CN116732477A - Sliding member having high abrasion-resistant coating film - Google Patents
Sliding member having high abrasion-resistant coating film Download PDFInfo
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- CN116732477A CN116732477A CN202211208524.0A CN202211208524A CN116732477A CN 116732477 A CN116732477 A CN 116732477A CN 202211208524 A CN202211208524 A CN 202211208524A CN 116732477 A CN116732477 A CN 116732477A
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- hard coating
- sliding member
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- coating film
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- 238000000576 coating method Methods 0.000 title claims abstract description 75
- 239000011248 coating agent Substances 0.000 title claims abstract description 74
- 238000005299 abrasion Methods 0.000 title abstract description 24
- 238000004458 analytical method Methods 0.000 claims abstract description 15
- 238000002485 combustion reaction Methods 0.000 claims abstract description 13
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 238000001887 electron backscatter diffraction Methods 0.000 claims abstract description 5
- 239000013078 crystal Substances 0.000 claims description 29
- 238000009826 distribution Methods 0.000 claims description 6
- 238000002050 diffraction method Methods 0.000 abstract description 3
- 238000005259 measurement Methods 0.000 description 17
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 16
- 239000011651 chromium Substances 0.000 description 14
- 239000007789 gas Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 11
- 239000000523 sample Substances 0.000 description 11
- 230000002093 peripheral effect Effects 0.000 description 8
- 238000007733 ion plating Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000013077 target material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 241000723353 Chrysanthemum Species 0.000 description 2
- 235000007516 Chrysanthemum Nutrition 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 238000010891 electric arc Methods 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- CXOWYMLTGOFURZ-UHFFFAOYSA-N azanylidynechromium Chemical compound [Cr]#N CXOWYMLTGOFURZ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 238000002524 electron diffraction data Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001105 martensitic stainless steel Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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
- 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
- C23C14/34—Sputtering
-
- 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
- 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
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Pistons, Piston Rings, And Cylinders (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The present application provides a sliding member which has excellent sliding characteristics such as abrasion resistance and peeling resistance even in a severe sliding environment of an internal combustion engine. The sliding member of the present application is a sliding member for an internal combustion engine comprising a hard coating film at least on the sliding surface, wherein the hard coating film contains Cr, al, N and C, the plastic deformation work amount measured by a nanoindentation test according to ISO14577-1 using a Vickers indenter under a load of 1000mN is 0.360 [ mu ] J or more and 0.560 [ mu ] J or less, and the area ratio of the black portion in the binary image of the inverse polar image orientation map obtained by EBSD (electron back scattering diffraction method: electron BackScatterDiffraction Pattern) analysis is 34.0% or more.
Description
Technical Field
The present application relates to a sliding member used in a severe sliding environment of an internal combustion engine such as an automobile engine, and having a coating film with high abrasion resistance on a sliding surface.
Background
Conventionally, for a sliding surface of a sliding member such as a piston ring used in a severe sliding environment of an internal combustion engine such as an automobile engine, a hard Cr coating such as Cr plating or CrN has been used to improve sliding characteristics such as abrasion resistance, scratch resistance, and peeling resistance.
In recent years, in order to cope with the high output of an engine and environmental restrictions, there has been a tendency that the load on the surface of a sliding member such as a piston ring is increased by combining several factors such as a high combustion temperature, an increase in cylinder internal pressure, a direct injection, a reduction in viscosity of lubricating oil, and the use of bioethanol fuel. Therefore, abrasion of the hard Cr coating film covering the surface of the sliding member is increased, and problems such as peeling and cracking occur.
In order to solve such a problem, a CrAlN hard coating film has been proposed which has a crystal structure containing at least Cr and Al as metal elements and at least N as a nonmetallic element, and in which the ratio of constituent elements in the coating film is defined to be a predetermined ratio, and the ratio of the micro vickers hardness to the press-in elastic modulus including poisson ratio is set to 0.05 or more, thereby improving abrasion resistance, crack resistance, and peeling resistance (see patent document 1).
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2017-057896
However, in recent internal combustion engines requiring further higher output and lower oil consumption, sliding members such as piston rings are placed in a more severe sliding environment, and further improvement in sliding characteristics such as abrasion resistance is required for a coating film coated on the sliding surface. The present application provides a sliding member which has excellent sliding characteristics such as abrasion resistance and peeling resistance even in a severe sliding environment of an internal combustion engine.
Disclosure of Invention
The present inventors have made studies to solve the above problems, and have found that the above problems can be solved by further adding C to a conventional CrAlN film to achieve grain refinement, and controlling the work amount of plastic deformation measured by a nanoindentation test and the area ratio of black parts in a binary image of an inverse polar diagram alignment chart (IPF Map) obtained by EBSD analysis to a specific range.
The present application provides a sliding member for an internal combustion engine, comprising a hard coating film at least on a sliding surface, wherein the hard coating film contains Cr, al, N and C, the plastic deformation work amount measured by a nanoindentation test according to ISO14577-1 using a Vickers indenter under a load of 1000mN is 0.360 [ mu ] J or more and 0.560 [ mu ] J or less, and the area ratio of a black part in a binary image of an inverse polar image orientation map obtained by EBSD (electron back scattering diffraction method: electron BackScatter Diffraction Pattern) analysis is 34.0% or more.
The hard coating preferably contains 0.3 to 2.0mass% of C, preferably 41.0 to 47.0mass% of Cr, and preferably 20.0 to 24.0mass% of Al.
Further, in the hard coating, the ratio of crystal grains of 1.0 μm or less is preferably 100% and the ratio of crystal grains of 0.5 μm or less is preferably 84.0% or more in the distribution of crystal grain diameters measured by the EBSD analysis.
Further, the drop area ratio of the hard coating is preferably 0.5% or less.
Further, it is preferable that the sliding member is a piston ring.
Effects of the application
According to the present application, a sliding member having excellent sliding characteristics such as wear resistance and peeling resistance can be provided even in a severe sliding environment of an internal combustion engine.
Drawings
Fig. 1 is a schematic cross-sectional view of a piston ring coated with a hard coating film as an embodiment of the present application.
Fig. 2 is a schematic view of an apparatus for depositing a hard coating on a piston ring by ion plating.
FIG. 3 is a binary image of an orientation chart of an inverse pole figure (figure substitute photograph) of a hard coating film obtained in examples and obtained by EBSD analysis
Fig. 4 is a graph showing the distribution of crystal particle diameters of the hard coating film of example 8.
Description of the reference numerals
10: piston rings; 11: a piston ring base material; 12: a hard coating; 20: a hard coating forming device; 21: a vacuum chamber; 22: a gas introduction pipe; 23: piping in a vacuum exhaust system; 24: a cathode; 25: an anode; 26: a control magnet; 27: a target material.
Detailed Description
The following describes specific embodiments, but each embodiment is described as an example of the present application, and does not necessarily specify the claimed application, and all of the features described in the embodiments are not necessarily required for solving the problems of the present application.
The terms "XX or more and YY or less" and "XX to YY" in the numerical ranges are meant to include the numerical ranges having the lower and upper limits as the endpoints unless otherwise specified. When numerical ranges are described in stages, the upper limit and the lower limit of each numerical range may be arbitrarily combined.
An embodiment of the present application is a sliding member for an internal combustion engine, which has a hard coating on at least a sliding surface. As a sliding member used in an internal combustion engine, a piston ring, a cylinder liner, a camshaft, and the like are exemplified, and a typical example using a piston ring as a sliding member will be described below.
The inventors of the present application have found that the above problems can be solved by optimizing the grain refinement and the solid solution strengthening and the film toughness by employing a hard film containing Cr, al, N, and C in a sliding member for an internal combustion engine having a hard film at least on the sliding surface, and further controlling the amount of plastic deformation work measured in a nanoindentation test of the hard film and the area ratio of black portions in a binary image of an inverse polar image obtained by EBSD analysis within specific ranges.
The hard coating film of the sliding member according to the present embodiment contains at least Cr and Al as metal elements and at least N and C as nonmetallic elements.
The composition of the hard coating can be analyzed by EPMA (electron probe microanalyzer: electron Probe MicroAnalyzer).
The content of C in the hard coating is preferably 0.3 to 2.0mass%, more preferably 0.5 to 1.1mass%. The content of C in the above range contributes to the refinement of crystal grains, and the film is dense, thereby further improving the abrasion resistance of the hard film.
The content of Cr in the hard coating is preferably 41.0 to 47.0mass%, more preferably 44.0 to 46.5mass%.
The content of Al in the hard coating is preferably 20.0 to 24.0mass%, more preferably 21.0 to 22.9mass%. When the content of Al is within the above range, the grain refinement and solid solution strengthening can be facilitated, the young's modulus of the film can be set to an appropriate value, and the abrasion resistance and adhesion of the hard film can be further improved.
The content of N in the hard coating is preferably 30.5 to 35.0mass%, more preferably 31.1 to 33.6mass%.
The plastic deformation work amount is the work amount consumed by plastic deformation, which is the work amount consumed by the deformation of the film by the pressure head pressed from the surface of the film in the nano indentation test, and the film is kept unchanged even if the pressure head is unloaded.
The hard coating film of the sliding member according to the present embodiment has a plastic deformation work amount of 0.360 μj to 0.560 μj, preferably 0.367 μj to 0.555 μj, measured by nanoindentation according to ISO14577-1 using a vickers indenter and a load of 1000 mN. When the amount of plastic deformation work is within the above range, both the adhesion and abrasion resistance of the hard coating can be achieved.
The hard coating film included in the sliding member of the present embodiment was obtained by EBSD (electron back scattering diffraction method: electron BackScatt)er Diffraction Pattern) the area ratio of the black part in the binarized image of the obtained inverse polar image alignment chart is 34.0% or more. The maximum analysis area of the EBSD to the crystal information is several microns 2 And compared with the extremely narrow TEM electron diffraction, the method has the characteristics of wide measurement range and capability of acquiring macroscopic crystal information. In the inverse polar plot, the fine crystal grains of the crystal (crystal grain size of 0.1 μm or less), pits (depressions) on the crystal surface, and amorphous particles were not discriminated by EBSD analysis and were observed as black portions. The area ratio of the black portion is the area ratio of the black portion when binarizing the inverse polar image alignment chart.
The area ratio of the black portion is preferably 35.6% or more. The upper limit of the area ratio of the black portion is not particularly limited, but is preferably 90% or less, more preferably 80% or less, and further preferably 70% or less.
In the hard coating film included in the sliding member according to the present embodiment, the ratio of crystal grains of 0.5 μm or less is preferably 84.0% or more, more preferably 84.7% or more in the distribution of crystal grain size measured by EBSD analysis. The upper limit of the ratio of the crystal grains of 0.5 μm or less is not particularly limited, and may be 100% or less, 99% or less, or 95% or less. When the crystal grain size is within the above range, a dense hard coating film is formed, and even if cracks are generated, the cracks are not easily connected, so that the peeling resistance is improved.
In arc ion plating, when a cathode material is evaporated by vacuum arc discharge, large molten particles called droplets (droplets) are generated, and therefore, it is a problem to suppress adhesion of the droplets to a film-forming object and a film being formed on the object as much as possible. When the droplets are excessively adhered, the surface of the film becomes a rough surface, resulting in a decrease in film properties such as sliding properties and abrasion resistance of the film.
The droplet area ratio is the area ratio of the white portion when the sliding member having the hard coating film is cut and the SEM image of the coating film portion is binarized.
The hard coating film of the sliding member according to the present embodiment preferably has a droplet area ratio of 0.5% or less, more preferably 0.4% or less. The lower limit of the droplet area ratio is not particularly limited, and may be 0%. When the droplet area ratio is in the above range, the film density is increased, and thus the film strength is improved, and further the abrasion resistance is improved.
The hard coating of the sliding member according to the present embodiment preferably has a micro vickers hardness of 1100HV or more and 1700HV or less, more preferably 1500HV or less. The film has high toughness by not excessively high micro Vickers hardness, and thus the adhesion is improved.
The Young's modulus of the hard coating film of the sliding member according to the present embodiment is preferably 315GPa or less, and more preferably 280GPa or less. The lower limit of Young's modulus is not particularly limited, but is usually 250GPa or more. Since the Young's modulus is in the above range, the coating film has high toughness, and the adhesion is improved.
The amount of plastic deformation work measured in the nanoindentation test of the hard coating, the area ratio of the black part in the binary image of the polar-inverted chart alignment chart obtained by EBSD analysis, and the droplet area ratio can be set to desired values by adjusting the method for producing the hard coating. More specifically, in the case of forming a hard coating by an ion plating method described below, there may be mentioned: (alloy of Cr50at%, al50 at%) was used as target; introducing methane gas, and setting the partial pressure ratio of the methane gas to 2-10 when the total gas flow rate of the nitrogen gas and the methane gas is 100; setting the pressure in the cavity to be more than 2.5 Pa; setting the arc current value to 70A-200A; setting the bias voltage to be 0V-50V; setting the target consumption volume per unit time to 2000mm 3 Over/h and 2100mm 3 And/or less.
The structure of the sliding member according to the present embodiment will be described in more detail below with reference to the drawings.
Fig. 1 is a cross-sectional view of a part of a piston ring as an example of the present embodiment. The piston ring 10 has hard coating 12 on its upper and lower surfaces and sliding surfaces (left side surfaces in the drawing). In the present embodiment, the piston ring 10 has the hard coating 12 on at least the sliding surface, but may have hard coatings on other surfaces, such as the upper and lower surface outer peripheral surfaces. The thickness of the hard coating on the sliding surface is not particularly limited, and is usually 3 μm or more, but may be 5 μm or more, and is usually 50 μm or less, but may be 30 μm or less. The piston ring is one form of a sliding member, and in addition to this, a piston, a bearing, a washer, and a valve lifter may be used as the sliding member.
In the case of a piston ring, the material of the base material 11 of the piston ring 10 is not particularly limited as long as it is a material that has been conventionally used as a base material of a piston ring. For example, stainless steel, etc. are preferably used, and specifically, martensitic stainless steel, silicochromed steel, etc. are preferably used.
The hard coating may be formed directly on the piston ring base material, or may be formed by a Cr plating coating, a chromium nitride coating, a titanium nitride coating, or the like. In addition, in the case where the base material is stainless steel, nitriding treatment may not be performed on the base material.
The hard coating can be formed by physical vapor deposition such as ion plating or sputtering. An example of forming a hard coating by ion plating will be described with reference to the drawings.
Fig. 2 is a schematic cross-sectional view showing an example of the apparatus 20 for forming a hard coating by ion plating. The vacuum chamber 21 is connected to a gas introduction pipe 22 and a vacuum exhaust system pipe 23, and the temperature inside the vacuum chamber 21 can be controlled by a heater (not shown). The apparatus 20 includes a cathode 24 and an anode 25, and a control magnet 26 is disposed at a distal end portion of the cathode 24 (right end portion of the cathode in the drawing), and an alloy target material 27 of Cr50at% and Al50at% is plasmatized and ionized by arc discharge.
A rotary table (not shown) in which piston rings are provided in a vacuum chamber 21 ionizes chromium and aluminum as target materials while introducing nitrogen gas and methane gas from a gas introduction pipe 22, and deposits the ionized chromium and aluminum on the piston ring surfaces. The operating conditions of the apparatus at this time can be such that the arc current is 70A to 200A, the bias voltage is 0V to 50V, the intra-cavity pressure is 2.5Pa or more, and the target consumption volume per unit time is 2000mm 3 To/hUpper and 2100mm 3 And/h or less, the heating temperature by the heater is 300-400 ℃, and the methane gas partial pressure ratio is 2-10 when the total gas flow rate of nitrogen gas and methane gas is 100.
The nitrogen content and the carbon content in the hard coating can be controlled by the internal pressure of the introduced gas and the partial pressure of methane gas.
The properties of the hard coating film may be controlled by changing the position and shape of the control magnet disposed around the cathode. For example, by disposing a magnet so as to surround the distal end portion of the cathode, the speed at which each arc spot moves on the cathode surface is increased, and the generated plasma extends to the vicinity of the piston ring, so that the ionization rate is increased, and a more dense hard coating can be easily formed.
Examples (example)
The present application will be described in detail with reference to examples, but the present application is not limited to the examples.
The physical properties of the hard coating were measured by the following apparatus.
< coating composition >
The measurement of the coating composition was performed by EPMA. EPMA-1720HT manufactured by Shimadzu corporation was used for the measurement of EPMA. The acceleration voltage is 15kV, the irradiation current is 50nA, the electron beam diameter is 100 μm, cr is pure Cr, al is Al 2 O 3 Quantitative analysis was performed with BN and C as graphite. The samples were prepared in the same order as the samples used in EBSD. The weight% of the sample was measured by the ratio of the intensity obtained in the standard sample to the intensity of the unknown sample, which was set to 100%. The weight% of each atom was calculated by normalizing the elements to be measured so that the total of the obtained weight% becomes 100%.
< Plastic deformation work amount >)
For the measurement of the work of plastic deformation of the hard coating, a Fischer Instruments nanoindentation tester, model HM-2000, was used. The measurement was performed by using a vickers indenter according to the measurement method of ISO14577-1, using a press-in load of 1000mN, and setting the time until the maximum press-in load to 30s (seconds). For the sample, a piston ring was used in which the outer peripheral surface of the piston ring, which was a measurement surface, was polished with sandpaper and diamond slurry after the piston ring, which was coated with a hard coating on the outer peripheral surface, was cut and resin-embedded. And obtaining the plastic deformation work load according to the load-pressing depth curve.
< EBSD analysis >)
In the measurement of the area ratio of the black portion and the crystal grain size in the binarized image of the polar plot obtained by EBSD analysis, FE-SEM (JSM-7100F manufactured by Japanese electronics Co., ltd.) and EBSD analysis software (Digiview IV manufactured by TSL) and image processing software (NS 2K-LT manufactured by Nano System Co., ltd.) were used. SEM images were measured at an acceleration voltage of 15.0kV, a measurement interval of 0.02 μm, and a measurement area of 20X 20. Mu.m. In the sample, a piston ring having a hard coating film on the outer peripheral surface thereof was cut and used, the outer peripheral sliding surface thereof was polished with a diamond slurry, then ultrasonically cleaned, ar ion milling was performed for the purpose of removing polishing marks, and then an electron beam was irradiated from the outer peripheral surface side to measure. An electron beam was irradiated onto the tilted sample, and a reflected electron diffraction pattern (chrysanthemum line) was measured from the scattered electron beam. The chrysanthemum pool line was analyzed to produce an antipodal map along each crystal orientation. An inverse polar diagram orientation map in a measurement region is created by collecting successive measurement points in an orientation difference of 5 DEG or less for each crystal grain as one crystal grain by an inverse polar diagram. As for the area ratio of the black portion, the image of the inverse polar image orientation map is binarized by image processing software. The threshold 80 was binarized, the crystal portion was set to be a white portion, the amorphous portion was set to be a black portion, and the area ratio of the black portion to the entire field of view was calculated. In the measurement of the crystal grain size, the length of each crystal grain was measured by using an inverse polar plot alignment chart, and the area ratio was calculated over the entire measurement region in the 0.1 μm interval. From the histogram of the crystal grain size distribution produced in the 0.1 μm interval, the ratio (area ratio) of the crystal grain size of 1 μm or less to the entire measurement surface was calculated. The measurement was performed with one sample and one field of view.
< drop area Rate >)
For the measurement of the droplet area ratio, SEM (SU-3500 manufactured by Hitachi high technology Co., ltd.) and image processing software (NS 2K-Ltd., nano System Co., ltd.) were used. In the sample, a piston ring coated with a hard coating on the outer peripheral surface was cut and used, and the sample was photographed at 1000 times from the outer peripheral sliding surface side subjected to surface polishing by grinding or the like. Then, the captured SEM image was binarized by using image processing software at a threshold 180, and the droplet portion was set to be a white portion and the non-droplet portion (film portion) was set to be a black portion. The area ratio of the white portion to the area of the entire visual field was set as the droplet area ratio, and the droplet area ratio was an average value of any three positions of one piston ring.
< examples, comparative examples >
A steel material corresponding to JIS G3651 SWOSC-V was prepared as a piston ring base material and processed into a piston ring shape (. Phi.73.0 mm. Times.1.0 mm in thickness). A hard coating was formed on a piston ring base material processed into a piston ring shape using an apparatus for forming a hard coating by ion plating, schematically shown in fig. 2. The formation of the hard coating was carried out under the conditions shown in table 1 below.
Next, the physical properties of the hard coating film formed were measured. The results are shown in table 2. In the examples, the crystal grain size of 2.0 μm or more was not present. Further, a binarized image of an inverse polar alignment chart obtained by EBSD analysis is shown in fig. 3, and a distribution of crystal particle diameters of the hard coating film of example 8 is shown in fig. 4.
< test of adhesion >)
The adhesion test was evaluated by an opening torsion test using a piston ring. The opening of the piston ring coated with the hard coating was sandwiched and twisted in the vertical direction, and the opening angle between the two openings and the apex of the 180 ° position from the opening when the coating was peeled was measured.
The film having an opening angle of 120 DEG or more and not peeled off is set as adhesion S, the film having 90 DEG or more to less than 120 DEG and peeled off is set as adhesion A, and the film having less than 90 DEG and peeled off is set as adhesion B.
< abrasion resistance test >)
In the abrasion resistance test, a piston ring was placed in an iron cylinder, and the piston ring was slid by compressed air. The contact of the piston ring with the cylinder is set by the tension of the piston ring. As the lubricating oil, a bearing oil having a light oil equivalent viscosity is used, in which hard fine particles are mixed. For the measurement of the abrasion loss, the sectional shape of the sliding surface on the outer periphery of the piston ring was measured by a contact coarser gauge, and the difference between the height before and after the test was used as the abrasion loss of the coating.
The abrasion resistance S is the film with abrasion loss less than 7 μm, the abrasion resistance A is the film with abrasion loss more than 7 μm and less than 10 μm, and the abrasion resistance B is the film with abrasion loss more than 10 μm.
TABLE 1
TABLE 1
| Target composition | Cr∶Al＝50∶50at％ |
| Arc current | 70～200A |
| Bias voltage | 0～50V |
| Intra-cavity pressure | 2.5Pa or more |
| Target consumption volume | 2000～2100mm 3 /h |
| Temperature heated by heater | 300～400℃ |
| Methane gas partial pressure ratio | 2～10 |
TABLE 2
Claims (6)
1. A sliding member for an internal combustion engine having a hard coating on at least a sliding surface,
in the case of the hard coating film described above,
comprises Cr, al, N and C,
the plastic deformation work amount measured by the nanoindentation test according to ISO14577-1 using a Vickers indenter and a load of 1000mN is 0.360 μJ or more and 0.560 μJ or less, and,
the area ratio of the black part in the binarized image of the inverse polar image orientation map obtained by EBSD analysis is 34.0% or more.
2. The sliding member according to claim 1, wherein,
the hard coating contains 0.3 to 2.0mass% of C.
3. The sliding member according to claim 1 or 2, wherein,
the hard coating contains 41.0 to 47.0mass% of Cr and 20.0 to 24.0mass% of Al.
4. The sliding member according to claim 1 or 2, wherein,
the hard coating has a crystal grain size distribution measured by the EBSD analysis, wherein the ratio of crystal grains of 0.5 [ mu ] m or less is 84.0% or more.
5. The sliding member according to claim 1 or 2, wherein,
the drop area ratio of the hard coating is less than 0.5%.
6. The sliding member according to claim 1 or 2, wherein,
the sliding member is a piston ring.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022031768A JP7093899B1 (en) | 2022-03-02 | 2022-03-02 | Sliding member with high wear resistant coating |
| JP2022-031768 | 2022-03-02 |
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| Publication Number | Publication Date |
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| CN116732477A true CN116732477A (en) | 2023-09-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211208524.0A Pending CN116732477A (en) | 2022-03-02 | 2022-09-30 | Sliding member having high abrasion-resistant coating film |
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| CN (1) | CN116732477A (en) |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005326378A (en) | 2004-05-17 | 2005-11-24 | Nsk Ltd | Method of measuring hardness or elastic modulus of thin film |
| JP4650157B2 (en) | 2005-01-12 | 2011-03-16 | マツダ株式会社 | Plating film for sliding part and method for forming the same |
| JP5036232B2 (en) | 2006-07-06 | 2012-09-26 | Ｔｐｒ株式会社 | Piston ring for internal combustion engine |
| JP5470014B2 (en) | 2009-12-04 | 2014-04-16 | 三菱エンジニアリングプラスチックス株式会社 | Resin composition for dielectric and dielectric antenna component |
| DE102012219930A1 (en) | 2012-10-31 | 2014-04-30 | Federal-Mogul Burscheid Gmbh | Sliding element, in particular piston ring, with a coating |
| JP6416066B2 (en) | 2015-09-15 | 2018-10-31 | Ｔｐｒ株式会社 | piston ring |
| JP6533818B2 (en) | 2017-10-20 | 2019-06-19 | 株式会社リケン | Sliding member and piston ring |
| JP7284700B2 (en) | 2019-12-17 | 2023-05-31 | 株式会社リケン | sliding mechanism |
-
2022
- 2022-03-02 JP JP2022031768A patent/JP7093899B1/en active Active
- 2022-09-30 CN CN202211208524.0A patent/CN116732477A/en active Pending
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| JP2023127838A (en) | 2023-09-14 |
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