G-CNT / boron nitride reinforced polyether-ether-ketone composite material as well as preparation method and application thereof

Abstract

The invention provides a G-CNT / boron nitride reinforced polyether-ether-ketone composite material as well as a preparation method and application thereof, and relates to the technical field of orthopedic implant materials. The G-CNT / boron nitride reinforced polyether-ether-ketone composite material is composed of a G-CNT hybrid material, spherical boron nitride particles and polyether-ether-ketone, and based on the total mass of the composite material, the G-CNT / boron nitride reinforced polyether-ether-ketone composite material contains 0.1-20 wt% of G-CNT, 0.1-5 wt% of boron nitride and the balance of polyether-ether-ketone. The invention aims to provide the novel G-CNT / boron nitride reinforced polyether-ether-ketone composite material aiming at the defects in the prior art. The novel G-CNT / boron nitride reinforced polyether-ether-ketone composite material is simple in process and low in cost, industrial production is easy to realize, and the wear resistance of the polyether-ether-ketone material can be remarkably improved.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of orthopedic implant materials, in particular to a G-CNT / boron nitride reinforced polyether ether ketone composite material and a preparation method and application thereof. BACKGROUND

[0002] Artificial joint replacement is an extremely effective method for treating bone joint injury, and can obviously improve the life quality of patients and enable patients with late-stage osteoarthritis to get rid of pain and distress.

[0003] An artificial joint prosthesis as an implant is subjected to corrosion of body fluid for a long time, and also subjected to different direction tensile force, pressure and self gravity, especially the hip and knee joints, and these complex stresses make the repeated wear of the artificial joint the primary factor affecting the service life of the joint prosthesis, which brings a severe challenge to the joint material. For a long time, people have been searching for new materials to improve the performance of the joint prosthesis, and trying to break through the limitation of the previous materials, increase the durability of the artificial joint prosthesis, reduce wear and tear, and thus prolong the service life of the artificial joint. Therefore, the selection of the joint prosthesis material plays an important role in the success or failure of the artificial joint replacement.

[0004] Wear is the main reason for the failure of joint materials, and further prevention of the occurrence of wear requires improvement of the friction and wear performance of joint materials. The friction and wear performance of an artificial joint is an important standard for evaluating the service life of the artificial joint. The friction coefficient of the original joint of human beings is extremely small and almost has no wear, but the friction coefficient of the artificial joint is much higher. When the bearing surface of the artificial joint moves, wear debris is generated in the process of friction with the interface, which causes joint wear, and thus failure occurs and is often accompanied by other symptoms, such as aseptic loosening of the prosthesis, fracture of the prosthesis and the like. Improving the friction performance of the existing joint material is one of the main research directions for solving the problem of insufficient service life of the current artificial joint material. There is an urgent need for a joint material with extremely low friction coefficient and wear loss and excellent comprehensive performance.

[0005] Polyether ether ketone is a kind of semi-crystalline polymer with good biocompatibility, and has good mechanical properties and physical and chemical stability, which has been widely used in the field of medical implant materials and shows good development prospect: (1) polyether ether ketone can be penetrated under X-ray without artifact, and has good visibility, which can help doctors to carry out surgery under the assistance of CT scan or magnetic resonance imaging, and the position of the implant can be adjusted in time during the operation, and the healing process is convenient to track after the operation; (2) the clinical results show that the elastic modulus of metal is much larger than that of bone, if used as an implant, most of the load originally borne by the bone will be borne by the implant, and the "stress shielding" effect occurs, which leads to the reduction of nutrients absorbed by the bone at this place, delays bone healing, and long time use can lead to osteoporosis and even degradation, and the flexural strength of polyether ether ketone composite material is similar to that of human cortical bone, and it is very suitable to be used as an implant; (3) polyether ether ketone has excellent biocompatibility, no cytotoxicity, mutagenicity and carcinogenicity, and does not cause allergy, and is certified by the FDA of the United States as an excellent long-term implant material; (4) polyether ether ketone has very excellent fatigue resistance, and can still maintain high mechanical strength under the condition of continuous cyclic loading.

[0006] Polyether ether ketone belongs to self-lubricating material, and the friction performance is even better than that of ultra-high molecular polyethylene. However, when it is used alone as a knee joint or hip joint material, the wear resistance of polyether ether ketone needs to be further improved. Researches show that the friction and wear performance of polyether ether ketone composite material reinforced by a reinforcing body is significantly improved. The polyether ether ketone composite material bone nail, bone plate, hip joint, intervertebral fusion cage and the like developed by In-vibio company in the United Kingdom have achieved good application effect. Therefore, a new type of polyether ether ketone composite material with excellent tribological performance is urgently needed to be used for manufacturing artificial joint prosthesis applied in human body fluid environment.

[0007] It is a very effective method to use solid self-lubricating fillers to improve the friction and wear performance of polyether ether ketone. Graphite, carbon fiber, glass fiber, carbon nanotube, silicon carbide, boron nitride and various nano oxides are often used as reinforcing fillers for reinforcing polyether ether ketone. Based on this, the application provides a G-CNT / boron nitride reinforced polyether ether ketone composite material and a preparation method and application thereof. SUMMARY

[0008] The purpose of the application is to provide a G-CNT / boron nitride reinforced polyether ether ketone composite material and a preparation method and application thereof, the preparation method of the composite material is simple, the cost is low, the industrial production is easy to realize, and the wear resistance of the polyether ether ketone material can be significantly improved.

[0009] In one aspect, the present application provides a G-CNT / boron nitride reinforced polyether ether ketone composite material, which is composed of G-CNT hybrid material, spherical boron nitride particles and polyether ether ketone, and contains 0.1-20 wt% of G-CNT hybrid material, 0.1-5 wt% of boron nitride, and the balance of polyether ether ketone, based on the total mass of the composite material.

[0010] Further, the G-CNT hybrid material is in the form of powder, and the preparation method thereof comprises: heating graphene / cobalt-glycolate precursor at a heating rate of 8-12 ℃ / min to 650-750 ℃ under the condition of continuously passing hydrogen / argon mixed gas, changing to continuously passing acetylene gas, and keeping the temperature at 650-750 ℃ for 25-35 min, and then cooling to room temperature, and collecting the product, and then cleaning with dilute sulfuric acid, ionized water and ethanol vacuum filtration, and drying to obtain the graphene / cobalt-glycolate precursor black powder.

[0011] Further, the preparation method of the graphene / cobalt-glycolate precursor comprises: dispersing graphene and cobalt acetate in ethylene glycol, stirring and then ultrasonicating to obtain a dispersion liquid, heating the dispersion liquid at 150-170 ℃ for 50-70 min, vacuum filtering and cleaning the obtained precipitate with deionized water and alcohol, and then heating at 75-85 ℃ under vacuum for 10-14 h to obtain the graphene / cobalt-glycolate precursor black powder.

[0012] Further, the specific surface area of the G-CNT hybrid material is 100-2000 m 2 / g, and the pore size is 2-50 nm.

[0013] Further, the particle size of the polyether ether ketone powder is 5-200 μm.

[0014] In another aspect, the present application also provides a preparation method of the G-CNT / boron nitride reinforced polyether ether ketone composite material, which comprises mixing G-CNT hybrid material, spherical boron nitride particles and polyether ether ketone, and then hot-pressing and forming.

[0015] Further, the mixing method is high-speed shearing, specifically, dispersing at 5000-25000 rpm for 30-60 min.

[0016] Further, the hot-pressing pressure is 20-100 MPa, the temperature is raised at a heating rate of 8-12 ℃ / min, the hot-pressing temperature is 300-400 ℃, and the pressure-keeping and heat-keeping time is 30-60 min.

[0017] The G-CNT / boron nitride reinforced polyether ether ketone composite material prepared in the present application is applied to the preparation of artificial joint materials, and the artificial joint is one or several of hip joint, knee joint and shoulder joint.

[0018] The beneficial effects of this invention are as follows: (1) The special structure of G-CNT hybrid materials gives them high specific surface area, high elastic modulus and excellent thermal conductivity. Spherical boron nitride particles have ultra-high hardness. G-CNT / boron nitride form a three-dimensional structural reinforcement. Adding G-CNT can form a transfer film on the surface of the composite material, which is beneficial to reducing the surface friction coefficient and wear rate. Boron nitride particles prevent large-area destruction of the internal band structure of polyetheretherketone, which is beneficial to the formation of a wear surface transfer film, which is beneficial to the improvement of surface wear resistance and the reduction of wear rate. In addition, boron nitride particles can enhance the adsorption of nearby molecular chains, inhibit the movement of molecular chains to the friction interface, thereby reducing adhesive friction and reducing the wear rate of the composite material.

[0019] (2) G-CNT / boron nitride reinforced polyether ether ketone composite material can improve the biocompatibility of the material, reduce the inflammatory response of macrophages, and have a certain osteogenic effect, so as to improve the bonding strength between bone tissue and prosthesis material interface.

[0020] (3) G-CNT / boron nitride reinforced polyether ether ketone composite material also has certain antibacterial properties.

[0021] (4) This invention can be applied to orthopedic implants such as artificial hip joints, artificial knee joints, and artificial shoulder joints. Attached Figure Description

[0022] Figure 1 This is a flowchart of the preparation method of the G-CNT / boron nitride reinforced polyether ether ketone composite material of the present invention.

[0023] Figure 2 This is a scanning electron microscope (SEM) image of the G-CNT hybrid material in Example 1 of this invention, 5 μM.

[0024] Figure 3 This is a scanning electron microscope (SEM) image of the G-CNT hybrid material in Example 1 of this invention, 1 μM.

[0025] Figure 4 This is a scanning electron microscope (SEM) image of the graphene / cobalt-glycolic acid precursor from Example 1 of this invention.

[0026] Figure 5 Example 1 of this invention: G-CNT hybrid material is a scanning electron microscope (SEM) image of a three-dimensional interpenetrating network structure formed by vertically growing carbon nanotubes (CNTs) on a graphene substrate. Detailed Implementation

[0027] The technical solution of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0028] This invention discloses a G-CNT / boron nitride reinforced polyetheretherketone composite material, wherein the composite material is composed of G-CNT hybrid material, spherical boron nitride particles and polyetheretherketone. Based on the total mass of the composite material, the G-CNT reinforced polyetheretherketone composite material contains 0.1 to 20 wt% G-CNT hybrid material, 0.1 to 5 wt% boron nitride, and the balance is polyetheretherketone.

[0029] The G-CNT hybrid material is in powder form, and its preparation method includes: dispersing graphene and cobalt acetate in ethylene glycol, stirring and sonicating to obtain a dispersion, heating the dispersion at 150-170℃ for 50-70 min, washing the obtained precipitate with deionized water and alcohol under vacuum filtration, and then heating it under vacuum at 75-85℃ for 10-14 h to obtain a black powder of graphene / cobalt-glycolic acid precursor; heating the graphene / cobalt-glycolic acid precursor to 650-750℃ under continuous hydrogen / argon mixed gas purging at a heating rate of 8-12℃ / min, changing to continuous acetylene gas purging, holding at 650-750℃ for 25-35 min, then cooling to room temperature, collecting the product, washing with dilute sulfuric acid, washing with deionized water and ethanol under vacuum filtration, and drying to obtain the final product.

[0030] The specific surface area of ​​the G-CNT hybrid material is 100~2000 m². 2 / g, with a pore size of 2~50nm; the particle size of the polyether ether ketone powder is 5~200μm.

[0031] The preparation process of this composite material is as follows: Figure 1 As shown, the specific process includes mixing G-CNT powder, spherical boron nitride particles, and polyetheretherketone powder using a high-speed shear dispersion method. The mixing speed is 5000~25000 rpm, and the mixing time is 30~60 min, forming a mixture of G-CNT, spherical boron nitride particles, and polyetheretherketone powder. Subsequently, the mixed powder is subjected to hot pressing treatment. The hot pressing pressure is 20~100 MPa, the temperature is increased at a rate of 8-12℃ / min, the hot pressing temperature is 300~400℃, and the holding time is 30~60 min.

[0032] In a specific embodiment of the present invention, the G-CNT hybrid material is prepared using the following process: Step 1: Preparation of graphene / cobalt-glycolic acid precursor (1) Weigh 100 g of mesoporous graphene and 500 g of cobalt acetate powder and disperse them in 50 L of ethylene glycol. Stir magnetically for 30 min at room temperature. (2) The above mixture was ultrasonically dispersed for 30 min to obtain a uniform dispersion; (3) Pour the dispersion into a 100 L round-bottom container and heat it in a constant temperature oil bath at 160°C for 60 min while maintaining magnetic stirring; (4) The precipitate was first washed with deionized water and then with alcohol under vacuum filtration. The precipitate was heated in a vacuum drying oven at 80°C for 12 h to obtain a black powder of graphene / cobalt-glycolic acid precursor. Step 2: Preparation of G-CNT hybrid materials (1) Weigh 100 g of graphene / cobalt-glycolic acid precursor into a crucible and place the crucible into a tubular furnace quartz tube; (2) at 100 cc min -1 A hydrogen / argon mixture (hydrogen gas fraction of 10%) is introduced into the tube furnace at a certain flow rate for 60 minutes to purge the air from the quartz tube.

[0033] (3) Keep the flow rate of the hydrogen / argon mixed gas constant and increase the temperature inside the tube furnace from room temperature to 700 ℃ at a heating rate of 10 ℃ / min; (4) Introduce acetylene gas into the tubular furnace for 30 min at a flow rate of 200 cc / min. -1 After stopping the acetylene gas supply, maintain the temperature at 700℃ for 30 minutes; (5) Cool the product to room temperature in the furnace and collect the product to obtain the G-CNT hybrid material. Wash the hybrid material with dilute sulfuric acid to remove the metal oxides on the surface, and then wash it several times with deionized water and ethanol under vacuum filtration. Dry it at 80°C for 12 h to obtain the final product G-CNT.

[0034] Example 1 This embodiment provides a G-CNT / boron nitride reinforced polyetheretherketone (PEEK) composite material, using PEEK powder with an average particle size of 20 μm; the reinforcing material is a G-CNT hybrid material with a specific surface area of ​​500 m². 2 / g; spherical boron nitride particles with an average particle size of 10μm.

[0035] The G-CNT hybrid material in this embodiment was prepared using the following process: Step 1: Preparation of graphene / cobalt-glycolic acid precursor (1) Weigh 100 g of mesoporous graphene and 500 g of cobalt acetate powder and disperse them in 50 L of ethylene glycol. Stir magnetically for 30 min at room temperature. (2) The above mixture was ultrasonically dispersed for 30 min to obtain a uniform dispersion; (3) Pour the dispersion into a 100 L round-bottom container and heat it in a constant temperature oil bath at 160°C for 60 min while maintaining magnetic stirring; (4) The precipitate was first washed with deionized water and then with alcohol under vacuum filtration. The precipitate was heated in a vacuum drying oven at 80°C for 12 h to obtain a black powder of graphene / cobalt-glycolic acid precursor. Step 2: Preparation of G-CNT hybrid materials (1) Weigh 100 g of graphene / cobalt-glycolic acid precursor into a crucible and place the crucible into a tubular furnace quartz tube; (2) at 100 cc min -1 A hydrogen / argon mixture (hydrogen gas fraction of 10%) is introduced into the tube furnace at a certain flow rate for 60 minutes to purge the air from the quartz tube.

[0036] (3) Keep the flow rate of the hydrogen / argon mixed gas constant and increase the temperature inside the tube furnace from room temperature to 700 ℃ at a heating rate of 10 ℃ / min; (4) Introduce acetylene gas into the tubular furnace for 30 min at a flow rate of 200 cc / min. -1 After stopping the acetylene gas supply, maintain the temperature at 700℃ for 30 minutes; (5) Cool the product to room temperature in the furnace and collect the product to obtain the G-CNT hybrid material. Wash the hybrid material with dilute sulfuric acid to remove the metal oxides on the surface, and then wash it several times with deionized water and ethanol under vacuum filtration. Dry it at 80°C for 12 h to obtain the final product G-CNT.

[0037] The composite material preparation process in the example is as follows: (1) The polyetheretherketone powder was screened using a sieve with a pore size of 20 μm; (2) Based on a total weight of 1000g, weigh G-CNT, spherical boron nitride particles and polyether ether ketone powder respectively using an electronic balance at a mass fraction of 5% / 5% / 90%; (3) Place the G-CNT hybrid material, spherical boron nitride particles and polyetheretherketone powder into a high-speed shear disperser; (4) The mixture was mixed at a speed of 10,000 rpm using a high-speed shear disperser to obtain a mixed powder; (5) The mixed powder is introduced into the mold cavity, the hot pressing pressure is 30MPa, the temperature is raised to 360℃ at a heating rate of 10℃ / min, the pressure and heat holding time is 45min, and then cooled to 100℃ in the mold, demolded and sampled to obtain G-CNT / boron nitride reinforced polyether ether ketone composite material. The frictional properties of the composite material were tested using linear reciprocating motion under dry friction conditions without lubrication. The grinding couple consisted of Si3N3 ceramic microspheres. The load was 50 N, the frequency was 2 Hz, the grinding head sliding stroke was 5 mm, and the test time was 30 min. The test results are shown in Table 1 below: Table 1 Properties of G-CNT / boron nitride reinforced polyetheretherketone composites Example 2 This embodiment provides a G-CNT / boron nitride reinforced polyetheretherketone (PEEK) composite material. The PEEK powder used has an average particle size of 20 μm; the reinforcing material is a G-CNT hybrid material with a specific surface area of ​​100 m². 2 / g; spherical boron nitride particles with an average particle size of 10μm.

[0038] The composite material preparation process is as follows: (1) The polyetheretherketone powder was screened using a sieve with a pore size of 20 μm; (2) Based on a total of 1000g, weigh G-CNT, boron nitride and polyether ether ketone powders respectively using an electronic balance at mass fractions of 0% / 100%, 1% / 1% / 98%, 3% / 3% / 94%, 5% / 5% / 90%, 10% / 10% / 80%, and 15% / 15% / 70%.

[0039] (3) Place the G-CNT hybrid material, spherical boron nitride particles and polyether ether ketone powder into a high-speed shear disperser.

[0040] (4) The mixture is mixed at a speed of 10,000 rpm using a high-speed shear disperser to obtain mixed powder.

[0041] (5) The mixed powder is introduced into the mold cavity, the hot pressing pressure is 30MPa, the temperature is raised to 360℃ at a heating rate of 10℃ / min, the pressure and heat holding time is 45min, and then cooled to 100℃ in the mold, demolded and sampled to obtain G-CNT / boron nitride reinforced polyether ether ketone composite material. The frictional properties of the composite material were tested using linear reciprocating motion under dry friction conditions without lubrication. The grinding pair consisted of Si3N3 ceramic microspheres; the load was 50 N, the frequency was 2 Hz, the grinding head sliding stroke was 5 mm, and the test time was 30 min. The results are shown in Table 2 below. Table 2 Properties of G-CNT / boron nitride reinforced polyetheretherketone composites Example 3 This embodiment provides a G-CNT / boron nitride reinforced polyetheretherketone (PEEK) composite material, using PEEK powder with an average particle size of 20 μm; the reinforcing material is a G-CNT hybrid material with a specific surface area of ​​1000 m². 2 / g; spherical boron nitride particles with an average particle size of 10μm.

[0042] The composite material preparation process is as follows: (1) The polyetheretherketone powder was screened using a sieve with a pore size of 20 μm; (2) Based on a total weight of 1000g, weigh G-CNT, spherical boron nitride particles and polyether ether ketone powder respectively using an electronic balance according to the following mass fractions: 0% / 100%, 1% / 1% / 98%, 3% / 3% / 94%, 5% / 5% / 90%, 10% / 10% / 80%, and 15% / 15% / 70%. (3) Place the G-CNT hybrid material, spherical boron nitride particles and polyetheretherketone powder into a high-speed shear disperser; (4) The mixture was mixed at a speed of 10,000 rpm using a high-speed shear disperser to obtain a mixed powder; (5) The mixed powder is introduced into the mold cavity, the hot pressing pressure is 30MPa, the temperature is raised to 360℃ at a heating rate of 10℃ / min, the pressure and heat holding time is 45min, and then cooled to 100℃ in the mold, demolded and sampled to obtain G-CNT / boron nitride reinforced polyether ether ketone composite material. (6) Testing the friction properties of the composite material. The test was conducted under dry friction conditions with no lubrication, using linear reciprocating motion. The grinding couple consisted of Si3N3 ceramic balls; the load was 50 N, the frequency was 2 Hz, the grinding head sliding stroke was 5 mm, and the test time was 30 min. The test results are shown in Table 3 below: Table 3 Properties of G-CNT / boron nitride reinforced polyetheretherketone composites Example 4 This embodiment provides a G-CNT / boron nitride reinforced polyetheretherketone (PEEK) composite material, using PEEK powder with an average particle size of 20 μm; the reinforcing material is a G-CNT hybrid material with a specific surface area of ​​1500 m². 2 / g; spherical boron nitride particles with an average particle size of 10μm.

[0043] The composite material preparation process is as follows: (1) The polyetheretherketone powder was screened using a sieve with a pore size of 20 μm; (2) Based on a total weight of 1000g, weigh G-CNT, spherical boron nitride particles and polyether ether ketone powder respectively using an electronic balance at mass fractions of 0% / 100%, 1% / 1% / 98%, 3% / 3% / 94%, 5% / 5% / 90%, 10% / 10% / 80%, and 15% / 15% / 70%.

[0044] (3) Place the G-CNT hybrid material, spherical boron nitride particles and polyether ether ketone powder into a high-speed shear disperser.

[0045] (4) The mixture is mixed at a speed of 10,000 rpm using a high-speed shear disperser to obtain mixed powder.

[0046] (5) The mixed powder is introduced into the mold cavity, the hot pressing pressure is 30MPa, the temperature is raised to 360℃ at a heating rate of 10℃ / min, the pressure and heat holding time is 45min, and then cooled to 100℃ in the mold, demolded and sampled to obtain G-CNT / boron nitride reinforced polyether ether ketone composite material.

[0047] The frictional properties of the composite material were tested using linear reciprocating motion under dry friction conditions without lubrication. The grinding couple consisted of Si3N3 ceramic microspheres; the load was 50 N, the frequency was 2 Hz, the grinding head sliding stroke was 5 mm, and the test time was 30 min. The test results are shown in Table 4 below. Table 4 Properties of G-CNT / boron nitride reinforced polyetheretherketone composites Comparative Example 1 This comparative example provides a graphene / boron nitride reinforced polyetheretherketone (PEEK) composite material, using PEEK powder with an average particle size of 20 μm; the reinforcing material is graphene nanosheets with a specific surface area of ​​500 m². 2 / g; spherical boron nitride particles with an average particle size of 10μm.

[0048] The composite material preparation process is as follows: (1) The polyetheretherketone powder was screened using a sieve with a pore size of 20 μm; (2) Based on a total weight of 1000g, weigh the graphene nanosheets, spherical boron nitride particles and polyether ether ketone powder using an electronic balance according to the following mass fractions: 0% / 100%, 1% / 1% / 98%, 3% / 3% / 94%, 5% / 5% / 90%, 10% / 10% / 80%, and 15% / 15% / 70%.

[0049] (3) Place the graphene nanosheets, spherical boron nitride particles and polyether ether ketone powder into a high-speed shear disperser.

[0050] (4) The mixture is mixed at a speed of 10,000 rpm using a high-speed shear disperser to obtain mixed powder.

[0051] (5) The mixed powder is introduced into the mold cavity, the hot pressing pressure is 30MPa, the temperature is raised to 360℃ at a heating rate of 10℃ / min, the pressure and heat holding time is 45min, and then cooled to 100℃ in the mold, demolded and sampled to obtain graphene nanosheets / boron nitride reinforced polyether ether ketone composite material.

[0052] The frictional properties of the composite material were tested using linear reciprocating motion under dry friction conditions without lubrication. The grinding couple consisted of Si3N3 ceramic microspheres; the load was 50 N, the frequency was 2 Hz, the grinding head sliding stroke was 5 mm, and the test time was 30 min. The test results are shown in Table 5 below. Table 5 Properties of graphene nanosheets / boron nitride reinforced polyetheretherketone composites Comparative Example 2 This comparative example provides a graphite / boron nitride reinforced polyetheretherketone (PEEK) composite material, using PEEK powder with an average particle size of 20 μm; the reinforcing material is graphite with a particle size of 3.6 μm; and spherical boron nitride particles with an average particle size of 10 μm.

[0053] The composite material preparation process is as follows: (1) The polyetheretherketone powder was screened using a sieve with a pore size of 20 μm; (2) Based on a total weight of 1000g, weigh out graphite, spherical boron nitride particles and polyether ether ketone powder using an electronic balance at mass fractions of 0% / 100%, 1% / 1% / 98%, 3% / 3% / 94%, 5% / 5% / 90%, 10% / 10% / 80%, and 15% / 15% / 70%, respectively.

[0054] (3) Place the graphite, spherical boron nitride particles and polyether ether ketone powder into a high-speed shear disperser.

[0055] (4) The mixture is mixed at a speed of 10,000 rpm using a high-speed shear disperser to obtain mixed powder.

[0056] (5) The mixed powder is introduced into the mold cavity, the hot pressing pressure is 30MPa, the temperature is raised to 360℃ at a heating rate of 10℃ / min, the pressure and heat holding time is 45min, and then cooled to 100℃ in the mold, demolded and sampled to obtain graphite / boron nitride reinforced polyether ether ketone composite material.

[0057] The frictional properties of the composite material were tested using linear reciprocating motion under dry friction conditions without lubrication. The grinding couple consisted of Si3N3 ceramic microspheres; the load was 50 N, the frequency was 2 Hz, the grinding head sliding stroke was 5 mm, and the test time was 30 min. The test results are shown in Table 6 below. Table 6 Properties of graphite / boron nitride reinforced polyetheretherketone composites Comparative Example 3 This comparative example provides a carbon fiber / boron nitride reinforced polyetheretherketone (PEEK) composite material, using PEEK powder with an average particle size of 20 μm; the reinforcing material is carbon fiber with a fiber diameter of 8 μm and a fiber length of 4 mm, and spherical boron nitride particles with an average particle size of 10 μm.

[0058] The composite material preparation process is as follows: (1) The polyetheretherketone powder was screened using a sieve with a pore size of 20 μm; (2) Based on a total weight of 1000g, weigh carbon fiber, spherical boron nitride particles and polyether ether ketone powder using an electronic balance at mass fractions of 0% / 100%, 1% / 1% / 98%, 3% / 3% / 94%, 5% / 5% / 90%, 10% / 10% / 80%, and 15% / 15% / 70%, respectively.

[0059] (3) Place the carbon fiber, spherical boron nitride particles and polyether ether ketone powder into a high-speed shear disperser.

[0060] (4) The mixture is mixed at a speed of 10,000 rpm using a high-speed shear disperser to obtain mixed powder.

[0061] (5) The mixed powder is introduced into the mold cavity, the hot pressing pressure is 30MPa, the temperature is raised to 360℃ at a heating rate of 10℃ / min, the pressure and heat holding time is 45min, and then cooled to 100℃ in the mold, demolded and sampled to obtain carbon fiber / boron nitride reinforced polyether ether ketone composite material.

[0062] The frictional properties of the composite material were tested using linear reciprocating motion under dry friction conditions without lubrication. The grinding couple consisted of Si3N3 ceramic microspheres; the load was 50 N, the frequency was 2 Hz, the grinding head sliding stroke was 5 mm, and the test time was 30 min. The test results are shown in Table 7 below. Table 7 Properties of carbon fiber / boron nitride reinforced polyetheretherketone composites Comparative Example 4 This comparative example provides a glass fiber / boron nitride reinforced polyetheretherketone (PEEK) composite material, using PEEK powder with an average particle size of 20 μm; the reinforcing material is glass fiber with a diameter of 8 μm and a length of 4 mm, and spherical boron nitride particles with an average particle size of 10 μm.

[0063] The composite material preparation process is as follows: (1) The polyetheretherketone powder was screened using a sieve with a pore size of 20 μm; (2) Based on a total weight of 1000g, weigh glass fiber, spherical boron nitride particles and polyether ether ketone powder using an electronic balance at mass fractions of 0% / 100%, 1% / 1% / 98%, 3% / 3% / 94%, 5% / 5% / 90%, 10% / 10% / 80%, and 15% / 15% / 70%, respectively.

[0064] (3) Place the glass fiber, spherical boron nitride particles and polyether ether ketone powder into a high-speed shear disperser.

[0065] (4) The mixture is mixed at a speed of 10,000 rpm using a high-speed shear disperser to obtain mixed powder.

[0066] (5) The mixed powder is introduced into the mold cavity, the hot pressing pressure is 30MPa, the temperature is raised to 360℃ at a heating rate of 10℃ / min, the pressure and heat holding time is 45min, and then cooled to 100℃ in the mold, demolded and sampled to obtain glass fiber / boron nitride reinforced polyether ether ketone composite material.

[0067] The frictional properties of the composite material were tested using linear reciprocating motion under dry friction conditions without lubrication. The grinding couple consisted of Si3N3 ceramic spheres; the load was 50 N, the frequency was 2 Hz, the grinding head sliding stroke was 5 mm, and the test time was 30 min. The test results are shown in Table 8 below. Table 8 Properties of Glass Fiber / Boron Nitride Reinforced Polyetheretherketone Composites Comparative Example 5 This comparative example provides a carbon nanotube / boron nitride reinforced polyetheretherketone composite material, using polyetheretherketone powder with an average particle size of 20 μm; the reinforcing material is carbon nanotubes with a diameter of 40 nm and spherical boron nitride particles with an average particle size of 10 μm.

[0068] The composite material preparation process is as follows: (1) The polyetheretherketone powder was screened using a sieve with a pore size of 20 μm; (2) Based on a total weight of 1000g, weigh carbon nanotubes, spherical boron nitride particles and polyether ether ketone powder using an electronic balance at mass fractions of 0% / 100%, 1% / 1% / 98%, 3% / 3% / 94%, 5% / 5% / 90%, 10% / 10% / 80%, and 15% / 15% / 70%, respectively.

[0069] (3) Place carbon nanotubes, spherical boron nitride particles and polyether ether ketone powder into a high-speed shear disperser.

[0070] (4) The mixture is mixed at a speed of 10,000 rpm using a high-speed shear disperser to obtain mixed powder.

[0071] (5) The mixed powder is introduced into the mold cavity, the hot pressing pressure is 30MPa, the temperature is raised to 360℃ at a heating rate of 10℃ / min, the pressure and heat holding time is 45min, and then cooled to 100℃ in the mold, demolded and sampled to obtain carbon nanotube / boron nitride reinforced polyether ether ketone composite material.

[0072] The frictional properties of the composite material were tested using linear reciprocating motion under dry friction conditions without lubrication. The grinding couple consisted of Si3N3 ceramic spheres; the load was 50 N, the frequency was 2 Hz, the grinding head sliding stroke was 5 mm, and the test time was 30 min. The test results are shown in Table 9 below: Table 9 Properties of carbon nanotube / boron nitride reinforced polyetheretherketone composites Comparative Example 6 This comparative example provides a silicon carbide / boron nitride reinforced polyetheretherketone composite material, using polyetheretherketone powder with an average particle size of 20 μm; the reinforcing material is silicon carbide with an average particle size of 10 μm, and spherical boron nitride particles with an average particle size of 10 μm.

[0073] The composite material preparation process is as follows: (1) The polyetheretherketone powder was screened using a sieve with a pore size of 20 μm; (2) Based on a total weight of 1000g, weigh out silicon carbide, boron nitride spherical particles and polyether ether ketone powder respectively using an electronic balance according to the following mass fractions: 0% / 100%, 1% / 1% / 98%, 3% / 3% / 94%, 5% / 5% / 90%, 10% / 10% / 80%, and 15% / 15% / 70%.

[0074] (3) Place silicon carbide, boron nitride spherical particles and polyether ether ketone powder into a high-speed shear disperser.

[0075] (4) The mixture is mixed at a speed of 10,000 rpm using a high-speed shear disperser to obtain mixed powder.

[0076] (5) The mixed powder is introduced into the mold cavity, the hot pressing pressure is 30MPa, the temperature is raised to 360℃ at a heating rate of 10℃ / min, the pressure and heat holding time is 45min, and then cooled to 100℃ in the mold, demolded and sampled to obtain silicon carbide / boron nitride reinforced polyether ether ketone composite material.

[0077] The frictional properties of the composite material were tested using linear reciprocating motion under dry friction conditions without lubrication. The grinding couple consisted of Si3N3 ceramic microspheres; the load was 50 N, the frequency was 2 Hz, the grinding head sliding stroke was 5 mm, and the test time was 30 min. The test results are shown in Table 10 below: Table 10 Properties of silicon carbide / boron nitride reinforced polyetheretherketone composites Comparative Example 7 This comparative example provides a boron nitride-reinforced polyetheretherketone (PEEK) composite material, using PEEK powder with an average particle size of 20 μm; the reinforcing material is spherical boron nitride particles with an average particle size of 10 μm.

[0078] The composite material preparation process is as follows: (1) The polyetheretherketone powder was screened using a sieve with a pore size of 20 μm; (2) Based on a total weight of 1000g, weigh out spherical boron nitride particles and polyether ether ketone powder using an electronic balance at mass fractions of 0% / 100%, 1% / 99%, 3% / 97%, 5% / 95%, 10% / 90%, and 15% / 85%, respectively. (3) Place the spherical boron nitride particles and polyether ether ketone powder into a high-speed shear disperser; (4) The mixture was mixed at a speed of 10,000 rpm using a high-speed shear disperser to obtain a mixed powder; (5) The mixed powder is introduced into the mold cavity, the hot pressing pressure is 30MPa, the temperature is raised to 360℃ at a heating rate of 10℃ / min, the pressure and heat holding time is 45min, and then cooled to 100℃ in the mold, demolded and sampled to obtain boron nitride reinforced polyether ether ketone composite material. (6) Testing the friction properties of the composite material. The test was conducted under dry friction conditions with no lubrication, using linear reciprocating motion. The grinding couple consisted of Si3N3 ceramic balls; the load was 50 N, the frequency was 2 Hz, the grinding head sliding stroke was 5 mm, and the test time was 30 min. The test results are shown in Table 11 below: Table 11 Properties of Boron Nitride Reinforced Polyether Ether Ketone Composites Comparative Example 8 This comparative example provides a G-CNT reinforced polyetheretherketone (PEEK) composite material, using PEEK powder with an average particle size of 20 μm; the reinforcing material is a G-CNT hybrid material with a specific surface area of ​​500 m². 2 / g.

[0079] The composite material preparation process is as follows: (1) The polyetheretherketone powder was screened using a sieve with a pore size of 20 μm; (2) Based on a total of 1000g, weigh G-CNT and polyether ether ketone powders using an electronic balance at mass fractions of 0% / 100%, 1% / 99%, 3% / 97%, 5% / 95%, 10% / 90%, and 15% / 85%, respectively.

[0080] (3) Place the G-CNT hybrid material and polyether ether ketone powder into a high-speed shear disperser.

[0081] (4) The mixture is mixed at a speed of 10,000 rpm using a high-speed shear disperser to obtain mixed powder.

[0082] (5) The mixed powder is introduced into the mold cavity, the hot pressing pressure is 30MPa, the temperature is raised to 360℃ at a heating rate of 10℃ / min, the pressure and heat holding time is 45min, and then cooled to 100℃ in the mold, demolded and sampled to obtain G-CNT reinforced polyether ether ketone composite material. The frictional properties of the composite material were tested using linear reciprocating motion under dry friction conditions without lubrication. The grinding pair consisted of Si3N3 ceramic microspheres; the load was 50 N, the frequency was 2 Hz, the grinding head sliding stroke was 5 mm, and the test time was 30 min. The results are shown in Table 12 below. Table 12 Properties of G-CNT Reinforced Polyetheretherketone Composites Finally, it should be noted that the above embodiments and comparative examples are only used to illustrate the present invention and are not intended to limit the technical solutions described in the present invention; those skilled in the art should understand that modifications or equivalent substitutions can still be made to the present invention; and all technical solutions and improvements that do not depart from the spirit and scope of the present invention should be covered within the scope of the claims of the present invention.

Claims

1. A G-CNT / boron nitride reinforced polyether ether ketone composite material, characterized in that, The composite material is composed of G-CNT hybrid material, spherical boron nitride particles and polyether ether ketone, wherein the G-CNT / boron nitride reinforced polyether ether ketone composite contains 0.1-20 wt% of G-CNT hybrid material, 0.1-5 wt% of boron nitride, and the balance of polyether ether ketone, based on the total mass of the composite material.

2. A G-CNT / boron nitride reinforced polyether ether ketone composite material according to claim 1, characterized in that, The G-CNT hybrid material is in powder form, and the preparation method comprises: heating the graphene / cobalt-glycolic acid precursor at a heating rate of 8-12 ℃ / min to 650-750 ℃ under continuous hydrogen / argon mixed gas, changing to continuous acetylene gas at 650-750 ℃ for 25-35 min, and then cooling to room temperature, collecting the product, and then washing with dilute sulfuric acid, ionized water and ethanol vacuum filtration, and drying to obtain the product.

3. A G-CNT / boron nitride reinforced polyether ether ketone composite material according to claim 2, characterized in that, The preparation method of the graphene / cobalt-glycolic acid precursor comprises: dispersing graphene and cobalt acetate in ethylene glycol, stirring and then ultrasonicating to obtain a dispersion liquid, heating the dispersion liquid at 150-170 ℃ for 50-70 min, vacuum filtering the obtained precipitate with deionized water and alcohol, and then heating at 75-85 ℃ under vacuum for 10-14 h to obtain a black powder of graphene / cobalt-glycolic acid precursor.

4. The G-CNT / boron nitride reinforced polyether ether ketone composite according to claim 1, characterized in that, The specific surface area of the G-CNT hybrid material is 100-2000 m 2 / g, and the pore size is 2-50 nm.

5. The G-CNT / boron nitride reinforced polyether ether ketone composite according to claim 1, characterized in that, The spherical boron nitride is in powder form, and the particle size is 1-30 μm; and the particle size of the polyether ether ketone powder is 5-200 μm.

6. A process for the preparation of a G-CNT / boron nitride reinforced polyether ether ketone composite material as claimed in any one of claims 1 to 5, characterized in that, The steps comprise mixing the G-CNT hybrid material, spherical boron nitride particles and polyether ether ketone, and then hot-pressing.

7. A method of preparing a G-CNT / boron nitride reinforced polyether ether ketone composite according to claim 6, characterized in that, The mixing method is high-speed shearing, specifically, dispersing at 5000-25000 rpm for 30-60 min.

8. A method of preparing a G-CNT / boron nitride reinforced polyether ether ketone composite according to claim 6, characterized in that, The hot-pressing pressure is 20-100 MPa, the temperature is raised at a heating rate of 8-12 ℃ / min, the hot-pressing temperature is 300-400 ℃, and the pressure holding and heat preservation time is 30-60 min.

9. The G-CNT / boron nitride reinforced polyether ether ketone composite material according to any one of claims 1-5 is applied to the preparation of artificial joint materials.

10. G-CNT / boron nitride reinforced polyether ether ketone composite material applications according to claim 9, characterized in that, The artificial joint comprises one or more of hip joint, knee joint and shoulder joint.

Images