EP1117856B1 - Procede permettant de recouvrir des pieces - Google Patents

Procede permettant de recouvrir des pieces Download PDF

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Publication number
EP1117856B1
EP1117856B1 EP99968252A EP99968252A EP1117856B1 EP 1117856 B1 EP1117856 B1 EP 1117856B1 EP 99968252 A EP99968252 A EP 99968252A EP 99968252 A EP99968252 A EP 99968252A EP 1117856 B1 EP1117856 B1 EP 1117856B1
Authority
EP
European Patent Office
Prior art keywords
coating
particles
alloy
metallic
embedded
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
EP99968252A
Other languages
German (de)
English (en)
Other versions
EP1117856A1 (fr
Inventor
Klaus Leo Wilbuer
Hans Hermann Urlberger
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 GmbH
Original Assignee
Enthone OMI Deutschland 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 Enthone OMI Deutschland GmbH filed Critical Enthone OMI Deutschland GmbH
Priority to EP99968252A priority Critical patent/EP1117856B1/fr
Publication of EP1117856A1 publication Critical patent/EP1117856A1/fr
Application granted granted Critical
Publication of EP1117856B1 publication Critical patent/EP1117856B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C25D15/02—Combined electrolytic and electrophoretic processes with charged materials
    • 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
    • C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt

Definitions

  • the invention relates to a method for coating workpieces, wherein a functional coating is deposited electrolytically, which in particular is corrosion and wear resistant, and that as at least phosphor and nickel-containing alloy is deposited from an electrolyte.
  • a functional coating is deposited electrolytically, which in particular is corrosion and wear resistant, and that as at least phosphor and nickel-containing alloy is deposited from an electrolyte.
  • the invention also relates to a covering in this regard.
  • metallic coatings are used primarily for functional coating of workpieces to ensure that the Use stress mechanisms that occur through suitable Surface properties, such as hardness, wear resistance, Friction or thermal and chemical resistance, invoice too wear.
  • Such protective coatings are usually produced by electroplating.
  • electrolytic deposition in which an electrocrystallization takes place, and on the other hand the electroless metal deposition without external current, in which it is a simple immersion process without an external power source and anodes is.
  • the metal deposition can be metallic in both processes as well as non-metallic workpiece surfaces. by virtue of the external currentless one finds a high degree of contour accuracy during the deposition Deposition is particularly useful when using workpieces with complex geometries very tight tolerances must be observed.
  • the electrolytic In this case, deposition is dependent on the geometry Distribution of local cathode current densities set clear limits.
  • the invention is based on the object of specifying a method for coating workpieces which, with a substantially higher installation rate of elemental phosphorus, enables increased wear resistance and hardness as well as improved corrosion-protection effect.
  • a coating in this regard should be specified.
  • This object is achieved in a generic method of the type mentioned according to the invention characterized in that an at least quaternary alloy with the components nickel, cobalt, tungsten and phosphorus is deposited as a coating, said alloy characterized by a phosphorus content, in particular for improving the corrosion properties 14-21 % By weight is marked, and that non-metallic particles are incorporated into the metallic matrix of the alloy for the purpose of changing the functional properties.
  • Such a method enables due to the electrolytic deposition and the associated reductive systematic reaction at the Interface between electrolyte and workpiece a rate of incorporation of phosphorus the metallic coating between 14 and 21 wt .-%.
  • the invention is also based on the surprising finding that through the common cathodic Deposition of nickel, cobalt, tungsten and phosphorus as well as in these metallic matrix built-in non-metallic particles an alloy coating is formed by a high corrosion resistance and Excellent wear resistance.
  • the cover an alloy with at least one further component, preferably made of Tin, lead, molybdenum, rhenium or vanadium, as a metal deposit cathodic deposit.
  • at least one further component preferably made of Tin, lead, molybdenum, rhenium or vanadium, as a metal deposit cathodic deposit.
  • non-metallic particles to be embedded in the metallic matrix of the coating in particular chemical compounds such as preferably carbides or carbide mixed crystals be used.
  • chemical compounds such as preferably carbides or carbide mixed crystals be used.
  • boron, silicon, Tungsten, vanadium and / or titanium carbide used.
  • particles with a grain size of 0.1 to 1.5 microns are used become.
  • the particles are different Concentrations stored over the course of the thickness of the coating.
  • the Particles added to the electrolyte as a disperse phase and in the galvanic deposition built into the alloy deposit is mainly due to adsorption, electrostatic attraction and due to mechanical inclusion.
  • This will be useful the particles are suspended in the galvanic bath by movement Electrolytes held. In a manner known per se, for example by Stirring or blowing air into the bath, it is possible to remove the particles in the To stay in balance.
  • To change the microporosity of the coating can, it is also useful to change the bath movement Concentration ratios of the particles in the alloy deposit influence.
  • coloring pigments preferably made of titanium dioxide, so that self-colored coatings result, which have a high light and Ensure weather resistance.
  • a corrosion-resistant and wear-resistant coating is also proposed according to the invention, which can be produced in particular by the method described above and is essentially composed of one 0.5 to 2.0 wt% tungsten 1.0 to 2.0 wt% cobalt 15 to 20 wt .-% phosphorus and at least 10 wt% nickel distinguished, with non-metallic particles being embedded in the metallic matrix of the alloy.
  • boron carbide with a volume fraction of 30 to 39% be embedded in the metallic matrix of the coating.
  • a metallic coating is created by galvanic alloy deposition formed from 0.5 to 2.0 wt .-% tungsten, 1.0 to 2.0 wt .-% Cobalt, 15 to 20 wt .-% phosphorus and a remaining proportion of nickel composed.
  • the metallic matrix of this alloy deposit shows also embedded non-metallic particles made of tetraborecarbide. This are during electrocrystallization due to mechanical inclusion, Adsorption or electrostatic attraction near the cathode in the Cover has been installed. For this purpose is in the Electrolytes used the tetraborarbide in the form of a deposition suspended fine powder, the particles having a grain size of 0.1 to 1.5 ⁇ m.
  • the particles are evenly concentrated in suspended in the electrolyte.
  • a differently concentrated Incorporation of the particles over the course of the thickness of the coating can be done by suitable change in the bath movement can be caused.
  • the on the coating formed in this way has a total content of 30 to 39 Vol .-% of incorporated tetraborarbide.
  • the coating Due to the interaction of the components nickel, cobalt, tungsten, Phosphorus and boron carbide, the coating has high durability both against acidic and alkaline corrosion media as well as oxidizing Acids.
  • the salt spray test according to DIN 50 used for corrosion testing 021 resulted for harsher conditions with the addition of copper chloride an exposure of over 485 h with a coating thickness of 60 ⁇ m and a base material made of steel.
  • the coating thus fulfills the requirements according to RAL-RG 660 for level 4/4 hydraulics in pit construction.
  • the coating is also characterized by high wear resistance. With an average roughness depth of approx. 2 to 3 ⁇ m, the Wear resistance according to TABER under abrasive test criteria determined.
  • friction rollers of the type CS-10 came under a bearing load of 9.81 N for use.
  • the coating reached after in the deposition state 10,000 revolutions an average wear value of 2.71 mg / 1000 revolutions, as in particular from the course of the determined wear removal values according to TABER in mg'1000 revolutions above the diagram showing revolutions U in the drawing is.
  • the running-in behavior of the friction rollers was not taken into account.
  • the Wear wear determined is below that for hard chrome coatings in accordance with RAL-RG 660 (1986) provided abrasion resistance of max. 5 mg 1000 Revolutions.
  • electrolytically deposited conventional nickel-phosphorus alloys wear values from 11 to 13 mg / 1000 revolutions, while for electrolessly deposited coatings an average abrasion resistance of 20 to 22 mg / 1000 Revolutions.

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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 Methods And Accessories (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)

Claims (14)

  1. Procédé permettant de recouvrir des pièces, dans lequel un revêtement fonctionnel est déposé. électrolytiquement, qui résiste en particulier à la corrosion et à l'usure et qui est déposé à partir d'un électrolyte comme au moins un alliage à faible teneur en phosphore et en nickel, caractérisé en ce qu'au moins un alliage quaternaire comprenant les composants nickel, cobalt, wolfram et phosphore est déposé comme revêtement, cet alliage étant caractérisé par une teneur en phosphore de 14 à 21 % en poids, en particulier pour améliorer les propriétés relatives à la corrosion, et caractérisé en ce que dans la matrice métallique de l'alliage, des particules non métalliques sont incorporées dans le but de modifier les propriétés fonctionnelles.
  2. Procédé selon la revendication 1, caractérisé en ce que, en fonction de l'utilisation du revêtement, un alliage présentant au moins un autre composant, de préférence l'étain, le plomb, le molybdène, le rhénium ou le vanadium est déposé de manière cathodique en tant que précipité métallique.
  3. Procédé selon l'une quelconque des revendications 1 et 2, caractérisé en ce que, comme particules non métalliques, en particulier des liaisons chimiques sont incorporées dans la matrice métallique du revêtement.
  4. Procédé selon au moins l'une quelconque des revendications 1 à 3 précédentes, caractérisé en ce que les particules non métalliques de carbure ou à cristaux mixtes de carbure sont incorporées dans la matrice métallique du revêtement.
  5. Procédé selon la revendication 4, caractérisé en ce. que du carbure de bore, de silicium, de wolfram, de vanadium et/ou de titane sont utilisés.
  6. Procédé selon l'une ou plusieurs des revendications 1 à 5 précédentes, caractérisé en ce que les particules sont utilisées en une taille de grains de 0,1 à 1,5 µm.
  7. Procédé selon l'une ou plusieurs des revendications 1 à 6 précédentes; caractérisé en ce que les particules sont incorporées en concentrations différentes sur le tracé de l'épaisseur du revêtement.
  8. Procédé selon l'une ou plusieurs des revendications 1 à 7 précédentes, caractérisé en ce que les particules sont ajoutées en phase dispersée aux électrolytes et lors du dépôt galvanique, sont incorporées dans le précipité d'alliage.
  9. Procédé selon l'une ou plusieurs des revendications 1 à 8 précédentes, caractérisé en ce que les particules sont maintenues en suspension dans l'électrolyte en remuant le bain galvanique.
  10. Procédé selon l'une ou plusieurs des revendications 1 à 9 précédentes, caractérisé en ce que la modification de. l'agitation du bain permet d'influer sur le rapport de concentration des particules dans le précipité d'alliage.
  11. Procédé selon l'une ou plusieurs des revendications 1 à 10 précédentes, caractérisé en ce que en outre, des pigments colorants, en particulier d'oxyde de titane, sont incorporés.
  12. Revêtement pouvant être produit en particulier par le procédé selon l'une ou plusieurs des revendications 1 à 11, caractérisé par une composition constituée essentiellement de
    0,5 à 2,0 % en poids de wolfram,
    1,0 à 2,0 % en poids de cobalt,
    15 à 20 % en poids de phosphore et
    au moins 10 % en poids de nickel,
       dans lequel l'alliage de particules non métallique est incorporé dans la matrice métallique.
  13. Revêtement selon la revendication 12, caractérisé en ce que le carbure de bore, en tant que particules non métalliques, est incorporé en un volume de 30 à 39 % dans la matrice métallique.
  14. Revêtement selon la revendication 13, caractérisé en ce que, en fonction de l'utilisation fonctionnelle du revêtement, celui-ci contient un autre composant, de préférence, le zinc, le plomb, le molybdène, le rhénium ou le vanadium.
EP99968252A 1998-09-01 1999-08-28 Procede permettant de recouvrir des pieces Expired - Lifetime EP1117856B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP99968252A EP1117856B1 (fr) 1998-09-01 1999-08-28 Procede permettant de recouvrir des pieces

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP98116503A EP0984082A1 (fr) 1998-09-01 1998-09-01 Procédé de revêtement des pièces
EP98116503 1998-09-01
PCT/EP1999/006358 WO2000012782A1 (fr) 1998-09-01 1999-08-28 Procede permettant de recouvrir des pieces
EP99968252A EP1117856B1 (fr) 1998-09-01 1999-08-28 Procede permettant de recouvrir des pieces

Publications (2)

Publication Number Publication Date
EP1117856A1 EP1117856A1 (fr) 2001-07-25
EP1117856B1 true EP1117856B1 (fr) 2004-11-10

Family

ID=8232559

Family Applications (2)

Application Number Title Priority Date Filing Date
EP98116503A Withdrawn EP0984082A1 (fr) 1998-09-01 1998-09-01 Procédé de revêtement des pièces
EP99968252A Expired - Lifetime EP1117856B1 (fr) 1998-09-01 1999-08-28 Procede permettant de recouvrir des pieces

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP98116503A Withdrawn EP0984082A1 (fr) 1998-09-01 1998-09-01 Procédé de revêtement des pièces

Country Status (6)

Country Link
US (1) US6635165B1 (fr)
EP (2) EP0984082A1 (fr)
AT (1) ATE282099T1 (fr)
DE (1) DE59911058D1 (fr)
ES (1) ES2233099T3 (fr)
WO (1) WO2000012782A1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060040126A1 (en) * 2004-08-18 2006-02-23 Richardson Rick A Electrolytic alloys with co-deposited particulate matter
DE102005061135A1 (de) * 2005-12-19 2007-06-28 Siemens Ag Kokille für eine Stranggussanlage und Verfahren zur Herstellung einer Kokille
US20070170068A1 (en) * 2006-01-24 2007-07-26 Usc, Llc Electrocomposite coatings for hard chrome replacement
US7897265B2 (en) * 2006-01-26 2011-03-01 Hamilton Sundstrand Corporation Low cost, environmentally favorable, chromium plate replacement coating for improved wear performance
DE102006041458A1 (de) * 2006-09-04 2008-03-20 Siemens Ag Flotationszelle
US20110162751A1 (en) * 2009-12-23 2011-07-07 Exxonmobil Research And Engineering Company Protective Coatings for Petrochemical and Chemical Industry Equipment and Devices
GB201103810D0 (en) * 2011-03-04 2011-04-20 G24 Innovations Ltd Photovoltaic cell
US20140014061A1 (en) * 2012-07-11 2014-01-16 Caterpillar Inc. High-phosphorous electroless nickel (hfen) treatment for bushingless connecting rod

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4468296A (en) * 1982-12-10 1984-08-28 At&T Bell Laboratories Process for electroplating palladium
JPS6411998A (en) * 1987-07-01 1989-01-17 Riken Kk Wear resistant sliding member
JP3333025B2 (ja) * 1993-12-08 2002-10-07 日本パーカライジング株式会社 金属材料の電気複合めっき方法および装置
US5628807A (en) * 1994-08-15 1997-05-13 Asahi Glass Company Ltd. Method for forming a glass product for a cathode ray tube
JP3391113B2 (ja) * 1994-10-07 2003-03-31 豊田合成株式会社 複合めっき方法

Also Published As

Publication number Publication date
ATE282099T1 (de) 2004-11-15
US6635165B1 (en) 2003-10-21
WO2000012782A1 (fr) 2000-03-09
EP0984082A1 (fr) 2000-03-08
ES2233099T3 (es) 2005-06-01
EP1117856A1 (fr) 2001-07-25
DE59911058D1 (de) 2004-12-16

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