EP1930478B1 - Composition d'un électrolyte et méthode de dépôt d'alliages quaternaires de cuivre - Google Patents

Composition d'un électrolyte et méthode de dépôt d'alliages quaternaires de cuivre Download PDF

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Publication number
EP1930478B1
EP1930478B1 EP20060025184 EP06025184A EP1930478B1 EP 1930478 B1 EP1930478 B1 EP 1930478B1 EP 20060025184 EP20060025184 EP 20060025184 EP 06025184 A EP06025184 A EP 06025184A EP 1930478 B1 EP1930478 B1 EP 1930478B1
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EP
European Patent Office
Prior art keywords
electrolyte composition
copper
composition according
acid
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.)
Expired - Fee Related
Application number
EP20060025184
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German (de)
English (en)
Other versions
EP1930478A1 (fr
Inventor
Pierre Lalanne
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
MacDermid Enthone Inc
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Enthone Inc
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Publication date
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Priority to EP20060025184 priority Critical patent/EP1930478B1/fr
Publication of EP1930478A1 publication Critical patent/EP1930478A1/fr
Application granted granted Critical
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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
    • 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
    • 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
    • C25D3/40—Electroplating: Baths therefor from solutions of copper from cyanide baths, e.g. with Cu+

Definitions

  • the present invention relates to an electrolyte composition as well as a method for the deposition of quaternary copper alloys.
  • the present invention relates to an electrolyte composition as well as a method for the deposition of bronze alloys which comprise copper, tin and zinc and a fourth alloying metal.
  • substrate surfaces can be coated with corresponding metal or alloy layers for decorative or functional reasons.
  • electroplating surface coatings are used in very different fields such as for example the automobile industry, the fittings industry or the manufacture of jewellery.
  • bronzes comprise a non negligible portion of heavy metals, such as for example lead, and they can also comprise portions of nickel which is suspected of provoking allergies if it is in direct contact with the skin.
  • substrates are often provided with nickel and/or chromium layers for decorative purposes. Since these substances are suspected of provoking allergies, it is endeavoured, in particular in the filed of the jewellery industry, to replace such coatings with harmless coatings that present the same or better properties.
  • an electrolyte composition for the deposition of a quaternary copper alloy on a substrate comprising at least copper, tin and zinc in form of the ions thereof as well as ions of a metal that is selected from the group consisting of indium, gallium and thallium.
  • Thallium is proved to be a brightener (grain refiner) in the electrodeposition of bronze alloys.
  • the deposit With a concentration of 0.05 g/l in the electrolyte, the deposit can contain up to 1 % of this elements.
  • an alloying metal selected from the group consisting of indium, gallium and thallium, makes it possible to deposit white, brilliant bronze alloy layers which do not release any noxious metals.
  • the thus deposited copper alloy layers can also be used as an alternative of nickel or chromium coatings.
  • the white metals such as tin, zinc as well as the metals from the group consisting of indium, gallium and thallium, can be widely varied in the electrolyte composition according to the invention, whereby copper alloy layers having surface properties that can be widely adjusted can be deposited.
  • the addition of a fourth alloying metal of the described type to bronze alloys on the base of copper, tin and zinc permits to clearly increase the corrosion resistance of the deposited layers against aggressive environmental influences such as for example salt water or human sweat. Furthermore, the hardness of the deposited alloy layers is significantly increased by the addition of the fourth alloying metal.
  • the electrolyte compositions according to the invention comprise cyanide besides the mentioned alloying metals.
  • the cyanide concentration can vary in a range comprised between 1 and 100 g/l according to the invention, wherein as cyanide source not only alkali-cyanides but also the alloying metals of the electrolyte composition in form of cyanide complexes, such as for example copper cyanide or zinc cyanide, can be added.
  • alloying metals of the electrolyte composition can be added in form of the soluble oxides, sulphates thereof or other suitable soluble compounds.
  • the electrolyte composition according to the invention comprises complexing agents for the complexation of the metals present in the electrolyte composition.
  • suitable complexing agents are for example nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), phosphonates such as for example the phosphonate that is distributed by the company Monsanto under the name "Dequest”, derivates or salts of the D-gluconic acid as well as alkali hydroxides.
  • NTA nitrilotriacetic acid
  • EDTA ethylenediaminetetraacetic acid
  • DTPA diethylenetriaminepentaacetic acid
  • phosphonates such as for example the phosphonate that is distributed by the company Monsanto under the name "Dequest”, derivates or salts of the D-gluconic acid as well as alkali hydroxides.
  • the electrolyte compositions according to the invention can comprise alkali salts of phosphonic acids, such as for example ethylenediaminetetra(methylphosphonic acid) (EDTMPA) or 1-hydroxyethylidenediphosphonic acid (HEDP or etidronic acid).
  • phosphonic acids such as for example ethylenediaminetetra(methylphosphonic acid) (EDTMPA) or 1-hydroxyethylidenediphosphonic acid (HEDP or etidronic acid).
  • the electrolyte composition according to the invention can content Rochelle salt (Sodiumpotassiumtartrat), and (or) glycolic acid, for example in form of alkali salts thereof. These salts function as conductive salts and as pH buffers to the electrolyte.
  • the electrolyte compositions according to the invention advantageously comprise surface-active agents, such as for example the additive distributed by the company Enthone under the name Brightener SW or also the betaine derivate distributed under the name ATC Solution No. 10.
  • the copper content of the electrolyte compositions can be comprised between 1 and 30 g/l.
  • the cyanide-copper-ratio is comprised between 1 : 1 and 10 : 1, calculated on the base of potassium cyanide.
  • the tin concentration of the electrolyte composition according to the invention can vary in a range comprised between 1 and 40 g/l, wherein it advantageously comprises a hydroxide-tin-ratio comprised between 1 : 1 and 5 : 1, calculated on the base of potassium hydroxide.
  • the zinc concentration of the electrolyte composition according to the invention can vary between 0.4 and 20 g/l.
  • the concentration of the fourth alloying metal selected from the group consisting of indium, gallium and thallium can vary between 0.1 and 10 g/l, depending on the selected complexing agent.
  • the aim of the invention is achieved by a method for the deposition of a quaternary copper alloy on a substrate comprising the process steps:
  • the set current density of the method according to the invention for the deposition of a corresponding quaternary copper alloy layer on the substrate is comprised between 0.05 and 5 A/dm2, preferably between 0.1 and 3 A/dm 2 .
  • the temperature during the step of contacting the substrate to be coated with the electrolyte composition according to the invention can vary between 20 and 80°C, preferably between 50 and 70°C. Below 50°C, the deposit is less bright, not homogeneous, colour is not uniform and corrosion resistance is less good. Above 70°C, the electrolyte generates too much break-down products and consumes more energy, more potassium hydroxide and more potassium cyanide. The consequence is a quick build-up of potassium carbonate, as also a rapid ageing of the electrolyte.
  • quaternary copper alloys having a layer thickness of up to 20 ⁇ m can be deposited, which are free of fissures and brilliant.
  • the deposited layers are uniform and present a high corrosion resistance.
  • the corrosion resistance to Neutral Salt Spray (according to the standard ISO 9227) for the same thickness of this deposit, plated on the same substrate, is minimum twice better than for the white ternary alloy copper/tin/zinc.
  • Corrosion resistance to artificial sweat (according to the standard ISO 3160-2) is also twice better than for the white ternary alloy copper/tin/zinc .
  • a deposit of 3 ⁇ m of copper/tin/zinc/indium according to the invention, plated on brass substrate resists more than 300 hours in the neutral salt spray test.
  • the comparative ternary white alloy copper/tin/zinc resists less than 120 hours.
  • the quaternary alloy resists 7 days, and the ternary alloy resists maximum 36 hours.
  • the alloying metals can vary within the deposited alloy layers depending on the set electrolyte composition.
  • the copper content of the deposited layers can vary between 52 and 55 % by mass
  • the tin content can vary between 23 and 35 % by mass
  • the zinc content can vary between 5 and 13 % by mass.
  • the content of the fourth alloying metal selected from the group consisting of indium, gallium and thallium can vary between 0.5 and 17 % by mass in the alloy layers deposited according to the invention, with a preferred content of 4 to 12% by mass in the alloy for optimum performances.
  • Aqueous electrolyte composition comprising
  • the deposit was corrosion and tarnish resistant, with a hardness of 510 HV 0.05 .
  • a plating barrel is filled with small pieces made of brass. Rotation speed of the barrel is adjusted at 8 rotations per minute. From the aqueous electrolyte described in example 1, at a temperature of 62°C, a current density of 0.15 A/dm 2 , in 120 minutes a 4 ⁇ m thick, white, fully bright and levelling deposits which contained 53.3% copper, 26.7% tin, 8.2% zinc and 11.7% indium were obtained.
  • Aqueous electrolyte composition comprising
  • Aqueous electrolyte composition comprising

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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 (12)

  1. Composition d'électrolyte pour le dépôt d'un alliage de cuivre quaternaire sur un substrat, comprenant au moins du cuivre, de l'étain et du zinc sous forme des ions de ceux-ci ainsi que des ions d'un métal qui est sélectionné dans le groupe composé d'indium, de gallium et de thallium, dans lequel la composition d'électrolyte comprend 1 à 30 g/l de cuivre, 0,4 à 20 g/l de zinc et 1 à 40 g/l d'étain.
  2. Composition d'électrolyte selon la revendication 1, comprenant un métal du groupe composé d'indium, de gallium et de thallium dans une concentration comprise entre 0,1 et 10 g/l.
  3. Composition d'électrolyte selon l'une des revendications précédentes, en outre comprenant du cyanure dans une concentration comprise entre 1 et 100 g/l.
  4. Composition d'électrolyte selon l'une des revendications précédentes, comprenant au moins un agent complexant pour les métaux contenus dans la composition d'électrolyte.
  5. Composition d'électrolyte selon la revendication 4, dans lequel l'agent complexant est sélectionné dans le groupe composé d'acide nitrilotriacétique (NTA), d'acide éthylènediaminetétracétique (EDTA), d'acide diéthylènetriaminepentacétique (DTPA), de Dequest®, d'un dérivé ou d'un sel d'acide D-gluconique ou de mélanges de ceux-ci.
  6. Composition d'électrolyte selon l'une des revendications précédentes, comprenant un hydroxyde alcalin ou un hydroxyde d'ammonium.
  7. Composition d'électrolyte selon l'une des revendications précédentes, en outre comprenant un composé du groupe composé d'acide éthylènediaminetétramethylphosphonique (EDTMPA), d'acide 1-hydroxyéthylidènediphosphonique (HEDP) ou de sels de ceux-ci.
  8. Composition d'électrolyte selon l'une des revendications précédentes, en outre comprenant de l'acide glycolique.
  9. Composition d'électrolyte selon l'une des revendications précédentes, comprenant un agent de surface.
  10. Procédé de dépôt d'un alliage de cuivre quaternaire sur un substrat, comprenant les étapes de procédé de:
    - mettre le substrat en contact avec une composition d'électrolyte qui comprend au moins 1 à 30 g/l de cuivre, 1 à 40 g/l d'étain et 0,4 à 20 g/l de zinc sous forme des ions de ceux-ci ainsi que des ions d'un métal sélectionné dans le groupe composé d'indium, de gallium et de thallium ;
    - appliquer une tension entre le substrat et une contre-électrode pour le dépôt galvanique d'une couche en alliage quaternaire sur le substrat.
  11. Procédé selon la revendication 10, dans lequel on détermine une densité de courant comprise entre 0,05 et 5 A/dm2 pour le dépôt de la couche en alliage.
  12. Couche en alliage de cuivre quaternaire déposé par placage électrolytique, dans lequel l'alliage comprend 52 à 55 % en poids de cuivre, 23 à 35 % en poids d'étain, 5 à 13 % en poids de zinc ainsi que 4 à 12 % en poids d'un métal sélectionné dans le groupe composé d'indium, de gallium et de thallium.
EP20060025184 2006-12-06 2006-12-06 Composition d'un électrolyte et méthode de dépôt d'alliages quaternaires de cuivre Expired - Fee Related EP1930478B1 (fr)

Priority Applications (1)

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EP1930478A1 EP1930478A1 (fr) 2008-06-11
EP1930478B1 true EP1930478B1 (fr) 2013-06-19

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3150744A1 (fr) 2015-09-30 2017-04-05 COVENTYA S.p.A. Bain d'électrodéposition pour le dépôt électrochimique d'un alliage cu-sn-zn-pd, procédé de dépôt électrochimique de cet alliage, substrat comprenant ledit alliage et utilisations de ce substrat

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT514427B1 (de) 2013-07-05 2015-01-15 W Garhöfer Ges M B H Ing Elektrolytbad sowie damit erhältliche Objekte bzw. Artikel
AT514818B1 (de) 2013-09-18 2015-10-15 W Garhöfer Ges M B H Ing Abscheidung von Cu, Sn, Zn-Beschichtungen auf metallischen Substraten
ITUB20152876A1 (it) * 2015-08-05 2017-02-05 Bluclad S R L Leghe stagno/rame contenenti palladio, metodo per la loro preparazione e loro uso.
EP3377505A2 (fr) * 2015-11-19 2018-09-26 Qatar Foundation For Education Science And Community Development Phosphonates de métaux de transition complexes
EP3540097A1 (fr) 2018-03-13 2019-09-18 COVENTYA S.p.A. Produits galvanisés et bain électrolytique approprié pour fournir de tels produits
FR3112559A1 (fr) * 2020-07-17 2022-01-21 Aveni Electrolyte et dépôt d’une couche barrière au cuivre dans un procédé Damascène
FR3118067B1 (fr) * 2020-12-18 2023-05-26 Linxens Holding Procédé de dépôt d’un alliage de bronze sur un circuit imprimé et circuit imprimé obtenu par ce procédé

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CH626657A5 (fr) * 1980-03-17 1981-11-30 Aliprandini P
US4389286A (en) * 1980-07-17 1983-06-21 Electrochemical Products, Inc. Alkaline plating baths and electroplating process
EP1091023A3 (fr) * 1999-10-08 2003-05-14 Shipley Company LLC Composition d'alliage et procédé de plaquage
US20050067297A1 (en) * 2003-09-26 2005-03-31 Innovative Technology Licensing, Llc Copper bath for electroplating fine circuitry on semiconductor chips
US20080078484A1 (en) * 2004-09-23 2008-04-03 Middlesex Silver Co. Limited Copper-Boron Master Alloy And Its Use In Making Silver-Copper Alloys
FI119038B (fi) * 2005-05-13 2008-06-30 Luvata Oy Menetelmä suprajohtavan elementin valmistamiseksi

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3150744A1 (fr) 2015-09-30 2017-04-05 COVENTYA S.p.A. Bain d'électrodéposition pour le dépôt électrochimique d'un alliage cu-sn-zn-pd, procédé de dépôt électrochimique de cet alliage, substrat comprenant ledit alliage et utilisations de ce substrat

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