WO2020004061A1 - ピストンリング - Google Patents
ピストンリング Download PDFInfo
- Publication number
- WO2020004061A1 WO2020004061A1 PCT/JP2019/023500 JP2019023500W WO2020004061A1 WO 2020004061 A1 WO2020004061 A1 WO 2020004061A1 JP 2019023500 W JP2019023500 W JP 2019023500W WO 2020004061 A1 WO2020004061 A1 WO 2020004061A1
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- WO
- WIPO (PCT)
- Prior art keywords
- piston ring
- coating
- dlc
- film
- gpa
- Prior art date
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- 238000000576 coating method Methods 0.000 claims abstract description 102
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Images
Classifications
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- 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
-
- 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
- C23C14/0605—Carbon
- C23C14/0611—Diamond
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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
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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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
- C23C28/044—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material coatings specially adapted for cutting tools or wear applications
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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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
- C23C28/046—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material with at least one amorphous inorganic material layer, e.g. DLC, a-C:H, a-C:Me, the layer being doped or not
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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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/40—Coatings including alternating layers following a pattern, a periodic or defined repetition
- C23C28/44—Coatings including alternating layers following a pattern, a periodic or defined repetition characterized by a measurable physical property of the alternating layer or system, e.g. thickness, density, hardness
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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
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
- C23C30/005—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process on hard metal substrates
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02F—CYLINDERS, PISTONS OR CASINGS, FOR COMBUSTION ENGINES; ARRANGEMENTS OF SEALINGS IN COMBUSTION ENGINES
- F02F5/00—Piston rings, e.g. associated with piston crown
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- 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
- F16J9/12—Details
- F16J9/22—Rings for preventing wear of grooves or like seatings
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- 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
- F16J9/28—Piston-rings, e.g. non-metallic piston-rings, seats therefor; Ring sealings of similar construction of non-metals
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Definitions
- the present invention relates to a piston ring used for a piston for an internal combustion engine.
- a DLC film is a film having an amorphous structure (amorphous structure) in which sp 2 bonds of carbon atoms corresponding to a graphite structure and sp 3 bonds of carbon atoms corresponding to a diamond structure are mixed.
- the component ratio of sp 2 (sp 2 / (sp 2 + sp 3)) if is large (low coefficient of friction has a solid lubricant) of graphite in the similar physical properties
- the component ratio of sp 3 (sp 3 / ( If sp 2 + sp 3 )) is large
- diamond-like physical properties excellent in hardness, wear resistance and chemical stability
- Patent Document 1 has an inclined structure in which the sp 2 ratio increases from the inner surface of the amorphous hard carbon film, which is the base material side, toward the outer surface, and the sp 2 ratio of the inner surface of the amorphous hard carbon film is increased.
- B% of sp 2 ratio of the outer surface side is a%
- the value of (B-a) is disclosed slide member 20 or more.
- a further sp less than 2 ratio of A 40%, preferably B of sp 2 ratio is greater than 65%, the density of the droplets of 300 [mu] m 2 or more sizes on the surface of the amorphous hard carbon film
- the number is 600 or less / mm 2
- sp 2 ratio in Patent Document 1 shows an amorphous ratio of sp 2 bonds to sp 2 bonds and sp 3 bonds in the hard carbon film (sp 2 / (sp 2 + sp 3)), electronic It means a value calculated based on a spectrum obtained by energy loss spectroscopy (Electron Energy Loss Spectroscopy: EELS).
- the droplet refers to a concave or convex portion formed on the surface of the amorphous hard carbon film due to the incorporation or dropping of the droplet particles, the density of the droplet, using a microscope,
- the number of concave or convex portions having a size of 300 ⁇ m 2 or more due to the incorporation or dropping of droplet particles present in a predetermined range of the surface can be visually counted and calculated, and of course, image processing and the like can be performed. It may be used to count.
- the sp 2 ratio on the base material side is relatively low means that the amorphous hard carbon film near the base material has relatively high strength.
- deformation of the base material can be suppressed, and peeling of the coating film due to the deformation can be prevented. That is, sufficient adhesion with the base material can be secured.
- the fact that the sp 2 ratio on the outer surface side is relatively high means that the bond strength of carbon atoms is relatively weak, that is, that the coating film is flexible. When foreign matter such as dust passes through the sliding surface, the surface of the coating serves as a cushion, which can prevent the coating from cracking and peeling.
- Patent Document 2 discloses a sliding member having an amorphous hard carbon film formed on at least one sliding surface, wherein the amorphous hard carbon film is continuously formed from a base material of the sliding member toward the surface. And / or a carbon layer whose Young's modulus is reduced stepwise, wherein the hydrogen concentration of the carbon layer is less than 5 atomic%.
- the thickness of the carbon layer from the base material side at least 0.5 ⁇ m has a Young's modulus exceeding 400 GPa, and the thickness at least 1.5 ⁇ m inward from the surface preferably has a Young's modulus of 350 GPa or less. It mentions that such Young's modulus is excellent in abrasion resistance and peeling resistance.
- the deposit in the engine lubricating oil is interposed in the sliding area between the piston ring and the cylinder bore, and forms a sliding environment in which abrasive wear occurs. That is, as compared with a sliding environment in which the engine lubricating oil is clean and the amount of deposit is small, abrasive wear progresses between the piston ring and the cylinder bore in an environment in which the engine lubricating oil is deteriorated.
- An object of the present invention is to provide a piston ring coated with a DLC film having a sufficient effect on abrasive wear as described above, having excellent wear resistance, and having a low aggressiveness on a cylinder bore sliding surface. I do.
- the inventors of the present invention have been studying to achieve the above-mentioned object, and have set the sp 2 component ratio and the hardness and Young's modulus of the coating measured by the nanoindentation method to specific ranges, respectively.
- the inventors have conceived of obtaining a DLC film having excellent property and low aggressiveness of a counterpart material, and completed the invention.
- the present invention relates to a piston ring used under engine lubricating oil and having a DLC coating on an outer peripheral sliding surface, wherein the DLC coating combines a transmission electron microscope (TEM) with an electron energy loss spectroscopy (EELS).
- TEM transmission electron microscope
- EELS electron energy loss spectroscopy
- the sp 2 component ratio measured by TEM-EELS is 0.5 to 0.85
- the hardness of the coating measured by the nanoindentation method is 12 GPa to 26 GPa
- the Young's modulus is 250 GPa or less. Which is a piston ring.
- the DLC film preferably has a Young's modulus of 200 GPa or less, and the DLC film has a cross section in the thickness direction observed from a 10,000-times image taken with a scanning electron microscope (SEM). It is preferable that the number of macro particles is 2 or less per 10 ⁇ m 2 .
- the DLC film preferably has a refractive index measured by a spectroscopic ellipsometer of 2.3 to 2.6 at a wavelength of 550 nm, preferably has a film hardness of 20 GPa or less.
- a base layer containing Si is preferably provided, and the thickness is preferably 1 ⁇ m or more.
- a piston ring coated with a DLC film which has a sufficient effect on abrasive wear, has excellent wear resistance, and has low aggressiveness on a cylinder bore sliding surface.
- A A schematic cross-sectional view of a piston ring in which a DLC film having a base layer is formed on a piston ring base material is shown.
- B A schematic cross-sectional view of a piston ring in which a DLC coating having a base layer is formed on a piston ring base having a base layer.
- a cross-sectional SEM image of the DLC film produced in Example 3 is shown (a photograph as a substitute for a drawing).
- B The schematic diagram for demonstrating the macro particle part of (A) is shown. 7 shows another cross-sectional SEM image of the DLC film produced in Example 3 (a photograph as a substitute for a drawing).
- 5 shows a cross-sectional SEM image of the DLC film produced in Comparative Example 1 (a photograph as a substitute for a drawing). 7 shows a cross-sectional SEM image of the DLC film produced in Comparative Example 2 (a photograph as a substitute for a drawing).
- a surface SEM image of the DLC film produced in Example 3 is shown (a photograph as a substitute for a drawing).
- B A surface SEM image of the DLC film produced in Comparative Example 1 is shown (a photograph as a substitute for a drawing).
- 5 shows a roughness curve of the surface of a DLC film produced in Example 3 (a photograph as a substitute for a drawing).
- a piston ring 10 according to the present embodiment shown in FIG. 1A is mounted in a piston ring groove (not shown) formed in a piston, and slides on an inner peripheral surface of a cylinder bore (not shown) by reciprocating motion of the piston. While reciprocating.
- the piston ring 10 according to the present embodiment may be used as any of a top ring, a second ring, and an oil ring.
- a two-piece oil ring body including an oil ring main body and a coil expander, and a three-piece structure including two segments (also referred to as side rails), an expander and a spacer. It can be applied to any of the oil ring segments.
- the piston ring 10 according to the present embodiment is mounted on an aluminum alloy piston and is preferably used as a piston ring for a cast iron cylinder bore.
- the material of the piston ring base material 11 is not particularly limited as long as it is a material conventionally used as a piston ring base material.
- stainless steel materials, steel materials and the like are preferably used, and specifically, martensitic stainless steel, silicon chrome steel and the like are suitably used.
- the piston ring 10 shown in FIG. 1A includes an underlayer 13 containing Cr, Ti, or Si on the smoothed outer peripheral surface of a piston ring base material 11, and a DLC film 12 thereon.
- the underlayer 13 By providing the underlayer 13, the adhesion between the DLC film 12 and the piston ring base material 11 can be improved. It is preferable that the thickness of the underlayer 13 is 0.2 ⁇ m or more and 1.0 ⁇ m or less. With such a film thickness, the adhesion between the DLC film 12 and the piston ring substrate 11 can be further improved. Note that the DLC film 12 may be formed directly on the smoothed outer peripheral surface of the piston ring substrate 11 without providing the underlayer 13.
- the method of smoothing the outer peripheral surface of the piston ring base material 11 before forming the DLC film 12 is not particularly limited, but it is preferable to adjust the surface roughness by performing a grinding process or a buff polishing process.
- the surface roughness of the piston ring base material 11 is preferably adjusted to a maximum height Rz of 0.5 ⁇ m or less according to JIS B0601 (2001).
- the piston ring 20 of FIG. 1B includes a base material layer 24 between a base layer 23 and a piston ring base material 21.
- the base layer 24 may be selected from a PVD coating, a Cr plating coating, and a nitrided layer.
- the thickness of the base layer 24 is not particularly limited, but is preferably 0.2 ⁇ m or more and 1.0 ⁇ m or less.
- the DLC film 12 used in the present embodiment is measured by a TEM-EELS / TEM 2 which is a combination of a Transmission Electron Microscope (TEM) and an Electron Energy Loss Spectroscopy (EELS) in combination with a TEM (Transmission Electron Microscope).
- TEM Transmission Electron Microscope
- EELS Electron Energy Loss Spectroscopy
- the (sp 2 + sp 3 ) structure ratio (hereinafter, also simply referred to as the sp 2 component ratio) may be 0.5 or more and 0.85 or less, and is preferably 0.5 or more and 0.8 or less.
- the sp 2 component ratio When the sp 2 component ratio is less than 0.5 (50%), the hardness of the coating film is high, and when a foreign substance such as abrasion powder or dust generated by depositing or sliding passes through the sliding surface, the DLC coating film becomes abrasive due to abrasive wear. The abrasion resistance is reduced and the internal stress is increased, so that it is easy to induce delamination inside the DLC film.
- the sp 2 component ratio exceeds 0.85 (85%)
- the sp 2 component ratio may be 0.55 or more, may be 0.60 or more, may be 0.65 or more, and may be 0.70 or more.
- the component ratio of sp 2 (sp 2 / (sp 2 + sp 3)) if is greater becomes the property similar to graphite, the component ratio of sp 3 (sp 3 / (sp 2 + sp 3)) is If it is large, it has physical properties similar to diamond. Therefore, by adjusting the component ratio, DLC films having various characteristics can be produced.
- the procedure for measuring the sp 2 component ratio by TEM-EELS is as follows. (1) An EELS spectrum is measured by an EELS analyzer. The measured EELS spectrum is fitted with a linear function before the peak and a cubic function after the peak to normalize the peak intensity. (2) Then, the data of the diamond and the data of graphite are illuminated, and the start positions of the peaks are aligned to correct the energy value. (3) With respect to the corrected data of (2), the total area within the range of 280 eV to 310 eV is obtained.
- the measured values are the average value of the three measured values extracted from the coating cross section at each of the three positions forming 90 ° on the opposite side of the piston ring in the circumferential direction of one piston ring. I do.
- the DLC film 12 used in the present embodiment preferably has a hardness measured by a nanoindentation method of 12 GPa or more and 26 GPa or less. If the hardness of the coating is less than 12 GPa, the hardness of the coating is low and the abrasion resistance of the DLC coating becomes insufficient, which is not preferable. If it exceeds 26 GPa, the wear of the DLC coating proceeds undesirably due to the abrasive wear sliding environment when used under engine lubricating oil after long-distance use. In an environment where abrasive wear can occur, the wear of itself and the wear of the mating material increase in proportion to the hardness of the DLC coating.
- the DLC film 12 preferably has a Vickers hardness of 1000 HV or more and 2000 HV or less, and may be 1700 HV or less and 1500 HV or less.
- the hardness of the coating is high.
- the thickness is not excessively hard because the coating formed on the surface causes the coating to be broken when the piston is deformed at the time of assembling the piston.
- the Vickers hardness was measured using a nano indentation measuring instrument manufactured by Fischer Instruments, Model HM-2000, and using a Vickers indenter, with a pressing load of 500 mN and a time until the maximum pressing load of 30 s (second). The hardness was measured. The measured value is an average value of three measured values extracted from the coating surface at the position on the opposite side of the abutment of the piston ring and three positions forming 90 ° on both sides in the circumferential direction of one piston ring. .
- the hardness measurement by the nano-indentation method uses a nano-indentation measuring instrument manufactured by Fischer Instruments, model HM-2000, and uses a Vickers indenter to apply a pressing load of 500 mN and a time for a maximum pressing load of 30 s (second). ), The indentation hardness was measured.
- the measured value is an average value of three measured values extracted from the coating surface at the position on the opposite side of the abutment of the piston ring and three positions forming 90 ° on both sides in the circumferential direction of one piston ring. .
- the surface hardness of the DLC film is high.
- the hardness of the coating surface is more preferably 12 GPa or more and 22 GPa or less, further preferably 12 GPa or more and 20 GPa or less, and particularly preferably 12 GPa or more and 18 GPa or less.
- the DLC film 12 used in the present embodiment preferably has a Young's modulus measured by a nanoindentation method of 250 GPa or less, more preferably 200 GPa or less, and preferably 180 GPa or less. If the Young's modulus exceeds 250 GPa, brittle fracture appears on the outermost surface layer of the DLC coating when foreign matter such as abrasion powder or dust generated by depositing or sliding passes through the surface of the DLC coating, resulting in increased wear.
- the lower limit is not particularly limited, but when the Young's modulus is 120 GPa or more, peeling inside the film is less likely to occur.
- the measurement of Young's modulus by the nanoindentation method uses a nanoindentation measuring instrument manufactured by Fischer Instruments, model HM-2000, and uses a Vickers indenter to apply a pressing load of 500 mN and a time for a maximum pressing load of 30 s (second). ).
- the Young's modulus is obtained from a load-indentation depth curve. Note that the measured value is an average of four measured values similar to the nanoindentation hardness measurement.
- the DLC film 12 used in the present embodiment has a 10,000-fold magnification of a cross section in the thickness direction of the film (a cross section orthogonal to the circumferential direction of the piston ring) photographed by a scanning electron microscope (SEM: Scanning Electron Microscope).
- SEM Scanning Electron Microscope
- the number of macro particles is preferably 2 or less per 10 ⁇ m 2 , more preferably 1.5 or less.
- the number of macro particles is 2 or less per 10 ⁇ m 2 , the occurrence of surface defects can be suppressed and the unevenness of the surface can be suppressed, so that the opponent aggressiveness can be reduced.
- FIG. 2A shows an example of a cross-sectional SEM image of the embodiment (Example 3 to be described later) immediately after the formation of the DLC film
- FIG. 3 shows a diagram schematically illustrating the image of FIG.
- a V-shaped interface FIG. 2 (B)
- FIG. 2 (B) shows a diagram schematically illustrating the image of FIG.
- FIG. 2 (B) shows a V-shaped interface (FIG. 2 (B)), which starts from the macroparticle (arrow a) and expands toward the coating surface (arrow d), is surrounded by a circle in the center of the image.
- This macro particle is formed early after the start of film formation, and indicates that the V-shaped interface starting from the macro particle continues to grow until the film formation is completed.
- the outside of the V-shaped interface in the coating also referred to as the outside of the macroparticle portion
- FIG. 3 shows an example of another cross-sectional SEM image immediately after the formation of the DLC film of the embodiment (Example 3 described later).
- 2 shows a case where a macroparticle portion is formed late in the film formation as compared with FIG. 2, and V surrounded by a macroparticle as a starting point (arrow a) expands toward the coating surface while being surrounded by a circle in the center of the image.
- One U-shaped interface is formed, and a bump protruding outward is formed on the surface of the coating.
- the outside of the V-shaped interface in the coating (also referred to as the outside of the macroparticle site) is a uniform and smooth surface where the coating is normal and no repeated pattern is observed.
- FIG. 4 shows an example of a cross-sectional SEM image immediately after the formation of the DLC film in the conventional mode (Comparative Example 1 described later).
- two V-shaped interfaces that expand toward the coating surface are formed overlapping, and the coating surface is formed with a number of bumps protruding to the outside.
- ing. 4 is different from FIGS. 2 and 3 in that the V-shaped interface starting from the macroparticles is formed so as to overlap in the thickness direction of the coating and in the direction perpendicular to the thickness direction (the sliding direction of the piston ring). That is, the number of macro particles that can be counted from the SEM image of the coating cross section is large. Further, the surface of the coating film in the SEM image of FIG. 4 has the largest unevenness as compared with the SEM images of FIGS. 2, 3, and 5.
- FIG. 5 shows an example of a cross-sectional SEM image of a conventional (Comparative Example 2 described later) immediately after the formation of a DLC film.
- the piston ring substrate side forms a stripe pattern parallel to the coating thickness direction, and two different coating layers are laminated.
- one V-shaped squashed interface slightly extending toward the coating surface from the macroparticles is formed, but does not affect the coating surface.
- the macroparticles form a single relatively large pit on the SEM image.
- macro particles similar to the pit form when exposed on the outermost surface of the film, they appear as pits even when observed from the surface of the film, and form irregularities on the surface.
- macro particles form a plurality of relatively large pits on this SEM image. It is considered that macro particles similar to this pit form appear as a plurality of pits even when observed from the surface of the coating when exposed to the outermost surface of the coating, and greatly affect the aggressiveness to the cylinder bore.
- FIG. 6 shows a cross-sectional SEM image of a cross-sectional SEM image immediately after the formation of the DLC film and a surface SEM image corresponding to FIGS.
- FIG. 6A shows a surface SEM image of the embodiment of FIG. 2 (Example 3 described later) immediately after the formation of the DLC film.
- FIG. 6B shows a surface SEM image of the conventional (comparative example 1 described later) of FIG. 4 immediately after the formation of the DLC film.
- three large bumps dome-shaped white dots on the photograph
- a diameter of 2 ⁇ m to 3 ⁇ m projecting from the surface formed by the macroparticles are observed. it can.
- Patent Document 1 specifies that the density of droplets having a size of 300 ⁇ m 2 or more (macroparticle diameter is 20 ⁇ m or more) on the coating surface is 600 / mm 2 or less. Even when macro particles are present, their diameter is at a level of 5 ⁇ m or less.
- FIG. 7A shows a roughness curve on the surface of the DLC film of FIG. 6A with a measurement magnification of 5000 times and a width of 100 times.
- the height of the peak corresponding to the aneurysm is at a level of 1.8 ⁇ m and 2.7 ⁇ m.
- FIG. 7B shows a roughness curve on the surface of the DLC film of FIG. 6B with a measurement magnification of 5000 times in length and 100 times in width.
- the peaks corresponding to the bumps form continuous irregularities in a roughness curve, and have a maximum height Rz of 3.8 ⁇ m.
- the surface of the DLC film shown in FIGS. 2, 3 and 5 has a maximum surface roughness Rz of 1.6 ⁇ m or less by a surface smoothing process as a final finish, and the roughness curve has a plateau. It is adjusted to have a shape.
- the surface of the DLC film in FIG. 4 is adjusted to have a maximum surface roughness Rz 2.0 ⁇ m or less and a rough surface with a roughness curve by a surface smoothing process as a final finish. ing.
- the number P of macro particles is defined as the number per 10 ⁇ m 2 , and is an average value of three places of one piston ring. The significance of this definition is that the number P of macro particles can be compared regardless of the thickness of the coating.
- P n / D (pieces / 10 ⁇ m 2 ).
- the cross section of the coating film in the 10,000 times magnification SEM image can be observed at a maximum of 8.5 ⁇ m in the vertical direction and a maximum of 12 ⁇ m in the horizontal direction, with the thickness direction of the coating being vertical.
- the reduction of macroparticles in the cross section observation of the DLC coating also reduces the presence of macroparticles on the coating surface, and reduces the aggressiveness on the cylinder bore sliding surface by reducing the area per pit or the number of pits on the coating surface. Will be reduced.
- the DLC coating of the present embodiment preferably has a refractive index measured by a spectroscopic ellipsometer of 2.3 to 2.6 at a wavelength of 550 nm.
- the refractive index may be 2.35 or more, or may be 2.4 or more.
- a spectroscopic ellipsometer for measuring a refractive index
- a spectroscopic ellipsometer (UVISEL manufactured by Horiba, Ltd.) can be used.
- the measurement condition is an ellipse having an incident angle of 70 degrees, a spot diameter of 1 mm and a major axis of 3 mm.
- the measured value is an average value of three measured values extracted from the coating surface at the position on the opposite side of the abutment of the piston ring and three positions forming 90 ° on both sides in the circumferential direction of one piston ring. .
- the DLC film preferably has a thickness of 1 ⁇ m or more, excluding the underlayer.
- the film thickness is at least 1 ⁇ m, preferably 30 ⁇ m or less, and more preferably 20 ⁇ m or less.
- the DLC film is a film mainly composed of amorphous carbon, but may contain hydrogen or may contain other unavoidable impurities.
- the hydrogen contained in the DLC coating is typically at most 5 at%, at most 3 at%, at most 2 at%, at most 1 at%, or at most 0.5 at%. .
- the method for manufacturing the DLC film according to the present embodiment is not particularly limited.
- a method of forming a coating film by using a filtered cathode vacuum (FCVA) method In the FCVA method, a DLC film may be formed with a single structure, and a DLC film is formed by changing a pulse bias voltage to be applied or by forming a film a plurality of times without changing a pulse bias voltage. Is also good.
- the applied pulse bias voltage is preferably higher than usual, for example, -1500 V to -3000 V, and more preferably -2000 V to -3000 V.
- Example 1 With the piston ring base set in the apparatus, the inside of the apparatus was evacuated to reduce the pressure, and then the base was heated. Thereafter, ion bombardment was performed with argon ions while a pulse bias voltage was applied to the substrate in the range of -500 to -1500 V. Next, using a sputtering method in an argon gas atmosphere, a bias voltage is set to a range of ⁇ 50 V to ⁇ 300 V with respect to the piston ring substrate, and then a Ti film is formed on the piston ring substrate as a base layer (adhesive layer). A film was formed.
- a first amorphous carbon layer and a second amorphous carbon layer were alternately formed and laminated on the Ti film.
- the first amorphous carbon layer is formed by sputtering using a carbon target under an argon gas atmosphere with a bias voltage applied to the piston ring substrate within a range of ⁇ 50 V to ⁇ 300 V.
- the second amorphous carbon layer is discharged at an arc current of 50 to 200 A using a carbon target in a state where a pulse bias voltage is applied to the piston ring substrate within a range of -500 V to -1500 V.
- the first amorphous carbon layer and the second amorphous carbon layer were formed without using a process gas containing hydrogen.
- the thickness of the first amorphous carbon layer was 2 nm, and the thickness of the second amorphous carbon layer was 398 nm.
- the first amorphous carbon layer of one layer and the second amorphous carbon layer of one layer were made into one set and two layers, and 38 sets were repeatedly laminated in units of one set and two layers. A 15 ⁇ m thick DLC coating was obtained.
- Example 2 A first amorphous carbon layer and a second amorphous carbon layer were repeatedly laminated in 25 sets, and after a surface smoothing process of a final finish, a DLC film having a thickness of 10 ⁇ m was obtained in the same manner as in Example 1, A DLC coating was obtained.
- Example 3 In the same manner as in Example 1, a Ti coating was formed as a base layer on the piston ring base material. Next, an amorphous carbon layer was formed on the Ti film. The amorphous carbon layer was formed by discharging with an arc current of 50 to 200 A using a carbon target while a pulse bias voltage was applied to the piston ring substrate within a range of -2000 V to -3000 V. The amorphous carbon layer was formed without using a process gas containing hydrogen. The thickness of one amorphous carbon layer was set to 400 nm, and 13 layers were repeatedly laminated to obtain a DLC film having a thickness of 5 ⁇ m after surface smoothing for final finishing.
- Example 4 The thickness of one amorphous carbon layer was 400 nm, and a 25-layer DLC coating was obtained in the same manner as in Example 3 except that a DLC coating having a thickness of 10 ⁇ m was obtained after a surface smoothing process of the final finish by repeatedly stacking 25 layers. Got.
- an amorphous carbon layer was formed on the Cr film.
- the amorphous carbon layer is discharged at an arc current of 50A to 100A using a carbon target in a state where a bias voltage is applied within a range of 0V to -100V with respect to the piston ring base material, and is formed into a final finish. After the surface smoothing, a DLC coating having an amorphous carbon layer thickness of 5 ⁇ m was obtained.
- an arc discharge was performed at a bias voltage of -1000 V and an arc current of 40 A for 90 seconds to form an adhesion layer made of white hard carbon, and then an arc discharge was performed again at a bias voltage of -170 V and an arc current of 40 A to perform 245 arc discharge.
- the heating and cooling were repeated eight times to form a black hard layer and a white hard layer having a total film thickness of 0.5 ⁇ m eight times.
- a DLC film having a thickness of 5 ⁇ m was formed.
- Example 3 In the same manner as in Example 1, a Ti coating was formed as a base layer on the piston ring base material. Next, an amorphous carbon layer was formed on the Ti film. The amorphous carbon layer was formed by discharging with an arc current of 50 to 200 A using a carbon target while applying a pulse bias voltage to the piston ring base material within a range of -3000 V to -3500 V. The amorphous carbon layer was formed without using a process gas containing hydrogen. The thickness of one amorphous carbon layer was 400 nm, and 38 layers were repeatedly laminated to obtain a DLC film having a thickness of 15 ⁇ m after the surface smoothing processing of the final finish.
- Example 4 In the same manner as in Example 1, a Ti coating was formed as a base layer on the piston ring base material. Next, a first amorphous carbon layer and a second amorphous carbon layer were alternately formed and laminated on the Ti film.
- the first amorphous carbon layer is formed by sputtering using a carbon target under an argon gas atmosphere with a bias voltage applied to the piston ring substrate within a range of ⁇ 50 V to ⁇ 300 V. Filmed.
- the second amorphous carbon layer is discharged at an arc current of 50 to 200 A using a carbon target in a state where a pulse bias voltage is applied to the piston ring substrate within a range of -100 V to -500 V. Filmed.
- the first amorphous carbon layer and the second amorphous carbon layer were formed without using a process gas containing hydrogen.
- the thickness of the first amorphous carbon layer was 2 nm
- the thickness of the second amorphous carbon layer was 398 nm.
- the first amorphous carbon layer of one layer and the second amorphous carbon layer of one layer are made into one set and two layers, and 13 sets are repeatedly laminated in units of one set and two layers. A 5 ⁇ m thick DLC coating was obtained.
- FIG. 9 shows the outline of the pin-on-plate reciprocating friction wear test.
- a martensitic stainless steel was used as a piston ring base material having a nominal diameter of 86 mm and a width in the sliding direction of 1.2 mm, and the DLC film of each of the above Examples and Comparative Examples was formed on the outer peripheral surface thereof.
- a piston ring having a working surface prepared was prepared.
- a piston ring member having a circumference of 20 mm was cut out from three positions, each of which was 90 ° on both sides and a position on the opposite side of the mating side of the piston ring, and tested.
- the piston ring member thus cut out was subjected to final finishing.
- the surface roughness of the piston ring member after final finishing was such that the roughness curve had a plateau shape, the maximum height Rz was 1.0 ⁇ m, and the upper test piece 100 was used.
- the lower test piece 110 is a material equivalent to JIS FC250.
- a plate having a width of 17 mm, a length of 70 mm, and a thickness of 14 mm is prepared, which simulates a flaky graphite cast iron cylinder bore having a hardness of HRB100 and a carbide precipitation of 3%.
- the surface was finished with # 600 emery paper and the surface roughness was 1.2 ⁇ m at maximum height Rz.
- test conditions of the wear amount measurement test are shown below.
- a used engine lubricating oil 0W-20 after 400 hours of operation of the actual engine was supplied to the sliding surface between the upper test piece 100 and the lower test piece 110 in an amount of 150 ⁇ l (microliter) for one hour.
- ⁇ Test conditions> ⁇ Stroke: 50mm ⁇ Load: 50N ⁇ Speed: 300 cycle / min ⁇ Temperature of lower specimen: 80 ° C (using lower specimen heater 122) ⁇ Test time: 60min
- the respective wear amount ratios are calculated for other examples and comparative examples, with the DLC film wear amount of Comparative Example 1 being 50, the mating material wear amount being 50, and the total wear amount being 100.
- DLC film wear amount ratio is 40 or less
- mating material wear amount ratio is 40 or less:
- S DLC film wear amount ratio is 50 or less
- mating material wear amount ratio is 40 or less:
- a DLC film wear amount ratio is 50 or less, and mating material wear amount ratio exceeds 40:
- the friction coefficient was 0.085 to 0.092 in the example and 0.091 to 0.105 in the comparative example.
- the friction coefficient was about 0.06 in both the examples and comparative examples.
- the friction and wear test described above was performed assuming an environment after long-term operation, abrasive friction occurred due to the deposit generated inside the engine contained in the used engine lubricant, and the friction coefficient was high. It is thought that it became.
- an adhesion test was performed to evaluate the peeling of the DLC film.
- the test method is as follows: using a cone-shaped diamond indenter used for Rockwell hardness C scale measurement in accordance with JIS B2245: 2016, pushing the DLC coating surface with a load of 150 kgf (1471 N), removing the load, and coating the area around the indentation. The presence or absence of peeling was confirmed. The test was performed three times each.
- FIG. 10 shows a laser micrograph showing whether or not the DLC film was peeled off in the above-mentioned adhesion test (a photograph as a substitute for a drawing).
- FIG. 10A is a laser microscope photograph of the surface of the coating film at a magnification of 200 times, and a circular black portion indicates an indentation due to an indenter.
- FIG. 10 (B) is a laser microscope photograph of the coating surface in which a portion surrounded by a square in FIG. 10 (A) is enlarged at a magnification of 1000, and a gray portion on the right side of the photograph indicates an indentation caused by an indenter.
- the laser microscope used was VK-X150 manufactured by Keyence. As a result of the adhesion test, no peeling occurred in any of the examples and comparative examples.
- the DLC film in which a large number of macroparticles exist in a stripe pattern in the cross section of the film many bumps were formed on the surface of the film immediately after the film formation, and the height of the bumps exceeded 3 ⁇ m. Therefore, after the surface smoothing process, it tends to be difficult to obtain a plateau-like smooth roughness curve without peaks as shown in FIG. 7B.
- the DLC film containing a large number of macroparticles has many pits (corresponding to valleys in the roughness curve of FIG. 8B) formed on the surface of the film after the surface smoothing process. , And his own wear progressed.
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Abstract
Description
自動車は走行に伴い、そのエンジンの内部にデポジットと呼ばれる堆積物が生成する。デポジットは、通常、燃料やエンジン潤滑油の不完全燃焼生成物等の堆積物である。近年の省燃費性向上のために、ガソリンエンジンにおいても、排気ガスを燃焼室内に再循環するEGR(Exhaust Gas Recirculation system)の導入や、直噴化により、エンジン潤滑油中に溶け込むデポジットの量が増加する傾向にある。
また、燃焼ガス中には、未燃の燃料に由来する炭化水素の他、酸化物や炭化物などが共存し、これらの物質からもデポジットが生成され、エンジン潤滑油中に滞留することになる。
本発明は、エンジン潤滑油下で使用され、外周摺動面にDLC被膜を有するピストンリングであって、前記DLC被膜は、透過型電子顕微鏡(TEM)に電子エネルギー損失分光法(EELS)を組み合わせたTEM-EELSで測定されるsp2成分比が0.5以上0.85以下であり、ナノインデンテーション法により測定される被膜の硬さが12GPa以上26GPa以下であり、且つヤング率が250GPa以下である、ピストンリング、である。
本実施形態に係るピストンリング10は、トップリング、セカンドリング、オイルリングの何れのピストンリングとして用いてもよい。なお、オイルリングに適用する場合は、オイルリング本体とコイルエキスパンダからなる2ピース構成オイルリングのオイルリング本体、及び2本のセグメント(サイドレールともいう)とエキスパンダ・スペーサからなる3ピース構成オイルリングのセグメント、のいずれにも適用することができる。
なお、本実施形態に係るピストンリング10は、アルミニウム合金製ピストンに装着され、鋳鉄製シリンダボアに対するピストンリングとして好ましく用いられる。
下地層13の膜厚は0.2μm以上1.0μm以下であることが好ましい。このような膜厚とすることで、DLC被膜12とピストンリング基材11との密着性をより向上させることができる。尚、下地層13を備えることなく、ピストンリング基材11の平滑化加工された外周面に直接DLC被膜12を成膜してもよい。
DLC被膜12の成膜前におけるピストンリング基材11の外周面の平滑化加工の方法は特に限定されないが、研削加工またはバフ研磨加工を施し、表面粗さを調整することが好ましい。ピストンリング基材11の表面粗さは、JIS B0601(2001)における最大高さRzで0.5μm以下に調整することが好ましい。
一般的にDLC被膜は、sp2の成分比(sp2/(sp2+sp3))が大きければグラファイトに似た物性となり、sp3の成分比(sp3/(sp2+sp3))が大きければダイヤモンドに似た物性となるので、その成分比を調整することにより、様々な特性をもつDLC被膜を作製することができる。
sp2成分比の測定は、TEM(日本電子製 電解放出形透過電子顕微鏡 JEM-2100F)と、EELS(Gatan製Model 863GIF Tridiem)を使用した。
(1)EELS分析装置によってEELSスペクトルを測定する。測定されたEELSスペクトルに対し、ピーク前を一次関数でフィットさせ、ピーク後を三次関数でフィットさせ、ピーク強度を規格化する。
(2)その後、ダイヤモンドのデータとグラファイトのデータを照らし合わせ、ピークの開始位置を揃えてエネルギー値の補正を行う。
(3)(2)の補正済みのデータに対し、280eV~310eVの範囲内の全面積を求める。
(4)sp2ピーク成分を分離するため、280-295eVの範囲で2ピーク(sp2のπ*ピークと、CHやアモルファスを含むσ*ピーク)が存在するとみなし、ピーク分離を行う。このうち285eV付近のピーク面積を求める(sp2ピーク面積)。
(5)上記(3)の面積に対する上記(4)の面積比を取る(sp2ピーク面積比)。この面積比について、グラファイトを100、ダイヤモンドを0とし、相対値からsp2の割合を求める。これをsp2成分比とする。
ビッカース硬さの測定は、フィッシャー・インストルメンツ製ナノインデンテーション測定器、型式HM-2000を使用し、ビッカース圧子を用いて、押し込み荷重500mN、最大押し込み荷重までの時間を30s(秒)として、押し込み硬さを測定した。
測定値は、一つのピストンリングの周方向において、ピストンリングの合い口反対側の位置と、両側90°を成す3箇所の各位置の被膜表面から抽出された3つの測定値の平均値とする。
ナノインデンテーション法での硬さ測定は、フィッシャー・インストルメンツ製ナノインデンテーション測定器、型式HM-2000を使用し、ビッカース圧子を用いて、押し込み荷重500mN、最大押し込み荷重までの時間を30s(秒)として、押し込み硬さを測定した。
測定値は、一つのピストンリングの周方向において、ピストンリングの合い口反対側の位置と、両側90°を成す3箇所の各位置の被膜表面から抽出された3つの測定値の平均値とする。
ナノインデンテーション法でのヤング率測定は、フィッシャー・インストルメンツ製ナノインデンテーション測定器、型式HM-2000を使用し、ビッカース圧子を用いて、押し込み荷重500mN、最大押し込み荷重までの時間を30s(秒)の条件で行った。ヤング率は、荷重-押込み深さ曲線から求められる。なお、測定値は、ナノインデンテーション硬さ測定と同様の4つの測定値の平均値とする。
図2(A)は、実施形態(後述の実施例3)のDLC被膜成膜直後の断面SEM画像の一例を示し、図2(B)はマクロパーティクル部位を説明するための、図2(A)の画像を模式的に表した図を示す。
図2(A)中、画像中央の円で囲まれた中に、マクロパーティクルを起点(矢印a)として、被膜表面(矢印d)に向かい拡開するV字状の界面(図2(B)中の矢印bで表す)が一つ形成され、被膜表面(矢印d)には外部に突出する瘤(矢印c)が形成されている。このマクロパーティクルは成膜開始後の初期に形成され、成膜が終了するまでマクロパーティクルを起点としたV字状の界面が成長を続けることを示している。被膜中のV字状の界面の外側(マクロパーティクル部位の外側ともいう)は、被膜の正常部位であり、繰り返される模様が観察されない均質で平滑な面である。
図5中fで示す円では、マクロパーティクルがこのSEM画像上では比較的大きい単一のピットを形成している。このピットの形態に類するマクロパーティクルは、被膜の最表面に露出した場合には、被膜表面から観察してもピットとして出現し、表面の凹凸を形成することになると考えられる。
図5中gで示す円では、マクロパーティクルがこのSEM画像上では比較的大きいピットを複数形成している。このピットの形態に類するマクロパーティクルは、被膜の最表面に露出した場合には、被膜表面から観察しても複数のピットとして出現し、シリンダボアへの攻撃性に大きく作用すると考察される。
図6(A)の表面SEM画像の円で囲まれた中に、マクロパーティクルにより形成された表面に突出する直径2μmから3μmの大きめの瘤(写真上のドーム状の白い点)が3つ観察できる。この観察によれば、被膜断面のV字状界面は、被膜層内では円錐状に形成されていると言うことができる。特許文献1では、被膜表面で300μm2以上(マクロパーティクルの直径が20μm以上)の大きさのドロップレットの密度が600個/mm2以下であることを規定しているが、本実施形態では、マクロパーティクルが存在した場合でも、その直径は5μm以下の水準にある。
図6(B)の表面SEM画像には、全域にマクロパーティクルにより形成された瘤が連続していることが観察できる。図7(B)に図6(B)のDLC被膜表面における、測定倍率を縦5000倍、横100倍とした粗さ曲線を示す。瘤に相当する山は粗さ曲線で連続した凹凸を形成し、最大高さRzとして3.8μmの水準にある。
図8(B)に示すように、図4のDLC被膜表面は、最終仕上げとして表面平滑化加工により表面粗さを最大高さRz2.0μm以下で、粗さ曲線の表面が粗い状態に調整されている。
本実施形態のDLC被膜は、DLC被膜断面に存在するマクロパーティクルの数が低減されており、よって図7(B)のようなより平滑な摺動面形成が可能となり、シリンダボア材への攻撃性を低くすることができる。
マクロパーティクルの数の測定方法について説明する。マクロパーティクルの数の測定はSEM(日本電子製 JSM-7001F)を使用した。一つのピストンリングの周方向において、ピストンリングの合い口反対側の位置と、両側90°を成す3箇所を切断し、各切断位置から抽出された一つのピストンリングの周方向に直交する断面の10,000倍の断面SEM画像から、被膜の厚さ方向に直交する方向に10μmの幅で挟まれ、被膜の厚さ方向に被膜表面から被膜の厚さDμmまでの囲まれた領域において存在するマクロパーティクル数n個をカウントする。すると被膜断面1カ所における単位面積あたりのマクロパーティクル数N(個/μm2)は、N=n/(10D)となる。マクロパーティクル数Pは、10μm2当たりの数と定義し、一つのピストンリングの3箇所の平均値とする。この定義の意義は、被膜の厚さに係わらず、マクロパーティクル数Pを比較できることである。ここで、P=n/D(個/10μm2)である。
本実施形態では、10,000倍の断面SEM画像においてP=2(個/10μm2)以下が好ましく、P=1.5(個/10μm2)以下がより好ましい。
屈折率を測定する分光エリプソメータとしては、分光エリプソメータ(株式会社堀場製作所製 UVISEL)を用いることができる。
測定条件は、入射角度が70度、スポット径が短径1mmで長径3mmの楕円とする。
測定値は、一つのピストンリングの周方向において、ピストンリングの合い口反対側の位置と、両側90°を成す3箇所の各位置の被膜表面から抽出された3つの測定値の平均値とする。
本実施形態では自身の耐摩耗性が向上することから、膜厚が少なくとも1μmで適用可能であり、30μm以下であることが好まく、20μm以下であることがより好ましい。
ピストンリング基材を装置内にセットした状態で、装置内を真空排気して減圧した後、基材を加熱した。その後に基材に対してパルスバイアス電圧を-500~-1500Vの範囲で印加した状態で、アルゴンイオンによりイオンボンバードを行った。
次にアルゴンガス雰囲気下でスパッタリング方式を用い、ピストンリング基材に対してバイアス電圧を-50V~-300Vの範囲に設定した後、下地層(接着層)としてTi被膜をピストンリング基材上に成膜した。
なお、第一のアモルファスカーボン層及び第二のアモルファスカーボン層の成膜に際しては、水素を含むプロセスガスを使用せずに実施した。また、第一のアモルファスカーボン層の厚みは2nmとし、第二のアモルファスカーボン層の厚みは398nmとした。そして1層の第一のアモルファスカーボン層と1層の第二のアモルファスカーボン層とを1組2層とし、この1組2層単位で繰り返し38組積層し、最終仕上げの表面平滑化加工後、厚さ15μmのDLC被膜を得た。
第一のアモルファスカーボン層及び第二のアモルファスカーボン層を、繰り返し25組積層し、最終仕上げの表面平滑化加工後、厚さ10μmのDLC被膜を得た以外は、実施例1と同様にして、DLC被膜を得た。
実施例1と同様に、下地層としてTi被膜をピストンリング基材上に成膜した。
次にTi被膜上にアモルファスカーボン層を成膜した。アモルファスカーボン層はピストンリング基材に対してパルスバイアス電圧を-2000V~-3000Vの範囲内で印加した状態でカーボンターゲットを用いて、アーク電流50~200Aで放電し、成膜した。なお、アモルファスカーボン層の成膜に際しては、水素を含むプロセスガスを使用せずに実施した。また、アモルファスカーボン層1層の厚みは400nmとし、13層繰り返し積層することで、最終仕上げの表面平滑化加工後、厚さ5μmのDLC被膜を得た。
アモルファスカーボン層1層の厚みは400nmとし、25層繰り返し積層することで、最終仕上げの表面平滑化加工後、厚さ10μmのDLC被膜を得た以外は、実施例3と同様にして、DLC被膜を得た。
ピストンリング基材をアークイオンプレーティング装置内にセットした状態で、装置内を真空排気して減圧した後、基材を加熱した。その後に基材に対してバイアス電圧を-500V~-1000Vの範囲で印加した状態で、Crターゲットを用いて、アーク電流50A~100Aで放電し、Crイオンボンバードを行った。
次にアークイオンプレーティングにて、ピストンリング基材に対してバイアス電圧を-10~-100Vの範囲で印加した状態で、Crターゲットを用いて、アーク電流50~100Aで放電し、下地層としてCr被膜をピストンリング基材上に成膜した。
次にCr被膜上にアモルファスカーボン層を成膜した。アモルファスカーボン層はピストンリング基材に対してバイアス電圧を0V~-100Vの範囲内で印加した状態でカーボンターゲットを用いて、アーク電流50A~100Aで放電し、成膜することで、最終仕上げの表面平滑化加工後、アモルファスカーボン層厚みが5μmのDLC被膜を得た。
ピストンリング基材をアークイオンプレーティング装置内にセットした状態で、装置内を真空排気して減圧した後、厚み10μmのCrN層を被覆した。その後、厚み0.2μmのCr中間層を被覆した。245℃までヒータ加熱を行いながら、バイアス電圧-700V、アーク電流40Aで10分間アーク放電を行った後、バイアス電圧-170V、アーク電流40Aでアーク放電を行って合計膜厚0.5μmの黒色(膜密度が高い)のアモルファスカーボン硬質層と白色(膜密度が低い)のアモルファスカーボン硬質層を成膜した後に、一旦125℃まで冷却した。
その後、バイアス電圧を-1000V、アーク電流40Aで90秒間、アーク放電を行って白色の硬質炭素からなる密着層を成膜後、再びバイアス電圧-170V、アーク電流40Aでアーク放電を行って、245℃までヒータ加熱を行い、合計膜厚0.5μmの黒色の硬質層と白色の硬質層を成膜するという昇温と冷却の繰り返しサイクルを8回行い、最終仕上げの表面平滑化加工後、総膜厚5μmのDLC被膜を成膜した。
実施例1と同様に、下地層としてTi被膜をピストンリング基材上に成膜した。
次にTi被膜上にアモルファスカーボン層を成膜した。アモルファスカーボン層はピストンリング基材に対してパルスバイアス電圧を-3000V~-3500Vの範囲内で印加した状態でカーボンターゲットを用いて、アーク電流50~200Aで放電し、成膜した。なお、アモルファスカーボン層の成膜に際しては、水素を含むプロセスガスを使用せずに実施した。また、アモルファスカーボン層1層の厚みは400nmとし、38層繰り返し積層することで、最終仕上げの表面平滑化加工後、厚さ15μmのDLC被膜を得た。
実施例1と同様に、下地層としてTi被膜をピストンリング基材上に成膜した。
次にTi被膜上に第一のアモルファスカーボン層と、第二のアモルファスカーボン層とを交互に成膜して積層した。ここで第一のアモルファスカーボン層はスパッタリング方式を用い、ピストンリング基材に対してバイアス電圧を-50V~-300Vの範囲内で印加した状態で、カーボンターゲットを用いてアルゴンガス雰囲気下にて成膜した。また、第二のアモルファスカーボン層は、ピストンリング基材に対してパルスバイアス電圧を-100V~-500Vの範囲内で印加した状態でカーボンターゲットを用いて、アーク電流50~200Aで放電し、成膜した。
なお、第一のアモルファスカーボン層及び第二のアモルファスカーボン層の成膜に際しては、水素を含むプロセスガスを使用せずに実施した。また、第一のアモルファスカーボン層の厚みは2nmとし、第二のアモルファスカーボン層の厚みは398nmとした。そして1層の第一のアモルファスカーボン層と1層の第二のアモルファスカーボン層とを1組2層とし、この1組2層単位で繰り返し13組積層し、最終仕上げの表面平滑化加工後、厚さ5μmのDLC被膜を得た。
図9に、ピンオンプレート式往復動摩擦摩耗試験の概要を示す。まず、マルテンサイト系ステンレス鋼を呼び径86mm、摺動方向の幅が1.2mmのピストンリング基材とし、その外周面に上記各実施例、各比較例のDLC被膜を成膜し、外周摺動面を加工したピストンリングを準備した。該ピストンリングの合い口反対側の位置と、両側90°を成す3箇所の各位置の3箇所から、周長20mmのピストンリング部材を切り出し、供試した。切り出したピストンリング部材は最終仕上げを行い、最終仕上げ後のピストンリング部材の表面粗さは、粗さ曲線がプラトー形状であり、最大高さRz1.0μmとし、上試験片100とした。
下試験片110は、JIS FC250相当材であり、硬さがHRB100、炭化物析出が3%の片状黒鉛鋳鉄製シリンダボアを見立てた幅17mm、長さ70mm、厚さ14mmのプレートを作製し、最終表面仕上げを#600エメリーペーパーにより行って、表面粗さは最大高さRzで1.2μmであった。
<試験条件>
・ストローク:50mm
・荷重:50N
・速度:300cycle/min
・下試験片の温度:80℃(下試験片加熱用ヒータ122使用)
・試験時間:60min
<摩耗量の評価>
DLC被膜摩耗量比が40以下で、かつ、相手材摩耗量比が40以下:S
DLC被膜摩耗量比が50以下で、かつ、相手材摩耗量比が40以下:A
DLC被膜摩耗量比が50以下で、かつ、相手材摩耗量比が40超える:B
DLC被膜摩耗量比が50を超え、かつ、相手材摩耗量比が40以下:C
DLC被膜摩耗量比が50を超え、かつ、相手材摩耗量比が40超える:D
試験方法は、JIS B2245:2016に準拠するロックウエル硬さCスケール測定に用いられる円すい形ダイヤモンド圧子を用いて、荷重150kgf(1471N)でDLC被膜表面に押し込み、荷重を除荷後、圧痕周りの被膜の剥離発生の有無を確認した。試験は各3回実施した。
マクロパーティクルが多く存在するDLC被膜は、表面平滑化加工後において被膜表面にピット(図8(B)の粗さ曲線における谷に相当)を多く形成することから、相手材摩耗量が多くなると同時に、自身の摩耗も進行した。
11、21 ピストンリング基材
12、22 DLC被膜
13、23 下地層
24 基材層
100 上試験片
110 下試験片
120 可動ブロック
122 下試験片加熱用ヒータ
Claims (7)
- エンジン潤滑油下で使用され、外周摺動面にDLC被膜を有するピストンリングであって、前記DLC被膜は、透過型電子顕微鏡(TEM) に電子エネルギー損失分光法(EELS)を組み合わせたTEM-EELSで測定されるsp2成分比が0.5以上0.85以下であり、ナノインデンテーション法により測定される被膜の硬さが12GPa以上26GPa以下であり、且つヤング率が250GPa以下である、ピストンリング。
- 前記DLC被膜のヤング率が200GPa以下である、請求項1に記載のピストンリング。
- 前記DLC被膜は、その厚さ方向の断面を、走査型電子顕微鏡(SEM)で撮影した10,000倍の画像から観察されるマクロパーティクルの数が、10μm2当たり2個以下である請求項1または2に記載のピストンリング。
- 前記DLC被膜は、分光エリプソメータにより測定された屈折率が、波長550nmにおいて2.3以上2.6以下である、請求項1から3のいずれか1項に記載のピストンリング。
- 前記DLC被膜は、被膜の硬さが20GPa以下である、請求項1から4のいずれか1項に記載のピストンリング。
- 前記DLC被膜は、Ti、Cr又はSiを含む下地層を備える、請求項1から5のいずれか1項に記載のピストンリング。
- 前記DLC被膜は、膜厚が1μm 以上である、請求項1から6のいずれか1項に記載のピストンリング。
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- 2019-06-13 KR KR1020217001883A patent/KR102498972B1/ko active IP Right Grant
- 2019-06-13 WO PCT/JP2019/023500 patent/WO2020004061A1/ja active Application Filing
- 2019-06-13 MX MX2020013741A patent/MX2020013741A/es unknown
- 2019-06-13 BR BR112020025012-0A patent/BR112020025012B1/pt active IP Right Grant
- 2019-06-13 US US17/254,546 patent/US11242929B2/en active Active
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Also Published As
Publication number | Publication date |
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EP3816486A4 (en) | 2022-03-02 |
EP3816486A1 (en) | 2021-05-05 |
CN112469930B (zh) | 2023-09-01 |
KR102498972B1 (ko) | 2023-02-16 |
MX2020013741A (es) | 2021-03-29 |
CN112469930A (zh) | 2021-03-09 |
US20210270370A1 (en) | 2021-09-02 |
BR112020025012B1 (pt) | 2022-02-08 |
KR20210013761A (ko) | 2021-02-05 |
BR112020025012A2 (pt) | 2021-03-23 |
US11242929B2 (en) | 2022-02-08 |
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