CN108660408A - Piston ring and its manufacturing method - Google Patents
Piston ring and its manufacturing method Download PDFInfo
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- CN108660408A CN108660408A CN201810263513.XA CN201810263513A CN108660408A CN 108660408 A CN108660408 A CN 108660408A CN 201810263513 A CN201810263513 A CN 201810263513A CN 108660408 A CN108660408 A CN 108660408A
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- Prior art keywords
- mass
- particles
- bismuth
- particle
- piston ring
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Classifications
-
- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/134—Plasma spraying
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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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
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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
Abstract
The present invention provides a kind of piston ring and its manufacturing method, which forms that wear resistance, marresistance and initial fitting property are excellent by adaptation well, and coordinates the aggressive low sputtered films of bismuth of object and obtain.Above-mentioned technical problem is solved by piston ring, which is provided with sputtered films of bismuth on at least sliding surface of piston ring base material 2, and the sputtered films of bismuth has Mo particles, Ni base self-melting alloy particles, and has Co alloy particles and/or Cr3C2Particle.At this moment, it is configured to by Mo particles, Ni base self-melting alloy particles and Co alloy particles and Cr3C2When the total content ratio of particle is set as 100 mass %, Ni base self-melting alloy particles are more than 20 mass % in the range of 40 mass % or less, Co alloy particles and Cr3C2For the total of particle more than 15 mass % in the range of 30 mass % or less, surplus is Mo particles.Can also include NiCr particles in sputtered films of bismuth.
Description
Technical field
The present invention relates to piston ring and its manufacturing methods.More specifically, the present invention relates to a kind of piston ring and its manufactures
Method, the piston ring formed well by adaptation wear resistance, marresistance and initial fitting property it is excellent and cooperation object
Aggressive low sputtered films of bismuth and obtain.
Background technology
In recent years, with the high-output power and high performance of internal combustion engine, the use environment of the slide units such as piston ring
Become more and more harsh, it is desirable that the slide unit with good wear resistance, marresistance.Piston ring is because of its peripheral surface and cylinder
Lining sliding, so requiring high wear resistance or marresistance etc. especially as periphery sliding surface.For such requirement,
It is proposed that the periphery sliding surface in piston ring is equipped with the technology of sputtered films of bismuth in Patent Documents 1 to 3.
In patent document 1, proposition have a kind of piston ring, for sequentially formed on sliding surface to include at least Mo powder,
The mixed-powder of Ni bases self-fluxing alloyed powder and Cu or Cu alloy powders carries out spraying plating bottom made of spraying plating, and contains Cu's
The piston ring of metallized surface layer, the Cu or Cu of the spraying plating bottom Mo at least containing 50~80 mass %, 1~12 mass % are closed
Gold, surplus：Ni base self-melting alloy etc..
Motion has a kind of sputtered films of bismuth in patent document 2, for by plasma spraying method in the periphery of piston ring base material
Piston ring sputtered films of bismuth obtained by spraying plating powder composition on sliding surface, the powder composition include molybdenum particle, nichrome grain
Son and chromium carbide particle, the median particle diameter of chromium carbide particle is set as in particular range etc..
Iing is proposed there is a kind of sputtered films of bismuth in patent document 3, sputtered films of bismuth includes molybdenum phase, chromium carbide phase and nichrome phase, molybdenum phase,
Chromium carbide phase and nichrome mutually deposit on the sliding surface of base material, the chromium carbide phase in pair direction vertical with the sliding surface of base material
The average value of thickness and the ratio between the thickness average value etc. of molybdenum phase be determined.
A kind of piston ring of motion in patent document 4, be the piston ring with sputtered films of bismuth, the sputtered films of bismuth at least to comprising
Mo powder, Cr3C2The raw material powder of the mixed-powder of powder and NiCr powder carries out spraying plating, and the average grain diameter of mixed-powder is 50 μm
More than, the average grain diameter of Mo powder is smaller than the average grain diameter of mixed-powder etc..
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2012-46821 bulletins
Patent document 2：No. WO2014/091831
Patent document 3：Japanese Unexamined Patent Publication 2015-214719 bulletins
Patent document 4：Japanese Unexamined Patent Publication 2016-102233 bulletins
Invention content
Technical problems to be solved by the inivention
The object of the present invention is to provide a kind of piston ring and its manufacturing method, the piston ring by adaptation well
It is excellent and coordinate the aggressive low sputtered films of bismuth of object and obtain to form wear resistance, marresistance and initial fitting property.
Technical teaching for solving the problem was
(1) piston ring of the invention on at least sliding surface of piston ring base material it is characterized in that, be provided with sputtered films of bismuth, institute
It states sputtered films of bismuth and contains Mo particles, Ni base self-melting alloy particles, and there is Co alloy particles and/or Cr3C2Particle.According to the hair
It is bright, due to including Ni base self-melting alloy particles and Co alloy particles and/or Cr3C2Particle, therefore it is special to form adaptation
Well, and the cooperation aggressive sputtered films of bismuth of object is reduced.
For the piston ring of the present invention, it is configured to：By the Mo particles, the Ni bases self-melting alloy particle and institute
State Co alloy particles and Cr3C2When the total content ratio of particle is set as 100 mass %, the Ni bases self-melting alloy particle exists
In the range of 20 mass % or more, 40 mass % or less, the Co alloy particles and Cr3C2The total of particle is more than 15 mass %
In the range of 30 mass % or less, surplus is Mo particles.
In the piston ring of the present invention, the sputtered films of bismuth can also include NiCr particles.
In the piston ring of the present invention, the content A of the preferably described Ni bases self-melting alloy particle and the NiCr particles
The ratio (A/B) of content B is 1.5 or more by quality ratio.
Can include the NiCr particles and institute comprising the NiCr particles in the piston ring of the present invention
State Cr3C2The granules structure of particle.
(2) manufacturing method of piston ring of the invention is it is characterized in that, to Mo powder, Ni bases self-fluxing alloyed powder, Co
Alloy powder and/or Cr3C2The mixed-powder composition of powder carries out plasma spraying, is slided in the periphery of piston ring base material
Sputtered films of bismuth is formed on face.
The effect of invention
In accordance with the invention it is possible to which provide adaptation forms wear resistance and excellent scratch resistance well, and coordinate object
The piston ring and its manufacturing method of aggressive low sputtered films of bismuth.
Description of the drawings
Fig. 1 is the sectional view for an example for indicating the piston ring of the present invention；
Fig. 2 (A)~Fig. 2 (D) is the section of the sputtered films of bismuth obtained in embodiment 1, embodiment 2 and comparative example 1, comparative example 2
Photo；
Fig. 3 is the structure principle chart of the high load type abrasion tester for check for wear.
Description of symbols
1 piston ring
2 piston ring base materials
3 sputtered films of bismuth
4 metallized surface layers
6 high load type abrasion testers
7 materials to be tested
8 revolving fragments
P is loaded
Specific implementation mode
Hereinafter, the piston ring and its manufacturing method to the present invention are described in detail.In addition, as long as the present invention is in its purport
In the range of, then it is not limited to the following embodiments and the accompanying drawings.
[piston ring]
The piston ring 1 of the present invention on at least sliding surface of piston ring base material 2 as shown in Figure 1, be provided with as feature
Sputtered films of bismuth 3.The sputtered films of bismuth 3 has Mo particles, Ni base self-melting alloy particles, and has Co alloy particles and/or Cr3C2Particle.
Such piston ring 1 passes through to Mo powder, Ni bases self-fluxing alloyed powder, Co alloy powders and/or Cr3C2The mixed powder of powder
Powder composition carries out plasma spraying, to form sputtered films of bismuth 3 on the periphery sliding surface of piston ring base material 2 to manufacture.Shape
It is especially good that adaptation can be formed at the piston ring 1 of sputtered films of bismuth 3, and reduces the cooperation aggressive sputtered films of bismuth of object.
Illustrate each structure of the piston ring 1 of the present invention.
＜ piston ring base materials ＞
As the piston ring base material 2 as the object for forming sputtered films of bismuth 3, can enumerate is made as the base material of piston ring 1
A variety of materials are not particularly limited.Such as various steel, stainless steel material, founding materials, cast steel material can be used
Deng.In these materials, it can enumerate and enumerate martensitic stain less steel, Chromador (SUP9 materials), chrome-vanadium steel (SUP10 materials), silicochromium
Steel (SWOSC-V materials) etc..In addition, as founding materials, boron cast iron, flake graphite cast iron, globular graphite casting can be preferably enumerated
Iron, CV cast irons etc..Piston ring base material 2 is made by the method for manufacturing general piston ring.
For piston ring base material 2, can also be pre-processed as needed.As pretreatment, it can enumerate and carry out surface throwing
Light adjusts the processing of surface roughness.The adjustment of the surface roughness can for example be illustrated using diamond abrasive grain to piston ring
The surface of base material 2 is ground processing, carries out the method etc. of surface polishing.
＜ sputtered films of bismuth ＞
Sputtered films of bismuth 3 is set on at least sliding surface of piston ring base material 2.The sputtered films of bismuth 3 has Mo particles, Ni base self-fluxing natures
Alloy particle, and there is Co alloy particles and/or Cr3C2Particle is by with Mo powder, Ni base self-melting alloy powder
End, Co alloy powders and/or Cr3C2The raw material powder of powder carries out spraying plating to form a film.
Sputtered films of bismuth 3 at being grouped as following composition：By Mo particles, Ni base self-melting alloy particle, Co alloy particles and
Cr3C2When the total content ratio of particle is set as 100 mass %, Ni base self-melting alloy particles 40 matter more than 20 mass %
In the range for measuring % or less, Co alloy particles and Cr3C2The total of particle 30 mass % ranges below more than 15 mass %
Interior, surplus is Mo particles.Content ratio is mass ratio, with Mo particles, Ni base self-melting alloy particles and Co alloy particles and
Cr3C2Particle amounts to the mode that content is 100 mass % and calculates respective quality %.The particle other than comprising these the case where
Under, the total for removing the particle is set as 100 mass % to calculate.
As raw material powder, in the range of not hindering effect that the present invention plays, such as can arbitrarily include Co, B,
Si, Cu, Al, Fe etc..Further, since the composition ratio in the content and raw material powder of each particle components of composition sputtered films of bismuth 3 is logical
Chang Xiangtong, therefore the content of each ingredient of sputtered films of bismuth 3 can be described as the component ratio of raw material powder.Therefore, in order to make sputtered films of bismuth 3
As desired component ratio, the use level for each powder for constituting raw material powder can be adjusted.In addition, being contained in spraying plating
The content of each particle of film 3 can quantitatively be obtained using backscattering measurement device.In addition, constitute each particle of sputtered films of bismuth 3
Content is usually consistent with the use level of each raw material powder of spraying plating raw material is contained in, therefore passes through each particle to sputtered films of bismuth 3
Content is measured, and also can determine the mixing ratio for each powder for constituting raw material powder.
(Mo particles)
Mo particles are the main elements for constituting sputtered films of bismuth 3, with NiCr self-melting alloy particle, Co alloy particles and Cr3C2Grain
Content other than the total content of son contains, for example, containing more than 40 mass %, in 60 mass % ranges below.As
The Mo powder of refractory metal can obtain wear resistance and excellent scratch resistance, and and living by containing within the above range
The sputtered films of bismuth of the excellent adhesion of plug ring base material.Content is less than 40 mass %, the wear resistance and scratch resistance of obtained sputtered films of bismuth 3
Property deterioration.On the other hand, when content is more than 60 mass %, become reason of high cost.
As long as the average grain diameter of Mo particles is identical with general spraying plating raw material powder degree, such as preferably 10 μm
Above, in 50 μm or less of range, from the viewpoint of adaptation, more preferably 20 μm or more, in 40 μm or less of range.
In the application, the average grain diameter of the Mo particles or other particle particle size distribution analyzer (such as Nikkiso Company Limited
The MICROTRAC HRA of manufacture) measure D50Value indicate.In addition, the shape etc. of Mo particles is not particularly limited, can make
Grain sintering particle.For being granulated sintering particle obtained from being granulated to Mo particles, the Mo powder of path is granulated,
Then, its sintering is made to obtain by heating.The average grain diameter of Mo particles for granulation is, for example, 1~10 μm.Mo particles
Vickers hardness is in the range of 320~420.It should be noted that for the Vickers hardness in the present invention, it is hard using micro- Vickers
Degree meter (Co., Ltd. akashi), to load at 0.05kgf random measurements 5, the average value for the result being used in combination indicates.
(NiCr self-melting alloy particle)
Ni base self-melting alloy particles are the main elements for constituting sputtered films of bismuth 3, are sprayed to Ni base self-fluxing alloyed powders
It plates and obtains.The Ni base self-melting alloy particles are the particles for containing the flux constituents such as boron or silicon by the alloy of Ni-based formation,
It is by carrying out melt processed etc. after spraying plating, alloy particle of the formation as raw material powder is few with that can obtain stomata
And the effect of the high sputtered films of bismuth of dhering strength.The Ni base self-melting alloy particles for containing Cr are made as powder raw material in the present invention
With.The Ni base self-melting alloy particles contain the Cr of 14~18 mass %, the boron of 2~4 mass %, the silicon of 3~4.5 mass %, 2
The iron of~5 mass %, micro inevitable impurity.And it is possible to the molybdenum containing 1~3 mass % and 1~4 mass %
One of copper or both.The adhesive of Mo of such Ni bases self-melting alloy as parent metal works.In addition, the Ni bases
Self-melting alloy is self-fluxing nature, therefore, has the advantages that obtain good wear resistance this.As Ni base self-melting alloy,
It is well known that NiCr self-melting alloy and NiCo self-melting alloy, but in the present invention, use NiCr self-melting alloy.It is special
It is not to be obtained in the present invention as new discovery：The NiCr self-melting alloy particles for being contained in sputtered films of bismuth 3 are had an effect so that
Mo particles and Co alloy particles or Cr3C2The difference of hardness of particle is reduced, play can prevent Co alloy particles caused by difference of hardness or
Cr3C2This effect that falls off of particle, as a result, having the advantages that inhibit to coordinate object aggressive.NiCr self-melting alloy
The Vickers hardness of particle is in the range of 700~850.
NiCr self-melting alloy particle is by Mo particles and Ni base self-melting alloy particles and Co alloy particles and Cr3C2Grain
When the total content ratio of son is set as 100 mass %, contain preferably more than 20 mass %, in 40 mass % ranges below.
By in this range, can further reach said effect.Content is less than 20 mass %, the effect that the adhesive as Mo works
Fruit weakens, then the interparticle adaptations of Mo reduce.On the other hand, when content is more than 40 mass %, then marresistance declines.It is more excellent
The content of choosing is to have the advantages that improve adaptation and marresistance in the range of 25 mass % or more, 35 mass % or less.
As long as the average grain diameter of NiCr self-melting alloy particles is identical with general spraying plating raw material powder degree, example
Such as it is preferably 15 μm or more, in 53 μm or less of range, from the viewpoint of wear resistance, more preferably 15 μm or more, 30 μm
In following range.The average grain diameter of NiCr self-melting alloy particles equally use particle size distribution analyzer (such as day machine fill strain
Formula commercial firm manufacture MICROTRAC HRA) measure value indicate.In addition, the shape etc. of NiCr self-fluxing alloyed powders does not have yet
It is particularly limited to, can be granulated sintering particle.The granulation being just granulated to NiCr self-melting alloy particles is sintered particle
For, the NiCr self-melting alloy particles of path are granulated, then, so that it is sintered by heating by obtains.For being granulated
The average grain diameters of NiCr self-melting alloy particles be, for example, 1~10 μm.
(Co alloy particles, Cr3C2Particle)
Co alloy particles and Cr3C2Particle be constitute sputtered films of bismuth 3 main element, be to comprising it either or both
Raw material powder carries out spraying plating and obtains.Co alloy particles have this feature of excelling in abrasion resistance, can by being contained in sputtered films of bismuth 3
Assign high wear resistance effect.On the other hand, Cr3C2Particle is hard particles, by being contained in sputtered films of bismuth 3, can give spraying plating
Film 3 brings good wear resistance or adaptation.In the present invention, Co alloy particles and Cr are contained by formation3C2One of particle
Or both sputtered films of bismuth 3, said effect can be played.In addition, Co alloy particles are the Co bases of the Cr containing 16~20 mass %
Alloy particle.
By Mo particles, Ni base self-melting alloy particles and Co alloy particles and Cr3C2The total content ratio of particle is set as
When 100 mass %, Co alloy particles and Cr3C2Particle contains preferably more than 15 mass %, in 30 mass % ranges below.
By controlling in the range, it can further reach said effect.Content be less than 15 mass %, the sputtered films of bismuth 3 of gained it is wear-resisting
Damage property and adaptation can deteriorate.On the other hand, when content is more than 30 mass %, for example also there is Cr on the surface of sputtered films of bismuth3C2Grain
In the case that son is fallen off, cooperation object aggressiveness may increase.More preferable content be 15 mass % or more, 25 mass % with
Under range in, have the advantages that wear resistance improves and inhibits cooperation object aggressive this.
Consider that the characteristic of obtained sputtered films of bismuth 3, selection contain Co alloy particles and Cr in mixed-powder3C2Both particles or
Contain any one.Such as in the case where obtaining focusing on sputtered films of bismuth 3 of corrosion resistance, Co alloy particles are selected,
It obtains in the case of focusing on wear resistance and the sputtered films of bismuth 3 of adaptation, selects Cr3C2Particle is obtaining this two
In the case of the sputtered films of bismuth 3 of effect, Co alloy particles and Cr are selected3C2Particle the two.In addition, containing only Co alloy granules
In the sputtered films of bismuth 3 of son, preferably makes above-mentioned content in the range of 17~23 mass %, containing only Cr3C2The sputtered films of bismuth 3 of particle
In, preferably make above-mentioned content in the range of 18~28 mass %, in the sputtered films of bismuth 3 containing the two, preferably makes total content
In the range of 35~55 mass %, and make the content of Co alloy particles in the range of 20~30 mass %, makes Cr3C2Grain
The content of son is in the range of 15~25 mass %.
Co alloy particles and Cr3C2As long as the average grain diameter of particle is identical with general spraying plating raw material powder degree,
Such as preferably 10 μm or more, in 45 μm or less of range, more preferably 10 μm or more, 30 μm from the viewpoint of wear resistance
In following range.The average grain diameter of these particles is again by with particle size distribution analyzer (such as Nikkiso Company Limited
The MICROTRAC HRA of manufacture) measure value indicate.In addition, Co alloy particles and Cr3C2Shape of particle etc. does not limit especially
It is fixed, can be granulated sintering particle.Sintering particle is granulated obtained from being just granulated to Co alloy particles or to Cr3C2Particle
It is granulated obtained from being granulated for sintering particle, to the powder of path to be granulated, then, it is carried out by heating
It is sintered and obtains.The average grain diameter example of particle for granulation is 1~10 μm.Cr3C2The Vickers hardness of particle is 1600~1800
In the range of.
(NiCr particles)
In sputtered films of bismuth 3, NiCr particles can be contained as needed.In general, NiCr particles are sometimes as imparting sputtered films of bismuth 3
The element of good wear resistance or adaptation and contain, but in the present invention, for wear resistance and adaptation, by making Co
Alloy particle and Cr3C2The particle of one or both of particle contains specified amount and meets these effects.In addition, as above-mentioned, lead to
Cross so that it is worked containing NiCr self-melting alloy particles with improve and piston ring base material 2 adaptation, or so that it is worked with
Reduce Mo particles and Co alloy particles or Cr3C2Difference of hardness between particle.Therefore, in the present invention, NiCr particles are not as must
Need technical characteristic and as any ingredient coordinate.In addition, the difference of NiCr self-melting alloy particle and NiCr particles due to
Boron or silicon are contained with specified ratio in NiCr self-melting alloy particles, therefore can be in the analysis carried out by fluorescent X-ray
It is middle by the two or difference or classification.
When containing NiCr particles in sputtered films of bismuth 3, the preferably content (A) of Ni bases self-melting alloy particle and NiCr particles
The ratio (A/B) of content (B) is 1.5 or more by quality ratio.By being set as the range, NiCr self-melting alloy grains can be realized
The function and effect of son.When ratio (A/B) is less than 1.5, the influence of NiCr particles relatively increases, and NiCr self-melting alloy particles rise
The adaptation improvement effect or difference of hardness reducing effect of effect are insufficient.In addition, NiCr are also free of in sputtered films of bismuth 3 sometimes
Son.The upper limit of ratio is not particularly limited, comprising in the case of, such as 20 can be set as.Including the case where NiCr particles
Content can be 0.01 mass % or more, 10 mass % or less range in.
When the case where containing NiCr particles in spraying plating raw material, as long as the average grain diameter of NiCr particles and general spraying plating
Raw material powder degree is identical, for example, it is preferable in 5 μm or more, 45 μm or less of range.The average grain diameter of NiCr particles is same
The value that sample can be measured with particle size distribution analyzer (such as Nikkiso Company Limited manufacture MICROTRAC HRA) indicates.
In addition, the shape etc. of NiCr particles is not particularly limited, can be granulated sintering particle.The Vickers hardness of NiCr particles is 400
In the range of~550.It should be noted that the NiCr particles and above-mentioned Cr3C2The granulated particles that particle is granulated
(it is expressed as " Cr3C2/ NiCr granulated particles ") Vickers hardness in the range of 1000~1200.
(other elements)
Other ingredients other than the above can also be contained in the mixed-powder as spraying plating raw material.As above-mentioned other
Ingredient, can enumerate such as Fe, C, Mn, S.These ingredients contain as impurity in which can not keep away sometimes.The content of above-mentioned impurity
As long as down to the degree for the effect for not hindering the present invention.
(film build method of sputtered films of bismuth)
Sputtered films of bismuth 3 is formed in by plasma spraying on the sliding surface of piston ring 1.Plasma spraying be use etc. from
The plasma jet that daughter spray gun generates, and above-mentioned raw material powder is used, which is heated, is accelerated, is become
At fusing or with its similar state, blow to the spraying plating of base material.Principle as it is well known, but apply electricity between a cathode and an anode
When pressure generates direct-current arc, working gas (argon gas etc.) ionization conveyed from rear generates plasma.It will be former using argon gas etc.
Feed powder end is transported in the plasma frame frame, and by being blown on piston ring base material 2, sputtered films of bismuth is formed on piston ring base material 2
3.The plasma spraying of the sputtered films of bismuth 3 of the present invention in this way is formed, compared with following HVOF spraying platings, due to raw material powder
Spraying plating is carried out under fusing or temperature proximate to it, therefore the distinctive effect of the present invention can be played.As sliding surface, can lift
Go out the periphery sliding surface of piston ring 1 and cylinder liner (not shown) contact slide, but can be arranged in other faces.
In addition, although not being the forming method for constituting the sputtered films of bismuth 3 of the present invention, HVOF (supersonic flame spraying, High
The abbreviation of Velocity Oxygen Fuel) spraying plating is spraying plating using the high speed jet flames of oxygen and fuel.It is specific and
Speech makes the mixed gas burning of the oxygen and fuel of high pressure, the combustion flame be reduced by nozzle, go out in an atmosphere in the combustion chamber
Existing moment generates gas expansion drastically, becomes ultrasonic injection.Raw material powder after being accelerated by high acceleration energy is several
Composition is not aoxidized or changes, highdensity sputtered films of bismuth 3 is formed on piston ring base material 2.Although the HVOF spraying plating film forming speeds
Quickly, but not temperature is improved, therefore raw material powder hardly happens fusing and carries out spraying plating.Therefore, as raw material powder, make
With small subparticle.
The thickness of sputtered films of bismuth 3 is not particularly limited, but is preferably, for example, 200 μm or more, in 600 μm or less of range.It is logical
Crossing has these thickness ranges, can play the distinctive effect of the present invention.
The void content of sputtered films of bismuth 3 is not particularly limited, and is preferably, for example, 5% or less in terms of area %.In addition, from based on spray
From the viewpoint of the compactness of plated film 3 and the wear resistance of Oil keeping, more preferable void content is 4% or less.In addition, void content
Lower limit is not particularly limited, but can for example have 0.5%.The measurement of void content can for example be divided by image analysis software
Analysis.
(application examples)
As application examples, metallized surface layer (not shown) can be arbitrarily arranged on sputtered films of bismuth 3.Metallized surface layer does not have
It is particularly limited to, can enumerate such as the layer containing Al, Fe, Cu.Metallized surface layer can also be with further reduction cooperation pair
As it is aggressive, so that initial fitting property is configured for the purpose of improving etc..This metallized surface layer can be by same with sputtered films of bismuth 3
Plasma spraying or arc spraying, gas spraying plating etc. be formed on sputtered films of bismuth 3.
[manufacturing method]
The manufacturing method of the piston ring 1 of the present invention is that have as feature on at least sliding surface of piston ring base material 2
The manufacturing method of the piston ring of sputtered films of bismuth 3, to Mo powder, Ni bases self-fluxing alloyed powder, Co alloy powders and/or Cr3C2Powder
Mixed-powder composition carry out plasma spraying, form sputtered films of bismuth 3 in the periphery sliding surface of piston ring base material 2.By this
Manufacturing method especially illustrates to be described in detail in column, therefore on the column that illustrates of above-mentioned piston ring to the formation of sputtered films of bismuth 3
The description thereof will be omitted herein.For raw material powder, arbitrary above-mentioned granulation can be used to be sintered powder.It should be noted that
In the application, the substance for constituting raw material powder is properly termed as " powder ", and the substance for constituting sputtered films of bismuth is properly termed as " particle ".
[embodiment]
Embodiment and comparative example are enumerated, present invention be described in more detail.
[embodiment 1]
Coordinate the Mo powder (45 mass %) that average grain diameter is 31 μm, the NiCr self-melting alloy powder that average grain diameter is 43 μm
Last (25 mass %) and to Cr3C2Powder (22.5 mass %) and NiCr powder (7.5 mass %) are granulated and are averaged
The Cr that grain size is 36 μm3C2/ NiCr is granulated sintering powder to adjust raw material powder.Table 1 is the use level of raw material powder.At this point,
By Mo powder, NiCr self-fluxing alloyed powders, Cr3C2When the content ratio that/NiCr is granulated sintering powder is set as 100 mass %,
NiCr self-fluxing alloyed powders are 25 mass %, Cr3C2It is 30 mass % (Cr that/NiCr, which is granulated sintering powder,3C2Powder：22.5 matter
% is measured, NiCr powder is 7.5 mass %), 45 mass % of surplus are Mo powder.In addition, NiCr self-fluxing alloyed powders at
It is Ni to be grouped as：70 mass %, Cr：17 mass %, B：3.5 mass %, Si：4 mass %, Fe：4 mass %, surplus：It can not keep away
The impurity exempted from.In addition, Cr3C2Powder is Cr at being grouped as：86 mass %, C：13 mass %, surplus：Inevitable impurity.
In addition, Cr3C2Powder is Ni at being grouped as：78 mass %, Cr：20 mass %, surplus：Inevitable impurity.At being grouped as
Analysis be the value quantitatively obtained using backscattering measurement device (Co., Ltd. NHVcorporation manufactures), be averaged
The D that grain size is measured using particle size distribution analyzer (Nikkiso Company Limited's manufacture, MICROTRAC HRA)50's
Value indicates.
Using the raw material powder, plasma spraying is carried out under the following conditions, in the piston ring formed by boron cast iron
The sputtered films of bismuth 3 of 300 μm of thickness is formed on the sliding surface of base material 2.Plasma spraying uses Sulzer Metco Co. Ltd. systems
The 9MB plasma spraying rifles made carry out, and spraying plating is carried out with 60~70V of voltage, electric current 500A.
The sputtered films of bismuth 3 of gained it is same as described above at being grouped as, use (HighVoltage plants of backscattering measurement device
Formula commercial firm manufactures) it is quantified, Mo identical as the composition of the raw material powder as raw material：45 mass %, NiCr self-fluxing natures are closed
Gold：25 mass %, Cr3C2：22.5 mass %, NiCr：7.5 mass %.In addition, the content A of NiCr self-melting alloy particles and
The ratio (A/B) of the content B of NiCr particles is with mass ratio for 3.3.
[embodiment 2]
In addition to changing raw material powder, the sputtered films of bismuth 3 of embodiment 2 is formed similarly to Example 1.The ingredient of sputtered films of bismuth 3
Form also identical as the composition of following raw material powders, Mo：50 mass %, NiCr self-melting alloy：30 mass %, Co alloys：20
Quality %.
Raw material powder be coordinate the Mo powder (50 mass %) that average grain diameter be 31 μm, NiCr that average grain diameter is 43 μm oneself
The powder of fusibleness alloy powder (30 mass %), the Co alloy powders (20 mass %) that average grain diameter is 31 μm, it is shown in table 1.This
When, Mo powder and the content ratio of NiCr self-fluxing alloyed powders and Co alloy powders are set as to each powder when 100 mass %
Content ratio it is identical as above-mentioned powder constituent.In addition, NiCr self-fluxing alloyed powders is same as Example 1 at being grouped as,
Co alloy powders are Co at being grouped as：49.8 mass %, Mo：28 mass %, Cr：18 mass %, Si：3.4 mass %, it is remaining
Amount：Inevitable impurity.
[embodiment 3]
In addition to change raw material powder as shown in table 1, the sputtered films of bismuth 3 of embodiment 3 is formed similarly to Example 1.Sputtered films of bismuth 3
It is also identical as the composition of the raw material powder of table 1 at being grouped as.In addition, in the embodiment 3, as NiCr self-melting alloy powder
End is 43 μm using average grain diameter, Ni：70 mass %, Cr：17 mass %, B：3 mass %, Si：4 mass %, Mo：2 matter
Measure %, Cu：3 mass %, surplus：Inevitable impurity it is different at the powder this point and embodiment 1 that are grouped as, except this with
Outer all same.
[embodiment 4~6]
In addition to change raw material powder as shown in table 1, the sputtered films of bismuth 3 of embodiment 4~6 is formed similarly to Example 1.Spraying plating
Film 3 it is also identical as the composition of the raw material powder of table 1 at being grouped as.In addition, the NiCr self-melting alloy powder of the embodiment 4~6
End is same as Example 1.
[comparative example 1]
In addition to changing raw material powder, the sputtered films of bismuth 3 of comparative example 1 is formed similarly to Example 1.Sputtered films of bismuth 3 at grouping
At, Mo identical as the composition of following raw material powders：33 mass %, NiCr alloys：17 mass %, Cr3C2：50 mass %.
Raw material powder is to coordinate the Mo powder (33 mass %) that average grain diameter is 31 μm, the NiCr powder that average grain diameter is 21 μm
Last (17 mass %), the Cr that average grain diameter is 21 μm3C2The mixed-powder of powder (50 mass %), it is shown in table 1.In addition, NiCr powder
End and Cr3C2Powder it is same as Example 1 at being grouped as.
[comparative example 2]
In addition to changing raw material powder, the sputtered films of bismuth 3 of comparative example 2 is formed similarly to Example 1.The ingredient of sputtered films of bismuth 3
Form also identical as the composition of following raw material powders, Mo：50 mass %, NiCr alloys：15 mass %, Cr3C2：35 mass %.
Raw material powder is to coordinate the Mo powder (50 mass %) that average grain diameter is 31 μm, the NiCr powder that average grain diameter is 22 μm
Last (15 mass %), the Cr that average grain diameter is 13 μm3C2The mixed-powder of powder (35 mass %), it is shown in table 1.In addition, NiCr powder
End and Cr3C2Powder it is same as Example 1 at being grouped as.
[comparative example 3,4]
In addition to change raw material powder as shown in table 1, the sputtered films of bismuth 3 of comparative example 3,4 is formed similarly to Example 1.Spraying plating
Film 3 it is also identical as the composition of the raw material powder of table 1 at being grouped as.In addition, the NiCr self-fluxing alloyed powders of the comparative example 3,4
It is same as Example 1.
Table 1
| Mo | NiCr self-melting alloy | Cr3C2 | NiCr | Co | |
| Embodiment 1 | 45 | 25 | 22.5 | 7.5 | - |
| Embodiment 2 | 50 | 30 | - | - | 20 |
| Embodiment 3 | 50 | 25 | 18.8 | 6.2 | - |
| Embodiment 4 | 40 | 35 | 19 | 6 | - |
| Embodiment 5 | 55 | 24 | 16 | 5 | - |
| Embodiment 6 | 45 | 20 | 28 | 7 | - |
| Comparative example 1 | 33 | - | 50 | 17 | - |
| Comparative example 2 | 50 | - | 35 | 15 | - |
| Comparative example 3 | 50 | - | 20 | 30 | - |
| Comparative example 4 | 70 | - | 20 | 10 | - |
(unit：Quality %)
[assay method and measurement result]
(wear resistance index and cooperation subject material wear resistance index)
Wear resistance index and cooperation subject material wear resistance index are measured by wear test.Wear test makes
With high load type abrasion tester 6 shown in Fig. 3, using identical as the piston ring obtained in Examples 1 to 6 and comparative example 1~4
Under conditions of obtained fixinig plate i.e. material to be tested 7, make material to be tested 7 (fixinig plate) and revolving fragment that object material 8 be coordinated to contact,
Apply load P to carry out.Here material to be tested 7 sells (φ 5mm, 58.9mm by three formed by flake graphite cast iron2) and it is outer
The integral type of disc of diameter 40mm, disk outer diameter are 40mm, and thickness includes that pin is 12mm inside.In addition, cooperation subject material 8
(revolving fragment) is the boron cast iron of outer diameter 40mm, thickness 12mm.Wear test condition is in lubricating oil：The oil product of suitable bobbin oil, oil
Temperature：125 DEG C, peripheral speed：1.65m/ seconds (1050rpm), interface pressure：76.4MPa test period：Under conditions of 8 hours
It carries out.
Wear resistance and cooperation subject material wear resistance, to be equivalent to each for examination of Examples 1 to 6 and comparative example 2~4
The wear extent of material is compared with the form that the wear extent of the material to be tested corresponding to comparative example 1 compares, as wear-resistant
Sex index.Therefore, the wear resistance index of each material to be tested is more less than 100, indicates that wear extent is got over for comparative example 1
It is small.Table 2 indicates result.
(dhering strength)
The measurement of closing force will be formed with the end face and not of the cylinder test piece of sputtered films of bismuth 3 on the basis of JIS H 8667
The end face for forming the cylinder test piece of sputtered films of bismuth 3 is integrated with heat-curing resin bonding, and the stretching of the both ends of this tin is tried
The upper and lower scroll chuck for testing machine is fixed, and carries out tension test.For tension test, tensile speed is set as 1mm/ minutes, it is right
Sputtered films of bismuth 3 from the interface peel of boron cast iron when or load when interlayer is peeling-off in sputtered films of bismuth 3 be measured, seek the load
Divided by the value obtained by the area of end face of cylinder.The value of the sputtered films of bismuth 3 of comparative example 1 is set as 100 (benchmark), to being equivalent to embodiment
1~6 and the closing force of each experiment Try material of comparative example 2~4 carry out relative evaluation, and as closing force exponential representation.Closing force
Index is bigger, and closing force is more excellent.In addition, the stripping at the interface with curable resin or the interlayer in curable resin layer
Stripping is excluded from evaluation.Table 2 indicates its result.
(evaluation)
As shown in table 2, the sputtered films of bismuth of Examples 1 to 6 is confirmed in wear resistance index and cooperation object material wear resistance
It is excellent compared with comparative example 1 in terms of index and closing force.
Table 2
[reference experiment 1]
It is known：By using the higher Ni bases self-melting alloy of hardness compared with NiCr alloys, can reduce Mo particles and
Cr3C2The difference of hardness of particle also uses Cr in addition, other than using Ni base self-melting alloy3C2/ NiCr is granulated agglomerated powder
End, it is believed that the Cr for preventing these difference of hardness from bringing3C2Particle falls off, and can inhibit the attack to cylinder liner.
Claims (6)
1. a kind of piston ring, wherein
Sputtered films of bismuth is provided on at least sliding surface of piston ring base material, there is the sputtered films of bismuth Mo particles, Ni base self-fluxing natures to close
Gold particle, and there is Co alloy particles and/or Cr3C2Particle.
2. piston ring as described in claim 1, wherein
By the Mo particles, the Ni bases self-melting alloy particle and the Co alloy particles and Cr3C2The total of particle contains
When ratio is set as 100 mass %, the Ni bases self-melting alloy particle more than 20 mass % in the range of 40 mass % or less,
The Co alloy particles and Cr3C2For the total of particle more than 15 mass % in the range of 30 mass % or less, surplus is Mo
Son.
3. piston ring as claimed in claim 1 or 2, the sputtered films of bismuth also includes NiCr particles.
4. piston ring according to any one of claims 1 to 3, wherein
The ratio (A/B) of the content A of the Ni bases self-melting alloy particle and the content B of the NiCr particles is by quality ratio
More than 1.5.
5. piston ring as described in claim 3 or 4, wherein
In the case where including the NiCr particles, including the NiCr particles and the Cr3C2The granules structure of particle.
6. a kind of manufacturing method of piston ring comprising：
To Mo powder, Ni bases self-fluxing alloyed powder and Co alloy powders and/or Cr3C2The mixed-powder composition of powder into
Row plasma carries out spraying plating, and sputtered films of bismuth is formed on the periphery sliding surface of piston ring base material.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004035852A1 (en) * | 2002-10-15 | 2004-04-29 | Kabushiki Kaisha Riken | Piston ring and thermal sprayed coating for use therein, and method for manufacture thereof |
| CN102325918A (en) * | 2009-02-26 | 2012-01-18 | 日本活塞环株式会社 | Piston ring |
| CN102345084A (en) * | 2010-07-29 | 2012-02-08 | 日本活塞环株式会社 | Piston ring |
| CN104838183A (en) * | 2012-12-11 | 2015-08-12 | 株式会社理研 | Piston ring sprayed coating, piston ring, and method for producing piston ring sprayed coating |
| CN105648382A (en) * | 2014-11-28 | 2016-06-08 | 日本活塞环株式会社 | Piston ring and manufacturing method thereof |
| CN106255774A (en) * | 2014-05-08 | 2016-12-21 | 株式会社理研 | Sliding component and piston ring |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2559283B2 (en) * | 1990-03-08 | 1996-12-04 | 帝国ピストンリング株式会社 | piston ring |
| JP4790135B2 (en) * | 2001-02-28 | 2011-10-12 | 日本ピストンリング株式会社 | Wear-resistant sliding member |
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- 2018-03-15 JP JP2018048455A patent/JP6985961B2/en active Active
- 2018-03-26 KR KR1020180034599A patent/KR102080540B1/en active IP Right Grant
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004035852A1 (en) * | 2002-10-15 | 2004-04-29 | Kabushiki Kaisha Riken | Piston ring and thermal sprayed coating for use therein, and method for manufacture thereof |
| CN102325918A (en) * | 2009-02-26 | 2012-01-18 | 日本活塞环株式会社 | Piston ring |
| CN102345084A (en) * | 2010-07-29 | 2012-02-08 | 日本活塞环株式会社 | Piston ring |
| CN104838183A (en) * | 2012-12-11 | 2015-08-12 | 株式会社理研 | Piston ring sprayed coating, piston ring, and method for producing piston ring sprayed coating |
| CN106255774A (en) * | 2014-05-08 | 2016-12-21 | 株式会社理研 | Sliding component and piston ring |
| CN105648382A (en) * | 2014-11-28 | 2016-06-08 | 日本活塞环株式会社 | Piston ring and manufacturing method thereof |
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| JP2018165402A (en) | 2018-10-25 |
| DK201870188A1 (en) | 2018-11-29 |
| KR20180109732A (en) | 2018-10-08 |
| KR102080540B1 (en) | 2020-02-24 |
| DK180330B1 (en) | 2020-11-25 |
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