WO2021140851A1 - Élément coulissant et segment de piston - Google Patents

Élément coulissant et segment de piston Download PDF

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Publication number
WO2021140851A1
WO2021140851A1 PCT/JP2020/046832 JP2020046832W WO2021140851A1 WO 2021140851 A1 WO2021140851 A1 WO 2021140851A1 JP 2020046832 W JP2020046832 W JP 2020046832W WO 2021140851 A1 WO2021140851 A1 WO 2021140851A1
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dlc
region
film
less
sliding member
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PCT/JP2020/046832
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English (en)
Japanese (ja)
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正明 高谷
シンルイ デン
祐司 島
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株式会社リケン
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Priority to JP2021531664A priority Critical patent/JP6938807B1/ja
Publication of WO2021140851A1 publication Critical patent/WO2021140851A1/fr

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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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16J—PISTONS; CYLINDERS; SEALINGS
    • F16J9/00—Piston-rings, e.g. non-metallic piston-rings, seats therefor; Ring sealings of similar construction
    • F16J9/26—Piston-rings, e.g. non-metallic piston-rings, seats therefor; Ring sealings of similar construction characterised by the use of particular materials

Definitions

  • the present invention relates to sliding members, particularly sliding members that require high reliability, such as automobile parts such as piston rings.
  • Examples of this hard carbon film include amorphous carbon called diamond-like carbon (DLC).
  • DLC diamond-like carbon
  • the structural essence of DLC is a mixture of diamond bonds (sp 3 bonds) and graphite bonds (sp 2 bonds) as carbon bonds. Therefore, DLC has hardness, abrasion resistance, thermal conductivity, and chemical stability similar to diamond, while having solid lubricity similar to graphite, and is therefore suitable as a protective film for, for example, automobile parts. is there.
  • Patent Document 1 discloses a piston ring formed by coating the outer peripheral surface with a hydrogen-free DLC (ta-C: tetrahedramal aminophorus Carbon) film.
  • a hydrogen-free DLC film is preferable in that it can avoid deterioration of wear resistance due to hydrogen separation in a high temperature environment.
  • the DLC film contains carbon as a main component, it generally tends to be inferior in heat resistance. That is, the conventional hydrogen-free DLC film has a problem that the hardness decreases in a high temperature environment of 400 ° C. or higher.
  • the sliding environment becomes extremely severe due to high temperature and high surface pressure.
  • the sliding environment of sliding members other than piston rings has been getting hotter.
  • the sliding member is desired to have high heat resistance, in which a decrease in hardness of the DLC film can be suppressed even in the above-mentioned high temperature environment.
  • the conventional hydrogen-free DLC film has a problem that when it is slid under a lubricating oil containing an organic molybdenum-based compound, the wear of the DLC film is promoted and sufficient wear resistance cannot be obtained.
  • an amorphous carbon film (DLC film) forming a sliding surface of a sliding member is provided with a predetermined amount of silicon (Si) and boron (B). It is said that high heat resistance and high wear resistance under a lubricating oil containing an organic molybdenum-based compound can be realized by adopting a component composition that contains carbon and the balance is substantially free of hydrogen. I got the knowledge of.
  • the present invention has a DLC film having excellent heat resistance, can obtain high wear resistance regardless of whether or not the lubricating oil contains an organic molybdenum compound, and has a lower friction coefficient. It is an object of the present invention to provide a sliding member capable of realizing the above.
  • a first region containing a predetermined amount of Si and B, and Si and B were formed on the surface of a hydrogen-free amorphous carbon film (DLC film).
  • DLC film hydrogen-free amorphous carbon film
  • the abstract structure of the present invention completed based on the above findings is as follows.
  • the surface of the amorphous carbon film contains silicon: 2 atomic% or more and 20 atomic% or less, and boron: 2 atomic% or more and 15 atomic% or less, and the balance is carbon, which is substantially hydrogen-free.
  • the first region having a composition and the second region having a component composition consisting of carbon and substantially free of hydrogen are mixed.
  • the thickness of the amorphous carbon film is 20 ⁇ m or less, the thickness of the amorphous carbon film exceeds 20 ⁇ m in the entire range in the thickness direction of the amorphous carbon film.
  • the first region and the second region are mixed in a cross section perpendicular to the thickness direction in a range of at least 20 ⁇ m from the surface of the amorphous carbon film in the thickness direction, and the first region in the cross section.
  • the sliding member according to (1) above, wherein B'/ (A'+ B') is 0.05 or more and 0.40 or less, where A'is the area of A'and the area of the second region is B'.
  • a piston ring made of the sliding member according to any one of (1) to (6) above, the outer peripheral surface of which is the sliding surface.
  • the sliding member of the present invention has a DLC film having excellent heat resistance, can obtain high wear resistance regardless of whether or not the lubricating oil contains an organic molybdenum compound, and realizes a further low coefficient of friction. It is possible to do.
  • FIG. 1 It is a schematic cross-sectional view of the sliding member 100 by 1st Embodiment of this invention. It is a figure which schematically explains a part of the manufacturing process of the sliding member 100 by 1st Embodiment of this invention. It is a schematic cross-sectional view of the sliding member 200 according to the 2nd Embodiment of this invention. It is sectional drawing of the piston ring 300 by one Embodiment of this invention. It is an SEM image of the surface of the DLC film in the invention example (No. 4) of Table 1.
  • FIG. It is a schematic diagram which shows the form of the reciprocating sliding test. It is a schematic diagram explaining the calculation method of the wear depth.
  • the sliding member 100 is used under lubricating oil, and has a base material 10 and a surface 20A formed on the base material 10. It has an amorphous carbon film (DLC film) 20 as a sliding surface. Further, optionally, an intermediate layer 12 may be provided between the base material 10 and the amorphous carbon film 20.
  • DLC film amorphous carbon film
  • the sliding member 200 is used under lubricating oil, and has a base material 10 and a surface 30A formed on the base material 10. It has an amorphous carbon film (DLC film) 30 as a sliding surface. Further, optionally, an intermediate layer (not shown) may be provided between the base material 10 and the amorphous carbon film 30.
  • DLC film amorphous carbon film
  • the sliding members 100 and 200 according to the present embodiment are used in the presence of a lubricating oil containing an organic molybdenum compound or in the presence of a lubricating oil containing no organic molybdenum compound. That is, the use of the sliding members 100 and 200 in combination with a lubricating oil containing an organic molybdenum compound or a lubricating oil not containing an organic molybdenum compound also constitutes the present invention. Further, the sliding members 100 and 200, an arbitrary mating sliding member, and a lubricating oil containing an organic molybdenum-based compound or a lubricating oil containing no organic molybdenum-based compound supplied to the sliding surfaces of both of them. A sliding structure including the above also constitutes the present invention.
  • the organic molybdenum-based compound is preferably one or more organic molybdenum-based compounds selected from molybdenum dithiocarbamate (Mo-DTC) and molybdenum dithiophosphate (Mo-DTP). These organic molybdenum compounds can be decomposed by heat due to sliding to form a tribo film of molybdenum disulfide (MoS 2) on the sliding surface of the mating material that slides with the DLC film.
  • Mo-DTC molybdenum dithiocarbamate
  • Mo-DTP molybdenum dithiophosphate
  • the material of the base material 10 is not particularly limited as long as it has the strength required as the base material of the sliding member.
  • preferred materials for the base material 10 include steel, martensitic stainless steel, austenitic stainless steel, and high-grade cast iron.
  • resin is mentioned as the material of the base material 10
  • the material of the base material 10 is an aluminum alloy or the like. Can be mentioned.
  • the roughness of the surface of the base material 10 is preferably 0.01 ⁇ m or more in arithmetic average roughness Ra.
  • the surface roughness of the base material 10 is less than 0.01 ⁇ m in Ra, the surface becomes almost a mirror surface, and the first DLC layer 14 and the second DLC layer 16 (see FIGS. 1 and 2) having appropriate surface roughness described later are formed. Because it cannot be done.
  • the upper limit of the surface roughness of the base material 10 applied to the first embodiment is not particularly limited, but the surface roughness of the base material 10 is 0.15 ⁇ m or less in Ra in consideration of the polishing allowance of the final surface polishing. Is preferable.
  • the surface roughness of the base material 10 can be controlled by adjusting the degree of polishing of the base material surface. Further, the surface of the base material can be honed to intentionally form the surface roughness.
  • the surface roughness of the base material 10 is not particularly limited, but it can be the same as when applied to the first embodiment.
  • the intermediate layer 12 has a function of relaxing the stress at the interface with the base material 10 by being formed between the base material 10 and the DLC films 20 and 30, and enhancing the adhesion of the DLC films 20 and 30.
  • the intermediate layer 12 is composed of one or more elements selected from the group consisting of Cr, Ti, Co, V, Mo, Si and W or their carbides, nitrides and carbonitrides. It is preferable to use the above.
  • the thickness of the intermediate layer 12 is preferably 0.1 ⁇ m or more, and more preferably 0.2 ⁇ m or more.
  • the thickness of the intermediate layer 12 is preferably 0.6 ⁇ m or less, and is 0. More preferably, it is 5.5 ⁇ m or less.
  • the intermediate layer 12 As a method for forming the intermediate layer 12, for example, a sputtering method can be mentioned.
  • the washed base material 10 is placed in the vacuum chamber of the PVD film forming apparatus, and the intermediate layer 12 is formed by sputter discharge of the target with Ar gas introduced.
  • the target may be selected from Cr, Ti, Co, V, Mo, Si and W.
  • the thickness of the intermediate layer 12 can be adjusted by adjusting the discharge time of the target.
  • the DLC film 20 applied to the first embodiment is formed on the surface of the base material 10 when the intermediate layer 12 is not formed, and when the intermediate layer 12 is formed, the DLC film 20 is formed on the surface of the base material 10. , Formed on the surface of the intermediate layer 12.
  • the DLC film 20 is composed of a first DLC layer (Si—B-containing H-free DLC layer) 14 containing a predetermined amount of Si and B, and a second DLC containing only C without containing Si and B.
  • the layers (H-free DLC layer) 16 are alternately laminated a plurality of times while having a predetermined surface roughness. Then, referring to FIG. 2 in addition to FIG.
  • the surface of the uppermost second DLC layer (H-free DLC layer) 16 having a predetermined surface roughness is polished by a predetermined amount to form the DLC film 20.
  • the first DLC layer (Si—B-containing H-free DLC layer) 14 is exposed on the surface 20A, and the first region (Si—B-containing region) 18A and the second DLC layer (H-free DLC layer) 16 remain.
  • the second region (ta-C region) 18B is mixed.
  • FIGS. 1 and 2 show an example in which the uppermost layer is the second DLC layer 16, the present invention is not limited to this, and the uppermost layer may be the first DLC layer 14.
  • a DLC film 20 is formed by polishing the surface of the uppermost first DLC layer 14 having a predetermined surface roughness by a predetermined amount, and the first DLC layer (Si—B-containing H) is formed on the surface 20A.
  • the first region (Si—B-containing region) 18A in which the free DLC layer (14) remains and the second region (ta-C region) 18B in which the second DLC layer (H-free DLC layer) 16 is exposed are mixed. Become.
  • the lowermost layer is not particularly limited, and may be the first DLC layer 14 or the second DLC layer 16.
  • the DLC film 30 applied to the second embodiment is formed on the surface of the base material 10 when the intermediate layer is not formed, and is intermediate when the intermediate layer is formed. Formed on the surface of the layer.
  • the DLC film 30 is composed of only C without containing Si and B, using the first DLC portion (Si—B-containing H-free DLC portion) 24 containing a predetermined amount of Si and B as a matrix.
  • the second DLC part (H-free DLC part) 26 has a film structure dispersed in the matrix.
  • the surface of the DLC film 30 has been polished by a predetermined amount, and as a result, the first region (Si-) in which the first DLC portion (Si—B-containing H-free DLC portion) 24 is exposed on the surface 30A of the DLC film 30.
  • the B-containing region) 28A and the second region (ta-C region) 28B where the second DLC portion (H-free DLC portion) 26 is exposed are mixed.
  • the first DLC layer 14 and the first DLC part 24 contain silicon: 2 atomic% or more and 20 atomic% or less, and boron: 2 atomic% or more and 15 atomic% or less, and the balance is carbon and is substantially hydrogen-free.
  • the first DLC layer 14 and the first DLC unit 24 preferably further contain a predetermined amount of one or both of nitrogen (N) and oxygen (O). The fact that it is amorphous carbon can be confirmed by Raman spectrum measurement using a Raman spectrophotometer (Ar laser).
  • the first DLC layer 14 and the first DLC part 24 are improved in the heat resistance of the DLC films 20 and 30 and the wear resistance under the lubricating oil containing the organic molybdenum compound.
  • the present inventors consider the action of obtaining such an effect as follows.
  • the carbon dangling bond in the DLC film and Mo in the lubricating oil combine to form hard molybdenum carbide (MoC) particles.
  • MoC molybdenum carbide
  • the MoC particles accelerate the wear of the DLC film.
  • the first DLC layer 14 and the first DLC part 24 contain a predetermined amount of Si and B, the dangling bond density of carbon in the first DLC layer 14 and the first DLC part 24 is reduced. As a result, the formation of hard MoC particles is suppressed. As a result, high wear resistance can be obtained under a lubricating oil containing an organic molybdenum compound.
  • the first DLC layer 14 and the first DLC unit 24 contain a predetermined amount of Si and B
  • the first DLC layer 14 is exposed as a sliding surface due to the reaction of Si and B with oxygen in a high temperature environment. It is considered that a dense SiO 2 film and a B 2 O 3 film are formed on the surface of the first DLC portion 24, and these films function as protective films to improve heat resistance.
  • the Si content is preferably 2 atomic% or more and 5 atomic% or more
  • the B content is preferably 2 atomic% or more and 5 atomic% or more
  • the Si content and B content are preferably 10 atomic% or more.
  • the Si content is preferably 20 atomic% or less and preferably 15 atomic% or less
  • the B content is preferably 15 atomic% or less and preferably 12 atomic% or less, and is preferably 10 atomic% or less. Is more preferable.
  • the total of the Si content and the B content is preferably 30 atomic% or less.
  • first DLC layer 14 and the first DLC part 24 contain hydrogen
  • the temperature of the first DLC layer 14 and the first DLC part 24 becomes high due to sliding
  • hydrogen is desorbed and the first DLC layer 14 and the first DLC part 24 deteriorate.
  • wear of the first DLC layer 14 and the first DLC portion 24 is promoted. Therefore, it is assumed that the first DLC layer 14 and the first DLC unit 24 do not substantially contain hydrogen. This makes it possible to avoid deterioration of wear resistance due to the release of hydrogen in a high temperature environment.
  • substantially free of hydrogen as used herein means that the hydrogen content in the first DLC layer 14 and the first DLC unit 24 is 3 atomic% or less.
  • the first DLC layer 14 and the first DLC unit 24 may contain nitrogen (N).
  • N nitrogen
  • BN has a layered lattice structure with low shear resistance, it exhibits a friction reducing effect, and Si 3 N 4 has excellent fracture toughness, which contributes to improvement of wear resistance.
  • the N content is preferably 5 atomic% or more.
  • the N content exceeds 15 atomic%, the formation of the sp 3 bond of carbon is inhibited, so that the first DLC layer and the first DLC portion having the desired hardness cannot be obtained, and the heat resistance and wear resistance Both deteriorate. Therefore, when the first DLC layer 14 and the first DLC unit 24 contain nitrogen, the N content thereof is 15 atomic% or less, preferably 12 atomic% or less.
  • the first DLC layer 14 and the first DLC unit 24 may contain oxygen (O).
  • O oxygen
  • the surfaces of the first DLC layer 14 and the first DLC portion 24 become hot due to sliding, oxide layers of SiO 2 and B 2 O 3 are likely to be formed, and the oxide layers of SiO 2 and B 2 O 3 are easily formed in the lubricating oil.
  • the O content is preferably 2 atomic% or more.
  • the total content of nitrogen and oxygen is preferably 15 atomic% or less.
  • the second DLC layer 16 and the second DLC portion 26 have a substantially hydrogen-free component composition composed of carbon.
  • the fact that it is amorphous carbon can be confirmed by Raman spectrum measurement using a Raman spectrophotometer (Ar laser).
  • the second DLC layer 16 and the second DLC portion 26 contribute to the improvement of the wear resistance under the lubricating oil containing no organic molybdenum compound and the reduction of the friction coefficient.
  • the present inventors consider the action of obtaining such an effect as follows.
  • the second DLC layer 16 and the second DLC portion 26 are substantially composed of carbon only, graphitization due to sliding heat is promoted, which contributes to a decrease in the friction coefficient. Further, by reducing the friction coefficient, the sliding load is reduced, and the amount of wear is suppressed under the lubricating oil containing no organic molybdenum compound.
  • the second DLC layer 16 and the second DLC section 26 are also substantially free of hydrogen. This makes it possible to avoid deterioration of wear resistance due to the release of hydrogen in a high temperature environment.
  • substantially free of hydrogen as used herein means that the hydrogen content in the second DLC layer 16 and the second DLC section 26 is 3 atomic% or less.
  • the hydrogen content of the DLC film is evaluated by RBS (Rutherford Backscattering Spectrometry) / HFS (Hydrogen Forward Scattering Spectroscopy) for the DLC film formed on a flat surface or a surface having a sufficiently large curvature. be able to.
  • RBS Rutherford Backscattering Spectrometry
  • HFS Hydrogen Forward Scattering Spectroscopy
  • the DLC film formed on an uneven sliding surface such as the outer peripheral surface of the piston ring is evaluated by combining RBS / HFS and SIMS (Secondary Ion Mass Spectrometry).
  • RBS / HFS is a known method for analyzing a film composition, it cannot be applied to the analysis of uneven surfaces. Therefore, RBS / HFS and SIMS are combined as follows.
  • a mirror-polished flat test piece (hardened SKH51 disk, ⁇ 25 ⁇ thickness 5 mm, hardness HRC60 to 63) is subjected to carbon to be measured as a reference value. Form a film.
  • the film is formed on the reference sample by introducing C 2 H 2 , Ar, and H 2 as atmospheric gases using a reactive sputtering method. Then, by varying the flow rate of H 2 and / or C 2 H 2 flow rate is introduced to adjust the amount of hydrogen contained in the carbon film. In this way, carbon films composed of hydrogen and carbon and having different hydrogen contents are formed, and the hydrogen content and carbon content of these are evaluated by RBS / HFS.
  • SIMS SIMS analysis
  • the hydrogen content and carbon content (unit: atomic%) obtained by RBS / HFS and the secondary ions of hydrogen and carbon obtained by SIMS.
  • an empirical formula calibration curve showing the relationship with the strength ratio.
  • the hydrogen content and the carbon content can be calculated from the secondary ionic strengths of hydrogen and carbon of SIMS measured on the outer peripheral surface of the actual piston ring.
  • the value of the secondary ionic strength by SIMS the average value of the secondary ionic strength of each element observed at least at a depth of 20 nm or more from the surface of the carbon film and in the range of 50 nm square is adopted.
  • the Si, B, N and O contents of the first DLC layer and the first DLC part shall be measured by X-ray photoelectron spectroscopy (XPS) under the following conditions.
  • XPS X-ray photoelectron spectroscopy
  • Quantitative analysis of elements in XPS is performed based on the photoelectron peak area. Since the peak area is proportional to the atomic concentration and the sensitivity of the electron of interest, the value obtained by dividing the peak area by the relative sensitivity coefficient is proportional to the atomic concentration. Therefore, relative quantification can be performed with the sum of the quantified values of each element as 100 atomic%.
  • first region (Si—B-containing region) 18A and the second region (ta-C region) 18B are mixed on the surface 20A of the DLC film 20. deep.
  • first region (Si—B containing region) 28A and the second region (taC region) 28B are mixed on the surface 30A of the DLC film 30. ..
  • B / (A + B) is 0.05 or more and 0.40 or less, that is, the first region (Si ⁇ ). It is important to combine the second region (ta-C region) 18B and 28A at a predetermined ratio while mainly containing the B-containing region) 18A and 28A.
  • B / (A + B) is set to 0.05 or more, preferably 0.10 or more.
  • B / (A + B) exceeds 0.40, the first region (Si—B-containing region) 18A and 28A is too small on the surfaces 20A and 30A of the DLC film, and the second region (ta-C region) 18B, 28B is excessive. In this case, the heat resistance and the wear resistance under the lubricating oil containing the organic molybdenum compound become insufficient. Therefore, B / (A + B) is set to 0.40 or less, preferably 0.35 or less.
  • B / (A + B) shall be calculated by the following method.
  • the first region (Si-B-containing region) and the second region (Ta-C region) are different in the scanning electron microscope (SEM) due to the presence or absence of Si and B. It can be observed as a contrast. Therefore, the area of each region in the field of view can be calculated by analyzing the obtained image and binarizing it. Specifically, any three places on the surface of the DLC film are observed by FE-SEM, and a secondary electron image is taken. The observation conditions are an acceleration voltage of 5 kV and a magnification of 10,000 times.
  • the captured image is binarized by image analysis software, the area of the first region is V1, the area of the second region is V2, V2 / (V1 + V2) is obtained for each captured image, and the obtained three values are countable. On average, it is B / (A + B).
  • first regions 18A and 28A and the second regions 18B and 28B are "mixed" on the surfaces 20A and 30A of the DLC film means that the first regions 18A and 28A and the second regions 18B are on the surfaces 20A and 30A of the DLC film. , 28B are distributed and exist.
  • the indentation hardness of the first regions 18A and 28A is smaller than the indentation hardness of the second regions 18B and 28B.
  • the indentation hardness of the first regions 18A and 28A is preferably 15 GPa or more and 35 GPa or less.
  • the indentation hardness is 15 GPa or more, the wear resistance of the DLC film is not insufficient.
  • the indentation hardness is 35 GPa or less, the toughness of the DLC film is not insufficient, and chipping and peeling are unlikely to occur.
  • the indentation hardness of the second regions 18B and 28B is preferably 25 GPa or more and 50 GPa or less. If the indentation hardness is 25 GPa or more, the wear resistance and heat resistance of the DLC film will not be insufficient. On the other hand, when the indentation hardness is 50 GPa or less, the load of finishing is not increased, so that the cost increase can be suppressed.
  • the thickness of the DLC films 20 and 30 is not particularly limited, but is preferably 0.5 ⁇ m or more and 50 ⁇ m or less. This is because if the thickness is 0.5 ⁇ m or more, the durability of the DLC film is not insufficient, and if it is 50 ⁇ m or less, the adhesion to the base material is insufficient and peeling does not occur. In the present invention, the thickness of the DLC film shall be measured by carotest or by observing the cross section of the resin-embedded film.
  • B'/ (A'+ B') is 0.05 or more and 0.40 or less is maintained, where A'is the area of the first region and B'is the area of the second region in the cross section. It is preferable to be done.
  • B'/ (A'+ B') shall be obtained according to the above-mentioned method for obtaining B / (A + B).
  • the DLC film is polished to form a first sample having a polished surface in which 45 to 55% of the thickness is exposed from the surface of the DLC film.
  • the polished surface of the first sample and the polished surface of the second sample are each observed by FE-SEM, and a secondary electron image is taken.
  • the captured image is binarized by image analysis software, the area of the first region is V1', the area of the second region is V2', and V2'/ (V1'+ V2') is obtained in each captured image and obtained.
  • the three values are countably averaged to obtain B'/ (A'+ B'). If B'/ (A'+ B') is 0.05 or more and 0.40 or less in both the first sample and the second sample, B'/ (A) in the entire range in the thickness direction of the DLC film. It is considered that the state in which'+ B') is 0.05 or more and 0.40 or less is maintained.
  • the DLC film is polished to have a first sample having a polished surface where a position of 10 ⁇ m from the surface of the DLC film is exposed in the thickness direction, and a first sample having a polished surface and a thickness direction from the surface of the DLC film.
  • the polished surface of the first sample and the polished surface of the second sample are each observed by FE-SEM, and a secondary electron image is taken.
  • the captured image is binarized by image analysis software, the area of the first region is V1', the area of the second region is V2', and V2'/ (V1'+ V2') is obtained in each captured image and obtained.
  • B'/ (A'+ B') is 0.05 or more and 0.40 or less in both the first sample and the second sample, B is in the range of at least 20 ⁇ m in the thickness direction from the surface of the DLC film. It is considered that the state in which'/ (A'+ B') is 0.05 or more and 0.40 or less is maintained.
  • the surface roughness of each of the first DLC layer 14 and the second DLC layer 16 is preferably 0.01 ⁇ m or more and 0.15 ⁇ m or less in terms of arithmetic mean roughness Ra.
  • a cross-sectional sample in the thickness direction of the DLC film is produced by focused ion beam (FIB) processing, a transmission electron microscope image (TEM image) is observed, and the adjacent TEM image is adjacent based on the change in brightness of the obtained TEM image.
  • FIB focused ion beam
  • TEM image transmission electron microscope image
  • the adjacent TEM image is adjacent based on the change in brightness of the obtained TEM image.
  • the surface shape (cross-sectional shape) of each DLC layer is defined as the boundary between adjacent layers where the change in brightness is halved.
  • the arithmetic average roughness Ra is obtained according to JIS B0601 (2001) using surface roughness measurement software or the like. The measurement shall be performed three times, and the average value of the three times shall be adopted.
  • each of the first DLC layer 14 and the second DLC layer 16 are not particularly limited, but a desired B / (A + B) is realized and a desired B'/ (A'+ B') is realized. ) Can be maintained as appropriate.
  • the surface roughness of the DLC films 20 and 30 is preferably 0.1 ⁇ m or less in terms of arithmetic mean roughness Ra. As a result, the aggression of the DLC film to the mating material can be reduced.
  • the DLC films 20 and 30 can be formed by using a PVD method such as ion plating by vacuum arc discharge (VA method) using a carbon target, for example.
  • VA method ion plating by vacuum arc discharge
  • the PVD method can form a DLC film having high hardness and excellent wear resistance containing almost no hydrogen.
  • a DLC film is formed by using the ion plating method by vacuum arc discharge, its hardness can be adjusted by a bias voltage applied to the base material or the like. Further, the film thickness of the DLC film can be adjusted by changing conditions such as the discharge time of the target.
  • FCVA method filter type cathode vacuum arc method
  • a carbon alloy target containing Si and B can be used for film formation of the first DLC layer (Si—B-containing H-free DLC layer) 14 and the first DLC portion (Si—B-containing H-free DLC portion) 24. That is, in order for the first DLC layer 14 and the first DLC portion 24 to contain a predetermined amount of Si and B, for example, graphite containing silicon carbide (SiC) and boron carbide (B 4 C) is used as the cathode material. By adjusting these contents in the cathode material, the Si content and the B content in the first DLC layer 14 and the first DLC unit 24 can be controlled. Further, in order to contain a predetermined amount of N and O in the first DLC layer 14 and the first DLC unit 24, N and O may be added to the carbon alloy target.
  • SiC silicon carbide
  • B 4 C boron carbide
  • a carbon target containing no Si and B can be used for film formation of the second DLC layer (H-free DLC layer) 16 and the second DLC part (H-free DLC part) 26.
  • a base material 10 having a surface roughness of 0.01 ⁇ m or more is prepared, and an intermediate layer 12 is optionally formed on the surface. To do. After that, a plurality of sets of a first DLC layer (Si—B-containing H-free DLC layer) 14 and a second DLC layer (H-free DLC layer) 16 are alternately arranged on the surface of the base material 10 or the surface of the intermediate layer 12. Laminate.
  • the surface of the base material 10 is provided with a predetermined surface roughness, and carbon fine particles (droplets) and the like are incorporated into the film in the process of film formation, so that the first DLC layer 14 and the first DLC layer 14 A predetermined surface roughness is provided on each surface of the 2DLC layer 16.
  • the laminated structure of the first DLC layer 14 and the second DLC layer 16 is a group that rotates a Si—B-containing carbon alloy target for forming the first DLC layer 14 and a carbon target for forming the second DLC layer 16. It can be obtained by arranging the base material in a concentric circle around the material. For example, if the Si—B-containing carbon alloy target and the carbon target are arranged so as to be offset by 180 °, a laminated structure of the first DLC layer 14 and the second DLC layer 16 can be obtained.
  • the thickness ratio of the first DLC layer 14 and the second DLC layer 16 can be controlled by adjusting the rotation speed of the base material and the target discharge current.
  • B / (A + B) is controlled in the range of 0.05 or more and 0.40 or less.
  • a Si—B-containing carbon alloy target for forming the first DLC portion 24 and a carbon target for forming the second DLC portion 26 are used. It can be obtained by arranging the rotating base material in a concentric circle around the base material. At that time, if the Si—B-containing carbon alloy target and the carbon target are arranged close to each other, a film structure in which the second DLC portion 26 is dispersed in the matrix of the first DLC portion 24 can be obtained.
  • the dispersion ratio of the first DLC unit 24 and the second DLC unit 26 can be controlled by adjusting the rotation speed of the base material and the target discharge current.
  • the hard regions 18A and 28A and the soft regions 18B and 28B can be mixed on the surfaces 20A and 30A of the DLC coatings 20 and 30, and B'
  • the state in which / (A'+ B') is 0.05 or more and 0.40 or less can be maintained.
  • the sliding members 100 and 200 include a piston ring, a piston, a piston pin, a tappet, a valve lifter, a shim, and a rocker arm used for a sliding portion of an internal combustion engine in which lubricating oil such as engine oil is interposed.
  • lubricating oil such as engine oil is interposed.
  • Cams, camshafts, timing gears, timing chains, etc., vanes, injectors, plungers, cylinders, etc. used in fuel supply systems, etc. can be applied to various products.
  • the piston ring 300 has a ring shape with four surfaces of an outer peripheral surface 32, an inner peripheral surface 34, and upper and lower surfaces 36A and 36B, and the outer peripheral surface 32 is shown in FIG. It is formed by the DLC film 20 shown or the DLC film 30 shown in FIG. That is, the piston ring 300 of the present embodiment is composed of the sliding member 100 or the sliding member 200, and its outer peripheral surface 22 is the surface 20A of the DLC film shown in FIG. 1 or the surface of the DLC film shown in FIG. It becomes 30A.
  • DLC films of various examples shown in Table 1 were formed on the surface of a base material (surface roughness Ra: 0.01 ⁇ m) which is a columnar body ( ⁇ 6 mm ⁇ height 14 mm) of SUJ2 material (JIS G 4805). A sliding member was obtained.
  • the intermediate layer shown in Table 1 was formed on the surface of the base material, and the DLC film shown in Table 1 was formed on the intermediate layer to obtain a sliding member.
  • a film forming apparatus by a vacuum arc method was used for the formation of the DLC film.
  • SiC silicon carbide
  • B 4 C boron carbide
  • Si-B-containing carbon alloy target made of graphite was prepared a carbon target containing no Si and B.
  • the Si—B-containing carbon alloy target and the carbon target were arranged around the rotating base material in a concentric circle centered on the base material, shifted by 180 °.
  • a DLC film having a laminated structure of a first DLC layer and a second DLC layer was formed.
  • the surface of the DLC film was polished by a predetermined amount to reduce Ra to 0.1 ⁇ m or less.
  • the thickness ratio of the first DLC layer and the second DLC layer is controlled by adjusting the target discharge current, and by variously changing this thickness ratio, B / (A + B) and B'/ ( A'+ B') was controlled.
  • B / (A + B) and B'/ ( A'+ B') was controlled.
  • one or both of nitrogen and oxygen were further contained in the Si—B-containing carbon alloy target for forming the first DLC layer.
  • a first DLC layer was formed using a B-containing carbon alloy target containing boron carbide (B 4 C) and made of graphite.
  • a first DLC layer was formed using a Si-containing carbon alloy target containing silicon carbide (SiC) and made of graphite.
  • the Si content, B content, N content, and O content of the first DLC layer were determined by the methods described above and are shown in Table 1.
  • the thickness of the DLC film was measured by the Carotest and is shown in Table 1.
  • the B / (A + B) on the surface of the DLC film was determined by the method described above and is shown in Table 1.
  • the values of the first sample and the second sample were obtained by the method described above, and are shown in Table 1.
  • the indentation hardness of the first region and the second region was measured and shown in Table 1.
  • the indentation hardness was measured using an ultra-fine indentation hardness tester manufactured by Elionix Inc. As a condition, the test was carried out using a Belkovic indenter under a load such that the indentation depth was about 1/10 of the thickness of the DLC film.
  • Lubricating oil (1) Base oil PAO (2) Engine oil 0W-8 (Mo-DTC additive-free oil) (3) Engine oil 0W-8 (Mo-DTC added oil) (4) Engine oil 0W-20 (Mo-DTC additive-free oil) (5) Engine oil 0W-20 (Mo-DTC added oil) Lubricating oil temperature: 80 ° C
  • the sliding member of the present invention has a DLC film having excellent heat resistance, can obtain high wear resistance regardless of whether or not the lubricating oil contains an organic molybdenum compound, and realizes a further low coefficient of friction. It is possible to do.

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

Abstract

L'invention concerne un élément coulissant qui présente un film DLC ayant une excellente résistance à la chaleur, grâce auquel une résistance à l'abrasion élevée peut être obtenue indépendamment du fait qu'une huile lubrifiante contienne un composé à base de molybdène organique, et grâce auquel un faible coefficient de frottement peut être obtenu. Un élément coulissant (100), selon la présente invention, comprend : un substrat (10) ; et un film de carbone amorphe (20) qui est formé sur le substrat (10) et a une surface (20A) faisant office de surface de glissement. La présente invention est caractérisée en ce que, sur la surface (20A) du film de carbone amorphe, une première région (18A) ayant une composition de constituants qui ne contient sensiblement pas d'hydrogène et contient 2-20 % atomique de silicium et 2-15 % atomique de bore, le reste étant constitué de carbone coexiste avec une seconde région (18B) ayant une composition de constituants qui ne contient sensiblement pas d'hydrogène et est constituée de carbone, et lorsque, sur la surface (20A), la superficie de la première région (18A) est définie comme étant A et la superficie de la seconde région (18B) est définie comme étant B, B/ (A+B) est de 0,05 à 0,40.
PCT/JP2020/046832 2020-01-10 2020-12-15 Élément coulissant et segment de piston WO2021140851A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1192935A (ja) * 1997-09-19 1999-04-06 Daido Steel Co Ltd 耐摩耗性硬質炭素被膜
JP2008286354A (ja) * 2007-05-21 2008-11-27 Nippon Piston Ring Co Ltd 摺動部材
JP2012530188A (ja) * 2009-06-18 2012-11-29 スルザー メタプラス ゲーエムベーハー 保護コーティング、保護コーティングを有するコーティング部材、並びに保護コーティングを製造するための方法
JP2015193918A (ja) * 2014-03-21 2015-11-05 株式会社豊田中央研究所 摺動部材および摺動機械

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1192935A (ja) * 1997-09-19 1999-04-06 Daido Steel Co Ltd 耐摩耗性硬質炭素被膜
JP2008286354A (ja) * 2007-05-21 2008-11-27 Nippon Piston Ring Co Ltd 摺動部材
JP2012530188A (ja) * 2009-06-18 2012-11-29 スルザー メタプラス ゲーエムベーハー 保護コーティング、保護コーティングを有するコーティング部材、並びに保護コーティングを製造するための方法
JP2015193918A (ja) * 2014-03-21 2015-11-05 株式会社豊田中央研究所 摺動部材および摺動機械

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