EP3794162B1 - Lubrifiants avec formation in situ de couches de dlc - Google Patents

Lubrifiants avec formation in situ de couches de dlc Download PDF

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Publication number
EP3794162B1
EP3794162B1 EP19749182.2A EP19749182A EP3794162B1 EP 3794162 B1 EP3794162 B1 EP 3794162B1 EP 19749182 A EP19749182 A EP 19749182A EP 3794162 B1 EP3794162 B1 EP 3794162B1
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EP
European Patent Office
Prior art keywords
mass
massen
bis
lubricant
lubricant composition
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Active
Application number
EP19749182.2A
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German (de)
English (en)
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EP3794162A1 (fr
Inventor
Martin Schweigkofler
Stefan Seemeyer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Klueber Lubrication Muenchen GmbH and Co KG
Original Assignee
Klueber Lubrication Muenchen SE and Co KG
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Publication of EP3794162A1 publication Critical patent/EP3794162A1/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
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • 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
    • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/04—Metals; Alloys
    • 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
    • C10M157/00—Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, each of these compounds being essential
    • C10M157/10—Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, each of these compounds being essential at least one of them being a compound containing atoms of elements not provided for in groups C10M157/02 - C10M157/08
    • 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
    • C10M2201/04—Elements
    • C10M2201/05—Metals; Alloys
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
    • C10M2207/124—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms containing hydroxy groups; Ethers thereof
    • C10M2207/1245—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms containing hydroxy groups; Ethers thereof used as thickening agent
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/2805—Esters 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/221—Six-membered rings containing nitrogen and carbon only
    • C10M2215/222—Triazines
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/223—Five-membered rings containing nitrogen and carbon only
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/30—Heterocyclic 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/055—Particles related characteristics
    • C10N2020/06—Particles of special shape or size
    • 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
    • C10N2040/02—Bearings
    • 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
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/015—Dispersions of solid lubricants
    • C10N2050/02—Dispersions of solid lubricants dissolved or suspended in a carrier which subsequently evaporates to leave a lubricant coating
    • 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
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/023—Multi-layer lubricant coatings
    • C10N2050/025—Multi-layer lubricant coatings in the form of films or sheets
    • 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
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10—Semi-solids; greasy

Definitions

  • the present invention relates to the use of novel lubricants for the formation of in-situ Diamond-Like-Carbon (DLC) layers.
  • the invention relates to a lubricant in the form of an oil or grease based on hydrocarbons, which contains non-ferrous metal particles and at the same time a non-ferrous metal deactivator.
  • the DLC layers are usually produced in a vacuum by depositing the carbon layers using chemical (CVD) or physical (PVD) vapor phase deposition processes.
  • CVD chemical
  • PVD physical vapor phase deposition processes.
  • U.S. 9,951,291 B2 describes the U.S. 9,951,291 B2 to provide the surface of a tribological system with a nanocomposite layer consisting of MoNx or VN 2 and copper by plasma treatment.
  • Hydrocarbon-based lubricants react under tribological stress on this layer to form a DLC coating, which is attributed to the catalytic effect of the copper.
  • a disadvantage of this method is that it is difficult to apply the layers under comparable conditions that are required for applying a DLC layer.
  • the copper contained in the layer can have negative effects on the lubricant at the points that are not exposed to the tribological load, such as increasing the viscosity or the lubricant becoming sludgy or pasty.
  • the WO 2016/065175 A1 describes the use of a lubricant composition for the in-situ formation of a diamond-like carbon (DLC) layer on a surface of a component in roller bearings and gears.
  • This lubricating composition contains an oil, synfluid poly-alpha-olefin 4 (PAO4), and an additive, 5% by mass cyclopropane carboxylic acid (CPCa).
  • the object of the present invention was therefore to provide a lubricant for the formation of in-situ Diamond-Like-Carbon (DLC) layers that meets the above requirements, in particular causes low coefficients of friction, long service lives and reduced signs of wear on the components .
  • DLC diamond-Like-Carbon
  • a lubricant composition consisting of an oil or grease based on hydrocarbons, non-ferrous metal nanoparticles and a non-ferrous metal deactivator as well as customary additives is provided.
  • This lubricant can be in the form of fats, pastes or oils.
  • the underlying lubricating oil contains synthetic hydrocarbons such as PAOs or mPAOs, mineral oil, native oils and derivatives of native oils, esters, polyglycols, phenyl ethers, silicone oils or perfluoropolyethers.
  • Organic or inorganic substances can be used as thickeners, in particular PTFE, graphite, metal oxides, boron nitride, molybdenum disulphide, phosphates, silicates, Sulfonates, polyimides, metal soaps, metal complex soaps, ureas and mixtures thereof, solid lubricants such as graphite or MoS 2 .
  • the non-ferrous metals are selected from the group consisting of metals of the first (Sc-Zn), second (Y-Cd) and third (La-Hg) period of the transition metals, Mn, Fe, Co, Cu, Y, Re, Os being particularly preferred , particularly preferably Cu is used. Alloys of the non-ferrous metals mentioned can also be used.
  • the ferrous metal deactivators or inhibitors are substances that protect the metallic surface of the nanoparticles from corrosive attack, for example from oxygen with the formation of oxides, or can at least slow down this attack.
  • the inhibitor is selected in such a way that the inhibitor interacts preferentially with the surface of the nanoparticle and not with the surface of the component (selective inhibitor).
  • heteroaromatic compounds are oxazoles, imidazoles, triazoles and triazines, which can have a wide variety of substituents.
  • reactive substances are acids, especially carboxylic acids and hydroxycarboxylic acids, for example oleic acid.
  • the non-ferrous metal deactivator inhibits the copper particles in the lubricant composition and protects them from aging. Under tribological stress, the copper particles release free copper surfaces and thus catalyze the polymerization or the formation of a DLC layer. When the tribological load is removed, the exposed copper surfaces are again inhibited by the excess non-ferrous metal deactivator.
  • the copper even in its inhibited form, has a positive influence on WEC (white etching cracks) and has a wear-protecting effect.
  • a lubricant composition which contains 0.01 to 5% by mass of non-ferrous metals is particularly preferred.
  • the particle size of the non-ferrous metals ranges from 1 to 5000 nm, preferably 1 to 500 nm, particularly preferably 1 to 50 nm.
  • the amount of inhibitors used can be up to the same mass fraction, preferably half the mass fraction, particularly preferably one tenth of the mass fraction compared to the nanoparticles.
  • Phenolic and aminic antioxidants are used as additives.
  • Succinic acid derivatives in particular amidized succinic acid semiesters or alkaline earth metal oxides, preferably calcium oxide and/or magnesium oxide and calcium, magnesium and/or sodium sulfonates or salts of dicarboxylic acids having 8 to 20 carbon atoms, preferably disodium sebacate, can also be used as corrosion protection additives.
  • EP/AW additives are used, which can contain sulfur and/or phosphorus as a component.
  • the gear oils can also contain standard gear oil packages as well as polymer-based defoamers and silicone-containing and silicone-free compounds.
  • Lubricating oil for medium-load gears e.g. for the automotive sector
  • Lubricating oil for heavily loaded gears e.g. for open drives in mills or rotary kilns as well as for industrial gears

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Lubricants (AREA)

Claims (6)

  1. Utilisation d'une composition de lubrifiant contenant 99,989 à 87,1 pourcents en masse d'un lubrifiant sous forme d'une graisse ou d'une huile y compris des additifs,
    0,01 à 10% en masse de nanoparticules de métaux non ferreux sélectionnées parmi le groupe constitué de métaux de la première (SC - Zn), deuxième (Y - Cd) et troisième (La-Hg) période des métaux de transition ainsi que leurs alliages, et
    0,001 à 2,9 % en masse d'un désactivateur de métaux non ferreux sélectionné parmi le groupe constitué de composés hétéroaromatiques, tels que des oxazoles, des imidazoles, des triazoles et/ou des triazines ou acides, en particulier des acides carboxyliques et acides hydroxycarboxyliques, en particulier des acides oléiques,
    pour la formation in situ d'une couche DLC (Diamond Like Carbon) sur une surface d'un composant dans des paliers à roulement, des paliers à glissement et des transmissions.
  2. Utilisation d'une composition de lubrifiant suivant la revendication 1, pour la formation in situ d'une couche DLC (Diamond Like Carbon) sur une surface d'un composant dans le domaine automobile.
  3. Utilisation d'une composition de lubrifiant suivant la revendication 1 ou 2, l'huile du lubrifiant est sélectionnée comme composant individuel ou en mélange parmi le groupe constitué d'hydrocarbures synthétiques, tels que les PAO ou mPAO, d'huile minérale, d'huiles vierges et de dérivées d'huiles vierges, d'esters, de polyglycols, de phényléthers, d'huiles de silicone ou de perfluorpolyéthers.
  4. Utilisation d'une composition de lubrifiant suivant une des revendications précédentes, le lubrifiant étant épaissi de manière à former une graisse avec un épaississant sous forme pure ou en mélange sélectionné parmi le groupe constitué de substances organiques ou anorganiques, en particulier PTFE, graphite, oxydes métalliques, nitrure de bore, disulfure de molybdène, de phosphates, de silicates, de sulfonates, de polyimides, de savons métalliques, de savons métalliques complexes, d'urées et leurs mélanges, de lubrifiants solides, tels le graphite ou le MoS2.
  5. Utilisation d'une composition de lubrifiant suivant la revendication 1, les nanoparticules de métaux non ferreux étant sélectionnées parmi Mn, Fe, Cu, Cu Y, Re, Os.
  6. Utilisation d'une composition de lubrifiant suivant la revendication 5, la taille de particule des métaux non ferreux allant de 500 à 3000 nm.
EP19749182.2A 2018-07-26 2019-07-18 Lubrifiants avec formation in situ de couches de dlc Active EP3794162B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102018005905 2018-07-26
DE102019004865.2A DE102019004865A1 (de) 2018-07-26 2019-07-11 Schmierstoffe mit in-situ-Bildung von DLC-Schichten
PCT/EP2019/000222 WO2020020477A1 (fr) 2018-07-26 2019-07-18 Lubrifiants avec formation in situ de couches de dlc

Publications (2)

Publication Number Publication Date
EP3794162A1 EP3794162A1 (fr) 2021-03-24
EP3794162B1 true EP3794162B1 (fr) 2023-06-07

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ID=67539390

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EP19749182.2A Active EP3794162B1 (fr) 2018-07-26 2019-07-18 Lubrifiants avec formation in situ de couches de dlc

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EP (1) EP3794162B1 (fr)
DE (1) DE102019004865A1 (fr)
WO (1) WO2020020477A1 (fr)

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016065175A1 (fr) * 2014-10-23 2016-04-28 Northwestern University Additifs lubrifiants, compositions de lubrifiant et leurs applications
US9951291B2 (en) 2015-05-22 2018-04-24 Uchicago Argonne, Llc Producing carbon-based boundary films from catalytically active lubricant additives

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Publication number Publication date
DE102019004865A1 (de) 2020-01-30
EP3794162A1 (fr) 2021-03-24
WO2020020477A1 (fr) 2020-01-30

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