US10385971B2 - Piston ring - Google Patents

Piston ring Download PDF

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US10385971B2
US10385971B2 US15/320,818 US201515320818A US10385971B2 US 10385971 B2 US10385971 B2 US 10385971B2 US 201515320818 A US201515320818 A US 201515320818A US 10385971 B2 US10385971 B2 US 10385971B2
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piston ring
alloy film
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US20170167609A1 (en
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Noriaki Chida
Masataka OKANO
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Nippon Piston Ring Co Ltd
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Nippon Piston Ring Co Ltd
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Assigned to NIPPON PISTON RING CO., LTD. reassignment NIPPON PISTON RING CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CHIDA, NORIAKI, OKANO, Masataka
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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
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
    • C23C14/025—Metallic sublayers
    • 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
    • C23C14/0641—Nitrides
    • 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
    • C23C14/0641—Nitrides
    • C23C14/0647—Boron nitride
    • 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
    • C23C14/14—Metallic material, boron or silicon
    • 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
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • 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
    • 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
    • C23C28/048—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 layers graded in composition or physical properties
    • 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
    • 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
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
    • C23C14/325—Electric arc evaporation
    • 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

Definitions

  • the present invention relates to a piston ring having excellent wear resistance, cracking resistance, and peeling resistance.
  • a piston ring used in an internal combustion engine is used under a harsh environment of high temperature and high pressure, requiring further improvement in wear resistance and the like.
  • an outer peripheral sliding surface of the piston ring slides and comes into contact with an inner peripheral surface of a cylinder liner, and thus requires particularly superior wear resistance.
  • a chrome plated film, a nitride layer, a hard film formed by a physical vapor deposition (PVD) method, or the like is used.
  • a chrome plated film, a nitriding treated film, or a hard film of chromium nitride (CrN, Cr 2 N), titanium nitride (TiN), or the like fabricated by a PVD method is formed on the outer peripheral sliding surface and top and bottom surfaces of the piston ring.
  • a piston ring used in an internal combustion engine of an alcohol fuel vehicle capable of running on an alcohol fuel, or a flexible-fuel vehicle (FFV) or a dual-fuel vehicle capable of running on two or more types of fuels such as gasoline, methanol, and ethanol is susceptible to wear resistant film cracking and peeling, resulting in a desire for even higher wear resistance.
  • the cracking and peeling of the wear resistant film is caused by a chemical reaction that occurs between the great amount of moisture produced from the alcohol included in the fuel and the wear resistant film formed on the outer peripheral sliding surface of the piston ring.
  • Patent Document 1 proposes a sliding member covered with a hard film having improved sliding characteristics and, in particular, peeling resistance.
  • the outer peripheral surface of the piston ring is covered with a hard film by arc ion plating, and the hard film is made of a CrN-based chromium nitride, and has a crystal lattice constant within a range of 0.4145-0.4200 nm and a Cr content of 30-49 at. %.
  • Patent Document 2 proposes a sliding member covered with a film having excellent wear resistance, scuffing resistance, and characteristics that do not cause an increase in the wear of an opposing material (aggressiveness against mated).
  • the outer peripheral surface of the sliding member is covered with a Cr—V—B—N alloy film, and the Cr—V—B—N alloy film is formed by a physical vapor deposition method, in particular an ion plating method, a vacuum deposition method, or a sputtering method, and has a V content of 0.1-30 mass % and a B content of 0.05-20 mass %.
  • Patent Document 3 proposes a sliding member on which a Cr—B—Ti—N alloy film having excellent wear resistance and scuffing resistance is formed.
  • the piston ring comprises a base material, a nitride layer, and a Cr—B—Ti—N alloy film, and the Cr—B—Ti—N alloy film is made to cover the outer peripheral sliding surface (sliding surface equivalent area) of the nitride layer by a PVD (physical vapor deposition) method, includes B in an amount of 0.05-10.0 mass %, Ti in an amount of 5.0-40.0 mass %, and N in an amount of 10.0-30.0 mass %, and has a remnant of Cr.
  • PVD physical vapor deposition
  • an internal combustion engine that uses an alcohol fuel or an alcohol-containing fuel is susceptible to wear resistant film cracking and peeling as a result of a chemical reaction that occurs between the great amount of moisture produced from the alcohol contained in the fuel and the wear resistant film formed on the outer peripheral sliding surface of the piston ring.
  • the present invention was made to resolve the above-described problems, and it is therefore an object of the present invention to provide a piston ring having higher wear resistance, cracking resistance, and peeling resistance.
  • a piston ring according to the present invention for resolving the above-described problems is a piston ring comprising a sliding surface covered with a Cr—B—V—N alloy film, wherein a B content is within a range of 0.1-1.5 mass % inclusive, a V content is within a range of 0.05-1 mass % inclusive, and a ratio [B content/V content] is within a range greater than 1 and 30 or less.
  • the piston ring according to the present invention may be configured so that the alloy film further includes Ti, the Ti content being within a range greater than 0 mass % and 8 mass % or less.
  • the piston ring according to the present invention may be configured so that the Ti content is within a range greater than 0 mass % and 8 mass % or less, the Cr content is within a range of 55-61 mass % inclusive, and the N content is within a range of 32-40 mass % inclusive when the alloy film further includes Ti, and the Cr content is within a range of 60-64 mass % inclusive and the N content is within a range of 31-39 mass % inclusive when the alloy film does not include Ti.
  • the piston ring according to the present invention may be configured so as to be mounted on an engine that uses an alcohol fuel or an alcohol-containing fuel.
  • the piston ring according to the present invention may be configured so that the alloy film is more porous on a base material side than a front surface side of the piston ring.
  • the piston ring according to the present invention may be configured so that a nitriding treated layer or a metal underlayer is provided as an underlayer of the alloy film.
  • a piston ring comprising a sliding surface having a Cr—B—V—N alloy film formed thereon, wherein a B content is within a range of 0.1-1.5 mass % inclusive, a V content is within a range of 0.05-1 mass % inclusive, and a ratio [B content/V content] is within a range greater than 1 and 30 or less, thereby achieving a piston ring comprising a wear resistant film having higher wear resistance, cracking resistance, and peeling resistance.
  • Such a piston ring may be preferably applied to an internal combustion engine that uses an alcohol fuel or an alcohol-containing fuel, for example, and achieves the effect of making it possible to suppress the occurrence of cracking and peeling to a greater degree than a conventional wear resistant film.
  • FIGS. 1A and 1B are schematic cross-sectional views illustrating an example of a piston ring according to the present invention.
  • FIG. 2 is a graph showing the relationship between a ratio [B content/V content] and a wear rate.
  • FIG. 3 is an explanatory view of an Amsler wear test method.
  • FIG. 4 is an explanatory view of a wear test method that uses an alcohol-containing fuel.
  • FIGS. 5A, 5B and 5C are images showing evaluation criteria for test results obtained by the wear test method illustrated in FIG. 4 .
  • a piston ring 10 ( 10 A, 10 B) according to the present invention, as illustrated in FIGS. 1A and 1B , is a piston ring comprising a sliding surface 11 covered with a Cr—B—V—N alloy film 3 .
  • a B content is within a range of 0.1-1.5 mass % inclusive
  • a V content is within a range of 0.05-1 mass % inclusive
  • a ratio [B content/V content] is within a range greater than 1 and 30 or less.
  • the alloy film 3 has high wear resistance, cracking resistance, and peeling resistance, may be preferably applied to an internal combustion engine that uses an alcohol fuel or an alcohol-containing fuel, for example, and achieves the effect of making it possible to suppress the occurrence of cracking and peeling to a greater degree than a conventional wear resistant film.
  • Examples of the materials used as a base material 1 of the piston ring 10 are various and not particularly limited.
  • materials such as various steel materials, stainless steel materials, casting materials, cast steel materials, and the like can be applied.
  • preferable examples include a martensitic stainless steel, a chromium manganese steel (SUPS) which is a spring steel, a chrome-vanadium steel (SUP 10), a silicon chrome steel (SWOSC-V), and the like.
  • SUPS chromium manganese steel
  • SUP 10 chrome-vanadium steel
  • SWOSC-V silicon chrome steel
  • the base material 1 may be pretreated as necessary.
  • the pretreatment include processing that polishes the front surface to adjust the surface roughness. This adjustment of the surface roughness is performed by, for example, methods such as lapping and polishing the front surface of the base material 1 using diamond abrasive grains.
  • An underlayer 2 of the alloy film 3 is provided as necessary to the base material 1 , as illustrated in FIG. 1B .
  • the underlayer 2 include a nitriding treated layer, a metal underlayer, and the like. While such an underlayer 2 is preferably formed on at least the outer peripheral sliding surface 11 on which sliding occurs upon contact by the piston ring 10 with a cylinder liner (not illustrated), the underlayer 2 may be formed on other surfaces, such as a top surface 12 and a bottom surface 13 and, as necessary, further on an inner peripheral surface 14 of the piston ring 10 .
  • the nitriding treated layer is a hard nitride layer formed as an underlayer by diffusing and carburizing nitrogen on the front surface of the stainless steel.
  • the nitriding treated layer is preferably used as the underlayer of the piston ring. It should be noted that the nitride treatment may be performed using conventionally known methods. While a thickness of the nitriding treated layer is not particularly limited, a thickness within a range 10-50 ⁇ m inclusive is preferred.
  • the metal underlayer examples include a metal layer of titanium or chromium.
  • the metal underlayer made of titanium or chromium may be formed by various film-forming means. Examples of applicable film-forming means include a vacuum deposition method, a sputtering method, and an ion plating method. While a thickness of the metal underlayer is not particularly limited, a thickness within a range 0.1-2 ⁇ m inclusive is preferred.
  • the alloy film 3 is provided on the base material 1 , or on the underlayer 2 when the underlayer 2 is provided on the base material 1 .
  • This alloy film 3 is preferably provided at least on the outer peripheral sliding surface 11 of the piston ring 10 .
  • the outer peripheral sliding surface 11 of the piston ring 10 comes into contact with the cylinder liner serving as an opposing material when the piston slides, and thus provision of the alloy film 3 to at least the outer peripheral sliding surface 11 makes it possible to achieve a piston ring with excellent wear resistance, cracking resistance, and peeling resistance.
  • the alloy film 3 may be formed on the top surface 12 and the bottom surface 13 serving as surfaces other than the outer peripheral sliding surface 11 and, as necessary, further formed on the inner peripheral surface 14 .
  • Examples of the alloy film 3 include a Cr—B—V—N alloy film.
  • Examples of the Cr—B—V—N alloy film include a quaternary Cr—B—V—N alloy film and quinary Cr—B—V—Ti—N alloy film. It should be noted that unavoidable impurities may be included in the alloy within a range that does not inhibit the effect of this alloy film 3 .
  • the quaternary Cr—B—V—N alloy film 3 is configured so that the B content is within a range of 0.1-1.5 mass % inclusive, the V content is within a range of 0.05-1 mass % inclusive, and the ratio [B content/V content] is within a range greater than 1 and 30 or less.
  • B solidifies in Cr—N, and is effective in increasing the fineness of crystals.
  • an alloy film that includes B increases toughness and improves wear resistance.
  • V forms a fine nitride, and is effective in improving toughness and heat resistance.
  • An alloy film that includes V can increase durability in an environment having poor lubrication.
  • the quinary Cr—B—V—Ti—N alloy film 3 is an alloy film in which the above-described quaternary Cr—B—V—N alloy film further includes Ti, and is similarly configured so that the B content is within a range of 0.1-1.5 mass % inclusive, the V content is within a range of 0.05-1 mass % inclusive, the ratio [B content/V content] is within a range greater than 1 and 30 or less, and further the Ti content is within a range greater than 0 mass % and 8 mass % or less.
  • Ti forms a fine nitride and acts so as to strengthen the underlying material.
  • an alloy film that includes Ti may exhibit effectiveness when applied to a piston ring used in an engine that uses an alcohol fuel or an alcohol-containing fuel, for example.
  • ethanol fuel for example, the alcohol and Ti or TiN chemically react, causing elution from the front surface of the alloy film 3 , and a reaction with moisture to form TiO 2 .
  • This TiO 2 then reacts with the alcohol to produce a metal alkoxide, condense, and form a polyoxy-titanium gel on the front surface of the alloy film 3 , thereby protecting the front surface.
  • the B content and the V content are within the above-described ranges, and the ratio [B content/V content] is within the above-described range, making it possible to exhibit excellent wear resistance.
  • the B content With a B content less than 0.1 mass %, the B content is too small and thus the V content must be significantly decreased to satisfy the ratio [B content/V content], possibly resulting in failure to exhibit adequate wear resistance.
  • wear resistance decreases.
  • the V content is too small and the inclusion of V does not produce the effect of improving wear resistance.
  • V content exceeds 1 mass %, the residual stress of the film increases, making the film susceptible to fine cracks, and resulting in deterioration in wear resistance. Further, from a cost perspective, an increased V content increases costs, making processing difficult in terms of the manufacture of the target (evaporation source) as well.
  • the wear resistance cannot be regarded as adequate. Further, when the ratio [B content/V content] exceeds 30, the B content is significantly large compared to the V content, resulting in a brittle and porous film tissue and thus a reduction in wear resistance. Further, processing is difficult in terms of the manufacture of the target (evaporation source) as well.
  • a more preferred range of the B content is within a range of 0.6-1.2 mass % inclusive.
  • a more preferred range of the V content is within a range of 0.1-0.5 mass % inclusive.
  • a more preferred range of the ratio [B content/V content] is within a range of 1.2-12 inclusive.
  • the quaternary or quinary alloy film 3 comprising these preferred ranges can exhibit higher wear resistance.
  • the Ti content is preferably within a range greater than 0 mass % and 8 mass % or less.
  • Ti contributes to strengthening the underlying material of the film in an alloy film and, with an alcohol fuel or an alcohol-containing fuel, forms polyoxy-titanium on the front surface due to chemical changes, thereby making it possible to further increase wear resistance.
  • a more preferred range of the Ti content is within a range of 1.9-7.1 mass % inclusive, which makes it possible to even further increase wear resistance.
  • the Cr content is within a range of 60-64 mass % inclusive, and the N content is within a range of 31-39 mass % inclusive.
  • the Cr content is within a range of 55-61 mass % inclusive, and the N content is within a range of 32-40 mass % inclusive.
  • the alloy film 3 is normally formed on at least the outer peripheral sliding surface 11 of the piston ring 10 by a PVD (physical vapor deposition) method.
  • PVD physical vapor deposition
  • Examples of the PVD method include an ion plating method, a vacuum deposition method, a sputtering method, and the like. While a thickness of the formed alloy film 3 is not particularly limited, a thickness within a range 3-20 ⁇ m inclusive is preferred.
  • the alloy film 3 thus formed is preferably more porous on the base material side than the front surface side (sliding surface side) of the piston ring.
  • Making the base material side more porous than the front surface side results in the alloy film on the base material side having a porous intermediate layer.
  • This intermediate layer is advantageous in that it acts so as to alleviate the stress between the alloy film 3 on the front surface side and the base material or underlayer, making it possible to improve an adhesive force.
  • the composition of the porous intermediate layer on the base material side is the same as the composition of the dense alloy film 3 on the front surface side, and can be formed by adjusting film formation conditions.
  • Such an intermediate layer may have a uniform composition in a thickness direction, or a composition that changes in the thickness direction, and the thickness, while not particularly limited, is within a range of 0.01-20 ⁇ m inclusive, for example, and preferably around 5 ⁇ m (3-8 ⁇ m inclusive).
  • the porous intermediate layer on the base material side and the dense alloy film 3 on the front surface side can be easily analyzed by image analysis using a cross-section section polisher (CP). These make it possible to change and control a bias voltage and a nitrogen gas pressure, for example. While not particularly limited, each of these can be formed by maintaining the nitrogen gas pressure inside the chamber at 50 mTorr and setting the bias voltage to ⁇ 7 V when forming the porous intermediate layer, and setting the nitrogen gas pressure to 25 mTorr and the bias voltage to ⁇ 7 V when forming the dense alloy film 3 , for example. Further, the porous intermediate layer can be formed by setting the nitrogen gas pressure inside the chamber to 25 mTorr and the bias voltage to 0 V. Further, the dense alloy film 3 can be formed by setting the nitrogen gas pressure inside the chamber to 9 mTorr and the bias voltage to ⁇ 10 V.
  • CP cross-section section polisher
  • the hardness of the alloy film 3 is preferably within a range of 1600-2000 inclusive by Vickers hardness (JIS B 7725, ISO 6507) Hv (0.05). Vickers hardness can be measured using a micro Vickers hardness tester (manufactured by Future-Tech) or the like, and “HV (0.05)” indicates the Vickers hardness at a load of 50 gf.
  • Another film may be provided on the alloy film 3 as necessary.
  • Examples of such a film include a diamond-like carbon.
  • the piston ring 10 according to the present invention exhibits high wear resistance, making it possible to preferably mount the piston ring 10 not only on an engine that uses a regular gasoline fuel, but also on an engine that uses an alcohol fuel or an alcohol-containing fuel. While the cylinder internal pressure inside the engine increases with a flex fuel vehicle that uses an alcohol fuel or an alcohol-containing fuel, making the piston ring having a conventional wear resistant film formed thereon susceptible to the occurrence of wear resistant film cracking and peeling, the piston ring 10 according to the present invention may be preferably applied to an internal combustion engine that uses an alcohol fuel or an alcohol-containing fuel, for example, and achieves the effect of making it possible to suppress the occurrence of cracking and peeling to a greater degree than a conventional wear resistant film.
  • the base material 1 was ultrasonically cleaned in an organic solvent in advance.
  • the Cr—B—V—N alloy film 3 was formed on the base material 1 .
  • the film was formed by generating an arc discharge on the front surface using an arc ion plating device and a Cr—B—V alloy having the same composition ratios as the composition ratios expected after film formation as the target. Further, nitrogen gas and, as necessary, a predetermined amount of inert gas (here, an argon gas) were introduced into the chamber that performed arc discharge, and a bias voltage of 5-30 V was applied to form the 20- ⁇ m Cr—B—V—N alloy films 3 of examples 1 to 3 and comparative examples 1 to 3, as shown in Table 1.
  • inert gas here, an argon gas
  • the obtained alloy films 3 comprised a porous intermediate layer on the base material side and a dense alloy film 3 on the front surface side, and the film was formed by maintaining the nitrogen gas pressure inside the chamber at 25 mTorr and setting the bias voltage to 0 V when forming the porous intermediate layer on the base material side, and setting the nitrogen gas pressure to 25 mTorr and the bias voltage to ⁇ 6V when forming the dense alloy film 3 on the front surface side.
  • the B content and the V content of the obtained alloy films 3 are shown in Table 1, and the Cr content and the N content were Cr content: 62.08 mass % and N content: 36.51 mass % in example 1, Cr content: 62.93 mass % and N content: 36.25 mass % in example 2, Cr content: 62:53 mass % and N content: 35.98 mass % in example 3, Cr content: 58.63 mass % and N content: 33.45 mass % in comparative example 1, Cr content: 62.61 mass % and N content: 36.24 mass % in comparative example 2, and Cr content: 61.37 mass % and N content: 36.12 mass % in comparative example 3.
  • a Cr—B—N tertiary alloy film was formed in place of the alloy films formed in each of the examples 1 to 3 and the comparative examples 1 to 3 described above. All other aspects were the same as those of the examples 1 to 3 and the comparative examples 1 to 3.
  • the wear rates are indicated in Tables 1 and 2, given 1 as the wear rate of this conventional example 1. A value less than 1 indicates a higher wear resistance than that of the conventional example 1.
  • the film formation conditions in this case include a nitrogen gas pressure of 25 mTorr and a bias voltage of ⁇ 16V, resulting in a dense film along the entire thickness direction.
  • the Cr content was 61.29 mass % and the N content was 37.20 mass %.
  • a Cr—B—V—Ti—N quinary alloy film was formed using a target that included Ti in the examples 1 to 3 and the comparative examples 1-3 described above. All other aspects were the same as those of the examples 1 to 3 and the comparative examples 1 to 3. It should be noted that, in example 8 only, the nitrogen gas pressure was set to 25 mTorr and the bias voltage was set to ⁇ 16V, resulting in a dense alloy film 3 along the entire thickness direction.
  • the B content, the V content, and the Ti content of the obtained alloy films 3 are shown in Table 2, and the Cr content and the N content were Cr content: 57.94 mass % and N content: 33.14 mass % in example 4, Cr content: 59.14 mass % and N content 34.70 mass % in example 5, Cr content: 59.55 mass % and N content: 35.85 mass % in example 6, Cr content: 59.99 mass % and N content: 36.58 mass % in example 7, Cr content: 59.74 mass % and N content: 35.72 mass % in example 8, Cr content: 56.39 mass % and N content: 31.27 mass % in comparative example 4, Cr content: 58.94 mass % and N content: 35.75 mass % in comparative example 5, Cr content: 51.28 mass % and N content: 26.75 mass % in comparative example 6, and Cr content: 56.89 mass % and N content: 31.70 mass % in comparative example 7.
  • the wear rates indicated in Tables 1 and 2 were measured by using an Amsler wear tester 30 illustrated in FIG. 3 , measurement samples 31 (length: 7 mm, width: 8 mm, height: 5 mm) obtained under the same conditions as those of the piston rings obtained in the conventional example 1, the examples 1 to 8, and the comparative examples 1 to 7 described above as stationary pieces, and a doughnut-shaped (outer diameter 40 mm, inner diameter 16 mm, thickness: 10 mm) object as an opposing material 32 (rotating piece), causing the measurement sample 31 and the opposing material 32 to come into contact, and then applying a load P.
  • a friction coefficient test was conducted using each of the measurement samples 31 under test conditions including a lubricant 33 : machine oil (kinematic viscosity: 1.01 at 100° C., and 2.2 at 40° C.), oil temperature: room temperature, rotating speed: 100 rpm, load: 400 N, test period: 21 hours, and boron cast iron as the opposing material 32 .
  • the oil drip rate from a drip tube 34 was 0.04 mL/min.
  • the opposing material 32 made from boron cast iron was first ground into a predetermined shape and then sequentially surface-ground after changing the fineness of the grinding stone, making adjustments so as to achieve a final roughness of 1-2 ⁇ m Rz (10-point average roughness, compliant with JIS B0601 (1994)).
  • the test results are shown in FIG. 2 and Tables 1 and 2 as wear rates.
  • the wear rates are each expressed as a rate given 1 as the amount of wear in the conventional example 1.
  • “Ex1” to “Ex8” are abbreviations for examples 1 to 8
  • “Co1” to “Co7” are abbreviations for comparative examples 1 to 7
  • “Conventional example 1” indicates conventional example 1.
  • the alloy films within the composition ranges according to the present invention all exhibited a wear rate of less than 1 and a high wear resistance. Based on these results, the B, V, and Ti contents illustrated in examples 1 to 8 in Tables 1 and 2 were clearly found to exhibit a favorable wear resistance compared to the conventional example 1 and the comparative examples 1 to 7 at least within the above-described ranges.
  • FIG. 4 is an explanatory view of a wear test method that uses an alcohol-containing fuel
  • FIGS. 5A, 5B and 5C are images showing evaluation criteria for the test results obtained using the wear test method.
  • the wear test was conducted using a tester 40 that performs the wear test method illustrated in FIG. 4 by simultaneously dripping an ethanol 43 A with 30% water added thereto and an engine oil 43 B from drip tubes 44 and 44 , respectively, setting the rotation speed of an opposing material 42 to 1500 rpm, and using FC 250 as the opposing material 42 .
  • the outer peripheral sliding surface 11 of the piston ring 10 having the alloy film 3 formed thereon was established as a measurement sample 41 , and the predetermined load P was applied.
  • FIGS. 5A, 5B and 5C are images showing the evaluation criteria for the test results.
  • a O mark indicates that cracking and peeling were not seen
  • a ⁇ mark indicates that cracking and peeling were not seen but adhesion was severe
  • an X mark indicates that cracking and peeling were seen.

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  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Pistons, Piston Rings, And Cylinders (AREA)
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JP6736018B2 (ja) * 2015-01-29 2020-08-05 株式会社ジェイテクト 低摩擦被膜製造方法
US11692248B2 (en) 2017-11-30 2023-07-04 Nippon Piston Ring Co., Ltd. Sliding member
DE102017221606A1 (de) * 2017-11-30 2019-06-06 Federal-Mogul Burscheid Gmbh Kolbenring
JP6889692B2 (ja) * 2018-10-10 2021-06-18 Ｔｐｒ株式会社 アルコール燃料用ピストン
JP7159111B2 (ja) * 2019-05-28 2022-10-24 日本ピストンリング株式会社 摺動部材と潤滑油との組み合わせ
EP4080033A4 (de) * 2020-01-27 2024-01-31 Kabushiki Kaisha Riken Kolbenring und verfahren zur herstellung davon

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EP3163130A4 (de) 2017-12-27
CN106415083A (zh) 2017-02-15
EP3163130A1 (de) 2017-05-03
WO2016002810A1 (ja) 2016-01-07

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