Self-lubricating PEEK-based composite material and preparation method thereof
By introducing polyarylene thioether ketone and polyarylene thioether amide into PEEK-based composites and blending them with polyether ether ketone, and by using epoxy-modified MoS2@CO-SiO2 nanomaterials and modified carbon fibers, the problem of poor self-lubricating effect of PEEK-based composites under high temperature and high load was solved, and the wear resistance and lubrication performance of the materials were improved.
Patent Information
- Application Number
- CN202610104505.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-01-26
- Publication Date
- 2026-04-14
AI Technical Summary
Existing PEEK-based composite materials have poor self-lubricating properties, especially under high temperature, high speed, and high load conditions, the coefficient of friction increases, wear intensifies, and the mechanical properties of the material are affected.
Polymer matrix is formed by blending polyarylene thioether ketone and polyarylene thioether amide with polyether ether ketone. Epoxy-modified MoS2@CO-SiO2 nanomaterials and modified carbon fibers are introduced to improve compatibility and lubrication performance through interfacial reaction and chemical bonding.
It significantly improves the self-lubricating effect and wear life of composite materials, making it suitable for tribological components under harsh conditions such as high temperature, high speed, and high load, while maintaining the excellent comprehensive performance of polyetheretherketone.
Smart Images
Figure SMS_1
Abstract
Description
Technical Field
[0001] This invention belongs to the field of polyetheretherketone composite material technology, specifically relating to a self-lubricating PEEK-based composite material and its preparation method. Background Technology
[0002] Polyetheretherketone (PEEK) is a high-performance polymer with excellent thermal stability, chemical stability, radiation resistance, and good mechanical properties. It is widely used in high-tech fields such as aerospace, automotive manufacturing, medical devices, electronics, and industrial bearings.
[0003] Polyetheretherketone (PEEK) possesses self-lubricating properties, making it a preferred material for components such as bearings and gears that require long-term exposure to friction. Mechanistically, PEEK's self-lubricating properties are primarily determined by its molecular structure, which contains numerous carbonyl groups. This structure allows PEEK to form a water film during friction, reducing friction. However, under extreme conditions such as high temperature, high speed, high load, and dry friction, the coefficient of friction of PEEK increases, leading to accelerated wear.
[0004] To improve the tribological properties of PEEK, existing technologies typically employ composite modification methods, introducing various lubricating and reinforcing phases into the PEEK matrix to prepare PEEK-based composite materials. Common improvement methods include adding solid lubricants or fiber materials; however, these materials exhibit poor interfacial compatibility with the PEEK matrix, resulting in the final material's self-lubricating effect failing to meet expectations and negatively impacting its mechanical properties, thus limiting its practical application value. Summary of the Invention
[0005] This invention provides a self-lubricating PEEK-based composite material and its preparation method, which can solve the problem of poor self-lubricating effect of PEEK-based composite materials in the prior art.
[0006] The objective of this invention can be achieved through the following technical solutions: A self-lubricating PEEK-based composite material, comprising the following raw materials by weight: 100 parts of polyetheretherketone resin, 10-15 parts of polyarylether thioetherketone, 5-10 parts of polyarylether thioether amide, 15-25 parts of epoxy-modified MoS2@CO-SiO2 nanomaterials, 4-12 parts of modified carbon fiber, and 1-2 parts of antioxidant. The modified carbon fiber is obtained by grafting carboxylated carbon fiber with 2-aminodiphenyl sulfide after acylation.
[0007] Polyether ether ketone (PEEK) resin itself has high thermal stability and a relatively stable structure, but its compatibility with inorganic materials is poor. This invention simultaneously adds polyarylene sulfide ketone (PASK) and polyarylene sulfide amide (PASA). The molecular chain structures of these two materials are similar to those of PEEK, and they have good thermal stability and good compatibility with PEEK. Polyarylene sulfide resins themselves also have good wear resistance and rigidity, improving the overall wear resistance. At the same time, the introduction of more polar sulfide bonds and amide bonds allows the amide groups to participate in interfacial reactions, enhancing the interfacial bonding force between the resin and the inorganic materials in the raw materials, and improving the self-lubricating properties of the material.
[0008] Furthermore, the epoxy-modified MoS2@C O The preparation steps for SiO2 nanomaterials are as follows: S1. Molybdenum disulfide was dispersed in an aqueous ethanol solution, and ammonia and ethyl silicate were added sequentially at room temperature. The mixture was stirred and reacted for 8–12 h. After filtration, washing, and vacuum drying, MoS2@SiO2 material was obtained. S2. Prepare a 0.2–0.6 M aqueous solution of cobalt nitrate hexahydrate. Immerse the MoS2@SiO2 material in the solution for 1–3 hours. After immersion, filter and dry, then heat-treat at 300–350℃ for 2–3 hours to obtain MoS2@C O -SiO2 nanomaterials; S3, MoS2@C O SiO2 nanomaterials were dispersed in deionized water to form a dispersion. The temperature was raised to 50-70℃, and an ethanol solution of silane coupling agent KH-560 was added dropwise to the dispersion. The mixture was stirred at a constant temperature for 2-4 hours. After filtration and drying, epoxy-modified MoS2@C was obtained. O -SiO2 nanomaterials.
[0009] Molybdenum disulfide (MoS2), as a solid lubricant, can form a continuous transfer film during friction, reducing the coefficient of friction. However, it is prone to oxidation at high temperatures, leading to an increase in the coefficient of friction. Encapsulating it with silica creates a core-shell structure, protecting the core molybdenum disulfide and effectively preventing high-temperature oxidation failure. Introducing cobalt into the silica coating allows cobalt oxide to form a dense, smooth "enamel layer" under frictional heat, covering the wear surface and isolating the frictional materials from direct contact, thus improving tribological properties. KH-560 was used to prepare MoS2@C... O - Grafting modification of the surface of SiO2 nanomaterials introduces epoxy groups, which promotes the formation of chemical bonds between the nanomaterials and polymers. The nanomaterials are dispersed and anchored in the matrix, resulting in long-lasting and efficient anti-wear properties.
[0010] Furthermore, the mass ratio of ethanol to water in the ethanol-water solution is (1:9) to (3:7). The concentration of molybdenum disulfide in aqueous ethanol solution is 0.5–1.5 g / L.
[0011] Furthermore, the ammonia water is added at an ammonia concentration of 1.0–2.0 mol / L.
[0012] Furthermore, the ethyl silicate is 9.0 to 10.5 times the mass of molybdenum disulfide.
[0013] Furthermore, the cobalt nitrate constitutes 10-20% of the mass of the MoS2@SiO2 material.
[0014] Further, in step S3, the dispersion contains MoS2@C O - The concentration of SiO2 nanomaterials is 100-200 g / L.
[0015] Further, in step S3, the concentration of silane coupling agent KH-560 in the ethanol solution of silane coupling agent KH-560 is 0.3 to 0.5 mol / L.
[0016] Further, in step S3, the ethanol solution of the silane coupling agent KH-560 is prepared according to the silane coupling agent KH-560 being MoS2@C O - Add 10-20% by mass of SiO2 nanomaterials dropwise.
[0017] Furthermore, the preparation steps of the modified carbon fiber are as follows: Carboxylated carbon fibers were dispersed in sulfonyl chloride at a concentration of 25–55 g / L, heated to 70 °C and reacted for 2–6 h. After filtration and drying, acylated carbon fibers were obtained. Acylated carbon fibers were dispersed in DMF at a concentration of 60–80 g / L. Triethylamine and 2-aminodiphenyl sulfide were added to the acylated carbon fiber dispersion, and the mixture was stirred at 40 °C for 8–12 h. After filtration, washing, and vacuum drying, modified carbon fibers were obtained.
[0018] In the above preparation, after the carboxyl groups on the surface of the carboxylated carbon fiber are partially acylated, the acyl chloride can react with the amino group on 2-aminodiphenyl sulfide to form an amide bond. Triethylamine absorbs the byproduct hydrogen chloride, and the carbon fiber surface is connected with the diphenyl sulfide molecular structure. The structure of the grafted layer can generate a strong π-π conjugation with the benzene rings of PEEK, PASK, and PASA. The sulfide bond can also interact with PASK and PASA. The modified carbon fiber has good affinity with the resin matrix, and its addition to the matrix can provide lubrication and reduce the wear rate. The residual carboxyl groups on the surface of the modified carbon fiber can react with the epoxy groups of the epoxy-modified MoS2@CO-SiO2 nanomaterials, and the materials are bonded together and uniformly dispersed.
[0019] Furthermore, the preparation steps of the carboxylated carbon fiber are as follows: Carbon fibers were impregnated in a mixed aqueous solution of ammonium persulfate and sulfuric acid at a concentration of 50–100 g / L, reacted at 40 °C for 3–4 h, filtered and washed until neutral, and dried to obtain carboxylated carbon fibers.
[0020] Furthermore, the concentration of ammonium persulfate in the mixed aqueous solution of ammonium persulfate and sulfuric acid is 1.5–2 mol / L, and the concentration of sulfuric acid is 2.0–2.3 mol / L.
[0021] Furthermore, the 2-aminodiphenyl sulfide constitutes 2-5% of the mass of the acylated carbon fiber; The triethylamine is 0.1 to 0.2% of the mass of the acylated carbon fiber dispersion.
[0022] Furthermore, the antioxidant is at least one of antioxidant 3114, antioxidant 1330, and antioxidant 9228.
[0023] This invention also provides a method for preparing a self-lubricating PEEK-based composite material, which includes the following steps: Step 1: Prepare the raw materials according to the proportions. Put the polyetheretherketone resin, polyaryletheretherketone, and polyaryletheretheramide into a mixer and mix them evenly. Then add the epoxy-modified MoS2@C O -SiO2 nanomaterials, modified carbon fibers, and antioxidants are mixed to obtain a mixture; Step 2: Feed the mixture into a screw extruder, set the temperature of the screw extruder to 240-360℃, melt extrude and granulate to obtain a self-lubricating PEEK-based composite material.
[0024] The beneficial effects of this invention are: 1. This invention uses polyetheretherketone, polyarylene thioetherketone, and polyarylene thioether amide to form a polymer matrix of PEEK-based composite material. The molecular structures of polyarylene thioetherketone and polyarylene thioether amide are similar to those of polyetheretherketone, and the polymers have good compatibility with each other. After blending, the inherent high temperature resistance of polyetheretherketone is maintained, and polar bonds are introduced through the molecular chain, which improves the compatibility of the matrix with other inorganic materials in the raw materials, and the overall wear resistance of the material is improved.
[0025] 2. In this invention, MoS2@C is modified with epoxy groups. O -SiO2 nanomaterials, as one of the lubricating components, effectively prevent the high-temperature oxidation failure of molybdenum disulfide through silica coating. Cobalt is added to the silica coating layer, and the cobalt oxide forms a "glaze layer" under frictional heat, protecting the friction surface of the material. The surface of the nanomaterials is modified with silane coupling agents and grafted with epoxy groups, enhancing the chemical bond with the polymer matrix and ensuring stable dispersion of the nanomaterials within the matrix, thus providing long-term friction reduction and wear resistance.
[0026] 3. In this invention, modified carbon fiber is used as one of the lubricating components. The modified carbon fiber is obtained by grafting carboxylated carbon fiber with 2-aminodiphenyl sulfide after acylation. The diphenyl sulfide structure grafted onto the fiber surface can promote its compatibility with the matrix, improve the affinity between the fiber and the polymer matrix, and prevent fiber agglomeration. The residual carboxyl groups on the fiber surface can also be used to modify MoS2@C with epoxy groups. O The epoxy groups on the surface of SiO2 nanomaterials react to form chemical bridges between lubricating components, thereby playing a continuous and synergistic role in reducing the material's friction coefficient and wear rate.
[0027] 4. Through the combined action of the polymer matrix and lubricating components, the composite material significantly improves its self-lubricating effect and wear resistance while maintaining the excellent comprehensive properties of polyetheretherketone (PEEK). It is especially suitable for preparing tribological components under harsh working conditions such as high temperature, high speed, and high load. Detailed Implementation
[0028] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.
[0029] Example 1
[0030] Preparation of epoxy-modified MoS2@C O -SiO2 nanomaterials: S1. Ethanol and deionized water were mixed at a mass ratio of 2:8 to obtain an ethanol aqueous solution. Molybdenum disulfide was weighed at a concentration of 1.0 g / L and added to the ethanol aqueous solution. The mixture was ultrasonically dispersed for 30 min. At room temperature, ammonia water (28 wt%) was added at a concentration of 1.5 mol / L. Then, ethyl silicate with a mass of 10 times that of molybdenum disulfide was added. The mixture was stirred and reacted for 12 h. After filtration, the filter residue was washed with deionized water until neutral and dried under vacuum at 70 °C for 8 h to obtain MoS2@SiO2 material.
[0031] S2. Prepare a 0.4M aqueous solution of cobalt nitrate hexahydrate. Immerse the MoS2@SiO2 material in the solution for 2 hours, with cobalt nitrate accounting for 15% of the MoS2@SiO2 material mass. After immersion, filter the solution. Dry the filter residue at 70℃ for 8 hours. Then, heat-treat the residue at 350℃ for 3 hours, increasing the temperature by 10℃ / min to 350℃, to obtain MoS2@SiO2. O -SiO2 nanomaterials.
[0032] S3. Dissolve silane coupling agent KH-560 in ethanol at a concentration of 0.4 mol / L to obtain an ethanol solution of silane coupling agent KH-560. Add MoS2@CO SiO2 nanomaterials were added to deionized water at a concentration of 150 g / L and ultrasonically dispersed for 30 min to form a dispersion. The mixture was then heated to 60 °C, and an ethanol solution of silane coupling agent KH-560 (MoS2@C) was added dropwise to the dispersion. O - 15% by mass of SiO2 nanomaterials were reacted at 60℃ with stirring for 3 hours. After filtration, the filter residue was dried at 70℃ for 12 hours to obtain epoxy-modified MoS2@C O -SiO2 nanomaterials.
[0033] Preparation of modified carbon fibers: Step 1: The carbon fiber is impregnated in a mixed aqueous solution of ammonium persulfate and sulfuric acid at a concentration of 80 g / L. The concentration of ammonium persulfate in the mixed aqueous solution of ammonium persulfate and sulfuric acid is 1.5 mol / L and the concentration of sulfuric acid is 2.0 mol / L. The reaction is carried out at 40℃ for 3 h. After filtration, it is washed with deionized water until neutral and dried at 80℃ for 10 h to obtain carboxylated carbon fiber.
[0034] Step 2: Disperse carboxylated carbon fibers at a concentration of 40 g / L in sulfonyl chloride, heat to 70°C and react for 5 h, filter, and vacuum dry at room temperature for 10 h to obtain acylated carbon fibers. Disperse the acylated carbon fibers at a concentration of 70 g / L in DMF to obtain an acylated carbon fiber dispersion. Add triethylamine at 0.2% of the mass of the acylated carbon fiber dispersion and 2-aminodiphenyl sulfide at 3% of the mass of the acylated carbon fibers. Stir and react at 40°C for 12 h. After filtration, wash the fibers three times with water and vacuum dry at 40°C for 24 h to obtain modified carbon fibers.
[0035] Preparation of self-lubricating PEEK-based composite materials: Step 1: According to the mass percentage, add 100 parts of polyetheretherketone resin, 13 parts of polyarylether thioetherketone, and 7 parts of polyarylether thioether amide to a mixer and mix thoroughly. Then add 20 parts of epoxy-modified MoS2@C O -SiO2 nanomaterials, 8 parts modified carbon fiber, 1 part antioxidant 3114 and 1 part antioxidant 9228 were mixed to obtain a mixture.
[0036] Step 2: Feed the mixture into a screw extruder. Set the temperature of the screw extruder to 240-360℃, with zone 1 at 240℃, zone 2 at 300℃, zone 3 at 340℃, zone 4 at 350℃, and zone 5 at 360℃. Melt extrusion granulation is performed to obtain a self-lubricating PEEK-based composite material.
[0037] Example 2
[0038] The only difference from Example 1 is that the epoxy-modified MoS2@C was prepared. OWhen using SiO2 nanomaterials, in step S2, the cobalt nitrate is adjusted to 20% of the mass of the MoS2@SiO2 material, and other conditions and steps are the same as in Example 1.
[0039] Example 3
[0040] The only difference from Example 1 is that the epoxy-modified MoS2@C was prepared. O When using SiO2 nanomaterials, in step S2, the cobalt nitrate is adjusted to 10% of the mass of the MoS2@SiO2 material, and other conditions and steps are the same as in Example 1.
[0041] Example 4
[0042] The only difference from Example 1 is that the epoxy-modified MoS2@C was prepared. O When using SiO2 nanomaterials, in step S3, the silane coupling agent KH-560 is adjusted to MoS2@C. O - 20% of the mass of SiO2 nanomaterials, with other conditions and steps the same as in Example 1.
[0043] Example 5
[0044] The only difference from Example 1 is that the epoxy-modified MoS2@C was prepared. O When using SiO2 nanomaterials, in step S3, the silane coupling agent KH-560 is adjusted to MoS2@C. O - 10% of the mass of SiO2 nanomaterials, with other conditions and steps the same as in Example 1.
[0045] Example 6
[0046] The only difference from Example 1 is that, in preparing the self-lubricating PEEK-based composite material, the epoxy groups were modified on MoS2@C O - The mass fraction of SiO2 nanomaterials was adjusted to 25 parts, and other conditions and steps were the same as in Example 1.
[0047] Example 7
[0048] The only difference from Example 1 is that, in preparing the self-lubricating PEEK-based composite material, the epoxy groups were modified on MoS2@C O - The mass fraction of SiO2 nanomaterials was adjusted to 15 parts, and other conditions and steps were the same as in Example 1.
[0049] Example 8
[0050] The only difference from Example 1 is that, when preparing the modified carbon fiber, 2-aminodiphenyl sulfide is added at 5% of the mass of the acylated carbon fiber, while the other conditions and steps are the same as in Example 1.
[0051] Example 9
[0052] The only difference from Example 1 is that, when preparing the modified carbon fiber, 2-aminodiphenyl sulfide is added at 2% of the mass of the acylated carbon fiber, and the other conditions and steps are the same as in Example 1.
[0053] Example 10
[0054] The only difference from Example 1 is that when preparing the self-lubricating PEEK-based composite material, the mass fraction of modified carbon fiber is adjusted to 12 parts, while other conditions and steps are the same as in Example 1.
[0055] Example 11
[0056] The only difference from Example 1 is that when preparing the self-lubricating PEEK-based composite material, the mass fraction of modified carbon fiber is adjusted to 4 parts, while other conditions and steps are the same as in Example 1.
[0057] Example 12
[0058] The only difference from Example 1 is that, in preparing the self-lubricating PEEK-based composite material, the mass fraction of polyetheretherketone resin was adjusted to 100 parts, the mass fraction of polyarylether thioetherketone was adjusted to 15 parts, and the mass fraction of polyarylether thioetheramide was adjusted to 5 parts. Other conditions and steps were the same as in Example 1.
[0059] Example 13
[0060] The only difference from Example 1 is that, in preparing the self-lubricating PEEK-based composite material, the mass fraction of polyetheretherketone resin was adjusted to 100 parts, the mass fraction of polyarylether thioetherketone was adjusted to 10 parts, and the mass fraction of polyarylether thioetheramide was adjusted to 10 parts. Other conditions and steps were the same as in Example 1.
[0061] Comparative Example 1
[0062] The only difference from Example 1 is that polyetheretherketone and polyaryletheramide are replaced by the same mass of polyetheretherketone when preparing the self-lubricating PEEK-based composite material. The preparation of other materials is the same as in Example 1.
[0063] Preparation of self-lubricating PEEK-based composite materials: Step 1: By weight, mix 120 parts of polyetheretherketone resin and 20 parts of epoxy-modified MoS2@C O -SiO2 nanomaterials, 8 parts modified carbon fiber, 1 part antioxidant 3114 and 1 part antioxidant 9228 are added to a mixer and mixed evenly to obtain a mixture.
[0064] Step 2: Feed the mixture into a screw extruder. Set the temperature of the screw extruder to 240-360℃, with zone 1 at 240℃, zone 2 at 300℃, zone 3 at 340℃, zone 4 at 350℃, and zone 5 at 360℃. Melt extrusion granulation is performed to obtain a self-lubricating PEEK-based composite material.
[0065] Comparative Example 2
[0066] The only difference from Example 1 is that MoS2@C was used when preparing the self-lubricating PEEK-based composite material. O -SiO2 nanomaterials replace epoxy groups in MoS2@C O -SiO2 nanomaterials.
[0067] Preparation of MoS2@C O -SiO2 nanomaterials: S1. Ethanol and deionized water were mixed at a mass ratio of 2:8 to obtain an ethanol aqueous solution. Molybdenum disulfide was weighed at a concentration of 1.0 g / L and added to the ethanol aqueous solution. The mixture was ultrasonically dispersed for 30 min. At room temperature, ammonia water (28 wt%) was added at a concentration of 1.5 mol / L. Then, ethyl silicate with a mass of 10 times that of molybdenum disulfide was added. The mixture was stirred and reacted for 12 h. After filtration, the filter residue was washed with deionized water until neutral and dried under vacuum at 70 °C for 8 h to obtain MoS2@SiO2 material.
[0068] S2. Prepare a 0.4M aqueous solution of cobalt nitrate hexahydrate. Immerse the MoS2@SiO2 material in the solution for 2 hours, with cobalt nitrate accounting for 15% of the MoS2@SiO2 material mass. After immersion, filter the solution. Dry the filter residue at 70℃ for 8 hours. Then, heat-treat the residue at 350℃ for 3 hours, increasing the temperature by 10℃ / min to 350℃, to obtain MoS2@SiO2. O -SiO2 nanomaterials.
[0069] The steps and conditions for preparing the modified carbon fiber are the same as in Example 1.
[0070] Preparation of self-lubricating PEEK-based composite materials: Step 1: According to the mass percentages, add 100 parts of polyetheretherketone resin, 13 parts of polyarylether thioetherketone, and 7 parts of polyarylether thioether amide to a mixer and mix thoroughly. Then add 20 parts of MoS2@C O -SiO2 nanomaterials, 8 parts modified carbon fiber, 1 part antioxidant 3114 and 1 part antioxidant 9228 were mixed to obtain a mixture.
[0071] Step 2: Feed the mixture into a screw extruder. Set the temperature of the screw extruder to 240-360℃, with zone 1 at 240℃, zone 2 at 300℃, zone 3 at 340℃, zone 4 at 350℃, and zone 5 at 360℃. Melt extrusion granulation is performed to obtain a self-lubricating PEEK-based composite material.
[0072] Comparative Example 3
[0073] The only difference from Example 1 is that, in preparing the self-lubricating PEEK-based composite material, epoxy-modified MoS2@C nanomaterials were replaced by an equal mass of epoxy-modified MoS2@SiO2 nanomaterials. O -SiO2 nanomaterials.
[0074] Preparation of epoxy-modified MoS2@SiO2 nanomaterials: S1. Ethanol and deionized water were mixed at a mass ratio of 2:8 to obtain an ethanol aqueous solution. Molybdenum disulfide was weighed at a concentration of 1.0 g / L and added to the ethanol aqueous solution. The mixture was ultrasonically dispersed for 30 min. At room temperature, ammonia water (28 wt%) was added at a concentration of 1.5 mol / L. Then, ethyl silicate with a mass of 10 times that of molybdenum disulfide was added. The mixture was stirred and reacted for 12 h. After filtration, the filter residue was washed with deionized water until neutral and dried under vacuum at 70 °C for 8 h to obtain MoS2@SiO2 material.
[0075] S2. Dissolve silane coupling agent KH-560 in ethanol at a concentration of 0.4 mol / L to obtain an ethanol solution of silane coupling agent KH-560. Add MoS2@SiO2 nanomaterials to deionized water at a concentration of 150 g / L and ultrasonically disperse for 30 min to form a dispersion. Heat to 60℃ and add the ethanol solution of silane coupling agent KH-560 dropwise to the dispersion. The silane coupling agent KH-560 is 15% of the mass of MoS2@SiO2 nanomaterials. Stir and react at 60℃ for 3 h. After filtration, dry the filter residue at 70℃ for 12 h to obtain epoxy-modified MoS2@SiO2 nanomaterials.
[0076] The steps and conditions for preparing the modified carbon fiber are the same as in Example 1.
[0077] Preparation of self-lubricating PEEK-based composite materials: Step 1: According to the mass percentage, add 100 parts of polyether ether ketone resin, 13 parts of polyarylether thioether ketone and 7 parts of polyarylether thioether amide into a mixer and stir until evenly mixed. Then add 20 parts of epoxy-modified MoS2@SiO2 nanomaterials, 8 parts of modified carbon fiber, 1 part of antioxidant 3114 and 1 part of antioxidant 9228, and stir to obtain a mixture.
[0078] Step 2: Feed the mixture into a screw extruder. Set the temperature of the screw extruder to 240-360℃, with zone 1 at 240℃, zone 2 at 300℃, zone 3 at 340℃, zone 4 at 350℃, and zone 5 at 360℃. Melt extrusion granulation is performed to obtain a self-lubricating PEEK-based composite material.
[0079] Comparative Example 4
[0080] The only difference from Example 1 is that, in preparing the self-lubricating PEEK-based composite material, molybdenum disulfide was used to replace the epoxy-modified MoS2@C by an equal mass. O -SiO2 nanomaterials.
[0081] The steps and conditions for preparing the modified carbon fiber are the same as in Example 1.
[0082] Preparation of self-lubricating PEEK-based composite materials: Step 1: According to the mass percentage, put 100 parts of polyether ether ketone resin, 13 parts of polyarylether thioether ketone and 7 parts of polyarylether thioether amide into a mixer and stir until evenly mixed. Then add 20 parts of molybdenum disulfide, 8 parts of modified carbon fiber, 1 part of antioxidant 3114 and 1 part of antioxidant 9228, and stir to obtain a mixture.
[0083] Step 2: Feed the mixture into a screw extruder. Set the temperature of the screw extruder to 240-360℃, with zone 1 at 240℃, zone 2 at 300℃, zone 3 at 340℃, zone 4 at 350℃, and zone 5 at 360℃. Melt extrusion granulation is performed to obtain a self-lubricating PEEK-based composite material.
[0084] Comparative Example 5
[0085] The only difference from Example 1 is that no epoxy-modified MoS2@C is added during the preparation of the self-lubricating PEEK-based composite material. O -SiO2 nanomaterials.
[0086] The steps and conditions for preparing the modified carbon fiber are the same as in Example 1.
[0087] Preparation of self-lubricating PEEK-based composite materials: Step 1: According to the mass percentage, put 100 parts of polyether ether ketone resin, 13 parts of polyarylether thioether ketone and 7 parts of polyarylether thioether amide into a mixer and mix evenly. Then add 8 parts of modified carbon fiber, 1 part of antioxidant 3114 and 1 part of antioxidant 9228 and mix to obtain a mixture.
[0088] Step 2: Feed the mixture into a screw extruder. Set the temperature of the screw extruder to 240-360℃, with zone 1 at 240℃, zone 2 at 300℃, zone 3 at 340℃, zone 4 at 350℃, and zone 5 at 360℃. Melt extrusion granulation is performed to obtain a self-lubricating PEEK-based composite material.
[0089] Comparative Example 6
[0090] The only difference from Example 1 is that the modified carbon fiber was replaced with an equal mass of carbon fiber when preparing the self-lubricating PEEK-based composite material.
[0091] Preparation of epoxy-modified MoS2@C O The steps and conditions for producing SiO2 nanomaterials are the same as in Example 1.
[0092] Preparation of self-lubricating PEEK-based composite materials: Step 1: According to the mass percentage, add 100 parts of polyetheretherketone resin, 13 parts of polyarylether thioetherketone, and 7 parts of polyarylether thioether amide to a mixer and mix thoroughly. Then add 20 parts of epoxy-modified MoS2@C O -SiO2 nanomaterials, 8 parts carbon fiber, 1 part antioxidant 3114 and 1 part antioxidant 9228 are mixed to obtain a mixture.
[0093] Step 2: Feed the mixture into a screw extruder. Set the temperature of the screw extruder to 240-360℃, with zone 1 at 240℃, zone 2 at 300℃, zone 3 at 340℃, zone 4 at 350℃, and zone 5 at 360℃. Melt extrusion granulation is performed to obtain a self-lubricating PEEK-based composite material.
[0094] Comparative Example 7
[0095] The only difference from Example 1 is that no modified carbon fiber is added when preparing the self-lubricating PEEK-based composite material.
[0096] Preparation of epoxy-modified MoS2@C O The steps and conditions for producing SiO2 nanomaterials are the same as in Example 1.
[0097] Preparation of self-lubricating PEEK-based composite materials: Step 1: According to the mass percentage, add 100 parts of polyetheretherketone resin, 13 parts of polyarylether thioetherketone, and 7 parts of polyarylether thioether amide to a mixer and mix thoroughly. Then add 20 parts of epoxy-modified MoS2@C O -SiO2 nanomaterials, 1 part antioxidant 3114 and 1 part antioxidant 9228 are mixed to obtain a mixture.
[0098] Step 2: Feed the mixture into a screw extruder. Set the temperature of the screw extruder to 240-360℃, with zone 1 at 240℃, zone 2 at 300℃, zone 3 at 340℃, zone 4 at 350℃, and zone 5 at 360℃. Melt extrusion granulation is performed to obtain a self-lubricating PEEK-based composite material.
[0099] The performance of the composite materials prepared in Examples 1-13 and Comparative Examples 1-7 was tested, and the results are shown in Table 1.
[0100] Tensile strength tests were performed according to the standard ASTM D638-2014 at a test speed of 5 mm / min.
[0101] The coefficient of kinetic friction and frictional properties against steel at 23℃ are tested in accordance with the standard GB / T 10006-2021.
[0102] The heat distortion temperature of the material is tested at 1.8 MPa in accordance with ISO 75 standard.
[0103] The material was heat-treated at 200℃ for 1000 hours, and the coefficient of dynamic friction was tested.
[0104] Table 1
[0105] As shown in Table 1, the PEEK-based composite materials of Examples 1-13 of this invention have the lowest dynamic friction coefficient of 0.09 at room temperature (23°C), and the dynamic friction coefficient remains relatively stable after high-temperature heat treatment with little variation. This indicates that the epoxy-modified MoS2@C added to the PEEK-based composite material has a significant effect on the dynamic friction coefficient. O -SiO2 nanomaterials and modified carbon fibers can maintain a low coefficient of friction for a long time at high temperatures, ensuring good self-lubricating effect under extreme conditions and reducing wear.
[0106] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.
[0107] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.
Claims
1. A self-lubricating PEEK-based composite material, characterized in that, By weight, it includes the following raw materials: 100 parts of polyetheretherketone resin, 10-15 parts of polyarylether thioetherketone, 5-10 parts of polyarylether thioether amide, and epoxy-modified MoS2@C O The mixture comprises 15-25 parts of SiO2 nanomaterials, 4-12 parts of modified carbon fibers, and 1-2 parts of antioxidants; the modified carbon fibers are obtained by grafting carboxylated carbon fibers with 2-aminodiphenyl sulfide after acylation.
2. The self-lubricating PEEK-based composite material according to claim 1, characterized in that, The epoxy-modified MoS2@C O The preparation steps for SiO2 nanomaterials are as follows: S1. Molybdenum disulfide was dispersed in an aqueous ethanol solution, and ammonia and ethyl silicate were added sequentially at room temperature. The mixture was stirred and reacted for 8–12 h. After filtration, washing, and vacuum drying, MoS2@SiO2 material was obtained. S2. Prepare a 0.2–0.6 M aqueous solution of cobalt nitrate hexahydrate. Immerse the MoS2@SiO2 material in the solution for 1–3 hours, filter and dry, and heat-treat at 300–350℃ for 2–3 hours to obtain MoS2@C O -SiO2 nanomaterials; S3, MoS2@C O SiO2 nanomaterials were dispersed in deionized water to form a dispersion. The temperature was raised to 50-70℃, and an ethanol solution of silane coupling agent KH-560 was added dropwise to the dispersion. The mixture was stirred at a constant temperature for 2-4 hours. After filtration and drying, epoxy-modified MoS2@C was obtained. O -SiO2 nanomaterials.
3. The self-lubricating PEEK-based composite material according to claim 2, characterized in that, The mass ratio of ethanol to water in the ethanol-water solution is (1:9) to (3:7). The concentration of molybdenum disulfide in aqueous ethanol solution is 0.5–1.5 g / L.
4. The self-lubricating PEEK-based composite material according to claim 2, characterized in that, The ammonia solution is added at an ammonia concentration of 1.0–2.0 mol / L; the ethyl silicate is 9.0–10.5 times the mass of molybdenum disulfide; and the cobalt nitrate is 10–20% of the mass of the MoS2@SiO2 material.
5. The self-lubricating PEEK-based composite material according to claim 2, characterized in that, In step S3, the dispersion contains MoS2@C O - The concentration of SiO2 nanomaterials is 100-200 g / L; The concentration of silane coupling agent KH-560 in the ethanol solution is 0.3–0.5 mol / L; the ethanol solution of silane coupling agent KH-560 is prepared according to the configuration of silane coupling agent KH-560 as MoS2@C O - Add 10-20% by mass of SiO2 nanomaterials dropwise.
6. The self-lubricating PEEK-based composite material according to claim 1, characterized in that, The preparation steps of the modified carbon fiber are as follows: Carboxylated carbon fibers were dispersed in sulfonyl chloride at a concentration of 25–55 g / L, heated to 70 °C and reacted for 2–6 h. After filtration and drying, acylated carbon fibers were obtained. Acylated carbon fibers were dispersed in DMF at a concentration of 60–80 g / L. Triethylamine and 2-aminodiphenyl sulfide were added to the acylated carbon fiber dispersion, and the mixture was stirred at 40 °C for 8–12 h. After filtration, washing, and vacuum drying, modified carbon fibers were obtained.
7. The self-lubricating PEEK-based composite material according to claim 6, characterized in that, The preparation steps of the carboxylated carbon fiber are as follows: Carbon fibers were impregnated in a mixed aqueous solution of ammonium persulfate and sulfuric acid at a concentration of 50–100 g / L. The concentration of ammonium persulfate in the mixed aqueous solution was 1.5–2 mol / L, and the concentration of sulfuric acid was 2.0–2.3 mol / L. The reaction was carried out at 40 °C for 3–4 h. The mixture was filtered, washed until neutral, and dried to obtain carboxylated carbon fibers.
8. The self-lubricating PEEK-based composite material according to claim 6, characterized in that, The 2-aminodiphenyl sulfide is 2-5% of the mass of the acylated carbon fiber; The triethylamine is 0.1 to 0.2% of the mass of the acylated carbon fiber dispersion.
9. The self-lubricating PEEK-based composite material according to claim 1, characterized in that, The antioxidant is at least one of antioxidant 3114, antioxidant 1330 and antioxidant 9228.
10. A method for preparing a self-lubricating PEEK-based composite material, characterized in that, The method for preparing the self-lubricating PEEK-based composite material as described in any one of claims 1-9 comprises the following steps: Step 1: Prepare the raw materials according to the proportions. Put the polyetheretherketone resin, polyaryletheretherketone, and polyaryletheretheramide into a mixer and mix them evenly. Then add the epoxy-modified MoS2@C O -SiO2 nanomaterials, modified carbon fibers, and antioxidants are mixed to obtain a mixture; Step 2: Feed the mixture into a screw extruder and melt-extrude and granulate to obtain the finished product.