Wear-resistant PEEK composite material and preparation method thereof

Abstract

The invention relates to the technical field of PEEK composite materials, in particular to a wear-resistant PEEK composite material and a preparation method thereof. The wear-resistant PEEK composite material is prepared from the following raw materials in parts by weight: 60-90 parts of polyether-ether-ketone resin or pretreated polyether-ether-ketone resin, 10-20 parts of polytetrafluoroethylene and 3-8 parts of a wear-resistant composite material, the pretreated polyether-ether-ketone resin is obtained through plasma treatment, and the pretreated polyether-ether-ketone resin is obtained. The wear-resistant PEEK composite material prepared by the invention has good wear resistance and mechanical properties.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of PEEK composite materials, and particularly relates to a wear-resistant PEEK composite material and a preparation method thereof. BACKGROUND

[0002] Polyether ether ketone (PEEK) composite material is a kind of high-performance thermoplastic engineering plastic, which has excellent high-temperature resistance, long-term use temperature up to 250 DEG C, good chemical stability, mechanical strength and biocompatibility. PEEK resin can further improve its mechanical properties or endow special functions by filling carbon fiber, glass fiber and other reinforcing phases or PTFE, graphene and other functional fillers, and is widely used in aerospace, medical devices, automobile industry and other fields. However, the friction coefficient of pure PEEK resin is high, and it is easy to wear under long-term friction condition, which limits its application in bearings, gears and other high wear-resistant scenes.

[0003] The existing wear-resistant PEEK composite material usually improves the friction performance by adding polytetrafluoroethylene or inorganic fillers. PTFE can effectively reduce the friction coefficient, but excessive addition will weaken the mechanical strength of the material; while the inorganic fillers can increase the hardness, but they are easy to fall off due to the large difference in polarity with PEEK and weak interface bonding, which often leads to the lack of interface bonding force of the matrix, and thus aggravates the wear. In addition, the poor dispersibility and weak interface compatibility of the traditional fillers make it difficult for the composite material to balance the comprehensive performance of low friction, high wear resistance and high strength, and a new interface optimization strategy is urgently needed.

[0004] In view of the above problems, the present application provides a composite material which is synergistically reinforced by plasma pretreatment of PEEK and functional wear-resistant fillers. The present application effectively solves the problems of interface peeling and filler agglomeration of traditional composite materials, reduces the wear rate and friction coefficient while maintaining the inherent strength of PEEK, and significantly expands its application potential in harsh working conditions such as artificial joints and aerospace bearings. SUMMARY

[0005] In view of the deficiencies in the prior art, the present application provides a wear-resistant PEEK composite material and a preparation method thereof.

[0006] To solve the above technical problems, the technical scheme adopted by the present application is as follows: A wear-resistant PEEK composite material, which is composed of the following raw materials by weight: 60-90 parts by weight of polyether ether ketone resin or pretreated polyether ether ketone resin, 10-20 parts by weight of polytetrafluoroethylene, and 3-8 parts by weight of wear-resistant composite material. The pre-treatment polyether ether ketone resin is treated by plasma of inert gas, oxygen and carbon dioxide. The polar functional groups such as hydroxyl, carboxyl and carbonyl containing oxygen and amino and imine group containing nitrogen are introduced on the surface of the resin. The specific surface area of the resin is increased. The surface of the treated PEEK workpiece can better store lubricating substances, and the bonding force between the solid lubricating coating and the PEEK workpiece is enhanced. The active groups can form hydrogen bonds or chemical bond with the amino group / hydroxyl group of the aminated / hydroxylated graphene and the carboxyl group of the carboxylated silicon dioxide in the wear-resistant composite material, thereby significantly enhancing the interface bonding force between the resin matrix and the wear-resistant filler. Meanwhile, the plasma treatment can etch the surface of the resin to form a micro-nano rough structure, further improving the mechanical interlocking effect. The synergistic effect effectively prevents the filler from falling off during friction, so that the wear-resistant composite material maintains the inherent strength of PEEK while significantly improving the wear resistance by optimizing the interface stress transfer. The polar surface after treatment is more conducive to the uniform dispersion of the filler, avoiding the local wear caused by agglomeration.

[0007] The pre-treatment polyether ether ketone resin is obtained by plasma treatment.

[0008] Preferably, the treatment gas of the plasma is composed of active gas and inert gas, and the volume ratio of the active gas to the inert gas is 10:90. The inert gas is any one of argon, helium or nitrogen. The active gas is any one of oxygen, carbon dioxide or hydrogen.

[0009] Preferably, the power of the plasma treatment is 50-100 W, the gas flow rate is 8-16 cm 3 / min, the treatment time is 30-70 min, and the treatment pressure is 0.08-0.15 Torr.

[0010] The reaction mechanism of the wear-resistant composite material is as follows: Amino / hydroxylated graphene oxide: the surface of graphene oxide is rich in active groups such as carboxyl and epoxy groups. Hydrolysis and condensation reaction occurs in ethanol / water system through silane coupling agent (amino silane or hydroxyl silane), and amino / hydroxylated graphene is obtained; Carboxylated silicon dioxide: sodium silicate solution and organic acid are used as raw materials. In the ethanol aqueous solution, Na2SiO3 is hydrolyzed to form silicic acid, which is further condensed to form amorphous silicon dioxide. The organic acid contains carboxyl and phenolic hydroxyl groups. Under alkaline conditions, the hydroxyl groups on the surface of SiO2 are combined through hydrogen bonds or esterification reaction. Ammonia with pH=10 promotes the condensation of silicic acid. Hydrochloric acid with pH=7 neutralizes the carboxyl groups and avoids excessive agglomeration, forming carboxylated silicon dioxide. The surface of the carboxylated silicon dioxide is rich in -COOH, which can react with -NH2 of the aminated graphene, improving the dispersibility and interface bonding force; The abrasion-resistant composite material is prepared by using the above-mentioned aminated graphene and carboxylated silicon dioxide as raw materials, and the amidation reaction of -NH 2 of the aminated graphene and -COOH of the carboxylated silicon dioxide occurs in an ethanol aqueous solution under heating to form a graphene-silicon dioxide hybrid network.

[0011] Preferably, the abrasion-resistant composite material comprises a reaction product of aminated / hydroxylated graphene and a carboxylated silicon dioxide material, wherein the weight ratio of the aminated / hydroxylated graphene to the carboxylated silicon dioxide material is (2-4):(3-5).

[0012] Preferably, the preparation of the abrasion-resistant composite material comprises: reacting the aminated / hydroxylated graphene and the carboxylated silicon dioxide material in a 30-50wt% ethanol aqueous solution at 60-80℃ for 3-5h.

[0013] Preferably, the preparation method of the aminated / hydroxylated graphene comprises: dispersing the graphene oxide in an alcohol solvent, and then reacting with a silane coupling agent selected from amino silane or hydroxyl silane at 60-80℃ for 8-15h.

[0014] Although PEEK resin has excellent high-temperature resistance, chemical stability and mechanical strength, the abrasion resistance and friction performance of the pure resin are still insufficient to meet the application scenarios of high load and high friction. Although the addition of PTFE can reduce the friction coefficient, it will sacrifice the hardness and mechanical strength of the material, resulting in limited improvement in abrasion resistance. There is an elastic interfacial phase between the inorganic rigid particles and the matrix resin. The existence of this elastic interfacial phase provides good interfacial bonding of the rigid particles with a certain deformation ability and the matrix. This structure can toughen the matrix with rigid particles. Therefore, it is necessary to add a multifunctional abrasion-resistant composite material to improve the comprehensive abrasion resistance of the material while maintaining the inherent properties of PEEK, introducing graphene, PTFE, etc. self-lubricating, high-hardness silicon dioxide and amino / carboxyl covalent bond strong interfacial bonding.

[0015] Preferably, the preparation method of the carboxylated silicon dioxide material comprises: reacting a sodium silicate solution with an organic acid at a pH of 8-11, and then separating after adjusting to neutral pH.

[0016] The organic acid is any one of humic acid, polyacrylic acid, and citric acid; preferably, the organic acid is polyacrylic acid.

[0017] Specifically, the preparation method of the abrasion-resistant composite material is as follows: S1, 2-5 parts by weight of graphene oxide and 200-400 parts by weight of anhydrous ethanol are ultrasonically dispersed for 1-4 h, 25-50 parts by weight of water, 2-5 parts by weight of acetic acid and 5-12 parts by weight of silane are added, and the mixture is reacted at 60-80℃ and 300-500 rpm for 8-15 h, and then suction filtered, washed and dried to obtain aminated or hydroxylated graphene; S2, 3-8 parts by weight of Na2SiO3·5H2O are dissolved in 50-120 parts by weight of 20wt% aqueous ethanol solution and stirred for 10-30 min, 7-14 parts by weight of an organic acid is added, and the mixture is stirred at 30-40℃ and 300-500 rpm for 20-50 min, the pH value is adjusted to 9.5-10.2 with 1 mol / L ammonia water, and the stirring is continued for 2-5 h; then the pH value is adjusted to 6.7-7.2 with 1 mol / L hydrochloric acid, and the stirring is continued for 15-50 min, and the mixture is left to stand for 3-6 h, centrifuged, washed and dried to obtain a carboxylated silica material; S3, 2-4 parts by weight of the aminated graphene, 3-5 parts by weight of the carboxylated silica material and 80-160 parts by weight of 30-50wt% aqueous ethanol solution are mixed and ultrasonically treated, and the mixture is reacted at 60-80℃ and 300-500 rpm for 3-5 h, and then suction filtered, washed and dried to obtain a wear-resistant composite material.

[0018] Preferably, the aminosilane is at least one of N-(6-aminohexyl)aminomethyltriethoxysilane, silane coupling agent KH-550, 4-aminobutyltriethoxysilane and 11-aminoundecyltriethoxysilane; and the hydroxysilane is at least one of 3-[bis(2-hydroxyethyl)amino]propane-triethoxysilane, tetra(2-hydroxyethoxy)silane and N-(3-acryloyloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane.

[0019] The wear-resistant composite material prepared by the application improves the compatibility and interface bonding performance between the rigid particles and the matrix through coupling agent, so as to better absorb and disperse external impact energy, improve the toughness of the composite material and enhance the impact strength. Specifically, the synergistic effect between the modified silica and graphene of the wear-resistant composite material significantly improves the tribological properties of PEEK. The plasma pretreatment introduces oxygen / nitrogen polar groups on the surface of PEEK, which greatly enhances the interface bonding force between the matrix and the filler. After the graphene is modified by amino / hydroxyl groups, the compatibility with PEEK is improved, and a three-dimensional reinforcing network is constructed with the carboxylated silica through covalent bonds. The addition of PTFE forms a low-friction transfer film, and the pretreatment of polyether ether ketone, polytetrafluoroethylene and wear-resistant composite material synergistically constructs a wear-resistant material system, so that the composite material can effectively disperse stress and inhibit crack propagation during friction, thereby significantly improving the wear resistance and mechanical properties. Through component optimization and interface regulation, the performance of the composite material is breakthroughly improved. The strong interface bonding between the pretreated PEEK and the functionalized filler solves the problem of easy interface peeling of traditional composite materials; the graphene-silica hybrid network endows the material with excellent anti-abrasive wear ability; and the lubricating effect of PTFE significantly reduces the friction coefficient.

[0020] The preparation method of the wear-resistant PEEK composite material comprises the following steps: mixing the raw materials according to the weight parts, adding them from the main feeding port of the double-screw extruder, melt blending and extruding to obtain the wear-resistant PEEK composite material.

[0021] Preferably, the extrusion temperature is 220-300 DEG C, and the screw rotation speed is 280-350 r / min.

[0022] The application provides a wear-resistant PEEK composite material and a preparation method thereof. Through interface chemical bonding and mechanical interlocking, the problems of filler aggregation and falling are solved. The wear-resistant composite material in the raw materials improves the compatibility and interface bonding performance between the rigid particles and the matrix through coupling agent, so as to better absorb and disperse external impact energy, improve the toughness of the composite material and enhance the impact strength.

[0023] 2、The process route of the application is simple, the raw materials are easy to obtain, and the large-scale production can be realized by one-step extrusion of the double-screw, which has good industrial popularization prospect. DETAILED DESCRIPTION

[0024] The above inventive content of the application will be further described in detail in combination with specific embodiments, but this should not be understood as limiting the scope of the above subject matter of the application to the following examples.

[0025] In the application, some raw materials are introduced, and other raw material substances not introduced are all commercially available: Polyether ether ketone resin was purchased from Shenzhen Datanghong Technology Co., Ltd., brand: 2299A*121754A.

[0026] Polytetrafluoroethylene was purchased from Dongguan Zhengtao Plastic Co., Ltd., model: XH0230KWA7SI.

[0027] Graphene oxide was purchased from Hubei Xiyu Hong Biological Medicine Technology Co., Ltd., item number: 1034343-98-0.

[0028] Humic acid was purchased from Jinan Hongqiao Chemical Co., Ltd., model: HQ-09.

[0029] Nanosilica was purchased from Qinghe County Chaotai Metal Material Co., Ltd., particle size / number: 100 nm.

[0030] Example 1 A wear-resistant PEEK composite material, consisting of the following raw materials by weight: 80 parts by weight of polyether ether ketone resin, 15 parts by weight of polytetrafluoroethylene, 5 parts by weight of wear-resistant composite material.

[0031] The wear-resistant composite material is a commercially available nanosilica.

[0032] The preparation method of the wear-resistant PEEK composite material, each raw material is mixed according to the weight part, added from the main feeding port of the twin-screw extruder, the extrusion temperature is 260℃, the screw rotation speed is 320r / min, the melt blending, after extrusion, the wear-resistant PEEK composite material is obtained.

[0033] Example 2 A wear-resistant PEEK composite material, consisting of the following raw materials by weight: 80 parts by weight of pretreated polyether ether ketone resin, 15 parts by weight of polytetrafluoroethylene, 5 parts by weight of wear-resistant composite material.

[0034] The pretreated polyether ether ketone resin is prepared as follows: polyether ether ketone resin is placed in a plasma treatment chamber, a mixed gas consisting of argon, oxygen and carbon dioxide in a volume ratio of 90:6:4 is introduced, the treatment time is 50 min, the plasma treatment power is 80W, the gas flow is 12 cm 3 / min, the treatment pressure is 0.12 Torr, and it is stored for standby.

[0035] The wear-resistant composite material is a commercially available nanosilica.

[0036] The preparation method of the wear-resistant PEEK composite material, each raw material is mixed according to the weight part, added from the main feeding port of the twin-screw extruder, the extrusion temperature is 260℃, the screw rotation speed is 320r / min, the melt blending, after extrusion, the wear-resistant PEEK composite material is obtained.

[0037] Example 3 A wear-resistant PEEK composite material is prepared from the following raw materials by weight: 80 parts by weight of pretreated polyether ether ketone resin, 15 parts by weight of polytetrafluoroethylene, and 5 parts by weight of wear-resistant composite material.

[0038] The pretreated polyether ether ketone resin is prepared as follows: polyether ether ketone resin is placed in a plasma treatment chamber, a mixed gas composed of argon, oxygen and carbon dioxide in a volume ratio of 90:6:4 is introduced for a treatment time of 50 min, the plasma treatment power is 80 W, the gas flow rate is 12 cm 3 / min, the treatment pressure is 0.12 Torr, and it is stored for standby use.

[0039] The preparation method of the wear-resistant composite material is as follows: Dissolve 5 parts by weight of Na2SiO3·5H2O in 80 parts by weight of 20wt% ethanol aqueous solution and stir for 15 min, add 10 parts by weight of humic acid, stir at 35℃, 400rpm for 30 min, adjust the pH value to 10 with 1mol / L ammonia water, continue to stir for 3h; then adjust the pH value to 7 with 1mol / L hydrochloric acid, continue to stir for 25 min, stand for 4h, centrifuge, wash, dry, and obtain the wear-resistant composite material.

[0040] The preparation method of the wear-resistant PEEK composite material is as follows: the raw materials are mixed by weight, added from the main feeding port of the twin-screw extruder, the extrusion temperature is 260℃, the screw rotation speed is 320r / min, the melt blending is carried out, and the wear-resistant PEEK composite material is obtained after extrusion.

[0041] Example 4 A wear-resistant PEEK composite material is prepared from the following raw materials by weight: 80 parts by weight of pretreated polyether ether ketone resin, 15 parts by weight of polytetrafluoroethylene, and 5 parts by weight of wear-resistant composite material.

[0042] The pretreated polyether ether ketone resin is prepared as follows: polyether ether ketone resin is placed in a plasma treatment chamber, a mixed gas composed of argon, oxygen and carbon dioxide in a volume ratio of 90:6:4 is introduced for a treatment time of 50 min, the plasma treatment power is 80 W, the gas flow rate is 12 cm 3 / min, the treatment pressure is 0.12 Torr, and it is stored for standby use.

[0043] The preparation method of the wear-resistant composite material is as follows: S1 5 parts by weight of Na2SiO3·5H2O was dissolved in 80 parts by weight of 20wt% ethanol aqueous solution and stirred for 15 min, 10 parts by weight of humic acid was added, and placed in 35℃, 400 rpm for 30 min, adjusted to pH 10 with 1 mol / L ammonia water, continue to stir for 3h; again with 1 mol / L hydrochloric acid pH value to 7, continue to stir for 25 min, stand for 4h, centrifugal, washing, drying, to get carboxylated silica material; S2, take 3 parts by weight of graphene, 4 parts by weight of the above carboxylated silica material and 100 parts by weight of 40wt% ethanol aqueous solution was mixed ultrasonic, at 70℃, 400 rpm for 4h, suction filtration, washing, drying, to get wear-resistant composite material.

[0044] The preparation method of the wear-resistant PEEK composite material, each raw material is mixed according to weight parts, added from the main feeding port of the twin screw extruder, the extrusion temperature is 260℃, the screw rotation speed is 320r / min, melt blending, after extrusion, the wear-resistant PEEK composite material is obtained.

[0045] Example 5 A wear-resistant PEEK composite material, which is composed of the following raw materials by weight parts: 80 parts by weight of pretreated polyether ether ketone resin, 15 parts by weight of polytetrafluoroethylene, 5 parts by weight of wear-resistant composite material.

[0046] The pretreated polyether ether ketone resin is prepared as follows: polyether ether ketone resin is put into a plasma treatment chamber, a mixed gas composed of argon, oxygen and carbon dioxide in a volume ratio of 90:6:4 is introduced, the treatment time is 50 min, the plasma treatment power is 80W, the gas flow is 12 cm 3 / min, the treatment pressure is 0.12 Torr, and it is stored for standby.

[0047] The preparation method of the wear-resistant composite material is as follows: S1, 3 parts by weight of graphene oxide and 300 parts by weight of absolute ethanol were ultrasonically dispersed for 2h, 35 parts by weight of water, 3 parts by weight of acetic acid and 8 parts by weight of amino silane were added, and reacted at 75℃, 400 rpm for 12h, suction filtration, washing, drying, to get aminated graphene; the amino silane is N-(6-aminohexyl) aminomethyl triethoxysilane; S2, 5 parts by weight of Na2SiO3·5H2O was dissolved in 80 parts by weight of 20wt% ethanol aqueous solution and stirred for 15 min, 10 parts by weight of humic acid was added, and placed in 35℃, 400 rpm for 30 min, adjusted to pH 10 with 1 mol / L ammonia water, continue to stir for 3h; again with 1 mol / L hydrochloric acid pH value to 7, continue to stir for 25 min, stand for 4h, centrifugal, washing, drying, to get carboxylated silica material; S3, 3 parts by weight of the above hydroxylated graphene, 4 parts by weight of the above carboxylated silica material and 100 parts by weight of 40wt% ethanol aqueous solution are mixed and ultrasonic treated, reacted at 70℃, 400rpm for 4h, suction filtered, washed and dried to obtain the wear-resistant composite material.

[0048] The method for preparing the wear-resistant PEEK composite material comprises mixing raw materials according to weight parts, adding from the main feeding port of the twin-screw extruder, extruding at a temperature of 260℃, and rotating the screw at a speed of 320r / min, melt blending, and extruding to obtain the wear-resistant PEEK composite material.

[0049] Example 6 A wear-resistant PEEK composite material is composed of the following raw materials according to weight parts: 80 parts by weight of polyether ether ketone resin or pretreated polyether ether ketone resin, 15 parts by weight of polytetrafluoroethylene, and 5 parts by weight of wear-resistant composite material.

[0050] The pretreated polyether ether ketone resin is prepared as follows: the polyether ether ketone resin is placed in a plasma treatment chamber, a mixed gas composed of argon, oxygen and carbon dioxide in a volume ratio of 90:6:4 is introduced, the treatment time is 50 min, the plasma treatment power is 80W, the gas flow rate is 12 cm 3 / min, the treatment pressure is 0.12 Torr, and it is stored for standby use.

[0051] The method for preparing the wear-resistant composite material is as follows: S1, 3 parts by weight of graphene oxide and 300 parts by weight of anhydrous ethanol are ultrasonic dispersed for 2h, 35 parts by weight of water, 3 parts by weight of acetic acid and 8 parts by weight of hydroxyl silane are added, and reacted at 75℃, 400rpm for 12h, suction filtered, washed and dried to obtain hydroxylated graphene; the hydroxyl silane is 3-[bis(2-hydroxyethyl)amino]propane-triethoxysilane; S2, 5 parts by weight of Na2SiO3·5H2O is dissolved in 80 parts by weight of 20wt% ethanol aqueous solution and stirred for 15min, 10 parts by weight of humic acid is added, stirred at 35℃, 400rpm for 30min, the pH value is adjusted to 10 with 1mol / L ammonia water, and continues to stir for 3h; then the pH value is adjusted to 7 with 1mol / L hydrochloric acid, and continues to stir for 25min, stands for 4h, centrifuged, washed and dried to obtain the carboxylated silica material; S3, 3 parts by weight of the above hydroxylated graphene, 4 parts by weight of the above carboxylated silica material and 100 parts by weight of 40wt% ethanol aqueous solution are mixed and ultrasonic treated, reacted at 70℃, 400rpm for 4h, suction filtered, washed and dried to obtain the wear-resistant composite material.

[0052] The preparation method of the wear-resistant PEEK composite material, each raw material is mixed according to weight parts, is added from the main feeding port of the twin-screw extruder, the extrusion temperature is 260 DEG C, the screw rotation speed is 320 r / min, the melt blending is carried out, and the wear-resistant PEEK composite material is obtained after extrusion.

[0053] Example 7 A wear-resistant PEEK composite material is composed of the following raw materials by weight parts: 80 parts by weight of pretreated polyether ether ketone resin, 15 parts by weight of polytetrafluoroethylene, and 5 parts by weight of wear-resistant composite material.

[0054] The pretreated polyether ether ketone resin is prepared as follows: the polyether ether ketone resin is placed in a plasma treatment chamber, a mixed gas composed of argon, oxygen and carbon dioxide in a volume ratio of 90:6:4 is introduced, the treatment time is 50 min, the plasma treatment power is 80 W, the gas flow is 12 cm 3 / min, the treatment pressure is 0.12 Torr, and it is stored for standby use.

[0055] The preparation method of the wear-resistant composite material is as follows: S1, 3 parts by weight of graphene oxide and 300 parts by weight of anhydrous ethanol are ultrasonically dispersed for 2 h, 35 parts by weight of water, 3 parts by weight of acetic acid and 4 parts by weight of amino silane and 4 parts by weight of hydroxyl silane are added, and reaction is carried out at 75 DEG C and 400 rpm for 12 h, and then suction filtration, washing and drying are carried out to obtain functionalized graphene; the amino silane is N-(6-aminohexyl) aminomethyl triethoxysilane; and the hydroxyl silane is 3-[bis(2-hydroxyethyl) amino] propane triethoxysilane; S2, 5 parts by weight of Na2SiO3·5H2O is dissolved in 80 parts by weight of 20wt% ethanol aqueous solution and stirred for 15 min, 10 parts by weight of humic acid is added, and stirring is carried out at 35 DEG C and 400 rpm for 30 min, 1 mol / L ammonia water is used to adjust the pH value to 10, and stirring is continued for 3 h; then 1 mol / L hydrochloric acid is used to adjust the pH value to 7, and stirring is continued for 25 min, and then standing is carried out for 4 h, centrifugation, washing and drying are carried out to obtain a carboxylated silicon dioxide material; S3, 3 parts by weight of the above functionalized graphene, 4 parts by weight of the above carboxylated silicon dioxide material and 100 parts by weight of 40wt% ethanol aqueous solution are mixed and ultrasonically treated, reaction is carried out at 70 DEG C and 400 rpm for 4 h, and then suction filtration, washing and drying are carried out to obtain a wear-resistant composite material.

[0056] The preparation method of the wear-resistant PEEK composite material, each raw material is mixed according to weight parts, is added from the main feeding port of the twin-screw extruder, the extrusion temperature is 260 DEG C, the screw rotation speed is 320 r / min, the melt blending is carried out, and the wear-resistant PEEK composite material is obtained after extrusion.

[0057] Example 8 A wear-resistant PEEK composite material is prepared from the following raw materials by weight: 80 parts by weight of pretreated polyether ether ketone resin, 15 parts by weight of polytetrafluoroethylene, and 5 parts by weight of wear-resistant composite material.

[0058] The pretreated polyether ether ketone resin is prepared as follows: polyether ether ketone resin is placed in a plasma treatment chamber, a mixed gas composed of argon, oxygen and carbon dioxide in a volume ratio of 90:6:4 is introduced for 50 min of treatment time, the plasma treatment power is 80 W, the gas flow rate is 12 cm 3 / min, the treatment pressure is 0.12 Torr, and it is stored for standby use.

[0059] The preparation method of the wear-resistant composite material is as follows: S1, 3 parts by weight of graphene oxide and 300 parts by weight of absolute ethanol are ultrasonically dispersed for 2 h, 35 parts by weight of water, 3 parts by weight of acetic acid, and 4 parts by weight of amino silane and 4 parts by weight of hydroxyl silane are added, and the mixture is reacted at 75℃ and 400 rpm for 12 h, then filtered, washed and dried to obtain functionalized graphene; the amino silane is N-(6-aminohexyl) aminomethyl triethoxysilane; the hydroxyl silane is 3-[bis(2-hydroxyethyl)amino]propane-triethoxysilane; S2, 5 parts by weight of Na2SiO3·5H2O is dissolved in 80 parts by weight of 20wt% aqueous ethanol solution and stirred for 15 min, 10 parts by weight of organic acid is added, and the mixture is stirred at 35℃ and 400 rpm for 30 min, then the pH value is adjusted to 10 with 1 mol / L ammonia water, and the stirring is continued for 3 h; then the pH value is adjusted to 7 with 1 mol / L hydrochloric acid, and the stirring is continued for 25 min, and then the mixture is left to stand for 4 h, centrifuged, washed and dried to obtain a carboxylated silica material; the organic acid is polyacrylic acid; S3, 3 parts by weight of the above functionalized graphene, 4 parts by weight of the above carboxylated silica material and 100 parts by weight of 40wt% aqueous ethanol solution are mixed and ultrasonically treated, and the mixture is reacted at 70℃ and 400 rpm for 4 h, then filtered, washed and dried to obtain a wear-resistant composite material.

[0060] The preparation method of the wear-resistant PEEK composite material is as follows: the raw materials are mixed by weight, and then added from the main feeding port of a twin-screw extruder; the extrusion temperature is 260℃, the screw rotation speed is 320r / min, and the materials are melt blended; and then the wear-resistant PEEK composite material is obtained after extrusion.

[0061] Test Example 1 The wear-resistant PEEK composite material prepared above is tested according to the national standard GB / T 3960-2016 "Plastics - Sliding friction and wear testing methods"; the test temperature is 23℃, the relative humidity is 50%, the average test is performed 4 times, and the average value is taken; the results are shown in Table 1.

[0062] Table 1 Wear resistance test of wear-resistant PEEK composite

[0063] Test Example 2 1. Tensile property test: The test was performed according to the method of national standard GB / T1040.3-2006 "Determination of tensile properties of plastics - Part 2: test conditions for moulded and extruded plastics". The wear-resistant PEEK composite prepared in each of the above examples was injection molded by an injection molding machine, and the test sample was a dumbbell-shaped 1A type with a thickness of 4 mm, a test speed of 1 mm / min, 5 parallel groups, and an average value was taken. The results are shown in Table 2.

[0064] 2. Impact property test: The test was performed according to the method of national standard GB / T1843-2008 "Determination of Izod impact strength". The thickness was 4 mm, 5 parallel groups were taken, and an average value was taken. The results are shown in Table 2.

[0065] Table 2 Mechanical property test of wear-resistant PEEK composite

[0066] From the above results, it can be seen that the wear-resistant PEEK composite prepared by the present application has good wear resistance and mechanical properties. Specifically, the performance improvement of the wear-resistant PEEK composite is closely related to the functionalization degree of the filler and the interface design. In Example 1, unmodified PEEK and nano-SiO2 were used, and due to the agglomeration of the filler and weak interface bonding, the friction coefficient was as high as 0.71, and the mechanical properties were the worst, with a tensile strength of 130.3 MPa and a notched impact strength of 25.6 kJ / m 2 ; In Example 2, plasma-treated PEEK and nano-SiO2 were used to improve the dispersibility through surface polar groups, and the friction coefficient was reduced to 0.63, the tensile strength was increased to 142.6 MPa, and the notched impact strength was 28.9 kJ / m 2 ; In Examples 3-4, humic acid-carboxylated SiO2 and graphene were combined, and the interface bonding was enhanced by covalent bonding of carboxyl-amino, and the friction coefficient was further reduced to 0.46, the tensile strength was 167.7 MPa, and the notched impact strength was 36.4 kJ / m 2 ; In Examples 5-7, aminated or hydroxylated graphene and carboxylated SiO2 were used to optimize stress transfer through a hybrid network, and the friction coefficient was significantly reduced to 0.11-0.24, the tensile strength was increased to 175.9 MPa, and the notched impact strength was 38.9 kJ / m 2 ; In Example 8, polyacrylic acid-carboxylated SiO2 was used to achieve the best comprehensive performance by means of long-chain molecular entanglement effect, and the friction coefficient was reduced to 0.08, the tensile strength was increased to 180.5 MPa, and the notched impact strength was 40.6 kJ / m 2, which verified the unique advantage of polymer carboxylic acid in interface reinforcement. Therefore, the synergistic effect of filler chemical modification and plasma treatment can precisely regulate the tribological and mechanical properties of PEEK composites, and the polyacrylic acid system shows the best industrial application potential.

Claims

1. A wear resistant PEEK composite material, characterized in that, Composed of the following raw materials by weight parts: 60-90 parts by weight of polyether ether ketone resin or pretreated polyether ether ketone resin, 10-20 parts by weight of polytetrafluoroethylene, 3-8 parts by weight of wear-resistant composite material; The pretreated polyether ether ketone resin is obtained by plasma treatment.

2. The wear resistant PEEK composite of claim 1, wherein, The treatment gas of the plasma is composed of active gas and inert gas, and the volume ratio of the active gas to the inert gas is 10:90; wherein the inert gas is any one of argon, helium or nitrogen; the active gas is any one of oxygen, carbon dioxide or hydrogen.

3. The wear resistant PEEK composite of claim 1, wherein, The power of the plasma treatment is 50-100 W, the gas flow is 8-16 cm 3 / min, the treatment time is 30-70 min, and the treatment pressure is 0.08-0.15 Torr.

4. The wear resistant PEEK composite of claim 1, wherein, The wear-resistant composite material comprises the reaction product of ammoniated / hydroxylated graphene and carboxylated silica material, wherein the weight ratio of ammoniated / hydroxylated graphene to carboxylated silica material is (2-4):(3-5).

5. The wear resistant PEEK composite of claim 4, wherein, The preparation of the wear-resistant composite material comprises: reacting ammoniated / hydroxylated graphene and carboxylated silica material in 30-50wt% ethanol aqueous solution at 60-80℃ for 3-5h.

6. The wear resistant PEEK composite of claim 4 or 5, wherein, The preparation method of the ammoniated / hydroxylated graphene comprises: dispersing graphene oxide in an alcohol solvent, and then reacting with a silane coupling agent at 60-80℃ for 8-15h, wherein the silane coupling agent is selected from amino silane or hydroxyl silane.

7. The wear resistant PEEK composite of claim 4 or 5, wherein, The preparation method of the carboxylated silica material comprises: reacting a sodium silicate solution with an organic acid at pH 8-11, and then separating after adjusting to neutral pH, wherein the organic acid is any one of humic acid, polyacrylic acid or citric acid.

8. The wear resistant PEEK composite of claim 6, wherein, The amino silane is at least one of N-(6-aminohexyl) aminomethyl triethoxysilane, silane coupling agent KH-550, 4-aminobutyl triethoxysilane and 11-aminoundecyl triethoxysilane; the hydroxyl silane is at least one of 3-[bis(2-hydroxyethyl) amino] propane-triethoxysilane, tetra(2-hydroxyethoxy) silane and N-(3-acryloyloxy-2-hydroxypropyl)-3-aminopropyl triethoxysilane.

9. The method of making a wear resistant PEEK composite according to any one of claims 1-8, wherein, The method comprises the following steps: mixing the raw materials according to the weight parts, adding from the main feeding port of the twin-screw extruder, melt blending, and then extruding to obtain the wear-resistant PEEK composite material.

10. The method for preparing the wear-resistant PEEK composite material as described in claim 9, characterized in that, The extrusion temperature is 220-300℃, and the screw rotation speed is 280-350r / min.

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