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EP0651071B1 - Procédé pour la production de pièces avec un revêtement résistant à l'usure - Google Patents

Procédé pour la production de pièces avec un revêtement résistant à l'usure Download PDF

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Publication number
EP0651071B1
EP0651071B1 EP94116862A EP94116862A EP0651071B1 EP 0651071 B1 EP0651071 B1 EP 0651071B1 EP 94116862 A EP94116862 A EP 94116862A EP 94116862 A EP94116862 A EP 94116862A EP 0651071 B1 EP0651071 B1 EP 0651071B1
Authority
EP
European Patent Office
Prior art keywords
copper
tin
resistant
layer
wear
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
EP94116862A
Other languages
German (de)
English (en)
Other versions
EP0651071A1 (fr
Inventor
Heinz-Günther Dr.(Ing.) Schenzel
Thomas Engert (Dipl.-Ing.)
Uwe Dr.Rer. Nat.(Dipl.-Phys.) Beck
Georg Prof. Dr. Rer. Nat.(Dipl.-Phys.) Reiners
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.)
Evonik Operations GmbH
Original Assignee
Degussa 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 Degussa GmbH filed Critical Degussa GmbH
Publication of EP0651071A1 publication Critical patent/EP0651071A1/fr
Application granted granted Critical
Publication of EP0651071B1 publication Critical patent/EP0651071B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • C23C28/3225—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only with at least one zinc-based layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates

Definitions

  • the invention relates to the process for the production of workpieces and objects made of non-corrosion-resistant metals and metal alloys which are coated with wear-resistant, non-metallic coatings of nitrides, carbides, borides, oxides or silicides of the elements of subgroup 4 to 6 of the periodic table, and in which a corrosion-resistant intermediate layer is arranged between the workpiece surface and the coating.
  • metals and metal alloys which are not very corrosion-resistant, with hard, wear-resistant and sometimes also decorative coatings made of nitrides, carbides, borides, oxides and silicides of the elements of the 4th to 6th subgroup of Periodic table, such as titanium, zirconium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten. These coatings are applied using the so-called PVD process (physical vapor deposition). Layers of titanium nitride and titanium carbide are preferred.
  • the coatings produced in this way have the disadvantage that they are brittle, porous and micro-cracked. Because of their stalk-like growth, these layers have a high so-called pinhole density. As a result, they do not offer good corrosion protection for the underlying material, especially since these layers separate behave in an electrochemically inert manner so that the less noble substrates are dissolved in a corrosive manner.
  • electroplated copper-tin alloys as corrosion-resistant coatings is also known from "Ullmanns Encyklopadie der Technischen Chemie, 4th edition, vol. 12, pages 190 to 194".
  • This object is achieved according to the invention in that an intermediate layer of a copper-tin alloy with 45 to 80% by weight of copper, 10 to 55% by weight of tin and 0 to 15% by weight of zinc is first electroplated on the objects and then the wear layer is by means of a PVD process is applied.
  • Alloys are preferably applied as the intermediate layer, which consist of 45 to 65% by weight of copper and 35 to 55% by weight of tin, or of 50 to 80% by weight of copper, 10 to 35% by weight of tin and 1 to 15% by weight.
  • Zinc exist.
  • These layers are very corrosion-resistant and have an electrochemical potential that comes close to that of brass and bronze alloys, which are often used as base materials. They also have a high hardness of around 600 HV and therefore offer a good transition between the PVD layers (1000-1500 HV) and the base material. Softer intermediate layers, like Palladium-nickel, too, promoted chipping of the PVD layers when subjected to mechanical stress.
  • Copper-tin alloy layers can be electroplated inexpensively on practically all base materials, whereby closed layers with uniform layer thicknesses are obtained even with complicated geometries.
  • Baths such as those described in DE-PS 33 39 541 have proven successful. They contain 1 to 60 g / l copper as copper cyanide, 7 to 30 g / l tin in the form of alkali tannate, 0.1 to 100 g / l of a complexing agent, 1 to 50 g / l free alkali metal cyanide, 1 to 50 g / l Alkali hydroxide, up to 50 g / l alkali carbonate and 0.05 to 5 g / l of an organic fatty acid compound or a naphthol.
  • the intermediate layers are preferably applied with a layer thickness between 0.1 and 10 ⁇ m.
  • the copper-tin or copper-tin-zinc layers can also take on the function of leveling and gloss formation.
  • a copper-tin-zinc layer is preferably used to achieve leveling and gloss formation.
  • Acidic copper electrolytes are usually used for leveling and glossing of rack goods. In the case of drumware, the acidic copper electrolytes can only level off but no gloss formation. With an electrolyte for the deposition of copper-tin-zinc layers, leveling and gloss formation are possible both for rack goods and for drum goods.
  • the copper-tin or copper-tin-zinc layers can be galvanically coated with a 0.1 ⁇ m thick gold layer .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Physical Vapour Deposition (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Laminated Bodies (AREA)

Claims (4)

  1. Procédé de production de pièces et objets de métaux et d'alliages métalliques non résistant à la corrosion, qui sont enduits de revêtements non métalliques, résistant à l'usure composés de nitrures, carbures, borures, oxydes de siliciures d'éléments du 4ème au 6ème groupe secondaire du système périodique et pour lesquels entre la surface de la pièce et le revêtement est placée une couche intermédiaire anticorrosion,
    caractérisé en ce qu'
    on applique d'abord sur les objets par galvanisation une couche intermédiaire d'un alliage d'étain et de cuivre comportant jusqu'à 80 % en poids de cuivre, 10 à 55 % en poids d'étain et de 0 à 15 % en poids de zinc et ensuite la couche d'usure au moyen d'un procédé PVD.
  2. Procédé selon la revendication 1,
    caractérisé en ce que
    comme couche intermédiaire on applique par galvanisation un alliage d'étain et de cuivre ayant 45 à 65 % en poids de cuivre et 35 à 55 % en poids d'étain.
  3. Procédé selon la revendication 1,
    caractérisé en ce que
    comme couche intermédiaire on applique par galvanisation un alliage de 50 à 80 % en poids de cuivre, 10 à 35 % en poids d'étain et 1 à 15 % en poids de zinc.
  4. Procédé selon les revendications 1 à 3,
    caractérisé en ce que
    comme couche d'usure on applique du nitrure de titane ou du carbure de titane.
EP94116862A 1993-10-27 1994-10-26 Procédé pour la production de pièces avec un revêtement résistant à l'usure Expired - Lifetime EP0651071B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4336664 1993-10-27
DE4336664A DE4336664A1 (de) 1993-10-27 1993-10-27 Werkstücke aus nichtkorrosionsbeständigen Metallen mit nach dem PVD-Verfahren aufgebrachten Überzügen

Publications (2)

Publication Number Publication Date
EP0651071A1 EP0651071A1 (fr) 1995-05-03
EP0651071B1 true EP0651071B1 (fr) 1997-07-30

Family

ID=6501152

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94116862A Expired - Lifetime EP0651071B1 (fr) 1993-10-27 1994-10-26 Procédé pour la production de pièces avec un revêtement résistant à l'usure

Country Status (4)

Country Link
US (1) US5494565A (fr)
EP (1) EP0651071B1 (fr)
JP (1) JP3347898B2 (fr)
DE (2) DE4336664A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1408141B1 (fr) * 2002-10-11 2014-12-17 Enthone Inc. Methode et électrolyte pour la deposition galvanique des bronzes
US7156904B2 (en) * 2003-04-30 2007-01-02 Mec Company Ltd. Bonding layer forming solution, method of producing copper-to-resin bonding layer using the solution, and layered product obtained thereby
US7029761B2 (en) * 2003-04-30 2006-04-18 Mec Company Ltd. Bonding layer for bonding resin on copper surface
US20060260948A2 (en) * 2005-04-14 2006-11-23 Enthone Inc. Method for electrodeposition of bronzes
AT514818B1 (de) * 2013-09-18 2015-10-15 W Garhöfer Ges M B H Ing Abscheidung von Cu, Sn, Zn-Beschichtungen auf metallischen Substraten
US9586381B1 (en) * 2013-10-25 2017-03-07 Steriplate, LLC Metal plated object with biocidal properties

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0571796A1 (fr) * 1992-05-27 1993-12-01 Linde Aktiengesellschaft Couche de protection superficielle et procédé pour sa préparation

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1970549A (en) * 1932-10-18 1934-08-21 City Auto Stamping Co Process of electroplating bronze
US4036602A (en) * 1975-11-26 1977-07-19 Chromalloy American Corporation Diffusion coating of magnesium in metal substrates
DE3339541C2 (de) * 1983-11-02 1986-08-07 Degussa Ag, 6000 Frankfurt Alkalisch-cyanidisches Bad zur galvanischen Abscheidung von Kupfer-Zinn-Legierungsüberzügen
US4557980A (en) * 1984-08-21 1985-12-10 Martin Processing, Inc. Radiation curable coating for film structure
JPS61119668A (ja) * 1984-11-16 1986-06-06 Seiko Instr & Electronics Ltd 亜鉛合金製携帯時計ケ−スの製造方法
JPH0816262B2 (ja) * 1987-01-08 1996-02-21 住友電気工業株式会社 電 線
US5192410A (en) * 1988-07-28 1993-03-09 Nippon Steel Corporation Process for manufacturing multi ceramic layer-coated metal plate
DE3829007A1 (de) * 1988-08-26 1990-03-01 Multi Arc Gmbh Verfahren zur plasmabeschichtung von gegenstaenden mit einem hartstoff
JPH03215658A (ja) * 1990-01-19 1991-09-20 Citizen Watch Co Ltd 装飾被膜の構造
FR2688234B1 (fr) * 1992-03-03 1995-03-24 Sarrel Procede de protection d'une piece en argent ou revetue d'argent.

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0571796A1 (fr) * 1992-05-27 1993-12-01 Linde Aktiengesellschaft Couche de protection superficielle et procédé pour sa préparation

Also Published As

Publication number Publication date
JPH07216560A (ja) 1995-08-15
DE4336664A1 (de) 1995-05-04
US5494565A (en) 1996-02-27
EP0651071A1 (fr) 1995-05-03
DE59403544D1 (de) 1997-09-04
JP3347898B2 (ja) 2002-11-20

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