EP0069701B1 - Verfahren zur Herstellung eines korrosionsbeständigen festen Schmiermittelüberzuges - Google Patents

Verfahren zur Herstellung eines korrosionsbeständigen festen Schmiermittelüberzuges Download PDF

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Publication number
EP0069701B1
EP0069701B1 EP82810275A EP82810275A EP0069701B1 EP 0069701 B1 EP0069701 B1 EP 0069701B1 EP 82810275 A EP82810275 A EP 82810275A EP 82810275 A EP82810275 A EP 82810275A EP 0069701 B1 EP0069701 B1 EP 0069701B1
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EP
European Patent Office
Prior art keywords
sulfide
coating
forming
metal
solid
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
Application number
EP82810275A
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English (en)
French (fr)
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EP0069701A1 (de
Inventor
Paul Niederhaeuser
Michel Maillat
Hans-Erich Hintermann
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CSEM Centre Suisse dElectronique et de Microtechnique SA Recherche et Développement
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Laboratoire Suisse de Recherches Horlogeres
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Priority claimed from CH650981A external-priority patent/CH642509A/fr
Application filed by Laboratoire Suisse de Recherches Horlogeres filed Critical Laboratoire Suisse de Recherches Horlogeres
Publication of EP0069701A1 publication Critical patent/EP0069701A1/de
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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

Definitions

  • Lamellar chalcogen compounds such as molybdenum sulfide
  • Lamellar chalcogen compounds have already been used successfully as solid lubricants in an environment containing very little oxygen and humidity, for example under vacuum (space equipment) and in gas atmospheres. inert (nuclear power plants).
  • attempts to use such solid lubricants in the Earth's atmosphere in the presence of oxygen and moisture have been unsuccessful, as these solid lubricants corrode to form oxidation products, as well as in sulfur dioxide and hydrogen sulfide in the case of molybdenum sulfide.
  • the object of the invention is to remedy these drawbacks and, for this purpose, the invention relates to a method for producing a solid lubricating coating, resistant to corrosion, on a surface resistant to corrosion and consisting of a sulfide-forming metal, characterized in that the surface is subjected to a plasma in an atmosphere containing hydrogen sulfide in order to form an adherent sulfide on this surface and in that the sulfided surface is exposed to a spray simultaneous cathodic of at least one solid lubricant, chosen from chalcogenic lamellar compounds, and at least one hydrophobic solid polymer, in order to form a composite coating in which the particles of the chalcogenic compound are protected by the hydrophobic polymer, the atmospheres in which have the sulfurization and the deposition of the coating take place free of free or bound oxygen.
  • the sulfurization treatment of the surface to be coated is carried out in the sputtering apparatus used for depositing the composite solid lubricant.
  • an atmosphere of an inert gas, such as argon, containing hydrogen sulphide is maintained in a proportion which can vary between 0.5 and 20% by volume, under a pressure generally of between 0.1 millibar and .000 1 millibar, more particularly between 0.06 millibar and 0.001 millibar, and an electrical discharge is maintained between the part to be coated functioning as an anode, and a cathode.
  • Hydrogen sulfide probably in ionized form, reacts effectively with the sulfide-forming metal.
  • sulfide-forming metal is meant here a metal or a metalloid which is sulfurizable when exposed as an electrode to an electric plasma in an atmosphere containing hydrogen sulfide.
  • the sulphide-forming metal can be chosen from nickel, cobalt, chromium, molybdenum, copper, silver, rhodium, ruthenium, tungsten, palladium, silicon, hafnium, niobium, titanium, tantalum, rhenium, osmium, iridium, platinum and their alloys.
  • the part to be coated is not made of a corrosion-resistant sulphide-forming metal and it must therefore first be coated with such a metal, the deposit of the latter having a thickness of at least 0 , 1 ⁇ m, preferably 0.5 to 5 kL m.
  • the sputtering technique is advantageously used by using a cathode made of the sulphide-forming metal, for example cobalt.
  • a direct or alternating high frequency electric voltage generally greater than 1 MHz, for example 13.56 MHz, with a power density between 2 W / cm 2 and 17 W / cm 2 , in particular between 3 W / cm 2 and 7 W / cm 2 .
  • the aim of which is to make the composite lubricating coating adhere firmly to its support
  • the simultaneous deposition of the chalcogenated lamellar compound and of the hydrophobic solid polymer which may be among the fluorocarbons, in particular polytetrafluoroethylene, polyimides and silicones, by sputtering in the same device as that used for sulfurization.
  • the chalcogenated lamellar compound and the hydrophobic solid polymer can be placed in separate cathodes connected in parallel, but it is preferable to place the two components in a common cathode, preferably in the form of a mixture of powders cold pressed under pressure from 100 to 10,000 bar, preferably from 3000 to 7,000 bar.
  • the powder particles advantageously have an average size of less than 4 ⁇ m, preferably less than 1 ⁇ m.
  • the relative proportions between the chalcogenated lamellar compound and the hydrophobic solid polymer are normally chosen so as to obtain a composite lubricating coating in which the proportion of the hydrophobic solid polymer is between 1 and 80%, more particularly between 5 and 40%, by weight. , of the composite coating.
  • the simultaneous sputtering of the lamcellar chalcogen compound and of the hydrophobic solid polymer, and the possible preliminary sputtering of the sulphide-forming metal, are maintained for times leading to layers of sufficient thickness, i.e. layers of thickness generally equal to 1.5 to 2 times the height of its roughness, measured between vertices and hollows.
  • the surfaces coated by the method according to the invention may belong to mechanical members of any kind which are intended to rub on other surfaces, for example shafts, bearings, ball or roller bearings, in particular members microtechnical instruments or timepieces, for example shafts and pivots of watch mechanisms, in particular pendulum shafts and watch gear wheels.
  • a high vacuum cathode sputtering apparatus is used in which the pressure can be adjusted between 0.1 millibar. and 0.0001 millibar.
  • the cathode holders can be brought to an alternating potential of several kV at a frequency of 13 MHz and the anode holders can be brought to a continuous negative potential of several kV.
  • Parts to be coated in steel, in this case discs for the ball / disc wear test, are fixed to an anode holder, facing two cathode holders, one of which is made of nickel for example, and the other consists of a MoS 2 / PTFE mixture in the ratio of 80/20 by weight, in particles of dimensions less than 1 ⁇ m and which was cold pressed under a pressure of 5000 bar.
  • the discs are stripped by subjecting them to ionic bombardment in a rare gas.
  • argon is preferably used as the rare gas.
  • the spray cathodes are masked by a screen, the argon pressure is 0.01 millibar the anode has a negative potential with respect to the mass of 800 V.
  • the specific cathode power is 3 , 3 W / cm 2 during the stripping, whereas it is 5.4 W / cm 2 in the subsequent operations.
  • the durations of the various treatments are generally 10 min. for pickling, 1 hour for depositing sulfurizable metal, 30 sec. for sulfurization and 30 min. for depositing the solid composite lubricant.
  • nickel can be replaced by cobalt, rhodium, ruthenium, chromium, tungsten, palladium, copper, silicon, hafnium, niobium, titanium, molybdenum, tantalum and their alloys as sulfur metals.
  • the bearings treated are of the RMB-RA 6190X - J 630/1 * type without cage.
  • the inner and outer rings were coated with MoS 2 + PTFE on a carrier layer of cobalt sulfide and, for comparison, with MoS 2 alone.
  • the balls were made of AISI 440C steel, respectively of AISI 52100 steel (DIN 100Cr6) coated with TiC.
  • the measurements were carried out in a relative humidity of 50%.
  • the rotation speed was 60 rpm.
  • Axes (in steel) of mechanical watch balance of caliber MST 522 were treated in the manner described in the previous example in order to successively receive a carrier layer of cobalt sulfide and a lubricant coating composite of MoS 2 and PTFE.
  • the pendulums fitted with the axes thus treated were subjected to a test using the Bassometer of the Swiss Laboratory for Horological Research for a total duration of 90 days during which the amplitude of the oscillation of the pendulums in the horizontal position was periodically measured. .
  • the axes were exposed to an atmosphere of 40 to 50% relative humidity and a temperature of 20 to 22 ° C.
  • the same test was applied to pendulums whose axes were coated with a layer of MoS 2 alone.
  • Table III Table III below, where each value is the average of the measurements carried out on 5 pieces.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Physical Vapour Deposition (AREA)
  • Rolling Contact Bearings (AREA)

Claims (15)

1. Verfahren zur Herstellung eines festen schmierenden, korrosionsfesten Ueberzugs auf einer korrosionsfesten Oberfläche, die aus einem Sulfid bildenden Metall besteht, dadurch gekennzeichnet, dass man die Oberfläche in einer Schwefelwasserstoff enthaltenden Atmosphäre einem Plasma aussetzt, um ein auf dieser Oberfläche haftendes Sulfid zu bilden, und dass man diese mit Schwefel gesäuerte Oberfläche einer gleichzeitigen kathodischen Zerstäubung von mindestens einem festen Schmiermittel, welches unter den lamellenförmigen schwefelhaltigen Zusammensetzungen gewählt ist, und von mindestens einem soliden hydrophoben Polymer aussetzt um einen zusammengesetzten Ueberzug zu bilden, in welchem die Partikel der schwefelhaltigen Zusammensetzung durch das hydrophobe Polymer geschützt sind, wobei die Atmosphären, in welchen die Sulfurierung und die Anbringung des Ueberzugs stattfinden, ohne freien oder gebundenen Sauerstoff sind.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Sulfid bildende Metall unter dem Nickel, dem Kobalt, dem Chrom, dem Molybdän, dem Kupfer, dem Silber, dem Rhodium und ihren Legierungen gewählt wird.
3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Sulfid bildende Metall aus Ruthenium und seinen Legierungen besteht.
4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Sulfid bildende Metall Wolfram, Palladium, Silizium, Hafnium, Niob, Titan, Tantal, Rhenium, Osmium, Iridium, Platin und ihre Legierungen ist.
5. Verfahren nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass die schwefelhaltige Zusammensetzung Molybdänsulfid ist.
6. Verfahren nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass das feste hydrophobe Polymer unter den Fluorkarbiden, insbesondere dem Polytetrafluorethylen, den Polyimiden und den Silikonen gewählt wird.
7. Verfahren nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass die schwefelhaltige Zusammensetzung und das feste hydrophobe Polymer, die für die Zerstäubung vorgesehen sind, in einer gemeinsamen Kathode gemischt werden.
8. Verfahren gemäss Anspruch 6, dadurch gekennzeichnet, dass man eine Kathode verwendet, die durch Kaltpressung einer Mischung der Pulver der schwefelhaltigen Zusammensetzung und des festen hydrophoben Polymers unter Anwendung eines Druckes von 100 bis 10 000 bar erhalten wurde, wobei der bevorzugte Pressdruck zwischen 3000 und 7000 bar liegt.
9. Verfahren gemäss Anspruch 6 oder 7, dadurch gekennzeichnet, dass die Pulver eine mittlere Partikelgrösse unter 4 µm aufweisen, wobei die bevorzugte mittlere Grösse unter 1 µm liegt.
10. Verfahren nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass es derart abgewickelt wird, dass ein schmierender Ueberzug gebildet wird, der 1 bis 80 % festes hydrophobes Polymer enthält, wobei das bevorzugte Verhältnis 5 bis 40 % beträgt.
11. Verfahren nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass ein schmierender Ueberzug gebildet wird, dessen Dicke 1,5 bis 2 mal die Höhe seiner zwischen Spitzen und Vertiefungen gemessener Rauheit aufweist.
12. Verfahren nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass die aus Sulfid bildendem Metall bestehende Oberfläche durch kathodische Zerstäubung des Metalls auf eine Auflage erhalten wird.
13. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die kathodische Zerstäubung des Sulfid bildenden Metalls mittels einer kontinuierlichen oder wechselnden elektrischen Hochfrequenz-Spannung ausgeführt wird.
14. Verfahren nach Anspruch 12 oder 13, dadurch gekennzeichnet, dass eine Lage von Sulfid bildendem Metall mit einer Dicke von mindestens 0,1 µrn gebildet wird, wobei die bevorzugte Dicke 0,5 µm beträgt.
15. Verfahren nach einem der Ansprüche 11 bis 13, dadurch gekennzeichnet, dass die Ablage des Sulfid bildenden Metalls, seine Schwefelung und die Bildung des zusammengesetzten Ueberzugs im gleichen geschützten Raum ausgeführt werden.
EP82810275A 1981-06-30 1982-06-28 Verfahren zur Herstellung eines korrosionsbeständigen festen Schmiermittelüberzuges Expired EP0069701B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CH431181 1981-06-30
CH650981A CH642509A (en) 1981-10-12 1981-10-12 Process for producing a corrosion-resistant solid lubricating coating on a surface of a moving member of a timepiece or of a microtechnical instrument
CH4311/81 1982-03-18
CH6509/81 1982-03-24

Publications (2)

Publication Number Publication Date
EP0069701A1 EP0069701A1 (de) 1983-01-12
EP0069701B1 true EP0069701B1 (de) 1985-09-18

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EP82810275A Expired EP0069701B1 (de) 1981-06-30 1982-06-28 Verfahren zur Herstellung eines korrosionsbeständigen festen Schmiermittelüberzuges

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US (1) US4415419A (de)
EP (1) EP0069701B1 (de)
AT (1) ATE15698T1 (de)
DE (1) DE3266380D1 (de)

Families Citing this family (15)

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DE3516933A1 (de) * 1985-05-10 1986-11-13 Deutsche Forschungs- und Versuchsanstalt für Luft- und Raumfahrt e.V., 5300 Bonn Verfahren zum aufbringen einer mos(pfeil abwaerts)2(pfeil abwaerts)-beschichtung auf ein substrat
JPH068503B2 (ja) * 1987-03-31 1994-02-02 セントラル硝子株式会社 含フツ素樹脂被膜の形成方法
BR8900933A (pt) * 1988-05-02 1990-10-09 Orient Watch Co Ltd Pelicula composta multipla,pelicula composta multipla de camadas multiplas e pelicula composta de camadas multiplas
US5262241A (en) * 1991-08-26 1993-11-16 Eeonyx Corporation Surface coated products
JP3063315B2 (ja) * 1991-10-15 2000-07-12 忠弘 大見 耐薬液性に優れた金属材並びにそれを用いた薬液処理装置又は薬液処理装置用部品
DK177291D0 (da) * 1991-10-24 1991-10-24 Gunnar Soerensen Fremgangsmaade til fremstilling af slidbestandige toersmoerende film
US5370778A (en) * 1992-11-19 1994-12-06 Iowa State University Research Foundation, Inc. Method for preparing basal oriented molybdenum disulfide (MoS2) thin films
DE19708880A1 (de) * 1997-03-05 1998-09-10 Widia Gmbh Schneideinsatz zum Zerspanen
AT406756B (de) * 1998-12-21 2000-08-25 Johannes Dr Heitz Fluorpolymer-beschichtungen mit guter haftung und guter abriebfestigkeit für den einsatz in der medizin sowie ein verfahren zu ihrer herstellung
US20030157270A1 (en) * 2002-02-19 2003-08-21 Xu Wang Process for plasma sulfurization in vacuum
US20100087346A1 (en) * 2006-03-31 2010-04-08 Honeywell International, Inc. Solid film lubricated high oxidation temperature rhenium material
US8741820B2 (en) * 2008-12-26 2014-06-03 Citizen Electronics Co., Ltd. Lubrication kit and small electronic device using the same
DE102016124734A1 (de) 2016-12-19 2018-06-21 Schaeffler Technologies AG & Co. KG Bauteil, insbesondere Wälzkörper
DE102020102645A1 (de) * 2020-02-03 2021-08-05 Klüber Lubrication München Se & Co. Kg Tribologisches System
CN114251365B (zh) * 2021-12-30 2022-11-22 西南交通大学 一种改善仿生水润滑轴承摩擦表面承载耐磨性能的方法

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CH365921A (de) * 1958-11-04 1962-11-30 Berghaus Elektrophysik Anst Verfahren zur Behandlung der Oberfläche von Metallkörpern
CH397377A (de) * 1959-01-23 1965-08-15 Berghaus Elektrophysik Anst Verfahren zur Oberflächenbehandlung von Metallkörpern
US3767559A (en) * 1970-06-24 1973-10-23 Eastman Kodak Co Sputtering apparatus with accordion pleated anode means
GB1299308A (en) * 1971-05-01 1972-12-13 Ceskoslovenska Akademie Ved Improvements in or relating to blades for rotary flow machines
FR2311102A1 (fr) * 1975-05-13 1976-12-10 Lucas Industries Ltd Procede de formation d'un metal et d'une substance de resine synthetique sur un substrat
DE2530002A1 (de) 1975-07-04 1977-01-27 Dow Corning Gmbh Verfahren zur verbesserung der schmiereigenschaften von festschmierstoffen
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FR2441444A1 (fr) * 1978-11-20 1980-06-13 Bar Lorforge Procede de traitement a chaud de masse metallique comportant une mise en forme de celle-ci avec un appareil de formage, permettant d'ameliorer notamment la duree de vie de ce dernier

Also Published As

Publication number Publication date
US4415419A (en) 1983-11-15
DE3266380D1 (en) 1985-10-24
EP0069701A1 (de) 1983-01-12
ATE15698T1 (de) 1985-10-15

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