Sliding member, rolling bearing, and cage
10465750 ยท 2019-11-05
Assignee
Inventors
Cpc classification
F16C2240/60
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
B32B27/322
PERFORMING OPERATIONS; TRANSPORTING
F16C33/4611
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F16C2208/32
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F16C33/206
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F16C2240/06
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F16C2202/04
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F16C2326/10
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F16C33/56
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F16C2202/20
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F16C33/201
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F16C19/463
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F16C9/02
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F16C2240/26
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
International classification
F16C33/20
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F16C33/46
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F16C33/56
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
Abstract
It is an object of the present invention to provide a sliding member, a rolling bearing, and a cage each having a sliding surface excellent in a sliding property thereof even in the presence of lubricating oil and under conditions of a high sliding speed and a high contact pressure. The sliding member is used under an oil lubrication environment and has a sliding layer formed on an iron-based metal material. The sliding layer consists of a foundation layer including heat-resistant resin and a first fluororesin layer both formed on a surface of the iron-based metal material. A second fluororesin layer is formed on a surface of the foundation layer. After the foundation layer and the second fluororesin layer are calcined, the second fluororesin layer is irradiated with radiation rays. The heat-resistant resin does not thermally decompose when the foundation layer and the second fluororesin layer are calcined.
Claims
1. A sliding member which is used under an oil lubrication environment and has a sliding layer formed on an iron-based metal material, wherein said sliding layer is made by forming a foundation layer comprising heat-resistant resin and a first fluororesin on a surface of said iron-based metal material; forming a second fluororesin layer on a surface of said foundation layer; and after said foundation layer and said second fluororesin layer are calcined, irradiating with radiation rays said second fluororesin layer, wherein said heat resistant resin is at least one resin selected from the group consisting of epoxy resin, polyester resin, amide-imide resin, imide resin, ether imide resin, imidazole resin, polyethersulfone resin, polysulfone resin, polyether etherketone resin and silicone resin; said heat-resistant resin does not thermally decompose when said foundation layer and said second fluororesin layer are calcined; and wherein said second fluororesin layer consists of polytetrafluoroetthylene resin; and said second fluororesin layer is irradiated with said radiation rays in a condition in which said second fluororesin layer is crosslinked.
2. A sliding member according to claim 1, wherein as a condition in which said second fluororesin layer is crosslinked, an irradiation temperature is in a range from a temperature lower than the melting point of the second fluororesin layer by 30 C. to a temperature higher than the melting point thereof by 20 C.; and an irradiation dose is more than 250 kGy and not more than 750 kGy.
3. A sliding member according to claim 1, wherein said radiation rays are electron beams.
4. A sliding member according to claim 1, wherein the second fluororesin, as compared with uncrosslinked polytetrafluoroethylene resin, shows a solid .sup.19F Magic Angle Spinning (MAS) Nuclear Magnetic Resonance (NMR) chart where in addition to 82 ppm, 122 ppm, 126 ppm of said uncrosslinked polytetrafluoroethylene resin, at least one chemical shift value ( ppm) selected from among 68 ppm, 70 ppm, 77 ppm, 80 ppm, 109 ppm, 112 ppm, 152 ppm, and 186 ppm appears or a signal intensity of a signal of a chemical shift value appearing at 82 ppm is higher than a signal intensity of said uncrosslinked polytetrafluoroethylene resin.
5. A sliding member according to claim 1, wherein a thickness of said sliding layer is not less than 5 m and less than 40 m.
6. A cage, made of an iron-based metal material, for retaining rolling elements of a rolling bearing, wherein said cage made of said iron-based metal material is formed of a sliding member according to claim 1; and an indentation hardness of a sliding layer irradiated with radiation rays measured in conformity to ISO14577 is 52 to 90 MPa.
7. A cage, made of an iron-based metal material, for retaining rolling elements of a rolling bearing, wherein said cage made of said iron-based metal material is formed of a sliding member according to claim 1; and a melting point of said second fluororesin layer irradiated with radiation rays is 265 to 310 C.
8. A rolling bearing having a cage made of an iron-based metal material according to claim 6.
9. A rolling bearing according to claim 8 which is used as a rolling bearing for a bid end portion of a connecting rod of an engine, a rolling bearing for a small end portion of said connecting rod thereof or a rolling bearing for a crankshaft-supporting shaft.
10. A rolling bearing having a cage made of an iron-based metal material according to claim 7.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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MODE FOR CARRYING OUT THE INVENTION
(12) The sliding member of the present invention has a sliding layer formed on an iron-based metal material. The sliding layer is composed of the foundation layer and a crosslinked fluororesin layer formed on the surface of the foundation layer.
(13) As the iron-based metal material, bearing steel, carburized steel, carbon steel for mechanical structure, cold rolled steel, and hot rolled steel are listed. After the iron-based metal material is processed into the configuration of the sliding member, the iron-based metal material is quenched and tempered to adjust its surface hardness to a predetermined one. In the case of a cage made of the iron-based metal material consisting of chrome-molybdenum steel (SCM415), it is preferable to use the iron-based metal material adjusted to 484 to 595 in its Hv value.
(14) The sliding layer is composed of the foundation layer formed on the surface of the iron-based metal material and the crosslinked fluororesin layer formed on the surface of the foundation layer.
(15) The foundation layer is a mixture layer containing heat-resistant resin and first fluororesin and improves the adhesiveness between the iron-based metal material and the crosslinked fluororesin layer.
(16) The heat-resistant resin does not pyrolytically decompose when the foundation layer and an upper layer film are calcined. That the heat-resistant resin does not pyrolytically decompose means that the heat-resistant resin does not start pyrolytic decomposition at temperatures at which the foundation layer and the upper layer film are calcined and within a period of time in which the foundation layer and the upper layer film are calcined. It is preferable that the heat-resistant resin has a functional group excellent in the adhesiveness between the heat-resistant resin and the iron-based metal material and a functional group which reacts with the first fluororesin in its molecular backbone or at its molecular end.
(17) As the heat-resistant resin, epoxy resin, polyester resin, amide-imide resin, imide resin, ether imide resin, imidazole resin, polyethersulfone resin, polysulfone resin, polyether ether ketone resin, and silicone resin are listed. It is possible to use urethane resin and acrylic resin which prevent fluororesin from contracting in forming the film in combination with the above-described heat-resistant resin.
(18) It is possible to use resin capable of dispersing in a water-based coating solution forming the foundation layer in a particulate form. As the first fluororesin, it is possible to preferably use PTFE particles, tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer (hereinafter referred to as PFA) particles, tetrafluoroethylene-hexafluoropropylene copolymer (hereinafter referred to as FEP) particles, and a mixture of two or more kinds of these first fluororesins.
(19) In addition to the heat-resistant resin and the first fluororesin, a nonionic surface active agent such as polyoxyethylene alkyl ether, an inorganic pigment such as carbon black, an aprotic solar solvent such as N-methyl-2-pyrrolidone which mixes with water arbitrarily, and water serving as a prime solvent are added to the water-based coating solution forming the foundation layer. It is possible to add a defoamer, a desiccant, a thickener, a leveling agent, and a cissing inhibitor to the water-based coating solution forming the foundation layer. As the water-based coating solution forming the foundation layer, primer paint EK series and ED series produced by DAIKIN INDUSTRIES, LTD. are exemplified.
(20) The second fluororesin layer is formed on the surface of the foundation layer and can be crosslinked with radiation rays. Although the first and second fluororesin layers may be identical to each other or different from each other, it is preferable to use the identical fluororesin. As the second fluororesin layer, PTFE, PFA, FEP, ethylene, and a tetrafluoroethylene copolymer (ETFE) are listed. These resins can be used singly or as a mixture. Of these resins, the PTFE excellent in its heat resistance and sliding property is preferable.
(21) The second fluororesin layer is obtained by applying an aqueous dispersion solution in which PTFE resin particles are dispersed to the foundation layer and drying the aqueous dispersion solution. As the aqueous dispersion solution in which the PTFE resin particles are dispersed, polyflon=PTFE enamel produced by DAIKIN INDUSTRIES, LTD. is exemplified.
(22) The method of forming the sliding layer on the surface of the iron-based metal material is described below.
(23) (1) Surface Treatment of Iron-Based Metal Material
(24) It is preferable to adjust the surface roughness (Ra) of the iron-based metal material to 1.0 to 2.0 m in advance by using shot blast or the like before the sliding layer is formed on the iron-based metal material and thereafter immerse the iron-based metal material in an organic solvent such as petroleum benzine to ultrasonically remove grease for five minutes to one hour.
(25) (2) Application of Water-Based Coating Solution Forming Foundation Layer to Iron-Based Metal Material
(26) To improve the dispersibility of an aqueous dispersion solution, before applying the water-based coating solution forming the foundation layer to the iron-based metal material, a ball mill is used to re-disperse the water-based coating solution by rotating the ball mil at 40 rpm for one hour. The re-dispersed water-based coating solution is filtered by using a 100-mesh metallic wire. Thereafter the filtered water-based coating solution is applied to the iron-based metal material by using a spray method.
(27) (3) Drying of Water-Based Coating Solution Forming Foundation Layer
(28) After the water-based coating solution is applied to the iron-based metal material, the water-based coating solution is dried. As a drying condition, it is preferable to dry the water-based coating solution inside a thermostatic bath where temperature was set to 90 C. for about 30 minutes. The thickness of the dried foundation layer is set to 2.5 to 20 m, favorably 5 to 20 m, and more favorably 10 to 15 m. In the case where the thickness of the dried foundation layer is less than 2.5 m, there is a fear that the metal base material is exposed owing to peeling of the film off the metal base material caused by poor adhesiveness of the film to the metal base material and initial wear of the film. In the case where the thickness of the dried foundation layer is not less than 20 m, there is a fear that a lubrication state deteriorates owing to the occurrence of crack during the formation of the film and the peeling of the film off the metal base material during an operation. By setting the thickness of the dried foundation layer to 2.5 to 20 m, it is possible to prevent the metal base material from being exposed by the initial wear of the film and thus the film from peeling off the metal base material for a long time during the operation.
(29) (4) Application of Water-Based Coating Solution Forming Second Fluororesin Layer to Iron-Based Metal Material
(30) To improve the dispersibility of the aqueous dispersion solution, before applying the water-based coating solution forming the second fluororesin layer to the iron-based metal material, the ball mill is used to re-disperse the water-based coating solution by rotating the ball mil at 40 rpm for one hour. The re-dispersed water-based coating solution is filtered by using the 100-mesh metallic wire. Thereafter the filtered water-based coating solution is applied to the foundation layer by using the spray method.
(31) (5) Drying of Water-Based Coating Solution Forming Second Fluororesin Layer
(32) After the water-based coating solution is applied to the foundation layer, the water-based coating solution is dried. As a drying condition, it is preferable to dry the water-based coating solution inside a thermostatic bath where temperature was set to 90 C. for about 30 minutes. The thickness of the dried second fluororesin layer is set to 2.5 to 20 m, favorably 5 to 20 m, and more favorably 10 to 15 m. In the case where the thickness of the dried second fluororesin layer is less than 2.5 m, there is a fear that the metal base material is exposed owing to peeling of the film off the metal base material caused by poor adhesiveness of the film to the metal base material and initial wear of the film. In the case where the thickness of the dried second fluororesin layer is not less than 20 m, there is a fear that a lubrication state deteriorates owing to the generation of crack in forming the film and the peeling of the film off the metal base material in operation. By setting the thickness of the dried second fluororesin layer to 2.5 to 20 m, it is possible to prevent the metal base material from being exposed by the initial wear of the film and thus the film from peeling of the film off the metal base material for a long time during the operation.
(33) As a method of applying the water-based coating solution forming the foundation layer to the iron-based metal material and a method of applying the water-based coating solution forming the second fluororesin layer to the foundation layer, it is possible to use methods such as a dipping method and a brush painting method, provided that the methods are capable of forming the films in addition to the spraying method. The spraying method is preferable because the spraying method is capable of decreasing the surface roughness of the film and the configuration of the films to be formed by the application of the water-based coating solution to a high extent and making the thickness of each layer uniform.
(34) (6) Calcination
(35) After the second fluororesin layer is dried, it is calcined in the air inside a heating furnace at a temperature not less than the melting point of the second fluororesin layer, preferably in a range from (melting point (Tm)+30 C.) to (melting point (Tm)+100 C.) for 5 to 40 minutes. In the case where the first fluororesin layer and the second fluororesin layer are both PTFE, it is preferable to calcine the second fluororesin layer for 30 minutes in the heating furnace set to 380 C.
(36) (7) Crosslinking of Second Fluororesin Layer
(37) The fluororesin layer is crosslinked by irradiating the calcined film at an irradiation temperature in a range from a temperature lower than the melting point of the second fluororesin layer by 30 C. to a temperature higher than the melting point thereof by 20 C. and favorably in a condition where an irradiation dose is more than 250 kGy and not more than 750 kGy. As the radiation rays, it is possible to use particle beams such as rays (particle beam of nucleus of helium-4 discharged from radionuclide which performs a collapse), rays (negative and positive electrons discharged from nucleus), and electron beams (having almost constant kinetic energy; created by accelerating thermal electron); and ionizing radiation rays such as rays (electromagnetic wave having a short wavelength emitted and absorbed by transitions of atomic nucleus and elementary particles between energy levels and by pair annihilation and pair production of elementary particles). Of these radiation rays, the electron beams and the rays are favorable from the standpoint of the crosslinking efficiency and operability thereof. The electron beams are more favorable. The electron beams have advantages that in using the electron beams, it is easy to obtain an electron beam irradiation apparatus, easy to perform an irradiation operation, and possible to adopt continuous irradiation processes.
(38) At irradiation temperatures other than the range from the temperature lower than the melting point of the second fluororesin layer by 30 C. to the temperature higher than the melting point thereof by 20 C., the crosslinking of the fluororesin layer does not fully proceed. Further an increase in the hardness of the fluororesin layer does not fully proceed. To efficiently crosslink the fluororesin layer, as an irradiation atmosphere, it is necessary to lower the oxygen concentration of an irradiation region by means of vacuuming or the injection of an inert gas into the irradiation region. It is preferable to set the range of the oxygen concentration to 0 to 300 ppm. To maintain the oxygen concentration in the above-described concentration range, the inert atmosphere formed by the means of the injection of the nitrogen gas into the irradiation region is preferable from the standpoint of operability and the cost.
(39) In the case where an irradiation dose is not more than 250 kGy, the fluororesin layer is insufficiently crosslinked. Consequently the sliding surface of the sliding layer of the sliding layer wears in a large amount. As a result, there is a case in which the metal base plate may be exposed. In the case where the irradiation dose is not less than 1000 kGy, the crosslinking proceeds more than a necessary extent. Consequently the film has a high hardness and brittles. As a result, there is a case in which the film is liable to be subjected to damage such as peeling thereof off the foundation layer. The upper limit of the irradiation dose is favorably not more than 900 kGy and more favorably not more than 750 kGy.
(40) By crosslinking the fluororesin layer at the irradiation temperature in the range from the temperature lower than the melting point of the second fluororesin layer by 30 C. to the temperature higher than the melting point thereof by 20 C. and at the irradiation dose more than 250 kGy and not more than 750 kGy, it is possible to adjust the surface hardness of the sliding layer indicated by an indentation hardness to 52 to 90 MPa, preferably 60 to 85 MPa. In the case where the indentation hardness is lower than 52 MPa, the wear amount of the sliding surface of the sliding layer is large. Consequently there is a case in which the metal base material may be exposed. In the case where the indentation hardness is higher than 90 MPa, the film has a high hardness and brittles. Consequently there is a case in which the film is liable to be subjected to damage such as peeling thereof off the foundation layer.
(41) By crosslinking the fluororesin layer at the irradiation temperature in the range from the temperature lower than the melting point of the second fluororesin layer by 30 C. to the temperature higher than the melting point thereof by 20 C. and at the irradiation dose more than 250 kGy and not more than 750 kGy, it is possible to lower the melting point of the second fluororesin layer down to 265 to 310 C., preferably 272 to 301 C. In the case where the melting point of the second fluororesin layer is higher than 310 C., the wear amount of the sliding surface of the sliding layer is large. Consequently there is a case in which the metal base material is exposed. In the case where the melting point of the second fluororesin layer is lower than 265 C., the film has a high hardness and brittles. Consequently there is a case in which the film is liable to be subjected to damage such as peeling thereof off the foundation layer.
(42) The thickness of the sliding layer obtained by carrying out the above-described method is not less than 5 m and less than 40 m, preferably not less than 15 m and less than 30 m. In the case where the thickness of the sliding layer is less than 5 m, there is a fear that the metal base material is exposed owing to peeling of the film off the foundation layer caused by poor adhesiveness of the film to the foundation layer and owing to initial wear of the film. In the case where the thickness of the sliding layer is not less than 40 m, there is a fear that a lubrication state deteriorates owing to the occurrence of crack in forming the film and owing to the peeling of the film off the foundation layer in operation. By setting the thickness of the sliding layer to not less than 5 m and less than 40 m, it is possible to prevent the metal base material from being exposed owing to the initial wear of the film and the peeling of the film off the foundation layer in operation.
(43) To evaluate the wear resistance of the sliding layer obtained by carrying out the above-described method in the air, the wear amount thereof was measured in a Sabang type friction wear test. Test conditions of specimens and mating members are shown below.
(44) (1) Preparation of Specimen
(45) Specimen: A sliding layer was formed on a metal flat plate made of SPCC whose size was 30 mm30 mm2 mm (thickness). As a foundation layer, primer paint (model number: EK-1909S21R) produced by DAIKIN INDUSTRIES, LTD. was used. As a second fluororesin layer, top paint (model number: EK-3700C21R) produced by DAIKIN INDUSTRIES, LTD. was used. Both paints were dried in a thermostatic bath where temperature was set to 90 C. for 30 minutes and calcined in a heating furnace where temperature was set to 380 C. for 30 minutes.
(46) Thereafter the specimens were irradiated with electron beams from a sliding layer side in the following conditions.
(47) Apparatus used: EPS-3000 produced by NHV Corporation.
(48) Accelerating voltage: 1.16 MeV
(49) Irradiation dose: 0 kGy (unirradiated) in an experimental example 1, 85 kGy in an experimental example 2, 250 kGy in an experimental example 3, 500 kGy in an experimental example 4, 750 kGy in an experimental example 5, and 1000 kGy in an experimental example 6.
(50) Dose rate: 3.9 kGy/s in the experimental example 2, and 6.1 kGy/s in the experimental examples 3, 4, 5, and 6
(51) Speed of conveyor: 3 m/minute in the experimental example 2, 2 m/minute in the experimental examples 3 and 5, 1 m/minute in the experimental examples 4 and 6.
(52) Temperature of film at irradiation time: 310 C.
(53) Atmosphere inside chamber at irradiation time: heated nitrogen
(54) Electron current: 8.1 mA in the experimental example 2, 12.7 mA in the experimental example 3, 4, 5, and 6.
(55) Irradiation width (in movement direction of conveyor): 27.5 cm
(56) (2) Films of Specimens of Experimental Examples
Experimental Example 1
(57) PTFE film (irradiation dose: 0 kGy, layer thickness: 20 m)
Experimental Example 2
(58) PTFE film (irradiation dose: 85 kGy, layer thickness: 20 m)
Experimental Example 3
(59) PTFE film (irradiation dose: 250 kGy, layer thickness: 20 m)
Experimental Example 4
(60) PTFE film (irradiation dose: 500 kGy, layer thickness: 20 m)
Experimental Example 5
(61) PTFE film (irradiation dose: 750 kGy, layer thickness: 20 m)
Experimental Example 6
(62) PTFE film (irradiation dose: 1000 kGy, layer thickness: 20 m)
(63) (3) Condition of Sabang Type Friction Wear Test
(64) Mating member: A quenched and tempered ring made of SUJ2 having 40 mm10 mm (width) and a subsidiary curvature of R60 mm
(65) Lubricating oil: not used
(66) Sliding speed: 0.05 m/s
(67) Load: 50N
(68) Sliding period of time: The test was conducted continuously for five minutes in the experimental example 1, and continuously for 60 minutes in the experimental examples 2, 3, 4, 5, and 6.
(69) Lubrication state: not lubricated
(70) (4) Results of Test
(71)
(72) As shown in
(73) To evaluate the wear resistance of the sliding layer obtained by carrying out the above-described method in the presence of grease, the Sabang type friction wear test was conducted to measure the wear amount of the specimen of the experimental example 4 under grease lubrication in following conditions. As a comparison, a test was conducted in the same conditions on an untreated specimen consisting of a metal flat plate made of SPCC whose size was length 30 mm, width 30 mm, and thickness 2 mm.
(74) (5) Condition of Sabang Type Friction Wear Test Under Grease Lubrication
(75) Mating member: A quenched and tempered ring made of SUJ2 having 40 mm10 mm (width) and a subsidiary curvature of R60 mm
(76) Kind of lubricant: grease (UnimaxR2 produced by KYODO YUSHI CO., LTD.)
(77) Amount of lubricant: 50 mg of lubricant was applied to the mating member (ring) by hand.
(78) Sliding speed: 0.05 m/s
(79) Load: 50N
(80) Sliding period of time: one hour or 10 hours
(81) (6)
(82) As shown in
(83) Description is made below on the fact that the second fluororesin layer of the sliding member has a crosslinked structure. Generally, since fluorine-based resin, particularly polytetrafluoroethylene resin is highly chemically stable and very stable for organic solvents, it is difficult to identify its molecular structure or molecular amount. The sliding member of the present invention has a three-dimensional structure formed by crosslinking the second fluororesin layer. Therefore it is difficult for the sliding member to dissolve in solvents. Thus it is very difficult to analyze its structure. But it is possible to identify the three-dimensional structure of the sliding member of the present invention by measurement and analysis made by using .sup.19F Magic Angle Spinning (MAS) Nuclear Magnetic Resonance (NMR) method (High speed magic angle nuclear magnetic resonance).
(84) The measurement was conducted on a suitable nuclide .sup.19F to be measured by using an NMR apparatus JNM-ECX400 produced by JEOL LTD. under conditions where a resonant frequency was 376.2 MHz, a MAS (Magnetic Angle Spinning) rotational speed was 15 kHz and 12 kHz, the amount of a sample was about 70 L in a 4 mm solid NMR tube, a waiting period of time (recycled delay time) was 10 seconds, and a measurement temperature was about 24 C.
(85) The structure of the second fluororesin layer (experimental example 1, 0 kGy) not irradiated with radiation rays was measured in the above-described conditions. As a result, at the MAS rotational speed of 15 kHz, signals of 82 ppm, 122 ppm, and 162 ppm were observed (upper step in
(86) The structure of a solid .sup.19F MAS NMR of the second fluororesin layer (experimental example 4, 500 kGy), irradiated with the radiation rays, which has an irradiation dose of 500 kGy was measured in the same condition as that used for the uncrosslinked second fluororesin layer. As a result, except for the spinning side band, signals of 68 ppm, 70 ppm, 80 ppm, 82 ppm, 109 ppm, 112 ppm, 122 ppm, 126 ppm, 152 ppm, and 186 ppm were observed (upper and lower steps in
(87) The structure of a solid .sup.19F MAS NMR of the second fluororesin layer (experimental example 6, 1000 kGy), irradiated with the radiation rays, which has an irradiation dose of 1000 kGy was measured in the same condition as that used for the uncrosslinked second fluororesin layer. As a result, except for the spinning side band, signals of 68 ppm, 70 ppm, 77 ppm, 80 ppm, 82 ppm, 109 ppm, 112 ppm, 122 ppm, 126 ppm, 152 ppm, and 186 ppm were observed (upper and lower steps in
(88) Expressing the F atom to which the above-described signals are assigned with an underline, it is known that 70 ppm is assigned to CFCF.sub.3; 109 ppm is assigned to CF.sub.2CF(CF.sub.3)CF.sub.2; 152 ppm is assigned to CFCF; and 186 ppm is assigned to CF (Beate Fuchs and Ulrich Scheler, Branching and Cross-Linking in Radiation-Modified Poly (tetrafluoroethylene): A Soli-State NMR Investigation. Macromolecules, 33, 120-124, the year two thousand).
(89) These signals indicate that fluorine atoms chemically non-equivalent are present and that the second fluororesin layer is crosslinked to form the three-dimensional structure. According to the description of the above-described document, it is known that the intensity of an observed signal is higher at the irradiation dose of 1000 kGy than at the irradiation dose of 500 kGy and becomes higher with an increase of the irradiation dose up to the irradiation dose of 3000 kGy. Regarding signals not described in the above-described document, it is conceivable that the second fluororesin layer has different structures according to the difference in irradiation conditions. That the crosslinking structure is formed is evident from the fact that the structures of CFCF.sub.3, CF.sub.2CF(CF.sub.3)CF.sub.2, CFCF, and CF are present.
(90) As shown in
(91) By irradiating the fluororesin layer with the radiation rays, the fluororesin is crosslinked, with the result that the surface hardness of the fluororesin layer increases. By so irradiating the fluororesin layer with the radiation rays that the indentation hardness of the film becomes 52 to 90 MPa, preferably 60 to 85 MPa, the fluororesin layer is allowed to have a high hardness. It is preferable to set the irradiation dose to 250 to 750 kGy. The surface hardness of the sliding layer can be adjusted by irradiating the fluororesin layer with the radiation rays in the range from 250 to 750 kGy in the irradiation dose.
(92) When the indentation hardness is lower than 52 MPa as a result of the irradiation, the wear amount of the sliding surface of the sliding layer is large. Consequently there is a case in which the metal base material may be exposed. When the indentation hardness is higher than 90 MPa, the film has a high hardness and brittles. Consequently there is a case in which the film is liable to be subjected to damage such as peeling thereof off the metal base material.
(93) By irradiating the fluororesin layer with the radiation rays, the fluororesin is crosslinked. Thereby the melting point of the fluororesin layer can be lowered. To allow the melting point of the fluororesin layer to be lowered to 265 to 310 C. and preferably 272 to 301 C., the calcine film is irradiated with the radiation rays at a temperature irradiation temperature in a range from a temperature lower by 30 C. than the melting point of the second fluororesin layer before the second fluororesin layer is irradiated with the radiation rays to a temperature higher the melting point thereof by 20 C. It is preferable to set the irradiation dose to 250 to 750 kGy. When the melting point is higher than 310 C. as a result of the irradiation, the wear amount of the sliding layer of the fluororesin layer is large. Consequently there is a case in which the metal base material may be exposed. When the melting point is lower than 265 C., the film has a high hardness and brittles. Consequently there is a case in which the film is liable to be subjected to damage such as peeling thereof off the metal base material.
(94) In the iron-based metal material having the sliding layer formed thereon, the sliding layer has excellent adhesiveness to the iron-based metal material, and the sliding surface of the sliding layer has excellent wear resistance in the presence of oil. Thus the iron-based metal material can be suitably used for a cage and a rolling bearing having the cage made of the iron-based metal material. The iron-based metal material is especially suitable for a rolling bearing, having needle rollers serving as rolling elements, for a bid end portion of a connecting rod of an engine, a rolling bearing for a small end portion of the connecting rod or a rolling bearing for a crankshaft-supporting shaft.
(95)
(96) A cage 1 has pockets 2 for holding the needle rollers. The interval between the needle rollers is retained by pillar parts 3 each positioned between the adjacent pockets and both-side annular portions 4, 5 fixing the pillar parts 3 thereto. To retain the needle rollers, each pillar part 3 is bent in mountain fold and valley fold at a central portion of the pillar part and has a complicated flat plate shape having a circular bulge in a planar view at portions of the pillar part 3 connected to the both-side annular portions 4, 5. As a method of producing the cage, it is possible to adopt a method of cutting out a circular ring from a formed and fabricated material and forming the pockets 2 by punch pressing and a method of forming a flat plate by press working, cutting it to a proper length, rolling a cut portion, and joining the cut portion by welding. The sliding layer of the fluororesin film is formed on the surface of the cage 1. The surface of the cage 1 on which the sliding layer is formed contacts lubricating oil or grease. It is preferable to form the sliding layer on the entire surface of the cage 1 including the surfaces of the pockets 2 which contact the needle rollers.
(97)
(98)
(99)
(100) The connecting rod 13 has a big-end portion 16 at a lower portion of a straight rod and a small-end portion 17 at an upper portion thereof. The crankshaft 12 is rotatably supported via a needle roller bearing 6a mounted on an engaging hole of the big-end portion 16 of the connecting rod 13. A piston pin 18 coupling the piston 11 and the connecting rod 13 to each other is rotatably supported via a needle roller bearing 6b mounted on an engaging hole of the small-end portion 17 of the connecting rod 13.
(101) By using the needle roller bearing excellent in its sliding property, two-cycle and four-cycle engines downsized or having a high output in which the needle roller bearing is used has excellent durability.
(102) Although the needle roller bearing is exemplified as a bearing with reference to
(103) Because the iron-based metal material having the sliding layer having formed thereon is excellent in its wear resistance under the grease lubrication consisting of base oil and a thickener, the iron-based metal material can be preferably used for the cage composed of the iron-based metal material and the rolling bearing having the cage. The grease deteriorates owing to temperature rise of the bearing caused by heat generation during a high-speed rotation and owing to mixing of metal abrasion powder generated by friction between rolling elements and the cage both made of steel into the grease. On the other hand, as shown in
(104) A bearing for a main motor of a railway vehicle is one example of a bearing to be lubricated with grease. In this bearing, a ball bearing is used as a bearing at a stationary side to cope with axial expansion and contraction of a main shaft caused by a temperature change, while as a bearing at a free side, a cylindrical roller bearing capable of coping with the expansion and contraction of the main shaft is used. As the bearing at the stationary side, a deep groove ball bearing is used. The deep groove ball bearing has steel balls and an iron plate-wave-type cage. The cylindrical bearing at the free side has a cylindrical roller made of steel and a machined brass cage. In the case where these bearings for the main motor are used at a high temperature and under a high-speed rotation, grease having lithium soap and mineral oil is used as a lubricant.
(105) Because the lubrication life of the grease used in the bearing for the main motor of the railway vehicle is short relative to the rolling fatigue life of the bearing, in the present situation, a grease refilling work (maintenance) is carried out in an overhaul of vehicles to be carried out for each predetermined travel distance. In the present maintenance cycle, in many cases, the deterioration of the grease progress because of the above-described reason. By applying the rolling bearing of the present invention to the bearing for the main motor of the railway vehicle, it is possible to extend the lubrication life of the grease and the maintenance cycle.
EXAMPLES
Examples 1 Through 7 and Comparative Examples 1 Through 4
(106) A cage (surface hardness of base material: Hv: 484 to 595), for a needle bearing, made of quenched and tempered chromium-molybdenum steel (SCM415) having a diameter of 44 mm and a width of 22 mm was prepared. A coating liquid identical to that used to form the foundation layer and the second fluororesin layer used in the experimental example 1 was applied to an iron-based metal material in the same condition as that of the experimental example 1 to form, dry, and calcine a surface sliding layer consisting of PTFE except that the thickness of the coating layer was set to the thickness described in table 1. Using an electron beam irradiation apparatus used in the experimental example 1, the second fluororesin layer was irradiated with electron beams having an irradiation dose shown in table 1. Regarding the irradiation dose of the electron beams, the irradiation dose in the experimental example 1 and that in the example 2 were equal to each other, the irradiation dose in the example 2 and that in the experimental example 3 were equal to each other, the irradiation dose in the example 3 and that in the example 6 were equal to that of the experimental example 4, the irradiation dose in the example 4 and that in the experimental example 5 were equal to each other, the irradiation dose in the example 5 and that in the experimental example 6 were equal to each other, and the irradiation dose in the example 7 was set to 260 kGy. A specimen of the comparative example 1 as well as that of the experimental example 1 was not irradiated with the electron beams. In a specimen of a comparative example 2, crack occurred at the stage of calcining a sliding film. Thus the irradiation of the electron beams and the evaluation test were discontinued. In a comparative example 3, without forming the foundation layer, the second fluororesin layer was formed directly on the iron-based metal material by using a coating liquid identical to that of the experimental example 1 and in a condition identical to that of the experimental example 1 and thereafter the second fluororesin layer was irradiated with the electron beams having an irradiation dose identical to that of the experimental example 4. In a comparative example 4, a silver-plated layer was formed on the surface the cage of the needle bearing made of the quenched and tempered chromium-molybdenum steel (SCM415) having a diameter of 44 mm and a width of 22 mm.
(107) The friction properties of surface-treated cages of the needle bearings were evaluated in the following method. FIG. 9 shows the outline of a wear amount testing apparatus.
(108) With a quenched and tempered concave mating member 19 made of SUJ2 having a Rockwell Hardness of HRC62 and a surface roughness of 0.1 to 0.2 mRa being pressed against a cage 1 mounted on a rotational shaft from a vertical direction, the cage 1 was rotated together with the rotational shaft to evaluate the friction property of a film formed on the surface of the cage 1 and measure the wear amount of the sliding surface of the film. The measuring conditions are as follows: load: 440N, lubricating oil: mineral oil (10W-30), sliding speed: 930.6 m/minute, and measured period of time: 100 hours. By visually observing peel-off amount of the film subjected to the above-described rotation of the cage, the adhesiveness of the PTFE film was evaluated. That the peel-off amount is large means that the peel-off area of a maximum peel-off portion is not less than 1 mm.sup.2. That the peel-off amount is small means that the peel-off area of a maximum peel-off portion is less than 1 mm.sup.2. The radius of a concave R part was set larger than the radius of the cage by 20 to 55 m. The amount of the lubricating oil used was so set that the half of the height of cage was immersed in the lubricating oil. Table 1 shows the results.
(109) Specimens to be immersed in lubricating oil were prepared. The specimens were subjected to a lubricating oil immersion test by carrying out the following method. Table 1 shows the results. The details of the test conditions, the specimens, and the measuring method are shown below.
(110) After three square bars coated with a film respectively were immersed for 200 hours in 2.2 g of lubricating oil [1 wt % of ZnDTP (LUBRIZOL677A produced by LUBRIZOL Corporation was added to poly--olefin: Lucant HL-10 (produced by Mitsui Chemicals, Inc.) having a temperature of 150 C., the concentration (unit of elution amount, ppm) of a component of each film which eluted in the lubricating oil were measured. The concentration was quantified by using X-ray fluorescence measurement [X-ray fluorescence measuring apparatus: Rigaku ZSX 100e (produced by Rigaku Corporation). As specimens, three square bars (total of surface areas: 774=.sup.2) made of SCM415 and having a dimension of 3 mm3 mm20 mm were used in each experimental example.
(111) TABLE-US-00001 TABLE 1 Example Comparative example 1 2 3 4 5 6 7 1 2 3 4 Material of sliding layer PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE Silver 2) plating Irradiation dose, kGy 85 250 500 750 1000 500 260 0 500 Thickness of sliding layer, m 20 20 20 20 20 5 30 20 40 20 20 Wear amount, m n = 1 20 7 10 8 8 5 9 20 Untestable 3) 12 n = 2 12 9 11 8 1) 5 10 20 Untestable 3) 11 Peel-off amount n = 1 Large Small Small Small Large Small Untestable 3) Small n - 2 Large Small Small Small Large Small Untestable 3) Small 1) Elution amount in immersion test, 0 0 0 0 0 0 0 0 0 0 600 ppm 1 Because the peel-off amount was large in 20 hours, the test was discontinued. In terms of the peel-off amount, the peel-off area of the maximum peel-off portion was not less than 2 mm.sup.2. 2) Without forming the foundation layer, the second fluororesin layer consisting of PTFE was formed directly on the base material. 3) Peeling occurred in the vicinity of the base material. Thus the test was discontinued.
Examples 8 Through 11 and Comparative Examples 5 Through 9
(112) As specimens whose indentation hardness were to be measured, metal flat plates each made of SPCC whose size was length 30 mm, width 30 mm, and thickness 2 mm were prepared. In a cage rotation test, cages (surface hardness of base material: Hv: 484 to 595), for a needle bearing, made of quenched and tempered chromium-molybdenum steel (SCM415) having a diameter of 40 mm and a width of 22 mm were prepared. The surface of each specimen was so roughened by blast treatment that the surface thereof had a surface roughness of Ra1 m. After the surface of each specimen was washed, a sliding layer was formed by using primer paint (model number: EK-1909S21R) produced by DAIKIN INDUSTRIES, LTD. for a foundation layer and top paint (model number: EK-3700C21R) produced by DAIKIN INDUSTRIES, LTD. for a second fluororesin layer. The primer paint and the top paint were dried in a thermostatic bath set to 90 C. for 30 minutes and thereafter calcined for 30 minutes in a heating furnace set to 380 C. Thereafter specimens were irradiated with electron beams to allow the indentation hardness of the surface of each sliding layer to have a predetermined hardness shown in table 2. The specimen of the comparative example 5 was not irradiated with the electron beams. The specimen of the comparative example 6 had an indentation hardness exceeding 85 MPa. The specimen of the comparative example 7 and that of the comparative example 2 showed the same result. In the specimens of the comparative examples 7 and 2, at the stage of calcining the sliding film, crack occurred. Thus the irradiation of the electron beams and the evaluation test were discontinued. In the specimen of the comparative example 8, without forming the foundation layer, the second fluororesin layer was formed directly on a metal base material by using the coating liquid identical to those of the examples and in the conditions identical to those of the examples. Thereafter the second fluororesin layer was irradiated with the electron beams to allow the indentation hardness of the surface of the sliding layer to have the same indentation hardness as that of the surface of the sliding layer of the example 9. In the specimen of the comparative example 9, the surface of a cage, for a needle bearing, made of quenched and tempered chromium-molybdenum steel (SCM415) having a diameter of 44 mm and a width of 22 mm was silver-plated. The specimen of the comparative example 9 and that of the comparative example 4 showed the same result.
(113) The wear amount of each surface-treated cage for a needle bearing and a lubricating oil immersion test were evaluated by the same method as that of the example 1. Table 2 shows the results.
(114) The indentation hardness of each of the obtained flat plate specimens was measured in a method conforming to ISO14577 by using a nanoindenter (G200) produced by Agilent Technologies, Inc. Each of the measured values shows an average value of depths (portion where hardness was stable) not affected by the surface roughness and the base material (SPCC). The indentation hardness of each specimen was measured at 10 portions. The measuring conditions were as follows: The configuration of the indenter was of a Berkovich type; a depth indentation was measured when a load of 5 mN was applied to each specimen; a load application speed was 10 mN/minute; and a measuring temperature was 25 C. Each indentation hardness was calculated from an indentation load and a displacement (area).
(115) TABLE-US-00002 TABLE 2 Example Comparative example 8 9 10 11 5 6 7 8 9 Material of sliding layer PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE Silver 2) plating Indentation hardness of sliding 60 80 85 80 45 95 80 layer, MPa Thickness of sliding layer, m 20 20 20 10 20 20 40 20 20 Wear amount, m 7 10 8 8 20 8 Untestable 3) 12 Peel-off amount Small Small Small Small Large Untestable 3) Small Elution amount in immersion 0 0 0 0 0 0 0 0 600 test, ppm 2) Without forming the foundation layer, the second fluororesin layer was formed directly on the base material. 3) Peeling occurred in the vicinity of the base material. Thus the test was discontinued.
Examples 12 Through 15 and Comparative Examples 10 Through 14
(116) A cage (surface hardness of base material: Hv: 484 to 595), for a needle bearing, made of quenched and tempered chromium-molybdenum steel (SCM415) having a diameter of 44 mm and a width of 22 mm was prepared. A sliding layer was formed by using the primer paint (model number: EK-1909S21R) produced by DAIKIN INDUSTRIES, LTD. for a foundation layer and the top paint (model number: EK-3700C21R) produced by DAIKIN INDUSTRIES, LTD. for a second fluororesin layer. Each sliding layer was dried in the thermostatic bath set to 90 C. for 30 minutes and thereafter calcined for 30 minutes in the heating furnace set to 380 C. Thereafter specimens were irradiated with electron beams to allow the melting point of each film to have a predetermined temperature shown in table 1. The specimen of the comparative example 10 was not irradiated with the electron beams. In the specimen of the comparative example 12, at the stage of calcining the sliding film, crack occurred. Thus the irradiation of the electron beams and the evaluation test were discontinued. In the specimen of the comparative example 13, without forming the foundation layer, the second fluororesin layer was formed directly on the iron-based metal material by using the coating liquid identical to those of the examples and in the conditions identical to those of the examples. Thereafter the second fluororesin layer was irradiated with the electron beams to allow the melting point of the sliding layer to have the same melting point as that of the sliding layer of the example 13. In the specimen of the comparative example 14, the surface of a cage, for a needle bearing, made of quenched and tempered chromium-molybdenum steel (SCM415) having a diameter of 44 mm and a width of 22 mm was silver-plated. The specimen of the comparative example 14 and that of the comparative example 4 showed an identical result.
(117) The melting point was measured by using a differential scanning calorimeter (produced by SII Nanotechnology Inc., product name: DSC6220). As a measured specimen, 10 to 15 mg of a fluororesin film enclosed in a specimen container made of aluminum (hereinafter referred to as aluminum pan) produced by SII Nanotechnology Inc. was used. As a reference, aluminum oxide (Al.sub.2O.sub.3), enclosed in the aluminum pan, whose amount was equal to that of the fluororesin film was used. Regarding the measuring condition, at the rate of temperature rise of 2 C./minute in an atmosphere where nitrogen flowed (200 mL/minute), the temperature was raised from 30 C. to 370 C. After the temperature was kept at 370 C. for 20 minutes, the temperature was lowered from 370 C. to 40 C. The peak top of the endothermic peak when the temperature was raised was set as the melting peak temperature, namely, the melting point.
(118) The wear amount of each surface-treated cage for a needle bearing and a lubricating oil immersion test were evaluated by the same method as that of the example 1. Table 3 shows the results.
(119) TABLE-US-00003 TABLE 3 Example Comparative example 12 13 14 15 10 11 12 13 14 Material of sliding layer PTFE PTFE PTFE PTFE PTFE PTFE PTFE PTFE Silver 2 plating Melting point, C. 301 284 272 284 321 258 321 284 Thickness of sliding layer, m 20 20 20 10 20 20 40 20 20 Wear amount, m 7 10 8 8 20 8 Untestable 3) 12 Peel-off amount Small Small Small Small Large Untestable 3) Small Elution amount in immersion test, 0 0 0 0 0 0 0 0 600 ppm 2) Without forming the foundation layer, the second fluororesin layer was formed directly on the base material. 3) Peeling occurred in the vicinity of the base material. Thus the test was discontinued.
INDUSTRIAL APPLICABILITY
(120) According to the present invention, it is possible to obtain the sliding member which can be restrained from wearing even in the presence of lubricating oil and under conditions of a high sliding speed and a high contact pressure. Therefore the sliding member of the present invention can be used for the cage, made of the iron-based metal material, which is used in the oil lubrication environment and for the rolling bearing having this cage.
EXPLANATION OF REFERENCE NUMERALS AND SYMBOLS
(121) 1: cage 2: pocket 3: pillar part 4: annular portion 5: annular portion 6: needle roller bearing 7: needle roller 8: inlet pipe 9: exhaust pipe 10: combustion chamber 11: piston 12: crankshaft 13: connecting rod 14: rotational central axis 15: balance weight 16: big end portion 17: small end portion 18: piston pin 19: concave mating member 20: load