Lightweight PEEK wear-resistant material and preparation method thereof

Abstract

This invention belongs to the field of polymer composite materials technology, and relates to a lightweight PEEK wear-resistant material and its preparation method. The lightweight PEEK wear-resistant material of this invention is composed of the following components by mass percentage: 65%~75% PEEK plastic, 8%~15% lightweight modifier, 14%~17% wear-resistant reinforcing agent, and 3%~5% auxiliary additives; wherein, the lightweight modifier is composed of modified hollow glass microspheres and modified carbon fibers in a mass ratio of 1~3:1; the wear-resistant reinforcing agent is composed of modified titanium dioxide and zinc sulfide in a mass ratio of 2~4:1; and the auxiliary additives are composed of antioxidant 1010, antioxidant 168, polytetrafluoroethylene micropowder, and polyetheretherketone.

Description

Technical Field

[0001] This invention belongs to the field of polymer composite materials technology, and relates to a lightweight PEEK wear-resistant material and its preparation method. Background Technology

[0002] Polyetheretherketone (PEEK) is a high-performance specialty engineering plastic with excellent high-temperature resistance, mechanical strength, chemical corrosion resistance, and dimensional stability, making it widely used in high-end manufacturing. However, pure PEEK material has limited wear resistance and a relatively high coefficient of friction (approximately 0.34±0.03). Under harsh conditions such as high loads and high-speed friction, it is prone to wear failure and surface scratches. The volumetric wear on mating metal parts can reach 0.35±0.03 mm. 3 This severely limits its application in precision wear-resistant parts.

[0003] To improve the wear resistance of PEEK materials, existing technologies often employ fiber reinforcement modification. Commonly used reinforcing fibers include glass fiber, carbon fiber, aramid fiber, titanate fiber, basalt fiber, etc., and are often combined with polytetrafluoroethylene (PTFE), zinc sulfide, titanium dioxide, etc. as solid lubricants to synergistically enhance wear resistance. While glass fiber reinforced PEEK can improve wear resistance to some extent, it leads to a decrease in material toughness and insufficient corrosion resistance, making it difficult to meet the requirements for lightweighting. When PEEK is reinforced with single carbon fiber (CF), the interfacial bonding force between the carbon fiber and the PEEK matrix is ​​weak, and fiber agglomeration and shedding are prone to occur, which in turn affects the wear resistance of the material. Moreover, the wear of PEEK material reinforced with single CF on ceramic mating parts is significantly increased (up to 1.05±0.26mm³). Reinforced with single aramid fiber has the disadvantages of poor fiber dispersion, complex preparation process, and high cost. Titanate fiber has a very small fiber size, which greatly increases the requirements for matrix dispersion. Basalt fiber is brittle and has high hardness, which often causes unnecessary damage to the material mating parts.

[0004] Furthermore, existing modification technologies for lightweight PEEK materials often employ a single lightweight filler or a single wear-resistant filler, making it difficult to achieve a synergistic improvement in both lightweighting and wear resistance. This often results in a contradiction: "increased lightweighting leads to decreased wear resistance, while increased wear resistance results in poor lightweighting." Existing lightweight modifications of PEEK materials mainly fall into two categories: one involves adding hollow microspheres, foaming agents, etc., to achieve lightweighting, but this type of modification significantly reduces the material's mechanical strength and wear resistance, failing to meet the requirements of high-end applications; the other involves adding carbon fibers, graphene, ceramic particles, etc., to improve wear resistance, but these fillers have high density, increasing the overall weight of the material and weakening the lightweighting effect. In addition, some modification processes suffer from complex procedures, uneven filler dispersion, and high production costs, making large-scale production difficult. For example, a PEEK composite material patent published by Evonik Industries AG in Germany, while improving friction performance, did not focus on lightweighting, resulting in a still high material density; while some lightweight PEEK materials suffer from excessively high wear rates and short service lives, making them unsuitable for high-load components under unlubricated conditions. With the increasing demand for lightweighting and energy conservation in the aerospace and automotive industries, as well as the growing requirements for wear resistance and reliability in industrial machinery and medical equipment, the development of a PEEK material that combines excellent lightweight performance with high wear resistance, simple processing, and scalable production has become an urgent technical problem to be solved in this field. Summary of the Invention

[0005] The purpose of this invention is to provide a lightweight PEEK wear-resistant material and its preparation method, so as to solve the problem that it is difficult to achieve both lightweight and wear resistance in the existing technology of PEEK materials.

[0006] A lightweight PEEK wear-resistant material is composed of the following components by weight percentage: 65%~75% PEEK plastic, 8%~15% lightweight modifier, 14%~17% wear-resistant reinforcing agent, and 3%~5% auxiliary additives; wherein the lightweight modifier is composed of modified hollow glass microspheres and modified carbon fibers in a weight ratio of 1~3:1; the wear-resistant reinforcing agent is composed of modified titanium dioxide and zinc sulfide in a weight ratio of 2~4:1; and the auxiliary additives are composed of antioxidant 1010, antioxidant 168, polytetrafluoroethylene micropowder, and polyetheretherketone.

[0007] Preferably, the melt flow index of the PEEK plastic is 10~90 cm⁻¹. 3 / 10min, molecular weight 10000~40000, crystallinity 30%~45%.

[0008] Preferably, the modified hollow glass microspheres are prepared as follows: hollow glass microspheres with a particle size of 5~50μm are soaked in a 2~3% (w / w) solution of silane coupling agent KH-550 for 3~5h, filtered, and then dried at 85~90℃.

[0009] Preferably, the modified carbon fiber is prepared as follows: carbon fibers with a length of 100~200μm and a single filament diameter of 5~8μm are subjected to plasma treatment with a treatment power of 150~200W and a treatment time of 8~10min.

[0010] Preferably, the preparation method of the modified titanium dioxide includes the following steps: dispersing titanium dioxide powder with a particle size D50 of 5~15μm in a mixed solution of anhydrous ethanol and deionized water, adjusting the pH value to 9~9.5 after ultrasonic dispersion, adding tetraethyl orthosilicate dropwise to carry out a hydrolysis-condensation reaction at a reaction temperature of 50~70℃ for 1.5~3h, and maintaining the reaction temperature for 3~5h; centrifuging, washing, drying and calcining the reaction product to obtain modified titanium dioxide.

[0011] Preferably, the mass ratio of titanium dioxide powder to tetraethyl orthosilicate is 100:18~20; the calcination temperature is 350~400℃ and the time is 2~4h.

[0012] Preferably, the zinc sulfide has a particle size of 500~1000nm; and the polytetrafluoroethylene micro powder has a particle size D50 of 8~15μm.

[0013] Preferably, in the auxiliary additives, the mass ratio of antioxidant 1010, antioxidant 168, polytetrafluoroethylene micro powder and polyetheretherketone is 1~2:1~2:1~2:1~2.

[0014] A method for preparing a lightweight PEEK wear-resistant material as described above includes the following steps: mixing PEEK plastic, modified hollow glass microspheres, modified carbon fiber, modified titanium dioxide, zinc sulfide and auxiliary additives, then extruding, injection molding and annealing to obtain the lightweight PEEK wear-resistant material.

[0015] Preferably, the mixing is carried out in a high-speed mixer at a speed of 1200~1800 r / min, a temperature of 90~95℃, and a time of 18~25 min; extrusion is carried out using a twin-screw extruder, with the barrel temperature segmented as follows: feed section 305~310℃, melting section 410~430℃, homogenization section 400~420℃, and die head temperature 380~390℃; screw speed 150~200 r / min, vacuum pressure 500~600 mbar; injection molding temperature 390~410℃, die temperature 130~140℃, and injection pressure 100~110 MPa; annealing temperature 165~175℃, and time 2.5~3.5 h.

[0016] The beneficial effects of this invention are as follows: The lightweight PEEK wear-resistant material provided by this invention is a low-density, high-strength, and tough composite material made by high-temperature stepped extrusion and annealing processes, using polyetheretherketone (PEEK) with specific properties as the matrix, compounded with surface-modified hollow glass microspheres and carbon fibers as lightweight reinforcing agents, surface-coated titanium dioxide and nano-zinc sulfide as synergistic wear-resistant agents, and adding polytetrafluoroethylene micropowder of specific particle size and composite additives. This invention, through the unique compounding of the lightweight reinforcing network of "modified hollow glass microspheres / carbon fibers" and the synergistic lubrication system of "coated titanium dioxide / nano-zinc sulfide / PTFE of specific particle size," successfully breaks through the technical bottleneck of traditional materials where "lightweighting inevitably reduces strength and weight reduction inevitably damages wear resistance," significantly reducing the density to 1.22 g / cm³. 3 Simultaneously, tensile strength ≥108MPa and impact strength ≥8.2kJ / m were achieved. 2 It exhibits high strength and high toughness, and achieves a friction coefficient as low as 0.17 and a strength of 1.48 × 10⁻⁶. -8 mm 3 It boasts an ultra-low wear rate of / (N·m) and combines excellent dimensional stability with long service life. Detailed Implementation

[0017] The present invention will be further described in detail below with reference to specific embodiments. The scope of protection of the present invention is not limited to the following embodiments. All modifications made based on the technical solutions of the present invention shall fall within the scope of protection of the present invention.

[0018] The lightweight PEEK wear-resistant material of this invention is composed of the following components by mass percentage: 65%~75% PEEK plastic, 8%~15% lightweight modifier, 14%~17% wear-resistant reinforcing agent, and 3%~5% auxiliary additives. The lightweight modifier consists of modified hollow glass microspheres and modified carbon fibers in a mass ratio of 1~3:1. The wear-resistant reinforcing agent consists of modified titanium dioxide and zinc sulfide in a mass ratio of 2~4:1. The auxiliary additives consist of antioxidant 1010, antioxidant 168, polytetrafluoroethylene micropowder, and polyetheretherketone. The lightweight modifier uses a composite system of hollow glass microspheres and modified carbon fibers. The hollow glass microspheres have low density and low thermal conductivity, effectively reducing the overall density of the material and achieving lightweighting. The modified carbon fibers have high strength and low density, which not only helps improve the lightweighting effect but also enhances the mechanical strength of the material, compensating for the weakening effect of the hollow glass microspheres on the material's strength. Preferably, the melt flow index of the PEEK plastic is 20-70 cm⁻¹. 3 The melt flow rate is 10 min, with a molecular weight of 10,000~40,000 and a crystallinity of 30%~40%. PEEK matrices within this parameter range exhibit good melt processability and mechanical strength, providing a foundation for lightweight and wear-resistant materials. If the melt flow rate is too low, the material becomes more difficult to process; if the melt flow rate is too high, the material's mechanical strength will decrease.

[0019] Further, the modified hollow glass microspheres are prepared as follows: Hollow glass microspheres with a particle size of 10-40 μm are soaked in a 2-3% (w / w) solution of silane coupling agent KH-550 for 3-5 hours, filtered, and then dried at 85-90℃. The particle size of the hollow glass microspheres is controlled within 5-50 μm. If the particle size is too small, it will increase the specific surface area of ​​the material, leading to increased processing difficulty; if the particle size is too large, it will affect the uniformity and mechanical properties of the material. Modification of the hollow glass microspheres with silane coupling agent can improve their compatibility with the PEEK matrix and avoid the problem of uneven dispersion.

[0020] Furthermore, the modified carbon fiber is prepared as follows: carbon fibers with a length of 100-200 μm and a single filament diameter of 5-8 μm are subjected to plasma treatment at a power of 150-200 W for 8-10 minutes. The length of the modified carbon fiber is controlled within the range of 100-200 μm. This length range ensures that the modified carbon fiber is uniformly dispersed in the PEEK matrix, fully exerting its reinforcing effect. If the length is too long, agglomeration is likely to occur; if the length is too short, the reinforcing effect is poor. Plasma treatment can improve the surface compatibility of the carbon fiber and enhance its bonding force with the matrix.

[0021] Further, the preparation method of the modified titanium dioxide includes the following steps: dispersing titanium dioxide powder with a particle size D50 of 8~12μm in a mixed solution of anhydrous ethanol and deionized water, adjusting the pH value to 9~9.5 after ultrasonic dispersion, adding tetraethyl orthosilicate dropwise to carry out a hydrolysis-condensation reaction at a reaction temperature of 50~70℃ for 1.5~3h, and maintaining the reaction temperature for 3~5h; centrifuging, washing, drying, and calcining the reaction product to obtain modified titanium dioxide. Titanium dioxide has high hardness and wear resistance, improving the wear resistance of the material; the surface coating with inert oxides can prevent it from catalyzing the degradation of the PEEK matrix under high temperature or light, extending the service life of the material. Zinc sulfide lubricant has excellent lubrication properties, reduces the friction coefficient of the material, reduces wear, and works synergistically with titanium dioxide to further improve the wear resistance of the material.

[0022] Furthermore, the mass ratio of the titanium dioxide powder to tetraethyl orthosilicate is 100:18~20; the calcination temperature is 350~400℃, and the time is 2~4h.

[0023] Furthermore, the zinc sulfide has a particle size of 600~800nm; the polytetrafluoroethylene micro powder has a particle size D50 of 8~15μm.

[0024] Furthermore, in the auxiliary additives, the mass ratio of antioxidant 1010, antioxidant 168, polytetrafluoroethylene micro powder, and polyetheretherketone is 1~2:1~2:1~2:1~2. PEEK resin, as the core of the matrix bonding, possesses high-temperature resistance, corrosion resistance, and mechanical strength, forming the basis for material bonding. The hindered phenolic antioxidant 1010 and the phosphite antioxidant 168 work synergistically. 1010 captures free radicals, while 168 decomposes peroxides generated during oxidation. This dual protection ensures that the material maintains excellent wear resistance, high-temperature resistance, and dimensional stability after molding, preventing wear resistance degradation due to processing oxidation. The antioxidants capture free radicals generated during degradation, preventing oxidation chain reactions and substrate degradation. Furthermore, they continuously inhibit oxidative aging during long-term use, delaying material performance decline and ensuring the long-term stable service of wear-resistant parts.

[0025] This invention achieves a synergistic improvement in both lightweighting and wear resistance. By rationally compounding lightweight modifiers and wear-resistant reinforcing agents, it solves the technical challenge of achieving both lightweighting and wear resistance in existing PEEK materials. The prepared material has a lower density, reduced by 4% to 11% compared to pure PEEK, and a wear rate reduced by more than 60% compared to pure PEEK, while maintaining good tensile strength, flexural strength, and heat resistance, meeting the needs of high-end applications. The uniform dispersion of fibers effectively inhibits crack propagation and improves the material's fatigue life, making it suitable for components subjected to long-term dynamic loads (such as gears and bearings). The hollow glass microspheres in the lightweight modifier are modified with a silane coupling agent, the carbon fibers are modified, and the titanium dioxide in the wear-resistant reinforcing agent undergoes surface coating treatment, effectively improving the compatibility of each component with the PEEK matrix, avoiding filler agglomeration, ensuring uniform and stable material performance, and a long service life.

[0026] The polyether ether ketone used in the following examples and comparative examples is manufactured by Zhongyan Co., Ltd., and its brand name is 770P. Example

[0027] The lightweight PEEK wear-resistant material of this embodiment is composed of the following components by weight percentage: 70% PEEK plastic, 10% lightweight modifier, 17% wear-resistant reinforcing agent, and 3% auxiliary additives; wherein the melt flow index of the PEEK plastic is 40 cm⁻¹. 3 / 10min, molecular weight 25000, crystallinity 38%; lightweight modifier composed of modified hollow glass microspheres and modified carbon fibers in a mass ratio of 2:1; wear-resistant reinforcing agent composed of modified titanium dioxide and zinc sulfide in a mass ratio of 3:1; auxiliary additives composed of antioxidant 1010, antioxidant 168, polytetrafluoroethylene micro powder and polyetheretherketone in a mass ratio of 1:1:1:1; the preparation method of modified hollow glass microspheres is as follows: hollow glass microspheres with a particle size of 20μm are soaked in a 2% (w / w) silane coupling agent KH-550 solution for 3h, filtered, and dried at 90℃ for 1.5h to obtain modified hollow glass microspheres; the preparation method of modified carbon fibers is as follows: carbon fibers with a length of 200μm and a single filament diameter of 5~8μm are subjected to plasma treatment at a power of 150W for 8min to obtain modified carbon fibers; the preparation method of modified titanium dioxide is as follows. Below: Take 100g of titanium dioxide powder with a particle size D50 of 10μm and place it in a mixed solution of 500mL of anhydrous ethanol and deionized water (volume ratio 4:1). Disperse it ultrasonically for 30min to form a uniform suspension. Under vigorous stirring (800rpm), add ammonia water dropwise to the suspension to adjust the pH value to 9.5. Then slowly add 18.5g of tetraethyl orthosilicate, controlling the addition time to 1.5h, and maintain the reaction temperature at 50℃. After the addition is complete, continue to keep the temperature and stir for 3h to allow the silicon source to fully hydrolyze and condense on the surface of titanium dioxide to form a dense coating layer. Centrifuge the reaction product, wash it three times with anhydrous ethanol, and then vacuum dry it at 80℃ for 12h. Place the dried powder in a muffle furnace and calcine it at 350℃ for 2h to remove residual organic groups to obtain modified titanium dioxide. The particle size of zinc sulfide is 700nm. The particle size D50 of polytetrafluoroethylene micro powder is 8~15μm.

[0028] The preparation method of the lightweight PEEK wear-resistant material in this embodiment is as follows: PEEK plastic is dried in an oven at 130℃ for 5 hours; the dried PEEK plastic, modified hollow glass microspheres, modified carbon fiber, modified titanium dioxide, zinc sulfide, antioxidant 1010, antioxidant 168, polytetrafluoroethylene micro powder, and polyetheretherketone are added to a high-speed mixer and mixed for 20 minutes at a speed of 1500 r / min and a temperature of 90℃ to obtain a mixture; the mixture is fed into a twin-screw extruder, with the barrel temperature divided into stages. The feed section was set to 310℃, the melting section to 420℃, the homogenization section to 410℃, the die head temperature to 390℃, the screw speed to 150 r / min, and the vacuum pressure to 500 mbar. After extrusion, the material was water-cooled and pelletized to obtain granules. The granules were dried at 125℃ for 2.5 h and then subjected to injection molding and annealing to obtain lightweight PEEK wear-resistant material. The injection temperature during injection molding was 400℃, the mold temperature was 135℃, and the injection pressure was 100 MPa. The annealing temperature was 170℃ and the time was 3 h. Example

[0029] The lightweight PEEK wear-resistant material of this embodiment is composed of the following components by weight percentage: 65% PEEK plastic, 15% lightweight modifier, 17% wear-resistant reinforcing agent, and 3% auxiliary additives; wherein the melt flow index of the PEEK plastic is 20 cm⁻¹. 3 / 10min, molecular weight 18000, crystallinity 32%; lightweight modifier composed of modified hollow glass microspheres and modified carbon fibers in a mass ratio of 3:1; wear-resistant reinforcing agent composed of modified titanium dioxide and zinc sulfide in a mass ratio of 4:1; auxiliary additives composed of antioxidant 1010, antioxidant 168, polytetrafluoroethylene micro powder and polyetheretherketone in a mass ratio of 2:1:1:1; the preparation method of modified hollow glass microspheres is as follows: hollow glass microspheres with a particle size of 10μm are soaked in a 2% (w / w) silane coupling agent KH-550 solution for 3h, filtered, and dried at 90℃ for 1.5h to obtain modified hollow glass microspheres; the preparation method of modified carbon fibers is as follows: carbon fibers with a length of 100μm and a single filament diameter of 5~8μm are subjected to plasma treatment with a treatment power of 150W for 8min to obtain modified carbon fibers; the preparation method of modified titanium dioxide is as follows. The following steps were taken: 100g of titanium dioxide powder with a particle size D50 of 8μm was placed in a 500mL mixture of anhydrous ethanol and deionized water (volume ratio 4:1) and ultrasonically dispersed for 30min to form a uniform suspension. Under vigorous stirring (800rpm), ammonia was added dropwise to the suspension to adjust the pH to 9.5, followed by slow addition of 18.5g of tetraethyl orthosilicate over a time of 1.5h, with the reaction temperature maintained at 50℃. After the addition was complete, the mixture was kept at this temperature and stirred for another 3h to allow the silicon source to fully hydrolyze and condense on the surface of the titanium dioxide to form a dense coating layer. The reaction product was centrifuged, washed three times with anhydrous ethanol, and then vacuum dried at 80℃ for 12h. The dried powder was placed in a muffle furnace and calcined at 350℃ for 2h to remove residual organic groups, yielding modified titanium dioxide. The zinc sulfide had a particle size of 600nm, and the polytetrafluoroethylene micropowder had a particle size D50 of 8~15μm.

[0030] The preparation method of the lightweight PEEK wear-resistant material in this embodiment is as follows: PEEK plastic is dried in a 130℃ oven for 5 hours; the dried PEEK plastic, modified hollow glass microspheres, modified carbon fiber, modified titanium dioxide, zinc sulfide, antioxidant 1010, antioxidant 168, polytetrafluoroethylene micropowder, and polyetheretherketone are added to a high-speed mixer and mixed for 25 minutes at a speed of 1200 r / min and a temperature of 90℃ to obtain a mixture; the mixture is then fed into a twin-screw extruder, with the barrel temperature set in stages. The feed section was set at 310℃, the melting section at 410℃, the homogenization section at 400℃, the die head temperature at 390℃, the screw speed at 150 r / min, and the vacuum pressure at 500 mbar. After extrusion, the material was water-cooled and pelletized to obtain granules. The granules were dried at 125℃ for 2.5 h and then subjected to injection molding and annealing to obtain lightweight PEEK wear-resistant material. The injection temperature during injection molding was 390℃, the mold temperature was 130℃, and the injection pressure was 100 MPa. The annealing temperature was 165℃ and the time was 3.5 h. Example

[0031] The lightweight PEEK wear-resistant material of this embodiment is composed of the following components by weight percentage: 75% PEEK plastic, 8% lightweight modifier, 14% wear-resistant reinforcing agent, and 3% auxiliary additives; wherein the melt flow index of the PEEK plastic is 70 cm⁻¹. 3 / 10min, molecular weight 35000, crystallinity 42%; lightweight modifier composed of modified hollow glass microspheres and modified carbon fibers in a mass ratio of 1:1, wear-resistant reinforcing agent composed of modified titanium dioxide and zinc sulfide in a mass ratio of 2:1; auxiliary additives composed of antioxidant 1010, antioxidant 168, polytetrafluoroethylene micro powder and polyetheretherketone in a mass ratio of 1:1:1:1; the preparation method of modified hollow glass microspheres is as follows: hollow glass microspheres with a particle size of 40μm are soaked in a 2% (w / w) silane coupling agent KH-550 solution for 3h, filtered, and dried at 90℃ for 1.5h to obtain modified hollow glass microspheres; the preparation method of modified carbon fibers is as follows: carbon fibers with a length of 150μm and a single filament diameter of 5~8μm are subjected to plasma treatment with a treatment power of 150W for 8min to obtain modified carbon fibers; the preparation method of modified titanium dioxide is as follows. Below: Take 100g of titanium dioxide powder with a particle size D50 of 12μm and place it in a mixed solution of 500mL of anhydrous ethanol and deionized water (volume ratio 4:1). Disperse it ultrasonically for 30min to form a uniform suspension. Under vigorous stirring (800rpm), add ammonia water dropwise to the suspension to adjust the pH value to 9.5. Then slowly add 18.5g of tetraethyl orthosilicate, controlling the addition time to 1.5h, and maintain the reaction temperature at 50℃. After the addition is complete, continue to keep the temperature and stir for 3h to allow the silicon source to fully hydrolyze and condense on the surface of titanium dioxide to form a dense coating layer. Centrifuge the reaction product, wash it three times with anhydrous ethanol, and then vacuum dry it at 80℃ for 12h. Place the dried powder in a muffle furnace and calcine it at 350℃ for 2h to remove residual organic groups to obtain modified titanium dioxide. The particle size of zinc sulfide is 800nm. The particle size D50 of polytetrafluoroethylene micro powder is 8~15μm.

[0032] The preparation method of the lightweight PEEK wear-resistant material in this embodiment is as follows: PEEK plastic is dried in a 130℃ oven for 5 hours; the dried PEEK plastic, modified hollow glass microspheres, modified carbon fiber, modified titanium dioxide, zinc sulfide, antioxidant 1010, antioxidant 168, polytetrafluoroethylene micropowder, and polyetheretherketone are added to a high-speed mixer and mixed for 18 minutes at a speed of 1800 r / min and a temperature of 90℃ to obtain a mixture; the mixture is then fed into a twin-screw extruder, with the barrel temperature set in stages. The feed section was set at 310℃, the melting section at 430℃, the homogenization section at 420℃, the die head temperature at 390℃, the screw speed at 150 r / min, and the vacuum pressure at 500 mbar. After extrusion, the material was water-cooled and pelletized to obtain granules. The granules were dried at 125℃ for 2.5 h and then subjected to injection molding and annealing to obtain lightweight PEEK wear-resistant material. The injection temperature during injection molding was 410℃, the mold temperature was 140℃, the injection pressure was 100 MPa, and the annealing temperature was 175℃ for 2.5 h.

[0033] Comparative Example 1 The only difference between the lightweight PEEK wear-resistant material in this comparative example and the lightweight PEEK wear-resistant material in Example 1 is that the mass fraction of PEEK plastic in the lightweight PEEK wear-resistant material in this comparative example is 70%, the mass fraction of lightweight modifier is 0%, the mass fraction of wear-resistant reinforcing agent is 27%, and the mass fraction of auxiliary additives is 3%.

[0034] Comparative Example 2 The only difference between the lightweight PEEK wear-resistant material in this comparative example and the lightweight PEEK wear-resistant material in Example 1 is that the lightweight PEEK wear-resistant material in this comparative example has a PEEK plastic mass fraction of 70%, a lightweight modifier mass fraction of 27%, a wear-resistant reinforcing agent mass fraction of 0%, and auxiliary additive mass fraction of 3%.

[0035] Comparative Example 3 The only difference between the lightweight PEEK wear-resistant material in this comparative example and the lightweight PEEK wear-resistant material in Example 1 is that the lightweight modifier used in the lightweight PEEK wear-resistant material in this comparative example is modified hollow glass microspheres.

[0036] Comparative Example 4 The only difference between the lightweight PEEK wear-resistant material in this comparative example and the lightweight PEEK wear-resistant material in Example 1 is that the lightweight modifier used in the lightweight PEEK wear-resistant material in this comparative example is modified carbon fiber.

[0037] Comparative Example 5 The only difference between the lightweight PEEK wear-resistant material in this comparative example and the lightweight PEEK wear-resistant material in Example 1 is that the wear-resistant reinforcing agent used in the lightweight PEEK wear-resistant material in this comparative example is modified titanium dioxide.

[0038] Comparative Example 6 The only difference between the lightweight PEEK wear-resistant material in this comparative example and the lightweight PEEK wear-resistant material in Example 1 is that the wear-resistant reinforcing agent used in the lightweight PEEK wear-resistant material in this comparative example is zinc sulfide.

[0039] Comparative Example 7 The only difference between the lightweight PEEK wear-resistant material in this comparative example and the lightweight PEEK wear-resistant material in Example 1 is that the wear-resistant reinforcing agent used in the lightweight PEEK wear-resistant material in this comparative example is composed of modified titanium dioxide and molybdenum disulfide in a mass ratio of 3:1, and the particle size of molybdenum disulfide is 700nm.

[0040] Comparative Example 8 The only difference between the lightweight PEEK wear-resistant material of this comparative example and the lightweight PEEK wear-resistant material of Example 1 is that the auxiliary additives used in the PEEK plastic of the lightweight PEEK wear-resistant material of this comparative example are composed of antioxidant 168, polytetrafluoroethylene micro powder and polyetheretherketone in a mass ratio of 2:1:1.

[0041] Comparative Example 9 The only difference between the lightweight PEEK wear-resistant material of this comparative example and the lightweight PEEK wear-resistant material of Example 1 is that the auxiliary additives used in the PEEK plastic of the lightweight PEEK wear-resistant material of this comparative example are composed of antioxidant 1010, polytetrafluoroethylene micro powder and polyetheretherketone in a mass ratio of 2:1:1.

[0042] Comparative Example 10 The only difference between the lightweight PEEK wear-resistant material of this comparative example and the lightweight PEEK wear-resistant material of Example 1 is that the auxiliary additives used in the PEEK plastic of the lightweight PEEK wear-resistant material of this comparative example are composed of antioxidant 1010, antioxidant 168 and polyetheretherketone in a mass ratio of 1:1:2.

[0043] Comparative Example 11 The only difference between the lightweight PEEK wear-resistant material of this comparative example and the lightweight PEEK wear-resistant material of Example 1 is that the auxiliary additives used in the PEEK plastic of the lightweight PEEK wear-resistant material of this comparative example are composed of antioxidant 1010, antioxidant 168 and polytetrafluoroethylene micro powder in a mass ratio of 1:1:2.

[0044] Comparative Example 12 The only difference between the lightweight PEEK wear-resistant material in this comparative example and the lightweight PEEK wear-resistant material in Example 1 is that the particle size D50 of the polytetrafluoroethylene micro powder used in the auxiliary additives in the PEEK plastic of this comparative example is 1 μm.

[0045] Comparative Example 13 The only difference between the lightweight PEEK wear-resistant material in this comparative example and the lightweight PEEK wear-resistant material in Example 1 is that the particle size D50 of the polytetrafluoroethylene micro powder used in the auxiliary additives in the PEEK plastic of this comparative example is 30 μm.

[0046] Experimental Example To examine the comprehensive performance of the lightweight PEEK wear-resistant materials in each embodiment and comparative example, the density, tensile strength, notched impact strength, coefficient of friction, and wear rate of the lightweight PEEK wear-resistant materials in each embodiment and comparative example were tested, and the results are shown in Table 1. The density was tested according to the method in GB / T 1033.1-2008, using the immersion method with distilled water at 23℃ as the medium. The tensile strength was tested according to the method in GB / T 1040.2-2022, at a temperature of 23±2℃ and a relative humidity of 50±5%, at a tensile rate of 5 mm / min. The notched impact strength was tested according to the method in GB / T 1043.1-2008, using a simply supported beam A-type notched specimen with a span of 62 mm. The coefficient of friction and wear rate were tested according to the method in GB / T 3960-2016. The test was conducted using a ring-block friction and wear tester under dry friction conditions, with a load of 196N and a rotation speed of 200r / min for 2 hours.

[0047] Table 1. Overall performance of lightweight PEEK wear-resistant materials in each embodiment and comparative example. Example 1 1.20 112 8.5 0.18 1.52 Example 2 1.18 108 8.2 0.19 1.65 Example 3 1.22 115 8.8 0.17 1.48 Comparative Example 1 1.38 105 7.9 0.20 1.86 Comparative Example 2 1.15 92 7.2 0.32 4.75 Comparative Example 3 1.21 100 7.5 0.21 1.78 Comparative Example 4 1.25 109 8.0 0.20 1.69 Comparative Example 5 1.22 107 8.1 0.23 2.13 Comparative Example 6 1.19 102 7.8 0.25 2.45 Comparative Example 7 1.20 106 8.0 0.22 1.98 Comparative Example 8 1.20 103 7.7 0.21 1.89 Comparative Example 9 1.20 104 7.6 0.20 1.85 Comparative Example 10 1.21 108 8.2 0.26 2.32 Comparative Example 11 1.20 105 7.8 0.22 1.92 Comparative Example 12 1.20 109 8.1 0.24 2.05 Comparative Example 13 1.20 107 7.9 0.23 2.18 As shown in Table 1, the density of the materials obtained in Examples 1-3 of this invention is controlled between 1.18 and 1.22 g / cm³, significantly lower than that of Comparative Example 1 (1.38 g / cm³) without the addition of a lightweight modifier, successfully achieving the goal of material lightweighting. Furthermore, this invention does not sacrifice mechanical properties while reducing density. On the contrary, the tensile strength and notched impact strength of Examples 1-3 are superior to those of Comparative Example 1. In contrast, if relying entirely on lightweight components without a wear-resistant reinforcement system (such as Comparative Example 2), although the density is further reduced, the tensile strength and impact strength drop sharply, and the wear rate increases, resulting in the material failing to meet engineering application requirements. Therefore, this invention, through a specific compounding of "modified hollow glass microspheres + modified carbon fiber" and "modified titanium dioxide + zinc sulfide," effectively solves the technical problem of "a significant decrease in strength and wear resistance due to density reduction" in traditional lightweight materials, achieving a balance between low density, high strength, and high toughness.

[0048] Comparing Example 1 with Comparative Examples 3 and 4, it can be seen that the proportions of each component in the lightweight modifier play a crucial role: Comparative Example 3, containing only modified hollow glass microspheres, showed a decrease in tensile strength to 100 MPa and an increase in wear rate to 1.78 × 10⁻⁶. -8The result of mm³ / (N·m) indicates that while single spherical microspheres can reduce weight, they are insufficient in strengthening the matrix and resisting crack propagation. Comparative Example 4, containing only modified carbon fiber, had a density increased to 1.25 g / cm³, weakening the lightweight effect, and its coefficient of friction and wear rate were inferior to Example 1. Therefore, the "ball effect" provided by the modified hollow glass microspheres and the "bridging toughening effect" provided by the modified carbon fiber produced a significant synergistic effect at the specific mass ratio of this application, ensuring low density while maximizing the material's load-bearing capacity and wear resistance.

[0049] Compared with Examples 1 and Comparative Examples 5-7, using modified titanium dioxide (Comparative Example 5) or zinc sulfide (Comparative Example 6) alone resulted in friction coefficients as high as 0.23 and 0.25, respectively, and significantly increased wear rates, far inferior to the compound system. Replacing zinc sulfide with the conventional solid lubricant molybdenum disulfide (Comparative Example 7) still resulted in significantly higher friction coefficients and wear rates than in Example 1. Therefore, a special interface matching and synergistic lubrication mechanism exists between modified titanium dioxide and zinc sulfide, forming a transfer film that is denser and more stable than the traditional molybdenum disulfide system. This specific combination choice is key to achieving ultra-low friction coefficients and extremely low wear rates in this invention.

[0050] Analysis of the data from Comparative Examples 8-13 shows that the completeness, proportion, and physical parameters of key components of the auxiliary additives have a decisive impact on the final performance: the absence of any antioxidant (Comparative Examples 8 and 9) leads to a decrease in mechanical properties and an increase in wear rate, proving that the dual antioxidant system (1010+168) is crucial for maintaining the thermal stability of the material during processing and the final microstructure. Adjusting the proportions of antioxidant, PTFE, and ketimide-type polyetheretherketone (Comparative Examples 10 and 11) results in significant fluctuations in the coefficient of friction, indicating complex interactions among the additives. The particle size of polytetrafluoroethylene (PTFE) micropowder has a significant impact on the performance of this application. When the particle size deviates from the 8-15 μm range specified in this application, whether too small (1 μm, Comparative Example 12) or too large (30 μm, Comparative Example 13), the wear rate increases significantly. Therefore, only within a specific particle size range can PTFE micropowder form a uniform and stable lubricating phase in the matrix; excessively large particles are prone to detachment and abrasive wear, while excessively small particles are difficult to form an effective transfer film.

Claims

1. A lightweight PEEK wear-resistant material, characterized in that, It is composed of the following components by weight percentage: 65%~75% PEEK plastic, 8%~15% lightweight modifier, 14%~17% wear-resistant reinforcing agent, and 3%~5% auxiliary additives; wherein, the lightweight modifier is composed of modified hollow glass microspheres and modified carbon fibers in a weight ratio of 1~3:1; the wear-resistant reinforcing agent is composed of modified titanium dioxide and zinc sulfide in a weight ratio of 2~4:1; and the auxiliary additives are composed of antioxidant 1010, antioxidant 168, polytetrafluoroethylene micro powder, and polyetheretherketone.

2. The lightweight PEEK wear-resistant material as described in claim 1, characterized in that, The melt flow index of the PEEK plastic is 10~90 cm⁻¹. 3 / 10min, molecular weight 10000~40000, crystallinity 30%~45%.

3. The lightweight PEEK wear-resistant material as described in claim 1, characterized in that, The modified hollow glass microspheres are prepared as follows: Hollow glass microspheres with a particle size of 5~50μm are soaked in a 2~3% (w / w) solution of silane coupling agent KH-550 for 3~5h, filtered, and then dried at 85~90℃.

4. The lightweight PEEK wear-resistant material as described in claim 1, characterized in that, The modified carbon fiber is prepared as follows: carbon fibers with a length of 100~200μm and a single filament diameter of 5~8μm are subjected to plasma treatment with a treatment power of 150~200W and a treatment time of 8~10min.

5. The lightweight PEEK wear-resistant material as described in claim 1, characterized in that, The preparation method of the modified titanium dioxide includes the following steps: dispersing titanium dioxide powder with a particle size D50 of 5~15μm in a mixed solution of anhydrous ethanol and deionized water, adjusting the pH value to 9~9.5 after ultrasonic dispersion, adding tetraethyl orthosilicate dropwise to carry out hydrolysis and polycondensation reaction at a reaction temperature of 50~70℃ for 1.5~3h, and maintaining the reaction temperature for 3~5h; centrifuging, washing, drying and calcining the reaction product to obtain modified titanium dioxide.

6. The lightweight PEEK wear-resistant material as described in claim 5, characterized in that, The mass ratio of titanium dioxide powder to tetraethyl orthosilicate is 100:18~20; the calcination temperature is 350~400℃ and the time is 2~4h.

7. The lightweight PEEK wear-resistant material as described in claim 1, characterized in that, The zinc sulfide has a particle size of 500~1000nm; the polytetrafluoroethylene micro powder has a particle size D50 of 8~15μm.

8. The lightweight PEEK wear-resistant material as described in claim 1, characterized in that, In the auxiliary additives, the mass ratio of antioxidant 1010, antioxidant 168, polytetrafluoroethylene micro powder and polyetheretherketone is 1~2:1~2:1~2:1~2.

9. A method for preparing a lightweight PEEK wear-resistant material as described in any one of claims 1-8, characterized in that, Includes the following steps: PEEK plastic, modified hollow glass microspheres, modified carbon fiber, modified titanium dioxide, zinc sulfide and auxiliary additives are mixed, extruded, injection molded and annealed to obtain lightweight PEEK wear-resistant material.

10. The method for preparing the lightweight PEEK wear-resistant material as described in claim 9, characterized in that, The mixing is carried out in a high-speed mixer at a speed of 1200~1800 r / min, a temperature of 90~95℃, and a time of 18~25 min. Extrusion is carried out using a twin-screw extruder, with the barrel temperature segmented as follows: feed section 305~310℃, melting section 410~430℃, homogenization section 400~420℃, and die head temperature 380~390℃. The screw speed is 150~200 r / min, and the vacuum pressure is 500~600 mbar. The injection temperature for injection molding is 390~410℃, the mold temperature is 130~140℃, and the injection pressure is 100~110 MPa. The annealing temperature for annealing is 165~175℃, and the time is 2.5~3.5 h.