un alliage de métal précieux sous la forme d'un sel soluble dans l'eau ;
    - au moins une matière de protéine soluble dans l'eau et/ou
    - au moins un acide sulfonique soluble dans l'eau et
    - au moins une substance nitrée soluble dans l'eau et
    - au moins un agent tensioactif soluble dans l'eau et
    - au moins une vitamine, à savoir la vitamine A, la vitamine B ou la vitamine H.
  2. Système de bain suivant la revendication 1, caractérisé en ce que la substance de protéine soluble dans l'eau se présente sous la forme d'un constituant d'acide aminé de protéine soluble dans l'eau sous forme d'acides et/ou de leurs dérivés et/ou de leurs sels qui sont présents en une quantité de 0,1 à 150 g/l de bain.
  3. Système de bain suivant la revendication 1 ou 2, caractérisé en ce que l'acide sulfonique soluble dans l'eau est présent sous forme d'acide et/ou d'un dérivé et/ou d'un sel en une quantité de 0,1 à 200 g/l de bain.
  4. Système de bain suivant l'une des revendications 1 à 3, caractérisé en ce que la substance nitrée soluble dans l'eau est présente sous forme d'acide et/ou sous la forme d'un dérivé et/ou sous la forme d'un sel en une quantité de 0,1 à 200 g/l de bain, notamment de 0,1 à 50 g/l de bain.
  5. Système de bain suivant l'une des revendications 1 à 4, caractérisé en ce que l'agent tensioactif soluble dans l'eau est présent en une quantité de 0,1 à 5 g/l de bain.
  6. Système de bain suivant l'une des revendications 1 à 5, caractérisé en ce qu'il est utilisé comme vitamine l'amide de l'acide nicotinique.
  7. Système de bain suivant l'une des revendications 3 à 6, caractérisé en ce qu'un dérivé de sulfone soluble dans l'eau est présent en temps qu'agent de brillantage en une quantité de 0,001 à 5 g/l de bain.
  8. Système de bain suivant l'une des revendications 1 à 7, caractérisé en ce que le pH est réglé avec mise en oeuvre d'un tampon entre 7 et 14, notamment entre 8 et 12.
  9. Système de bain suivant l'une des revendications 1 à 8, caractérisé en ce que la concentration en or dans un bain de dorure pur est comprise entre 0,5 et 30 g/l de bain, de préférence entre 1 et 10 g/l de bain.
  10. Système de bains suivant l'une des revendications 1 à 8, caractérisé en ce que la concentration d'argent dans un bain d'argent pur est comprise entre 0,5 et 60 g/l de bain, de préférence entre 2 et 40 g/l de bain.
EP00940346A 1999-06-19 2000-06-08 Systeme de bain pour depot de metaux par voie galvanique Expired - Lifetime EP1190118B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19928047 1999-06-19
DE19928047A DE19928047A1 (de) 1999-06-19 1999-06-19 Schadstoffarme bis schadstoffreie wäßrige Systeme zur galvanischen Abscheidung von Edelmetallen und Edelmetall-Legierungen
PCT/EP2000/005287 WO2000079030A1 (fr) 1999-06-19 2000-06-08 Systeme de bain pour depot de metaux par voie galvanique

Publications (2)

Publication Number Publication Date
EP1190118A1 EP1190118A1 (fr) 2002-03-27
EP1190118B1 true EP1190118B1 (fr) 2010-07-21

Family

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Family Applications (1)

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EP00940346A Expired - Lifetime EP1190118B1 (fr) 1999-06-19 2000-06-08 Systeme de bain pour depot de metaux par voie galvanique

Country Status (4)

Country Link
US (1) US6620304B1 (fr)
EP (1) EP1190118B1 (fr)
DE (2) DE19928047A1 (fr)
WO (1) WO2000079030A1 (fr)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1162289A1 (fr) * 2000-06-08 2001-12-12 Lucent Technologies Inc. Bain pour l'electrodeposition de palladium et processus pour l'electrodeposition
US20040043159A1 (en) * 2002-08-30 2004-03-04 Shipley Company, L.L.C. Plating method
DE10356449B3 (de) * 2003-12-03 2005-01-27 Atotech Deutschland Gmbh Bad, Verwendung des Bades und Verfahren zum außenstromlosen Abscheiden von Silber
US20080035489A1 (en) 2006-06-05 2008-02-14 Rohm And Haas Electronic Materials Llc Plating process
WO2009061984A2 (fr) * 2007-11-09 2009-05-14 Technic, Inc. Procédé de métallisation de conducteurs de cellule photovoltaïque par électroplaquage avec une attaque minimale sur les matériaux de construction sous-jacents
CN101724872B (zh) * 2008-10-20 2013-05-08 长沙铂鲨环保设备有限公司 一种无氰镀金盐溶液
EP2780762B1 (fr) 2011-11-15 2017-06-28 Ashwin-Ushas Corporation, Inc. Dispositif électrochromique à polymères complémentaires
GB201200482D0 (en) * 2012-01-12 2012-02-22 Johnson Matthey Plc Improvements in coating technology
CN102691081B (zh) * 2012-06-11 2016-01-20 东莞市闻誉实业有限公司 一种电镀银溶液及电镀方法
US9207515B2 (en) 2013-03-15 2015-12-08 Ashwin-Ushas Corporation, Inc. Variable-emittance electrochromic devices and methods of preparing the same
EP2971263A1 (fr) * 2013-03-15 2016-01-20 Enthone, Inc. Dépôt électrolytique d'argent comprenant des nanoparticules de polymère fluoré
US9632059B2 (en) 2015-09-03 2017-04-25 Ashwin-Ushas Corporation, Inc. Potentiostat/galvanostat with digital interface
US9482880B1 (en) 2015-09-15 2016-11-01 Ashwin-Ushas Corporation, Inc. Electrochromic eyewear
CN105420770A (zh) * 2015-11-30 2016-03-23 苏州市金星工艺镀饰有限公司 一种防变色无氰镀银电镀液及其电镀方法
WO2018215057A1 (fr) 2017-05-23 2018-11-29 Saxonia Edelmetalle Gmbh Préparation de sel de métal noble, procédé pour la production de celle-ci et son utilisation pour l'électrodéposition
EP3841233A1 (fr) * 2018-08-21 2021-06-30 Umicore Galvanotechnik GmbH Électrolyte pour le dépôt d'argent sans cyanure
KR102476608B1 (ko) 2021-11-19 2022-12-13 (주)피이솔브 은도금액

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4406755A (en) 1982-03-08 1983-09-27 Technic Inc. Bright palladium electrodeposition
US4673472A (en) * 1986-02-28 1987-06-16 Technic Inc. Method and electroplating solution for deposition of palladium or alloys thereof
DE3805627A1 (de) 1988-02-24 1989-09-07 Wieland Edelmetalle Goldbad
CH681893A5 (fr) 1990-10-26 1993-06-15 Thomas Allmendinger
US6251249B1 (en) * 1996-09-20 2001-06-26 Atofina Chemicals, Inc. Precious metal deposition composition and process

Also Published As

Publication number Publication date
WO2000079030A1 (fr) 2000-12-28
EP1190118A1 (fr) 2002-03-27
US6620304B1 (en) 2003-09-16
DE50015960D1 (de) 2010-09-02
DE19928047A1 (de) 2000-12-21

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