US20190100714A1 - Sliding system - Google Patents

Sliding system Download PDF

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Publication number
US20190100714A1
US20190100714A1 US16/149,640 US201816149640A US2019100714A1 US 20190100714 A1 US20190100714 A1 US 20190100714A1 US 201816149640 A US201816149640 A US 201816149640A US 2019100714 A1 US2019100714 A1 US 2019100714A1
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Prior art keywords
nitride film
sliding
chromium nitride
lubricating oil
ppm
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US16/149,640
Inventor
Shigeru Hotta
Hiroyuki Mori
Mamoru Tohyama
Masaru Okuyama
Keiji Hayashi
Kazuyoshi MANABE
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Toyota Motor Corp
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Toyota Motor Corp
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Assigned to TOYOTA JIDOSHA KABUSHIKI KAISHA reassignment TOYOTA JIDOSHA KABUSHIKI KAISHA ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MORI, HIROYUKI, OKUYAMA, MASARU, HOTTA, SHIGERU, TOHYAMA, MAMORU, HAYASHI, KEIJI, MANABE, Kazuyoshi
Publication of US20190100714A1 publication Critical patent/US20190100714A1/en
Abandoned legal-status Critical Current

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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16NLUBRICATING
    • F16N15/00Lubrication with substances other than oil or grease; Lubrication characterised by the use of particular lubricants in particular apparatus or conditions
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04Mixtures of base-materials and additives
    • C10M169/044Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
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    • C10M103/06Metal compounds
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    • C10M135/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/08Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
    • C10M135/10Sulfonic acids or derivatives thereof
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    • C10M135/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/12Thio-acids; Thiocyanates; Derivatives thereof
    • C10M135/14Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
    • C10M135/18Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the groups
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    • C10M137/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04Phosphate esters
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    • C10M141/00Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/10Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
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    • C10M149/02Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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    • C10M169/04Mixtures of base-materials and additives
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01BMACHINES OR ENGINES, IN GENERAL OR OF POSITIVE-DISPLACEMENT TYPE, e.g. STEAM ENGINES
    • F01B3/00Reciprocating-piston machines or engines with cylinder axes coaxial with, or parallel or inclined to, main shaft axis
    • F01B3/0002Reciprocating-piston machines or engines with cylinder axes coaxial with, or parallel or inclined to, main shaft axis having stationary cylinders
    • F01B3/0017Component parts, details, e.g. sealings, lubrication
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01MLUBRICATING OF MACHINES OR ENGINES IN GENERAL; LUBRICATING INTERNAL COMBUSTION ENGINES; CRANKCASE VENTILATING
    • F01M9/00Lubrication means having pertinent characteristics not provided for in, or of interest apart from, groups F01M1/00 - F01M7/00
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16HGEARING
    • F16H57/00General details of gearing
    • F16H57/04Features relating to lubrication or cooling or heating
    • F16H57/041Coatings or solid lubricants, e.g. antiseize layers or pastes
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    • C10M2201/00Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06Metal compounds
    • C10M2201/061Carbides; Hydrides; Nitrides
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    • C10M2201/00Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/086Chromium oxides, acids or salts
    • C10M2201/0863Chromium oxides, acids or salts used as base material
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    • C10M2203/00Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/003Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions used as base material
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    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28Amides; Imides
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    • C10M2217/00Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/028Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a nitrogen-containing hetero ring
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    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046Overbasedsulfonic acid salts
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    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
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    • C10M2223/00Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
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    • C10N2010/12Groups 6 or 16
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    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
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    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
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    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
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    • C10N2030/52Base number [TBN]
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    • C10N2050/14Composite materials or sliding materials in which lubricants are integrally molded
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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • F16NLUBRICATING
    • F16N2200/00Condition of lubricant
    • F16N2200/06Film thickness

Definitions

  • the present disclosure relates to a sliding system that can reduce a coefficient of friction applied between sliding surfaces according to a new combination of a sliding surface and a lubricating oil.
  • sliding members that configured to move relative to each other while in sliding contact.
  • a sliding system in this specification, for example, a sliding machine
  • sliding resistance sliding resistance
  • Such a reduction in sliding resistance is generally achieved by reducing a coefficient of friction acting between sliding surfaces.
  • the coefficient of friction acting between the sliding surfaces differs according to surface states of the sliding surfaces and a lubrication state between the sliding surfaces.
  • surface modification of sliding surfaces and improvement of a lubricant (lubricating oil) supplied between sliding surfaces have been studied. Details related thereto are described in, for example, the following patent documents.
  • Japanese Patent No. 6114730 a sliding surface covered with a chromium nitride film and a lubricating oil containing an oil-soluble molybdenum compound formed of a Mo trinuclear body are combined, and thus both low friction characteristics and high wear resistance are achieved.
  • Japanese Patent No. 6114730 since a general engine oil is assumed as the lubricating oil, specific friction characteristics only for when the oil temperature is 80° C. are described in Japanese Patent No. 6114730.
  • the present disclosure provides a sliding system that can reduce a coefficient of friction according to a new combination of a siding coating and a lubricating oil that were previously unknown.
  • the inventors conducted extensive studies in order to address the above problems, and found that a coefficient of friction between sliding surfaces can be reduced according to a new combination of a specific chromium nitride film and a lubricating oil containing a molybdenum dialkyldithiocarbamate (Mo-DTC). Moreover, they found that both low friction characteristics and high wear resistance can be achieved. This result was expanded to complete the present disclosure to be described below.
  • a sliding system is a sliding system including a pair of sliding members having opposing sliding surfaces adapted to move relative to each other and a lubricating oil interposed between the opposing sliding surfaces. At least one of the sliding surfaces is a covered surface covered with a chromium nitride film.
  • the lubricating oil contains a molybdenum dialkyldithiocarbamate (simply referred to as a “Mo-DTC”) which is an oil-soluble molybdenum compound.
  • a mass ratio of Mo of the Mo-DTC with respect to the entire lubricating oil is 50 ppm to 800 ppm.
  • a sliding system in which a coefficient of friction between sliding surfaces is reduced is obtained according to a combination of sliding surfaces covered with a specific chromium nitride film and a lubricating oil containing a Mo-DTC. According to the sliding system of the aspect of the present disclosure, it is possible to reduce sliding resistance and friction loss, improve movement performance of various machines, and save energy.
  • the chromium nitride film according to the aspect of the present disclosure can exhibit low friction characteristics and also excellent wear resistance. Therefore, the sliding system is suitable for a drive system machine that is operated for a long time under severe conditions from a boundary lubrication (friction) condition to a mixed lubrication (friction) condition.
  • a coefficient of friction between the sliding surfaces may be 0.06 or less or 0.055 or less.
  • a sliding surface formed of the chromium nitride film has a wear depth, which is an index of wear resistance, of 1 ⁇ 4 or less or 1 ⁇ 6 or less, compared to a sliding surface made of a steel material of the related art.
  • the sliding system of the aspect of the present disclosure is suitable for a hybrid vehicle internal combustion engine or a drive transmission device (such as a transmission and a differential gear) in which the oil temperature rises gently.
  • the sliding system specifically, a sliding machine
  • an adsorption reaction of a Mo-DTC contained in the lubricating oil is promoted.
  • other additives which are in a competitive adsorption relationship with the Mo-DTC or its constituent elements (for example, Mo) are easily adsorbed on the sliding surface.
  • a relatively large amount of a molybdenum sulfide compound having a MoS 2 structure is (thickly) adsorbed on the covered surface (sliding surface) formed of a chromium nitride film.
  • the molybdenum sulfide compound having a MoS 2 structure has a layered structure, and exhibits low shear characteristics. Therefore, it is thought that, even in a wide range of operation situations including boundary friction, the coefficient of friction on the sliding surface formed of a chromium nitride film is reduced.
  • the chromium nitride film according to the aspect of the present disclosure is generally harder than a substrate (for example, a steel material) of the sliding member and is not easily transferred to the sliding surface on the counterpart sliding side. Therefore, according to the sliding system of the present disclosure, in the presence of the above lubricating oil, high wear resistance is also exhibited and excellent low friction characteristics are stably exhibited for a long time.
  • the chromium nitride film according to the aspect of the present disclosure may include Cr and N.
  • Cr and N are mainly present as CrN, but some thereof may be Cr 2 N (dichromium nitride) or the like.
  • an amount of atoms constituting the entire chromium nitride film is set as 100 atom %, preferably, there is 32 atom % to 47 atom % of N, and the balance is Cr.
  • N may be 35 atom % to 44 atom %.
  • a small amount (for example, 1 atom % or less in total) of a doping element (for example, O, B) may be contained in the chromium nitride film as long as low friction characteristics of the chromium nitride film are not inhibited or the amount is within a range in which the low friction characteristics are improved.
  • the film composition in this specification is specified by an electron beam microanalyzer (EPMA).
  • the chromium nitride film according to the aspect of the present disclosure easily exhibits low friction characteristics when it has a specific crystal structure. That is, in the chromium nitride film, a relative area which is an area ratio of the (111) plane with respect to the (200) plane obtained when the film is analyzed by X-ray diffraction is 20% to 30%. In addition, the relative area may be 22% to 28%, or the relative area may be 23% to 27%.
  • the area ratio (relative area) of each surface in this specification is calculated by image analysis based on profiles obtained by X-ray diffraction.
  • Another aspect of the present disclosure relates to a sliding system including a pair of sliding members having opposing sliding surfaces adapted to move relative to each other and a lubricating oil interposed between the opposing sliding surfaces. At least one of the sliding surfaces is a covered surface covered with a chromium nitride film.
  • the lubricating oil contains a molybdenum dialkyldithiocarbamate which is an oil-soluble molybdenum compound.
  • a mass ratio of Mo of the molybdenum dialkyldithiocarbamate with respect to the entire lubricating oil is 50 ppm to 800 ppm.
  • the “sliding system” in the present disclosure is sufficient as long as it includes a sliding member and a lubricating oil, and is not limited to a complete body as a machine, but includes a combination of mechanical elements constituting a part thereof.
  • the sliding system of the present disclosure may be appropriately referred to as a sliding structure, a sliding machine (for example, an engine and a transmission) or the like.
  • the covered surface formed of a chromium nitride film according to the present disclosure may be formed on at least one of sliding surfaces of opposing sliding members configured to move relative to each other.
  • both opposing sliding surfaces are covered surfaces formed of a chromium nitride film.
  • x to y in this specification includes a lower limit x and an upper limit y.
  • a range such as “a to b” may be newly set with various numerical values described in this specification or arbitrary numerical values included in a numerical value range as a new lower limit or upper limit.
  • FIG. 1A shows profiles of chromium nitride films according to samples obtained by X-ray diffraction
  • FIG. 1B is an enlarged view of an X-ray diffraction profile of a chromium nitride film according to a 3;
  • FIG. 2A is a bar graph in which coefficients of friction of samples are compared
  • FIG. 2B is a bar graph in which wear depths of samples are compared
  • FIG. 3 is a scatter diagram showing a relationship between surface roughness and coefficients of friction of samples
  • FIG. 4 is a scatter diagram showing a relationship between relative areas and coefficients of friction of samples
  • FIG. 5 is a graph showing a relationship between Mo amounts of a Mo-DTC and coefficients of friction according to the sample 3 and a sample C1;
  • FIG. 6 is a schematic diagram showing an example of a molecular structure (R: alkyl group) of a Mo-DTC.
  • One, two or more components that are arbitrarily selected in this specification may be added to the above components of the present disclosure. Content described in this specification can be appropriately applied to not only the entire sliding system of the present disclosure but also to sliding members and a lubricating oil constituting the sliding system.
  • a lubricating oil according to an embodiment of the present disclosure contains a Mo-DTC (refer to FIG. 6 ), the type of base oil, the inclusion of other additives, and the like are not limited.
  • the Mo-DTC is too small, it is difficult for low friction characteristics to be exhibited, but if an amount of the Mo-DTC is excessive, there is no problem.
  • Mo is a type of rare metal, a smaller total amount of Mo contained is preferable.
  • a mass ratio of Mo of the Mo-DTC with respect to the entire lubricating oil is 50 ppm to 800 ppm, preferably 200 ppm to 700 ppm, and more preferably 300 ppm to 600 ppm.
  • ppmMo a mass ratio of Mo with respect to the entire lubricating oil
  • an upper limit of a total amount of Mo is preferably 400 ppmMo and more preferably 300 ppmMo with respect to the entire lubricating oil.
  • the lubricating oil may contain a compound other than the Mo-DTC.
  • a compound other than the Mo-DTC For example, at least one of a phosphorus compound having a mass ratio of P that is preferably 200 ppm to 1,500 ppm and more preferably 400 ppm to 1,200 ppm with respect to the entire lubricating oil, a sulfur compound having a mass ratio of S that is preferably 500 ppm to 3,000 ppm or more preferably 1,000 ppm to 2,700 ppm with respect to the entire lubricating oil, and a nitrogen compound having a mass ratio of N that is preferably 200 ppm to 2,000 ppm and more preferably 500 ppm to 1,500 ppm with respect to the entire lubricating oil may be contained in the lubricating oil.
  • a phosphorus compound having a mass ratio of P that is preferably 200 ppm to 1,500 ppm and more preferably 400 ppm to 1,200 ppm with respect to the entire lubricating oil
  • Examples of such a phosphorus compound include a molybdenum dialkyldithiophosphate (Mo-DTP), a zinc dialkyl dithiophosphate (Zn-DTP), a phosphate ester and amine salts thereof, a phosphite and amine salts thereof, and a thiophosphate ester.
  • Examples of the sulfur compound include metal sulfonates other than Mo-DTCs, Mo-DTPs, and Zn-DTPs, metal phenates, metal salicylates, sulfide olefins, sulfides, sulfurized fats and oils, thiadiazoles, thiocarbamates, and thiocarbonates.
  • nitrogen compound examples include succinic acid imide, succinic acid ester, aliphatic amines, aromatic amines, thiadiazoles, triazoles, imidazoles, and thiocarbamates.
  • Mo-DTC preferentially acts on a sliding surface (covered surface) covered with a chromium nitride film, and is thought to contribute to forming, for example, a molybdenum sulfide compound (such as MoS2) that can reduce a coefficient of friction.
  • a film formation method of a chromium nitride film according to an embodiment of the present disclosure is not limited.
  • a desired chromium nitride film may be efficiently formed by, for example, an arc ion plating (AIP) method, a sputtering (SP) method, and specifically, a physical vapor deposition (PVD) method such as an unbalanced magnetron sputtering (UBMS) method.
  • AIP arc ion plating
  • SP sputtering
  • PVD physical vapor deposition
  • UMS unbalanced magnetron sputtering
  • the AIP method is a method in which, for example, in a reaction gas (processing gas), a metal target (evaporation source) is arc discharged as a negative electrode, metal ions generated from the metal target react with reaction gas particles, and a dense coating is formed on a coated surface to which a bias voltage (negative pressure) is applied.
  • a metal target evaporation source
  • the target may be metal Cr
  • the reaction gas may be N 2 gas.
  • a target or a reaction gas containing the doping element may be used.
  • a composition, a structure, and the like of the chromium nitride film can be adjusted by adjusting a gas pressure of the reaction gas.
  • a gas pressure of the reaction gas For example, if a monolayer film made of CrN can be obtained by adjusting a pressure of N 2 gas, it is possible to obtain a composite film made of CrN and Cr 2 N.
  • the SP method is a method in which a target is set as a negative electrode side, a coated surface is set as a positive electrode side, a voltage is applied, inert gas atomic ions generated by a glow discharge collide with a target surface, and released target particles (atoms and molecules) are deposited on the coated surface to form a coating.
  • sputtering is performed using metal Cr as a target and Ar gas as an inert gas, released Cr atoms (ions) react with N 2 gas, and thereby a chromium nitride film can be formed on the sliding surface.
  • a type, a form, a sliding form, and the like of sliding members according to an embodiment of the present disclosure are not limited as long as they have sliding surfaces adapted to move relative to each other with a lubricating oil interposed therebetween.
  • Specific forms and applications of a sliding system including such sliding members are not limited, and the sliding system can be widely applied to various machines and devices for which a reduction in sliding resistance and a reduction in mechanical loss due to sliding are required.
  • the sliding system of the embodiment of the present disclosure is suitably used for a drive system unit (such as an engine and a transmission) of an automobile and the like.
  • sliding member constituting such a sliding system
  • a cam a valve lifter, a follower, a shim, a valve, and a valve guide constituting a valve system and a piston, a piston ring, a piston pin, a crankshaft, a gear, a rotor, and a rotor housing.
  • test components sliding members covered with a chromium nitride film and a plurality of lubricating oils with varying blending amounts of a Mo-DTC (oil-soluble molybdenum compound) were prepared, and a Block-on-Ring friction test was performed on the various combinations.
  • Mo-DTC oil-soluble molybdenum compound
  • a plurality of block type (6.3 mm ⁇ 15.7 mm ⁇ 10.1 mm) substrates made of a quenched steel material (JISSUS440C) were prepared. Surfaces (coated surfaces) of the substrates were mirror-finished (surface roughness Ra: 0.08 ⁇ m).
  • a steel material JISSCM420
  • the carburizing surface hardness HV of 700 was also mirror-finished at a similar surface roughness.
  • Test components in which various chromium nitride films shown in Table 1 were formed on the surfaces of the substrates were prepared.
  • the film formation of the chromium nitride film was performed by the arc ion plating (AIP) method or the sputtering (SP) method.
  • a target made of metal Cr was arc discharged.
  • Film formation of a chromium nitride film containing O was performed using a gas mixture of N 2 gas and O 2 gas as a reaction gas.
  • a proportion of an amount of O in that case was 0.1 volume % with respect to the entire gas mixture.
  • film formation of a chromium nitride film containing B was performed using a Cr-B alloy (Cr-5 mass % B) for a target.
  • Film formation according to the sputtering method was performed by sputtering a target made of metal Cr using Ar gas, and reacting released Cr atoms (ions) with N 2 gas.
  • N 2 gas was 0.5 Pa to 6 Pa.
  • Film compositions of the samples were quantified by EPMA (JXA-8200 commercially available from JEOL Ltd.).
  • the film hardness was measured by a nanoindenter testing machine (TRIBOSCOPE commercially available from HYSITRON).
  • the film thickness was specified from a wear mark obtained by Calotest commercially available from CMS.
  • Table 1 shows the obtained film compositions and film properties of the samples.
  • the surface shape (roughness) according to this example was measured by a white interference method non-contact surface shape measuring machine (NewView5022 commercially available from Zygo).
  • FIG. 1A is an enlarged view of the profile according to the sample 3.
  • An engine oil was assumed as a lubricating oil used for a friction test.
  • a plurality of sample oils shown in Table 2 were prepared.
  • additives shown in Table 1 were added to a base oil (hydrocarbon base oil/YUBASE8 commercially available from SK lubricants), and the mixture was then heated and stirred at 60° C. for 30 minutes.
  • the additives used at that time were as follows.
  • test components were combined and a Block-on-Ring friction test (simply referred to as a “friction test”) was performed.
  • the test components were formed into block test pieces with a sliding surface width of 6.3 mm, and an S-10 standard test piece (a hardness HV of 800, a surface roughness of 1.7 to 2.0 ⁇ mRzjis, commercially available from FALEX) made of a carburized steel material (AISI4620) was used as a ring test piece (an outer diameter of ⁇ 35 mm and a width of 8.8 mm).
  • the friction test was performed at a test load of 133 N (Hertz surface pressure: 210 MPa), a sliding speed of 0.3 m/s, and an oil temperature of 40° C. (constant) for 30 minutes.
  • a ⁇ average value for 1 minute immediately before the test ended was set as a coefficient of friction of each sliding surface in this test.
  • FIG. 2A shows a bar graph in which coefficients of friction of the test components are compared.
  • the sliding surfaces of the test component after the friction test were measured by the above non-contact surface shape measuring machine, and the wear depth and surface roughness thereof were obtained.
  • FIG. 2B shows a bar graph in which the wear depths are compared.
  • FIG. 3 shows a relationship between the surface roughness and the coefficient of friction according to the test components.
  • FIG. 4 shows a relationship between a coefficient of friction of the test components and a relative area of the (111) plane with respect to the (200) plane of the chromium nitride film of the test components.
  • FIG. 5 shows a relationship between a Mo amount of the Mo-DTC to which each of the sample oils was added and the coefficient of friction of the test components.
  • FIG. 2A it was found that, when a lubricating oil containing a Mo-DTC (Mo amount: 500 ppm) was used, despite the low oil temperature of 40° C., the coefficient of friction of only the sample 3 was lower than those of the other samples.
  • FIG. 2B it was confirmed that the wear depth of the sample 3 was much smaller than that of the sample C1, and the sample 3 exhibited excellent wear resistance.
  • a sliding surface of one sliding member may be the sliding surface of the embodiment, or both sliding surfaces may be the sliding surface of the embodiment.
  • a sliding member having the same configuration except that the chromium nitride film of the embodiment is not provided may be used as the other sliding member.

Abstract

A sliding system includes a pair of sliding members having opposing sliding surfaces adapted to move relative to each other, and a lubricating oil interposed between the opposing sliding surfaces. Here, at least one of the sliding surfaces is a covered surface covered with a specific chromium nitride film. The lubricating oil contains an oil-soluble molybdenum compound formed of a molybdenum dialkyldithiocarbamate. In the chromium nitride film, when an amount of atoms constituting the entire chromium nitride film is set as 100 atom %, there is 32 atom % to 47 atom % of N, the balance is Cr, and a relative area which is an area ratio of the (111) plane with respect to the (200) plane obtained when the chromium nitride film is analyzed by X-ray diffraction is 20% to 30%.

Description

    INCORPORATION BY REFERENCE
  • The disclosure of Japanese Patent Application No. 2017-193626 filed on Oct. 3, 2017 including the specification, drawings and abstract is incorporated herein by reference in its entirety.
  • BACKGROUND 1. Technical Field
  • The present disclosure relates to a sliding system that can reduce a coefficient of friction applied between sliding surfaces according to a new combination of a sliding surface and a lubricating oil.
  • 2. Description of Related Art
  • Many machines include sliding members that configured to move relative to each other while in sliding contact. In a system including such sliding members (referred to as a “sliding system” in this specification, for example, a sliding machine), when a resistance force (sliding resistance) applied to the sliding part is reduced, it is possible to improve performance and reduce an energy required for operation. Such a reduction in sliding resistance is generally achieved by reducing a coefficient of friction acting between sliding surfaces.
  • The coefficient of friction acting between the sliding surfaces differs according to surface states of the sliding surfaces and a lubrication state between the sliding surfaces. Thus, in order to reduce the coefficient of friction, surface modification of sliding surfaces and improvement of a lubricant (lubricating oil) supplied between sliding surfaces have been studied. Details related thereto are described in, for example, the following patent documents.
  • SUMMARY
  • In Japanese Patent No. 6114730, a sliding surface covered with a chromium nitride film and a lubricating oil containing an oil-soluble molybdenum compound formed of a Mo trinuclear body are combined, and thus both low friction characteristics and high wear resistance are achieved. However, in Japanese Patent No. 6114730, since a general engine oil is assumed as the lubricating oil, specific friction characteristics only for when the oil temperature is 80° C. are described in Japanese Patent No. 6114730.
  • The present disclosure provides a sliding system that can reduce a coefficient of friction according to a new combination of a siding coating and a lubricating oil that were previously unknown.
  • The inventors conducted extensive studies in order to address the above problems, and found that a coefficient of friction between sliding surfaces can be reduced according to a new combination of a specific chromium nitride film and a lubricating oil containing a molybdenum dialkyldithiocarbamate (Mo-DTC). Moreover, they found that both low friction characteristics and high wear resistance can be achieved. This result was expanded to complete the present disclosure to be described below.
  • <<Sliding System>>
  • (1) A sliding system according to an aspect of the present disclosure is a sliding system including a pair of sliding members having opposing sliding surfaces adapted to move relative to each other and a lubricating oil interposed between the opposing sliding surfaces. At least one of the sliding surfaces is a covered surface covered with a chromium nitride film. In the chromium nitride film, when an amount of atoms constituting the entire chromium nitride film is set as 100 atom %, there is N of 32 atom % to 47 atom %, and the balance is Cr, and a relative area which is an area ratio of a (111) plane with respect to a (200) plane obtained when the chromium nitride film is analyzed by X-ray diffraction is 20% to 30%. The lubricating oil contains a molybdenum dialkyldithiocarbamate (simply referred to as a “Mo-DTC”) which is an oil-soluble molybdenum compound. A mass ratio of Mo of the Mo-DTC with respect to the entire lubricating oil is 50 ppm to 800 ppm.
  • (2) A sliding system in which a coefficient of friction between sliding surfaces is reduced is obtained according to a combination of sliding surfaces covered with a specific chromium nitride film and a lubricating oil containing a Mo-DTC. According to the sliding system of the aspect of the present disclosure, it is possible to reduce sliding resistance and friction loss, improve movement performance of various machines, and save energy.
  • In addition, the chromium nitride film according to the aspect of the present disclosure can exhibit low friction characteristics and also excellent wear resistance. Therefore, the sliding system is suitable for a drive system machine that is operated for a long time under severe conditions from a boundary lubrication (friction) condition to a mixed lubrication (friction) condition.
  • For example, in the sliding system, even if the temperature (simply referred to as an “oil temperature”) of the lubricating oil is 60° C. or lower or 50° C. or lower, a coefficient of friction between the sliding surfaces may be 0.06 or less or 0.055 or less. In addition, a sliding surface formed of the chromium nitride film has a wear depth, which is an index of wear resistance, of ¼ or less or ⅙ or less, compared to a sliding surface made of a steel material of the related art. Thus, the sliding system of the aspect of the present disclosure is suitable for a hybrid vehicle internal combustion engine or a drive transmission device (such as a transmission and a differential gear) in which the oil temperature rises gently.
  • (3) A mechanism through which a combination of a specific chromium nitride film and a lubricating oil containing a Mo-DTC according to the aspect of the present disclosure exhibits low friction characteristics and the like is not clearly known, but it is currently thought as follows.
  • When the sliding system (specifically, a sliding machine) according to the aspect of the present disclosure is activated, on the sliding surface formed of a chromium nitride film, an adsorption reaction of a Mo-DTC contained in the lubricating oil is promoted. Accordingly, other additives which are in a competitive adsorption relationship with the Mo-DTC or its constituent elements (for example, Mo) are easily adsorbed on the sliding surface. As a result, it is thought that a relatively large amount of a molybdenum sulfide compound having a MoS2 structure is (thickly) adsorbed on the covered surface (sliding surface) formed of a chromium nitride film. The molybdenum sulfide compound having a MoS2 structure has a layered structure, and exhibits low shear characteristics. Therefore, it is thought that, even in a wide range of operation situations including boundary friction, the coefficient of friction on the sliding surface formed of a chromium nitride film is reduced.
  • Here, the chromium nitride film according to the aspect of the present disclosure is generally harder than a substrate (for example, a steel material) of the sliding member and is not easily transferred to the sliding surface on the counterpart sliding side. Therefore, according to the sliding system of the present disclosure, in the presence of the above lubricating oil, high wear resistance is also exhibited and excellent low friction characteristics are stably exhibited for a long time.
  • (4) Other than (inevitable) impurities, the chromium nitride film according to the aspect of the present disclosure may include Cr and N. In the chromium nitride film, Cr and N are mainly present as CrN, but some thereof may be Cr2N (dichromium nitride) or the like. Based on this, in the chromium nitride film according to the aspect of the present disclosure, when an amount of atoms constituting the entire chromium nitride film is set as 100 atom %, preferably, there is 32 atom % to 47 atom % of N, and the balance is Cr. In addition, N may be 35 atom % to 44 atom %. Here, a small amount (for example, 1 atom % or less in total) of a doping element (for example, O, B) may be contained in the chromium nitride film as long as low friction characteristics of the chromium nitride film are not inhibited or the amount is within a range in which the low friction characteristics are improved. Here, the film composition in this specification is specified by an electron beam microanalyzer (EPMA).
  • In addition, the chromium nitride film according to the aspect of the present disclosure easily exhibits low friction characteristics when it has a specific crystal structure. That is, in the chromium nitride film, a relative area which is an area ratio of the (111) plane with respect to the (200) plane obtained when the film is analyzed by X-ray diffraction is 20% to 30%. In addition, the relative area may be 22% to 28%, or the relative area may be 23% to 27%. Here, the area ratio (relative area) of each surface in this specification is calculated by image analysis based on profiles obtained by X-ray diffraction.
  • (5) Another aspect of the present disclosure relates to a sliding system including a pair of sliding members having opposing sliding surfaces adapted to move relative to each other and a lubricating oil interposed between the opposing sliding surfaces. At least one of the sliding surfaces is a covered surface covered with a chromium nitride film. In the chromium nitride film, when an amount of atoms constituting the entire chromium nitride film is set as 100 atom %, there is 32 atom % to 47 atom % of N, the balance is Cr and 1 atom % or less of a doping element, and a relative area which is an area ratio of a (111) plane with respect to a (200) plane obtained when the chromium nitride film is analyzed by X-ray diffraction is 20% to 30%. The lubricating oil contains a molybdenum dialkyldithiocarbamate which is an oil-soluble molybdenum compound. A mass ratio of Mo of the molybdenum dialkyldithiocarbamate with respect to the entire lubricating oil is 50 ppm to 800 ppm.
  • <<Others>>
  • (1) The “sliding system” in the present disclosure is sufficient as long as it includes a sliding member and a lubricating oil, and is not limited to a complete body as a machine, but includes a combination of mechanical elements constituting a part thereof. The sliding system of the present disclosure may be appropriately referred to as a sliding structure, a sliding machine (for example, an engine and a transmission) or the like.
  • The covered surface formed of a chromium nitride film according to the present disclosure may be formed on at least one of sliding surfaces of opposing sliding members configured to move relative to each other. Of course, more preferably, both opposing sliding surfaces are covered surfaces formed of a chromium nitride film.
  • (2) Unless otherwise specified, “x to y” in this specification includes a lower limit x and an upper limit y. A range such as “a to b” may be newly set with various numerical values described in this specification or arbitrary numerical values included in a numerical value range as a new lower limit or upper limit.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • Features, advantages, and technical and industrial significance of exemplary embodiments of the disclosure will be described below with reference to the accompanying drawings, in which like numerals denote like elements, and wherein:
  • FIG. 1A shows profiles of chromium nitride films according to samples obtained by X-ray diffraction;
  • FIG. 1B is an enlarged view of an X-ray diffraction profile of a chromium nitride film according to a 3;
  • FIG. 2A is a bar graph in which coefficients of friction of samples are compared;
  • FIG. 2B is a bar graph in which wear depths of samples are compared;
  • FIG. 3 is a scatter diagram showing a relationship between surface roughness and coefficients of friction of samples;
  • FIG. 4 is a scatter diagram showing a relationship between relative areas and coefficients of friction of samples;
  • FIG. 5 is a graph showing a relationship between Mo amounts of a Mo-DTC and coefficients of friction according to the sample 3 and a sample C1; and
  • FIG. 6 is a schematic diagram showing an example of a molecular structure (R: alkyl group) of a Mo-DTC.
  • DETAILED DESCRIPTION OF EMBODIMENTS
  • One, two or more components that are arbitrarily selected in this specification may be added to the above components of the present disclosure. Content described in this specification can be appropriately applied to not only the entire sliding system of the present disclosure but also to sliding members and a lubricating oil constituting the sliding system.
  • <<Lubricating Oil>>
  • As long as a lubricating oil according to an embodiment of the present disclosure contains a Mo-DTC (refer to FIG. 6), the type of base oil, the inclusion of other additives, and the like are not limited. When an amount of the Mo-DTC is too small, it is difficult for low friction characteristics to be exhibited, but if an amount of the Mo-DTC is excessive, there is no problem. However, because Mo is a type of rare metal, a smaller total amount of Mo contained is preferable. Therefore, regarding an amount of the Mo-DTC according to an embodiment of the present disclosure, a mass ratio of Mo of the Mo-DTC with respect to the entire lubricating oil is 50 ppm to 800 ppm, preferably 200 ppm to 700 ppm, and more preferably 300 ppm to 600 ppm. Here, when a mass ratio of Mo with respect to the entire lubricating oil is expressed as ppm, it is also appropriately expressed as “ppmMo.” When a Mo compound other than the Mo-DTC or the like is contained in the lubricating oil, an upper limit of a total amount of Mo is preferably 400 ppmMo and more preferably 300 ppmMo with respect to the entire lubricating oil.
  • The lubricating oil may contain a compound other than the Mo-DTC. For example, at least one of a phosphorus compound having a mass ratio of P that is preferably 200 ppm to 1,500 ppm and more preferably 400 ppm to 1,200 ppm with respect to the entire lubricating oil, a sulfur compound having a mass ratio of S that is preferably 500 ppm to 3,000 ppm or more preferably 1,000 ppm to 2,700 ppm with respect to the entire lubricating oil, and a nitrogen compound having a mass ratio of N that is preferably 200 ppm to 2,000 ppm and more preferably 500 ppm to 1,500 ppm with respect to the entire lubricating oil may be contained in the lubricating oil.
  • Examples of such a phosphorus compound include a molybdenum dialkyldithiophosphate (Mo-DTP), a zinc dialkyl dithiophosphate (Zn-DTP), a phosphate ester and amine salts thereof, a phosphite and amine salts thereof, and a thiophosphate ester. Examples of the sulfur compound include metal sulfonates other than Mo-DTCs, Mo-DTPs, and Zn-DTPs, metal phenates, metal salicylates, sulfide olefins, sulfides, sulfurized fats and oils, thiadiazoles, thiocarbamates, and thiocarbonates. Examples of the nitrogen compound include succinic acid imide, succinic acid ester, aliphatic amines, aromatic amines, thiadiazoles, triazoles, imidazoles, and thiocarbamates. Even in such a lubricating oil containing an (oil-soluble) compound other than a Mo-DTC, the Mo-DTC preferentially acts on a sliding surface (covered surface) covered with a chromium nitride film, and is thought to contribute to forming, for example, a molybdenum sulfide compound (such as MoS2) that can reduce a coefficient of friction.
  • <<Chromium Nitride Film>>
  • A film formation method of a chromium nitride film according to an embodiment of the present disclosure is not limited. A desired chromium nitride film may be efficiently formed by, for example, an arc ion plating (AIP) method, a sputtering (SP) method, and specifically, a physical vapor deposition (PVD) method such as an unbalanced magnetron sputtering (UBMS) method.
  • The AIP method is a method in which, for example, in a reaction gas (processing gas), a metal target (evaporation source) is arc discharged as a negative electrode, metal ions generated from the metal target react with reaction gas particles, and a dense coating is formed on a coated surface to which a bias voltage (negative pressure) is applied. In the present embodiment, for example, the target may be metal Cr, and the reaction gas may be N2 gas. In addition, in the case of a chromium nitride film containing Cr and a doping element other than N, a target or a reaction gas containing the doping element may be used. Furthermore, in addition to adjusting components of the target and the reaction gas, a composition, a structure, and the like of the chromium nitride film can be adjusted by adjusting a gas pressure of the reaction gas. For example, if a monolayer film made of CrN can be obtained by adjusting a pressure of N2 gas, it is possible to obtain a composite film made of CrN and Cr2N.
  • The SP method is a method in which a target is set as a negative electrode side, a coated surface is set as a positive electrode side, a voltage is applied, inert gas atomic ions generated by a glow discharge collide with a target surface, and released target particles (atoms and molecules) are deposited on the coated surface to form a coating. In the present embodiment, for example, sputtering is performed using metal Cr as a target and Ar gas as an inert gas, released Cr atoms (ions) react with N2 gas, and thereby a chromium nitride film can be formed on the sliding surface.
  • <<Applications>>
  • A type, a form, a sliding form, and the like of sliding members according to an embodiment of the present disclosure are not limited as long as they have sliding surfaces adapted to move relative to each other with a lubricating oil interposed therebetween. Specific forms and applications of a sliding system including such sliding members are not limited, and the sliding system can be widely applied to various machines and devices for which a reduction in sliding resistance and a reduction in mechanical loss due to sliding are required. For example, the sliding system of the embodiment of the present disclosure is suitably used for a drive system unit (such as an engine and a transmission) of an automobile and the like. Examples of the sliding member constituting such a sliding system include a cam, a valve lifter, a follower, a shim, a valve, and a valve guide constituting a valve system and a piston, a piston ring, a piston pin, a crankshaft, a gear, a rotor, and a rotor housing.
  • SUMMARY
  • A plurality of test components (sliding members) covered with a chromium nitride film and a plurality of lubricating oils with varying blending amounts of a Mo-DTC (oil-soluble molybdenum compound) were prepared, and a Block-on-Ring friction test was performed on the various combinations. The embodiment of the present disclosure will be described in more detail based on the test results.
  • Production of Samples (1) Substrate
  • A plurality of block type (6.3 mm×15.7 mm×10.1 mm) substrates made of a quenched steel material (JISSUS440C) were prepared. Surfaces (coated surfaces) of the substrates were mirror-finished (surface roughness Ra: 0.08 μm).
  • As a comparative sample (a sample C1 in Table 1) not covered with a chromium nitride film, a steel material (JISSCM420) that was simply carburized was prepared. The carburizing surface (hardness HV of 700) was also mirror-finished at a similar surface roughness.
  • (2) Film Formation of Chromium Nitride Film
  • Test components (samples 1 to 5) in which various chromium nitride films shown in Table 1 were formed on the surfaces of the substrates were prepared. The film formation of the chromium nitride film was performed by the arc ion plating (AIP) method or the sputtering (SP) method.
  • In the film formation according to the arc ion plating method, in N2 gas (reaction gas) adjusted to 0.3 Pa to 6 Pa, a target made of metal Cr was arc discharged. Film formation of a chromium nitride film containing O was performed using a gas mixture of N2 gas and O2 gas as a reaction gas. Here, a proportion of an amount of O in that case was 0.1 volume % with respect to the entire gas mixture. In addition, film formation of a chromium nitride film containing B was performed using a Cr-B alloy (Cr-5 mass % B) for a target.
  • Film formation according to the sputtering method was performed by sputtering a target made of metal Cr using Ar gas, and reacting released Cr atoms (ions) with N2 gas. In this case, N2 gas was 0.5 Pa to 6 Pa.
  • <<Measurement and Analysis of Chromium Nitride Film>>
  • (1) Film composition and film properties
  • Film compositions of the samples were quantified by EPMA (JXA-8200 commercially available from JEOL Ltd.). The film hardness was measured by a nanoindenter testing machine (TRIBOSCOPE commercially available from HYSITRON). The film thickness was specified from a wear mark obtained by Calotest commercially available from CMS. Table 1 shows the obtained film compositions and film properties of the samples. Here, the surface shape (roughness) according to this example was measured by a white interference method non-contact surface shape measuring machine (NewView5022 commercially available from Zygo).
  • (2) Structure of Film
  • The chromium nitride films of the samples were analyzed by X-ray diffraction. The profiles obtained accordingly are superimposed in FIG. 1A. In addition, FIG. 1B is an enlarged view of the profile according to the sample 3.
  • Based on the profile shown in FIGS. 1A and 1B, a relative area of the (111) plane with respect to the (200) plane was obtained according to the above-described method. The relative areas of the samples calculated in this manner are shown in Table 1. As can be understood from the profiles of the samples, in all of the samples, Cr was not detected and CrN was mainly detected. However, only in the sample 3, Cr2N was detected in addition to CrN. Table 1 also shows whether Cr2N was detected or not.
  • <<Lubricating Oil>>
  • An engine oil was assumed as a lubricating oil used for a friction test. A plurality of sample oils shown in Table 2 were prepared. In order to prepare the sample oil, additives shown in Table 1 were added to a base oil (hydrocarbon base oil/YUBASE8 commercially available from SK lubricants), and the mixture was then heated and stirred at 60° C. for 30 minutes. The additives used at that time were as follows.
      • Mo-DTC: Adeka Sakura Lube 165 commercially available from ADEKA
      • Zn-DTP: 1371 commercially available from Lubrizol (Secondary alkyl type/antiwear agent and antioxidant)
      • Overbased calcium sulfonate: 6477C commercially available from Lubrizol (Base number: 300 mgKOH)
      • Polybutenyl succinimide: 6412 commercially available from Lubrizol (Ashless dispersant)
  • Representative element contents contained in the sample oils are shown in Table 2. Contents of contained elements were obtained from data of contents of elements contained in additives and blending proportions of additives shown in Table 1.
  • <<Block-On-Ring Friction Test>>
  • (1) The test components and a sample oil D were combined and a Block-on-Ring friction test (simply referred to as a “friction test”) was performed. In the friction test, the test components were formed into block test pieces with a sliding surface width of 6.3 mm, and an S-10 standard test piece (a hardness HV of 800, a surface roughness of 1.7 to 2.0 μmRzjis, commercially available from FALEX) made of a carburized steel material (AISI4620) was used as a ring test piece (an outer diameter of φ 35 mm and a width of 8.8 mm). In this case, the friction test was performed at a test load of 133 N (Hertz surface pressure: 210 MPa), a sliding speed of 0.3 m/s, and an oil temperature of 40° C. (constant) for 30 minutes. A μ average value for 1 minute immediately before the test ended was set as a coefficient of friction of each sliding surface in this test.
  • FIG. 2A shows a bar graph in which coefficients of friction of the test components are compared. In addition, the sliding surfaces of the test component after the friction test were measured by the above non-contact surface shape measuring machine, and the wear depth and surface roughness thereof were obtained. FIG. 2B shows a bar graph in which the wear depths are compared. FIG. 3 shows a relationship between the surface roughness and the coefficient of friction according to the test components. In addition, FIG. 4 shows a relationship between a coefficient of friction of the test components and a relative area of the (111) plane with respect to the (200) plane of the chromium nitride film of the test components.
  • (2) The test component of the sample 3 or C1 and one of the sample oils A to D were combined and the above friction test was performed in the same manner, and the coefficient of friction in each case was obtained. FIG. 5 shows a relationship between a Mo amount of the Mo-DTC to which each of the sample oils was added and the coefficient of friction of the test components.
  • <<Evaluation>> (1) Friction Characteristics
  • As can be clearly understood from FIG. 2A, it was found that, when a lubricating oil containing a Mo-DTC (Mo amount: 500 ppm) was used, despite the low oil temperature of 40° C., the coefficient of friction of only the sample 3 was lower than those of the other samples. In addition, as can be clearly understood from FIG. 2B, it was confirmed that the wear depth of the sample 3 was much smaller than that of the sample C1, and the sample 3 exhibited excellent wear resistance.
  • (2) Surface Roughness
  • As can be clearly understood from FIG. 3, there was no particular correlation between the surface roughness and the coefficient of friction of the sliding surface. This can be clearly understood when comparing the sample 1 and the sample 3 whose coefficients of friction were greatly different despite the fact that the surface roughnesses of the sliding surfaces were substantially the same. Thus, low friction characteristics of the sample 3 were not thought to be caused by smoothing of the sliding surface.
  • (3) Structure of Chromium Nitride Film
  • As can be clearly understood from FIG. 4, it was found that, unlike the other samples, in the sample 3 exhibiting low friction characteristics, a relative area of the (111) plane with respect to the (200) plane of the chromium nitride film was within a limited specific range. That is, it was found that low friction characteristics were exhibited more in the chromium nitride film in which the (111) plane was mixed to some extent (20% to 30%) than in the chromium nitride film in which the orientation of the (200) plane was strong. The reason for this is inferred to have been the fact that, in the chromium nitride film having a relative area within a certain range, a sulfur compound of Mo was more likely to be formed on the film due to competitive adsorption of the Mo-DTC and other oil additives.
  • (4) Mo-DTC Amount (Mo Equivalence)
  • As can be clearly understood from FIG. 5, when an amount of the Mo-DTC was too small, the coefficient of friction of the sample 3 was not much different from the coefficient of friction of the sample C1. However, it was found that, when an amount of the Mo in Mo-DTC was 50 ppm or more or preferably 200 ppm or more, the sample 3 having a specific chromium nitride film clearly exhibited low friction characteristics unlike the sample C1.
  • (5) Consideration
  • Based on the above results, it can be clearly understood that, when a specific structure chromium nitride film having a relative area of the (111) plane with respect to the (200) plane within a predetermined range and a lubricating oil containing a predetermined amount or more of the Mo-DTC were combined, low friction characteristics were exhibited also in a low temperature range. The reason for this is inferred to have been that, only in the case in which the sliding surface was formed of a specific chromium nitride film, the Mo-DTC adsorbed on or reacted with the sliding surface, and a molybdenum sulfide compound (for example, MoS2) exhibiting low shear characteristics was formed. Therefore, this was thought to reduce the boundary friction coefficient when the molybdenum sulfide compound was directly in contact with the sliding surface and thus the coefficient of friction of the entire macro contact part was reduced.
  • TABLE 1
    Film structure
    (X-ray diffraction results)
    Film properties Relative
    Film composition Film Film area
    Sample Production (atom %) hardness thickness (111)/(200)
    No. Name method Cr N O B (GPa) (μm) (%) Cr2N CrN Cr Note
    1 B SP method 62.4 37.6 24.1 2 3.4 B
    2 T AIP 50.7 49.3 16.9 13 34 A
    3 N method 60.9 39.1 21.5 8 24.7 A A
    4 T-O 49.7 40.5 9.8 22.4 13 28.5 A
    5 N-B 48.7 50.0 1.3 21.0 9 75.8 A
    C1 (Carburized (HV SCM
    material) 700) 420
    “—,” “◯,” and “Δ” shown in X-ray diffraction results are as follows.
    —: there was no substantial diffraction peak.
    A: there was a strong diffraction peak
    B: there was a weak diffraction peak
  • TABLE 2
    Blending amount of additives
    Name (the balance: base oil) (mass %)
    of Overbased
    sample calcium Polybutenyl Contents of contained elements (ppm)
    oil Mo-DTC Zn-DTP sulfonate succinimide Mo S P Zn Ca N
    A 0 0.8 2.0 6.0 0 2,036 800 884 2,400 900
    B 0.06 25 2,064 800 884 2,400 925
    C 0.17 100 2,147 800 884 2,400 1,000
    D 0.56 500 2,591 800 884 2,400 1,400
  • Between the pair of sliding members, a sliding surface of one sliding member may be the sliding surface of the embodiment, or both sliding surfaces may be the sliding surface of the embodiment. When the sliding surface of one sliding member was used as the sliding surface of the embodiment, a sliding member having the same configuration except that the chromium nitride film of the embodiment is not provided may be used as the other sliding member.

Claims (6)

What is claimed is:
1. A sliding system including a pair of sliding members having opposing sliding surfaces adapted to move relative to each other and a lubricating oil interposed between the opposing sliding surfaces,
wherein at least one of the sliding surfaces is a covered surface covered with a chromium nitride film,
in the chromium nitride film, when an amount of atoms constituting the entire chromium nitride film is set as 100 atom %, there is N of 32 atom % to 47 atom %, and the balance is Cr, and a relative area which is an area ratio of a (111) plane with respect to a (200) plane obtained when the chromium nitride film is analyzed by X-ray diffraction is 20% to 30%,
the lubricating oil contains a molybdenum dialkyldithiocarbamate which is an oil-soluble molybdenum compound, and
a mass ratio of Mo of the molybdenum dialkyldithiocarbamate with respect to the entire lubricating oil is 50 ppm to 800 ppm.
2. The sliding system according to claim 1, wherein the mass ratio of Mo of the molybdenum dialkyldithiocarbamate with respect to the entire lubricating oil is 200 ppm to 700 ppm.
3. The sliding system according to claim 1, wherein the chromium nitride film contains Cr2N together with CrN.
4. The sliding system according to claim 1, wherein the lubricating oil contains at least one of a phosphorus compound, a sulfur compound, and a nitrogen compound,
wherein a mass ratio of P of the phosphorus compound with respect to the entire lubricating oil is 200 ppm to 1,500 ppm,
a mass ratio of S of the sulfur compound with respect to the entire lubricating oil is 500 ppm to 3,000 ppm, and
a mass ratio of N of the nitrogen compound with respect to the entire lubricating oil is 200 ppm to 2,000 ppm.
5. The sliding system according to claim 1, wherein the sliding system is a hybrid vehicle internal combustion engine or a drive transmission device including a transmission.
6. A sliding system including a pair of sliding members having opposing sliding surfaces adapted to move relative to each other and a lubricating oil interposed between the opposing sliding surfaces,
wherein at least one of the sliding surfaces is a covered surface covered with a chromium nitride film,
in the chromium nitride film, when an amount of atoms constituting the entire chromium nitride film is set as 100 atom %, there is 32 atom % to 47 atom % of N, the balance is Cr and 1 atom % or less of a doping element, and a relative area which is an area ratio of a (111) plane with respect to a (200) plane obtained when the chromium nitride film is analyzed by X-ray diffraction is 20% to 30%,
the lubricating oil contains a molybdenum dialkyldithiocarbamate which is an oil-soluble molybdenum compound, and
a mass ratio of Mo of the molybdenum dialkyldithiocarbamate with respect to the entire lubricating oil is 50 ppm to 800 ppm.
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