WO2001068790A2 - Couches de protection a faible friction et reduisant l'usure et leur procede de depot - Google Patents

Couches de protection a faible friction et reduisant l'usure et leur procede de depot Download PDF

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Publication number
WO2001068790A2
WO2001068790A2 PCT/DE2001/001094 DE0101094W WO0168790A2 WO 2001068790 A2 WO2001068790 A2 WO 2001068790A2 DE 0101094 W DE0101094 W DE 0101094W WO 0168790 A2 WO0168790 A2 WO 0168790A2
Authority
WO
WIPO (PCT)
Prior art keywords
protective layers
layer
carbon
graphite
gpa
Prior art date
Application number
PCT/DE2001/001094
Other languages
German (de)
English (en)
Other versions
WO2001068790A3 (fr
Inventor
Andreas Mucha
Bernd Rother
Original Assignee
Mat Gmbh Dresden
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
Priority claimed from DE10024899A external-priority patent/DE10024899A1/de
Application filed by Mat Gmbh Dresden filed Critical Mat Gmbh Dresden
Priority to AU56118/01A priority Critical patent/AU5611801A/en
Publication of WO2001068790A2 publication Critical patent/WO2001068790A2/fr
Publication of WO2001068790A3 publication Critical patent/WO2001068790A3/fr

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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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • C23C14/0057—Reactive sputtering using reactive gases other than O2, H2O, N2, NH3 or CH4
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0605—Carbon

Definitions

  • the invention relates to the fields of materials technology, chemistry and mechanical engineering and relates to low-friction and wear-reducing protective layers, such as those e.g. on tribologically and / or corrosively stressed components, such as on valve inserts, on ball bearings or on forming tools and on medical implants, and a method for their deposition.
  • Low-friction and wear-reducing protective layers are known ways of improving the service life and / or the performance of tribological pairings. Layers made of carbon or with a high proportion of carbon are of particular importance here, as a rule low friction coefficients in the range of 0.1 can be combined with low wear. Very early indications of such friction and wear-reducing properties of carbon layers deposited from gas discharges in hydrocarbons were given by Schmellenmeier, H., Experimentelletechnik der Physik 1 (1953) 49.
  • the layers are deposited with the exception of the last system with ion support.
  • polycrystalline diamond can also be deposited without ion support, but then at temperatures in the range of 800 to 1000 ° C.
  • the ion-supported layer deposition enables the deposition of low-friction and low-wear layers even at temperatures below 200 ° C.
  • the ion support serves to generate a primarily mechanically stable carbon crosslinking with the highest possible spatial degree of crosslinking with the highest possible proportion of the tetragonal sp 3 bonds. Both layer-forming or layer-modifying ions can be used to support the layer growth.
  • a general aim of the methods for the deposition of hard and wear-resistant carbon layers is the generation of the highest possible proportion of tetrahedral carbon bonds (diamond bond) in the layers.
  • a simple indication of these proportions is the mass density of the layers.
  • the mass density of diamond with 3.51 g / cm 3 and that of graphite with 2.25 g / cm 3 apply as limit values. Density values in the range of 2.8 g / cm 3 are given for pure carbon layers with high proportions of tetrahedral bonds (J. Vac. Sei. Technol. A12 (1994) 1457-1462).
  • the object of the invention is to provide a carbon-based, low-friction and wear-reducing protective layer and a method for its deposition, the protective layer being relative to the prior art can be easily and largely stress-free and adhered to various base materials.
  • the method according to the invention works on the basis of the solid atomization of a graphite target or a graphite-containing target using carbon monoxide and / or carbon dioxide as the working gas or as a component of the working gas.
  • the incorporation of oxygen is largely suppressed due to the gaseous oxidation products of the carbon.
  • Target-based carbon are essentially neutral carbon atoms in the energetic ground state with only minimal kinetic energy.
  • Working gas-based carbon is energetically activated in a variety of ways in the plasma of the gas discharge, which for molecular working gases includes the generation of ions, neutral and ionized molecular components and energetically excited atomic and molecular species.
  • Significant effects for the layer growth are additionally achieved by dissociated oxygen portions of the working gas, which is related to the known preferential oxidation of graphitically bound carbon compared to tetragonally bound carbon.
  • the hardness, the modulus of elasticity and the high wear resistance of the layers according to the invention indicate a high proportion of tetrahedral carbon.
  • mass densities in the range of 1.8 + 0.2 g / cm 3 are measured on the layers, which is significantly lower than the mass density of graphite. Similar mass densities are known from fullerene layers (Applied Surface Science 86 (1995) p. 595). However, these are characterized by low plastic hardness and modulus of elasticity as the layers deposited by means of the method according to the invention.
  • a typical feature of this new structure of pure carbon layers according to the invention is the low density in connection with plastic hardness values in the range from 5 to 30 GPa, advantageously from 10 to 15 GPa, and elastic modulus values in the range from 50 to 200 GPa, advantageously in the range from 90 to 150 GPa.
  • a high level of biocompatibility can also be demonstrated for the protective layers according to the invention.
  • values as good as those on polystyrene substrates specially prepared for cell colonization experiments are measured on the protective layers of different thicknesses.
  • Polished samples of hardened high-speed steel are positioned in a "vacuum apparatus in such a way that they are fixed directly under a downward-facing round magnetron of 16 cm in diameter equipped with a graphite target.
  • the target-sample distance is 10 cm.
  • the samples are on one Fixed substrate holder, which has an electrical contact.
  • the vacuum chamber is evacuated to a base pressure of 5 x 10 ⁇ Pa.
  • the samples are then glow cleaned in an argon atmosphere at a pressure of 10 Pa.
  • the base pressure for the coating is then reduced again to 5 x 10 ⁇ 3 Pa.
  • the gas inlet for carbon monoxide is now opened so that a pressure of 5 x 10 "2 Pa is established in the vacuum chamber when the main valve is throttled.
  • the target's operating voltage is 540 V. After a coating time A layer thickness of 3.6 ⁇ m is reached within 2 hours and the process is ended.
  • the protective layers are evaluated by means of friction tests in an oscillation tribometer. which works on the pin-washer principle.
  • a hard metal ball with a diameter of 6 mm fixed in a receptacle is loaded with a load of 2 N and rubbed over the surface of the layer with a frequency of 3 Hz and an amplitude difference of 2 mm.
  • a constant coefficient of friction of 0.15 is measured after a short running-in phase.
  • the friction track depth is only 30 to 40 nm.
  • Carbon-based protective layers according to the prior art, such as aC: H layers are already under 10 x 10 3 rubbing cycles to a depth of more than 100 under identical load conditions nm rubbed.
  • the hardness and the modulus of elasticity of the 3.6 ⁇ m thick layer was determined by means of recording hardness measurements, a Vickers diamond being used as the indenter. From the measurements, a final load of 50 mN and a penetration depth of 0.4 ⁇ m for the layers a plastic hardness of 13.6 + 0.4 GPa and an elastic modulus of 98 + 2 GPa were determined.
  • a mass density of 1.8 + 0.2 g / cm 3 was determined for layers with a thickness of 3.6 ⁇ m by weighing large flat samples before and after the coating, the coating being carried out under the same conditions, and by measuring the layer thickness. This value was confirmed by means of suspension tests with detached layer particles of layers of different thicknesses and identically deposited in a mixture of methanol and bromoform.
  • Needle-shaped samples made of stainless steel with a diameter of 1 mm and a length of 50 mm are positioned in a vacuum chamber which is equipped with two magnetrons.
  • the magnetrons are equipped with a graphite and a chrome target.
  • the holder for the samples is designed in such a way that multiple layers can be used to apply a uniform layer over the circumference.
  • a first coating step an approximately 50 nm thick Cr layer is now deposited on the circumference of the needle.
  • the graphite target is activated and the chrome target is switched off.
  • an approx. 30 nm thick intermediate layer of carbon is deposited, which is sputtered with argon as the working gas.
  • the substrates are still biased at -2 kV.
  • the third and last coating step is the deposition of the actual wear protection layer. The deposition is carried out by atomizing the graphite target in a CO atmosphere with the same parameter sets as in Example 1. After two hours of coating time, a uniform layer thickness of 1 ⁇ m is achieved on the circumference of the needle.
  • the layers could be deposited firmly and evenly on the samples.
  • the same layer properties as for the layers deposited in Example 1 could be measured on parallel coated specimens.

Landscapes

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

Abstract

L'invention concerne le domaine de la technique des matières et plus particulièrement des couches protectrices, telles que celles utilisées, par exemple, sur des inserts de soupape ou des outils de formage, ainsi que leur procédé de dépôt. L'objectif de l'invention est l'obtention, de façon relativement simple, de couches de protection appliquées sur différentes matières de base, dans une large mesure sans contrainte et d'une grande adhérence, et de créer un procédé de dépôt de telles couches. Cet objectif est atteint grâce à un procédé selon lequel les couches de protection sont déposées par pulvérisation d'une cible de graphite et/ou d'une cible contenant du graphite, du monoxyde de carbone et/ou du dioxyde de carbone étant amené pour la décharge de gaz destinée à la cible et/ou la décharge de gaz destinée à la formation des couches, partiellement identiques, avant et/ou pendant le dépôt, en tant que gaz de travail ou en tant que composant du gaz de travail. Cet objectif est également atteint grâce à l'obtention de couches de protection qui contiennent une proportion pouvant être supérieure à 95 % atomiques de carbone, présentent une masse volumique comprise dans la plage 1,6-2,0 g/cm3, ainsi que des valeurs de dureté plastique de 5-30 GPa ou des valeurs de module d'élasticité comprises entre 50 et 200 GPa.
PCT/DE2001/001094 2000-03-16 2001-03-16 Couches de protection a faible friction et reduisant l'usure et leur procede de depot WO2001068790A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU56118/01A AU5611801A (en) 2000-03-16 2001-03-16 Low-friction protective layers that reduce wear and tear and a method for depositing same

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE10013834 2000-03-16
DE10013834.9 2000-03-16
DE10024899.3 2000-05-12
DE10024899A DE10024899A1 (de) 2000-03-16 2000-05-12 Reibungsarme und verschleißmindernde Schutzschichten und Verfahren zu ihrer Abscheidung

Publications (2)

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WO2001068790A2 true WO2001068790A2 (fr) 2001-09-20
WO2001068790A3 WO2001068790A3 (fr) 2001-12-06

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AU (1) AU5611801A (fr)
WO (1) WO2001068790A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2334841A1 (fr) * 2008-09-12 2011-06-22 Brigham Young University Films contenant un gaz oxygéné infusé et leurs procédés de préparation

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0293662A2 (fr) * 1987-06-02 1988-12-07 International Business Machines Corporation Procédé de fabrication d'un disque d'enregistrement magnétique comprenant un film mince d'un alliage métallique avec un revêtement de carbone hydrogéné
US5411797A (en) * 1988-04-18 1995-05-02 Board Of Regents, The University Of Texas System Nanophase diamond films
US5476713A (en) * 1990-11-07 1995-12-19 Sony Corporation Magneto-optical recording medium

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63190798A (ja) * 1987-02-03 1988-08-08 Toray Ind Inc ダイヤモンド状薄膜の製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0293662A2 (fr) * 1987-06-02 1988-12-07 International Business Machines Corporation Procédé de fabrication d'un disque d'enregistrement magnétique comprenant un film mince d'un alliage métallique avec un revêtement de carbone hydrogéné
US5411797A (en) * 1988-04-18 1995-05-02 Board Of Regents, The University Of Texas System Nanophase diamond films
US5476713A (en) * 1990-11-07 1995-12-19 Sony Corporation Magneto-optical recording medium

Non-Patent Citations (6)

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Title
DE MARTINO C ET AL: "Improvement of mechanical properties of a-C:H by silicon addition" DIAMOND AND RELATED MATERIALS, ELSEVIER SCIENCE PUBLISHERS, AMSTERDAM, NL, Bd. 6, Nr. 5-7, 1. April 1997 (1997-04-01), Seiten 559-563, XP004081096 ISSN: 0925-9635 *
LACERDA R G ET AL: "HARD HYDROGENATED CARBON FILMS WITH LOW STRESS" APPLIED PHYSICS LETTERS, AMERICAN INSTITUTE OF PHYSICS. NEW YORK, US, Bd. 73, Nr. 5, 3. August 1998 (1998-08-03), Seiten 617-619, XP000778936 ISSN: 0003-6951 *
NOBILI L ET AL: "A-C(:H) AND A-CNX(:H) FILMS DEPOSITED BY MAGNETRON SPUTTERING AND PACVD" THIN SOLID FILMS, ELSEVIER-SEQUOIA S.A. LAUSANNE, CH, Bd. 317, Nr. 1/2, 1. April 1998 (1998-04-01), Seiten 359-362, XP000667839 ISSN: 0040-6090 *
PATENT ABSTRACTS OF JAPAN vol. 012, no. 472 (C-551), 9. Dezember 1988 (1988-12-09) & JP 63 190798 A (TORAY IND INC), 8. August 1988 (1988-08-08) *
SAVVIDES N ET AL: "HARDNESS AND ELASTIC MODULUS OF DIAMOND AND DIAMOND-LIKE CARBON FILMS" THIN SOLID FILMS, ELSEVIER-SEQUOIA S.A. LAUSANNE, CH, Bd. 228, Nr. 1 / 2, 15. Mai 1993 (1993-05-15), Seiten 289-292, XP000381097 ISSN: 0040-6090 *
SCHULTRICH B ET AL: "ELASTIC MODULUS AS A MEAASURE OF DIAMOND LIKENESS AND HARDNESS OF AMORPHOUS CARBON FILMS" DIAMOND AND RELATED MATERIALS, ELSEVIER SCIENCE PUBLISHERS, AMSTERDAM, NL, Bd. 5, Nr. 9, 1. Juli 1996 (1996-07-01), Seiten 914-918, XP000685026 ISSN: 0925-9635 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2334841A1 (fr) * 2008-09-12 2011-06-22 Brigham Young University Films contenant un gaz oxygéné infusé et leurs procédés de préparation
EP2334841A4 (fr) * 2008-09-12 2013-07-17 Univ Brigham Young Films contenant un gaz oxygéné infusé et leurs procédés de préparation

Also Published As

Publication number Publication date
AU5611801A (en) 2001-09-24
WO2001068790A3 (fr) 2001-12-06

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