EP3794162B1 - Lubricants with in-situ formation of dlc layers - Google Patents

Lubricants with in-situ formation of dlc layers 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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mass
massen
bis
lubricant
lubricant composition
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EP19749182.2A
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German (de)
French (fr)
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EP3794162A1 (en
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Martin Schweigkofler
Stefan Seemeyer
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Klueber Lubrication Muenchen GmbH and Co KG
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Klueber Lubrication Muenchen SE and Co KG
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    • 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

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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)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Lubricants (AREA)

Description

Die vorliegende Erfindung betrifft die Verwendung neuartiger Schmierstoffe für die Bildung von in-situ Diamond-Like-Carbon (DLC)-Schichten. Insbesondere betrifft die Erfindung einen Schmierstoff in Form eines Öls oder Fettes auf Kohlenwasserstoffbasis, der Buntmetallpartikel und gleichzeitig einen Buntmetalldeaktivator enthält.The present invention relates to the use of novel lubricants for the formation of in-situ Diamond-Like-Carbon (DLC) layers. In particular, 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.

Die Entwicklung von neuen Schmierstoffen muss mit der allgemeinen Weiterentwicklung der Technik einhergehen, die neue und höhere Anforderungen an die Schmierstoffzusammensetzungen stellt. In verschiedenen Bereichen der Fahrzeugtechnik und Industrie werden immer höhere Anforderungen an die Schmierstoffe gestellt, die insbesondere die Verringerung von Reibung und Verschleiß betreffen. Dabei sollen immer weniger Schmierstoffe eingesetzt werden, um die Kosten zu senken. Dies bedeutet, dass Schmierstoffe immer leistungsfähiger werden und gleichzeitig die Ressourcen geschont werden sollen.The development of new lubricants must go hand in hand with the general advancement of technology, which places new and higher demands on the lubricant compositions. In various areas of vehicle technology and industry, the demands placed on lubricants are increasing, in particular to reduce friction and wear. Fewer and fewer lubricants are to be used in order to reduce costs. This means that lubricants are becoming more and more efficient and at the same time resources are to be conserved.

Es wurde daher vorgeschlagen, in der Fahrzeugtechnik bewegliche Teile mit DLC-Schichten zu versehen, wobei der Verschleiß und die Reibung minimiert werden können und so die Fahrzeugteile leistungsstärker und emissionsärmer zu machen. Die DLC-Schichten werden durch Abscheidung der Kohlenstoffschichten mit den Verfahren der chemischen (CVD)- oder physikalischen (PVD)- Gasphasenabscheidung meist im Vakuum erzeugt. So beschreibt beispielsweise die US 9 951 291 B2 die Oberfläche eines Tribosystems per Plasmabehandlung mit einer Nanokompositschicht bestehend aus MoNx oder VN2 und Kupfer zu versehen. Schmierstoffe auf Kohlenwasserstoffbasis reagieren unter tribologischer Belastung auf dieser Schicht unter Ausbildung einer DLC-Beschichtung, was auf die katalytische Wirkung des Kupfers zurückgeführt wird. Nachteilig an diesem Verfahren ist jedoch, dass es schwierig ist, die Schichten unter vergleichbaren Bedingungen, die für das Aufbringen einer DLC-Schicht benötigt wird, aufzubringen. Des weiteren kann das Kupfer, das in der Schicht enthalten ist, an den Stellen, die nicht der tribologischen Belastung ausgesetzt sind, negative Einflüsse auf das Schmiermittel haben, wie z.B. die Erhöhung der Viskosität oder das Verschlammen oder Verpasten des Schmiermittels. Die WO 2016/065175 A1 beschreibt die Verwendung einer Schmiermittelszusammensetzung zur in-situ Bildung einer Diamond-Like-Carbon (DLC)-Schicht auf einer Oberfläche eines Bauteils in Wälzlagern und Getrieben. Diese Schmiermittelszusammensetzung enthält ein Öl, Synfluid Poly-alpha-olefin 4 (PAO4), und ein Additiv, 5 Massen-% Cyclopropancarbonsaüre (CPCa).It was therefore proposed to provide moving parts in vehicle technology with DLC layers, whereby wear and tear and friction can be minimized and the vehicle parts are therefore more powerful and have fewer emissions close. The DLC layers are usually produced in a vacuum by depositing the carbon layers using chemical (CVD) or physical (PVD) vapor phase deposition processes. For example, 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, however, is that it is difficult to apply the layers under comparable conditions that are required for applying a DLC layer. Furthermore, 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).

Die Aufgabe der vorliegenden Erfindung bestand daher darin, einen Schmierstoff für die Bildung von in-situ Diamond-Like-Carbon (DLC)-Schichten bereitzustellen, der den oben genannten Anforderungen entspricht, insbesondere niedrige Reibwerte, lange Laufzeiten und reduzierte Verschleißerscheinungen auf den Bauteilen bewirkt.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 .

Hierzu wird erfindungsgemäß eine Schmiermittelzusammensetzung bestehend aus einem Öl oder Fett auf Kohlenwasserstoffbasis, Buntmetall-Nanopartikeln und einem Buntmetalldeaktivator sowie üblichen Additiven bereitgestellt.For this purpose, according to the invention, 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.

Dieses Schmiermittel kann in Form von Fetten, Pasten oder Ölen vorliegen. Das zugrunde liegende Schmieröl enthält synthetische Kohlenwasserstoffe wie PAOs oder mPAOs, Mineralöl, native Öle und Derivate von nativen Ölen, Ester, Polyglykole, Phenylether, Silikonöle oder Perfluorpolyether. Als Verdicker können organische oder anorganische Stoffe verwendet werden, insbesondere PTFE, Graphit, Metalloxide, Bornitrid, Molybdändisulfid, Phosphate, Silikate, Sulfonate, Polyimide, Metallseifen, Metallkomplexseifen, Harnstoffe und deren Gemische, Festschmierstoffe wie Graphit oder MoS2.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 .

Die Buntmetalle werden ausgewählt aus der Gruppe bestehend aus Metallen der ersten (Sc - Zn), zweiten (Y - Cd) und dritten (La - Hg) Periode der Übergangsmetalle, besonders bevorzugt sind Mn, Fe, Co, Cu Y, Re, Os, insbesondere bevorzugt wird Cu verwendet. Außerdem können Legierungen der genannten Buntmetalle verwendet werden.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.

Die Bundmetalldeaktivatoren bzw. die Inhibitoren sind Substanzen, die die metallische Oberfläche der Nanoteilchen vor einem korrosiven Angriff, beispielsweise von Sauerstoff unter Bildung von Oxiden schützen oder diesen Angriff zumindest verlangsamen können.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.

Dies sind in der Regel Substanzen, die koordinative Bindungen mit den Oberflächenatomen der Nanoteilchen eingehen können. Es können auch reaktive Substanzen, die Monolagen auf den Metalloberflächen bilden, verwendet werden. Die Auswahl des Inhibitors erfolgt so, dass der Inhibitor bevorzugt mit der Oberfläche des Nanoteilchens und nicht mit der Oberfläche des Bauteiles wechselwirkt (selektiver Inhibitor).These are usually substances that can form coordinate bonds with the surface atoms of the nanoparticles. Reactive substances that form monolayers on the metal surfaces can also be used. 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).

Diese Substanzen weisen häufig aromatische Ringe sowie Heteroatome mit freien Elektronenpaaren auf, die als Donoren fungieren können.These substances often have aromatic rings and heteroatoms with lone pairs of electrons that can act as donors.

Beispiele für heteroaromatische Verbindungen sind Oxazole, Imidazole Triazole, und Triazine, die verschiedenste Substituenten aufweisen können. Beispiele für reaktive Substanzen sind Säuren, besonders Carbonsäuren und Hydroxycarbonsäuren, beispielsweise Ölsäure.Examples of heteroaromatic compounds are oxazoles, imidazoles, triazoles and triazines, which can have a wide variety of substituents. Examples of reactive substances are acids, especially carboxylic acids and hydroxycarboxylic acids, for example oleic acid.

Der Buntmetalldeaktivator inhibiert beispielsweise die Kupferpartikel in der Schmiermittelzusammensetzung und schützt sie vor Alterung. Unter tribologischer Belastung setzen die Kupferpartikel freie Kupfer-Oberflächen frei und katalysieren damit die Polymerisation bzw. die Ausbildung einer DLC-Schicht. Wenn die tribologische Belastung entfernt wird, werden die freien Kupfer-Oberflächen durch den Überschuss an Buntmetalldeaktivator erneut inhibiert. Dabei hat das Kupfer, auch in seiner inhibierten Form, einen positiven Einfluss auf WEC (white etching cracks) und weist eine verschleißschützende Wirkung auf.For example, 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.

Die erfindungsgemäße Schmiermittelzusammensetzung enthält, wie im Anspruch 1 beschrieben, 99,989 bis 80 Massen-% Schmierstoff auf Basis eines Fett oder Öls einschließlich Additive,

  • 0,01 bis 10 Massen-% Buntmetalle sowie
  • 0,001 bis 10 Massen-% Buntmetalldeaktivator.
The lubricant composition according to the invention contains, as described in claim 1, 99.989 to 80% by mass of a lubricant based on a fat or oil, including additives,
  • 0.01 to 10% by mass of non-ferrous metals and
  • 0.001 to 10% by mass of non-ferrous metal deactivator.

Besonders bevorzugt ist eine Schmiermittelzusammensetzung, die 0,01 bis 5 Massen-% Buntmetalle enthält. Die Partikelgröße der Buntmetalle reicht von 1 bis 5000 nm, bevorzugt 1 bis 500 nm, insbesondere bevorzugt 1 bis 50 nm.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.

Die Menge an Inhibitoren kann (bezogen auf den Gehalt an Nanoteilchen) bis zum gleichen Massengehalt eingesetzt werden, bevorzugt die Hälfte des Massenanteiles, besonders bevorzugt ein Zehntel der Massenanteile verglichen mit den Nanoteilchen.The amount of inhibitors used (based on the content of nanoparticles) 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.

Als Additive werden phenolische und aminische Antioxidantien eingesetzt. Des weiteren können als Korrosionsschutzadditive Bernsteinsäurederivate, insbesondere amidisierte Bernsteinsäurehalbester oder Erdalkalioxide, bevorzugt Calciumoxid und/oder Magnesiumoxid sowie Calcium-, Magnesium- und/oder Natriumsulfonate bzw. salze von Dicarbonsäuren mit 8 bis 20 C-Atomen, bevorzugt Dinatriumsebacat verwendet werden. Darüber hinaus werden EP/AW-Additive eingesetzt, die als Bestandteil Schwefel und/oder Phosphor enthalten können.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. In addition, EP/AW additives are used, which can contain sulfur and/or phosphorus as a component.

Die Getriebeöle können außerdem Standard-Getriebeölpackages enthalten sowie Entschäumer auf Polymerbasis, sowie silikonhaltige und silikonfreie Verbindungen.The gear oils can also contain standard gear oil packages as well as polymer-based defoamers and silicone-containing and silicone-free compounds.

Anhand der nachfolgenden Beispiele wird die Erfindung näher erläutert.The invention is explained in more detail on the basis of the following examples.

Beispiel 1example 1

Schmieröl für mittelbelastetes Getriebe, z.B. für den Automotive-BereichLubricating oil for medium-load gears, e.g. for the automotive sector

Für ein Schmieröl für ein mittelbelastetes Getriebe werden

  • 99,989 Massen-% bis 98,9 Massen-% Schmieröl bestehend aus
    89,85 bis 66,70 Massen-% eines PAO-Gemisches der Viskosität 68 bis 680 cst bei 40°C, 10,0 Massen-% bis 30,0 Massen-% Diester der Viskosität 25 bis 100 cst bei 40°C, 0,05 Massen-% bis 3,0 Massen-% Getriebeöladditivpackage sowie 0,1 Massen-% bis 0,3 Massen-% Entschäumer,
  • 0,01 Massen-% bis 1,00 Massen-% Partikel von Übergangsmetallen ausgewählt aus Cu, Mn, Fe, Co, Y, Re, Os mit Partikelgrößen von 500 bis 3000 nm und
  • 0,001 Massen-% bis 0,100 Massen-% Buntmetallinhibitoren ausgewählt aus Triazolen, Oxazolen, Thiazolen, Triazinen oder Carbonsäuren verwendet.
For a lubricating oil for a medium-duty transmission
  • 99.989% by mass to 98.9% by mass lubricating oil consisting of
    89.85 to 66.70% by mass of a PAO mixture with a viscosity of 68 to 680 cst at 40°C, 10.0% by mass to 30.0% by mass of diester with a viscosity of 25 to 100 cst at 40°C, 0.05% by mass to 3.0% by mass gear oil additive package and 0.1% by mass to 0.3% by mass defoamer,
  • 0.01% by mass to 1.00% by mass of particles of transition metals selected from Cu, Mn, Fe, Co, Y, Re, Os with particle sizes of 500 to 3000 nm and
  • 0.001% by mass to 0.100% by mass of non-ferrous metal inhibitors selected from triazoles, oxazoles, thiazoles, triazines or carboxylic acids.

Beispiel 2example 2

Schmieröl für hochbelastetes Getriebe, z.B. für offene Antriebe in Mühlen oder Drehrohröfen sowie für IndustriegetriebeLubricating oil for heavily loaded gears, e.g. for open drives in mills or rotary kilns as well as for industrial gears

Für ein Schmieröl für ein hochbelastetes Getriebe werden

  • 98,91 Massen-% bis 87,1 Massen-% Schmieröl bestehend aus
    89,85 bis 66,70 Massen-% eines PAO-Gemisches der Viskosität 68 bis 680 cst bei 40°C, 10,0 Massen-% bis 30,0 Massen-% Diester der Viskosität 25 bis 100 cst bei 40°C, 0,05 Massen-% bis 3,0 Massen-% Getriebeöladditivpackage sowie 0,1 Massen-% bis 0,3 Massen-% Entschäumer,
  • 1,0 Massen-% bis 10,0 Massen-% Partikel von Übergangsmetallen ausgewählt aus Cu, Mn, Fe, Co, Y, Re, Os mit Partikelgrößen von 500 bis 3000 nm und 0,09 Massen-% bis 2,9 Massen-% Buntmetallinhibitoren ausgewählt aus Triazolen, Oxazolen, Thiazolen, Triazinen oder Carbonsäuren verwendet.
For a lubricating oil for a highly loaded transmission
  • 98.91% by mass to 87.1% by mass lubricating oil consisting of
    89.85 to 66.70% by mass of a PAO mixture with a viscosity of 68 to 680 cst at 40°C, 10.0% by mass to 30.0% by mass of diester with a viscosity of 25 to 100 cst at 40°C, 0.05% by mass to 3.0% by mass gear oil additive package and 0.1% by mass to 0.3% by mass defoamer,
  • 1.0% by mass to 10.0% by mass of particles of transition metals selected from Cu, Mn, Fe, Co, Y, Re, Os with particle sizes of 500 to 3000 nm and 0.09% by mass to 2.9% by mass of non-ferrous metal inhibitors selected from triazoles, oxazoles, thiazoles, triazines or carboxylic acids.

Beispiel 3Example 3

Langzeitschmierfett mit breitem Anwendungsbereich für Wälz- und GleitlagerLong-term lubricating grease with a wide range of applications for roller and plain bearings

In einem Schmierfett mit Langzeitwirkung, das in einem breiten Anwendungsbereich eingesetzt werden kann, sind

  • 99,989 Massen-% - 98,9 Massen-% Schmierfett bestehend aus
    86,8 - 73,0 Massen-% PAO der Viskosität 45 cst, 12,0 bis 20,0 Massen-% eines Verdickungsmittels ausgewählt aus der Klasse von Lithium-Komplexseifen, 1,0 bis 4,0 Massen-% aminischer und phenolischer Antioxidantien sowie 0,2 bis 3,0 Massen-% EP/AW-Additive auf Basis S/P-Chemie,
  • 0,01 Massen-% bis 1,00 Massen-% Partikel von Übergangsmetallen ausgewählt aus Cu, Mn, Fe, Co, Y, Re, Os mit Partikelgrößen von 500 bis 3000 nm und
  • 0,001 Massen-% bis 0,100 Massen-% Buntmetallinhibitoren ausgewählt aus Triazolen, Oxazolen, Thiazolen, Triazinen oder Carbonsäuren enthalten.
In a long-lasting grease that can be used in a wide range of applications
  • 99.989% by mass - 98.9% by mass lubricating grease consisting of
    86.8-73.0% by mass of PAO with a viscosity of 45 cst, 12.0 to 20.0% by mass of a thickener selected from the class of lithium complex soaps, 1.0 to 4.0% by mass of aminic and phenolic Antioxidants and 0.2 to 3.0% by mass of EP/AW additives based on S/P chemistry,
  • 0.01% by mass to 1.00% by mass of particles of transition metals selected from Cu, Mn, Fe, Co, Y, Re, Os with particle sizes of 500 to 3000 nm and
  • 0.001% by mass to 0.100% by mass of non-ferrous metal inhibitors selected from triazoles, oxazoles, thiazoles, triazines or carboxylic acids.

Beispiel 4example 4

Langzeitschmierfett mit exzellentem VerschleißschutzLong-term lubricating grease with excellent wear protection

Ein Schmierfett mit Langzeitwirkung und einem exzellentem Verschleißschutzwirkung besteht aus

  • 98,91 Massen-% bis 87,1 Massen-% Schmierfett bestehend aus
    86,8 bis 73,0 Massen-% PAO der Viskosität 45 cst, 12,0 bis 20,0 Massen-% eines Verdickungsmittels ausgewählt aus der Klasse von Lithium-Komplexseifen, 1,0 bis 4,0 Massen-% aminischer und phenolischer Antioxidantien sowie 0,2 bis 3,0 Massen-% EP/AW-Additive auf Basis S/P-Chemie,
  • 1,0 Massen-% bis 10,0 Massen-% Partikel von Übergangsmetallen ausgewählt aus Cu, Mn, Fe, Co, Y, Re, Os mit Partikelgrößen von 500 bis 3000 nm und 0,09 Massen-% bis 2,9 Massen-% Buntmetallinhibitoren ausgewählt aus Triazolen, Oxazolen, Thiazolen, Triazinen oder Carbonsäuren.
A lubricating grease with a long-term effect and an excellent anti-wear effect consists of
  • 98.91% by mass to 87.1% by mass of lubricating grease consisting of
    86.8 to 73.0% by mass of PAO with a viscosity of 45 cst, 12.0 to 20.0% by mass of a thickener selected from the class of lithium complex soaps, 1.0 to 4.0% by mass of aminic and phenolic Antioxidants and 0.2 to 3.0% by mass of EP/AW additives based on S/P chemistry,
  • 1.0% by mass to 10.0% by mass of particles of transition metals selected from Cu, Mn, Fe, Co, Y, Re, Os with particle sizes from 500 to 3000 nm and 0.09% by mass to 2.9% by mass -% non-ferrous metal inhibitors selected from triazoles, oxazoles, thiazoles, triazines or carboxylic acids.

Beispiel 5Example 5

Wälzlagerfett mit hohem VerschleißschutzRoller bearing grease with high wear protection

Ein Wälzlagerfett mit hoher Verschleißschutzwirkung enthält

  • 99,989 Massen-% bis 98,9 Massen-% Schmierfett bestehend aus
    92,8 bis 80,0 Massen-% PAO der Viskosität 45 cst, 6,0 bis 10,0 Massen-% eines Verdickungsmittels ausgewählt aus der Klasse von Lithium-Einfachseifen, 1,0 bis 4,0 Massen-% aminischer und phenolischer Antioxidantien sowie 0,2 bis 6,0 Massen-% EP/AW-Additive auf Basis S/P-Chemie,
  • 0,01 Massen-% bis 1,00 Massen-% Partikel von Übergangsmetallen ausgewählt aus Cu, Mn, Fe, Co, Y, Re, Os mit Partikelgrößen von 500 bis 3000 nm und
  • 0,001 Massen-% bis 0,100 Massen-% Buntmetallinhibitoren ausgewählt aus Triazolen, Oxazolen, Thiazolen, Triazinen oder Carbonsäuren.
Contains a roller bearing grease with a high anti-wear effect
  • 99.989% by mass to 98.9% by mass of lubricating grease consisting of
    92.8 to 80.0% by mass of PAO of viscosity 45 cst, 6.0 to 10.0% by mass of a thickener selected from the class of lithium simple soaps, 1.0 to 4.0% by mass of aminic and phenolic Antioxidants and 0.2 to 6.0% by mass of EP/AW additives based on S/P chemistry,
  • 0.01% by mass to 1.00% by mass of particles of transition metals selected from Cu, Mn, Fe, Co, Y, Re, Os with particle sizes of 500 to 3000 nm and
  • 0.001% by mass to 0.100% by mass of non-ferrous metal inhibitors selected from triazoles, oxazoles, thiazoles, triazines or carboxylic acids.

Claims (6)

  1. Use of a lubricant composition containing
    99.989 to 87.1% w/w lubricant in the form of a fat or oil, including additives,
    0.01 to 10% w/w non-ferrous metal particles, selected form the group consisting of metals of the first (Sc - Zn), second (Y - Cd) and third (La - Hg) period of transition metals, as well as their alloys, and
    0.001 to 2.9% w/w non-ferrous metal deactivator selected from the group consisting of heteroaromatic compounds, such as oxazoles, imidazoles, triazoles and/or triazines or acids, particularly carboxylic acids and hydroxycarboxylic acids, in particular oleic acids,
    to form a diamond-like carbon (DLC) layer in-situ on a surface of a component in antifriction bearings, sliding bearings and gear mechanisms.
  2. The use of a lubricant composition according to claim 1, to form a diamond-like carbon (DLC) layer in-situ on a surface of a component in the automotive sector in-situ.
  3. The use of a lubricant composition according to claim 1 or 2, wherein the oil of the lubricant is selected, as individual component or in mixtures, from the group consisting of synthetic hydrocarbons, such as PAOs or mPAOs, mineral oil, native oils and derivatives of native oils, esters, polyglycols, phenyl ethers, silicone oils or perfluoropolyethers.
  4. The use of a lubricant composition according to one of the preceding claims, wherein the lubricant is selected, with a thickener in pure form or in mixtures, from the group consisting of organic or inorganic substances, in particular PTFE, graphite, metal oxides, boron nitride, molybdenum disulphide, phosphates, silicates, sulphonates, polyimides, metal soaps, metal complex soaps, urea and mixtures thereof, solid lubricants such as graphite or MoS2, and thickened to form a fat.
  5. The use of a lubricant composition according to claim 1, wherein the non-ferrous metal nanoparticles are selected from Mn, Fe, Co, Cu Y, Re and Os.
  6. The use of a lubricant composition according to claim 5, wherein the particle size of the non-ferrous metals ranges from 500 to 3000 nm.
EP19749182.2A 2018-07-26 2019-07-18 Lubricants with in-situ formation of dlc layers Active EP3794162B1 (en)

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DE102019004865.2A DE102019004865A1 (en) 2018-07-26 2019-07-11 Lubricants with in-situ formation of DLC layers
PCT/EP2019/000222 WO2020020477A1 (en) 2018-07-26 2019-07-18 Lubricants with in-situ formation of dlc layers

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WO2016065175A1 (en) * 2014-10-23 2016-04-28 Northwestern University Lubricant additives, lubricant compositions, and applications of same
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