EP2768932B1 - System comprising two friction members and a lubricating medium - Google Patents

System comprising two friction members and a lubricating medium Download PDF

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Publication number
EP2768932B1
EP2768932B1 EP12780220.5A EP12780220A EP2768932B1 EP 2768932 B1 EP2768932 B1 EP 2768932B1 EP 12780220 A EP12780220 A EP 12780220A EP 2768932 B1 EP2768932 B1 EP 2768932B1
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Prior art keywords
friction
dcx
dlc
coating
modtc
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EP12780220.5A
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German (de)
French (fr)
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EP2768932A1 (en
EP2768932B8 (en
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Philippe Maurin-Perrier
Christophe Heau
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Hydromecanique et Frottement SAS
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HEF SAS
Hydromecanique et Frottement SAS
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
    • C10M111/02—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a non-macromolecular organic compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
    • C10M135/18—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the groups
    • 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
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • C23C30/005—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process on hard metal substrates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M103/00—Lubricating compositions characterised by the base-material being an inorganic material
    • C10M103/06—Metal compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/72—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing sulfur, selenium or tellurium
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06—Metal compounds
    • C10M2201/061—Carbides; Hydrides; Nitrides
    • C10M2201/0613—Carbides; Hydrides; Nitrides used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type compounds
    • C10M2219/068—Thiocarbamate metal salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2080/00—Special pretreatment of the material to be lubricated, e.g. phosphatising or chromatising of a metal

Definitions

  • the invention relates to the technical field of tribology in a lubricated medium.
  • the invention relates to friction parts operating in a lubricated medium comprising a friction modifier, such as for example automobile components.
  • a friction modifier such as for example automobile components.
  • DLC coatings are also known to perform a second function which is to protect coatings against wear.
  • Such an additive is advantageously MoDTC which, in a hot rubbing contact, reacts chemically to give rise to the formation of compounds of the MoS 2 type perfectly known by a person skilled in the art to act as a solid lubricant.
  • the invention therefore resides in the combination of the effects of chromium nitride and MoDTC making it possible to significantly reduce the coefficient of friction, without however altering the hardness.
  • the invention relates to a system comprising two friction parts and a lubricated medium comprising a friction modifier between the two parts, the friction modifier being MoDTC, a coating being applied to one of the parts, and the other piece being steel.
  • the coating is chromium nitride applied to a external surface of the part, which presents an NaCl type crystallization whose microhardness is 1800 +/- 200 HV.
  • Friction tests were carried out in order to evaluate the behavior in a lubricated medium comprising a MoDTC friction modifier, of a DLC coating and of a chromium nitride coating, recalling, in a perfectly known manner, that in the case of a DLC coating, in order to reinforce its mechanical resistance, an underlayer, for example of chromium nitride, can be deposited.
  • an underlayer for example of chromium nitride
  • All the layers comprise a coating of chromium nitride produced by magnetron reactive sputtering.
  • the first step is to clean the steel specimens, which are then positioned on supports placed in the vacuum deposition chamber.
  • the interior of the machine and the parts to be coated are heated to a temperature of 150°C for 2 hours, in order to degas the parts and the machine. deposit.
  • the parts are subjected to ion pickling in an argon atmosphere, the purpose of which is to eliminate the thin layers of natural oxide and thus allow strong adhesion of the coating.
  • the deposition of chromium nitride is obtained by reactive magnetron sputtering of a Cr target in an argon/nitrogen mixture.
  • the nitrogen flow is controlled by an optical measurement of the Cr emission in the plasma, so that the deposit contains 40+/-5 atomic % nitrogen.
  • a deposit of CrN is obtained exhibiting fcc crystallization of the NaCl type, the microhardness of which is 1800+/-200 Hv.
  • an aC:H type DLC coating is deposited by the PACVD technique, by cracking a hydrocarbon in a plasma, here, acetylene.
  • DCX-1 the final deposition of an aC-type layer is carried out by magnetron cathodic sputtering of a graphite target.
  • DCX-2 a plasma of pure oxygen is generated and the deposit is bombarded with ions from the plasma for 10 minutes, which makes it possible to modify the surface chemistry of the deposit.
  • the plane consists of a steel specimen, polished to an Ra level of 0.02 ⁇ m.
  • the ball is made of 100Cr6 steel and has a diameter of 10 mm.
  • the coatings are applied to the ball.
  • the load applied to the ball is 10N, which gives a Hertzian contact diameter of 140 ⁇ m and an average pressure of 0.68 GPa.
  • the ball is animated by an alternating movement, the stroke of which is 10 mm.
  • the sliding velocity follows a sine-like profile, the mean value of which is 3.5 cm/s.
  • the test is carried out for a period of 15,000 cycles at a temperature of 110°C.
  • the conditions of sliding speed, pressure and temperature are such that the friction reducing additive reacts to fulfill its role.
  • the ball is observed and the diameter of the friction mark or wear mark is measured, from which the worn volume is calculated.
  • the attached graph ( figure 1 ) summarizes the average wear rates (worn volume reduced to the number of friction cycles). For each coating, 3 tests were carried out, the average wear was calculated.
  • the error bars represent, not an error, but the smallest value and the largest value for these 3 trials.
  • the low coefficient of friction is mainly due to the friction reduction additive: MoDTC.
  • the DLC combination facing a steel friction antagonist, MoDTC is not compatible to achieve the two functions, namely, to resist wear on the one hand, and to obtain a coefficient of friction as low as possible on the other hand, whereas the claimed combination, namely, chromium nitride and MoDTC advantageously makes it possible to perform these two functions.
  • the invention also relates to the use of parts thus coated and working in a lubricated medium containing MoDTC in the automotive field, in particular for engines and gearboxes.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Physical Vapour Deposition (AREA)
  • Lubricants (AREA)
  • Sliding-Contact Bearings (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Gears, Cams (AREA)

Description

L'invention concerne le domaine technique de la tribologie en milieu lubrifié.The invention relates to the technical field of tribology in a lubricated medium.

Plus particulièrement, l'invention concerne les pièces de frottement fonctionnant en milieu lubrifié comportant un modificateur de frottement, comme par exemple des composants automobiles. On pourra éventuellement se référer aux documents US 2010/295251 , US 5582414 , et WO 2011/110413 , qui décrivent des pièces de frottement en milieu lubrifié.More particularly, the invention relates to friction parts operating in a lubricated medium comprising a friction modifier, such as for example automobile components. Reference may be made to the documents US 2010/295251 , US5582414 , and WO 2011/110413 , which describe friction parts in a lubricated environment.

Il est notoirement connu pour un homme du métier d'utiliser des revêtements minces du type DLC afin de réduire le frottement de composants mécaniques fonctionnant en milieu lubrifié.It is well known for a person skilled in the art to use thin coatings of the DLC type in order to reduce the friction of mechanical components operating in a lubricated medium.

Les revêtements DLC sont également connus pour remplir une deuxième fonction qui est de protéger les revêtements contre l'usure.DLC coatings are also known to perform a second function which is to protect coatings against wear.

Toujours en ayant pour objectif de permettre une réduction significative du coefficient de frottement, on a proposé de rajouter un additif modificateur de frottement. Un tel additif est avantageusement le MoDTC qui, dans un contact frottant à chaud, réagit chimiquement pour donner lieu à la formation de composés du type MoS2 parfaitement connus par un homme du métier pour agir en tant que lubrifiant solide.Still with the aim of allowing a significant reduction in the coefficient of friction, it has been proposed to add a friction modifier additive. Such an additive is advantageously MoDTC which, in a hot rubbing contact, reacts chemically to give rise to the formation of compounds of the MoS 2 type perfectly known by a person skilled in the art to act as a solid lubricant.

A partir de cet état de la technique, il peut paraître intéressant de combiner les effets du DLC et du MoDTC pour bénéficier de l'effet de synergie des deux, afin de réduire encore plus le coefficient de frottement.From this state of the art, it may seem interesting to combine the effects of DLC and MoDTC to benefit from the synergistic effect of the two, in order to further reduce the coefficient of friction.

On pourra éventuellement se référer aux documents US 2007/078067 et US 2010/247004 , ainsi qu'au document HAQUE publié en 2007 intitulé « Non-ferrous coating/lubricant interactions in tribological contacts : Assessment of tribofilms », qui décrivent des pièces de frottement revêtues de DLC et un milieu lubrifié comprenant du MoDTC.Reference may be made to the documents US 2007/078067 and US 2010/247004 , as well as to the HAQUE document published in 2007 entitled “Non-ferrous coating/lubricant interactions in tribological contacts: Assessment of tribofilms”, which describe friction parts coated with DLC and a lubricated medium comprising MoDTC.

Toutefois, il est apparu, suite à des essais réalisés, qu'une telle combinaison ne donne pas des résultats satisfaisants. Notamment, il a été observé, que les revêtements DLC qui contiennent de l'hydrogène, présentent un taux d'usure important, en présence du MoDTC. Lorsque le revêtement DLC n'est pas hydrogéné, le phénomène d'usure est moins important mais dans ce cas, l'application, relève d'une technique complexe et coûteuse.However, it appeared, following tests carried out, that such a combination does not give satisfactory results. In particular, it has been observed that DLC coatings which contain hydrogen exhibit a high rate of wear in the presence of MoDTC. When the DLC coating is not hydrogenated, the phenomenon of wear is less significant, but in this case the application involves a complex and costly technique.

D'une manière surprenante et inattendue des essais ont démontré que dans un milieu lubrifié, comportant un modificateur de frottement MoDTC, le fait de remplacer le revêtement DLC par un revêtement de nitrure de chrome, donne des résultats particulièrement satisfaisants tant au niveau de la réduction du coefficient de frottement que de la protection de la pièce considérée contre l'usure.Surprisingly and unexpectedly, tests have shown that in a lubricated medium, comprising a MoDTC friction modifier, replacing the DLC coating with a chromium nitride coating gives particularly satisfactory results both in terms of reduction the coefficient of friction and the protection of the part under consideration against wear.

Autrement dit, à l'inverse du DLC utilisé dans un milieu lubrifié et comportant un modificateur de frottement MoDTC où apparaît un phénomène d'usure, un tel phénomène n'intervient pas avec le nitrure de chrome.In other words, unlike DLC used in a lubricated medium and comprising a MoDTC friction modifier where a wear phenomenon appears, such a phenomenon does not occur with chromium nitride.

L'invention réside donc dans la combinaison des effets du nitrure de chrome et du MoDTC permettant de réduire de manière significative le coefficient de frottement, sans pour autant altérer la dureté.The invention therefore resides in the combination of the effects of chromium nitride and MoDTC making it possible to significantly reduce the coefficient of friction, without however altering the hardness.

Plus précisément, l'invention se rapporte à un système comprenant deux pièces de frottement et un milieu lubrifié comportant un modificateur de frottement entre les deux pièces, le modificateur de frottement étant du MoDTC, un revêtement étant appliqué sur l'une des pièces, et l'autre pièce étant en acier. Le revêtement est du nitrure de chrome appliqué sur une surface externe de la pièce, qui présente une cristallisation type NaCl dont la microdureté est de 1800 +/- 200 HV.More specifically, the invention relates to a system comprising two friction parts and a lubricated medium comprising a friction modifier between the two parts, the friction modifier being MoDTC, a coating being applied to one of the parts, and the other piece being steel. The coating is chromium nitride applied to a external surface of the part, which presents an NaCl type crystallization whose microhardness is 1800 +/- 200 HV.

Cette sélection du nitrure de chrome va à l'encontre des connaissances générales de l'homme du métier qui utilise désormais et quasiment exclusivement le DLC en milieu lubrifié, ne comportant pas de modificateur de frottement en lieu et place du nitrure de chrome.This selection of chromium nitride goes against the general knowledge of a person skilled in the art who now and almost exclusively uses DLC in a lubricated medium, not comprising any friction modifier instead of chromium nitride.

Le document HAQUE publié en 2008 "Tribochemical interactions of friction modifier and antiwear additives with CrN coating under boundary lubrication conditions" décrit le préambule de la revendication 1.The HAQUE document published in 2008 "Tribochemical interactions of friction modifier and antiwear additives with CrN coating under boundary lubrication conditions" describes the preamble of claim 1.

Des essais de frottement ont été effectués afin d'évaluer le comportement dans un milieu lubrifié comportant un modificateur de frottement MoDTC, d'un revêtement DLC et d'un revêtement de nitrure de chrome, en rappelant, de manière parfaitement connue, que dans le cas d'un revêtement DLC, afin de renforcer sa résistance mécanique, on peut déposer une sous-couche, par exemple, de nitrure de chrome. On renvoie au tableau ci-après qui montre les tests effectués sur quatre revêtements, à savoir, DCX-0, DCX-1, DCX-2, DCX-3, le revêtement DCX-3 étant conforme à l'invention. Référence Description DCX-0 CrN (0,8 µm) + DLC (2,0 µm) DCX-1 CrN (0,8 µm) + DLC (2,0 µm) + a-C (0,8µ) DCX-2 CrN (0,8 µm) + DLC (2,0 µm) + finition plasma O2 DCX-3 CrN (0,8 µm) Friction tests were carried out in order to evaluate the behavior in a lubricated medium comprising a MoDTC friction modifier, of a DLC coating and of a chromium nitride coating, recalling, in a perfectly known manner, that in the case of a DLC coating, in order to reinforce its mechanical resistance, an underlayer, for example of chromium nitride, can be deposited. Reference is made to the table below which shows the tests carried out on four coatings, namely, DCX-0, DCX-1, DCX-2, DCX-3, the DCX-3 coating being in accordance with the invention. Reference Description DCX-0 CrN (0.8µm) + DLC (2.0µm) DCX-1 CrN (0.8µm) + DLC (2.0µm) + aC (0.8µ) DCX-2 CrN (0.8 µm) + DLC (2.0 µm) + O 2 plasma finish DCX-3 CrN (0.8µm)

L'ensemble des couches comporte un revêtement de nitrure de chrome élaboré par pulvérisation cathodique réactive magnétron. Pour l'ensemble des revêtements, on procède dans un premier temps au nettoyage des éprouvettes en acier qui sont ensuite positionnées sur des supports placés dans l'enceinte de dépôt sous vide. Pendant le pompage et l'évacuation de l'enceinte, on procède à un chauffage de l'intérieur de la machine et des pièces à revêtir, à une température de 150°C pendant 2h, dans le but de dégazer les pièces et la machine de dépôt. Ensuite, les pièces sont soumises à un décapage ionique dans une atmosphère d'argon, dont le but est d'éliminer les couches minces d'oxyde naturel et ainsi de permettre une forte adhérence du revêtement. Le dépôt de nitrure de chrome est obtenu par pulvérisation cathodique magnétron réactive d'une cible de Cr dans un mélange argon/azote. Le débit d'azote est asservi à une mesure optique de l'émission du Cr dans le plasma, de sorte que le dépôt contient 40+/-5 % atomique d'azote. Ainsi, on obtient un dépôt de CrN présentant une cristallisation cfc type NaCl, dont la microdureté est de 1800+/-200 Hv. Pour les revêtements DCX-0, DCX-1 et DCX-2, on dépose un revêtement de DLC type a-C:H par technique PACVD, en craquant un hydrocarbure dans un plasma, ici, de l'acétylène. Dans le cas de DCX-1, on procède au dépôt final d'une couche de type a-C par pulvérisation cathodique magnétron d'une cible de graphite. Dans le cas de DCX-2, on génère un plasma d'oxygène pur et on bombarde le dépôt par des ions issus du plasma pendant 10minutes, ce qui permet de modifier la chimie de surface du dépôt.All the layers comprise a coating of chromium nitride produced by magnetron reactive sputtering. For all the coatings, the first step is to clean the steel specimens, which are then positioned on supports placed in the vacuum deposition chamber. During pumping and evacuation of the enclosure, the interior of the machine and the parts to be coated are heated to a temperature of 150°C for 2 hours, in order to degas the parts and the machine. deposit. Then, the parts are subjected to ion pickling in an argon atmosphere, the purpose of which is to eliminate the thin layers of natural oxide and thus allow strong adhesion of the coating. The deposition of chromium nitride is obtained by reactive magnetron sputtering of a Cr target in an argon/nitrogen mixture. The nitrogen flow is controlled by an optical measurement of the Cr emission in the plasma, so that the deposit contains 40+/-5 atomic % nitrogen. Thus, a deposit of CrN is obtained exhibiting fcc crystallization of the NaCl type, the microhardness of which is 1800+/-200 Hv. For the DCX-0, DCX-1 and DCX-2 coatings, an aC:H type DLC coating is deposited by the PACVD technique, by cracking a hydrocarbon in a plasma, here, acetylene. In the case of DCX-1, the final deposition of an aC-type layer is carried out by magnetron cathodic sputtering of a graphite target. In the case of DCX-2, a plasma of pure oxygen is generated and the deposit is bombarded with ions from the plasma for 10 minutes, which makes it possible to modify the surface chemistry of the deposit.

Ces essais ont été réalisés avec un tribomètre alternatif en configuration bille sur plan. Pour ces essais, le plan est constitué d'une éprouvette en acier, polie à un niveau de Ra de 0,02 µm. La bille est en acier 100Cr6 et a un diamètre de 10 mm. Pour tous les essais, les revêtements sont appliqués sur la bille.These tests were carried out with an alternating tribometer in a ball-on-plane configuration. For these tests, the plane consists of a steel specimen, polished to an Ra level of 0.02 µm. The ball is made of 100Cr6 steel and has a diameter of 10 mm. For all the tests, the coatings are applied to the ball.

La charge appliquée sur la bille est de 10N, ce qui donne un diamètre Hertzien de contact de 140 µm et une pression moyenne de 0,68 GPa.The load applied to the ball is 10N, which gives a Hertzian contact diameter of 140 µm and an average pressure of 0.68 GPa.

La bille est animée d'un mouvement alternatif, dont la course est de 10 mm. La vitesse de glissement suit un profil de type sinus, dont la valeur moyenne est de 3,5 cm/s.The ball is animated by an alternating movement, the stroke of which is 10 mm. The sliding velocity follows a sine-like profile, the mean value of which is 3.5 cm/s.

Le test est conduit pendant une durée de 15 000 cycles à une température de 110°C. Les conditions de vitesse de glissement, de pression et de température, sont telles que l'additifs de réduction de frottement réagit pour remplir sont rôle. A l'issue du test, on observe la bille et on mesure le diamètre de la trace de frottement ou trace d'usure, à partir duquel, on calcule le volume usé. Le graphique annexé (figure 1) résume les vitesses d'usure moyenne (volume usé ramené au nombre de cycles de frottement). Pour chaque revêtement, 3 essais ont été effectués, l'usure moyenne a été calculée. Les barres d'erreur représentent, non pas une erreur, mais la valeur la plus petite et la valeur la plus grande pour ces 3 essais.The test is carried out for a period of 15,000 cycles at a temperature of 110°C. The conditions of sliding speed, pressure and temperature are such that the friction reducing additive reacts to fulfill its role. At the end of the test, the ball is observed and the diameter of the friction mark or wear mark is measured, from which the worn volume is calculated. The attached graph ( figure 1 ) summarizes the average wear rates (worn volume reduced to the number of friction cycles). For each coating, 3 tests were carried out, the average wear was calculated. The error bars represent, not an error, but the smallest value and the largest value for these 3 trials.

Pour chacun des essais et pour les différents revêtements, les mesures ont été effectuées en présence d'une huile automobile du commerce contenant le modificateur de frottement MoDTC.For each of the tests and for the various coatings, the measurements were carried out in the presence of a commercial automotive oil containing the friction modifier MoDTC.

Il ressort de ce graphique les observations suivantes :

  • Pour le revêtement DCX-0, l'usure est particulièrement importante, ce qui n'est, du reste, pas le cas pour le même type de revêtement en milieu lubrifié ne comportant pas de modificateur de frottement MoDTC.
  • Pour le revêtement DCX-1, l'ajout d'une couche carbone amorphe non-hydrogéné par-dessus le DLC, tend à réduire la vitesse d'usure d'un facteur d'environ 2,9.
  • Pour le revêtement DCX-2, on voit que la modification de la surface DLC par un plasma d'oxygène, n'a pas d'influence significative sur la vitesse d'usure du DLC, alors que l'énergie de surface est complètement modifiée.
  • Le revêtement DCX-3, conforme à l'invention, présente une usure nulle en fin d'essai, le diamètre de frottement est très légèrement supérieur au diamètre initial de contact. Le nitrure de chrome présente une dureté de l'ordre de 1800 Hv.
The following observations emerge from this graph:
  • For the DCX-0 coating, the wear is particularly high, which is not, moreover, the case for the same type of coating in a lubricated medium not comprising any MoDTC friction modifier.
  • For the DCX-1 coating, the addition of a non-hydrogenated amorphous carbon layer on top of the DLC tends to reduce the wear rate by a factor of approximately 2.9.
  • For the DCX-2 coating, we see that the modification of the DLC surface by an oxygen plasma, has no significant influence on the wear rate of the DLC, while the surface energy is completely modified. .
  • The DCX-3 coating, in accordance with the invention, shows zero wear at the end of the test, the friction diameter is very slightly greater than the initial contact diameter. Chromium nitride has a hardness of around 1800 Hv.

Le tableau ci-dessous résume les valeurs de vitesse d'usure moyenne qui apparaissent sur le graphe annexé. Référence Vitesse d'usure en µm3/cycle DCX-0 1,68 DCX-1 0,56 DCX-2 1,26 DCX-3 0,42 Acier 0,45 The table below summarizes the average wear rate values that appear on the attached graph. Reference Wear rate in µm 3 /cycle DCX-0 1.68 DCX-1 0.56 DCX-2 1.26 DCX-3 0.42 Steel 0.45

Le tableau ci-dessous donne les coefficients de frottement en fin d'essai. Référence Coefficient de frottement DCX-0 0,031+/-0,016 DCX-1 0,032+/-0,009 DCX-2 0,025+/-0,003 DCX-3 0,031+/-0,001 Acier 0,040+/-0,005 The table below gives the friction coefficients at the end of the test. Reference Coefficient of friction DCX-0 0.031+/-0.016 DCX-1 0.032+/-0.009 DCX-2 0.025+/-0.003 DCX-3 0.031+/-0.001 Steel 0.040+/-0.005

Il ressort de ces tableaux, que toutes les solutions comportant un revêtement présentent des coefficients de frottement moyens similaires.It emerges from these tables that all the solutions comprising a coating have similar average coefficients of friction.

La forte dispersion dans le cas du DCX-0 est liée à l'usure. On note que les coefficients de frottement les plus bas sont obtenus pour les dépôts les plus usés.The high dispersion in the case of DCX-0 is related to wear. It is noted that the lowest coefficients of friction are obtained for the most worn deposits.

Le faible coefficient de frottement est essentiellement dû à l'additif de réduction de frottement : le MoDTC.The low coefficient of friction is mainly due to the friction reduction additive: MoDTC.

A titre d'exemple et comme le montre la dernière ligne des tableaux, le test d'une bille non revêtue face à un plan non revêtu donne un coefficient de frottement de 0,040+/-0,005. La vitesse d'usure moyenne est de 0,45. Bien que cette solution résiste aussi à l'usure, grâce aux additifs anti-usure de l'huile, elle donne toutefois un coefficient de frottement plus élevé de 30 %.By way of example and as shown in the last line of the tables, the test of an uncoated ball facing an uncoated plane gives a coefficient of friction of 0.040+/-0.005. The average wear rate is 0.45. Although this solution also resists wear, thanks to the anti-wear additives in the oil, it nevertheless gives a 30% higher coefficient of friction.

A titre de comparaison, le frottement d'une bille revêtue DLC (DCX-0) face à un plan, acier en utilisant une huile SAE 5W30 (sans aucun modificateur de frottement), donne une vitesse d'usure de 0,3+/-0,05 µm3/ cycle, par contre le coefficient de frottement se stabilise à 0,12. Dans une huile SAE 5W30 comportant un additif de réduction de frottement de type acide gras, la vitesse d'usure est de 0,32+/-0,05 µm3/ cycle et le coefficient de frottement est de 0,08.For comparison, friction of a DLC coated ball (DCX-0) against a plane, steel using SAE 5W30 oil (without any friction modifiers), gives a wear rate of 0.3+/ -0.05 μm 3 / cycle, on the other hand the coefficient of friction stabilizes at 0.12. In an SAE 5W30 oil comprising a fatty acid type friction reduction additive, the wear rate is 0.32+/-0.05 μm 3 /cycle and the coefficient of friction is 0.08.

Il ressort de ce qui précède, que les revêtements de DLC de type DCX-0 résistent bien à l'usure dans des huiles sans MoDTC en observant que ces huiles ne permettent pas d'obtenir des coefficients de frottement aussi bas que celles contenant du MoDTC.It emerges from the foregoing that DLC coatings of the DCX-0 type resist wear well in oils without MoDTC, observing that these oils do not make it possible to obtain coefficients of friction as low as those containing MoDTC. .

Autrement dit, la combinaison DLC face à un antagoniste de frottement en acier, MoDTC n'est pas compatible pour réaliser les deux fonctions, à savoir, résister à l'usure d'une part, et obtenir un coefficient de frottement aussi bas que possible d'autre part, alors que la combinaison revendiquée, à savoir, nitrure de chrome et MoDTC permet avantageusement de réaliser ces deux fonctions.In other words, the DLC combination facing a steel friction antagonist, MoDTC is not compatible to achieve the two functions, namely, to resist wear on the one hand, and to obtain a coefficient of friction as low as possible on the other hand, whereas the claimed combination, namely, chromium nitride and MoDTC advantageously makes it possible to perform these two functions.

L'invention concerne également l'utilisation de pièces ainsi revêtues et travaillant dans un milieu lubrifié contenant du MoDTC dans le domaine de l'automobile, notamment pour les moteurs et les boîtes de vitesses.The invention also relates to the use of parts thus coated and working in a lubricated medium containing MoDTC in the automotive field, in particular for engines and gearboxes.

Claims (4)

  1. A system comprising two friction parts and a lubricated environment having a friction modifier between the two parts, the friction modifier being MoDTC, a coating being applied to one of the parts, characterized in that the other part is steel and in that the coating is chromium nitride applied to an outer surface of the part, which has a NaCl type crystallisation with a microhardness of 1800 +/- 200 HV.
  2. Use of the system according to claim 1 in the automotive field.
  3. Use according to claim 2 in the engines field.
  4. Use according to claim 2 in the gearboxes field.
EP12780220.5A 2011-10-21 2012-10-03 System comprising two friction members and a lubricating medium Active EP2768932B8 (en)

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PCT/FR2012/052236 WO2013057407A1 (en) 2011-10-21 2012-10-03 Friction piece operating in a lubricated medium

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Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016032782A1 (en) * 2014-08-27 2016-03-03 Shell Oil Company Methods for lubricating a diamond-like carbon coated surface, associated lubricating oil compositions and associated screening methods
JP6392625B2 (en) * 2014-10-14 2018-09-19 大同工業株式会社 Chain bearing, pin, and chain using the same
CN105424524B (en) * 2015-12-16 2019-07-23 上海大学 The method that high-temp in-situ generates the test of solid lubricant film tribological property
JP6849204B2 (en) 2016-03-30 2021-03-24 出光興産株式会社 Lubricating oil composition
JP2019066002A (en) * 2017-10-03 2019-04-25 株式会社豊田中央研究所 Sliding system

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5582414A (en) * 1993-06-07 1996-12-10 Teikoku Piston Ring Co., Ltd. Sliding member and method for manufacturing the same
US20100295251A1 (en) * 2006-11-14 2010-11-25 Takuma Sekiya Chromium nitride ion-plating coating and its production method, as well as piston ring used for internal combustion engine
WO2011110413A1 (en) * 2010-03-09 2011-09-15 Federal-Mogul Burscheid Gmbh Sliding element, in particular a piston ring, and method for coating a sliding element

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04368A (en) * 1990-04-17 1992-01-06 Riken Corp Wear resistant coating film and production thereof
RU2025543C1 (en) * 1992-03-24 1994-12-30 Марк Григорьевич Карпман Wear resistant ion-plasma coating and method to obtain wear resistant coating
US5449547A (en) * 1993-03-15 1995-09-12 Teikoku Piston Ring Co., Ltd. Hard coating material, sliding member coated with hard coating material and method for manufacturing sliding member
JPH06265023A (en) * 1993-03-15 1994-09-20 Teikoku Piston Ring Co Ltd Rigid convering material, slide member covered therewith, and manufacture thereof
JP3408366B2 (en) * 1995-09-28 2003-05-19 日本ピストンリング株式会社 Sliding member for compressor
US5650381A (en) * 1995-11-20 1997-07-22 Ethyl Corporation Lubricant containing molybdenum compound and secondary diarylamine
JP2001335878A (en) 2000-05-30 2001-12-04 Teikoku Piston Ring Co Ltd Sliding member
JP4244379B2 (en) * 2003-07-16 2009-03-25 三菱マテリアル株式会社 Surface coated cemented carbide cutting tool with excellent wear resistance with high surface coating layer in high speed cutting
JP4614427B2 (en) * 2003-08-06 2011-01-19 日産自動車株式会社 Low friction sliding mechanism, manual transmission and final reduction gear
JP4824407B2 (en) * 2003-08-06 2011-11-30 Ｊｘ日鉱日石エネルギー株式会社 System having DLC contact surface, method of lubricating the system, and lubricating oil for the system
US7951756B2 (en) * 2003-08-06 2011-05-31 Nippon Oil Corporation System having DLC contact surfaces, method of lubricating the system, and lubricant for the system
JP2006144848A (en) 2004-11-17 2006-06-08 Jtekt Corp Bearing for rocker arm
KR100706387B1 (en) * 2005-08-05 2007-04-10 현대자동차주식회사 Coating method of engine valve cap
JP4848545B2 (en) 2005-09-30 2011-12-28 Ｄｏｗａサーモテック株式会社 Hard coating member and method for producing the same
JP4784248B2 (en) * 2005-10-05 2011-10-05 トヨタ自動車株式会社 Sliding structure and sliding method
JP2007205564A (en) 2006-01-06 2007-08-16 Toyota Motor Corp Sliding member and clutch
JP4968619B2 (en) * 2006-07-31 2012-07-04 日産自動車株式会社 Hard carbon coating
JP4333794B2 (en) * 2007-11-06 2009-09-16 トヨタ自動車株式会社 Sliding structure
KR101036333B1 (en) * 2007-12-05 2011-05-25 (주)어플라이드플라즈마 Plasma thin film deposition system and it`s method for high wear resistance and low friction coefficient thin film deposition on components in automatic system and automobile

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5582414A (en) * 1993-06-07 1996-12-10 Teikoku Piston Ring Co., Ltd. Sliding member and method for manufacturing the same
US20100295251A1 (en) * 2006-11-14 2010-11-25 Takuma Sekiya Chromium nitride ion-plating coating and its production method, as well as piston ring used for internal combustion engine
WO2011110413A1 (en) * 2010-03-09 2011-09-15 Federal-Mogul Burscheid Gmbh Sliding element, in particular a piston ring, and method for coating a sliding element

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CN103917630A (en) 2014-07-09
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JP2019060499A (en) 2019-04-18
US20140274826A1 (en) 2014-09-18
JP7442427B2 (en) 2024-03-04
FR2981728A1 (en) 2013-04-26
BR112014008486A2 (en) 2017-04-25
JP7042760B2 (en) 2022-03-28
WO2013057407A1 (en) 2013-04-25
TW201341521A (en) 2013-10-16
EP2768932B8 (en) 2022-02-16
FR2981728B1 (en) 2014-07-04

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