EP0984082A1 - Procédé de revêtement des pièces - Google Patents
Procédé de revêtement des pièces Download PDFInfo
- 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- Withdrawn
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 45
- 239000011248 coating agent Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 21
- 230000008569 process Effects 0.000 title claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 24
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 16
- 239000011574 phosphorus Substances 0.000 claims abstract description 16
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 12
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 10
- 239000010941 cobalt Substances 0.000 claims abstract description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 10
- 239000010937 tungsten Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract 2
- 239000002245 particle Substances 0.000 claims description 17
- 229910045601 alloy Inorganic materials 0.000 claims description 13
- 239000000956 alloy Substances 0.000 claims description 13
- 230000008021 deposition Effects 0.000 claims description 12
- 238000005260 corrosion Methods 0.000 claims description 10
- 230000007797 corrosion Effects 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 9
- 239000011159 matrix material Substances 0.000 claims description 7
- 229910052580 B4C Inorganic materials 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 4
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000013528 metallic particle Substances 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 238000004040 coloring Methods 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 238000009713 electroplating Methods 0.000 claims description 2
- 150000001247 metal acetylides Chemical class 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 229910002059 quaternary alloy Inorganic materials 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims description 2
- 229910001096 P alloy Inorganic materials 0.000 abstract description 2
- FIOBDUSJUICPHU-UHFFFAOYSA-N [P].[W].[Ni].[Co] Chemical group [P].[W].[Ni].[Co] FIOBDUSJUICPHU-UHFFFAOYSA-N 0.000 abstract 1
- 238000004070 electrodeposition Methods 0.000 abstract 1
- 238000000151 deposition Methods 0.000 description 11
- 238000009434 installation Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007714 electro crystallization reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- MESMHYWPVMTHDU-UHFFFAOYSA-N [P].[B].[W].[Ni].[Co] Chemical compound [P].[B].[W].[Ni].[Co] MESMHYWPVMTHDU-UHFFFAOYSA-N 0.000 description 1
- IGOJDKCIHXGPTI-UHFFFAOYSA-N [P].[Co].[Ni] Chemical compound [P].[Co].[Ni] IGOJDKCIHXGPTI-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
Images
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)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP98116503A EP0984082A1 (fr) | 1998-09-01 | 1998-09-01 | Procédé de revêtement des pièces |
| AT99968252T ATE282099T1 (de) | 1998-09-01 | 1999-08-28 | Verfahren zum beschichten von werkstücken |
| 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 |
| US09/786,300 US6635165B1 (en) | 1998-09-01 | 1999-08-28 | Method for coating workpieces |
| PCT/EP1999/006358 WO2000012782A1 (fr) | 1998-09-01 | 1999-08-28 | Procede permettant de recouvrir des pieces |
| ES99968252T ES2233099T3 (es) | 1998-09-01 | 1999-08-28 | Procedimiento para el recubrimiento de piezas de trabajo. |
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)
| 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)
| 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)
| 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)
| 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 |
-
1998
- 1998-09-01 EP EP98116503A patent/EP0984082A1/fr not_active Withdrawn
-
1999
- 1999-08-28 WO PCT/EP1999/006358 patent/WO2000012782A1/fr not_active Ceased
- 1999-08-28 EP EP99968252A patent/EP1117856B1/fr not_active Expired - Lifetime
- 1999-08-28 AT AT99968252T patent/ATE282099T1/de not_active IP Right Cessation
- 1999-08-28 US US09/786,300 patent/US6635165B1/en not_active Expired - Lifetime
- 1999-08-28 ES ES99968252T patent/ES2233099T3/es not_active Expired - Lifetime
- 1999-08-28 DE DE59911058T patent/DE59911058D1/de not_active Expired - Lifetime
Patent Citations (3)
| 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)
| Title |
|---|
| DATABASE WPI Section Ch Week 8908, Derwent World Patents Index; Class L02, AN 89-058686, XP002093797 * |
Cited By (2)
| 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 |
|---|---|
| DE59911058D1 (de) | 2004-12-16 |
| EP1117856B1 (fr) | 2004-11-10 |
| ES2233099T3 (es) | 2005-06-01 |
| ATE282099T1 (de) | 2004-11-15 |
| US6635165B1 (en) | 2003-10-21 |
| EP1117856A1 (fr) | 2001-07-25 |
| WO2000012782A1 (fr) | 2000-03-09 |
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