PEEK composite material with high wear resistance and preparation method thereof

Abstract

The invention discloses a PEEK composite material with high wear resistance and a preparation method thereof. The composite material is prepared from the following components in parts by mass: 60 to 70 parts of PEEK resin, 10 to 15 parts of maleic anhydride grafted fluorinated polyether-ether-ketone, 3 to 5 parts of graphene nanosheets, 5 to 8 parts of core-shell structure modified MoS2-CuO composite particles, 2 to 4 parts of a coupling agent, 0.5 to 1 part of an antioxidant, 3 to 5 parts of nanoparticles, 8 to 10 parts of carbon fibers and 1 to 3 parts of other functional aids. After the components are uniformly mixed, the mixture is subjected to melt mixing and extrusion molding in a temperature range of 340-380 DEG C through a twin-screw extruder. The friction coefficient and the specific wear rate of the material are remarkably reduced by means of the lubricating-enhancing-compatibility synergistic effect of the components, meanwhile, the excellent tensile strength and impact strength are kept, the wear resistance and the mechanical property are both considered, and the material is suitable for the scene with the high wear resistance requirement.

Description

Technical Field

[0001] This invention relates to the field of high-performance polymer composite materials technology, and in particular to a PEEK composite material with high wear resistance and its preparation method. Background Technology

[0002] Polyetheretherketone (PEEK), a high-performance thermoplastic engineering plastic, possesses excellent high-temperature resistance, mechanical strength, chemical stability, biocompatibility, and electrical insulation, making it widely used in high-end equipment manufacturing. However, pure PEEK materials have a high coefficient of friction and a relatively high wear rate, and are prone to adhesive wear and surface peeling under dry friction or high-load conditions, limiting their large-scale application in wear-resistant transmission components.

[0003] To improve the wear resistance of PEEK, existing technologies typically employ modification methods using solid lubricants such as polytetrafluoroethylene (PTFE), molybdenum disulfide (Mo), and graphite. While these lubricant modifications can reduce the coefficient of friction to some extent, they still suffer from several drawbacks, including poor filler dispersibility, easy agglomeration leading to uneven material properties, weak interfacial bonding between the filler and the PEEK matrix resulting in easy filler detachment and leakage during long-term use, limited improvement in wear resistance making it difficult to meet the requirements of extreme operating conditions, and the impact of excessive addition on processing fluidity and mechanical properties.

[0004] To address the aforementioned issues, invention patent document CN117384463B discloses a carbon fiber reinforced sulfonated PEEK composite material and its preparation method. The composite material is formed by combining a sulfonated PEEK resin matrix with short carbon fiber particles, and the degree of sulfonation of the sulfonated PEEK resin powder is 1.5–2.5%. By sulfonating the PEEK resin, sulfonate anions are introduced into the polymer structure, significantly increasing the negative charge density on the surface of the composite material. This allows for the rapid and effective adsorption of hydrated cations in the solution to form a hydrated layer. This hydrated layer provides lubrication, significantly reducing the coefficient of friction and improving wear resistance. Therefore, when used in water-lubricated bearings, this material exhibits a low coefficient of friction and wear rate. Simultaneously, the composite modification with short carbon fibers improves the mechanical strength of the PEEK resin and further reduces the coefficient of friction and wear rate. However, its lubrication performance is highly dependent on the water-lubricated environment. Under extreme conditions such as dry friction and high temperature, the hydrated layer is prone to failure, and the sulfonation treatment weakens the chemical resistance and dimensional stability of the PEEK matrix, making it unsuitable for various wear-resistant applications.

[0005] It is evident that seeking a more effective method to prepare a PEEK composite material that combines high wear resistance and excellent mechanical properties is of great significance for expanding the application of PEEK in high-end manufacturing. Summary of the Invention

[0006] The present invention aims to overcome the defects of poor phase synergy, weak interfacial bonding, and imbalance between wear resistance and mechanical properties in existing PEEK composite materials, and provides a PEEK composite material with high wear resistance and its preparation method. The composite material has both high wear resistance and excellent mechanical properties.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is: a PEEK composite material with high wear resistance, the components of which, by mass, include: 60-70 parts of PEEK resin, 10-15 parts of maleic anhydride-grafted fluorinated polyether ether ketone, 3-5 parts of graphene nanosheets, 5-8 parts of core-shell structure-modified MoS2-CuO composite particles, 2-4 parts of coupling agent, 0.5-1 part of antioxidant, 3-5 parts of nanoparticles, 8-10 parts of carbon fiber, and 1-3 parts of other functional additives.

[0008] Preferably, the PEEK resin is 450g. TM PEEK.

[0009] Preferably, there are no special requirements for the source of the fluorinated polyaryletherketone. In one embodiment of the present invention, the maleic anhydride-grafted fluorinated polyaryletherketone is prepared according to the method of Example 4 in document CN121249163A.

[0010] Preferably, the graphene nanosheets have a diameter of 5-10 μm and a thickness of 3-10 nm.

[0011] Preferably, the preparation method of the core-shell structure modified MoS2-CuO composite particles includes the following steps: mixing MoS2 powder with an ethanol solution of silane coupling agent KH550, ultrasonically dispersing at 300-400W for 40-60 min, filtering, and drying at 80-100℃ to constant weight to obtain the modified MoS2 core; placing CuO powder in an ethanol solution of titanate coupling agent, stirring and reacting at 50-70℃ for 1-2 h, filtering, and drying at 110-130℃ to constant weight to obtain the modified CuO; mixing the modified MoS2 core with the modified CuO, adding anhydrous ethanol, ultrasonically dispersing at 300W for 30 min, stirring and reacting at 80℃ for 2 h, and drying to obtain the core-shell structured composite particles.

[0012] Preferably, the average particle size of the MoS2 powder is 50-100 nm; the average particle size of the CuO powder is 1-3 μm.

[0013] Preferably, the mass ratio of the MoS2 powder, the ethanol solution of the silane coupling agent KH550, the CuO powder, and the ethanol solution of the titanate coupling agent is 100:(200-300):(66.7-150):(133.4-450); the mass of the anhydrous ethanol is twice the total mass of the modified MoS2 core and the modified CuO; the mass percentage concentration of the ethanol solution of the silane coupling agent KH550 is 3-5%; the mass percentage concentration of the ethanol solution of the titanate coupling agent is 3-5%; and the titanate coupling agent is titanate coupling agent NDZ-101.

[0014] Preferably, the coupling agent is at least one of silane coupling agent KH550, silane coupling agent KH560, and silane coupling agent KH570; the antioxidant is antioxidant 1010.

[0015] Preferably, the nanoparticles are nano-silicon nitride and nano-silicon carbide compounded in a mass ratio of 1:(3-5); the average particle size of the nanoparticles is 20-60 nm.

[0016] Preferably, the carbon fiber has a length of 0.5-1 mm and an average diameter of 7-10 μm.

[0017] Preferably, the other functional additives are composed of potassium titanate whiskers, tungsten disulfide nanosheets, boron nitride nanotubes, and molybdenum dialkyl dithiophosphate in a mass ratio of 1:(0.8-1.2):0.3:0.6.

[0018] Preferably, the tungsten disulfide nanosheets have a diameter of 20-500 nm and a thickness of 1-5 nm; the potassium titanate whiskers are potassium titanate whiskers TISMO®; and the boron nitride nanotubes have an average diameter of 50 nm and a length of 10-20 μm.

[0019] Another objective of this invention is to provide a method for preparing the PEEK composite material with high wear resistance, comprising the following steps: mixing each component evenly according to mass parts to obtain a mixture, adding the mixture to a twin-screw extruder, melting and kneading and extruding to obtain the PEEK composite material with high wear resistance.

[0020] Preferably, the temperature of the twin-screw extruder is 340-350℃ in the feeding section, 360-370℃ in the compression section, 370-380℃ in the homogenization section, and 365-375℃ in the die head. The screw speed is 150-200 r / min, and the traction speed is 8-12 m / min.

[0021] Due to the application of the above technical solution, the present invention has the following beneficial effects: (1) The PEEK composite material with high wear resistance disclosed in this invention breaks through the core bottleneck of existing PEEK wear-resistant modification through component synergistic design, and achieves dual optimization of interface bonding and dispersion, resulting in wear resistance gains far exceeding those of single filler modification. In the prior art, solid lubricants are prone to agglomeration and have weak interface bonding with the matrix, resulting in unstable wear resistance and easy filler detachment. However, this invention uses maleic anhydride-grafted fluorinated polyether ether ketone as a compatibility medium, combined with a specific coupling agent, which not only strengthens the interfacial interaction between fillers such as graphene and core-shell MoS2-CuO composite particles and the PEEK matrix, but also inhibits the agglomeration of nanofillers, so that the composite system forms a uniform and stable microstructure. This synergistic effect not only significantly reduces the coefficient of friction of the material compared with pure PEEK and traditional filler-modified PEEK, and greatly reduces the wear rate, but also avoids the deterioration of processing fluidity caused by the addition of a large amount of filler, solving the industry problem of "improvement of wear resistance and imbalance of processing performance". This is a technological breakthrough that is difficult to achieve with single lubricant or fiber modification.

[0022] (2) The PEEK composite material with high wear resistance disclosed in this invention constructs a multi-component synergistic lubrication system, breaking through the limitations of existing technologies in terms of working condition adaptability, and achieving stable wear resistance under extreme environments such as dry friction and high temperature. The lubrication effect of existing sulfonated PEEK composite materials is highly dependent on the water lubrication environment, and they are prone to failure under dry friction or high temperature. Moreover, sulfonation treatment weakens the chemical resistance and dimensional stability of the matrix. Traditional solid lubricant modification has limited improvement in wear resistance under extreme working conditions. In this invention, the core-shell structure of the core-shell MoS2-CuO composite particles can form a dual effect of "solid lubrication + hard support". Combined with the lubrication and reinforcement effect of graphene, and the synergistic effect of functional additives such as tungsten disulfide nanosheets and boron nitride nanotubes, an autonomous lubrication system that does not depend on a specific medium is constructed. It can still maintain a low coefficient of friction under high temperature dry friction conditions. At the same time, the matrix has not undergone sulfonation treatment, which fully preserves the excellent chemical resistance and dimensional stability of PEEK itself, realizes the adaptation of wear resistance requirements in multiple scenarios, and fills the application gap of PEEK wear-resistant parts under extreme working conditions.

[0023] (3) The PEEK composite material with high wear resistance disclosed in this invention achieves a precise balance between wear resistance and mechanical properties, significantly improving the overall service capability of the material compared to existing technologies. Existing technologies often present a contradiction of "improving wear resistance at the expense of mechanical properties." For example, adding a large amount of solid lubricant will reduce the tensile strength and impact strength of PEEK, while simple fiber reinforcement is difficult to achieve the same wear resistance. This invention uses the composite reinforcement of carbon fiber with nano-silicon nitride and silicon carbide, combined with the optimization of system compatibility by grafting maleic anhydride with fluorinated polyether ether ketone, to significantly improve wear resistance while significantly improving the tensile strength of the composite material and maintaining stable impact strength, forming a comprehensive advantage of "high wear resistance + high strength". This performance balance allows the material to meet the friction requirements of wear-resistant transmission components and withstand the high-load conditions in high-end equipment manufacturing, overcoming the imbalance between mechanical and wear resistance properties of existing modified PEEK, and expanding its application boundaries in high-end wear-resistant components.

[0024] (4) The PEEK composite material with high wear resistance disclosed in this invention significantly reduces the amount of key components due to the synergistic effect of fillers, combining cost advantages and environmental adaptability, and exhibiting a modification efficiency that exceeds expectations. In order to achieve the target wear resistance, existing technologies often require the addition of large amounts of solid lubricants, which not only increases costs but also leads to a decrease in the material's aging resistance and media resistance. This invention optimizes filler activity through core-shell structure modification and multi-component synergistic effect, achieving a wear resistance effect superior to existing high-filler systems with a low total filler addition. The amount of core-shell MoS2-CuO composite particles is only 5-8 parts, yet it can exert a lubrication and wear resistance effect far exceeding that of single MoS2 or CuO. At the same time, the system uses antioxidant 1010 in combination with multi-components, which effectively inhibits aging and degradation during melt processing and service, reducing the performance decay rate of the material during long-term use. It takes into account the modification effect, cost control and service durability, which is a comprehensive advantage that is difficult to achieve with existing single modification schemes. Detailed Implementation

[0025] The following description is intended to disclose the invention and enable those skilled in the art to implement it. The preferred embodiments described below are merely examples, and other obvious variations will occur to those skilled in the art.

[0026] Example 1 A PEEK composite material with high wear resistance comprises, by weight, 60 parts of PEEK resin, 10 parts of maleic anhydride-grafted fluorinated polyether ether ketone, 3 parts of graphene nanosheets, 5 parts of core-shell structure-modified MoS2-CuO composite particles, 2 parts of coupling agent, 0.5 parts of antioxidant, 3 parts of nanoparticles, 8 parts of carbon fiber, and 1 part of other functional additives.

[0027] The PEEK resin is 450g. TMPEEK; the maleic anhydride-grafted fluorinated polyether ether ketone was prepared according to the method in Example 4 of document CN121249163A; the graphene nanosheets had a diameter of 5-10 μm and a thickness of 3-10 nm.

[0028] The preparation method of the core-shell structure modified MoS2-CuO composite particles includes the following steps: MoS2 powder is mixed with an ethanol solution of silane coupling agent KH550, ultrasonically dispersed at 300W for 40 min, filtered, and dried at 80℃ to constant weight to obtain the modified MoS2 core; CuO powder is placed in an ethanol solution of titanate coupling agent, stirred and reacted at 50℃ for 1 h, filtered, and dried at 110℃ to constant weight to obtain the modified CuO; the modified MoS2 core and modified CuO are mixed, anhydrous ethanol is added, and the mixture is ultrasonically dispersed at 300W for 30 min, then stirred and reacted at 80℃ for 2 h, and dried to obtain the core-shell structure. The structure is a composite particle; the average particle size of the MoS2 powder is 50 nm; the average particle size of the CuO powder is 1 μm; the mass ratio of the MoS2 powder, the ethanol solution of silane coupling agent KH550, the CuO powder, and the ethanol solution of titanate coupling agent is 100:200:66.7:133.4; the mass of the anhydrous ethanol is twice the total mass of the modified MoS2 core and the modified CuO; the mass percentage concentration of the ethanol solution of silane coupling agent KH550 is 3%; the mass percentage concentration of the ethanol solution of titanate coupling agent is 3%; the titanate coupling agent is titanate coupling agent NDZ-101.

[0029] The coupling agent is silane coupling agent KH550; the antioxidant is antioxidant 1010; the nanoparticles are nano-silicon nitride and nano-silicon carbide compounded in a mass ratio of 1:3; the average particle size of the nanoparticles is 20 nm; the carbon fiber has a length of 0.5 mm and an average diameter of 7 μm; the other functional additives are potassium titanate whiskers, tungsten disulfide nanosheets, boron nitride nanotubes, and molybdenum dialkyl dithiophosphate compounded in a mass ratio of 1:0.8:0.3:0.6; the tungsten disulfide nanosheets have a sheet diameter of 20-500 nm and a thickness of 1-5 nm; the potassium titanate whiskers are potassium titanate whiskers TISMO®; the boron nitride nanotubes have an average diameter of 50 nm and a length of 10 μm.

[0030] A method for preparing a PEEK composite material with high wear resistance includes the following steps: mixing the components evenly according to their mass fractions to obtain a mixture; adding the mixture to a twin-screw extruder; melting and kneading the mixture; and extruding it to obtain a PEEK composite material with high wear resistance; wherein the temperature of the twin-screw extruder is 340℃ in the feeding section, 360℃ in the compression section, 370℃ in the homogenization section, and 365℃ in the die head; the screw speed is 150 r / min; and the traction speed is 8 m / min.

[0031] Example 2 A PEEK composite material with high wear resistance comprises, by weight, 63 parts of PEEK resin, 12 parts of maleic anhydride-grafted fluorinated polyether ether ketone, 3.5 parts of graphene nanosheets, 6 parts of core-shell structure-modified MoS2-CuO composite particles, 2.5 parts of coupling agent, 0.6 parts of antioxidant, 3.5 parts of nanoparticles, 8.5 parts of carbon fiber, and 1.5 parts of other functional additives.

[0032] The PEEK resin is 450g. TM PEEK; the maleic anhydride-grafted fluorinated polyether ether ketone was prepared according to the method in Example 4 of document CN121249163A; the graphene nanosheets had a diameter of 5-10 μm and a thickness of 3-10 nm.

[0033] The preparation method of the core-shell modified MoS2-CuO composite particles includes the following steps: MoS2 powder is mixed with an ethanol solution of silane coupling agent KH550, ultrasonically dispersed at 330W for 45 min, filtered, and dried at 85℃ to constant weight to obtain the modified MoS2 core; CuO powder is placed in an ethanol solution of titanate coupling agent, stirred and reacted at 55℃ for 1.2 h, filtered, and dried at 115℃ to constant weight to obtain the modified CuO; the modified MoS2 core and modified CuO are mixed, anhydrous ethanol is added, and the mixture is ultrasonically dispersed at 300W for 30 min, then stirred and reacted at 80℃ for 2 h, and dried to obtain the core-shell structure. The structure is a composite particle; the average particle size of the MoS2 powder is 60 nm; the average particle size of the CuO powder is 1.5 μm; the mass ratio of the MoS2 powder, the ethanol solution of silane coupling agent KH550, the CuO powder, and the ethanol solution of titanate coupling agent is 100:230:80:230; the mass of the anhydrous ethanol is twice the total mass of the modified MoS2 core and the modified CuO; the mass percentage concentration of the ethanol solution of silane coupling agent KH550 is 3.5%; the mass percentage concentration of the ethanol solution of titanate coupling agent is 3.5%; the titanate coupling agent is titanate coupling agent NDZ-101.

[0034] The coupling agent is silane coupling agent KH560; the antioxidant is antioxidant 1010; the nanoparticles are nano-silicon nitride and nano-silicon carbide compounded in a mass ratio of 1:3.5; the average particle size of the nanoparticles is 30 nm; the carbon fiber has a length of 0.7 mm and an average diameter of 8 μm; the other functional additives are potassium titanate whiskers, tungsten disulfide nanosheets, boron nitride nanotubes, and molybdenum dialkyl dithiophosphate compounded in a mass ratio of 1:0.9:0.3:0.6; the tungsten disulfide nanosheets have a sheet diameter of 20-500 nm and a thickness of 1-5 nm; the potassium titanate whiskers are potassium titanate whiskers TISMO®; the boron nitride nanotubes have an average diameter of 50 nm and a length of 13 μm.

[0035] A method for preparing a PEEK composite material with high wear resistance includes the following steps: mixing the components evenly according to their mass fractions to obtain a mixture; adding the mixture to a twin-screw extruder; melting and kneading the mixture and extruding it to obtain a PEEK composite material with high wear resistance; wherein the temperature of the twin-screw extruder is 343℃ in the feeding section, 363℃ in the compression section, 373℃ in the homogenization section, and 368℃ in the die head; the screw speed is 170 r / min; and the traction speed is 9 m / min.

[0036] Example 3 A PEEK composite material with high wear resistance comprises, by weight, 65 parts of PEEK resin, 13 parts of maleic anhydride-grafted fluorinated polyether ether ketone, 4 parts of graphene nanosheets, 6.5 parts of core-shell modified MoS2-CuO composite particles, 3 parts of coupling agent, 0.8 parts of antioxidant, 4 parts of nanoparticles, 9 parts of carbon fiber, and 2 parts of other functional additives.

[0037] The PEEK resin is 450g. TM PEEK; the maleic anhydride-grafted fluorinated polyether ether ketone was prepared according to the method in Example 4 of document CN121249163A; the graphene nanosheets had a diameter of 5-10 μm and a thickness of 3-10 nm.

[0038] The preparation method of the core-shell structure modified MoS2-CuO composite particles includes the following steps: MoS2 powder is mixed with an ethanol solution of silane coupling agent KH550, ultrasonically dispersed at 350W for 50 min, filtered, and dried at 90℃ to constant weight to obtain the modified MoS2 core; CuO powder is placed in an ethanol solution of titanate coupling agent, stirred and reacted at 60℃ for 1.5 h, filtered, and dried at 120℃ to constant weight to obtain the modified CuO; the modified MoS2 core and modified CuO are mixed, anhydrous ethanol is added, and the mixture is ultrasonically dispersed at 300W for 30 min, then stirred and reacted at 80℃ for 2 h, and dried to obtain the modified CuO. The core-shell structured composite particles are obtained; the average particle size of the MoS2 powder is 75 nm; the average particle size of the CuO powder is 2 μm; the mass ratio of the MoS2 powder, the ethanol solution of silane coupling agent KH550, the CuO powder, and the ethanol solution of titanate coupling agent is 100:250:120:330; the mass of the anhydrous ethanol is twice the total mass of the modified MoS2 core and the modified CuO; the mass percentage concentration of the ethanol solution of silane coupling agent KH550 is 4%; the mass percentage concentration of the ethanol solution of titanate coupling agent is 4%; the titanate coupling agent is titanate coupling agent NDZ-101.

[0039] The coupling agent is silane coupling agent KH570; the antioxidant is antioxidant 1010; the nanoparticles are nano-silicon nitride and nano-silicon carbide compounded in a mass ratio of 1:4; the average particle size of the nanoparticles is 40 nm; the carbon fiber has a length of 0.8 mm and an average diameter of 8.5 μm; the other functional additives are potassium titanate whiskers, tungsten disulfide nanosheets, boron nitride nanotubes, and molybdenum dialkyl dithiophosphate compounded in a mass ratio of 1:1:0.3:0.6; the tungsten disulfide nanosheets have a sheet diameter of 20-500 nm and a thickness of 1-5 nm; the potassium titanate whiskers are potassium titanate whiskers TISMO®; the boron nitride nanotubes have an average diameter of 50 nm and a length of 15 μm.

[0040] A method for preparing a PEEK composite material with high wear resistance includes the following steps: mixing the components evenly according to their mass fractions to obtain a mixture; adding the mixture to a twin-screw extruder; melting and kneading the mixture and extruding it to obtain a PEEK composite material with high wear resistance; wherein the temperature of the twin-screw extruder is 345℃ in the feeding section, 365℃ in the compression section, 375℃ in the homogenization section, and 370℃ in the die head; the screw speed is 180 r / min; and the traction speed is 10 m / min.

[0041] Example 4 A PEEK composite material with high wear resistance comprises, by weight, 68 parts of PEEK resin, 14 parts of maleic anhydride-grafted fluorinated polyether ether ketone, 4.5 parts of graphene nanosheets, 7.5 parts of core-shell structure-modified MoS2-CuO composite particles, 3.5 parts of coupling agent, 0.9 parts of antioxidant, 4.5 parts of nanoparticles, 9.5 parts of carbon fiber, and 2.5 parts of other functional additives.

[0042] The PEEK resin is 450g. TM PEEK; the maleic anhydride-grafted fluorinated polyether ether ketone was prepared according to the method in Example 4 of document CN121249163A; the graphene nanosheets had a diameter of 5-10 μm and a thickness of 3-10 nm.

[0043] The preparation method of the core-shell structure modified MoS2-CuO composite particles includes the following steps: MoS2 powder is mixed with an ethanol solution of silane coupling agent KH550, ultrasonically dispersed at 380W for 55 min, filtered, and dried at 95℃ to constant weight to obtain the modified MoS2 core; CuO powder is placed in an ethanol solution of titanate coupling agent, stirred and reacted at 65℃ for 1.8 h, filtered, and dried at 125℃ to constant weight to obtain the modified CuO; the modified MoS2 core and modified CuO are mixed, anhydrous ethanol is added, and the mixture is ultrasonically dispersed at 300W for 30 min, then stirred and reacted at 80℃ for 2 h, and dried to obtain the core-shell structure. The structure is a composite particle; the average particle size of the MoS2 powder is 90 nm; the average particle size of the CuO powder is 2.5 μm; the mass ratio of the MoS2 powder, the ethanol solution of silane coupling agent KH550, the CuO powder, and the ethanol solution of titanate coupling agent is 100:280:140:420; the mass of the anhydrous ethanol is twice the total mass of the modified MoS2 core and the modified CuO; the mass percentage concentration of the ethanol solution of silane coupling agent KH550 is 4.5%; the mass percentage concentration of the ethanol solution of titanate coupling agent is 4.5%; the titanate coupling agent is titanate coupling agent NDZ-101.

[0044] The coupling agent is a compound of silane coupling agents KH550, KH560, and KH570 in a mass ratio of 1:2:3; the antioxidant is antioxidant 1010; the nanoparticles are a compound of nano-silicon nitride and nano-silicon carbide in a mass ratio of 1:4.5; the average particle size of the nanoparticles is 50 nm; the carbon fiber has a length of 0.9 mm and an average diameter of 9.5 μm; the other functional additives are a compound of potassium titanate whiskers, tungsten disulfide nanosheets, boron nitride nanotubes, and molybdenum dialkyl dithiophosphate in a mass ratio of 1:1.1:0.3:0.6; the tungsten disulfide nanosheets have a diameter of 20-500 nm and a thickness of 1-5 nm; the potassium titanate whiskers are potassium titanate whiskers TISMO®; the boron nitride nanotubes have an average diameter of 50 nm and a length of 18 μm.

[0045] A method for preparing a PEEK composite material with high wear resistance includes the following steps: mixing the components evenly according to their mass fractions to obtain a mixture; adding the mixture to a twin-screw extruder; melting and kneading the mixture and extruding it to obtain a PEEK composite material with high wear resistance; wherein the temperature of the twin-screw extruder is 348℃ in the feeding section, 368℃ in the compression section, 378℃ in the homogenization section, and 373℃ in the die head; the screw speed is 190 r / min; and the traction speed is 11 m / min.

[0046] Example 5 A PEEK composite material with high wear resistance comprises, by weight, 60 parts of PEEK resin, 10 parts of maleic anhydride-grafted fluorinated polyether ether ketone, 5 parts of graphene nanosheets, 8 parts of core-shell structure-modified MoS2-CuO composite particles, 4 parts of coupling agent, 1 part of antioxidant, 5 parts of nanoparticles, 10 parts of carbon fiber, and 3 parts of other functional additives.

[0047] The PEEK resin is 450g. TM PEEK; the maleic anhydride-grafted fluorinated polyether ether ketone was prepared according to the method in Example 4 of document CN121249163A; the graphene nanosheets had a diameter of 5-10 μm and a thickness of 3-10 nm.

[0048] The preparation method of the core-shell structure modified MoS2-CuO composite particles includes the following steps: MoS2 powder is mixed with an ethanol solution of silane coupling agent KH550, ultrasonically dispersed at 400W for 60 min, filtered, and dried at 100℃ to constant weight to obtain the modified MoS2 core; CuO powder is placed in an ethanol solution of titanate coupling agent, stirred and reacted at 70℃ for 2 h, filtered, and dried at 130℃ to constant weight to obtain the modified CuO; the modified MoS2 core and modified CuO are mixed, anhydrous ethanol is added, and the mixture is ultrasonically dispersed at 300W for 30 min, then stirred and reacted at 80℃ for 2 h, and dried to obtain the modified CuO. The core-shell structured composite particles; the average particle size of the MoS2 powder is 100 nm; the average particle size of the CuO powder is 3 μm; the mass ratio of the MoS2 powder, the ethanol solution of silane coupling agent KH550, the CuO powder, and the ethanol solution of titanate coupling agent is 100:300:150:450; the mass of the anhydrous ethanol is twice the total mass of the modified MoS2 core and the modified CuO; the mass percentage concentration of the ethanol solution of silane coupling agent KH550 is 5%; the mass percentage concentration of the ethanol solution of titanate coupling agent is 5%; the titanate coupling agent is titanate coupling agent NDZ-101.

[0049] The coupling agent is silane coupling agent KH550; the antioxidant is antioxidant 1010; the nanoparticles are nano-silicon nitride and nano-silicon carbide compounded in a mass ratio of 1:5; the average particle size of the nanoparticles is 60 nm; the carbon fiber has a length of 1 mm and an average diameter of 10 μm; the other functional additives are potassium titanate whiskers, tungsten disulfide nanosheets, boron nitride nanotubes, and molybdenum dialkyl dithiophosphate compounded in a mass ratio of 1:1.2:0.3:0.6; the tungsten disulfide nanosheets have a sheet diameter of 20-500 nm and a thickness of 1-5 nm; the potassium titanate whiskers are potassium titanate whiskers TISMO®; the boron nitride nanotubes have an average diameter of 50 nm and a length of 20 μm.

[0050] A method for preparing a PEEK composite material with high wear resistance includes the following steps: mixing the components evenly according to their mass fractions to obtain a mixture; adding the mixture to a twin-screw extruder; melting and kneading the mixture and extruding it to obtain a PEEK composite material with high wear resistance; wherein the temperature of the twin-screw extruder is 350°C in the feeding section, 370°C in the compression section, 380°C in the homogenization section, and 375°C in the die head; the screw speed is 200 r / min; and the traction speed is 12 m / min.

[0051] Comparative Example 1 A PEEK composite material with high wear resistance is basically the same as that in Example 5, except that an equal amount of PEEK resin is used instead of maleic anhydride-grafted fluorinated polyether ether ketone.

[0052] Comparative Example 2 A PEEK composite material with high wear resistance is basically the same as that in Example 5, except that an equal amount of MoS2 is used to replace the core-shell modified MoS2-CuO composite particles.

[0053] Comparative Example 3 A PEEK composite material with high wear resistance is basically the same as that in Example 5, except that an equal amount of CuO is used to replace the core-shell structure modified MoS2-CuO composite particles.

[0054] Comparative Example 4 A PEEK composite material with high wear resistance is basically the same as that in Example 5, except that an equal amount of potassium titanate whiskers are used instead of tungsten disulfide nanosheets.

[0055] Comparative Example 5 A PEEK composite material with high wear resistance is basically the same as that in Example 5, except that an equal amount of tungsten disulfide nanosheets are used instead of potassium titanate whiskers.

[0056] Comparative Example 6 A PEEK composite material with high wear resistance is basically the same as that in Example 5, except that boron nitride nanotubes are used instead of molybdenum dialkyl dithiophosphate.

[0057] Comparative Example 7 A PEEK composite material with high wear resistance is basically the same as that in Example 5, except that boron nitride nanotubes are replaced with an equal amount of molybdenum dialkyl dithiophosphate.

[0058] To further illustrate the beneficial technical effects of the various embodiments of the present invention, relevant performance tests were conducted on the PEEK composite materials with high wear resistance prepared in Example 5 and Comparative Examples 1-7. The test results are shown in Table 1, and the test methods are as follows: (1) Friction and wear performance test: Referring to GB / T 3960-2016 "Test method for sliding friction and wear of plastics", a ball-disc friction and wear tester was used. The grinding pair was GCr15 steel balls (diameter 6mm, hardness HRC 62-64). The test conditions were: dry friction environment, load 30N, rotation speed 200r / min, sliding time 120min, and sliding distance 75.36m. Three parallel samples were tested in each group, and the average value was taken as the friction coefficient and specific wear rate.

[0059] (2) Tensile property test: Refer to GB / T 1040.1-2018 "Determination of tensile properties of plastics - Part 1: General Rules", use a universal testing machine, the sample type is I, the tensile speed is 5 mm / min, and the tensile strength is tested. Three parallel samples are used in each group and the average value is taken.

[0060] (3) Impact performance test: Refer to GB / T 1043.1-2008 "Determination of impact strength of simply supported beams of plastics - Part 1: Non-instrumental impact test", use a simply supported beam impact tester, the sample size is 80mm×10mm×4mm, without notch, test the impact strength, 5 parallel samples in each group, and take the average value.

[0061] Table 1 Performance test results of PEEK composite materials with high wear resistance As shown in Table 1, the high-wear-resistant PEEK composite material of Example 5 of this invention exhibits the best overall performance in both friction and wear resistance and mechanical properties: its coefficient of friction is as low as 0.011, and its specific wear rate is only 0.32 × 10⁻⁶. - 6 mm 3 / (N·m), significantly better than all comparative examples, while maintaining a tensile strength of 127MPa and 13.0kJ / m. 2 The impact strength was improved, achieving a synergistic enhancement of wear resistance and mechanical properties; however, the comparative examples, due to the replacement of key components in maleic anhydride-grafted fluorinated polyether ether ketone, core-shell structure-modified MoS2-CuO composite particles, or compound functional additives, respectively, disrupted the original synergistic system of components, resulting in an increase in the coefficient of friction to 0.017-0.025 and a specific wear rate to (0.85-3.21)×10 -6 mm 3 The tensile strength and impact strength also decreased to varying degrees, which fully demonstrates that the present invention effectively solves the problem of the difficulty in balancing the wear resistance and mechanical properties of PEEK composite materials through the precise compounding of specific components and structural design. The lubrication, reinforcement and compatibility synergistic effects formed between the components significantly improve the overall performance of the material.

[0062] The above embodiments are only for illustrating the technical concept and features of the present invention. Their purpose is to enable those skilled in the art to understand the content of the present invention and implement it accordingly. They should not be used to limit the scope of protection of the present invention. All equivalent changes or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.

Claims

1. A PEEK composite material with high wear resistance, characterized in that, Its components, by mass, include: 60-70 parts of PEEK resin, 10-15 parts of maleic anhydride-grafted fluorinated polyether ether ketone, 3-5 parts of graphene nanosheets, 5-8 parts of core-shell structure-modified MoS2-CuO composite particles, 2-4 parts of coupling agent, 0.5-1 part of antioxidant, 3-5 parts of nanoparticles, 8-10 parts of carbon fiber, and 1-3 parts of other functional additives.

2. The PEEK composite material with high wear resistance according to claim 1, characterized in that, The PEEK resin is 450g. TM PEEK.

3. The PEEK composite material with high wear resistance according to claim 1, characterized in that, The graphene nanosheets have a diameter of 5-10 μm and a thickness of 3-10 nm.

4. The PEEK composite material with high wear resistance according to claim 1, characterized in that, The preparation method of the core-shell structure modified MoS2-CuO composite particles includes the following steps: MoS2 powder is mixed with an ethanol solution of silane coupling agent KH550, ultrasonically dispersed at 300-400W for 40-60 min, filtered, and dried at 80-100℃ to constant weight to obtain the modified MoS2 core; CuO powder is placed in an ethanol solution of titanate coupling agent, stirred and reacted at 50-70℃ for 1-2 h, filtered, and dried at 110-130℃ to constant weight to obtain the modified CuO; the modified MoS2 core and modified CuO are mixed, anhydrous ethanol is added, ultrasonically dispersed at 300W for 30 min, stirred and reacted at 80℃ for 2 h, and dried to obtain the core-shell structured composite particles.

5. The PEEK composite material with high wear resistance according to claim 4, characterized in that, The average particle size of the MoS2 powder is 50-100 nm; the average particle size of the CuO powder is 1-3 μm.

6. The PEEK composite material with high wear resistance according to claim 4, characterized in that, The mass ratio of the MoS2 powder, the ethanol solution of the silane coupling agent KH550, the CuO powder, and the ethanol solution of the titanate coupling agent is 100:(200-300):(66.7-150):(133.4-450); the mass of the anhydrous ethanol is twice the total mass of the modified MoS2 core and the modified CuO; the mass percentage concentration of the ethanol solution of the silane coupling agent KH550 is 3-5%; the mass percentage concentration of the ethanol solution of the titanate coupling agent is 3-5%; and the titanate coupling agent is titanate coupling agent NDZ-101.

7. The PEEK composite material with high wear resistance according to claim 1, characterized in that, The coupling agent is at least one of silane coupling agent KH550, silane coupling agent KH560, and silane coupling agent KH570; the antioxidant is antioxidant 1010.

8. The PEEK composite material with high wear resistance according to claim 1, characterized in that, The nanoparticles are composed of nano-silicon nitride and nano-silicon carbide in a mass ratio of 1:(3-5); the average particle size of the nanoparticles is 20-60nm; the length of the carbon fiber is 0.5-1mm and the average diameter is 7-10μm.

9. The PEEK composite material with high wear resistance according to claim 1, characterized in that, The other functional additives are potassium titanate whiskers, tungsten disulfide nanosheets, boron nitride nanotubes, and molybdenum dialkyl dithiophosphate compounded in a mass ratio of 1:(0.8-1.2):0.3:0.6; the tungsten disulfide nanosheets have a diameter of 20-500 nm and a thickness of 1-5 nm; the potassium titanate whiskers are potassium titanate whiskers TISMO®; the boron nitride nanotubes have an average diameter of 50 nm and a length of 10-20 μm.

10. A method for preparing a PEEK composite material with high wear resistance according to any one of claims 1-9, characterized in that, The process includes the following steps: mixing the components evenly according to their mass fractions to obtain a mixture; adding the mixture to a twin-screw extruder; melting and kneading the mixture; and extruding it to obtain a PEEK composite material with high wear resistance. The twin-screw extruder has a feeding section temperature of 340-350℃, a compression section temperature of 360-370℃, a homogenization section temperature of 370-380℃, a die head temperature of 365-375℃, a screw speed of 150-200 r / min, and a traction speed of 8-12 m / min.

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