WO2016111162A1 - 組合せオイルコントロールリング - Google Patents
組合せオイルコントロールリング Download PDFInfo
- Publication number
- WO2016111162A1 WO2016111162A1 PCT/JP2015/085791 JP2015085791W WO2016111162A1 WO 2016111162 A1 WO2016111162 A1 WO 2016111162A1 JP 2015085791 W JP2015085791 W JP 2015085791W WO 2016111162 A1 WO2016111162 A1 WO 2016111162A1
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- WIPO (PCT)
- Prior art keywords
- control ring
- oil control
- plating film
- combined oil
- spacer expander
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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
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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
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
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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
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
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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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/02—Pretreatment of the material to be coated
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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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/24—Nitriding
- C23C8/26—Nitriding of ferrous surfaces
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
- C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
- C25D5/611—Smooth layers
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/615—Microstructure of the layers, e.g. mixed structure
- C25D5/617—Crystalline layers
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
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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
- F16J9/06—Piston-rings, e.g. non-metallic piston-rings, seats therefor; Ring sealings of similar construction using separate springs or elastic elements expanding the rings; Springs therefor ; Expansion by wedging
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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
- F16J9/06—Piston-rings, e.g. non-metallic piston-rings, seats therefor; Ring sealings of similar construction using separate springs or elastic elements expanding the rings; Springs therefor ; Expansion by wedging
- F16J9/064—Rings with a flat annular side rail
- F16J9/065—Spring expander with massive cross-section
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
- C25D7/0685—Spraying of electrolyte
Definitions
- the present invention relates to a combined oil control ring (hereinafter also referred to as “combined oil ring” or “oil ring”) that is mounted on an engine piston and performs oil control.
- combined oil ring hereinafter also referred to as “combined oil ring” or “oil ring”
- the increase in combustion temperature and the improvement in combustion efficiency due to direct injection are due to the problem of oil sludge caused by engine lubricating oil sticking or sticking to side rails and spacer expanders, and the side rails and side rail inner peripheral surfaces. There is also a problem of wearing the ears of the spacer expander in contact.
- the side rail is thinned to reduce the section modulus and the followability coefficient is increased, and for the problem of sticking / adhesion, a method of forming an oil repellent film such as a fluorine-containing film on the surface
- various methods such as a method of performing chrome plating or nitriding treatment have been proposed.
- Patent Document 1 discloses that the specific dimensions of the pressure ring are 1.0 mm or less and the combined oil ring is 2.0 mm or less.
- Patent Document 2 discloses a method of forming a liquid repellent film by a sol-gel method from a metal alkoxide and a fluoroalkyl group-substituted metal alkoxide in which a part of the alkoxyl group is substituted with a fluoroalkyl group. is suggesting.
- Patent Document 3 discloses that a spacer expander is nitrided
- the tension variation increases due to the increase in Young's modulus due to nitriding and the increase in the deployment length (circumferential length) of the spacer expander. Therefore, it becomes difficult to manufacture with a predetermined tolerance width. For example, if a nitride layer having a thickness of 30 ⁇ m is formed on the entire surface of the spacer expander by gas nitriding, the tension will increase by 18 N compared to the tension before the nitride layer is formed, making it difficult to manage the tension.
- the first step of applying 1-5 ⁇ m of Ni, Cr or Cu film as an anti-nitriding layer on the surface of the wire for manufacturing the spacer expander the wire is formed into an axial waveform by gear forming. Teaches a method of manufacturing a spacer expander comprising a second step, a third step in which a pressing piece (ear portion) is formed by shearing on the inner peripheral portion of the corrugated wire, and a fourth step in which nitriding treatment is applied to the shearing surface.
- Patent Document 6 discloses that a spacer expander is used in a nitriding treatment process due to chipping / peeling of the Ni plating film at the corners of the corrugated shape and exposure of the base material due to the thin plating thickness when forming the spacer expander gear. It teaches that in order to prevent the panda body, in particular, the corrugated corners from being nitrided, surfaces other than the shear surface should be covered with a 1-7 ⁇ m thick Ni plating film having a Ni diffusion layer.
- Patent Document 7 teaches that the Ni plating film suppresses the adhesion of oil sludge in terms of surface free energy and hydrogen bonding force.
- the Ni plating film functions well as an anti-nitriding film or anti-adhesion / glue film, but defects that cause chipping or peeling of the Ni plating film itself are introduced depending on the manufacturing conditions. In some cases, in reality, further studies are required on the preferred structure of the Ni plating film.
- An object of the present invention is to provide a combined oil control ring having low tension, little tension variation, and excellent wear resistance and sludge resistance.
- the inventors of the present invention have found that there is no defect by adjusting the crystal orientation of the plating film, the structure, etc. within a predetermined range. It was conceived that a plating film that does not cause chipping or peeling can be formed.
- the combination oil control ring of the present invention has a pair of annular side rails having a joint and an axial waveform having an ear portion interposed between them and pressing the inner peripheral surface of the side rail on the inner peripheral portion.
- a combined oil control ring comprising a spacer expander having a shape, wherein a nitride layer is formed on the side rail pressing surface of the ear, and a plating film is formed on the entire surface of the spacer expander excluding the portion where the nitride layer is formed.
- the plated coating is characterized in that the Vickers hardness is 300 HV0.01 or less.
- the ratio of the diffraction intensity (I (111) ) of the (111) plane to the diffraction intensity (I (200) ) of the ( 200 ) plane Is preferably 2.0 or less, and the texture coefficient of the (200) plane is preferably 1.1 or more.
- the plating film does not contain columnar crystals having an average diameter of less than 0.2 ⁇ m.
- the film thickness of the plating film is preferably 1 to 7 ⁇ m.
- the surface roughness of the plating film is preferably 0.005 to 0.4 ⁇ m in terms of centerline average roughness (Ra 75 ).
- the plating film is preferably a Ni plating film.
- the nitride layer preferably has a thickness of 30 ⁇ m or more.
- the combined oil control ring of the present invention preferably has a combined tension of 5 to 20 N.
- the combined oil control ring of the present invention has a crystal structure in which the preferential orientation of the (111) plane is suppressed and the ratio of the (200) plane is increased in the plating film coated on the spacer expander hoop material. It is possible to obtain a plating film that hardly causes chipping or peeling. This plating film functions as a reliable anti-nitriding film, and enables the formation of a thick nitride layer on the side rail pressing surface of the spacer expander ear. In addition, if the surface roughness of the plating film is 0.005 to 0.4 ⁇ m in terms of the centerline average roughness (Ra 75 ), it will contribute to the suppression of sticking and sticking by oil sludge, with less tension variation and low tension. A combined oil control ring with excellent wear resistance and sludge resistance can be obtained, which can contribute to lower fuel consumption even in harsh usage environments due to improved combustion efficiency.
- FIG. 1 is a sectional view of the combined oil ring
- FIG. 2 is a perspective view of a part of the spacer expander.
- the combination oil ring (1) is composed of a pair of annular side rails (3, 3) having a joint and a spacer expander (2) that supports the side rails (3, 3).
- the spacer expander (2) The inner peripheral part of the side is provided with an ear part (4) for pressing the inner peripheral surface of the side rail (3, 3), and the outer peripheral part is provided with a shaft for supporting the side rail (3, 3) as required.
- a support portion (5) protruding in the direction is provided.
- the connecting part of the ear part (4) and the support part (5) is called the middle hand part (6).
- a nitride layer is formed on the side rail pressing surface (7) of the ear (4), and the Ni plating film is coated on the entire surface of the spacer expander excluding the portion where the nitride layer is formed.
- the Ni plating film is covered with a band-shaped hoop wire before being formed into a spacer expander.
- a hoop wire coated with a Ni plating film is first formed into an axial waveform to form continuous peaks (10) and valleys (20) as shown in FIG.
- the ear part (4) is formed on the inner peripheral part of the peak part (10) and the valley part (20), and the support part (5) and the middle hand part (6) are formed on the outer peripheral part.
- a shear surface (side rail pressing surface (7)) having no Ni plating film is formed on the middle portion (6) side of the ear portion (4).
- the nitride layer is formed only on this shearing surface.
- the coated Ni plating film should not have defects such as chipping or peeling even after being molded from a hoop wire to a spacer expander. Desired.
- the Ni plating film of the present invention has a Vickers hardness of about 350 to 550 HV0.01 when it is plated. At this level of hardness, the elongation is as small as about 6%, so that the Ni plating film is chipped or peeled off during processing of the spacer expander. Therefore, the hardness of the Ni plating film is reduced to 300 HV0.01 or less by heat treatment.
- the heat treatment is preferably performed at a temperature of 500 to 700 ° C. in a non-oxidizing atmosphere (for example, N 2 atmosphere). Considering productivity, it is more preferable to set the temperature at 550 ° C. or higher for 1 minute or shorter.
- the non-oxidizing atmosphere is preferably 200 ppm or less in terms of oxygen concentration.
- the hardness of the Ni plating film thus heat-treated is more preferably 270 HV0.01 or less, and further preferably 250 HV0.01 or less. As an example, when the hardness is 250 HV0.01 or less, these Ni plating films are said to exhibit elongation of 10% or more.
- the diffraction intensity of the (111) plane to the (200) plane diffraction intensity (I (200)) (I (111))
- the ratio (I (111) / I (200) ) is preferably 2.0 or less. It is more preferable if it is 1.8 or less. More preferably, the diffraction intensity (I (200) ) of the (200) plane is maximized. When the diffraction intensity (I (200) ) of the (200) plane is maximized, the ratio (I (111) / I (200) ) is preferably 0.8 or less.
- the texture coefficient of the (200) plane is preferably 1.1 or more.
- I (hkl) is the X-ray diffraction intensity of the measured (hkl) plane (the maximum of the measured X-ray diffraction intensity is converted to 100)
- I 0 (hkl) is the JCPDS file. It is a standard X-ray diffraction intensity described in No. 04-0850.
- File number 04-0850 contains 8 types of (hkl) plane standard X-rays (111), (200), (220), (311), (222), (400), (331), (420) Although the diffraction intensity is listed, in the present invention, for the sake of simplicity, the diffraction intensity is defined using the X-ray diffraction intensities of only the three types (hkl) planes (111), (200), and (220).
- (hkl) surface texture coefficient I (hkl) / I 0 (hkl) ⁇ [1/3 ⁇ I (111) / I 0 (111) + I (200) / I 0 (200) + I (220) / I 0 (220) )] -1 ...
- I 0 (111) is 100
- I 0 (200) is 42
- I 0 (220) is 21.
- the texture coefficient of the (200) plane is more preferably 1.2 or more, and further preferably 1.3 or more. When the diffraction intensity (I (200) ) of the (200) plane is maximized, it is more preferable that the texture coefficient of the (200) plane is 1.8 or more.
- the Ni plating film of the present invention preferably has no columnar crystals penetrating in the thickness direction of the film, and preferably has no columnar crystals having an average diameter of less than 0.2 ⁇ m.
- the columnar structure means one having an aspect ratio (length / diameter) of 2 or more, and if the aspect ratio is less than 2, it is classified as a granular structure.
- the Ni plating film of the present invention is recrystallized by heat treatment, but at this time, it is preferable to grow to a particle size of an appropriate size with few defects. Therefore, it is preferable to be composed of granular crystals having an average particle diameter of 0.2 to 3 ⁇ m and / or columnar crystals having an average diameter of 0.2 to 3 ⁇ m.
- the average particle size of the granular crystals is more preferably from 0.3 to 2 ⁇ m, even more preferably from 0.5 to 1.5 ⁇ m.
- the average diameter of the columnar crystals is more preferably from 0.3 to 2 ⁇ m, further preferably from 0.5 to 1.5 ⁇ m.
- the average particle diameter and the average diameter can be obtained by extracting granular crystals and columnar crystals and performing image analysis.
- the Ni plating film of the present invention preferably has a thickness of 1 to 7 ⁇ m. 3 to 6.5 ⁇ m is more preferable, and 4 to 6 ⁇ m is more preferable.
- the mirror surface state is preferable, but if the surface portion is a bright Ni plating film, the surface roughness in these ranges can be obtained.
- the surface roughness Ra 75 of the Ni plating film is more preferably 0.005 to 0.25 ⁇ m, and further preferably 0.005 to 0.15 ⁇ m.
- the combined oil ring of the present invention preferably has an axial width (A) of the support portion (5) of 0.07 mm or more. It is more preferably 0.09 mm or more, and further preferably 0.11 mm or more.
- the nitride layer formed on the side rail pressing surface (7) of the spacer expander ear (4) preferably has a thickness of 30 ⁇ m or more from the viewpoint of wear resistance. It is more preferably 35 ⁇ m or more, and further preferably 40 ⁇ m or more. The upper limit is preferably 60 ⁇ m from the viewpoint of productivity.
- the combination oil ring of the present invention has a nitride layer formed only on the side rail pressing surface of the spacer expander, so that the tension variation is small and the tension can be reduced.
- the tension can be 5-20 N.
- the spacer expander is not limited, but austenitic stainless steel made of SUS304 is used as the base material. Since the surface is covered with a passive film, it is preferable to perform electrolytic degreasing by hydrochloric acid-based electropolishing, activation by hydrochloric acid cleaning, and Ni strike plating by a wood bath as pretreatment of Ni plating.
- various plating baths such as Watt bath and sulfamic acid bath can be used.
- dispersion strengthened plating is not preferable, and additives such as a brightening agent are preferably set to the minimum necessary for ensuring a predetermined surface roughness and a uniform film thickness.
- the Ni plating film of the present invention does not require the presence of a diffusion phase between the base material and the Ni plating as long as Ni strike plating is applied as a pretreatment, but the diffusion phase is not necessary in the softening heat treatment for hardness adjustment. Although it is preferable that it is formed, it does not cause inconvenience.
- Heat treatment at 550 ° C. or higher and within 1 minute considering productivity is partial or extremely thin even if a diffusion phase is formed. Even if there is no diffusion phase, a Ni plating film having a structure in which Ni strike plating is applied and the ratio of the (200) plane is increased functions sufficiently as an anti-nitriding film.
- Molding to the spacer expander is made from the hoop wire coated with the Ni plating film through the steps of gear molding, coiling, constant-size cutting, and abutment surface finishing including local bending and shearing. . Since the ear portion is formed by shearing on the inner peripheral side after the first-stage gear formation on the peak portion and the valley portion, there is no Ni plating film on the side rail pressing surface of the ear portion. If the thickness of the Ni plating film is too thick, the Ni plating film may cover a part of the pressing surface, but there is no problem if the thickness is within 10 ⁇ m. Although the tension of the spacer expander can be controlled by adjusting the deployment length, it is important to suppress variations in the exact shape and the deployment length in terms of accuracy.
- the nitriding treatment of the present invention preferably uses gas nitriding using a gas containing NH 3 in order to form a nitrided layer having a thickness of 30 ⁇ m or more.
- salt bath nitriding can be used, it is difficult to form a thick nitrided layer.
- the base material of the spacer expander is SUS304, it is preferable to add ammonium chloride at a predetermined timing in order to reduce the passive film prior to nitriding.
- the nitriding temperature is preferably 470 to 600 ° C., and the nitriding time may be selected according to the desired thickness of the nitrided layer.
- Ni plating Ni plating was performed under the following conditions using a rolled strip-like SUS304 hoop wire rod (0.3R at the end) of 2.50 mm ⁇ 0.25 mm.
- Pretreatment Electrolytic degreasing-Acid activity-Ni strike Ni plating bath: Semi-bright Ni plating bath (Ni solution of sulfamic acid + Ni chloride) + Boric acid + additive A), bright Ni plating bath (sulfamic acid Ni solution + Ni chloride) + Boric acid + additive B) Bath temperature: 50 °C Initial pH: 2.8 Current density: 8 A / dm 2 Time: Semi-bright Ni plating 60 seconds, Bright Ni plating 30 seconds
- Ni plating film-coated hoop wire was subjected to softening heat treatment at 600 ° C. for 30 seconds in a N 2 atmosphere (oxygen concentration 50 ppm) after washing with hot water and drying.
- the maximum intensity of the three diffraction intensities is taken as 100, and the (111), (200), and (220) diffraction intensities are converted, and the (111) plane with respect to the (200) plane diffraction intensity (I (200) )
- the ratio of the diffraction intensity (I (111) ) (I (111) / I (200) ) and the texture coefficient of the (200) plane were obtained.
- I (111) / I (200) was 1.25
- the texture coefficient of the (200) plane was 1.35.
- FIG. 5 shows an SEM photograph.
- the Ni plating film of Example 1 was composed of a Ni strike layer (31), a semi-bright Ni plating layer (32), and a bright Ni plating layer (33), and the film thickness was about 5 ⁇ m. Further, there were no columnar crystals penetrating in the thickness direction of the film, and columnar crystals having an average diameter of less than 0.2 ⁇ m were not observed. The average particle size of the granular structure was 0.8 ⁇ m.
- Spacer expander and side rail molding The spacer expander is made from the hoop wire coated with the Ni plating film, using ordinary gear molding, etc., nominal diameter 82.5 mm, combined nominal width 2.5 mm, combined thickness 2.8 It was molded to be a combined oil ring of mm and tension 23 N ⁇ 3.0 N.
- the side rail is formed by coiling from a rolled strip-shaped SUS440B hoop wire rod (0.3R at the end) of 2.30 mm ⁇ 0.40 mm, and a CrN film is formed on the outer peripheral surface by ion plating.
- An oil sludge resistant coating composition containing C6FMA, PolySiMA, and SiMA was coated on the entire surface of the side rail.
- Example 2-5 Comparative Examples 1-3 Except for changing the current density and initial pH as shown in Table 1 and adjusting the plating time to a film with a film thickness of about 5 ⁇ m, the same plating conditions and manufacturing conditions as in Example 1 were used, and the nominal diameter was 82.5 mm. A combined oil ring having a combined nominal width of 2.5 mm, a combined thickness of 2.8 mm, and a tension of 23 N ⁇ 3.0 N was produced.
- film hardness before and after heat treatment, surface roughness after heat treatment, X-ray diffraction measurement, SEM structure observation, film thickness and surface hardness of nitrided layer, and tension were measured, and the results were Tables 1 and 2 show. The table also shows the results of various tests of Example 1.
- FIGS. 6 and 7 show the X-ray diffraction profile and SEM photograph of the film cross section of Example 3
- FIGS. 8 and 9 show the X-ray diffraction profile and SEM photograph of the film cross section of Comparative Example 1, respectively.
- a plating film was formed at a current density of 5 to 10 A / dm 2 and an initial pH in the range of 2.8 to 4.7, and further heat treatment at 600 ° C. for 30 seconds. It was observed that the hardness was 300 HV or less, I (111) / I (200) was 2.0 or less, and there were no fine columnar crystals with an average diameter of less than 0.2 ⁇ m. On the other hand, as the initial pH increased, I (111) / I (200) was larger than 2.0, and fine columnar crystals having an average diameter of less than 0.2 ⁇ m were also observed as shown in the SEM photograph of FIG. Furthermore, defects were also observed in the structure of fine columnar crystals having an average diameter of less than 0.2 ⁇ m.
- the nitride layer could be formed as thick as 27 to 43 ⁇ m in any of Examples 1 to 5 and Comparative Examples 1 to 3.
- the results of the tension measurement show that in Examples 1 to 5, the average tension is almost the target value (23 N), the standard deviation is 0.28 to 0.39 ⁇ N, the process capability Cp value is 2.56 to 3.57, and the CpK value is 2.45 to 3.25 showed sufficient process capability.
- Comparative Examples 1 to 3 the Cpk value in the process capability is remarkably low. For example, in Comparative Example 2, the Cpk value is negative, indicating that the average tension is out of specification.
- Oil sludge resistance test 1 In the actual machine oil sludge resistance test, the same engine used in the actual machine endurance test was used, and the oil rings of Examples 1 to 4 were installed in each cylinder. It was performed under the condition of cyclic operation that continuously repeats the operating conditions from the state to the maximum output speed and the hot and cold water temperature conditions from low temperature to high temperature. Also in this test, the ring used for the engine was used for the top ring and the second ring.
- Example 6 A strip-shaped SUS304 hoop wire (rolled at 0.3R) of 2.2 mm x 0.275 mm was used for the spacer expander, and a rolled SUS440B hoop wire (2.00 mm x 0.40 mm) was used for the side rail (0.3 mm at the end). R) was used, and a combined oil ring was prepared in the same manner as in Example 1, except that the nominal diameter was 75.0 mm, the combined nominal width was 2.0 mm, the combined thickness was 2.5 mm, and the tension was 7.5 N ⁇ 2.0 N. . As for the tension of the combination oil ring of Example 6, the average tension was 7.23 N, the standard deviation was 0.33 N, the Cp value was 2.02, and the Cpk value was 1.75.
- Oil sludge resistance test 2 For Example 6 as well, an actual oil sludge resistance test was conducted using the engine with the displacement of 1500 cm 3 described above. Here, the combination oil ring of Example 6 was used for all four cylinders. As a result of taking out the piston from each cylinder after observing a predetermined time and observing the oil ring, there was no adhesion between the spacer expander and the side rail, and the oil ring was taken out from the piston and subjected to ultrasonic cleaning in acetone for a certain period of time. The amount of deposits was extremely small, and it was confirmed that even in a combination oil ring with low tension, excellent oil sludge resistance was exhibited.
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Abstract
Description
X線回折プロファイルで、(200)面の回折強度(I(200))に対する(111)面の回折強度(I(111))の比(I(111)/I(200))は2.0以下であることが好ましく、前記(200)面の組織係数は1.1以上であることが好ましい。
(hkl)面の組織係数=I(hkl)/I0(hkl)・[(1/n)・Σ(I(hkl)/I0(hkl))]-1 …(1)
により定義され、I(hkl)は測定された(hkl)面のX線回折強度(測定されたX線回折強度の最大のものを100として換算している)、I0(hkl)はJCPDSファイル番号04-0850に記載されている標準X線回折強度である。ファイル番号04-0850には(111)、(200)、(220)、(311)、(222)、(400)、(331)、(420)の8種類の(hkl)面の標準X線回折強度が載っているが、本発明では、簡単のため、(111)、(200)、(220)の3種類の(hkl)面のみのX線回折強度を用いて定義する。したがって、本発明においては、
(hkl)面の組織係数= I(hkl)/I0(hkl)・[1/3・I(111)/I0(111)+I(200)/I0(200)
+I(220)/I0(220))]-1 …(2)
と定義する。ちなみに、I0(111)は100、I0(200)は42、I0(220)は21である。(200)面の組織係数は1.2以上であればより好ましく、1.3以上であればさらに好ましい。(200)面の回折強度(I(200))が最大となった場合は、(200)面の組織係数は1.8以上となればさらに好ましい。
[1] Niめっき
2.50 mm×0.25 mmの圧延した帯状のSUS304フープ線材(端部は0.3R)を用い、次の条件でNiめっきを行った。
前処理:電解脱脂-酸活性-Niストライク
Niめっき浴:半光沢Niめっき浴(スルファミン酸Ni溶液+塩化Ni
+ホウ酸+添加剤A)、及び
光沢Niめっき浴(スルファミン酸Ni溶液+塩化Ni
+ホウ酸+添加剤B)
浴温:50℃
初期pH:2.8
電流密度:8 A/dm2
時間:半光沢Niめっき 60秒、光沢Niめっき30秒
Niめっき皮膜被覆フープ線材は、湯洗浄、乾燥後に、N2雰囲気中(酸素濃度50 ppm)、600℃、30秒の軟化熱処理を行った。
Niめっき皮膜の硬さ測定は、被覆面に平行な鏡面研磨した表面について、マイクロビッカース硬さ試験機を使用し試験力0.098 N(10 g)で行った。実施例1のNiめっき皮膜の硬さは、熱処理前は435 HV0.01、熱処理後は245 HV0.01であった。
表面粗さは、熱処理後のフープ線材について、触針式表面粗さ測定機を用いて中心線平均粗さ(Ra75)を測定した。実施例1の中心線平均粗さ(Ra75)は0.16μmであった。
X線回折強度は、鏡面研磨した被覆面に平行な表面について、管電圧40 kV、管電流30 mAのCu-Kα線を使用して2θがNiの(111)、(200)及び(220)の各面の回折線位置をカバーする2θ=35~90°の範囲で測定した。図4に実施例1で得られたX線回折プロファイルを示す。3つの回折強度のうちの最大強度を100として、(111)、(200)、(220)の各回折強度を換算し、 (200)面の回折強度(I(200))に対する(111)面の回折強度(I(111))の比(I(111)/I(200))、及び(200)面の組織係数を求めた。実施例1のI(111)/I(200)は1.25、(200)面の組織係数は1.35であった。
膜厚測定と組織観察は、被覆面に垂直な鏡面研磨した断面の走査電子顕微鏡(SEM)で観察した写真を用いて行った。図5にSEM写真を示す。実施例1のNiめっき皮膜は、Niストライク層(31)、半光沢Niめっき層(32)及び光沢Niめっき層(33)から構成され、膜厚は約5μmであった。また、皮膜の厚さ方向に貫通する柱状晶は無く、平均径0.2μm未満の柱状晶も観察されなかった。なお、粒状組織の平均粒径は0.8μmであった。
スペーサエキスパンダは、上記Niめっき皮膜を被覆したフープ線材から、通常のギア成形等を用い、呼び径82.5 mm、組合せ呼び幅2.5 mm、組合せ厚さ2.8 mm、張力23 N±3.0 Nの組合せオイルリングとなるように成形した。サイドレールは、2.30 mm×0.40 mmの圧延した帯状のSUS440Bフープ線材(端部は0.3R)からコイリングにより成形し、外周面にイオンプレーティングによるCrN皮膜を形成し、さらに特許文献8に開示のC6FMA、PolySiMA、及びSiMAを含有する耐オイルスラッジ用コーティング組成物をサイドレールの全表面に被覆した。
スペーサエキスパンダの耳部のサイドレール押圧面への窒化処理は、脱脂洗浄後、NH3:90%、N2:10%のガス窒化雰囲気中、570℃、80分の条件で行った。窒化層の厚さは27μm、であった。
組合せオイルリングの張力測定サンプルとして20セット準備し、特許文献9に示される張力測定装置を用いて張力を測定した。平均22.91 N、標準偏差0.31 N、工程性能指数Cp 3.23、Cpk 3.13であった。
電流密度と初期pHを表1に示すように変更し、めっき時間を調整して約5μmの膜厚の皮膜とした以外は、実施例1と同じめっき条件、同じ製造条件で、呼び径82.5 mm、組合せ呼び幅2.5 mm、組合せ厚さ2.8 mm、張力23 N±3.0 Nの組合せオイルリングを作製した。実施例1と同様に、熱処理前後の皮膜硬さ、熱処理後の表面粗さ、X線回折測定、SEM組織観察、窒化層の膜厚及び表面硬さ、並びに張力の測定を行い、その結果を表1及び表2に示す。表には実施例1の各種試験の結果も併せて示す。また、実施例3のX線回折プロファイル及び皮膜断面のSEM写真を図6及び図7に、比較例1のX線回折プロファイル及び皮膜断面のSEM写真を図8及び図9に示す。
排気量が2400 cm3の4気筒ガソリンエンジンを用い、各気筒それぞれに実施例1~4のオイルリングを装着し、6,500 rpm、全負荷(WOT:Wide Open Throttle)の運転条件で実機耐久試験を行った。ここで、トップリング及びセカンドリングは、当該エンジン用として使用されていたリングを使用した。所定時間経過後の各オイルリングについて、張力を再度測定した結果、実施例1は22.15 N、実施例2は22.34 N、実施例3は22.11 N、実施例4は22.26 Nであった。いずれも、規格内に十分入る特性を示しており、スペーサエキスパンダの耳部の摩耗による張力減退は全く生じなかった。
実機耐オイルスラッジ試験は、上記実機耐久試験に用いたのと同じエンジンを使って、各気筒それぞれに実施例1~4のオイルリングを装着し、エンジンオイルには市場回収劣化オイルを用い、停止状態から最高出力回転数までの運転条件と、低温から高温までの湯水温条件を連続的に繰り返すサイクリック運転を実施する条件で行った。この試験においても、トップリングとセカンドリングは、当該エンジン用として使用されていたリングを使用した。所定時間経過後、各気筒からピストンを取り出してオイルリングを観察した結果、スペーサエキスパンダとサイドレールの間の固着は無く、オイルリングをピストンから取り出し、アセトン中で一定時間超音波洗浄した結果、付着物も極微量であり、実施例1~4の組合せオイルリングは、耐オイルスラッジ性に優れていることが確認された。
スペーサエキスパンダ用に2.2 mm×0.275 mmの圧延した帯状のSUS304フープ線材(端部は0.3R)を用い、サイドレール用に2.00 mm×0.40 mmの圧延した帯状のSUS440Bフープ線材(端部は0.3R)を用い、呼び径75.0 mm、組合せ呼び幅2.0 mm、組合せ厚さ2.5 mm、張力7.5 N±2.0 Nとなるように成形した以外は、実施例1と同様にして組合せオイルリングを作製した。実施例6の組合せオイルリングの張力は、平均張力が7.23 N、標準偏差が0.33 N、Cp値が2.02、Cpk値が1.75であった。
排気量が1500 cm3の4気筒ガソリンエンジンを用い、4気筒全てに実施例6の組合せオイルリングを装着し、6,000 rpm、全負荷(WOT:Wide Open Throttle)の運転条件で実機耐久試験を行った。トップリング及びセカンドリングは、当該エンジン用として使用されていたリングを使用した。所定時間経過後の各オイルリングについて、張力を再度測定した結果、7.15 N、7.09 N、7.12 N、7.04 Nで、いずれも規格内に十分入る特性を示しており、スペーサエキスパンダの耳部の摩耗による張力減退は全く生じなかった。
実施例6についても、上記の排気量1500 cm3のエンジンを使って、実機耐オイルスラッジ試験を行った。ここでは、4気筒全てに実施例6の組合せオイルリングを使用した。所定時間経過後、各気筒からピストンを取り出してオイルリングを観察した結果、スペーサエキスパンダとサイドレールの間の固着は無く、オイルリングをピストンから取り出し、アセトン中で一定時間超音波洗浄した結果、付着物も極微量であり、低張力の組合せオイルリングにおいても、優れた耐オイルスラッジ性を示すことが確認された。
Claims (9)
- 合口を有する一対の円環状のサイドレールと、それらの間に介在し内周部に前記サイドレールの内周面を押圧する耳部を有する軸方向波形形状のスペーサエキスパンダよりなる組合せオイルコントロールリングであって、前記耳部のサイドレール押圧面に窒化層が形成され、前記窒化層が形成された部分を除く前記スペーサエキスパンダの全面にめっき皮膜が被覆され、前記めっき皮膜は、ビッカース硬さが300 HV0.01以下であることを特徴とする組合せオイルコントロールリング。
- 請求項1に記載の組合せオイルコントロールリングにおいて、めっき皮膜被覆面のX線回折プロファイルで、(200)面の回折強度(I(200))に対する(111)面の回折強度(I(111))の比(I(111)/I(200))が2.0以下であることを特徴とする組合せオイルコントロールリング。
- 請求項2に記載の組合せオイルコントロールリングにおいて、前記(200)面の組織係数が1.1以上であることを特徴とする組合せオイルコントロールリング。
- 請求項1~3のいずれかに記載の組合せオイルコントロールリングにおいて、前記めっき皮膜が平均径0.2μm未満の柱状晶を含まないことを特徴とする組合せオイルコントロールリング。
- 請求項1~4のいずれかに記載の組合せオイルコントロールリングにおいて、前記めっき皮膜の膜厚が1~7μmであることを特徴とする組合せオイルコントロールリング。
- 請求項1~5のいずれかに記載の組合せオイルコントロールリングにおいて、前記めっき皮膜の表面粗さが中心線平均粗さ(Ra75)で0.005~0.4μmであることを特徴とする組合せオイルコントロールリング。
- 請求項1~6のいずれかに記載の組合せオイルコントロールリングにおいて、前記めっき皮膜がNiめっき皮膜であることを特徴とする組合せオイルコントロールリング。
- 請求項1~7のいずれかに記載の組合せオイルコントロールリングにおいて、前記窒化層の厚さが30μm以上であることを特徴とする組合せオイルコントロールリング。
- 請求項1~8のいずれかに記載の組合せオイルコントロールリングにおいて、組合せ張力が5~20 Nであることを特徴とする組合せオイルコントロールリング。
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2015
- 2015-01-09 JP JP2015002946A patent/JP5980966B2/ja not_active Expired - Fee Related
- 2015-12-22 EP EP15877035.4A patent/EP3244099B1/en active Active
- 2015-12-22 WO PCT/JP2015/085791 patent/WO2016111162A1/ja active Application Filing
- 2015-12-22 US US15/536,799 patent/US10352446B2/en active Active
- 2015-12-22 KR KR1020177022235A patent/KR101863107B1/ko active IP Right Grant
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Also Published As
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JP2016128700A (ja) | 2016-07-14 |
US20170350508A1 (en) | 2017-12-07 |
JP5980966B2 (ja) | 2016-08-31 |
US10352446B2 (en) | 2019-07-16 |
EP3244099B1 (en) | 2019-12-04 |
KR20170097226A (ko) | 2017-08-25 |
KR101863107B1 (ko) | 2018-05-31 |
EP3244099A1 (en) | 2017-11-15 |
EP3244099A4 (en) | 2018-07-04 |
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