High-wear-resistance PEEK composite material and preparation method thereof
By introducing PEEK-BN and MoS2 sulfonated polyether ether ketone composites into PEEK composites, and utilizing in-situ polymerization and electrostatic self-assembly technology, the problem of easy agglomeration of nanofillers in PEEK composites was solved, the wear resistance and thermal conductivity of the materials were improved, and the stability and performance uniformity of the materials at high temperatures were achieved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- 安徽赛诺新材料科技有限公司
- Filing Date
- 2026-02-13
- Publication Date
- 2026-05-12
AI Technical Summary
Existing PEEK composite materials exhibit poor wear resistance during friction and wear processes. The nanofillers are prone to agglomeration, leading to uneven performance, and are also prone to detachment at high temperatures, affecting the material's service life and performance stability.
A composite material of PEEK-BN and MoS2 sulfonated polyether ether ketone was used. Polymer segments were formed by in-situ polymerization of polyether ether ketone on boron nitride. Combined with electrostatic self-assembly technology, the nanosheets were uniformly dispersed. The dispersibility and compatibility were improved by end-hydroxyl hyperbranched polysiloxane, forming a stable interfacial bonding network.
It improves the wear resistance and thermal conductivity of PEEK composite materials, ensures stable material performance under long-term frictional thermal cycling, prevents the agglomeration and shedding of nanofillers, and maintains the basic mechanical and thermal conductivity of the material.
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of materials science and technology, specifically relating to a high wear-resistant PEEK composite material and its preparation method. Background Technology
[0002] Polyetheretherketone (PEEK) is a linear polymer whose macromolecular backbone is composed of aryl, ketone, and ether bonds. As a semi-crystalline aromatic thermoplastic engineering plastic, PEEK possesses significant advantages such as excellent dimensional stability, strong radiation resistance, high toughness, and ease of extrusion and injection molding. It also exhibits excellent processing performance and high molding efficiency. Due to these superior comprehensive properties, PEEK materials have been widely used in high-tech fields such as the automotive industry, precision instruments, aerospace, chemical industry, medical devices, and electronics.
[0003] However, with the continuous advancement of industrialization, the problems of equipment failure and economic losses caused by friction and wear are becoming increasingly prominent in pillar industries of the national economy, such as metallurgy, machining, petrochemicals, transportation, aerospace, and precision instrument manufacturing. Specifically, the performance degradation and frequent replacement of key mechanical equipment components due to friction and wear during long-term operation not only significantly increases equipment maintenance costs but also restricts the promotion and application of some advanced mechanical equipment and high-end manufacturing technologies. In addition, the wear resistance of single-component polyetheretherketone (PEEK) materials under dry friction conditions is limited, making it difficult to meet the stringent requirements for multifunctional properties of materials in complex service environments. This, to some extent, limits the application scope and depth of PEEK materials.
[0004] To improve the tribological properties of PEEK materials, existing technologies typically employ polytetrafluoroethylene (PTFE) and inorganic nanofillers to modify the PEEK matrix. Filling PTFE particles into the PTFE matrix can significantly improve the wear resistance of the composite material while maintaining the excellent properties of PTFE itself. Filling a small number of nano-sized particles into the polymer matrix can utilize their small size and surface effects to improve the wear resistance of the composite material while maintaining the excellent properties of the matrix.
[0005] Nanoparticles are considered effective reinforcing phases due to their small size and surface effects, significantly improving the wear resistance of polymers at relatively low addition levels. However, these fillers still face several key challenges in practical applications: First, nanofillers have large specific surface areas and high surface energy, making them prone to agglomeration in the polymer matrix and difficult to achieve uniform dispersion. Filler agglomeration can lead to stress concentration points within the composite material, causing uneven performance distribution and severely weakening its intended reinforcing effect on the matrix. Second, the amount of filler added is significantly sensitive to range: excessive filling can disrupt the continuity of the PEEK matrix, weaken interfacial bonding strength, and hard fillers are prone to detachment during friction, forming large wear debris. This debris exerts a significant plowing effect at the friction interface, accelerating material wear. In addition, during the friction process, some filler particles debond and fall off due to weak bonding with the matrix interface. The detached wear debris enters the contact surface, which not only increases the mechanical interlocking and frictional resistance of the interface, but may also further damage the material surface and mating parts through the furrowing effect. Especially when the filler is unevenly dispersed, the agglomerates are more likely to fall off under shearing action, thereby aggravating the wear process. Summary of the Invention
[0006] The purpose of this invention is to provide a high wear-resistant PEEK composite material and its preparation method, so as to solve the problem of poor wear resistance of PEEK composite materials.
[0007] The objective of this invention can be achieved through the following technical solutions: The first aspect of the present invention provides a high wear-resistant PEEK composite material, which, by weight, comprises the following raw materials: 25-30 parts of polyether ether ketone powder, 47-52 parts of PEEK-BN, 13-18 parts of polytetrafluoroethylene powder, and 5-10 parts of MoS2 sulfonated polyether ether ketone composite material.
[0008] Furthermore, the PEEK-BN is prepared through the following steps: Hydroxylated boron nitride nanosheets, hydroxyl-terminated hyperbranched polysiloxane, hydroquinone, 4,4'-difluorobenzophenone, and diphenyl sulfone were mixed and stirred for 30 min under nitrogen protection. Toluene, calcium carbonate, and potassium carbonate were then added. After the addition was complete, the temperature was raised to 125-130℃ and maintained for 4-5 h. Then, the temperature was raised to 300-320℃ and maintained for another 2-4 h. After the reaction was completed, the product was pulverized, washed with acetone and water, and vacuum dried to obtain PEEK-BN. PEEK-BN is obtained by in-situ polymerization of polyether ether ketone (PEEK) on boron nitride using hydroxylated boron nitride nanosheets as raw material. The polymer segments formed by PEEK on boron nitride improve the dispersibility and compatibility of boron nitride with the matrix. In this invention, hydroxyl-terminated hyperbranched polysiloxane is introduced during the in-situ polymerization process. The introduced hydroxyl-terminated hyperbranched polysiloxane is anchored on the surface of BN, and its three-dimensional hyperbranched structure forms a soft steric hindrance layer around BN. This barrier effectively resists the approach and aggregation of BN sheets during high-temperature melting and processing, fundamentally solving the problem of dispersion stability of nanofillers in high-viscosity melts. The mass ratio of hydroxylated boron nitride nanosheets to hydroquinone is 1:5; The molar ratio of hydroquinone to 4,4'-difluorobenzophenone is 1:1.2-1.5; The ratio of 4,4'-difluorobenzophenone, diphenyl sulfone, toluene, calcium carbonate, and potassium carbonate is 0.1 mol: 20 mL: 50 mL: 0.1 mol: 0.05 mol.
[0009] Furthermore, the amount of hydroxyl-terminated hyperbranched polysiloxane added is 4%–6% of the mass of hydroxylated boron nitride nanosheets, and the mass fraction of hydroxylated boron nitride nanosheets in PEEK-BN is 5%–10%.
[0010] Furthermore, the hydroxyl-terminated hyperbranched polysiloxane is prepared via the following steps: Under nitrogen protection, tetraethyl orthosilicate, diol and p-toluenesulfonic acid are mixed and the reaction temperature is controlled in the range of 110-160℃. During this period, the distillation temperature is kept below 78℃ until the distillation temperature drops to 55℃ and heating is stopped to obtain hydroxyl-terminated hyperbranched polysiloxane.
[0011] Furthermore, the ratio of tetraethyl orthosilicate to diol is 1 mol: 3.5-4 mol, and the amount of p-toluenesulfonic acid added is 0.5% of the mass of tetraethyl orthosilicate.
[0012] Furthermore, the diol is one of 1,2-hexanediol, 1,2-pentanediol, and neopentanediol.
[0013] Furthermore, it also includes 0.01-0.05 parts of an antioxidant, wherein the antioxidant is antioxidant 3114. The isocyanuric acid heterocyclic skeleton of antioxidant 3114 has inherent structural advantages in terms of high-temperature stability, anti-discoloration properties, and interfacial interactions, and is therefore more suitable for the processing and application of high-temperature engineering plastics such as PEEK.
[0014] Furthermore, the MoS2 sulfonated polyether ether ketone composite material is prepared by the following steps: Molybdenum disulfide nanosheets were added to a hexadecyltrimethylammonium bromide (CTAB) solution and ultrasonically dispersed for 30-60 min. After centrifugation and drying, CTAB-MoS2 was obtained. CTAB-MoS2 was added to water to form a dispersion, then sulfonated polyether ether ketone powder was added, and the mixture was stirred at room temperature for 1-3 hours. After solid-liquid separation (centrifugation or filtration), the mixture was washed with water and dried to obtain the MoS2 sulfonated polyether ether ketone composite material. The concentration of the hexadecyltrimethylammonium bromide solution was 0.1 mol / L, and the mass fraction of CTAB-MoS2 in the water dispersion was 2%.
[0015] Molybdenum disulfide nanosheets were obtained from commercially available MoS2 powder via ultrasonic exfoliation. The resulting MoS2 nanosheets typically carried a negative charge on their surface (due to negatively charged groups at edges or defects), while the CTAB-MoS2 surface exhibited a positive charge (-N). + (CH3)3). Sulfonate group (-SO3) - It ionizes in water and carries a negative charge, which interacts with the positive charge (-N) on the surface of CTAB-MoS2. + (CH3)3) They are tightly bound together by electrostatic attraction. MoS2 nanosheets are uniformly coated on the SPEEK surface, forming a core-shell structure of MoS2 sulfonated polyether ether ketone. This process is carried out at room temperature and pressure, without the need for high-temperature and high-pressure equipment such as hydrothermal reactors. Electrostatic self-assembly enables MoS2 nanosheets to form a uniform coating layer on the surface of sulfonated polyether ether ketone.
[0016] Furthermore, the mass fraction of MoS2 in the MoS2 sulfonated polyether ether ketone composite material is 40%–60%; the degree of sulfonation of the sulfonated polyether ether ketone is 5%–15%.
[0017] A second aspect of this invention provides a method for preparing a high-wear-resistant PEEK composite material, comprising the following steps: The raw materials are mixed and then uniformly mixed by mechanical blending, followed by ball milling. After blending, the mixture is poured into a mold, pre-pressed, and hot-pressed to obtain a high-wear-resistant PEEK composite material. Further, mechanical blending is performed: ball milling is conducted at a speed of 400-500 r / min for a milling time of 150-180 min. Pre-compression conditions: pressure set to 3-5 MPa, time 1-5 min; The conditions for hot pressing are a temperature of 360-380℃, a pressure of 10-15MPa, and a holding time of 50-80min.
[0018] The beneficial effects of this invention are: This invention provides a high-wear-resistant PEEK composite material and its preparation method. The invention incorporates PEEK-BN and MoS2 sulfonated polyether ether ketone (PEEK) composites to improve the wear resistance of PEEK composites. PEEK-BN is obtained by in-situ polymerization of PEEK on boron nitride using hydroxylated boron nitride nanosheets. The polymer segments formed by PEEK on boron nitride improve the dispersibility and compatibility between boron nitride and the matrix. The MoS2 sulfonated PEEK composite material is obtained by electrostatic self-assembly to form a uniform coating layer of MoS2 nanosheets on the surface of sulfonated PEEK. The highly efficient thermally conductive network provided by PEEK-BN diffuses frictional heat, and the strong interfacial bonding network maintains the overall stiffness of the material, preventing excessive deformation from damaging the lubricating film. MoS2 is continuously supplied under milder and more stable interfacial conditions, forming and maintaining a high-quality transfer film. This ensures that the BN reinforcing phase does not agglomerate or fail under long-term frictional thermal cycling, thereby maintaining the long-term stability of the material's basic mechanical and thermal properties. Detailed Implementation
[0019] 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.
[0020] Obviously, the following description is merely some examples or embodiments of this application. Those skilled in the art can apply this application to other similar scenarios without any inventive effort. Furthermore, it is understood that although the effort involved in such development may be complex and lengthy, for those skilled in the art related to the content disclosed in this application, any changes to design, manufacturing, or production based on the technical content disclosed in this application are merely conventional technical means and should not be construed as insufficient disclosure of the content of this application.
[0021] However, there may be instances where unnecessary detailed descriptions are omitted. For example, detailed descriptions of well-known matters or repetitive descriptions of essentially the same structure may be omitted. This is to avoid making the following description unnecessarily lengthy and to facilitate understanding by those skilled in the art. Furthermore, the following description is provided to enable those skilled in the art to fully understand this application and is not intended to limit the subject matter of the claims.
[0022] Unless otherwise specified, all embodiments and optional embodiments of this application can be combined to form new technical solutions, and all technical features and optional technical features of this application can be combined to form new technical solutions.
[0023] The following is a detailed description of a high wear-resistant PEEK composite material and its preparation method according to an embodiment of this application.
[0024] The following is a detailed description with reference to specific examples.
[0025] Example 1
[0026] This embodiment provides a high-wear-resistant PEEK composite material, comprising the following raw materials by weight: 27 parts polyetheretherketone powder, 50 parts PEEK-BN, 15 parts polytetrafluoroethylene powder, and 8 parts MoS2 sulfonated polyetheretherketone composite material. The PEEK-BN is prepared through the following steps: Under nitrogen protection, tetraethyl orthosilicate, diol, and p-toluenesulfonic acid are mixed, and the reaction temperature is controlled within the range of 110-160℃. During this period, the distillation temperature is kept below 78℃ until the distillation temperature drops to 55℃ and heating is stopped to obtain hydroxyl-terminated hyperbranched polysiloxane. The ratio of tetraethyl orthosilicate to diol is 1 mol: 3.5 mol, and the amount of p-toluenesulfonic acid added is 0.5% of the mass of tetraethyl orthosilicate. The diol is 1,2-hexanediol.
[0027] Hydroxylated boron nitride nanosheets, hydroxyl-terminated hyperbranched polysiloxane, hydroquinone, 4,4'-difluorobenzophenone, and diphenyl sulfone were mixed and stirred for 30 min under nitrogen protection. Toluene, calcium carbonate, and potassium carbonate were then added. After the addition was complete, the temperature was raised to 130 °C and the reaction was maintained for 4 h. Then, the temperature was raised to 300 °C and maintained for another 4 h. After the reaction was completed, the product was pulverized, washed with acetone and water, and vacuum dried to obtain PEEK-BN.
[0028] The mass ratio of hydroxylated boron nitride nanosheets to hydroquinone is 1:5; the molar ratio of hydroquinone to 4,4'-difluorobenzophenone is 1:1.3; the mass ratio of 4,4'-difluorobenzophenone, diphenyl sulfone, toluene, calcium carbonate, and potassium carbonate is 0.1 mol: 20 mL: 50 mL: 0.1 mol: 0.05 mol; the amount of hydroxyl-terminated hyperbranched polysiloxane added is 5% of the mass of hydroxylated boron nitride nanosheets, and the mass fraction of hydroxylated boron nitride nanosheets in the PEEK-BN is 10%.
[0029] The MoS2 sulfonated polyether ether ketone composite material is prepared through the following steps: Molybdenum disulfide nanosheets were added to a hexadecyltrimethylammonium bromide (CTAB) solution and ultrasonically dispersed for 50 min. After centrifugation and drying, CTAB-MoS2 was obtained. CTAB-MoS2 was added to water to prepare a dispersion, then sulfonated polyether ether ketone powder was added, and the mixture was stirred at room temperature for 2 hours. After solid-liquid separation (centrifugation), the mixture was washed with water and dried to obtain the MoS2 sulfonated polyether ether ketone composite material. The concentration of the hexadecyltrimethylammonium bromide solution was 0.1 mol / L, the mass fraction of CTAB-MoS2 in the water dispersion was 2%, the mass fraction of MoS2 in the MoS2 sulfonated polyether ether ketone composite material was 50%, and the degree of sulfonation of the sulfonated polyether ether ketone was 10%.
[0030] The preparation method of this high wear-resistant PEEK composite material includes the following steps: Polyether ether ketone powder, PEEK-BN, polytetrafluoroethylene powder and MoS2 sulfonated polyether ether ketone composite material were mixed and uniformly mixed by mechanical blending, and then ball-milled at a speed of 500 r / min for 160 min. After blending, the mixture is poured into a mold and pre-pressed: the mold is placed on a flat vulcanizing machine with a pressure of 5 MPa and a time of 2 min; then hot-pressed: the temperature is raised to 365℃ and the pressure is set to 12 MPa and held for 1 h; finally, after air cooling to room temperature, the mixture is demolded to obtain a high wear-resistant PEEK composite material.
[0031] Example 2
[0032] This embodiment provides a high wear-resistant PEEK composite material, which, by weight, comprises the following raw materials: 30 parts of polyetheretherketone powder, 47 parts of PEEK-BN, 13 parts of polytetrafluoroethylene powder, and 10 parts of MoS2 sulfonated polyetheretherketone composite material. Specifically, the PEEK-BN and MoS2 sulfonated polyetheretherketone composite material are the same as in Example 1.
[0033] The remaining raw materials and preparation methods are the same as in Example 1.
[0034] Example 3
[0035] This embodiment provides a high wear-resistant PEEK composite material, which, by weight, comprises the following raw materials: 29 parts of polyetheretherketone powder, 48 parts of PEEK-BN, 16 parts of polytetrafluoroethylene powder, and 7 parts of MoS2 sulfonated polyetheretherketone composite material. Specifically, the PEEK-BN is the same as in Example 1; the MoS2 sulfonated polyetheretherketone composite material is the same as in Example 1.
[0036] The remaining raw materials and preparation methods are the same as in Example 1.
[0037] Example 4
[0038] This embodiment provides a high wear-resistant PEEK composite material, which, by weight, comprises the following raw materials: 25 parts of polyetheretherketone powder, 52 parts of PEEK-BN, 18 parts of polytetrafluoroethylene powder, and 5 parts of MoS2 sulfonated polyetheretherketone composite material. Specifically, the PEEK-BN is the same as in Example 1; the MoS2 sulfonated polyetheretherketone composite material is the same as in Example 1.
[0039] The remaining raw materials and preparation methods are the same as in Example 1.
[0040] Example 5
[0041] This embodiment provides a high wear-resistant PEEK composite material. The difference between this embodiment and Example 1 lies in the preparation process of PEEK-BN. Specifically, PEEK-BN is prepared through the following steps: Under nitrogen protection, tetraethyl orthosilicate, diol, and p-toluenesulfonic acid are mixed, and the reaction temperature is controlled within the range of 110-160℃. During this period, the distillation temperature is kept below 78℃ until the distillation temperature drops to 55℃ and heating is stopped to obtain hydroxyl-terminated hyperbranched polysiloxane. The ratio of tetraethyl orthosilicate to diol is 1 mol: 3.5 mol, and the amount of p-toluenesulfonic acid added is 0.5% of the mass of tetraethyl orthosilicate. The diol is 1,2-pentanediol.
[0042] Hydroxylated boron nitride nanosheets, hydroxyl-terminated hyperbranched polysiloxane, hydroquinone, 4,4'-difluorobenzophenone, and diphenyl sulfone were mixed and stirred for 30 min under nitrogen protection. Toluene, calcium carbonate, and potassium carbonate were then added. After the addition was complete, the temperature was raised to 130 °C and the reaction was maintained for 4 h. Then, the temperature was raised to 300 °C and maintained for another 4 h. After the reaction was completed, the product was pulverized, washed with acetone and water, and vacuum dried to obtain PEEK-BN.
[0043] The mass ratio of hydroxylated boron nitride nanosheets to hydroquinone is 1:5; the molar ratio of hydroquinone to 4,4'-difluorobenzophenone is 1:1.3; the mass ratio of 4,4'-difluorobenzophenone, diphenyl sulfone, toluene, calcium carbonate, and potassium carbonate is 0.1 mol: 20 mL: 50 mL: 0.1 mol: 0.05 mol; the amount of hydroxyl-terminated hyperbranched polysiloxane added is 5% of the mass of hydroxylated boron nitride nanosheets, and the mass fraction of hydroxylated boron nitride nanosheets in the PEEK-BN is 10%.
[0044] The remaining raw materials and preparation methods are the same as in Example 1.
[0045] Example 6
[0046] This embodiment provides a high wear-resistant PEEK composite material. The difference between this embodiment and Example 1 lies in the preparation process of PEEK-BN. Specifically, PEEK-BN is prepared through the following steps: Under nitrogen protection, tetraethyl orthosilicate, diol, and p-toluenesulfonic acid are mixed, and the reaction temperature is controlled within the range of 110-160℃. During this period, the distillation temperature is kept below 78℃ until the distillation temperature drops to 55℃ and heating is stopped to obtain hydroxyl-terminated hyperbranched polysiloxane. The ratio of tetraethyl orthosilicate to diol is 1 mol: 3.5 mol, and the amount of p-toluenesulfonic acid added is 0.5% of the mass of tetraethyl orthosilicate. The diol is neopentyl glycol.
[0047] Hydroxylated boron nitride nanosheets, hydroxyl-terminated hyperbranched polysiloxane, hydroquinone, 4,4'-difluorobenzophenone, and diphenyl sulfone were mixed and stirred for 30 min under nitrogen protection. Toluene, calcium carbonate, and potassium carbonate were then added. After the addition was complete, the temperature was raised to 130 °C and the reaction was maintained for 4 h. Then, the temperature was raised to 300 °C and maintained for another 4 h. After the reaction was completed, the product was pulverized, washed with acetone and water, and vacuum dried to obtain PEEK-BN.
[0048] The mass ratio of hydroxylated boron nitride nanosheets to hydroquinone is 1:5; the molar ratio of hydroquinone to 4,4'-difluorobenzophenone is 1:1.3; the mass ratio of 4,4'-difluorobenzophenone, diphenyl sulfone, toluene, calcium carbonate, and potassium carbonate is 0.1 mol: 20 mL: 50 mL: 0.1 mol: 0.05 mol; the amount of hydroxyl-terminated hyperbranched polysiloxane added is 5% of the mass of hydroxylated boron nitride nanosheets, and the mass fraction of hydroxylated boron nitride nanosheets in the PEEK-BN is 10%.
[0049] The remaining raw materials and preparation methods are the same as in Example 1.
[0050] Example 7
[0051] The difference between this embodiment and Example 1 lies in the preparation process of PEEK-BN. Specifically, PEEK-BN is prepared through the following steps: Hydroxylated boron nitride nanosheets, hydroxyl-terminated hyperbranched polysiloxane (same as in Example 1), hydroquinone, 4,4'-difluorobenzophenone, and diphenyl sulfone were mixed and stirred for 30 min under nitrogen protection. Toluene, calcium carbonate, and potassium carbonate were then added. After the addition was complete, the temperature was raised to 130°C and the reaction was maintained for 4 h. Then the temperature was raised to 300°C and maintained for another 4 h. After the reaction was completed, the product was pulverized, washed with acetone and water, and vacuum dried to obtain PEEK-BN.
[0052] The mass ratio of hydroxylated boron nitride nanosheets to hydroquinone is 1:5; the molar ratio of hydroquinone to 4,4'-difluorobenzophenone is 1:1.2; the mass ratio of 4,4'-difluorobenzophenone, diphenyl sulfone, toluene, calcium carbonate, and potassium carbonate is 0.1 mol: 20 mL: 50 mL: 0.1 mol: 0.05 mol; the amount of hydroxyl-terminated hyperbranched polysiloxane added is 4% of the mass of hydroxylated boron nitride nanosheets, and the mass fraction of hydroxylated boron nitride nanosheets in the PEEK-BN is 10%.
[0053] The remaining raw materials and preparation methods are the same as in Example 1.
[0054] Example 8
[0055] The difference between this embodiment and Example 1 lies in the preparation process of PEEK-BN. Specifically, PEEK-BN is prepared through the following steps: Hydroxylated boron nitride nanosheets, hydroxyl-terminated hyperbranched polysiloxane (same as in Example 1), hydroquinone, 4,4'-difluorobenzophenone, and diphenyl sulfone were mixed and stirred for 30 min under nitrogen protection. Toluene, calcium carbonate, and potassium carbonate were then added. After the addition was complete, the temperature was raised to 130°C and the reaction was maintained for 4 h. Then the temperature was raised to 300°C and maintained for another 4 h. After the reaction was completed, the product was pulverized, washed with acetone and water, and vacuum dried to obtain PEEK-BN.
[0056] The mass ratio of hydroxylated boron nitride nanosheets to hydroquinone is 1:5; the molar ratio of hydroquinone to 4,4'-difluorobenzophenone is 1:1.5; the mass ratio of 4,4'-difluorobenzophenone, diphenyl sulfone, toluene, calcium carbonate, and potassium carbonate is 0.1 mol: 20 mL: 50 mL: 0.1 mol: 0.05 mol; the amount of hydroxyl-terminated hyperbranched polysiloxane added is 6% of the mass of hydroxylated boron nitride nanosheets, and the mass fraction of hydroxylated boron nitride nanosheets in the PEEK-BN is 10%.
[0057] The remaining raw materials and preparation methods are the same as in Example 1.
[0058] Comparative Example 1
[0059] The difference between this comparative example and Example 1 is that PEEK-BN is replaced with boron nitride nanosheets and polyether ether ketone powder in a mass ratio of 1:10, while the other raw materials and preparation methods remain the same as in Example 1.
[0060] Comparative Example 2
[0061] This comparative example differs from Example 1 in that PEEK-BN is replaced with a mixture of boron nitride and polyether ether ketone treated with a silane coupling agent at a mass ratio of 1:10. The coupling agent-treated BN is prepared through the following steps: Hydroxylated boron nitride was ultrasonically dispersed in an ethanol solution, followed by the addition of silane coupling agent KH-550. The mixture was stirred and reacted at 40°C for 30 minutes. After centrifugation, filtration, drying, and washing with water, the coupling agent-treated boron nitride (BN) was obtained. The ratio of hydroxylated boron nitride to silane coupling agent KH-550 was 10 g: 10 mL.
[0062] The remaining raw materials and preparation methods are the same as in Example 1.
[0063] Comparative Example 3
[0064] The difference between this comparative example and Example 1 is that no terminal hydroxyl hyperbranched polysiloxane is added during the preparation of PEEK-BN, while the other raw materials and preparation methods remain the same as in Example 1.
[0065] Test case
[0066] 1. Tribological property testing: Standard: Refer to GB / T 3960-2016 "Test Method for Sliding Friction and Wear of Plastics" Parameters: Load 10N, 20N, 30N; Speed 400–600 r / min; Dry friction / grease lubrication (lithium-based grease); Wear pair Φ10mm 45# steel balls (HRC 60±2); Test time 7000s (or until stable wear stage is reached).
[0067] Characterization: Coefficient of friction (COF) data collection; Wear rate calculation: I = V / ( F · t ); In the formula V Wear volume (mm) 3 ); F : Load (N); t Time (h).
[0068] 2. Mechanical property testing: Mechanical property testing: Refer to GB / T 1041-2008, with sample size of 10mm×10mm×4mm, compression rate of 5mm / min, and determine compressive strength.
[0069] 3. Thermal conductivity test: Thermal conductivity (W / m·K) was measured at room temperature (25℃) using a thermal conductivity meter.
[0070] Performance tests were conducted on Examples 1-8 and Comparative Examples 1-3, and the results are shown in Table 1: Table 1
[0071] Based on Table 1 and the test data from Examples 1-8 and Comparative Examples 1-3, it can be seen that adding PEEK-BN and MoS2 sulfonated polyether ether ketone composites can improve the wear resistance and thermal conductivity of PEEK composites. Comparative Example 1 is a physical blend of unmodified BN nanosheets; Comparative Example 2 uses KH550 silane coupling agent to modify boron nitride nanosheets; Comparative Example 3 is conventional in-situ polymerization of PEEK coated with BN, without the use of hydroxyl-terminated hyperbranched polysiloxanes. In Comparative Example 1, the BN nanosheets are prone to agglomeration, leading to increased stress concentration at the friction interface. While Comparative Examples 2 and 3 improved the dispersion of boron nitride nanosheets, the bonding energy of the silane coupling agent in Comparative Example 2 was relatively weak, failing to provide protection during subsequent high-temperature heating. A comparison between Comparative Example 3 and Example 1 revealed that the structural integrity of hyperbranched siloxanes at high temperatures is crucial for maintaining the continuity of the lubricating film. Comparative Example 3 lacked terminal hydroxyl hyperbranched polysiloxanes, resulting in slight agglomeration during high-temperature processing. Therefore, Example 1 achieved stable high-temperature dispersion and a strong, tough matrix through strong covalent interfaces and three-dimensional steric hindrance.
[0072] 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.
[0073] 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 high wear-resistant PEEK composite material, characterized in that, By weight, it includes the following raw materials: 25-30 parts of polyetheretherketone powder, 47-52 parts of PEEK-BN, 13-18 parts of polytetrafluoroethylene powder and 5-10 parts of MoS2 sulfonated polyetheretherketone composite material.
2. The high wear-resistant PEEK composite material according to claim 1, characterized in that, The PEEK-BN is prepared by the following steps: Hydroxylated boron nitride nanosheets, hydroxyl-terminated hyperbranched polysiloxane, hydroquinone, 4,4'-difluorobenzophenone, and diphenyl sulfone were mixed and stirred under nitrogen protection. Toluene, calcium carbonate, and potassium carbonate were then added. After the addition was complete, the temperature was raised to 125-130℃ and the reaction was maintained for 4-5 hours. Then, the temperature was raised to 300-320℃ and the reaction was maintained for another 4 hours to obtain PEEK-BN.
3. The high wear-resistant PEEK composite material according to claim 2, characterized in that, The amount of hydroxyl-terminated hyperbranched polysiloxane added is 4%–6% of the mass of hydroxylated boron nitride nanosheets, and the mass fraction of hydroxylated boron nitride nanosheets in PEEK-BN is 5%–10%.
4. The high wear-resistant PEEK composite material according to claim 1, characterized in that, Hydroxyl-terminated hyperbranched polysiloxanes are prepared by the following steps: Under nitrogen protection, tetraethyl orthosilicate, diol and p-toluenesulfonic acid are mixed and reacted to obtain hydroxyl-terminated hyperbranched polysiloxane.
5. The high wear-resistant PEEK composite material according to claim 4, characterized in that, The ratio of tetraethyl orthosilicate to diol is 1 mol: 3.5-4 mol, and the amount of p-toluenesulfonic acid added is 0.5% of the mass of tetraethyl orthosilicate.
6. The high wear-resistant PEEK composite material according to claim 4, characterized in that, The diol is one of 1,2-hexanediol, 1,2-pentanediol, and neopentanediol.
7. The high wear-resistant PEEK composite material according to claim 1, characterized in that, The MoS2 sulfonated polyether ether ketone composite material is prepared by the following steps: Molybdenum disulfide nanosheets were added to a hexadecyltrimethylammonium bromide solution and ultrasonically dispersed. After centrifugation and drying, CTAB-MoS2 was obtained. CTAB-MoS2 was added to water to form a dispersion, and then sulfonated polyether ether ketone powder was added. The mixture was stirred at room temperature for 1-3 hours. After solid-liquid separation, water washing, and drying, the MoS2 sulfonated polyether ether ketone composite material was obtained.
8. The high wear-resistant PEEK composite material according to claim 7, characterized in that, The mass fraction of MoS2 in the MoS2 sulfonated polyether ether ketone composite material is 40%–60%; the degree of sulfonation of the sulfonated polyether ether ketone is 5%–15%.
9. A method for preparing a high wear-resistant PEEK composite material, used to prepare the high wear-resistant PEEK composite material according to any one of claims 1-8, characterized in that, Includes the following steps: The raw materials are mixed and mechanically blended until homogeneous, then ball-milled. After blending, the mixture is poured into a mold, pre-pressed, and hot-pressed to obtain a high-wear-resistant PEEK composite material.
10. The method for preparing a high wear-resistant PEEK composite material according to claim 9, characterized in that, Mechanical blending: ball milling, with a rotation speed of 400-500 r / min and a milling time of 150-180 min; Pre-compression conditions: pressure set to 3-5 MPa, time 1-5 min; The conditions for hot pressing are a temperature of 360-380℃, a pressure of 10-15MPa, and a holding time of 50-80min.