EP0984082A1 - Procédé de revêtement des pièces - Google Patents

Procédé de revêtement des pièces Download PDF

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Publication number
EP0984082A1
EP0984082A1 EP98116503A EP98116503A EP0984082A1 EP 0984082 A1 EP0984082 A1 EP 0984082A1 EP 98116503 A EP98116503 A EP 98116503A EP 98116503 A EP98116503 A EP 98116503A EP 0984082 A1 EP0984082 A1 EP 0984082A1
Authority
EP
European Patent Office
Prior art keywords
coating
particles
alloy
phosphorus
nickel
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.)
Withdrawn
Application number
EP98116503A
Other languages
German (de)
English (en)
Inventor
Klaus Leo Wilbuer
Hans Hermann Dr. 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
Metallveredlung GmbH and Co KG
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, Metallveredlung GmbH and Co KG filed Critical Enthone OMI Deutschland GmbH
Priority to EP98116503A priority Critical patent/EP0984082A1/fr
Priority to EP99968252A priority patent/EP1117856B1/fr
Priority to DE59911058T priority patent/DE59911058D1/de
Priority to ES99968252T priority patent/ES2233099T3/es
Priority to AT99968252T priority patent/ATE282099T1/de
Priority to PCT/EP1999/006358 priority patent/WO2000012782A1/fr
Priority to US09/786,300 priority patent/US6635165B1/en
Publication of EP0984082A1 publication Critical patent/EP0984082A1/fr
Withdrawn legal-status Critical Current

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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
    • 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 that to form a functional, in particular corrosion-resistant and wear-resistant, metallic coating at least phosphor and nickel-containing alloy is deposited from an electrolyte.
  • the invention further relates to a cover in this regard.
  • metallic coatings are used primarily for functional coating of workpieces in order to intended use of stress mechanisms due to suitable surface properties, such as hardness, Wear resistance, friction or thermal and chemical Consistency to take into account.
  • suitable surface properties such as hardness, Wear resistance, friction or thermal and chemical Consistency to take into account.
  • the production of such protective coatings is usually done by electroplating.
  • electrolytic deposition in which one Electrocrystallization takes place
  • external currentless electrochemical metal deposition which is a simple Immersion process without external power source and anodes.
  • metal deposition can be applied to both metallic and non-metallic workpiece surfaces can be applied.
  • 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 is to be specified.
  • This object is achieved in a method of the type mentioned according to the invention characterized in that electrolytically an at least quaternary alloy with the components nickel, cobalt, tungsten and phosphorus is deposited as a coating.
  • Such a method enables due to the electrolytic deposition and the associated reductive reaction system at the interface between the electrolyte and the workpiece, an installation rate of Phosphorus in the metallic coating between 14 and 21 wt .-%.
  • the invention is also based on the surprising finding that through common cathodic deposition of nickel, cobalt, tungsten and Phosphorus is an alloy coating that is characterized by a high Excellent corrosion resistance and wear resistance.
  • non-metallic particles preferably carbides or carbide mixed crystals, in the metallic matrix of the coating is embedded around the Corrosion resistance, wear resistance and hardness additionally increase.
  • boron, silicon, tungsten, vanadium and / or Titanium carbide used. It is also advantageous if for this purpose particles with a grain size of 0.1 to 1.5 ⁇ m can be used. Alternatively, you can also ultrafine particles with diameters in the nanometer range or particles with a grain size of more than 1.5 ⁇ m depending on the desired Edge layer properties find application.
  • Another Characteristic of the invention are the particles in 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 by moving the galvanic bath 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 appropriate 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 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 portion of nickel put together.
  • 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 the electrolyte is suspended.
  • a differently concentrated Incorporation of the particles over the course of the thickness of the coating can be done by appropriate changes in the bath movement are caused.
  • the on the coating thus formed has a total 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 value 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.

Landscapes

  • 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)
EP98116503A 1998-09-01 1998-09-01 Procédé de revêtement des pièces Withdrawn EP0984082A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
EP98116503A EP0984082A1 (fr) 1998-09-01 1998-09-01 Procédé de revêtement des pièces
EP99968252A EP1117856B1 (fr) 1998-09-01 1999-08-28 Procede permettant de recouvrir des pieces
DE59911058T DE59911058D1 (de) 1998-09-01 1999-08-28 Verfahren zum beschichten von werkstücken
ES99968252T ES2233099T3 (es) 1998-09-01 1999-08-28 Procedimiento para el recubrimiento de piezas de trabajo.
AT99968252T ATE282099T1 (de) 1998-09-01 1999-08-28 Verfahren zum beschichten von werkstücken
PCT/EP1999/006358 WO2000012782A1 (fr) 1998-09-01 1999-08-28 Procede permettant de recouvrir des pieces
US09/786,300 US6635165B1 (en) 1998-09-01 1999-08-28 Method for coating workpieces

Applications Claiming Priority (1)

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

Publications (1)

Publication Number Publication Date
EP0984082A1 true EP0984082A1 (fr) 2000-03-08

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 After (1)

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

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)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007071542A1 (fr) * 2005-12-19 2007-06-28 Siemens Aktiengesellschaft Revetement pour coquille destinee a une installation de coulee continue, et procede de revetement correspondant
WO2008028796A1 (fr) * 2006-09-04 2008-03-13 Siemens Aktiengesellschaft Cellule de flottation avec revêtement résistant a l'usure

Families Citing this family (6)

* 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
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
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

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6411998A (en) * 1987-07-01 1989-01-17 Riken Kk Wear resistant sliding member
EP0709493A2 (fr) * 1994-10-07 1996-05-01 Toyoda Gosei Co., Ltd. Méthode pour le revêtement composite
US5628807A (en) * 1994-08-15 1997-05-13 Asahi Glass Company Ltd. Method for forming a glass product for a cathode ray tube

Family Cites Families (2)

* 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
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6411998A (en) * 1987-07-01 1989-01-17 Riken Kk Wear resistant sliding member
US5628807A (en) * 1994-08-15 1997-05-13 Asahi Glass Company Ltd. Method for forming a glass product for a cathode ray tube
EP0709493A2 (fr) * 1994-10-07 1996-05-01 Toyoda Gosei Co., Ltd. Méthode pour le revêtement composite

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 8908, Derwent World Patents Index; Class L02, AN 89-058686, XP002093797 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007071542A1 (fr) * 2005-12-19 2007-06-28 Siemens Aktiengesellschaft Revetement pour coquille destinee a une installation de coulee continue, et procede de revetement correspondant
WO2008028796A1 (fr) * 2006-09-04 2008-03-13 Siemens Aktiengesellschaft Cellule de flottation avec revêtement résistant a l'usure

Also Published As

Publication number Publication date
ATE282099T1 (de) 2004-11-15
ES2233099T3 (es) 2005-06-01
EP1117856A1 (fr) 2001-07-25
DE59911058D1 (de) 2004-12-16
US6635165B1 (en) 2003-10-21
WO2000012782A1 (fr) 2000-03-09
EP1117856B1 (fr) 2004-11-10

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