WO2004027120A1 - Couches noires - Google Patents

Couches noires Download PDF

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Publication number
WO2004027120A1
WO2004027120A1 PCT/EP2003/010302 EP0310302W WO2004027120A1 WO 2004027120 A1 WO2004027120 A1 WO 2004027120A1 EP 0310302 W EP0310302 W EP 0310302W WO 2004027120 A1 WO2004027120 A1 WO 2004027120A1
Authority
WO
WIPO (PCT)
Prior art keywords
copper
compound
bismuth
tin
ionogenic
Prior art date
Application number
PCT/EP2003/010302
Other languages
German (de)
English (en)
Inventor
Klaus Leyendecker
Günther WIRTH
Klaus Reissmüller
Franz Gassner
Original Assignee
Omg Galvanotechnik Gmbh
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Omg Galvanotechnik Gmbh filed Critical Omg Galvanotechnik Gmbh
Priority to AU2003270208A priority Critical patent/AU2003270208A1/en
Publication of WO2004027120A1 publication Critical patent/WO2004027120A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C12/00—Alloys based on antimony or bismuth
    • 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

Definitions

  • the present invention relates to dark bismuth-tin-copper alloys, ionic bismuth, tin and copper compounds containing electrolyte compositions and a method for producing the alloys.
  • the invention also relates to the use of the alloys for decorative and functional purposes.
  • the black dyeing of copper, brass or bronze with a solution of copper nitrate (so-called “black brandy"), with a solution of potassium hydroxide and potassium persulfate (so-called “persulfate pickling") or with a selenium-containing dyeing process
  • the black dyeing of iron with a solution is known Arsenic trioxide and iron sulfate in hydrochloric acid (so-called “arsenic staining") and the blackening of silver by the so-called "sulfur liver staining”.
  • electrolytic processes for producing layers with a gray or black intrinsic color are known, such as black nickel, black zinc, black chrome, black ruthenium or tin-nickel alloys.
  • EP-B-0 808 921 describes the electrolytic production of a Sn-Cu-Pd alloy with a white luster and the use thereof for decorative purposes.
  • JP-A-59023895 describes the electrolytic generation of a black coating from a ternary Sn-Ni-Cu alloy.
  • the invention was therefore based on the object of providing a coating material and a method for its production in which the problems mentioned can be avoided.
  • US-A-5, 368,814 describes a lead-free solder with a low solidus line, which mainly consists of bismuth and tin (ie in each case approx. 50%, based on the total amount of bismuth and tin) and in addition an effective amount of one contains physical and mechanical properties reinforcing third component, such as indium, copper, silver or combinations thereof (eg 4% copper).
  • the alloy is described as a particularly useful joining material in microelectronic applications.
  • a scratch-resistant bronze alloy based on copper as the main component which also contains 1-13% by weight of tin, not more than 18% by weight of zinc, 0.5-6% by weight of bismuth, 0.05-3% by weight of antimony contains as 1% by weight of phosphorus and less than 4% by weight of lead is described in US-A-6,419,766.
  • Copper-based casting alloys containing small amounts of bismuth and tin e.g. in US-A-5,487,867 (0.1-7 wt% bismuth and optionally 2-6 wt% tin), US-A-4,789,094 (1.5-7 wt% bismuth and 1-12 wt% tin ) and in US-A-5,330,712 (0.1-7 wt% bismuth and up to 16 wt% tin).
  • the invention thus relates to an alloy comprising a) 1-15% by weight tin, b) 19-60% by weight copper, c) 30-80% by weight bismuth and d) 0-10% by weight. % oxidic oxygen and its use for decorative or functional purposes.
  • the invention further relates to a coated article comprising a substrate and a layer of an alloy according to the present invention.
  • the invention further relates to an electrolyte composition for producing the alloy according to the invention, comprising a) at least one ionogenic tin compound, b) at least one ionogenic copper compound, and c) at least one ionogenic bismuth compound.
  • the invention also relates to an electrolytic method for producing dark alloy layers, comprising the steps a) providing a substrate to be coated as a cathode, b) providing an electrolyte composition according to the invention, c) electrolytically depositing a dark alloy layer according to the invention on the substrate, and d ) optionally aftertreatment of the dark alloy layer produced in step c).
  • the alloy according to the invention comprises 1-15% tin, 19-60% copper, 30-80% bismuth and 0-10% oxidic oxygen. All percentages based on the alloy are intended to mean% by weight below.
  • the alloys of the present invention are characterized by a dark color.
  • the dark color can vary depending on the exact composition of the alloy between brown, gray, dark blue, gray-blue and black.
  • the color can also be varied by increasing the oxygen content (e.g. gray / anthracite: 0% O; dark gray - black: 1 - 2% O).
  • alloys of the present invention can also contain small amounts of other metals such as iron or aluminum.
  • Small amounts are to be understood here as meaning amounts which are not more than 5% by weight, preferably 2% by weight and particularly preferably 0.5% by weight.
  • the alloy consists essentially of 1-15% tin, 19-60% copper, 30-80% bismuth and 0-10% oxidic oxygen and inevitable impurities.
  • contaminants can e.g. impurities resulting from the manufacturing process or the starting materials used, such as nitrogen, phosphorus, carbon.
  • these contaminants are present in the alloy in amounts that are no more than 3.0% by weight.
  • impurities are preferably present in amounts which are not more than 1.0% by weight and particularly preferably not more than 0.5% by weight.
  • the amount of inevitable impurities in the alloys of the present invention is about 0 to about 3.0% by weight, preferably 0 to 1.0% by weight, and particularly preferably 0 to 0.5% by weight.
  • the alloy is essentially free of one or more elements selected from nickel, lead, selenium, chromium and antimony. It is particularly preferred that the alloy be substantially free of at least two elements, more preferably free of at least three of these elements, and most preferably free of all of the elements listed.
  • the expression "essentially free of” means that the amount of these elements in the alloy is less than 2% by weight.
  • the amount is preferably less than 1% by weight, particularly preferably less than 0.5% by weight. %, and most preferably less than 0.1% by weight.
  • the alloys of this embodiment have the additional advantage that they contain no toxic or allergy-causing elements and accordingly the use of toxic or allergy-causing substances in the production of the alloys can be avoided.
  • the alloy is essentially free of one or more elements selected from silver, gold, palladium, platinum, ruthenium, rhodium or iridium.
  • the expression "essentially free of” is as defined above.
  • the alloys of this embodiment have the additional advantage that they are particularly inexpensive to manufacture.
  • the alloy is essentially free of zinc, the expression “essentially free of” as defined above.
  • the alloys of this embodiment are distinguished by a particularly pronounced resistance to mechanical stress.
  • the amount of tin is 1-15%, preferably 1-10% and particularly preferably 1-2%.
  • the amount of copper is 19-60%, preferably 29-60% and especially 39-60%.
  • the amounts of bismuth are 30-80%, especially 35-70% and particularly preferably 39-60%.
  • the metals forming the alloy i.e. Tin, copper and bismuth, as well as any other metals that may be present, can also be in oxidic form. Accordingly, the amount of oxidic oxygen in the alloys according to the invention is 0-10% by weight, preferably 0-5% and particularly preferably 0-2%.
  • the alloys of the invention are obtainable by electrodeposition from an electrolytic solution. First, a substrate to be coated is provided and switched as a cathode.
  • the substrate is not limited and can consist of an electrically conductive but also an electrically non-conductive material. In the latter case, it is preferred to first coat the material to be coated with an electrically conductive material, for example a metal such as palladium or copper. Tin, copper, zinc or alloys of these metals, such as bronze or brass, are suitable as electrically conductive substrates.
  • an electrically conductive material for example a metal such as palladium or copper. Tin, copper, zinc or alloys of these metals, such as bronze or brass, are suitable as electrically conductive substrates.
  • plastics, ceramic materials or glass are suitable as electrically non-conductive substrates, for example.
  • the alloy components are provided in the form of an electrolyte composition which contains at least one ionogenic tin compound, at least one ionogenic copper compound and at least one ionogenic bismuth compound.
  • the electrolyte composition can have a suitable solvent or solvent mixture.
  • An aqueous electrolyte composition is particularly preferably used.
  • the ionic tin, copper and bismuth compounds are in no way limited as long as they are suitable for electrolytic deposition. Typically, preference is given to those compounds which can be dissolved in the selected solvent.
  • Compounds in which tin is present in oxidation states +2 and / or +4 are preferably used as the tin compound.
  • Compounds in which copper is present in oxidation states +1 and / or +2 are preferably used as the copper compound.
  • Compounds in which bismuth is present in oxidation states +3 and / or +5 are preferably used as bismuth compounds.
  • the ionogenic tin compound is particularly preferably selected from tin sulfates, tin chlorides, tin sulfonates, tin oxalates, sodium stannates, potassium stannates and mixtures thereof.
  • the ionogenic copper compound is preferably selected from copper sulfates, copper chlorides, copper sulfonates, copper oxalates, copper oxides and copper cyanides, complex copper compounds and mixtures thereof.
  • the ionic bismuth compound is preferably selected from bismuth nitrates, bismuth carbonates, bismuth citrates, complex bismuth compounds and mixtures thereof.
  • Usual additives can be added to the electrolyte composition as required. These can be auxiliaries for adjusting the pH, such as alkalis (for example potassium, sodium or ammonium hydroxide), inorganic acids (for example hydrochloric acid, sulfuric acid, phosphoric acid or boric acid) and their salts, buffers or organic acids (for example hydroxycarboxylic acids, Citric acid or its salts) act.
  • alkalis for example potassium, sodium or ammonium hydroxide
  • inorganic acids for example hydrochloric acid, sulfuric acid, phosphoric acid or boric acid
  • buffers or organic acids for example hydroxycarboxylic acids, Citric acid or its salts
  • Conductive salts e.g. alkali salts of hydrochloric acid, sulfuric acid, phosphoric acid
  • complexing agents e.g. EDTA
  • wetting agents e.g. anionic, cationic or zwitterionic surfactants
  • brightening agents e.g. organic nitrogen
  • the electrolyte compositions can be selected, for example, from alkaline (cyanide-containing or cyanide-free), acidic or neutral electrolyte compositions.
  • An alkaline, cyanide-containing electrolyte composition according to the invention can, for example
  • g / l metal compound in the present invention refers to the amount of metal atom in the compound in g, counterions not being included.
  • the copper compound is preferably selected from sulfates, chlorides, sulfonates, oxalates or oxides.
  • Potassium or sodium stannate is preferably used as the tin compound.
  • a nitrate, carbonate or citrate compound is preferably used as the bismuth compound.
  • cyanide compound Sodium or potassium cyanide is preferably used as the cyanide compound.
  • Resistant surfactants e.g. cationic surfactants
  • polyhydric alcohols e.g. Glycol or organic nitrogen compounds, e.g. polymeric reaction products of epichlorohydrin and amines
  • organic nitrogen compounds e.g. polymeric reaction products of epichlorohydrin and amines
  • the pH of the electrolyte composition is preferably adjusted to a strongly alkaline range (e.g. pH 11-13).
  • An alkaline, cyanide-free electrolyte composition according to the invention can, for example
  • Sodium or potassium stannate is preferably used as the tin compound.
  • a sulfate, chloride, oxalate or oxide compound is preferably used as the copper compound.
  • a nitrate, citrate or carbonate compound is preferably used as the bismuth compound.
  • Resistant surfactants e.g. cationic surfactants
  • polyhydric alcohols e.g. Glycol
  • organic nitrogen compounds e.g. polymeric reaction products of epichlorohydrin and amines
  • organic acids and their salts phosphonic acids, phosphonates, gluconates, glucoheptonic acids, glucoheptonates and ethylenediaminetetraacetic acid can be used as complexing agents.
  • the pH of the electrolyte composition is preferably adjusted to be strongly alkaline (e.g. pH 11-13).
  • a neutral electrolyte composition according to the invention can, for example
  • a sulfate, chloride, sulfonate, oxalate or oxide compound is preferably used as the copper compound.
  • a sulfate or chloride compound or sodium or potassium stannate is preferably used as the tin compound.
  • a nitrate, citrate or carbonate compound is preferably used as the bismuth compound.
  • Tetrasodium pyrophosphate for example, is suitable as a complexing agent.
  • Resistant surfactants e.g. cationic surfactants
  • polyhydric alcohols e.g. Glycol
  • organic nitrogen compounds e.g. polymeric reaction products of epichlorohydrin and amines
  • the pH of the electrolyte composition is preferably adjusted to a neutral range (pH 6-8).
  • a further neutral electrolyte composition according to the invention can, for example
  • Sodium or potassium stannate is preferably used as the tin compound.
  • a sulfate, chloride, oxalate or oxide compound is preferably used as the copper compound.
  • a nitrate, citrate or carbonate compound is preferably used as the bismuth compound.
  • Resistant surfactants e.g. cationic surfactants
  • polyhydric alcohols e.g. Glycol or organic nitrogen compounds, e.g. polymeric reaction products of epichlorohydrin and amines
  • organic nitrogen compounds e.g. polymeric reaction products of epichlorohydrin and amines
  • organic acids and their salts phosphonic acids, phosphonates, gluconates, glucoheptonic acids, glucoheptonates and ethylenediaminetetraacetic acid can be used as complexing agents.
  • the pH of the electrolyte composition is preferably adjusted to a neutral range (pH 6-8).
  • An acidic electrolyte composition according to the invention can, for example
  • a sulfate, chloride, sulfonate, oxalate or oxide compound is preferably used as the copper compound.
  • a sulfate or chloride compound or sodium or potassium stannate is preferably used as the tin compound.
  • a nitrate, citrate or carbonate compound is preferably used as the bismuth compound.
  • the pH of the electrolyte composition is preferably adjusted to an acidic range (e.g. pH 1 to 5).
  • the ratio of the metals in the alloy can be influenced in a manner known to those skilled in the art by the ratio of the metals in the electrolyte composition, by the type and amount of any further additives, and by the deposition parameters, such as current density, temperature or flow rate.
  • Anodes made of insoluble materials such as platinized titanium or graphite, can be used as the counter electrode.
  • Soluble anodes made from bismuth, copper, tin or alloys made from these metals are also possible.
  • the temperature during the electrolytic deposition is preferably selected so that it is in a range from approximately 20-70 ° C., preferably in a range from 50-60 ° C.
  • the current density in the electrolyte solution is preferably set to a range of approximately 0.1-5 A / dm 2 , preferably 0.2-0.5 A / dm 2 .
  • the deposition rates are preferably in a range of approximately 0.01-0.5 ⁇ m / minute, preferably 0.05-0.1 // m / minute.
  • the process can produce layer thicknesses of 0.005 - 5 ⁇ m, preferably 0.5 - 1 ⁇ m.
  • the alloys can optionally be subjected to a post-treatment step in order to further stabilize the color of the alloy.
  • the alloy layer is treated with an oxygen-releasing substance.
  • the coated substrate is preferably immersed in a solution of this substance.
  • Oxygen-releasing substances are suitable, for example, peroxide or persulfate compounds, such as hydrogen peroxide or ammonium persulfate.
  • the concentration of the aftertreatment solution is preferably 0.01 g / l - 5 g / l.
  • Typical diving times are between 1 and 20 minutes.
  • the alloys according to the invention have a characteristic blue-gray to black color and are suitable for use for decorative purposes, e.g. as a covering material for clothing accessories, such as buttons or zippers.
  • the coatings are characterized by good resistance to wear due to mechanical stress or cleaning.
  • the dark alloy layers can also be used for functional purposes, e.g. can be used as absorbent layers in solar applications.
  • the alloys are also free of toxic or expensive substances and offer further advantages in terms of economy and usability.
  • An alkaline, cyanide-containing electrolyte has the following composition:
  • a brown-black alloy layer can be deposited with this electrolyte.
  • the color can be additionally stabilized with the after-treatment listed under Example 6.
  • An alkaline electrolyte has the following composition
  • a blue-gray-black alloy layer can be deposited with this electrolyte.
  • the deposition rate was approximately 0.05 ⁇ m / minute.
  • the color can be additionally stabilized with the after-treatment listed under Example 6.
  • a neutral electrolyte has the following composition
  • a black alloy layer can be deposited with this electrolyte.
  • the deposition rate was approximately 0.05 ⁇ m / minute.
  • the color can be additionally stabilized with the after-treatment listed under Example 6.
  • An acidic electrolyte has the following composition
  • Example 5 At 60 ° C and 0.5 A / dm 2 , a black alloy layer can be deposited with this electrolyte.
  • the pH of the electrolytes was 2.5 +/- 0.5.
  • the color can be additionally stabilized with the aftertreatment listed under Example 5.
  • Example 5
  • Another neutral electrolyte has the following composition
  • a gray, anthracite-colored alloy layer can be deposited with this electrolyte.
  • the deposition rate was approximately 0.05 ⁇ m / minute. There was no further stabilization of the color by post-treatment.
  • the aftertreatment was carried out with

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

L'invention concerne un alliage qui comprend 1 - 15 % d'étain, 19 60 % de cuivre et 30 - 80 % de bismuth, un procédé électrolytique et des compositions électrolytiques pour la production d'un tel alliage, et les utilisations de ce dernier.
PCT/EP2003/010302 2002-09-17 2003-09-16 Couches noires WO2004027120A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003270208A AU2003270208A1 (en) 2002-09-17 2003-09-16 Dark layers

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10243139.6 2002-09-17
DE2002143139 DE10243139A1 (de) 2002-09-17 2002-09-17 Dunkle Schichten

Publications (1)

Publication Number Publication Date
WO2004027120A1 true WO2004027120A1 (fr) 2004-04-01

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AU (1) AU2003270208A1 (fr)
DE (1) DE10243139A1 (fr)
WO (1) WO2004027120A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008098666A1 (fr) * 2007-02-14 2008-08-21 Umicore Galvanotechnik Gmbh Électrolyte cuivre-étain et procédé de dépôt de couches de bronze
WO2010003621A1 (fr) * 2008-07-10 2010-01-14 Umicore Galvanotechnik Gmbh Electrolyte cuivre-étain amélioré et procédé de dépôt de couches de bronze
WO2015000010A1 (fr) * 2013-07-05 2015-01-08 Ing. W. Garhöfer Gesellschaft M.B.H. Bain d'électrolyte ainsi que objets ou articles qui sont revêtus à l'aide du bain
WO2015091854A3 (fr) * 2013-12-19 2015-09-11 Schlenk Metallfolien Gmbh & Co. Kg Liquides électro-conducteurs à base de complexes métal-diphosphonate

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US7157152B2 (en) * 2002-06-13 2007-01-02 Nihon New Chrome Co., Ltd. Copper-tin-oxygen alloy plating
US7867625B2 (en) 2002-06-13 2011-01-11 Nihon New Chrome Co., Ltd. Copper-tin-oxygen alloy plating

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008098666A1 (fr) * 2007-02-14 2008-08-21 Umicore Galvanotechnik Gmbh Électrolyte cuivre-étain et procédé de dépôt de couches de bronze
EP1961840A1 (fr) * 2007-02-14 2008-08-27 Umicore Galvanotechnik GmbH Electrolyte de cuivre-étain et procédé pour le dépôt de couches de bronze
US8211285B2 (en) 2007-02-14 2012-07-03 Umicore Galvanotechnik Gmbh Copper-tin electrolyte and method for depositing bronze layers
WO2010003621A1 (fr) * 2008-07-10 2010-01-14 Umicore Galvanotechnik Gmbh Electrolyte cuivre-étain amélioré et procédé de dépôt de couches de bronze
WO2015000010A1 (fr) * 2013-07-05 2015-01-08 Ing. W. Garhöfer Gesellschaft M.B.H. Bain d'électrolyte ainsi que objets ou articles qui sont revêtus à l'aide du bain
WO2015091854A3 (fr) * 2013-12-19 2015-09-11 Schlenk Metallfolien Gmbh & Co. Kg Liquides électro-conducteurs à base de complexes métal-diphosphonate

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