Sliding member and method for producing the same

Abstract

To provide a sliding member for reducing peeling and property changes of an overlay layer and maintaining sliding characteristics even when using alternate fuel, and to provide a method for producing the same.SOLUTION: A sliding member 10 comprises a resin overlay layer 13. The overlay layer 13 comprises a binder resin 21, and 10 to 20 vol% of a fluororesin compound 22 dispersed and added to the binder resin 21. When the overlay layer 13 is divided into an upper layer 31 and a lower layer 32 in the middle of a thickness direction, in the overlay layer 13, the ratio of the amount of the fluororesin compound 22 in the upper layer to that in the lower layer is 1.5 or greater.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] This embodiment relates to a sliding member and a method for manufacturing the same.

Background Art

[0002] Conventionally, there is a known sliding member provided with an overlay layer formed of resin on the surface of a bearing alloy layer that slides with a mating member. In the overlay layer, additives such as solid lubricants are dispersed in a binder resin serving as a skeleton. In recent years, from the perspective of decarbonization, the use of bio-derived alternative fuels instead of petroleum-derived fuels has been under consideration. However, it is known that when using this alternative fuel, acids are generated in the lubricating oil used for lubricating equipment. Additives contained in conventional overlay layers include those that dissolve in acids, such as calcium carbonate. Thus, when the additives contained in the overlay layer dissolve, acids easily penetrate the overlay layer. When the acids that have penetrated the overlay layer reach the boundary between the overlay layer and the bearing alloy layer, they cause corrosion of the bearing alloy layer. When the bearing alloy layer corrodes, the overlay layer is likely to peel off from the bearing alloy layer. In addition, the acids that have penetrated the overlay layer cause changes in the properties and structure of the binder resin. As a result, there is a problem that the original function of the overlay layer deteriorates, leading to a decrease in sliding characteristics.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] Therefore, an object is to provide a sliding member and a method for manufacturing the same that reduce peeling and property changes of the overlay layer and maintain sliding characteristics even when using bio-derived alternative fuels by further improving oil repellency.

Means for Solving the Problem

[0005] In order to solve the above problems, a sliding member according to an embodiment includes a resin overlay layer. This overlay layer includes a binder resin and 10 to 20 vol% of a fluororesin compound dispersed and added to the binder resin. When the overlay layer is divided into an upper layer and a lower layer in the middle in the thickness direction, the relationship of the ratio value of the abundance of the fluororesin compound contained in the overlay layer is upper layer / lower layer = 1.5 or more.

[0006] Thereby, the sliding member of the present embodiment has increased oil repellency of the overlay layer, and penetration of lubricating oil into the overlay layer is prevented. Therefore, even when the acid generated by the use of alternative fuel is contained in the lubricating oil, the sliding member of the present embodiment can reduce the swelling of the overlay layer and the deterioration accompanying the change in structure. Further, the sliding member of the present embodiment reduces the penetration of lubricating oil containing acid into the interface between the overlay layer and the bearing alloy layer, and can reduce the corrosion of the bearing alloy layer. As a result, the sliding member of the present embodiment maintains the strength of the overlay layer and reduces the peeling of the overlay layer from the bearing alloy layer. Therefore, by further improving the oil repellency, even when using a bio-derived alternative fuel, the peeling and property changes of the overlay layer can be reduced, and the sliding characteristics can be maintained.

[0007] Moreover, a manufacturing method of a sliding member including a resin overlay layer according to an embodiment includes a mixing step, a coating step, and a standing step. The mixing step mixes a fluororesin compound with a binder resin to produce a mixed resin. The coating step applies the mixed resin produced in the mixing step in a film shape on the surface of a base material by spray coating. The standing step stands the mixed resin applied in the coating step for a preset period.

[0008] Accordingly, in the method for manufacturing the sliding member of the present embodiment, when forming the overlay layer, by securing a predetermined period in the standing step after applying the mixed resin, the fluororesin compound contained in the mixed resin is present more on the upper layer side of the overlay layer. Therefore, the oil repellency of the overlay layer of the sliding member of the present embodiment is improved. Accordingly, it is possible to improve the oil repellency of the sliding member and maintain the sliding characteristics accompanying therewith without adding complicated steps or special processing.

Brief Description of the Drawings

[0009]

Figure 1

Figure 2

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Embodiments for Carrying Out the Invention

[0010] Hereinafter, a sliding member according to an embodiment will be described with reference to the drawings. As shown in Fig. 2, the sliding member 10 includes a backing layer 11, a bearing alloy layer 12, and an overlay layer 13, and slides with a mating member (not shown). The bearing alloy layer 12 is provided on the mating member side (not shown) of the backing layer 11. The overlay layer 13 is provided on the mating member side of the bearing alloy layer 12, that is, on the side opposite to the backing layer 11. The outermost surface of the overlay layer 13, that is, the end face on the side opposite to the backing layer 13, forms a sliding surface 14 that slides with the mating member (not shown). The backing layer 11 is formed of, for example, Fe or an alloy containing Fe. The bearing alloy layer 12 is formed of, for example, various metals such as Cu, Sn, Zn, Al, or alloys thereof. These backing layer 11 and bearing alloy layer 12 are examples, and any metal or alloy can be used as long as it performs the required function. Further, the sliding member 10 may include one or more intermediate layers between the layers, such as between the backing layer 11 and the bearing alloy layer 12, and between the bearing alloy layer 12 and the overlay layer 13.

[0011] As shown in Fig. 1, the overlay layer 13 includes a binder resin 21 and a fluororesin compound 22. The binder resin 21 is a resin that forms the skeleton of the overlay layer 13. The binder resin 21 can be arbitrarily selected according to the use of the sliding member 10. The binder resin 21 is formed of, for example, one or more selected from polyimide resin, polyamideimide resin, epoxy resin, phenol resin, polyamide resin, and elastomer.

[0012] The fluororesin compound 22 is added to the overlay layer 13 and is present in a dispersed state in the overlay layer 13. The fluororesin compound 22 is a resin having oil repellency and containing F (fluorine) in the molecule of the monomer, such as polytetrafluoroethylene resin (PTFE) for example. The fluororesin compound 22 is contained in the overlay layer 13 at 10 to 20 vol%. The fluororesin compound 22 can be used not limited to the PTFE resin as long as it has oil repellency. The fluororesin compound 22 can use various resins such as tetrafluoroethylene·perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene·hexafluoropropylene copolymer (FEP), tetrafluoroethylene·ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene·ethylene copolymer (ECTFE), etc.

[0013] In the overlay layer 13, the value of the ratio of the abundance of the fluororesin compound 22 dispersed in the binder resin 21 is different between the upper layer side closer to the sliding surface 14 and the lower layer side closer to the backing layer. Specifically, the overlay layer 13 is virtually divided into an upper layer 31 and a lower layer 32 at an intermediate line L that is the middle in the thickness direction. At this time, the side closer to the sliding surface 14 than the intermediate line L is the upper layer 31, and the side closer to the backing layer 11 than the intermediate line L is the lower layer 32. Let the value of the ratio of the abundance of the fluororesin compound 22 contained in the overlay layer 13 in the upper layer 31 be R1, and the value of the ratio of the abundance of the fluororesin compound 22 contained in the overlay layer 13 in the lower layer 32 be R2. In this embodiment, a relationship of R1 / R2 ≧ 1.5 holds between these values of the ratio of the abundance. That is, the overlay layer 13 contains more fluororesin compound 22 on the upper layer 31 side than on the lower layer 32 side with respect to the intermediate line L.

[0014] The value of the abundance ratio of the fluororesin compound 22 is determined by elemental analysis using an EPMA apparatus. Specifically, as shown in FIGS. 1 and 2, a cross-section in the thickness direction of the overlay layer 13 is analyzed by surface analysis to obtain a fluorine concentration map. The obtained fluorine concentration map is divided into an upper layer 31 and a lower layer 32 with the intermediate line L as the boundary, and the average value of the fluorine concentration in the upper layer 31 and the average value of the fluorine concentration in the lower layer 32 are calculated. The average value of the fluorine concentration (mass %) in the upper layer 31 is defined as the value R1 of the abundance ratio, and the average value of the fluorine concentration (mass %) in the lower layer 32 is defined as the value R2 of the abundance ratio. Then, based on these values R1 and R2 of the abundance ratio, R1 / R2, which is the relationship of the values of the abundance ratio between the upper layer 31 and the lower layer 32, is calculated.

[0015] In addition to the above, the overlay layer 13 contains a solid lubricant 41. The overlay layer 13 contains 10 to 30 vol% of the solid lubricant 41. The solid lubricant 41 is 2 one or more selected from MoS 2 graphite, and hBN. Among these, it is preferable that the solid lubricant 41 has a specific gravity of 1.5 times or more that of the fluororesin compound 22. Therefore, the solid lubricant 41 is preferably 2 MoS as a specific solid lubricant. In this case, the solid lubricant 41 may contain only 2 MoS as a specific solid lubricant, or may be a mixture in which other solid lubricants 41 such as graphite are mixed in addition to 2 MoS. Further, a strength modifier may be added to the overlay layer 13. The strength modifier is used to adjust the strength of the overlay layer 13. It is preferable that the strength modifier has acid resistance. Although 3 CaCO is generally used as the strength modifier, considering acid resistance to nitric acid and the like derived from the products during combustion, for example, 2 TiO, 2 SiO, 4 BaSO, one or more selected from ZnS are preferably used.

[0016] Next, a method for manufacturing the sliding member 10 having the above configuration will be described. The binder resin 21 and the fluororesin compound 22 are mixed in the mixing step as shown in FIG. 3 and produced as a mixed resin (S101). The fluororesin compound 22 is mixed with the binder resin 21 dissolved in a solvent such as an organic solvent. The fluororesin compound 22 is mixed with the binder resin 21 so as to be contained in the finally produced overlay layer 13 at 10 to 20 vol%. When the solid lubricant 41 is added to the overlay layer 13, the solid lubricant 41 is mixed with the binder resin 21 so as to be contained in the finally produced overlay layer 13 at 10 to 30 vol%.

[0017] The mixed resin in which the binder resin 21, the fluororesin compound 22, and the solid lubricant 41 are mixed in the mixing step is applied in a film shape on the surface of the base material by spray coating in the coating step (S102). The base material is, for example, a material in which the bearing alloy layer 12 is laminated on the backing layer 11. In the coating step, the mixed resin is applied to the base material heated by preheating by spray coating that sprays the mixed resin. Thereby, the mixed resin is applied in a film shape on the surface of the base material.

[0018] When the coating step is completed, the mixed resin applied to the base material is allowed to stand for a preset standing period in the standing step (S103). That is, the mixed resin applied to the base material is held in a quiet state without applying, for example, vibration during the standing period. As a result, the surface of the mixed resin applied to the base material by spraying is leveled, and the surface roughness is reduced. Further, in this standing step, a difference occurs in the ratio values R1 and R2 of the abundance in the thickness direction of the fluororesin compound 22 contained in the mixed resin. That is, the fluororesin compound 22, which is less compatible with the binder resin, is less likely to settle toward the backing layer 11 side in the thickness direction and is likely to be located on the upper layer 31 side closer to the sliding surface 14. In particular, when the solid lubricant 41 is mixed in the mixed resin, the solid lubricant 41 having a larger specific gravity moves predominantly to the lower layer 32, contributing to an increase in the ratio value R1 of the abundance of the fluororesin compound 22 in the upper layer 31. This standing step is preferably about 3 to 5 minutes.

[0019] When the standing process is completed, the substrate coated with the mixed resin is heated in a heating furnace in the drying process (S104). By heating, the mixed resin is dried, and the solvent that dissolves the binder resin constituting the mixed resin is removed. That is, the mixed resin applied to the surface of the substrate is dried. As a result, the mixed resin cures in a state where there is a difference in the ratio values R1 and R2 of the abundance of the fluororesin compound 22 contained therein. As a result, the overlay layer 13 is formed in a state where the fluororesin compound 22 is present in a larger amount in the upper layer 31 than in the lower layer 32. Further, the surface of the overlay layer 13 is formed in a smooth state by leveling in the standing process.

[0020] Next, the operation and effects of the sliding member of the present embodiment will be described. (Regarding Examples and Conventional Examples) As samples for examples and conventional examples of the sliding member 10, those in which an Al alloy bearing alloy layer 12 is laminated on a half-cut-shaped back metal layer 11 as a substrate were used. After the bearing alloy layer 12 was subjected to a finishing treatment on the surface and impurities were removed by washing and degreasing, the overlay layer 13 was formed by the manufacturing method shown in FIG. 3 above. The overlay layer 13 in each sample contains 10 to 20 vol% of the fluororesin compound 22 added to the binder resin 21 made of PAI. As the fluororesin compound 22, PTFE is used. Further, in the overlay layer 13 of each sample, in addition to the fluororesin compound 22, 20 vol% of MoS is added as the solid lubricant 41 to the binder resin 21. 2 However, sample 7, which is a conventional example for comparison, contains 20 vol% of MoS as the solid lubricant 41 in the binder resin 21 made of PAI. 2 and 10 vol% of CaCO 3 are added. That is, in sample 7, the fluororesin compound 22 is not added to the binder resin 21. The calcium carbonate used in this conventional example is used as a skeleton material to increase the strength of the overlay layer 13.

[0021] Samples 1 to 6 shown in Fig. 4 have different standing times after the mixed resin is applied in the standing process shown in Fig. 3. Specifically, Sample 1 has moved on to the drying process with a standing time of 0. Similarly, Samples 2 to 6 have moved on to the drying process with standing times of 1 to 5 minutes respectively. Sample 7, which is a conventional example, does not include the standing process in the first place.

[0022] (Regarding oil repellency) The oil repellency of the sliding member 10 of the present embodiment was verified from the state in which lubricating oil was dropped onto the overlay layer 13 and the oil droplet spread. For Samples 1 to 7, after the overlay layer 13 was formed, 10 μl of lubricating oil was dropped onto the surface of the overlay layer 13. Samples 1 to 7 measured the equivalent circle diameter of the oil droplet spreading 2 seconds after the lubricating oil was dropped. VG22 was used as the lubricating oil. The diameter of the equivalent circle is the diameter of a circle having the same area as the area where the oil droplet spreads. That is, the equivalent circle diameter is calculated based on the area measured after 2 seconds from dropping the lubricating oil onto the overlay layer 13 of each sample and the oil droplet spreads.

[0023] The wetting area and equivalent circle diameter of this oil droplet become smaller as the oil repellency of the overlay layer 13 increases. For Samples 1 to 6, the equivalent circle diameter is all 9.5 mm or less. Thus, the overlay layer 13 obtained by adding the fluororesin compound 22 to the binder resin 21 exhibits high oil repellency. On the other hand, in Sample 7 which is a conventional example, since the fluororesin compound 22 is not contained in the overlay layer 13, the equivalent circle diameter is larger compared to Samples 1 to 6.

[0024] (Regarding the ratio value of the abundance of the fluororesin compound) According to Samples 1 to 6, the oil repellency becomes higher when the relationship R1 / R2 of the ratio value of the abundance of the fluororesin compound 22 is 1.5 or more compared to when R1 / R2 is less than 1.5. That is, it shows that the oil repellency becomes higher as the fluororesin compound 22 is present more on the upper layer 31 side than on the lower layer 32 side. Therefore, as in Samples 4 to 6, when the relationship R1 / R2 of the ratio value of the abundance increases, the oil repellency also improves.

[0025] Samples 1 to 6 are made of a binder resin 21, a fluororesin compound 22, and a solid lubricant 41, MoS 2 This solid lubricant 41, MoS 2 has a specific gravity 1.5 times or more than that of PTFE, which is the fluororesin compound 22. Therefore, the solid lubricant 41 contained in the mixed resin is more likely to settle inside the binder resin 21 than the fluororesin compound 22 in the standing step, and is accumulated on the lower layer 32 side. As a result, the value R1 of the ratio of the amount of the fluororesin compound 22 in the upper layer 31 is relatively higher than the value R2 of the ratio of the amount of the fluororesin compound 22 in the lower layer 32. The settling of the solid lubricant 41 depends on the standing time in the standing step. Therefore, it is preferable to secure 3 minutes or more for the standing step. On the other hand, if the standing step exceeds 3 minutes, the effect on the relationship R1 / R2 of the ratio of the amount of the fluororesin compound 22 decreases and the number of steps increases. Therefore, the standing step may be limited to about 5 to 10 minutes while securing 3 minutes or more.

[0026] In this way, by ensuring an appropriate standing time in the standing step, the fluororesin compound 22 contained in the mixed resin applied in the application step is unevenly distributed in the upper layer 31 rather than in the lower layer 32. This improves the oil repellency of the overlay layer 13 on the side of the upper layer 31 that comes into contact with the lubricating oil. As a result, when the sliding member 10 slides against a counter member (not shown), the penetration of the lubricating oil into the overlay layer 13 is reduced. Also, according to Fig. 4, it can be seen that the oil repellency, which is indexed by the equivalent circle diameter, depends on the standing time in the standing step, but is only slightly affected by the concentration of the fluororesin compound 22.

[0027] (Acid resistance) Next, the resistance to acid, that is, the acid resistance of the sliding member 10 was examined under the conditions shown in FIG. The acid resistance was verified based on the influence of the mixing amount (vol%) of PTFE contained in the overlay layer 13 using Samples 8 to 10 as shown in FIG. 6. In Sample 8, the mixing amount of PTFE is 10 vol%, in Sample 7, the mixing amount of PTFE is 5 vol%, and for comparison, in Sample 10, the mixing amount of PTFE is 0%. Samples 8 to 10 were all added with a solid lubricant, and the overlay layer 13 was formed under the same conditions except for the mixing amount of PTFE. Samples 8 to 10 were immersed in the lubricating oil added with an acid as shown in FIG. 5 and left for 100 hours while heating and stirring. The temperature during heating was set to about 100° C., which is the temperature at which the lubricating oil reaches during the operation of the internal combustion engine to which the sliding member 10 is applied. As the acid added, nitric acid was selected as the acid generated during the use of the alternative fuel. Nitric acid penetrates into the overlay layer 13 and reaches the interface between the bearing alloy layer 12 and the overlay layer 13, which causes corrosion of the bearing alloy layer 12. In particular, for example, CaCO 3 When additives with low acid resistance such as etc. are contained in the overlay layer 13, these additives are dissolved by the generated acid. As a result, the acid generated from the alternative fuel such as nitric acid penetrates into the overlay layer 13 while dissolving the additives, and easily reaches the interface between the bearing alloy layer 12 and the overlay layer 13.

[0028] After leaving each sample under conditions approximating operation as described above, a tape was attached to the overlay layer 13, and by peeling off this tape, it was confirmed whether peeling occurred in the overlay layer 13. As a result, as shown in FIG. 6, in sample 8 where the mixing amount of PTFE was 10 vol%, no peeling occurred with respect to nitric acid. In sample 9 where the mixing amount of PTFE was 5 vol%, minute peeling occurred. In sample 10 where no PTFE was mixed, peeling occurred over the entire test surface. From these results, sample 8 was judged as qualified, and sample 9 and sample 10 where the mixing amount of PTFE was less than 10 vol% were judged as unqualified. The acid resistance improves as the mixing amount of PTFE in the overlay layer 13 increases. Therefore, the mixing amount of PTFE in the overlay layer 13 in the sliding member 10 of the present embodiment is set to 10 vol% or more. On the other hand, if the mixing amount of PTFE in the overlay layer becomes excessive, there is a possibility that functions originally required for the overlay layer 13, such as fatigue resistance, become insufficient. Therefore, the mixing amount of PTFE in the overlay layer 13 is preferably 10 vol% to 20 vol%.

[0029] (Regarding fatigue resistance) Next, the fatigue resistance of the sliding member 10 was verified using the conditions shown in FIG. 7. The fatigue resistance was verified after subjecting samples having a PTFE mixing amount of 10 vol% and 20 vol% among samples 1 to 6 shown in FIG. 4 above to the acid resistance test. The fatigue test was performed with each sample having an inner diameter of 56 mm, a length of 15 mm, and a thickness of 1.5 mm as shown in the conditions of FIG. 7. The fatigue test was performed while lubricating with VG68 at 100°C, with a rotational speed of 3250 rpm, while changing the surface pressure at the time of contact with a mating member made of S55C. The sliding member 10 was subjected to the fatigue test at a predetermined surface pressure, and was judged as qualified at that surface pressure if no peeling occurred in the overlay layer 13. The surface pressure was set to an initial value of 10 MPa, and the test was performed while increasing by 10 MPa each time if no peeling occurred, and the upper limit value was set to 100 MPa.

[0030] As shown in FIGS. 8 and 9, as a result of the fatigue resistance test, the sliding member 10 showed higher fatigue resistance when the PTFE contained in the overlay layer 13 was 20 vol% than when it was 10 vol%. Samples 1 to 6 used in the fatigue resistance test have all undergone an acid resistance test. Therefore, the sample shown in FIG. 9 with a higher mixing amount of PTFE has higher oil repellency and, as a result, higher acid resistance compared to the sample shown in FIG. 8. Therefore, the sample shown in FIG. 9 is less likely to have peeling of the overlay layer 13 and has improved fatigue resistance. On the other hand, as can be seen from FIGS. 8 and 9, samples 4 to 6 that ensured sufficient standing time in FIG. 3 exhibited sufficiently high fatigue resistance even when the mixing amount of PTFE was 10 vol%. From these facts, in the embodiment of the present invention where the mixing amount of PTFE is 10 vol% to 20 vol% and the ratio R1 / R2 of the abundance relationship is 1.5 or more, even when using a bio-derived alternative fuel, peeling and property changes of the overlay layer 13 can be reduced, and the sliding characteristics can be maintained.

[0031] As described above, in the sliding member 10 of the present embodiment, the increase in the oil repellency of the overlay layer 13 prevents the penetration of lubricating oil into the overlay layer 13. Therefore, the sliding member 10 of the present embodiment can reduce the deterioration associated with the swelling and structural changes of the overlay layer 13 even when the acid generated by the use of alternative fuel is contained in the lubricating oil. Further, in the sliding member 10 of the present embodiment, the penetration of lubricating oil containing acid into the interface between the bearing alloy layer 12 and the overlay layer 13 is reduced, and the corrosion of the bearing alloy layer 12 can be reduced. As a result, the strength of the overlay layer 13 of the sliding member 10 of the present embodiment is maintained, and the peeling of the overlay layer 13 from the bearing alloy layer 12 is reduced. Therefore, the sliding characteristics can be maintained.

[0032] Further, when forming the overlay layer 13 of the sliding member 10 of the present embodiment, by ensuring a predetermined time in the standing process after applying the mixed resin, more of the fluororesin compound 22 contained in the mixed resin exists on the upper layer 31 side of the overlay layer 13. Therefore, the oil repellency of the overlay layer 13 of the sliding member 10 of the present embodiment is improved. That is, the sliding member 10 of the present embodiment can improve the oil repellency by providing a standing process in the manufacturing process. Therefore, it is possible to improve the oil repellency of the sliding member 10 and maintain the sliding characteristics associated therewith without adding complicated processes or special processing.

[0033] The present invention described above is not limited to the above-described embodiment, and can be applied to various embodiments without departing from the gist thereof.

Explanation of reference numerals

[0034] In the drawings, 10 represents a sliding member, 13 represents an overlay layer, 21 represents a binder resin, 22 represents a fluororesin compound, 31 represents an upper layer, 32 represents a lower layer, and 41 represents a solid lubricant.

Claims

1. A sliding member comprising a resin overlay layer, wherein the overlay layer comprises a binder resin and 10 to 20 vol% of a fluororesin compound dispersed and added in the binder resin, and when the overlay layer is divided into an upper layer and a lower layer at the middle in the thickness direction, the relationship of the value of the abundance ratio of the fluororesin compound contained in the overlay layer is upper layer / lower layer = 1.5 or more, a sliding member.

2. the overlay layer further comprises 10 to 30 vol% of a solid lubricant, and contains at least one or more specific solid lubricants whose specific gravity is 1.5 times or more that of the fluororesin compound, the sliding member according to Claim 1.

3. The specific solid lubricant contains MoS ２ and the sliding member according to Claim 2.

4. A method for manufacturing a sliding member comprising a resin overlay layer, comprising a mixing step of mixing a fluororesin compound into a binder resin to produce a mixed resin, a coating step of coating the mixed resin produced in the mixing step in a film form on the surface of a substrate by spray coating, a standing step of standing the mixed resin coated in the coating step for a preset period, and a method for manufacturing a sliding member.

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